Mildewproof antibacterial halogen-free flame-retardant PC / ABS laser engraving master batch and preparation method and application thereof

Abstract

The application provides a mildew-proof antibacterial halogen-free flame-retardant PC / ABS laser engraving master batch and a preparation method and application thereof, and relates to the technical field of PC / ABS alloy materials. The mildew-proof antibacterial halogen-free flame-retardant PC / ABS laser engraving master batch is prepared from the following raw materials in parts by mass: 20-70 parts of polycarbonate, 20-70 parts of acrylonitrile-butadiene-styrene plastic, 10-80 parts of modified CaCO3 particles, 10-75 parts of modified Mg(OH)2 particles, 1-5 parts of modified inorganic mildew-proof antibacterial agent, 0.1-8 parts of modified laser absorber, 0.2-1.0 parts of dispersant, 0.1-0.5 parts of antioxidant, 0.1-1 part of lubricant, and 0.2-1.0 parts of plasticizer. The surface-modified Mg(OH)2 powder, the modified inorganic mildew-proof antibacterial agent and the laser absorber can be uniformly dispersed in the PC / ABS alloy product, and the mildew-proof antibacterial performance, the flame-retardant performance and the laser engraving effect of the PC / ABS alloy product are effectively improved in a synergistic manner.

Description

Technical Field

[0001] This invention relates to the field of PC / ABS alloy material technology, and in particular to a mildew-proof, antibacterial, halogen-free, flame-retardant PC / ABS laser-engraved masterbatch, its preparation method, and its application. Background Technology

[0002] PC / ABS alloy is an important engineering plastic that combines the high strength and heat resistance of polycarbonate (PC) with the easy processability and high impact strength of acrylonitrile-butadiene-styrene copolymer (ABS). It is widely used in the automotive, electronics, chemical, pharmaceutical, and biological industries. However, with the continuous improvement of people's living standards, traditional PC / ABS alloy products can no longer meet the demands for safety, health, and comfort. For example, traditional PC / ABS alloy products are flammable plastics (oxygen index (OI) < 22%), failing to meet the fire safety requirements of automotive and electronic products. Furthermore, traditional PC / ABS alloy products are prone to bacterial and mold growth under certain temperature and humidity conditions, posing varying degrees of harm to the environment and human health. In addition, during storage, handling, and long-term contact and friction, traditionally printed or sprayed markings on PC / ABS alloy products are easily blurred or damaged, making identification difficult. Therefore, developing new wear-resistant, stable, mildew-resistant, antibacterial, halogen-free, and flame-retardant PC / ABS alloy materials to meet the needs of modern PC / ABS alloy products is of great significance.

[0003] Currently, flame-retardant PC / ABS alloy materials on the market typically use halogenated flame retardants, such as bromine-based flame retardants. While effective, these are costly and environmentally unfriendly, producing large amounts of toxic and corrosive hydrogen halide gases during fires, significantly hindering escape and firefighting efforts. In recent years, industry and academia have been actively developing new flame retardants to replace halogenated ones, such as halogen-free flame retardants (phosphorus-based, nitrogen-based, and inorganic flame retardants) and nano-flame retardants, to achieve more environmentally friendly and safer flame-retardant effects. Besides flame-retardant performance, anti-mildew, antibacterial, and wear-resistant properties are also important requirements for modern PC / ABS alloy products. Currently, there are two common methods to improve the anti-mildew and antibacterial properties of PC / ABS alloy products: one is to add a certain proportion of organic or natural anti-mildew and antibacterial agents. However, these agents are relatively toxic, have a short duration of action, and poor heat resistance, and are gradually being phased out in modern PC / ABS alloy products. The other method is to add a certain proportion of inorganic metal ion-based anti-mildew and antibacterial agents (such as silver, copper, zinc ion compounds, and titanium oxides). These agents have high safety, good anti-mildew and antibacterial properties, heat resistance, and chemical stability, and are widely used in building materials, coatings, plastics, textiles, and other fields. Laser engraving, also known as laser marking, is a technology that uses a high-energy-density laser beam to etch or mark the surface of materials. Its advantages include fast marking speed, beautiful image marking, high resolution, wear resistance, wide range, low cost, strong anti-counterfeiting properties, and environmental friendliness, eliminating the need for ink. These advantages make laser engraving an important technology in modern manufacturing, especially in applications requiring fine and permanent marking. However, traditional PC / ABS materials suffer from localized thermal deformation and color changes during laser engraving, failing to achieve optimal laser engraving results. To meet the needs of modern PC / ABS alloy products, those skilled in the art urgently need to develop a mildew-resistant, antibacterial, halogen-free flame-retardant PC / ABS laser engraving masterbatch with broad-spectrum anti-mildew and antibacterial properties, flame retardant properties, and good laser engraving effect, as well as its preparation method and application. Summary of the Invention

[0004] The purpose of this invention is to provide a mildew-proof, antibacterial, halogen-free, flame-retardant PC / ABS laser engraving masterbatch, its preparation method, and its application, in order to solve the problems of bacteria and mold growth on traditional PC / ABS alloy products under certain temperature and humidity conditions, as well as the problems of blurred and incomplete markings on traditionally printed or sprayed PC / ABS alloy products, which make identification difficult.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a mildew-proof, antibacterial, halogen-free, flame-retardant PC / ABS laser-engraved masterbatch, prepared from the following raw materials in parts by weight:

[0007] 20-70 parts polycarbonate, 20-70 parts acrylonitrile-butadiene-styrene plastic, 10-80 parts modified CaCO3 particles, 10-75 parts modified Mg(OH)2 particles, 1-5 parts modified inorganic antifungal and antibacterial agent, 0.1-8 parts modified laser absorber, 0.2-1.0 parts dispersant, 0.1-0.5 parts antioxidant, 0.1-1 parts lubricant, and 0.2-1.0 parts plasticizer.

