A laser-weldable glass fiber reinforced PBT / ASA / POK alloy material

Abstract

This invention provides a laser-weldable glass fiber reinforced PBT / ASA / POK alloy material. The alloy material comprises the following components per 100 parts by weight: PBT resin: 30-45 parts by weight; ASA resin: 10-20 parts by weight; POK resin: 10-20 parts by weight; glass fiber: 28-32 parts by weight; compatibilizer: 1-10 parts by weight; antioxidant: 0.2-2.0 parts by weight; lubricant: 0.2-2.0 parts by weight. The invention involves uniformly mixing PBT, ASA, POK, glass fiber, compatibilizer, antioxidant, and lubricant using a mixer, followed by granulation using a twin-screw extruder to obtain the glass fiber reinforced PBT / ASA / POK alloy material. This method is easily scalable for mass production. By adjusting the proportions of different components in the PBT / ASA / POK alloy material, alloy materials with low warpage, high strength, hydrolysis resistance, and wear resistance can be obtained.

Description

Technical Field

[0001] This invention belongs to the field of molecular composite material modification technology, and relates to a laser-weldable glass fiber reinforced PBT / ASA / POK alloy material. Background Technology

[0002] Polybutylene terephthalate (PBT) is a crystalline polymer with excellent properties such as high heat resistance, fatigue resistance, weather resistance, and low water absorption. It is widely used in automotive parts, electronics, and household goods. Pure PBT material has low surface hardness and a high coefficient of friction, resulting in poor wear resistance. As a crystalline material, it has poor toughness, and glass fiber reinforced PBT is prone to warping and deformation during injection molding. Furthermore, due to the presence of ester groups in its molecules, PBT is highly susceptible to high-temperature hydrolysis.

[0003] ASA is a non-crystalline terpolymer composed of acrylonitrile, styrene, and acrylate. It exhibits good weather resistance and can be used under prolonged exposure to sunlight, wind, and rain. It has high gloss, high toughness, and can withstand significant external forces. It also shows good resistance to acids, alkalis, and salts, and is not easily corroded. Disadvantages: It is not resistant to high temperatures and has poor flowability.

[0004] Polyketone (POK) is a highly crystalline polymer, a novel green polymer material synthesized from carbon monoxide and olefins (ethylene, propylene). It possesses high wear resistance, hydrolysis resistance, excellent chemical resistance, and good flowability and molding processability. Disadvantages include relatively low heat resistance and rigidity (flexural modulus: 1800 MPa).

[0005] When existing PBT / ASA alloy materials are used in fields such as automotive micro motor housings, they are prone to warping during the welding process. Furthermore, when the metal shaft carrying the gear directly mates with the housing bushing structure, it suffers from poor wear resistance, making the housing bushing structure particularly susceptible to wear. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a PBT / ASA / POK alloy material and its preparation method. By mixing PBT resin with ASA, POK, glass fiber and compatibilizers and other additives, and then extruding and granulating, a low-warpage, high-strength, hydrolysis-resistant, and wear-resistant alloy material is obtained. This material is widely used in the manufacturing of automotive micro motor housings and can be laser-welded.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a PBT / ASA / POK alloy material, wherein the alloy material comprises the following components based on 100 parts by weight of the total alloy material:

[0009] PBT resin: 30-45 parts by weight;

[0010] ASA resin: 10-20 parts by weight;

[0011] POK resin: 10-20 parts by weight;

[0012] Glass fiber: 28-32 parts by weight;

[0013] Compatibilizer: 1 part by weight - 10 parts by weight;

[0014] Antioxidant: 0.2 parts by weight - 2.0 parts by weight;

[0015] Lubricant: 0.2 parts by weight - 2.0 parts by weight;

[0016] The compatibilizer comprises maleic anhydride-grafted products and / or glycidyl methacrylate-grafted products; wherein the maleic anhydride-grafted products comprise SAN-g-MAH and / or PS-g-MAH; and the glycidyl methacrylate-grafted products comprise any one or a combination of at least two of SAN-g-GMA, PS-g-GMA, BA / MMA-g-GMA, or POK-g-GMA.

[0017] The infrared transmittance of the alloy material at a 980nm laser wavelength is ≥10%.

[0018] As a preferred embodiment of the present invention, the viscosity of the PBT resin is 0.8~1.2 dl / g; the acrylate content in the ASA resin is 50wt%-60wt%, and the particle size of the ASA resin is <10 mesh; the melt index of the POK resin is 6g / 10min-60g / 10min.

[0019] As a preferred embodiment of the present invention, the glass fiber is alkali-free reinforced glass fiber.

