Polymerase chain reaction (PCR)-polycarbonate (PC) composite material with high recovery ratio and flame-retardant and laser etching effects

Abstract

The invention relates to the technical field of polycarbonate composite materials, in particular to a high-recovery-ratio PCR-PC (Polymerase Chain Reaction-Polycarbonate) composite material with flame-retardant and laser etching effects, which comprises the following components in parts by weight: 72-98.6 parts by mass of PCR-PC; 1-10 parts by mass of a toughening agent; 0.2 to 10 parts by mass of a flame retardant; 0.05 to 2 parts by mass of an anti-dripping agent; 0.05 to 2 parts by mass of an antioxidant; 0.05 to 2 parts by mass of toner; the invention has the following beneficial effects: the PCR-PC source is from daily production and life, carbon dioxide emission is reduced, energy consumption is also reduced, and the used laser etching powder has the advantages of small addition amount, substantial improvement of laser etching effect, no influence on the mechanical property, flame retardation and other properties of the composite material, and is suitable for industrial production. And the used flame retardants are halogen-free flame retardants, are environment-friendly, meet and conform to national and international management and control and regulations, and do not cause secondary pollution to the environment.

Description

[Technical Field]

[0001] This invention relates to the field of polycarbonate composite materials technology, and in particular to a PCR-PC composite material with a high recycling ratio that also has flame retardant and laser engraving effects. [Background Technology]

[0002] Plastic surfaces are characterized by low oil content, low adhesion, and low surface energy, making them difficult to bond with other materials. Laser engraving is a non-contact surface treatment method that utilizes the high energy density of a laser beam to irradiate the workpiece surface, causing chemical or physical changes in the surface material and leaving a permanent mark.

[0003] PC (polycarbonate) material possesses excellent comprehensive properties (mechanical properties, dimensional stability, toughness, heat resistance, UV resistance, and electrical properties, etc.). PC itself has a UL94V-2 flame retardant rating and will drip when exposed to fire. To meet material requirements (such as toughening, improving molding and processing performance, reducing residual deformation, and enhancing flame retardancy), PC needs to be modified.

[0004] With the development of laser engraving technology and consumer acceptance, the technique of using lasers to engrave and mark on the surface of plastic products such as polycarbonate has been widely applied. Various patterns can be quickly marked on plastic materials by simply adding laser engraving masterbatch or other processing aids and then irradiating them with a laser. Currently, many plastic materials use laser engraving to mark logos, graphics, fonts, manufacturer information, product parameters, and usage instructions. However, for certain plastic products, such as chargers and power supply casings, where the plastic material is flame-retardant PC, the addition of flame retardants and anti-drip agents can limit the effectiveness of laser marking, resulting in blurry, unclear, and poorly legible markings.

[0005] In view of this, it is necessary to provide a PCR-PC composite material with a high recycling ratio that also has flame retardant and laser engraving effects to solve the above problems. [Summary of the Invention]

[0006] The technical problem this invention aims to solve is that while laser marking can be used to engrave marks on the surface of plastic products such as polycarbonate, for certain plastic products, such as chargers and power supply casings, the addition of flame-retardant and anti-dripping agents limits the effectiveness of laser marking due to the limitations of the PC plastic material itself. This results in blurry and unclear markings with low readability. Therefore, this invention provides a PCR-PC composite material with a high recycling ratio that combines flame retardancy and laser engraving effect to solve the above problems.

[0007] The solution to the technical problem of this invention is:

[0008] A PCR-PC composite material with high recyclability, flame retardancy, and laser engraving effect, characterized by comprising the following components in parts by weight:

[0009] PCR-PC, 72–98.6 parts by weight;

[0010] Toughening agent, 1-10 parts by weight;

[0011] Flame retardant, 0.2–10 parts by weight;

[0012] Anti-dripping agent, 0.05–2 parts by weight;

[0013] Antioxidant, 0.05–2 parts by weight;

[0014] Pigment powder, 0.05 to 2 parts by weight;

[0015] Laser engraving powder, 0.05 to 2 parts by weight.

[0016] The flame retardant effect in this invention refers to the ability of the material to achieve flame retardant performance and fire resistance rating requirements at a thickness of ≤1.6mm without adding halogenated flame retardants.