[0008] Preferably, the method for preparing the modified CaCO3 particles includes the following steps: mixing CaCO3 particles, a first surface modifier, and a first lubricant, and reacting to obtain modified CaCO3 particles;

[0009] The first surface modifier includes one or more of silane coupling agents, aluminate esters, titanate coupling agents, and pentaerythritol stearate coupling agents;

[0010] The first lubricant includes one or more of N,N'-ethylene bis-stearamide, N,N'-ethylene bis-oleamide, stearic acid, and zinc stearate;

[0011] The mass ratio of the CaCO3 particles, the first surface modifier, and the first lubricant is 100:0.3-1:0.5-2;

[0012] The reaction temperature is 90–100°C, and the reaction time is 8–15 min.

[0013] Preferably, the method for preparing the modified Mg(OH)2 particles includes the following steps: mixing and reacting Mg(OH)2 particles, a second surface modifier, and a second lubricant to obtain modified Mg(OH)2 particles;

[0014] The second surface modifier includes one or more of the following: silane coupling agent, stearic acid, oleic acid, isocyanate, titanate and aluminate;

[0015] The second lubricant includes one or more of N,N'-ethylene bisoleamide, N,N'-ethylene bisstearamide, polyethylene wax, and zinc stearate;

[0016] The mass ratio of the Mg(OH)2 particles, the second surface modifier, and the second lubricant is 100:0.3-1.5:0.5-2;

[0017] The reaction temperature is 90–110℃, and the reaction time is 7–15 min.

[0018] Preferably, the preparation method of the modified inorganic antifungal and antibacterial agent includes the following steps: mixing and reacting the inorganic antifungal and antibacterial agent with a third surface modifier to obtain the modified inorganic antifungal and antibacterial agent;

[0019] The inorganic antifungal and antibacterial agent includes one or more of the following: titanium dioxide, tin dioxide, silver oxide, copper oxide, cuprous oxide, copper sulfate, zinc oxide, and calcium phosphate.

[0020] The third surface modifier includes one or more of the following: silane coupling agent, titanate, aluminate, phosphate, isocyanate, borate, zinc stearate, and polyethylene wax.

[0021] The mass ratio of the inorganic antifungal and antibacterial agent to the third surface modifier is 100:0.5-2.0;

[0022] The reaction temperature is 90–100°C, and the reaction time is 6–15 min.

[0023] Preferably, the method for preparing the modified laser absorber includes the following steps: mixing and reacting the laser absorber with a fourth surface modifier to obtain the modified laser absorber;

[0024] The laser absorber includes one or more of carbon black, mica powder, basic copper phosphate, copper chromium black, tin oxide, titanium oxide, indium oxide, bismuth oxide, phthalocyanine blue, and phthalocyanine green.

[0025] The fourth surface modifier includes one or more of the following: silane coupling agent, aluminate, titanate, phosphate ester, oleate, zinc stearate, and polyethylene wax.

[0026] The reaction temperature is 90–100°C, and the reaction time is 8–15 min;

[0027] The mass ratio of the laser absorber to the fourth surface modifier is 100:0.3-1.

[0028] Preferably, the dispersant comprises one or more of sodium polyacrylate, nonylphenol polyoxyethylene ether phosphate, polyacrylamide, aminosilane, and sodium dodecylbenzene sulfonate;

[0029] The antioxidants include one or more of the following: tert-butylhydroquinone, tea polyphenols, 2,6-di-tert-butyl-4-methylphenol, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], diisooctyl phosphite, triphenyl phosphite, and diphenyloctyl phosphite.

[0030] Preferably, the lubricant comprises one or more of N,N'-ethylene bis-stearamide, N,N'-ethylene bis-oleamide, polyethylene wax, paraffin wax, stearic acid, and zinc stearate;

[0031] The plasticizer includes one or more of dibutyl phthalate, dioctyl phthalate, di(2-ethylhexyl) sebate, tricresyl phosphate, triphenyl phosphate, and tri(2-ethylhexyl) phosphate.

[0032] This invention also provides a method for preparing the above-mentioned anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch, comprising the following steps:

[0033] Polycarbonate, acrylonitrile-butadiene-styrene plastic, modified CaCO3 particles, modified Mg(OH)2 particles, modified inorganic antifungal and antibacterial agent, modified laser absorber, dispersant, antioxidant, lubricant and plasticizer are mixed, extruded and granulated to obtain antifungal, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch.

[0034] Preferably, the granulation temperature is 210–250°C, the granulation pressure is ≤10MPa, and the granulation current is 50–110A.

[0035] The present invention also provides an application of the above-mentioned anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser engraving masterbatch in electronic product casings, switch covers / button markings, cosmetic packaging materials, automotive interior buttons and dashboards, machine keyboards / buttons, or security anti-counterfeiting labels.

[0036] The present invention has at least the following beneficial effects:

[0037] The anti-mildew, antibacterial, halogen-free, flame-retardant PC / ABS laser engraving masterbatch provided by this invention has excellent broad-spectrum anti-mildew, antibacterial and flame-retardant properties, as well as good laser engraving effect. It can be widely used in electronic product shells, switch covers / button markings, cosmetic packaging materials, automotive interior buttons and dashboards, machine keyboards / buttons or security anti-counterfeiting labels, etc., with immeasurable economic and social benefits. Detailed Implementation

[0038] This invention provides a mildew-proof, antibacterial, halogen-free, flame-retardant PC / ABS laser-engraved masterbatch, prepared from the following raw materials in parts by weight:

