Flame-retardant glass fiber reinforced polyamide 66 material with clear laser etching

Abstract

The invention discloses a laser etching clear flame-retardant glass fiber reinforced polyamide 66 material, and belongs to the technical field of high polymer materials. The laser etching clear flame-retardant glass fiber reinforced polyamide 66 material is prepared from the following raw materials in parts by weight: 40 to 55 parts of PA66 resin, 30 parts of glass fiber, 10 to 20 parts of flame retardant, 1.5 to 5 parts of flame-retardant synergist, 0.5 part of antioxidant, 0.5 part of lubricant, 0.2 to 1 part of black masterbatch and 0.5 to 2 parts of functional additive.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a laser-engraved clear flame-retardant glass fiber reinforced polyamide 66 material. Background Art

[0002] Polyamide resin has excellent comprehensive mechanical properties, good fluidity, high mechanical strength, good corrosion resistance, and good wear resistance, self-lubrication and electrical insulation, making it widely used in the automotive and home appliance fields.

[0003] However, in the field of electronics and electrical and new energy vehicles, the requirements for the strength and flame retardancy of polyamide 66 materials are becoming increasingly higher. The performance of conventional polyamide 66 materials cannot meet the requirements of many high-strength and high-flame-retardant products. In this case, the strength and flame retardancy can be improved by reinforcing with flame-retardant glass fiber to meet the strength requirements of various components and expand the application scope of polyamide 66.

[0004] With the continuous improvement of consumers' demand for personalization, enterprises' improvement of product source traceability efficiency and accuracy, and increasingly stringent global environmental protection requirements, traditional ink labels cannot meet the requirements, while laser engraving technology can solve the above problems and achieve the goal of precise positioning and no environmental pollution. Therefore, under the premise of ensuring high strength and high flame retardant properties, it is of great significance to improve the laser engraving ability of polyamide 66 materials. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention proposes a laser-engraved clear flame-retardant glass fiber reinforced polyamide 66 material.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A laser-carved clear flame-retardant glass fiber reinforced polyamide 66 material, comprising the following raw materials in parts by weight:

[0008] 40-55 parts of PA66 resin,

[0009] Glass fiber 30 parts,

[0010] Flame retardant 10-20 parts,

[0011] Flame retardant synergist 1.5-5 parts,

[0012] 0.5 parts of antioxidant,

[0013] 0.5 parts of lubricant,

[0014] Black masterbatch 0.2-1 part

[0015] And 0.5-2 parts of functional additives.

[0016] Optionally, the surface of the glass fiber is coated with a silane-based sizing agent.

[0017] Optionally, the antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, tris[2,4-di-tert-butylphenyl]phosphite.

[0018] Optionally, the lubricant is NN-hexylene bis-hard amide.

[0019] Optionally, the black masterbatch is one or more of 40wt% carbon black masterbatch and carbon black powder in a PA6 carrier.

[0020] Optionally, the functional auxiliary agent is ultrafine calcium carbonate or anhydrous lithium chloride.

[0021] Optionally, the flame retardant is a red phosphorus flame retardant, a brominated polystyrene flame retardant, or a diethylaluminum hypophosphite flame retardant.

[0022] Optionally, the flame retardant synergist is at least one of antimony trioxide and anhydrous zinc borate.

[0023] A preparation method of a laser-carved clear flame-retardant glass fiber reinforced polyamide 66 material comprises the following steps: 10-20 parts by weight of a flame retardant, 1.5-5 parts by weight of a flame retardant synergist, 0.5 parts by weight of an antioxidant, 0.5 parts by weight of a lubricant, 0.2-1 parts by weight of a black masterbatch and 0.5-2 parts by weight of a functional additive are mixed evenly, and then 40-55 parts by weight of a PA66 resin are added and mixed evenly; 30 parts by weight of glass fiber are added, and the laser-carved clear flame-retardant glass fiber reinforced polyamide 66 material is obtained after melting, extruding, cooling and air-drying.

[0024] Optionally, melting and extrusion are carried out in a twin-screw extruder, wherein the temperature of zone 1 is 180-200°C, the temperature of zones 2 to 5 is 260-270°C, the temperature of zones 6 to 9 is 250-260°C, the head temperature is 260-270°C, and the screw speed is 400rpm.

[0025] Beneficial effects of the present invention:

[0026] 1. The present invention uses polyamide 66 resin as the base material, and then fully mixes it with antioxidants, lubricants, black masterbatches, functional additives, flame retardant synergists and flame retardant premixes, and finally introduces glass fibers through side feeding, so that the present invention has the characteristics of flame retardant glass fiber reinforced laser engraving clarity;

[0027] 2. The preparation method of the present invention is simple, the obtained material is pollution-free, and is easy for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The present invention will be further described below in conjunction with the accompanying drawings.

[0029] Figure 1 It is a schematic diagram of the laser engraving test results of Examples 1 to 3 of the present application and Comparative Examples 1 to 3. DETAILED DESCRIPTION

[0030] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] In Examples 1-3 and Comparative Examples 1-3, laser-engraved clear flame-retardant glass fiber reinforced polyamide 66 materials were prepared, and their weight proportions were as shown in Table 1.

[0032]

[0033]

[0034] Table 1 Formulas of Examples 1-3 and Comparative Examples 1-3

[0035] Note: The relative viscosity of polyamide 66 resin is 2.7±0.03; the surface of the glass fiber is coated with a silane-based sizing agent, the short cut length is 3.0-4.5 mm, and the diameter of the glass fiber is 12-14 μm.

