A high-gwfi value, laser markable glass fiber reinforced mca / pa6 flame retardant composite material and a preparation method thereof

Abstract

The application belongs to the technical field of polymer composites, and discloses a glass fiber reinforced MCA / PA6 flame-retardant composite material with high GWFI value and laser markability and a preparation method thereof. According to weight parts, the glass fiber reinforced MCA / PA6 flame-retardant composite material with high GWFI value and laser markability comprises 59-71 parts of PA6 resin, 7-13 parts of modified MCA flame retardant, 15-30 parts of short glass fiber, 0.5-2 parts of titanium white powder, 0.1-0.5 parts of laser engraving powder, 0.3-1 part of lubricant and 0.3-1 part of antioxidant. The material has excellent glow wire flame retardant performance, and simultaneously has good mechanical properties and laser markability.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, specifically to a high GWFI value, laser-markable glass fiber reinforced MCA / PA6 flame-retardant composite material and its preparation method. Background Technology

[0002] PA6, polymerized from caprolactam monomers, possesses characteristics such as wear resistance, chemical corrosion resistance, good mechanical properties, and ease of modification and processing. It is an important engineering material widely used in automotive, communications, electronics, and mechanical parts industries. However, due to the extreme operating environments PA6 frequently encounters in electronics applications, such as high temperatures and short circuits, flammability becomes a potential safety hazard. Therefore, in the electronics field, PA6 materials are required to have a glow wire flammability index (GWFI) of 960℃ and good mechanical properties. Furthermore, special electronic components also require the material to be laser-markable.

[0003] Melamine cyanurate (MCA), a nitrogen-based flame retardant developed in the 1980s, boasts advantages such as high flame retardant efficiency, halogen-free, low toxicity, low smoke, and low cost, leading to its widespread application in polyamide flame retardancy. However, MCA is prone to agglomeration during mechanical blending, resulting in uneven dispersion in PA6 and affecting its flame retardant effect. Furthermore, the improvement in PA6 flame retardancy by MCA is insufficient to offset the negative impact of the glass fiber "wick effect," and MCA / PA6 flame retardant materials lack laser-markable properties. These shortcomings limit the material's application to some extent. Therefore, appropriate technical solutions are needed to improve the dispersion of MCA in PA6, reduce the impact of the glass fiber "wick effect" on GWFI performance, and endow PA6 with laser-markable properties. This has significant theoretical and practical value for expanding the application of glass fiber reinforced MCA / PA6 flame retardant materials in the electronics and electrical fields.

[0004] Chinese patent CN 115637042 A discloses a high glow wire ignition temperature nitrogen-based flame-retardant nylon modified material prepared by melt blending 50-80 parts of nylon resin, 10-25 parts of modified nitrogen-based flame retardant MCA, 15-25 parts of modified alkali-free glass fiber, and 0.5-5 parts of processing aids using a twin-screw extruder. However, the tensile strength of this material can only reach a maximum of 79 MPa, its mechanical properties are relatively low, the flame retardant content is high, and it is quite brittle, making it difficult to meet the requirements of higher-end electronic and electrical appliance housings. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the above-mentioned background technology and provide a high GWFI value, laser-markable glass fiber reinforced MCA / PA6 flame-retardant composite material and its preparation method. This material has excellent glow wire properties, as well as good mechanical properties and laser-markable characteristics.

[0006] To achieve the objectives of this invention, the high GWFI value, laser-markable glass fiber reinforced MCA / PA6 flame-retardant composite material of this invention, by weight, comprises 59-71 parts of PA6 resin, 7-13 parts of modified MCA flame retardant, 15-30 parts of short glass fiber, 0.5-2 parts of titanium dioxide, 0.1-0.5 parts of laser engraving powder, 0.3-1 parts of lubricant, and 0.3-1 parts of antioxidant.

[0007] Furthermore, in some embodiments of the present invention, the titanium dioxide is rutile titanium dioxide.

[0008] Furthermore, in some embodiments of the present invention, the modification method of the modified MCA flame retardant is as follows: using anhydrous ethanol as a solvent, dilute hydrochloric acid is added to the reaction solution of MCA, sodium silicate and nano-lignin under stirring until the reaction system is completely reacted. During the reaction, the temperature of the reaction system is controlled at a constant temperature of 60℃-80℃. After the reaction is completed, the coated MCA is obtained by filtration, washing, drying and pulverizing. Finally, an organosilicon surfactant solution is mixed into the coated MCA, and the modified MCA flame retardant is obtained after drying again.