[0039] The composition comprises: 20-70 parts polycarbonate, 20-70 parts acrylonitrile-butadiene-styrene plastic, 10-80 parts modified CaCO3 particles, 10-75 parts modified Mg(OH)2 particles, 1-5 parts modified inorganic antifungal and antibacterial agent, 0.1-8 parts modified laser absorber, 0.2-1.0 parts dispersant, 0.1-0.5 parts antioxidant, 0.1-1 part lubricant, and 0.2-1.0 parts plasticizer; preferably, 30-60 parts polycarbonate, 30-60 parts acrylonitrile-butadiene-styrene plastic, 20-60 parts modified CaCO3 particles, 20-55 parts modified Mg(OH)2 particles, and modified inorganic antifungal agent. The composition comprises: 2-4 parts antibacterial agent, 1-7 parts modified laser absorber, 0.3-0.9 parts dispersant, 0.2-0.4 parts antioxidant, 0.3-0.9 parts lubricant, and 0.4-0.8 parts plasticizer; more preferably, 40-50 parts polycarbonate, 40-50 parts acrylonitrile-butadiene-styrene plastic, 30-40 parts modified CaCO3 particles, 30-45 parts modified Mg(OH)2 particles, 3-4 parts modified inorganic antifungal and antibacterial agent, 3-5 parts modified laser absorber, 0.5-0.7 parts dispersant, 0.3-0.4 parts antioxidant, 0.4-0.6 parts lubricant, and 0.5-0.6 parts plasticizer.

[0040] In this invention, the method for preparing the modified CaCO3 particles includes the following steps: mixing CaCO3 particles, a first surface modifier, and a first lubricant, and reacting to obtain modified CaCO3 particles.

[0041] In this invention, the first surface modifier includes one or more of silane coupling agents, aluminate esters, titanate coupling agents, and pentaerythritol stearate coupling agents.

[0042] In this invention, the first lubricant includes one or more of N,N'-ethylene bis-stearamide, N,N'-ethylene bis-oleamide, stearic acid, and zinc stearate.

[0043] In this invention, the mass ratio of the CaCO3 particles, the first surface modifier, and the first lubricant is 100:0.3-1:0.5-2, preferably 100:0.4-0.8:0.8-1.8, and more preferably 100:0.5-0.7:1-1.5.

[0044] In this invention, the reaction temperature is 90-100°C, preferably 92-98°C, more preferably 94-96°C, and even more preferably 95°C; the reaction time is 8-15 min, preferably 10-14 min, and even more preferably 12-13 min.

[0045] In this invention, the method for preparing the modified Mg(OH)2 particles includes the following steps: mixing and reacting Mg(OH)2 particles, a second surface modifier, and a second lubricant to obtain modified Mg(OH)2 particles.

[0046] In this invention, the second surface modifier includes one or more of silane coupling agents, stearic acid, oleic acid, isocyanate, titanate and aluminate.

[0047] In this invention, the second lubricant comprises one or more of N,N'-ethylene bisoleamide, N,N'-ethylene bisstearamide, polyethylene wax, and zinc stearate.

[0048] In this invention, the mass ratio of the Mg(OH)2 particles, the second surface modifier, and the second lubricant is 100:0.3-1.5:0.5-2, preferably 100:0.5-1.2:0.8-1.8, more preferably 100:0.6-1:1-1.5, and even more preferably 100:0.8-1:1.2-1.5.

[0049] In this invention, the reaction temperature is 90-110°C, preferably 95-105°C, more preferably 98-102°C, and even more preferably 100°C; the reaction time is 7-15 min, preferably 8-13 min, and even more preferably 10-11 min.

[0050] In this invention, the preparation method of the modified inorganic antifungal and antibacterial agent includes the following steps: mixing and reacting the inorganic antifungal and antibacterial agent with a third surface modifier to obtain the modified inorganic antifungal and antibacterial agent.

[0051] In this invention, the inorganic antifungal and antibacterial agent includes one or more of titanium dioxide, tin dioxide, silver oxide, copper oxide, cuprous oxide, copper sulfate, zinc oxide, and calcium phosphate.

[0052] In this invention, the third surface modifier includes one or more of the following: silane coupling agent, titanate, aluminate, phosphate, isocyanate, borate, zinc stearate, and polyethylene wax.

[0053] In this invention, the mass ratio of the inorganic antifungal and antibacterial agent to the third surface modifier is 100:0.5 to 2.0, preferably 100:0.7 to 1.8, more preferably 100:0.9 to 1.5, and even more preferably 100:1.1 to 1.3.

[0054] In this invention, the reaction temperature is 90-100°C, preferably 92-98°C, more preferably 94-96°C, and even more preferably 95°C; the reaction time is 6-15 min, preferably 8-13 min, more preferably 9-12 min, and even more preferably 10 min.

[0055] In this invention, the preparation method of the modified laser absorber includes the following steps: mixing and reacting the laser absorber with a fourth surface modifier to obtain the modified laser absorber.

[0056] In this invention, the laser absorber includes one or more of carbon black, mica powder, basic copper phosphate, copper chromium black, tin oxide, titanium oxide, indium oxide, bismuth oxide, phthalocyanine blue, and phthalocyanine green.

[0057] In this invention, the fourth surface modifier includes one or more of the following: silane coupling agent, aluminate, titanate, phosphate ester, oleate, zinc stearate, and polyethylene wax.

[0058] In this invention, the reaction temperature is 90-100°C, preferably 92-98°C, more preferably 94-96°C, and even more preferably 95°C; the reaction time is 8-15 min, preferably 9-14 min, more preferably 10-13 min, and even more preferably 11-12 min.

[0059] In this invention, the mass ratio of the laser absorber to the fourth surface modifier is 100:0.3 to 1, preferably 100:0.3 to 1, more preferably 100:0.3 to 1, and even more preferably 100:0.3 to 1.

[0060] In this invention, the dispersant includes one or more of sodium polyacrylate, nonylphenol polyoxyethylene ether phosphate, polyacrylamide, aminosilane, and sodium dodecylbenzene sulfonate.

[0061] In this invention, the antioxidant includes one or more of the following: tert-butylhydroquinone, tea polyphenols, 2,6-di-tert-butyl-4-methylphenol, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], diisooctyl phosphite, triphenyl phosphite, and diphenyloctyl phosphite.

[0062] In this invention, the lubricant includes one or more of N,N'-ethylene bis-stearamide, N,N'-ethylene bis-oleamide, polyethylene wax, paraffin wax, stearic acid, and zinc stearate.