[0036] The preparation methods of Examples 1-3 and Comparative Examples 1-3 are the same, comprising the following steps:

[0037] The antioxidant, lubricant, black masterbatch, functional additive, flame retardant synergist and flame retardant are mixed evenly with a high-speed mixer, and then mixed evenly with the polyamide 66 resin that has been fully dried in advance, and then added to the main feeding barrel of the twin-screw extruder, and then glass fiber is added from the side feeding port of the twin-screw extruder. The materials are melted, extruded, cooled, air-dried, and pelletized to obtain laser-carved clear flame-retardant glass fiber reinforced polyamide 66 material, wherein the temperature of zone 1 of the twin-screw extruder is 180-200°C, the temperature of zones 2 to 5 is 260-270°C, the temperature of zones 6 to 9 is 250-260°C, the head temperature is 260-270°C, and the screw speed is 400rpm.

[0038] The above examples 1-3 and comparative examples 1-3 were injection molded into flame retardant strips and high gloss panels at an injection temperature of 2555-275°C. UL94 standard flame retardant performance tests and laser engraving experiments were performed. The test results are shown in Tables 2 and Figure 1 .

[0039] Table 2 Test results

[0040]

[0041] Remark:

[0042] Flame retardant performance: using UL94 standard test method, 1.6mm thickness;

[0043] Laser engraving clarity: The more *, the clearer the laser engraving effect;

[0044] From Table 1, Table 2 and Figure 1 It can be seen that the laser engraving effect of the diethyl aluminum hypophosphite flame retardant system is better than that of the red phosphorus flame retardant system and the bromine flame retardant system; in the flame retardant enhanced PA66 material, the carbon black masterbatch and carbon black powder have little difference in the clarity of laser engraving, but the laser engraving color of carbon black powder is slightly whiter; both functional additives can improve the clarity of laser engraving, especially the introduction of anhydrous Li Cl, the clarity of the material laser engraving is significantly improved, and the laser engraving color is the whitest. It should also be noted that in some previous literature, although the use of functional additives improves the clarity, it may have an adverse effect on the color of the laser engraving product, resulting in a yellowish final color. By comparing the various embodiments of the present application with the comparative examples, it can be found that after the introduction of functional additives in the embodiments of the present application, they are all whiter than the comparative examples, and not yellowish.

[0045] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0046] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A laser engraved clear flame retardant glass fiber reinforced polyamide 66 material, characterized in that: It includes the following raw materials in parts by weight: 40-55 parts of PA66 resin, Glass fiber 30 parts, Flame retardant 10-20 parts, Flame retardant synergist 1.5-5 parts, 0.5 parts of antioxidant, 0.5 parts of lubricant, Black masterbatch 0.2-1 part, And 0.5-2 parts of functional additives.

2. The laser engraved clear flame retardant glass fiber reinforced polyamide 66 material according to claim 1 is characterized in that: The surface of the glass fiber is coated with a silane-based sizing agent.

3. The laser engraved clear flame retardant glass fiber reinforced polyamide 66 material according to claim 1 is characterized in that: The antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and tris[2,4-di-tert-butylphenyl]phosphite.

4. The laser engraved clear flame retardant glass fiber reinforced polyamide 66 material according to claim 1 is characterized in that: The lubricant is NN-hexylene bis-hard amide.

5. The laser engraved clear flame retardant glass fiber reinforced polyamide 66 material according to claim 1 is characterized in that: The black masterbatch is one or more of 40wt% carbon black masterbatch and carbon black powder in a PA6 carrier.

6. The laser engraved clear flame retardant glass fiber reinforced polyamide 66 material according to claim 1 is characterized in that: The functional additive is ultrafine calcium carbonate or anhydrous lithium chloride.

7. The laser engraved clear flame retardant glass fiber reinforced polyamide 66 material according to claim 1 is characterized in that: The flame retardant is a red phosphorus flame retardant, a brominated polystyrene flame retardant or a diethyl aluminum hypophosphite flame retardant.

8. The laser engraved clear flame retardant glass fiber reinforced polyamide 66 material according to claim 1 is characterized in that: The flame retardant synergist is at least one of antimony trioxide and anhydrous zinc borate.

9. A method for preparing laser-engraved clear flame-retardant glass fiber reinforced polyamide 66 material, characterized in that: The following steps are involved: 10-20 parts by weight of flame retardant, 1.5-5 parts by weight of flame retardant synergist, 0.5 parts by weight of antioxidant, 0.5 parts by weight of lubricant, 0.2-1 parts by weight of black masterbatch and 0.5-2 parts by weight of functional additive are mixed evenly, and then 40-55 parts by weight of PA66 resin are added and mixed evenly; then 30 parts by weight of glass fiber are added, and after melting, extrusion, cooling and air-drying, the laser-carved clear flame-retardant glass fiber reinforced polyamide 66 material is obtained.

10. The method for preparing the laser-engraved clear flame-retardant glass fiber reinforced polyamide 66 material according to claim 9, characterized in that: Melting and extrusion are carried out in a twin-screw extruder, wherein the temperature of zone 1 is 180-200°C, the temperature of zones 2 to 5 is 260-270°C, the temperature of zones 6 to 9 is 250-260°C, the head temperature is 260-270°C, and the screw speed is 400rpm.

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