[0009] Further, in some embodiments of the present invention, the modification method of the modified MCA flame retardant is as follows: using anhydrous ethanol as a solvent, MCA, sodium silicate and nano-lignin are added to a single-layer glass reactor equipped with mechanical stirring in a weight ratio of 7-9:0.5-2:0.5-2. Then, dilute hydrochloric acid is slowly added dropwise under stirring until the reaction system in the reactor is completely reacted. After the addition of dilute hydrochloric acid is completed, stirring is continued for 2-4 hours. The temperature of the reaction system is controlled at a constant temperature of 60℃-80℃ using a water bath. After the reaction is completed, the coated MCA is obtained by filtration, washing, drying and pulverizing. Finally, an organosilicon surfactant solution is mixed into the coated MCA, and after drying again, the modified MCA flame retardant is obtained.

[0010] Furthermore, in some embodiments of the present invention, in the modification method of the modified MCA flame retardant, the amount of anhydrous ethanol is 2-4 times the total mass of the three materials MCA, sodium silicate and nano-lignin, and the concentration of dilute hydrochloric acid is 2wt%-5wt%.

[0011] Furthermore, in some embodiments of the present invention, in the modification method of the modified MCA flame retardant, the organosilicon surfactant is one or more of the following: polyether-type organosilicon surfactant, alkanolamide-type organosilicon surfactant, phosphate ester-type organosilicon surfactant, carboxylate-type organosilicon surfactant, sulfonate-type organosilicon surfactant, and quaternary ammonium salt-type organosilicon surfactant.

[0012] Furthermore, in some embodiments of the present invention, in the modification method of the modified MCA flame retardant, the organosilicon surfactant solution is an aqueous solution, wherein the content of the organosilicon surfactant is 3wt%-5wt%.

[0013] Furthermore, in some embodiments of the present invention, the amount of the organosilicon surfactant solution is 3wt%-8wt% of the coated MCA.

[0014] Furthermore, in some embodiments of the present invention, more than 90% of the length of the short glass fibers is distributed between 0.15mm and 0.5mm.

[0015] Furthermore, in some embodiments of the present invention, the laser engraving powder is one or more of nano bismuth oxide powder, nano tin antimony oxide powder, Merck Iriotec8815 ​​powder, Merck Iriotec8208 powder, Merck Iriotec8825 powder and Merck Iriotec8850 powder.

[0016] Furthermore, in some embodiments of the present invention, the lubricant is one or more of OP wax, E wax, calcium stearate, aluminum stearate, silicone powder, ethylene bis-stearamide, and pentaerythritol stearate.

[0017] Furthermore, in some embodiments of the present invention, the antioxidant is one or more of antioxidant 1010, antioxidant 1098, antioxidant 245, antioxidant 1076, antioxidant 3391, antioxidant 445, antioxidant H10, antioxidant HS-02, antioxidant S9228, antioxidant 168, antioxidant P-EPQ, antioxidant PEP-36, antioxidant 626, and antioxidant 608.

[0018] The laser engraving powder, lubricant, and antioxidant in the composite material described in this invention are not limited to the above-mentioned items; the examples are merely illustrative.

[0019] Furthermore, the present invention also provides a method for preparing the aforementioned high GWFI value, laser-markable glass fiber reinforced MCA / PA6 flame-retardant composite material. The method is as follows: firstly, PA6 resin, modified MCA flame retardant, laser engraving powder, titanium dioxide, lubricant and antioxidant are mixed evenly to obtain a premix. Finally, the premix is ​​fed into a twin-screw extruder in a certain weight ratio using a feeding weighing scale through a main feeder and short glass fibers through a side feeder for melt blending and extrusion granulation to obtain the glass fiber reinforced MCA / PA6 flame-retardant composite material.

[0020] Compared with the prior art, the advantages of the present invention are as follows:

[0021] (1) In this invention, nano-lignin, sodium silicate and organosilicon surfactant are used to modify MCA flame retardant. After modification, the dispersibility and char formation of MCA flame retardant in PA6 are improved, and the flame retardant performance of glow wire is further improved.

[0022] (2) In the glass fiber reinforced MCA / PA6 composite material prepared by the present invention, most of the glass fiber length can be retained at 60%-80%, and the length is mainly distributed in 0.1-0.35mm. This allows the glass fiber to have a certain reinforcing effect while reducing its "wick effect" on the material during combustion to a certain extent, thereby further improving the glow wire flame retardant performance of the composite material.

