High-recycle-content PCR-PC composite material having both flame-retarding and laser-engraving effects

Abstract

The present application relates to the technical field of polycarbonate composite materials, and specifically relates to a high-recycle-content PCR-PC composite material having both flame-retarding and laser-engraving effects. The composite material 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, 0.2-10 parts by mass of flame retardants, 0.05-2 parts by mass of an anti-dripping agent, 0.05-2 parts by mass of an antioxidant, 0.05-2 parts by mass of a color powder, and 0.05-2 parts by mass of a laser engraving powder. The present application has the following beneficial effects: the PCR-PC in the present application comes from daily production and life, the utilization of which reduces both the emissions of carbon dioxide and the consumption of energy; the laser engraving powder used is added in a small amount, significantly improves the laser engraving effect, and has no influence on the mechanical properties, flame retardance and other properties of the composite material; moreover, the flame retardants used are all halogen-free flame retardants, are environmentally friendly, meet and comply with national and international controls and regulations, and do not cause any secondary pollution to the environment.

Description

A PCR-PC composite material with high recycling ratio, flame retardation and laser engraving effect TECHNICAL FIELD

[0001] The present application relates to the technical field of polycarbonate composite materials, and in particular to a PCR-PC composite material with high recycling ratio, flame retardation and laser engraving effect. BACKGROUND

[0002] Plastic surfaces have characteristics such as low oiliness, low adhesion and low surface energy, which make it difficult to bond with other materials. Laser engraving is a non-contact surface treatment method for workpieces, which is a technology that uses the high energy density characteristics of a laser beam to irradiate the surface of a workpiece, causing chemical or physical changes in the surface layer of the workpiece, thereby leaving permanent marks on the surface of the workpiece.

[0003] PC (polycarbonate) material has excellent comprehensive performance (mechanical properties, dimensional stability, toughness, heat resistance, ultraviolet (UV) resistance and electrical properties, etc.). The flame retardation performance and grade of PC itself is UL94V-2, and it will drip when on fire. In order to meet the material requirements (such as toughening, improving the forming processing performance, reducing residual deformation and improving flame retardation, etc.), PC needs to be modified.

[0004] With the development of laser engraving technology and the recognition of consumers, the technology of using laser to engrave and mark on the surface of plastic products such as polycarbonate has been widely used. Laser irradiation of plastic materials simply added with laser engraving masterbatch or laser engraving aids and other processing aids can quickly mark various patterns. At present, many manufacturers use laser engraving to mark some signs, graphics and font information and product parameter usage instructions on plastic materials, but for some specific plastic products such as chargers and power supply housings, the plastic material is flame-retardant PC, which will limit the PC plastic material substrate due to the increase of flame retardants and anti-dripping agents. When laser marking is performed, the marked graphics may be unclear and have low recognition.

[0005] Therefore, it is necessary to provide a PCR-PC composite material with high recycling ratio, flame retardation and laser engraving effect to solve the above problems. SUMMARY

[0006] The following is a summary of the subject matter described in detail in this document. This summary is not intended to limit the scope of protection of the claims.

[0007] The technical problem to be solved by the present application is: using laser to engrave and mark on the surface of polycarbonate and other plastic products, but for some specific plastic products, such as chargers, power supply shells and the like, the plastic material is flame-retardant PC, which will be limited by the PC plastic material substrate due to the increase of flame retardant and anti-dripping agent, and when laser marking is performed, the problems of unclear and indistinct marking graphics and low recognition will occur. The present application provides a PCR-PC composite material with high recycling ratio and flame-retardant and engraving effects to solve the above problems.

[0008] The present application provides a PCR-PC composite material with high recycling ratio and flame-retardant and engraving effects, which comprises the following components by mass fraction:

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

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

[0011] Flame retardant, 0.2-10 parts by mass;

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

[0013] Antioxidant, 0.05-2 parts by mass;

[0014] Color powder, 0.05-2 parts by mass;

[0015] Engraving powder, 0.05-2 parts by mass.