[0063] In this invention, the plasticizer includes one or more of dibutyl phthalate, dioctyl phthalate, di(2-ethylhexyl) sebacic acid, tricresyl phosphate, triphenyl phosphate, and tri(2-ethylhexyl) phosphate.

[0064] This invention also provides a method for preparing the above-mentioned anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch, comprising the following steps:

[0065] In this invention, polycarbonate, acrylonitrile-butadiene-styrene plastic, modified CaCO3 particles, modified Mg(OH)2 particles, modified inorganic antifungal and antibacterial agent, modified laser absorber, dispersant, antioxidant, lubricant and plasticizer are mixed, extruded and granulated to obtain antifungal, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch.

[0066] In this invention, the granulation temperature is 210–250°C, preferably 220–240°C, more preferably 225–235°C, and even more preferably 230°C; the granulation pressure is ≤10 MPa, preferably 3–10 MPa, and even more preferably 5–8 MPa; the granulation current is 50–110 A, preferably 60–100 A, more preferably 70–90 A, and even more preferably 80 A.

[0067] The present invention also provides an application of the above-mentioned anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser engraving masterbatch in electronic product casings, switch covers / button markings, cosmetic packaging materials, automotive interior buttons and dashboards, machine keyboards / buttons, or security anti-counterfeiting labels.

[0068] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0069] Example 1

[0070] (1) Preparation of modified CaCO3 particles: 1 kg of CaCO3 powder with a particle size of 2500-3500 mesh was dried at 105℃ for 2 hours for later use. The dried CaCO3 powder, zinc stearate, and pentaerythritol stearate coupling agent (manufacturer: Guangdong Jiadelai Technology Co., Ltd., grade PETS) were added to a temperature-controlled high-speed mixer and mixed at 100℃ and 500 r / min for 12 min to obtain surface-modified and activated modified CaCO3 particles. The reaction temperature was controlled at 100℃. The amount of zinc stearate was 1.5% of the mass of calcium carbonate, and the amount of pentaerythritol stearate coupling agent was 0.7% of the mass of calcium carbonate.

[0071] (2) Preparation of modified Mg(OH)2 particles: 1 kg of Mg(OH)2 particles with a particle size of 3500-4500 mesh were dried at 105℃ for 2 hours for later use. The dried Mg(OH)2 particles, stearic acid, and N,N'-ethylene bis-stearamide (manufacturer: Changzhou Kesai Chenggong Plastic Materials Co., Ltd., specification WAX2003) surface modifier were added to a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 12 min to obtain modified Mg(OH)2 particles. The reaction temperature was controlled at 100℃. The amount of stearic acid was 1.0% of the mass of Mg(OH)2, and the amount of N,N'-ethylene bis-stearamide was 1.1% of the mass of Mg(OH)2.

[0072] (3) Preparation of modified inorganic antifungal and antibacterial agent: 0.5 kg of silver oxide was dried at 105 °C for 2 hours for later use. The dried silver oxide (manufacturer: Xilong Scientific Co., Ltd.) and titanate (manufacturer: Nanjing Tengchuan Technology Co., Ltd., grade TC-130) and polyethylene wax (manufacturer: Hubei Boshi Chemical Co., Ltd., grade R-110) surface modifier were added to a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 12 min to obtain the modified inorganic antifungal and antibacterial agent. The reaction temperature was controlled at 95 °C. The amount of titanate was 0.8% of the mass of silver oxide, and the amount of N,N'-ethylene bis-stearamide was 0.9% of the mass of silver oxide.

[0073] (4) Preparation of modified laser absorber: 0.5 kg of phthalocyanine blue was dried at 105 °C for 2 hours for later use. The dried phthalocyanine blue (manufacturer: Yuhong Pigment Co., Ltd., grade PB15:3) and titanate ester (manufacturer: Nanjing Tengchuan Technology Co., Ltd., grade TC-130) surface modifier were added to a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 12 min to obtain the modified laser absorber. The reaction temperature was controlled at 95 °C and the amount of titanate ester was 0.7% of the mass of phthalocyanine blue.

[0074] Preparation of anti-mildew, antibacterial, halogen-free, flame-retardant PC / ABS laser-engraved masterbatch:

[0075] Weigh out 14 parts of polycarbonate by weight (manufacturer: Jiangsu Dingchengxin Engineering Plastics Co., Ltd.The following materials were added to a mixer and stirred at 600 rpm for 25 minutes to obtain a mildew-resistant, antibacterial, halogen-free, flame-retardant PC / ABS laser-engraved masterbatch: 6 parts of acrylonitrile-butadiene-styrene plastic (manufacturer: Shanghai Heyiyuan Plastic Raw Materials Co., Ltd., ASG-30), 20 parts of modified CaCO3 particles, 51 parts of modified Mg(OH)2 particles, 3 parts of modified silver oxide, 4 parts of modified phthalocyanine blue, 0.6 parts of dispersant nonylphenol polyoxyethylene ether phosphate, 0.3 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of lubricant zinc stearate, and 0.6 parts of plasticizer triphenyl phosphate. The mixture was then added to a twin-screw extruder and extruded and granulated at a temperature of 230℃, a current of 80A, and a pressure of 7MPa.

[0076] Example 2

[0077] (1) Preparation of modified CaCO3 particles: 1 kg of CaCO3 powder with a particle size of 2500-3500 mesh was dried at 105℃ for 2 hours for later use. The dried CaCO3 powder, N,N'-ethylene bis-stearamide, and titanate coupling agent were added to a temperature-controlled high-speed mixer and mixed at 95℃ and a stirring rate of 500 r / min for 15 min to obtain surface-modified and activated modified CaCO3 particles. The amount of N,N'-ethylene bis-stearamide was 1.8% of the mass of calcium carbonate, and the amount of titanate coupling agent was 0.5% of the mass of calcium carbonate.