[0023] (3) By adding laser engraving powder, titanium dioxide and modified MCA, the composite material can be marked with "white-black" information by laser marking machine. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. Additional aspects and advantages of this invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It should be understood that the following description is merely illustrative and not intended to limit the invention.

[0025] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0026] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0027] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including the ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0028] The singular form includes the plural objects of discussion unless the context clearly indicates otherwise. "Optional" or "any one" means that the matter or event described thereafter may or may not occur, and the description includes both the possibility that the event occurs and the possibility that the event does not occur.

[0029] Approximate terms used in the specification and claims to modify quantities indicate that the invention is not limited to that specific quantity, but also includes acceptable modifications close to that quantity that do not alter the relevant essential function. Correspondingly, the use of "about," "approximately," etc., to modify a numerical value means that the invention is not limited to that precise value. In some instances, approximate terms may correspond to the precision of the instrument used to measure the value. In this application's specification and claims, scope definitions can be combined and / or interchanged, unless otherwise stated, these scopes include all subscopes contained therein.

[0030] The indefinite articles “a” and “an” preceding an element or component of this invention do not impose any limitation on the quantity (i.e., number of times) of the element or component. Therefore, “an” or “a” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers only to the singular form.

[0031] Furthermore, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., described below refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms are not necessarily directed at the same embodiment or example. Moreover, the technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.

[0032] Unless otherwise specified, more than 90% of the short glass fibers described in the embodiments and comparative examples of this invention are distributed between 0.15mm and 0.5mm in length.

[0033] Example 1

[0034] A high GWFI value, laser-markable glass fiber reinforced MCA / PA6 flame-retardant composite material is prepared as follows:

[0035] (1) Preparation of modified MCA flame retardant: MCA, sodium silicate and nano lignin were added to a single-layer glass reactor with mechanical stirring in a weight ratio of 8:1.5:1. Anhydrous ethanol with a weight of 3 times the weight of the material was added as solvent. Then, 3wt% dilute hydrochloric acid was slowly added dropwise to the reaction solution under stirring until the system was completely reacted. After the dilute hydrochloric acid was added, stirring was continued for 3 hours. The temperature of the reaction system was controlled at 70℃ in a water bath. After the reaction was completed, coated MCA was obtained by filtration, washing, drying and pulverizing. Finally, 5wt% alkanolamide type organosilicon surfactant solution was mixed into the coated MCA, wherein the content of organosilicon surfactant was 4wt%. After drying again, modified MCA flame retardant was obtained.

[0036] (2) Preparation of glass fiber reinforced MCA / PA6 flame retardant composite material: First, 68 parts of PA6 resin, 9 parts of modified MCA flame retardant obtained in step (1), 0.3 parts of nano bismuth oxide powder, 1.7 parts of rutile titanium dioxide, 0.5 parts of ethylene bis-stearamide and 0.5 parts of 1098 antioxidant were put into a high-speed mixer and mixed evenly to obtain a premix. Finally, 80 parts of the premix were fed into a twin-screw extruder by the main feeder and 20 parts of short glass fiber by the side feeder to obtain glass fiber reinforced MCA / PA6 flame retardant composite material.

[0037] Example 2

[0038] A high GWFI value, laser-markable glass fiber reinforced MCA / PA6 flame-retardant composite material is prepared as follows:

[0039] (1) Preparation of modified MCA flame retardant: MCA, sodium silicate and nano-lignin were added to a single-layer glass reactor with mechanical stirring in a weight ratio of 7:2:0.5. Anhydrous ethanol with a weight of 2 times the material was added as a solvent. Then, 2wt% dilute hydrochloric acid was slowly added dropwise to the reaction solution under stirring until the system reacted completely. After the dilute hydrochloric acid was added, stirring was continued for 4 hours. The temperature of the reaction system was controlled at 80℃ in a water bath. After the reaction was completed, coated MCA was obtained by filtration, washing, drying and pulverizing. Finally, 8wt% phosphate ester type organosilicon surfactant solution was mixed into the coated MCA, wherein the organosilicon surfactant content was 3wt%. After drying again, modified MCA flame retardant was obtained.

[0040] (2) Preparation of glass fiber reinforced MCA / PA6 flame retardant composite material: Same as in Example 1.