[0016] The flame-retardant effect in the present application refers to that the material can achieve the flame-retardant performance and fireproof grade requirement under the thickness of (≤1.6mm) without adding halogen-containing flame retardant.

[0017] The engraving effect in the present application refers to that the surface of the material is smooth after engraving, the handwriting is clear, and the color is not easy to fade.

[0018] The selected PCR-PC is one or more of the following: secondary recycled bisphenol A type polycarbonate, polyester type polycarbonate, organic silicon copolymer type PC, cyclohexane bisphenol A type polycarbonate or bisphenol TMC synthesized high-temperature-resistant polycarbonate. The melt mass flow rate of PCR-PC is (10-50) g / 10 min (300℃ / 1.2kg), the weight average molecular weight is 20000-50000, the molecular weight distribution is 1-2.5, and it can also be new material PC.

[0019] The selected toughening agent is one or more of a core-shell type acrylate-PMMA type toughening agent, a core-shell type acrylate-SAN type toughening agent, a core-shell type silicone-PMMA type toughening agent, a core-shell type silicone-SAN type toughening agent, a cross-linked type methacrylate-methyl methacrylate type toughening agent, a butadiene-styrene-methyl methacrylate type toughening agent, or a silicone rubber-methyl methacrylate type toughening agent.

[0020] The selected flame retardant can be one or more of a hypophosphite flame retardant, a sulfonate-based flame retardant, a silicone-based flame retardant, and the like, as well as derivatives thereof.

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

[0022] The selected antioxidant can be one or more of a hindered phenol, a phosphite, or a thio antioxidant, and the like.

[0023] The selected toner is a carbon black material, including one or more of pure carbon black, supported carbon black sand, and unsupported carbon black sand.

[0024] The selected engraving powder can be one or more of carbon black, antimony oxide, zinc antimonide, aluminum antimonide, or nickel antimonide.

[0025] The present application provides a product, which is prepared by using a processing aid to obtain a PCR-PC composite material with a high recycling ratio and both flame retardation and engraving effects.

[0026] Compared with the related art, the present application has the following beneficial effects:

[0027] 1. The flame retardants used in the present application are all halogen-free flame retardants, which are environmentally friendly, meet and comply with national and international regulations and provisions, and do not cause secondary pollution to the environment.

[0028] 2. The engraving powder used in the present application has a small addition amount and significantly improves the engraving effect without affecting the mechanical properties and flame retardation of the composite material.

[0029] 3. The PCR-PC used in the present application is derived from daily production and life, such as drinking water bottles, optical disc slices, and automobile headlight shells, which reduces carbon dioxide emissions and also reduces energy consumption.

[0030] Other aspects can be apparent after reading and understanding the detailed description. DETAILED DESCRIPTION

[0031] In order to further illustrate the technical means adopted by the present application and its effects, the following embodiments of the present application are described in detail.

[0032] The present application provides a PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect, which comprises the following components by mass fraction:

[0033] PCR-PC, 72-98.6 mass fraction;

[0034] Toughening agent, 1-10 mass fraction;

[0035] Flame retardant, 0.2-10 mass fraction;

[0036] Anti-dripping agent, 0.05-2 mass fraction;

[0037] Antioxidant, 0.05-2 mass fraction;

[0038] Color powder, 0.05-2 mass fraction;

[0039] Laser engraving powder, 0.05-2 mass fraction.

[0040] The flame retardation in the present application refers to that the material can achieve the flame retardation performance and fire resistance level requirement under the thickness of (≤1.6mm) without adding halogen-containing flame retardant.

[0041] The laser engraving effect in the present application refers to that the surface of the material is smooth after laser engraving, the handwriting is clear and durable and not easy to fade.