[0017] The laser engraving effect in this invention refers to the smooth surface of the material after laser engraving, clear lettering, and durability that prevents fading.

[0018] The selected PCR-PC is one or more of the following: bisphenol A type polycarbonate, polyester type polycarbonate, organosilicon copolymer PC, cyclohexane bisphenol A type polycarbonate, and high-temperature resistant polycarbonate synthesized from bisphenol TMC. The melt mass flow rate MI of the PCR-PC is (10-50) g / 10 min (300℃ / 1.2 kg), the weight average molecular weight is 20,000-50,000, and the molecular weight distribution is 1-2.5. It can also be virgin PC.

[0019] The selected toughening agent is one or more of the following: core-shell acrylate-PMMA toughening agent, core-shell acrylate-SAN toughening agent, core-shell silicone-PMMA toughening agent, core-shell silicone-SAN toughening agent, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent, and silicone rubber-methyl methacrylate toughening agent, in combination and used together.

[0020] The selected flame retardant may be one or more of the following: hypophosphite flame retardant, sulfonate flame retardant, organosilicon flame retardant, and their derivatives.

[0021] The selected anti-dripping agent is a fluorinated PTFE material, including core-shell coated PTFE material and uncoated PTFE (pure powder) material.

[0022] The selected antioxidants can be one or more of hindered phenols, phosphites, thiolated antioxidants, etc., in combination and use.

[0023] The selected color powder is carbon black material, including one or more of pure carbon black, carrier-supported carbon black sand and carrier-free carbon black sand.

[0024] The selected laser engraving powder can be one or more of carbon black, antimony oxide, zinc antimony, aluminum antimony, and nickel antimony, and can be used in combination.

[0025] A product characterized in that it is prepared using processing aids to obtain a PCR-PC composite material with high recovery ratio and both flame retardant and laser engraving effects.

[0026] The beneficial effects of this invention are:

[0027] 1. All flame retardants used in this invention are halogen-free flame retardants, which are environmentally friendly and meet national and international control and regulations, and will not cause secondary pollution to the environment;

[0028] 2. The laser engraving powder used in this invention has the advantages of low addition amount, significant improvement in laser engraving effect, and no impact on the mechanical, flame retardant and other properties of composite materials.

[0029] 3. The PCR-PC used in this invention comes from everyday production and life, such as drinking water bottles, CDs, and car headlight housings. It reduces carbon dioxide emissions while also reducing energy consumption.

Detailed Implementation Methods

[0030] To further illustrate the technical means and effects of the present invention, the following describes the embodiments of the present invention in detail.

[0031] This invention provides a PCR-PC composite material with high recyclability, flame retardancy, and laser engraving effect, characterized in that it comprises the following components in parts by weight:

[0032] PCR-PC, 72–98.6 parts by weight;

[0033] Toughening agent, 1-10 parts by weight;

[0034] Flame retardant, 0.2–10 parts by weight;

[0035] Anti-dripping agent, 0.05–2 parts by weight;

[0036] Antioxidant, 0.05–2 parts by weight;

[0037] Pigment powder, 0.05 to 2 parts by weight;

[0038] Laser engraving powder, 0.05 to 2 parts by weight.

[0039] The flame retardant effect in this invention refers to the ability of the material to achieve flame retardant performance and fire resistance rating requirements at a thickness of ≤1.6mm without adding halogenated flame retardants.

[0040] The laser engraving effect in this invention refers to the smooth surface of the material after laser engraving, clear lettering, and durability that prevents fading.

[0041] The selected PCR-PC is one or more of the following: bisphenol A type polycarbonate, polyester type polycarbonate, organosilicon copolymer PC, cyclohexane bisphenol A type polycarbonate, and high-temperature resistant polycarbonate synthesized from bisphenol TMC. The melt mass flow rate MI of the PCR-PC is (10-50) g / 10 min (300℃ / 1.2 kg), the weight average molecular weight is 20,000-50,000, and the molecular weight distribution is 1-2.5. It can also be virgin PC.