[0041] Example 3

[0042] A high GWFI value, laser-markable glass fiber reinforced MCA / PA6 flame-retardant composite material is prepared as follows:

[0043] (1) Preparation of modified MCA flame retardant: MCA, sodium silicate and nano lignin were added to a single-layer glass reactor with mechanical stirring in a weight ratio of 9:0.5:2. Anhydrous ethanol with a weight of 4 times the weight of the material was added as a solvent. Then, 5wt% dilute hydrochloric acid was slowly added dropwise to the reaction solution under stirring until the system was completely reacted. After the dilute hydrochloric acid was added, stirring was continued for 2 hours. The temperature of the reaction system was controlled at 60℃ in a water bath. After the reaction was completed, coated MCA was obtained by filtration, washing, drying and pulverizing. Finally, 3wt% alkanolamide type organosilicon surfactant solution was mixed into the coated MCA, wherein the content of organosilicon surfactant was 5wt%. After drying again, modified MCA flame retardant was obtained.

[0044] (2) Preparation of glass fiber reinforced MCA / PA6 flame retardant composite material: Same as in Example 1.

[0045] Example 4

[0046] A high GWFI value, laser-markable glass fiber reinforced MCA / PA6 flame-retardant composite material is prepared as follows:

[0047] (1) Preparation of modified MCA flame retardant: Same as in Example 1.

[0048] (2) Preparation of glass fiber reinforced MCA / PA6 flame retardant composite material: First, 67.9 parts of PA6 resin, 13 parts of modified MCA flame retardant obtained in step (1), 0.1 parts of Merck Iriotec 8850 powder, 2 parts of rutile titanium dioxide, 1 part of ethylene bis-stearamide and 1 part of 1098 antioxidant were put into a high-speed mixer and mixed evenly to obtain a premix. Finally, 85 parts of the premix were fed into a twin-screw extruder by the main feeder and 15 parts of short glass fiber by the side feeder to obtain glass fiber reinforced MCA / PA6 flame retardant composite material.

[0049] Example 5

[0050] A high GWFI value, laser-markable glass fiber reinforced MCA / PA6 flame-retardant composite material is prepared as follows:

[0051] (1) Preparation of modified MCA flame retardant: Same as in Example 1.

[0052] (2) Preparation of glass fiber reinforced MCA / PA6 flame retardant composite material: First, 61.4 parts of PA6 resin, 7 parts of modified MCA flame retardant obtained in step (1), 0.5 parts of Merck Iriotec 8815 powder, 0.5 parts of rutile titanium dioxide, 0.3 parts of ethylene bis-stearamide and 0.3 parts of 1098 antioxidant were put into a high-speed mixer and mixed evenly to obtain a premix. Finally, 70 parts of the premix were fed into a twin-screw extruder by the main feeder and 30 parts of short glass fiber by the side feeder to obtain glass fiber reinforced MCA / PA6 flame retardant composite material.

[0053] Example 6

[0054] A high GWFI value, laser-markable glass fiber reinforced MCA / PA6 flame-retardant composite material is prepared as follows:

[0055] (1) Preparation of modified MCA flame retardant: Same as in Example 1.

[0056] (2) Preparation of glass fiber reinforced MCA / PA6 flame retardant composite material: First, 59 parts of PA6 resin, 9 parts of modified MCA flame retardant obtained in step (1), 0.3 parts of nano bismuth oxide powder, 1.1 parts of rutile titanium dioxide, 0.3 parts of calcium stearate and 0.3 parts of 1010 antioxidant were put into a high-speed mixer and mixed evenly to obtain a premix. Finally, 70 parts of the premix were fed into a twin-screw extruder by the main feeder and 30 parts of glass fiber by the side feeder to obtain glass fiber reinforced MCA / PA6 flame retardant composite material.

[0057] Comparative Example 1

[0058] Preparation of glass fiber reinforced MCA / PA6 flame retardant composite material: First, 59 parts of PA6 resin, 9 parts of MCA flame retardant, 0.3 parts of nano bismuth oxide powder, 1.1 parts of rutile titanium dioxide, 0.3 parts of calcium stearate, and 0.3 parts of 1098 antioxidant were added to a high-speed mixer and mixed evenly to obtain a premix. Finally, 70 parts of the premix were fed into a twin-screw extruder by a feeding metering scale through the main feeder and 30 parts of glass fiber through the side feeder for melt blending and extrusion granulation to obtain glass fiber reinforced MCA / PA6 flame retardant composite material.

[0059] Comparative Example 2

[0060] (1) Preparation of modified MCA flame retardant: Same as in Example 1.