[0042] The selected PCR-PC is one or more compounds of secondary recycled bisphenol A type polycarbonate, polyester type polycarbonate, organic silicon copolymer type polycarbonate, cyclohexane bisphenol A type polycarbonate or bisphenol TMC synthesized high-temperature-resistant polycarbonate, the melt mass flow rate MI of PCR-PC is (10-50) g / 10min (300℃ / 1.2kg), the weight average molecular weight is 20000-50000, the molecular weight distribution is 1-2.5, and it can also be new PC.

[0043] The selected toughening agent is one or more than one compound of core-shell type acrylate-PMMA type toughening agent, core-shell type acrylate-SAN type toughening agent, core-shell type organic silicon-PMMA type toughening agent, core-shell type organic silicon-SAN type toughening agent, cross-linked type methacrylate-methyl methacrylate type toughening agent, butadiene-styrene-methyl methacrylate type toughening agent or organic silicon rubber-methyl methacrylate type toughening agent.

[0044] The selected flame retardant can be one or more of the following: hypophosphite flame retardant (e.g., vinyl aluminum hypophosphite flame retardant, vinyl hypophosphite), sulfonate flame retardant (e.g., 1,3-phenylene phosphonic acid (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 retardant (e.g., benzenesulfonyl potassium benzenesulfonate (KSS), potassium perfluorobutylsulfonate (PPFBS), sodium 2,4,5-trichlorobenzenesulfonate (STB)), silicone flame retardant (e.g., polysilaborane and its derivatives flame retardant, cross-linked polydimethylsiloxane (PDMS) and its derivatives), and the like, and their derivatives.

[0045] The selected anti-dripping agent is a fluorine-based PTFE material, including a core-shell coated PTFE material and a non-coated PTFE (pure powder type) material.

[0046] The selected antioxidant can be one or more of the following: hindered phenol (e.g., (β-3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl acrylate), phosphite (e.g., tris(2,4-di-tert-butylphenyl) phosphite, dioctadecyl alcohol pentaerythritol diphosphite), or thio antioxidant, and the like.

[0047] The selected toner is a carbon black material, including one or more of the following: pure carbon black, supported carbon black sand, and unsupported carbon black sand.

[0048] The selected engraving powder can be one or more of the following: carbon black, antimony oxide, zinc antimonide, aluminum antimonide, or nickel antimonide.

[0049] Comparative Example 1

[0050] A PCR-PC composite material with high recovery ratio and both flame retardant and engraving effects, including the following components by mass: 83.7 parts of PCR-PC, 6 parts of toughening agent, 7.5 parts of phosphorus-based flame retardant, 0.2 parts of sulfonate-based flame retardant, 0.3 parts of anti-dripping agent, 0.3 parts of antioxidant, and 2 parts of toner.

[0051] The selected PCR-PC is a crushed material of a secondary recycled CD, specifically, Mait 10040, with MI = 59.2 g / 10 min (300°C / 1.2 kg), weight average molecular weight between 49,000 and 50,000, and molecular weight distribution between 1.5 and 2.0.

[0052] The selected toughening agent is a core-shell structure, the core is silicon / acrylic acid, and the shell is MMA copolymer, specifically, Japan Mitsubishi impact modifier S-2030, which can significantly improve the impact resistance of resin and engineering plastics, and has excellent heat aging resistance and hydrolysis resistance.

[0053] The selected flame retardant is a combination of sulfonate flame retardant and phosphorus flame retardant, the sulfonate flame retardant is specifically PSS-K of Japan SONY company, which has a small amount of addition and can achieve flame retardation and fire rating under a thickness of (≤1.6mm), and the phosphorus flame retardant is specifically Hengqiao industry CG-693, which has good flame retardation effect and is environmentally friendly.

[0054] The selected anti-dripping agent is a coated PTFE (pure powder type), specifically FA500H of Japan Daikin, which has a small amount of addition and a significant anti-dripping effect.

[0055] The selected antioxidant is a combination of hindered phenol and phosphite, specifically tetraethylene glycol ester, i.e. 1010, which has a significant synergistic effect and the characteristics of a small amount of addition, significant antioxidant and anti-yellowing effect.