[0078] (2) Preparation of modified Mg(OH)2 particles: 1 kg of Mg(OH)2 particles with a particle size of 3500-4500 mesh were dried at 105℃ for 2 hours for later use. The dried Mg(OH)2 particles, silane coupling agent (manufacturer: Yunsheng Chemical (Shandong) Co., Ltd., grade KH570) and polyethylene wax surface modifier were added to a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 10 min to obtain modified Mg(OH)2 particles. The reaction temperature was controlled at 110℃. The amount of silane coupling agent was 1.5% of the mass of Mg(OH)2, and the amount of polyethylene wax was 0.8% of the mass of Mg(OH)2.

[0079] (3) Preparation of modified inorganic antifungal and antibacterial agent: 0.5 kg of calcium phosphate was dried at 105 °C for 2 hours for later use. The dried calcium phosphate (manufacturer: Shandong Duoju Chemical Co., Ltd.) was added to a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 12 min to obtain the modified inorganic antifungal and antibacterial agent. The reaction temperature was controlled at 95 °C. The amount of aluminate was 0.8% of the mass of calcium phosphate, and the amount of borate was 0.9% of the mass of calcium phosphate.

[0080] (4) Preparation of modified laser absorber: 0.5 kg of tin oxide was dried at 105 °C for 2 hours for later use. The dried tin oxide (manufacturer: Shandong Huian Chemical Co., Ltd.) and oleate (manufacturer: Jiangsu Haian Petrochemical Plant, grade: polysorbate 80) surface modifier were added to a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 12 min to obtain the modified laser absorber. The reaction temperature was controlled at 95 °C and the amount of oleate was 0.7% of the mass of tin oxide.

[0081] Preparation of anti-mildew, antibacterial, halogen-free, flame-retardant PC / ABS laser-engraved masterbatch:

[0082] According to the mass fractions, weigh 14 parts of PC resin, 6 parts of ABS resin, 30 parts of modified CaCO3 particles, 41 parts of modified Mg(OH)2 particles, 3 parts of modified silver oxide, 4 parts of modified phthalocyanine blue, 0.6 parts of dispersant nonylphenol polyoxyethylene ether phosphate, 0.3 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of lubricant zinc stearate, and 0.6 parts of plasticizer triphenyl phosphate. Add them to a mixer and stir at 600 r / min for 25 min to mix evenly. Then add the evenly mixed material to a twin-screw extruder and extrude and granulate it under the conditions of temperature 230℃, current 80A, and pressure 7MPa to obtain anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch.

[0083] Example 3

[0084] (1) Preparation of modified CaCO3 particles: 1 kg of CaCO3 powder with a particle size of 2500-3500 mesh was dried at 105℃ for 2 hours for later use. The dried CaCO3 powder, N,N'-ethylene bisoleamide, and silane coupling agent were added to a temperature-controlled high-speed mixer and mixed at 90℃ and 500 r / min for 15 min to obtain surface-modified and activated modified CaCO3 particles. The amount of N,N'-ethylene bisoleamide was 2% of the mass of calcium carbonate, and the amount of silane coupling agent was 0.8% of the mass of calcium carbonate.

[0085] (2) Preparation of modified Mg(OH)2 particles: 1 kg of Mg(OH)2 particles with a particle size of 3500-4500 mesh were dried at 105℃ for 2 hours for later use. The dried Mg(OH)2 particles were added to a temperature-controlled high-speed mixer with isocyanate and zinc stearate surface modifier and mixed at a stirring rate of 600 r / min for 10 min to obtain modified Mg(OH)2 particles. The reaction temperature was controlled at 110℃. The amount of isocyanate was 0.8% of the mass of Mg(OH)2 and the amount of zinc stearate was 15% of the mass of Mg(OH)2.

[0086] (3) Preparation of modified inorganic antifungal and antibacterial agent: 0.5 kg of copper sulfate was dried at 105 °C for 2 hours for later use. The dried copper sulfate and isocyanate were added to a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 12 min to obtain the modified inorganic antifungal and antibacterial agent. The reaction temperature was controlled at 95 °C and the amount of titanate was 1.2% of the mass of copper sulfate.

[0087] (4) Preparation of modified laser absorber: 0.5 kg of mica powder was dried at 105 °C for 2 hours for later use. The dried mica powder and oleate surface modifier were added to a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 15 min to obtain the modified laser absorber. The reaction temperature was controlled at 90 °C and the amount of oleate was 1% of the mass of mica powder.

[0088] Preparation of anti-mildew, antibacterial, halogen-free, flame-retardant PC / ABS laser-engraved masterbatch:

[0089] According to the mass fractions, weigh 14 parts of PC resin, 6 parts of ABS resin, 40 parts of modified CaCO3 particles, 31 parts of modified Mg(OH)2 particles, 3 parts of modified silver oxide, 4 parts of modified phthalocyanine blue, 0.6 parts of dispersant nonylphenol polyoxyethylene ether phosphate, 0.3 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of lubricant zinc stearate, and 0.6 parts of plasticizer triphenyl phosphate. Add them to a mixer and stir at 600 r / min for 25 min to mix evenly. Then add the evenly mixed material to a twin-screw extruder and extrude and granulate it under the conditions of temperature 230℃, current 80A, and pressure 7MPa to obtain anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch.

[0090] Example 4

[0091] (1) Preparation of modified CaCO3 particles: 1 kg of CaCO3 powder with a particle size of 2500-3500 mesh was dried at 105℃ for 2 hours for later use. The dried CaCO3 powder was mixed with N,N'-ethylene bisoleamide and silane coupling agent in a temperature-controlled high-speed mixer at 95℃ and a stirring rate of 500 r / min for 15 min to obtain surface-modified and activated modified CaCO3 particles. The reaction temperature was controlled at 100℃. The amount of N,N'-ethylene bisoleamide was 2% of the mass of calcium carbonate, and the amount of silane coupling agent was 0.3% of the mass of calcium carbonate.