[0061] (2) Preparation of glass fiber reinforced MCA / PA6 flame retardant composite material: except that glass fibers with a length greater than 0.5 mm are used, the same as in Example 6.

[0062] Comparative Example 3

[0063] (1) Preparation of modified MCA flame retardant: Same as in Example 1.

[0064] (2) Preparation of glass fiber reinforced MCA / PA6 flame retardant composite material: First, 59.3 parts of PA6 resin, 9 parts of modified MCA flame retardant obtained in step (1), 1.1 parts of rutile titanium dioxide, 0.3 parts of calcium stearate and 0.3 parts of 1010 antioxidant were put into a high-speed mixer and mixed evenly to obtain a premix. Finally, 70 parts of the premix were fed into a twin-screw extruder by the main feeder and 30 parts of glass fiber by the side feeder to obtain glass fiber reinforced MCA / PA6 flame retardant composite material.

[0065] Comparative Example 4

[0066] (1) The modified MCA flame retardant was prepared in the same way as in Example 1.

[0067] (2) Preparation of glass fiber reinforced MCA / PA6 flame retardant composite material: First, 60.1 parts of PA6 resin, 9 parts of modified MCA flame retardant obtained in step (1), 0.3 parts of nano bismuth oxide powder, 0.3 parts of calcium stearate and 0.3 parts of 1010 antioxidant were put into a high-speed mixer and mixed evenly to obtain a premix. Finally, 70 parts of the premix were fed into a twin-screw extruder by the main feeder and 30 parts of glass fiber by the side feeder to obtain glass fiber reinforced MCA / PA6 flame retardant composite material.

[0068] Material testing methods

[0069] The Glow Wire Flammability Index (GWFI) characterizes the flame retardant performance of a product: tested according to IEC 60695 standard.

[0070] Mechanical properties: Tensile strength was tested according to ISO 527.

[0071] Color difference ΔE before and after laser marking: First, a 60mm×6mm×2mm sample square plate is laser marked with a laser marking machine. The marking pattern is a circular area with a diameter of 20mm. Then, the color difference ΔE before and after laser marking is tested using a colorimeter according to ISO 7724 / 3 standard.

[0072] All test specimens were prepared using an injection molding machine, and the test results are shown in Table 1.

[0073] Table 1. Performance test results of composite materials prepared in each embodiment and comparative example.

[0074]

[0075]

[0076] Table 1 shows the performance test results of the glass fiber reinforced MCA / PA6 flame-retardant composite materials prepared in each embodiment and comparative example. The test results in Table 1 show that the flame-retardant composite material prepared by this invention has excellent resistance to glow wire, mechanical properties, and laser marking characteristics.

[0077] Specifically, as can be seen from Examples 1-3, the modified MCA flame retardant prepared in this invention exhibits good overall performance in PA6 composite material applications.

[0078] As can be seen from Examples 1 and 4-6, the mechanical properties of the composite material of the present invention are improved with the increase of glass fiber content, while the GWFI performance of the material is almost unaffected, and the excellent laser marking effect is maintained.

[0079] The comparison between Example 6 and Comparative Example 1 shows that the modified MCA flame retardant prepared in this invention has better mechanical properties and GWFI performance than the unmodified MCA flame retardant. This indicates that the dispersibility and char formation of the modified MCA flame retardant in PA6 are improved, and the flame retardant efficiency of the mechanical properties is further improved.

[0080] A comparison of Example 6 and Comparative Example 2 shows that if the original length of the glass fiber used in the side-feeding is >0.5mm, although the mechanical properties are high, the composite material will exhibit a more severe "wick effect" during combustion, causing the product GWFI to fail the 960℃ test.

[0081] A comparison of Example 6 with Comparative Examples 1 and 3-4 shows that by adding laser engraving powder, titanium dioxide, and modified MCA in combination, the composite material of the present invention can be marked with clearer information using a laser marking machine.