[0056] The selected toner is carrier carbon black, specifically Kunshan Furui polymer material 8086, which has the characteristics of strong dyeing capacity, stable color phase, high blackness, and good dispersibility.

[0057] The selected engraving powder is modified antimony trioxide ATO, specifically Brofos-ATO-20 of Bohua, which has good weather resistance and stability, and also has dyeing effect, which can reduce the amount of toner and reduce cost.

[0058] The selected processing machine is a double-screw extruder, the processing temperature is 280-290℃, and the screw rotation speed is 400-600rpm.

[0059] In the preparation of the PCR-PC composite material with high recycling ratio and flame retardation and engraving effect, the components are weighed according to the above ratio, the mixture of the components is mixed and transported by the screw, fully melted and compounded, then extruded by the machine head die, drawn, cooled, and pelletized to obtain the finished product, and finally the particles are injection molded into products at about 280℃, then laser marking is performed using a Dazhu laser EP-12 model laser marking machine under the conditions of current 20A, marking speed 1000mm / s, and frequency 17kHz, to obtain white engraving patterns.

[0060] Example 1

[0061] The PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect comprises the following components in parts by mass: 83.7 parts of PCR-PC, 6 parts of toughening agent, 7.5 parts of phosphorus-based flame retardant, 0.2 parts of sulfonate-based flame retardant, 0.3 parts of anti-dripping agent, 0.3 parts of antioxidant, 1.5 parts of color powder and 0.5 parts of laser engraving powder.

[0062] The selected PCR-PC is broken material of twice recycled CD, specifically, Meit 10040, MI = 59.2 g / 10 min (300℃ / 1.2 kg), weight average molecular weight is between 49000-50000, and molecular weight distribution is between 1.5-2.0.

[0063] The selected toughening agent is core-shell structure, the core is silicon / acrylic acid, and the shell is MMA copolymer, specifically, S-2030 of Japan Mitsubishi Impact Modifier, which can significantly improve the impact resistance of resin and engineering plastic, and has excellent heat aging resistance and hydrolysis resistance.

[0064] The selected flame retardant is a combination of sulfonate-based flame retardant and phosphorus-based flame retardant, the sulfonate-based flame retardant is PSS-K of Japan SONY, which has less addition amount and can achieve flame retardation requirement and fireproof grade under thickness (≤1.6 mm), and the phosphorus-based flame retardant is CG-693 of Hengqiao Industry, which has good flame retardation effect and is environment-friendly.

[0065] The selected anti-dripping agent is coated PTFE (pure powder type), specifically, FA500H of Japan Daikin, which has less addition amount and significant anti-dripping effect.

[0066] The selected antioxidant is a combination of hindered phenol and phosphite, specifically, tetraethyl pyromellitate, i.e. 1010, which has significant synergistic effect, and has the characteristics of less addition amount, significant antioxidant and anti-yellowing effect.

[0067] The selected color powder is carrier carbon black, specifically, Kunshan Furui High Polymer Material 8086, which has the characteristics of strong dyeing capacity, stable color phase, high blackness and good dispersibility.

[0068] The selected laser engraving powder is modified antimony trioxide ATO, specifically, Brofos-ATO-20 of Bohua, which has good weather resistance and stability, and has dyeing effect, which can reduce the addition amount of color powder and reduce cost.

[0069] The selected processing machine is a double-screw extruder, the processing temperature is 280-290℃, and the screw rotation speed is 400-600 rpm.

[0070] When the PCR-PC composite material with high recycling ratio and both flame-retardant and laser-engraving effects is prepared, the components are weighed according to the above-mentioned proportions, the mixture of the components is fully melted and compounded after being mixed and transported by the screw, and then the mixture is extruded by the die head, drawn, cooled, and pelletized to obtain the finished product. Finally, the pellets are injection molded into products at about 280°C, and then laser marking is performed using a Dagu laser EP-12 laser marking machine under the conditions of a current of 20 A, a marking speed of 1000 mm / s, and a frequency of 17 kHz, to obtain white laser-engraved patterns.