[0092] (2) Preparation of modified Mg(OH)2 particles: 1 kg of Mg(OH)2 particles with a particle size of 3500-4500 mesh were dried at 105℃ for 2 hours for later use. The dried Mg(OH)2 particles were added to an aluminate ester and N,N'-ethylene bisoleamide surface modifier in a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 12 min to obtain modified Mg(OH)2 particles. The reaction temperature was controlled at 100℃. The amount of aluminate ester was 1.3% of the mass of Mg(OH)2, and the amount of N,N'-ethylene bisoleamide was 1.8% of the mass of Mg(OH)2.

[0093] (3) Preparation of modified inorganic antifungal and antibacterial agent: 0.5 kg of cuprous oxide was dried at 105 °C for 2 hours for later use. The dried cuprous oxide, borate ester, and silane coupling agent were added to a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 12 min to obtain the modified inorganic antifungal and antibacterial agent. The reaction temperature was controlled at 95 °C. The amount of borate ester was 0.5% of the mass of cuprous oxide, and the amount of silane coupling agent was 0.6% of the mass of cuprous oxide.

[0094] (4) Preparation of modified laser absorber: 0.5 kg of phthalocyanine blue was dried at 105 °C for 2 hours for later use. The dried basic copper phosphate and polyethylene wax surface modifier were added to a temperature-controlled high-speed mixer and mixed at a stirring rate of 600 r / min for 15 min to obtain the modified laser absorber. The reaction temperature was controlled at 90 °C and the amount of polyethylene wax was 0.3% of the mass of basic copper phosphate.

[0095] Preparation of anti-mildew, antibacterial, halogen-free, flame-retardant PC / ABS laser-engraved masterbatch:

[0096] According to the mass fractions, weigh 14 parts of PC resin, 6 parts of ABS resin, 20 parts of modified CaCO3 particles, 51 parts of modified Mg(OH)2 particles, 2 parts of modified silver oxide, 5 parts of modified phthalocyanine blue, 0.6 parts of dispersant nonylphenol polyoxyethylene ether phosphate, 0.3 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of lubricant zinc stearate, and 0.6 parts of plasticizer triphenyl phosphate. Add them to a mixer and stir at 600 r / min for 25 min to mix evenly. Then add the evenly mixed material to a twin-screw extruder and extrude and granulate it under the conditions of temperature 230℃, current 80A, and pressure 7MPa to obtain anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch.

[0097] Example 5

[0098] Anti-mold, antibacterial, halogen-free flame-retardant PC / ABS laser engraving masterbatch was prepared using modified CaCO3 particles, modified Mg(OH)2 particles, modified inorganic antifungal and antibacterial agents, and modified laser absorbers obtained in Example 1.

[0099] According to the mass fractions, weigh 14 parts of PC resin, 6 parts of ABS resin, 20 parts of modified CaCO3 particles, 51 parts of modified Mg(OH)2 particles, 4 parts of modified silver oxide, 3 parts of modified phthalocyanine blue, 0.6 parts of dispersant nonylphenol polyoxyethylene ether phosphate, 0.3 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of lubricant zinc stearate, and 0.6 parts of plasticizer triphenyl phosphate. Add them to a mixer and stir at 600 r / min for 25 min to mix evenly. Then add the evenly mixed material to a twin-screw extruder and extrude and granulate it under the conditions of temperature 230℃, current 80A, and pressure 7MPa to obtain anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch.

[0100] Example 6

[0101] Anti-mold, antibacterial, halogen-free flame-retardant PC / ABS laser engraving masterbatch was prepared using modified CaCO3 particles, modified Mg(OH)2 particles, modified inorganic antifungal and antibacterial agents, and modified laser absorbers obtained in Example 1.

[0102] According to the mass fractions, weigh 14 parts of PC resin, 6 parts of ABS resin, 30 parts of modified CaCO3 particles, 41 parts of modified Mg(OH)2 particles, 2 parts of modified silver oxide, 5 parts of modified phthalocyanine blue, 0.6 parts of dispersant nonylphenol polyoxyethylene ether phosphate, 0.3 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of lubricant zinc stearate, and 0.6 parts of plasticizer triphenyl phosphate. Add them to a mixer and stir at 600 r / min for 25 min to mix evenly. Then add the evenly mixed material to a twin-screw extruder and extrude and granulate it under the conditions of temperature 230℃, current 80A, and pressure 7MPa to obtain anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch.

[0103] Example 7

[0104] Anti-mold, antibacterial, halogen-free flame-retardant PC / ABS laser engraving masterbatch was prepared using modified CaCO3 particles, modified Mg(OH)2 particles, modified inorganic antifungal and antibacterial agents, and modified laser absorbers obtained in Example 1.

[0105] According to the mass fractions, weigh 14 parts of PC resin, 6 parts of ABS resin, 30 parts of modified CaCO3 particles, 41 parts of modified Mg(OH)2 particles, 4 parts of modified silver oxide, 3 parts of modified phthalocyanine blue, 0.6 parts of dispersant nonylphenol polyoxyethylene ether phosphate, 0.3 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of lubricant zinc stearate, and 0.6 parts of plasticizer triphenyl phosphate. Add them to a mixer and stir at 600 r / min for 25 min to mix evenly. Then add the evenly mixed material to a twin-screw extruder and extrude and granulate it under the conditions of temperature 230℃, current 80A, and pressure 7MPa to obtain anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch.

[0106] Example 8

[0107] Anti-mold, antibacterial, halogen-free flame-retardant PC / ABS laser engraving masterbatch was prepared using modified CaCO3 particles, modified Mg(OH)2 particles, modified inorganic antifungal and antibacterial agents, and modified laser absorbers obtained in Example 1.