[0082] Those skilled in the art will readily understand that the above description is merely an embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A glass fiber reinforced MCA / PA6 flame retardant composite material with high GWFI value, laser markable, characterized in that, The glass fiber reinforced MCA / PA6 flame-retardant composite contains, in parts by weight, 59-71 parts of PA6 resin, 7-13 parts of modified MCA flame retardant, 15-30 parts of short glass fiber, 0.5-2 parts of titanium white powder, 0.1-0.5 parts of laser engraving powder, 0.3-1 part of lubricant, and 0.3-1 part of antioxidant; More than 90% of the length of the short glass fiber is distributed in the range of 0.15mm-0.5mm; The modification method of the modified MCA flame retardant is as follows: anhydrous ethanol is used as a solvent, and dilute hydrochloric acid is slowly added to the reaction solution of MCA, sodium silicate and nano-lignin under stirring until the reaction system is completely reacted, the temperature of the reaction system is controlled at 60-80℃ in the reaction, and after the reaction is completed, the coated MCA is prepared through filtration, washing, drying and crushing, and finally, the organic silicon surfactant solution is mixed in the coated MCA, and the modified MCA flame retardant is prepared after drying again. In the modification method of the modified MCA flame retardant, the amount of anhydrous ethanol is 2-4 times the total mass of MCA, sodium silicate and nano-lignin, and the concentration of dilute hydrochloric acid is 2wt%-5wt%. The nano-lignin, sodium silicate and organic silicon surfactant are used to modify the MCA flame retardant, the dispersibility and combustion carbonization of the modified MCA flame retardant in PA6 are improved, and the glowing wire flame retardant performance is further improved. Through the compounding addition of laser engraving powder, titanium white powder and modified MCA, the obtained composite material can be marked with "white and black" information by a laser marking machine.

2. The high GWFI value, laser markable, glass-fiber reinforced MCA / PA6 flame retardant composite material according to claim 1, characterized in that, The titanium white powder is rutile titanium white powder.

3. The high GWFI value, laser markable, glass-fiber reinforced MCA / PA6 flame retardant composite material according to claim 1, characterized in that, The modification method of the modified MCA flame retardant is as follows: MCA, sodium silicate and nano-lignin are added into a single-layer glass reaction kettle with mechanical stirring in a weight ratio of 7-9:0.5-2:0.5-2, and then dilute hydrochloric acid is slowly added to the reaction system in the reaction kettle under stirring until the reaction system is completely reacted, the stirring is continued for 2-4h after the addition of dilute hydrochloric acid is completed, a water bath is used to control the temperature of the reaction system at 60-80℃ in the reaction, and after the reaction is completed, the coated MCA is prepared through filtration, washing, drying and crushing, and finally, the organic silicon surfactant solution is mixed in the coated MCA, and the modified MCA flame retardant is prepared after drying again.

4. The high GWFI value, laser markable, glass-fiber reinforced MCA / PA6 flame retardant composite material according to claim 1, characterized in that, In the modification method of the modified MCA flame retardant, the organic silicon surfactant is one or more of polyether type, alkanol amide type, phosphate type, carboxylate type, sulfonate type and quaternary ammonium salt type; in the modification method of the modified MCA flame retardant, the organic silicon surfactant solution is an aqueous solution, and the content of the organic silicon surfactant is 3wt%-5wt%.

5. High GWFI value, laser markable, glass-fiber reinforced MCA / PA6 flame retardant composite material according to claim 4, characterized in that, The amount of the organic silicon surfactant solution is 3wt%-8wt% of the coated MCA.

6. The high GWFI value, laser markable, glass-fiber reinforced MCA / PA6 flame retardant composite material according to claim 1, characterized in that, The laser engraving powder is one or more of nano bismuth oxide powder, nano tin antimony oxide powder, Merck Iriotec 8815 powder, Merck Iriotec 8208 powder, Merck Iriotec 8825 powder and Merck Iriotec 8850 powder.

7. The high GWFI value, laser markable, glass-fiber reinforced MCA / PA6 flame retardant composite material according to claim 1, characterized in that, The lubricant is one or more of OP wax, E wax, calcium stearate, aluminum stearate, silicone powder, ethylene bis-stearamide and pentaerythritol stearate.

8. The high GWFI value, laser markable, glass-fiber reinforced MCA / PA6 flame retardant composite material according to claim 1, characterized in that, The antioxidant is one or both of antioxidant 1010 and antioxidant 1098.

9. Process for the production of a high-GWFI value, laser markable glass fiber reinforced MCA / PA 6 flame retardant composite material according to any one of claims 1 to 8, characterized in that, The method is: first, uniformly mixing PA6 resin, modified MCA flame retardant, laser engraving powder, titanium white powder, lubricant and antioxidant to obtain a premix, and finally, using a feeding metering scale to feed the premix into a twin-screw extruder through main feeding and the short glass fiber through side feeding in a certain weight ratio to perform melt blending and extrusion granulation, thereby obtaining the glass fiber reinforced MCA / PA6 flame retardant composite material.

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