[0071] After the above comparative examples and examples are implemented, the same components are reproduced and implemented, the comparative example 1 and the example 1 are melt-extruded and pelletized, and then the pellets in each comparative example and example are injection molded into standard test bars on an injection molding machine, and then laser marking is performed using a laser marking machine. The standard test bars are tested according to the performance of the materials obtained by standard testing, and the test results are shown in Table 1.

[0072] Table 1 test results

[0073] From the test results of the comparative example 1 and the example 1, it can be seen that the application realizes the preparation of a PCR-PC composite material with high recycling ratio and both flame-retardant and laser-engraving effects by using a processing aid.

[0074] In summary, the beneficial effects of the application are:

[0075] 1. The flame retardants used in the application are all halogen-free flame retardants, which are environmentally friendly, meet and comply with national and international regulations and provisions, and do not cause secondary pollution to the environment.

[0076] 2. The laser-engraving powder used in the application has a small addition amount and significantly improves the laser-engraving effect without affecting the mechanical properties and flame-retardant properties of the composite material.

[0077] 3. The PCR-PC used in the application is derived from daily production and life, such as drinking water bottles, optical disc slices, and automobile headlight shells, which reduces carbon dioxide emissions and also reduces energy consumption.

[0078] It should be noted that the application is not limited to the above-mentioned embodiments, and any simple modification, equivalent change, and modification of the above-mentioned embodiments based on the technical solution of the application by any person skilled in the art falls within the protection scope of the application.

Claims

1. A PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect, comprising the following components by mass fraction: PCR-PC, 72-98.6 mass fraction; toughening agent, 1-10 mass fraction; flame retardant, 0.2-10 mass fraction; anti-dripping agent, 0.05-2 mass fraction; antioxidant, 0.05-2 mass fraction; toner, 0.05-2 mass fraction; laser engraving powder, 0.05-2 mass fraction.

2. The PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect according to claim 1, wherein, The PCR-PC is one or more of the following: bisphenol A type polycarbonate, polyester type polycarbonate, organic silicon copolymer type polycarbonate, cyclohexane bisphenol A type polycarbonate, or bisphenol TMC synthetic high-temperature-resistant polycarbonate.

3. The PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect according to claim 1, wherein, The melt mass flow rate of the PCR-PC is (10-50) g / 10 min (300℃ / 1.2 kg), the weight average molecular weight is 20000-50000, and the molecular weight distribution is 1-2.

5.

4. The PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect according to claim 1, wherein, The toughening agent is one or more of the following: core-shell type acrylate-PMMA toughening agent, core-shell type acrylate-SAN toughening agent, core-shell type organic silicon-PMMA toughening agent, core-shell type organic silicon-SAN toughening agent, cross-linked type methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent, or organic silicon rubber-methyl methacrylate toughening agent.

5. The PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect according to claim 1, wherein, The flame retardant is one or more of the following: hypophosphite flame retardant, sulfonate-based flame retardant, organic silicon-based flame retardant, and their derivatives.

6. The PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect according to claim 1, wherein, The anti-dripping agent is fluorine-based PTFE material, including core-shell coated PTFE material and non-coated PTFE (pure powder type) material.

7. The PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect according to claim 1, wherein, The antioxidant is one or more of the following: hindered phenol, phosphite, or thio.

8. The PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect according to claim 1, wherein, The toner is carbon black material, including one or more of the following: pure carbon black, supported carbon black sand, and unsupported carbon black sand.

9. The PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect according to claim 1, wherein, The laser engraving powder is one or more of the following: carbon black, antimony oxide, zinc antimonide, aluminum antimonide, or nickel antimonide.

10. The PCR-PC composite material with high recovery ratio, flame retardation and laser engraving effect according to claim 1, wherein, The processing machine selected is a twin-screw extruder, the processing temperature is 280-290℃, and the screw rotation speed is 400-600 rpm.

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