[0108] According to the mass fractions, weigh 14 parts of PC resin, 6 parts of ABS resin, 40 parts of modified CaCO3 particles, 31 parts of modified Mg(OH)2 particles, 2 parts of modified silver oxide, 5 parts of modified phthalocyanine blue, 0.6 parts of dispersant nonylphenol polyoxyethylene ether phosphate, 0.3 parts of antioxidant 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of lubricant zinc stearate, and 0.6 parts of plasticizer triphenyl phosphate. Add them to a mixer and stir at 600 r / min for 25 min to mix evenly. Then add the evenly mixed material to a twin-screw extruder and extrude and granulate it under the conditions of temperature 230℃, current 80A, and pressure 7MPa to obtain anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch.

[0109] Example 9

[0110] Anti-mold, antibacterial, halogen-free flame-retardant PC / ABS laser engraving masterbatch was prepared using modified CaCO3 particles, modified Mg(OH)2 particles, modified inorganic antifungal and antibacterial agents, and modified laser absorbers obtained in Example 1.

[0111] Weigh out 14 parts PC resin, 6 parts ABS resin, 40 parts modified CaCO3 particles, 31 parts modified Mg(OH)2 particles, 4 parts modified silver oxide, 3 parts modified phthalocyanine blue, 0.6 parts dispersant nonylphenol polyoxyethylene ether phosphate, 0.3 parts antioxidant 2,6-di-tert-butyl-4-methylphenol, 0.5 parts lubricant zinc stearate, and 0.6 parts plasticizer triphenyl phosphate. Add these to a mixer and stir at 600 r / min for 25 min until homogeneous. Then, add the homogeneous mixture to a twin-screw extruder and extrude and granulate it under the conditions of 230℃, 80A current, and 7MPa pressure to obtain anti-mildew, antibacterial, halogen-free flame-retardant PC / ABS laser-engraved masterbatch.

[0112] Comparative Example 1

[0113] The difference between Comparative Example 1 and Example 1 is that the CaCO3 particles were not surface modified, while the other operations were the same as in Example 1.

[0114] Comparative Example 2

[0115] The difference between Comparative Example 2 and Example 2 is that the Mg(OH)2 particles were not surface modified, while the other operations were the same as in Example 2.

[0116] Comparative Example 3

[0117] The difference between Comparative Example 3 and Example 3 is that the inorganic antifungal and antibacterial agent was not surface modified, while the other operations were the same as in Example 3.

[0118] Comparative Example 4

[0119] The difference between Comparative Example 4 and Example 4 is that the laser absorber was not surface modified, while the other operations were the same as in Example 4.

[0120] Comparative Example 5

[0121] The difference between Comparative Example 5 and Example 5 is that the CaCO3 particles and Mg(OH)2 particles were not surface modified, while the other operations were the same as in Example 5.

[0122] Comparative Example 6

[0123] The difference between Comparative Example 6 and Example 6 is that the CaCO3 particles and inorganic antifungal and antibacterial agents were not surface modified, while the other operations were the same as in Example 6.

[0124] Comparative Example 7

[0125] The difference between Comparative Example 7 and Example 7 is that the CaCO3 particles and laser absorber were not surface modified, while the other operations were the same as in Example 7.

[0126] Comparative Example 8

[0127] The difference between Comparative Example 8 and Example 8 is that the CaCO3 particles, Mg(OH)2 particles and inorganic antifungal and antibacterial agent were not surface modified, while the other operations were the same as in Example 8.

[0128] Comparative Example 9

[0129] The difference between Comparative Example 9 and Example 9 is that the CaCO3 particles, Mg(OH)2 particles and laser absorber were not surface modified, while the other operations were the same as in Example 9.

[0130] Forty parts of the products obtained in Examples 1-9 and Comparative Examples 1-9 were taken respectively, and mixed evenly with 30 parts of PC and 30 parts of ABS resin. The mixture was then injection molded at 230°C using an injection molding machine to prepare standard specimens and conduct performance tests. The test results are shown in Table 1.

[0131] Antibacterial properties, antifungal properties, limiting oxygen index and vertical flame retardant properties were tested in accordance with national standards GB / T20944.3-2008, GB / T24346-2009, GB / T 2046-1993 and UL-94V. The test results are shown in Table 1 below.

[0132] Laser engraving effect test: The pattern was engraved using a laser engraving machine (power 500W, frequency 20KHz, laser wavelength 1064nm, laser engraving speed 1000 mm / s). The laser engraving effect was judged based on the clarity of the outline and the depth of the pattern. The laser engraving effect is indicated by "☆", and the more "☆" there are, the better the laser engraving effect. The test results are shown in Table 1 below.

[0133] Table 1. Performance test results of samples prepared in Examples 1-9 and Comparative Examples 1-9

[0134]

[0135]

[0136] As shown in Table 1, the modified Mg(OH)2 micropowder and modified inorganic antifungal and antibacterial agent effectively improved the antifungal and antibacterial properties of the PC / ABS alloy, as well as its flame retardancy and limiting oxygen index. Simultaneously, the addition of the modified laser absorber enhanced the laser engraving effect of the PC / ABS alloy material and significantly reduced the application cost of PVC products. A comparison of the results of Examples 1-9 and Comparative Examples 1-9 shows that the unmodified CaCO3 particles, Mg(OH)2 micropowder, inorganic antifungal and antibacterial agent, and laser absorber did not provide ideal antifungal and antibacterial properties, flame retardancy, and laser engraving effect for the PC / ABS alloy material. This is because the surface-modified Mg(OH)2 micropowder, modified silver oxide, and phthalocyanine blue can be uniformly dispersed in the PC / ABS alloy product, effectively and synergistically improving its antifungal and antibacterial properties, flame retardancy, and laser engraving effect.