[0042] The selected toughening agent is one or more of the following: core-shell acrylate-PMMA toughening agent, core-shell acrylate-SAN toughening agent, core-shell silicone-PMMA toughening agent, core-shell silicone-SAN toughening agent, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent, and silicone rubber-methyl methacrylate toughening agent, in combination and used together.

[0043] The selected flame retardant may be a combination of one or more of the following: hypophosphite flame retardants (e.g., vinyl aluminum hypophosphite, vinyl hypophosphite), sulfonate flame retardants (e.g., 1,3-phenylene phosphate (2,6-tolyl) tetraester, tetraphenyl bisphenol A diphosphate and its derivatives flame retardant (BDP), tetraphenyl resorcinol diphosphate and its derivatives (RDP) flame retardant, triphenyl phosphate (TPP) flame retardant), sulfonate flame retardants (e.g., potassium benzenesulfonylbenzenesulfonate (KSS), potassium perfluorobutyl sulfonate (PPFBS), sodium 2,4,5-trichlorobenzenesulfonate (STB)), organosilicon flame retardants (e.g., polysiloxane and its derivatives flame retardant, cross-linked polydimethylsiloxane (PDMS) and its derivatives), and their derivatives.

[0044] The selected anti-dripping agent is a fluorinated PTFE material, including core-shell coated PTFE material and uncoated PTFE (pure powder) material.

[0045] The selected antioxidants can be one or more of the following: hindered phenols (e.g., (β-3,5-di-tert-butyl-4-hydroxyphenyl) acrylate), phosphites (e.g., tris(2,4-di-tert-butylphenyl) phosphites, pentaerythritol diphosphite), and thiolated antioxidants, in combination and use.

[0046] The selected color powder is carbon black material, including one or more of pure carbon black, carrier-supported carbon black sand and carrier-free carbon black sand.

[0047] The selected laser engraving powder can be one or more of carbon black, antimony oxide, zinc antimony, aluminum antimony, and nickel antimony, and can be used in combination.

[0048] Comparative Example 1

[0049] A PCR-PC composite material with high recycling ratio and both flame retardant and laser engraving effect comprises the following components in parts by weight: 83.7 parts PCR-PC, 6 parts toughening agent, 7.5 parts phosphorus-based flame retardant, 0.2 parts sulfonate-based flame retardant, 0.3 parts anti-dripping agent, 0.3 parts antioxidant, and 2 parts colorant.

[0050] The selected PCR-PC is the crushed material of CDs (discs) recycled in the secondary process. Specifically, it is MITE 10040 with a molecular weight of 59.2 g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight between 49,000 and 50,000, and a molecular weight distribution between 1.5 and 2.0.

[0051] The selected toughening agent has a core-shell structure, with the core being silicon / acrylic acid and the shell being an MMA copolymer. Specifically, it is Mitsubishi S-2030, an impact modifier from Japan, which can significantly improve the impact resistance of resins and engineering plastics, while also exhibiting excellent heat aging resistance and hydrolysis resistance.

[0052] The selected flame retardant is a combination of sulfonate flame retardant and phosphorus flame retardant. The sulfonate flame retardant is PSS-K from Sony Corporation of Japan. It requires a small amount and can meet the flame retardant requirements and fire rating at a thickness of ≤1.6mm. The phosphorus flame retardant is CG-693 from Hengqiao Industry. It has good flame retardant effect and is environmentally friendly.

[0053] The selected anti-dripping agent is coated PTFE (pure powder), specifically Daikin FA500H from Japan, which requires a small amount and has a significant anti-dripping effect.

[0054] The selected antioxidant is a combination of hindered phenols and phosphites, specifically pentylenetetroxide ester, i.e. 1010. It has a significant synergistic effect and features low addition amount and significant antioxidant and anti-yellowing effects.

[0055] The selected pigment is carrier-based carbon black, specifically Kunshan Furis Polymer Material 8086, which has the characteristics of strong dyeing ability, stable hue, high blackness, and good dispersibility.

[0056] The selected laser engraving powder is modified antimony oxide (ATO), specifically Brofos-ATO-20 from Bohuas Nano. It has good weather resistance and stability, as well as dyeing effect, which can reduce the amount of pigment added and lower costs.