[0020] As a preferred embodiment of the present invention, the antioxidant comprises any one or a combination of at least two of the following: triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (245), pentaerythritol tetrakis[methyl-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010), N,N'-1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hexamethylenediamine (1098), n-octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate (1076), tris(2,4-di-tert-butylphenyl) phosphite (168), dialkyl thiodipropionate (DLTP), or tetra(2,4-di-tert-butylphenyl-4,4'-biphenyl) bisphosphonate (P-EPQ).

[0021] As a preferred embodiment of the present invention, the lubricant comprises any one or a combination of at least two of pentaerythritol stearate (PETS), N,N'-ethylenebis-stearamide (EBS), metal salt ionomers of ethylene-acrylic acid copolymers, or stearic acid erucamide.

[0022] Secondly, the present invention provides a method for preparing the aforementioned alloy material, the method comprising the following steps:

[0023] After mixing the raw materials according to the formula, the mixture is extruded, drawn into strips, and granulated by a twin-screw extruder to obtain PBT / ASA / POK alloy materials.

[0024] In a preferred embodiment of the present invention, the mixing speed is 80 r / min-120 r / min and the stirring time is 15 min-20 min.

[0025] As a preferred embodiment of the present invention, the screw diameter φ of the twin-screw extruder is 36mm and the length-to-diameter ratio L / D is 40.

[0026] As a preferred embodiment of the present invention, the temperatures of the twin-screw extruder from the feed port to the die outlet are sequentially 80℃-215℃, 200℃-225℃, 210℃-235℃, 210℃-235℃, 220℃-245℃, 220℃-245℃, 230℃-250℃, 230℃-250℃, 215℃-240℃, and 215℃-245℃; the twin-screw speed of the twin-screw extruder is 300r / min-400r / min.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] This invention produces an alloy material with low warpage, high strength, hydrolysis resistance, wear resistance, and suitable for laser welding by mixing PBT resin with ASA, POK, glass fiber, compatibilizers, and other additives, optimizing the dosage ratio, and granulating it through a twin-screw extruder.

[0029] The PBT / ASA / POK alloy material obtained by twin-screw extrusion granulation was injection molded into ISO test specimens. The temperature of each section of the injection molding machine was controlled at 220~265℃. The tensile strength, flexural modulus, impact strength, infrared transmittance, and tensile strength retention rate (double 85 / 1000h test (85℃ / 85%RH)) were tested. The properties are as follows:

[0030] (1) Tensile strength: ≥110MPa;

[0031] (2) Flexural modulus: ≥7500MPa;

[0032] (3) Notched impact strength: ≥8kJ / m 2 ;

[0033] (4) Tensile strength retention rate (double 85 / 1000h) ≥ 75%;

[0034] (5) Infrared transmittance (2mm): ≥10%. Detailed Implementation

[0035] To better illustrate the present invention and facilitate understanding of its technical solutions, the present invention will be further described in detail below. However, the following embodiments are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention.

[0036] The present invention provides a PBT / ASA / POK alloy material, wherein the alloy material comprises the following components based on 100 parts by weight of the total alloy material:

[0037] PBT resin: 30-45 parts by weight;

[0038] ASA resin: 10-20 parts by weight;

[0039] POK resin: 10-20 parts by weight;

[0040] Glass fiber: 28-32 parts by weight;

[0041] Compatibilizer: 1 part by weight - 10 parts by weight;

[0042] Antioxidant: 0.2 parts by weight - 2.0 parts by weight;

[0043] Lubricant: 0.2 parts by weight - 2.0 parts by weight;

[0044] The compatibilizer comprises maleic anhydride-grafted products and / or glycidyl methacrylate-grafted products; wherein the maleic anhydride-grafted products comprise SAN-g-MAH and / or PS-g-MAH; and the glycidyl methacrylate-grafted products comprise any one or a combination of at least two of SAN-g-GMA, PS-g-GMA, BA / MMA-g-GMA, or POK-g-GMA.

[0045] The infrared transmittance of the alloy material at a 980nm laser wavelength is ≥10%.

[0046] The amount of PBT resin used can be 35 parts by weight, 37 parts by weight, or 40 parts by weight, etc., but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The amount of ASA resin used can be 10 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, or 20 parts by weight, etc., but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The amount of POK resin used can be 10 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, or 20 parts by weight, etc., but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The amount of glass fiber used can be 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, or 32 parts by weight, etc. The amount of compatibilizer used can be 1 part by weight. The amounts of antioxidant can be 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.7 parts by weight, or 2.0 parts by weight, but are not limited to the listed values; other unlisted values ​​within this range are also applicable. The amounts of lubricant can be 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.7 parts by weight, or 2.0 parts by weight, but are not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0047] In this invention, a glass fiber reinforced PBT / ASA / POK alloy material is used. ASA improves the warpage and flatness of the material, and enhances its toughness. POK improves the material's wear resistance and chemical resistance. Simultaneously, through the action of a compatibilizer, it becomes compatible with PBT, and the ester groups are capped, significantly improving the material's hydrolysis resistance.