[0137] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A mildew-proof and antibacterial halogen-free flame-retardant PC / ABS laser-engravable master batch, characterized in that, The raw materials are prepared by the following quality parts: Polycarbonate 20~70 parts, acrylonitrile-butadiene-styrene plastic 20~70 parts, modified CaCO3 particles 10~80 parts, modified Mg(OH)2 particles 10~75 parts, modified inorganic mildew-resistant antibacterial agent 1~5 parts, modified laser absorber 0.1~8 parts, dispersant 0.2~1.0 parts, antioxidant 0.1~0.5 parts, lubricant 0.1~1 parts, plasticizer 0.2~1.0 parts; The preparation method of the modified CaCO3 particles comprises the following steps: mixing CaCO3 particles, a first surface modifier and a first lubricant, and reacting to obtain modified CaCO3 particles; The first surface modifier comprises one or more of silane coupling agent, aluminate, titanate coupling agent and pentaerythritol stearate coupling agent; The first lubricant comprises one or more of N,N'-ethylene bis-stearamide, N,N'-ethylene bis-oleamide, stearic acid and zinc stearate; The mass ratio of the CaCO3 particles, the first surface modifier and the first lubricant is 100:0.3~1:0.5~2; The preparation method of the modified Mg(OH)2 particles comprises the following steps: mixing Mg(OH)2 particles, a second surface modifier and a second lubricant, and reacting to obtain modified Mg(OH)2 particles; The second surface modifier comprises one or more of silane coupling agent, stearic acid, oleic acid, isocyanate, titanate and aluminate; The second lubricant comprises one or more of N,N'-ethylene bis-oleamide, N,N'-ethylene bis-stearamide, polyethylene wax and zinc stearate; The mass ratio of the Mg(OH)2 particles, the second surface modifier and the second lubricant is 100:0.3~1.5:0.5~2; The preparation method of the modified inorganic mildew-resistant antibacterial agent comprises the following steps: mixing inorganic mildew-resistant antibacterial agent with a third surface modifier, and reacting to obtain modified inorganic mildew-resistant antibacterial agent; The inorganic mildew-resistant antibacterial agent comprises one or more of titanium dioxide, tin dioxide, silver oxide, copper oxide, cuprous oxide, copper sulfate, zinc oxide and calcium phosphate; The third surface modifier comprises one or more of silane coupling agent, titanate, aluminate, phosphate, isocyanate, borate, zinc stearate and polyethylene wax; The mass ratio of the inorganic mildew-resistant antibacterial agent and the third surface modifier is 100:0.5~2.0; The preparation method of the modified laser absorber comprises the following steps: mixing laser absorber with a fourth surface modifier, and reacting to obtain modified laser absorber; The laser absorber comprises one or more of carbon black, mica powder, basic copper phosphate, copper-chromium black, tin oxide, titanium oxide, indium oxide, bismuth oxide, phthalocyanine blue and phthalocyanine green; The fourth surface modifier comprises one or more of silane coupling agent, aluminate, titanate, phosphate, oleate and zinc stearate, polyethylene wax; The mass ratio of the laser absorber and the fourth surface modifier is 100:0.3~1.

2. The anti-mildew and anti-microbial halogen-free flame-retardant PC / ABS laser-engravable master batch according to claim 1, characterized in that, The temperature of the reaction in the preparation method of the modified CaCO3 particles is 90~100℃, and the reaction time is 8~15min.

3. The anti-mildew and anti-microbial halogen-free flame-retardant PC / ABS laser-engravable master batch according to claim 2, characterized in that, The temperature of the reaction in the preparation method of the modified Mg(OH)2 particles is 90-110 DEG C, and the reaction time is 7-15 min. 4.The anti-mildew and anti-microbial halogen-free flame-retardant PC / ABS laser-engravable master batch according to any one of claims 1-3, characterized in that, The temperature of the reaction in the preparation method of the modified inorganic mildew-proof and antibacterial agent is 90-100 DEG C, and the reaction time is 6-15 min.

5. The anti-mildew and anti-microbial halogen-free flame-retardant PC / ABS laser-engravable master batch according to claim 4, characterized in that, The temperature of the reaction in the preparation method of the modified laser absorbing agent is 90-100 DEG C, and the reaction time is 8-15 min. 6.The anti-mildew and anti-microbial halogen-free flame-retardant PC / ABS laser-engravable master batch according to claim 5, characterized in that, The dispersant includes one or more of sodium polyacrylate, nonylphenol polyoxyethylene ether phosphate, polyacrylamide, amino silane and sodium dodecyl benzene sulfonate; The antioxidant includes one or more of tert-butyl hydroquinone, tea polyphenol, 2,6-di-tert-butyl-4-methylphenol, beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propyl octadecyl ester, tetra[beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, phenyl diisooctyl phosphite, triphenyl phosphite and diphenyl octyl phosphite.

7. The anti-mildew and anti-microbial halogen-free flame-retardant PC / ABS laser-engravable master batch according to claim 6, characterized in that, The lubricant includes one or more of N,N'-ethylene bis stearamide, N,N'-ethylene bis oleamide, polyethylene wax, paraffin wax, stearic acid and zinc stearate; The plasticizer includes one or more of dibutyl phthalate, dioctyl phthalate, di(2-ethylhexyl) adipate, tricresyl phosphate, triphenyl phosphate and tris(2-ethylhexyl) phosphate.

8. The preparation method of the anti-mildew and anti-microbial halogen-free flame-retardant PC / ABS laser-engravable master batch according to any one of claims 1-7, characterized in that, The method includes the following steps: The polycarbonate, acrylonitrile-butadiene-styrene plastic, modified CaCO3 particles, modified Mg(OH)2 particles, modified inorganic mildew-proof and antibacterial agent, modified laser absorbing agent, dispersant, antioxidant, lubricant and plasticizer are mixed, extruded and granulated to obtain the mildew-proof and antibacterial halogen-free flame-retardant PC / ABS laser engraving master batch.

9. The method for preparing the anti-mildew and anti-microbial halogen-free flame-retardant PC / ABS laser-engravable master batch according to claim 8, characterized in that, The temperature of the granulation is 210-250 DEG C, the pressure of the granulation is ≤10 MPa, and the current of the granulation is 50-110 A.

10. The application of the mildew-proof and antibacterial halogen-free flame-retardant PC / ABS laser engraving master batch in electronic product shell, switch cover / button identification, cosmetic packaging material, automobile interior button and instrument panel, machine keyboard / button or security anti-fake identification.

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