[0057] The selected processing machine is a twin-screw extruder with a processing temperature of 280–290℃ and a screw speed of 400–600 rpm.

[0058] In preparing this PCR-PC composite material with high recovery ratio, flame retardancy, and laser engraving effect, the corresponding weight parts of the components are weighed according to the above ratio. The mixture of each component material is fully melted and compounded after being mixed and conveyed by a screw. Then, it is extruded through a die head, drawn into strips, cooled, and pelletized to obtain the finished product. Finally, the particles are injection molded into the product at about 280°C. Then, a Han's Laser EP-12 laser marking machine is used to perform laser marking under the conditions of 20A current, 1000mm / s marking speed, and 17KH / Z frequency to obtain white laser engraved patterns.

[0059] Example 1

[0060] A PCR-PC composite material with high recycling ratio and both flame retardant and laser engraving effects comprises the following components in parts by weight: 83.7 parts PCR-PC, 6 parts toughening agent, 7.5 parts phosphorus-based flame retardant, 0.2 parts sulfonate-based flame retardant, 0.3 parts anti-dripping agent, 0.3 parts antioxidant, 1.5 parts colorant, and 0.5 parts laser engraving powder.

[0061] The selected PCR-PC is the crushed material of CDs (discs) recycled in the secondary process. Specifically, it is MITE 10040 with a molecular weight of 59.2 g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight between 49,000 and 50,000, and a molecular weight distribution between 1.5 and 2.0.

[0062] The selected toughening agent has a core-shell structure, with the core being silicon / acrylic acid and the shell being an MMA copolymer. Specifically, it is Mitsubishi S-2030, an impact modifier from Japan, which can significantly improve the impact resistance of resins and engineering plastics, while also exhibiting excellent heat aging resistance and hydrolysis resistance.

[0063] The selected flame retardant is a combination of sulfonate flame retardant and phosphorus flame retardant. The sulfonate flame retardant is PSS-K from Sony Corporation of Japan. It requires a small amount and can meet the flame retardant requirements and fire rating at a thickness of ≤1.6mm. The phosphorus flame retardant is CG-693 from Hengqiao Industry. It has good flame retardant effect and is environmentally friendly.

[0064] The selected anti-dripping agent is coated PTFE (pure powder), specifically Daikin FA500H from Japan, which requires a small amount and has a significant anti-dripping effect.

[0065] The selected antioxidant is a combination of hindered phenols and phosphites, specifically pentylenetetroxide ester, i.e. 1010. It has a significant synergistic effect and features low addition amount and significant antioxidant and anti-yellowing effects.

[0066] The selected pigment is carrier-based carbon black, specifically Kunshan Furis Polymer Material 8086, which has the characteristics of strong dyeing ability, stable hue, high blackness, and good dispersibility.

[0067] The selected laser engraving powder is modified antimony oxide (ATO), specifically Brofos-ATO-20 from Bohuas Nano. It has good weather resistance and stability, as well as dyeing effect, which can reduce the amount of pigment added and lower costs.

[0068] The selected processing machine is a twin-screw extruder with a processing temperature of 280–290℃ and a screw speed of 400–600 rpm.

[0069] In preparing this PCR-PC composite material with high recovery ratio, flame retardancy, and laser engraving effect, the corresponding weight parts of the components are weighed according to the above ratio. The mixture of each component material is fully melted and compounded after being mixed and conveyed by a screw. Then, it is extruded through a die head, drawn into strips, cooled, and pelletized to obtain the finished product. Finally, the particles are injection molded into the product at about 280°C. Then, a Han's Laser EP-12 laser marking machine is used to perform laser marking under the conditions of 20A current, 1000mm / s marking speed, and 17KH / Z frequency to obtain white laser engraved patterns.

[0070] After implementation, the comparative examples and embodiments were reproduced using the same components. Comparative Example 1 and Example 1 were melt-extruded and granulated, and then the particles from each comparative example and embodiment were injection molded into standard test strips using an injection molding machine. These strips were then laser-marked. The test results of the materials obtained according to standard tests are shown in Table 1.

[0071] Table 1 Test Results

[0072]

[0073] The test results of Comparative Example 1 and Example 1 show that the present invention utilizes processing aids to prepare a PCR-PC composite material with high recovery ratio, flame retardancy, and laser engraving effect.

[0074] The beneficial effects of this invention are:

[0075] 1. All flame retardants used in this invention are halogen-free flame retardants, which are environmentally friendly and meet national and international control and regulations, and will not cause secondary pollution to the environment;

[0076] 2. The laser engraving powder used in this invention has the advantages of low addition amount, significant improvement in laser engraving effect, and no impact on the mechanical, flame retardant and other properties of composite materials.

[0077] 3. The PCR-PC used in this invention comes from everyday production and life, such as drinking water bottles, CDs, and car headlight housings. It reduces carbon dioxide emissions while also reducing energy consumption.

[0078] It should be noted that the present invention is not limited to the above embodiments. Any simple modifications, equivalent changes and alterations made by those skilled in the art to the above embodiments based on the technical solutions of the present invention shall fall within the protection scope of the present invention.

Claims

1. A PCR-PC composite material with high recycling ratio, flame retardancy, and laser engraving effect, characterized in that, The components include the following parts by weight: PCR-PC, 72–98.6 parts by weight; Toughening agent, 1-10 parts by weight; Flame retardant, 0.2–10 parts by weight; Anti-dripping agent, 0.05–2 parts by weight; Antioxidant, 0.05–2 parts by weight; Pigment powder, 0.05 to 2 parts by weight; Laser engraving powder, 0.05 to 2 parts by weight.

2. The PCR-PC composite material with high recycling ratio, flame retardancy, and laser engraving effect as described in claim 1, characterized in that: The PCR-PC is one or more of the following: bisphenol A type polycarbonate, polyester type polycarbonate, organosilicon copolymer PC, cyclohexane bisphenol A type polycarbonate, and high-temperature resistant polycarbonate synthesized from bisphenol TMC after secondary recovery.

3. The PCR-PC composite material with high recycling ratio, flame retardancy, and laser engraving effect as described in claim 1, characterized in that: The PCR-PC has a melt flow rate MI = (10-50) g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight of 20,000-50,000, and a molecular weight distribution of 1-2.

5.

4. The PCR-PC composite material with high recycling ratio, flame retardancy, and laser engraving effect as described in claim 1, characterized in that: The toughening agent is one or more of the following: core-shell acrylate-PMMA toughening agents, core-shell acrylate-SAN toughening agents, core-shell organosilicon-PMMA toughening agents, core-shell organosilicon-SAN toughening agents, cross-linked methacrylate-methyl methacrylate toughening agents, butadiene-styrene-methyl methacrylate toughening agents, and organosilicon rubber-methyl methacrylate toughening agents.

5. The PCR-PC composite material with high recycling ratio, flame retardancy, and laser engraving effect as described in claim 1, characterized in that: The flame retardant is a combination of one or more of the following: hypophosphite flame retardants, sulfonate flame retardants, organosilicon flame retardants, and their derivatives.

6. The PCR-PC composite material with high recycling ratio, flame retardancy, and laser engraving effect as described in claim 1, characterized in that: The anti-dripping agent is a fluorinated PTFE material, including core-shell coated PTFE material and uncoated PTFE (pure powder) material.

7. The PCR-PC composite material with high recycling ratio, flame retardancy, and laser engraving effect as described in claim 1, characterized in that: The antioxidant is a combination of one or more hindered phenols, phosphites, and thiocyanates.

8. The PCR-PC composite material with high recycling ratio, flame retardancy, and laser engraving effect as described in claim 1, characterized in that: The color powder is a carbon black material, comprising one or more of pure carbon black, carrier-supported carbon black sand, and carrier-free carbon black sand.

9. The PCR-PC composite material with high recycling ratio, flame retardancy, and laser engraving effect as described in claim 1, characterized in that: The laser engraving powder is one or more of carbon black, antimony oxide, zinc antimony, aluminum antimony, and nickel antimony, in combination.

10. The PCR-PC composite material with high recycling ratio, flame retardancy, and laser engraving effect as described in claim 1, characterized in that: The selected processing machine is a twin-screw extruder with a processing temperature of 280-290℃ and a screw speed of 400-600 rpm.

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