[0048] The addition of ASA and POK inhibits or disrupts the crystallization rate and crystallinity of PBT, giving the material a certain degree of light transmittance, which can meet the requirements of laser welding.

[0049] In this invention, the alloy material is placed on top of the laser-absorbing material during welding. Therefore, it needs to have high laser transmission efficiency to ensure that the underlying laser-absorbing material fully absorbs the laser and melts, allowing the alloy material to bond with the underlying laser-absorbing material, and then cools and solidifies. Consequently, the laser transmission efficiency of the alloy material affects the welding effect. This invention uses an LPKF TMG3 device to test the laser transmission efficiency of the plastic parts. Since the LPKF TMG3 uses a laser wavelength of 980nm, this is referred to here as infrared transmittance.

[0050] The present invention uses LPKF equipment to test the infrared transmittance at 980nm (the thickness of the color plate made of alloy material is 2mm): ≥10%.

[0051] At the same time, it is also necessary to control the amount of each raw material. If too much PBT resin is used, the product's laser transmittance will decrease; if too little is used, the product's strength will decrease. If too much ASA resin is used, the product's strength will decrease; if too little is used, the warpage will increase. If too much POK resin is used, the product's rigidity will decrease; if too little is used, the product's hydrolysis resistance will deteriorate.

[0052] As a preferred embodiment of the present invention, the viscosity of the PBT resin is 0.8 dl / g to 1.2 dl / g, for example, 0.8 dl / g, 0.9 dl / g, 1 dl / g, 1.1 dl / g, or 1.2 dl / g, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The acrylate content in the ASA resin is 50 wt% to 60 wt%, for example, 50 wt%, 52 wt%, 54 wt%, 56 wt%, 58 wt%, or 60 wt%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The particle size of the ASA resin is <10 mesh. The melt index of the POK resin is 6 g / 10 min to 60 g / 10 min, for example, 6 g / 10 min, 10 g / 10 min, 20 g / 10 min, 30 g / 10 min, 40 g / 10 min, 50 g / 10 min, etc. g / 10min or 60 g / 10min, etc., but not limited to the listed values, other unlisted values ​​within this range also apply.

[0053] As a preferred embodiment of the present invention, the glass fiber is alkali-free reinforced glass fiber, especially alkali-free reinforced glass fiber specifically for polyester.

[0054] The compatibilizer described in this invention is used to increase the binding of PBT with ASA and POK, thereby improving compatibility. The maleic anhydride and glycidyl methacrylate units in the compatibilizer used in this invention are, after research and verification, units that superiorly improve the compatibility of PBT with ASA and POK.

[0055] As a preferred embodiment of the present invention, the antioxidant comprises any one or a combination of at least two of the following: triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (245), pentaerythritol tetrakis[methyl-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010), N,N'-1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hexamethylenediamine (1098), n-octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate (1076), tris(2,4-di-tert-butylphenyl) phosphite (168), dialkyl thiodipropionate (DLTP), or tetra(2,4-di-tert-butylphenyl-4,4'-biphenyl) bisphosphonate (P-EPQ).

[0056] In this invention, antioxidants can effectively inhibit the degradation and deterioration of materials due to heat during processing and use, thus ensuring smooth processing and extending the service life of plastic parts.

[0057] As a preferred embodiment of the present invention, the lubricant comprises any one or a combination of at least two of pentaerythritol stearate (PETS), N,N'-ethylenebis-stearamide (EBS), metal salt ionomers of ethylene-acrylic acid copolymers, or stearic acid erucamide.

[0058] The specific embodiments of this invention also provide a method for preparing the aforementioned alloy material, the method comprising the following steps:

[0059] After mixing the raw materials according to the formula, the mixture is extruded, drawn into strips, and granulated by a twin-screw extruder to obtain PBT / ASA / POK alloy materials.

[0060] In this invention, the material undergoes melting, mixing, and shearing in a twin-screw extruder, and is then extruded from the twin-screw extruder.

[0061] As a preferred embodiment of the present invention, the mixing speed is 80 r / min-120 r / min, such as 80, 90, 100, 110 or 120, but not limited to the listed values; other unlisted values ​​within this range are also applicable. The stirring time is 15 min-20 min, such as 15 min, 16 min, 17 min, 18 min, 19 min or 20 min, but not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0062] As a preferred embodiment of the present invention, the temperatures of the twin-screw extruder from the feed port to the die outlet are sequentially 180℃-215℃, 200℃-225℃, 210℃-235℃, 210℃-235℃, 220℃-245℃, 220℃-245℃, 230℃-250℃, 230℃-250℃, 215℃-240℃, and 215℃-245℃; the twin-screw speed of the twin-screw extruder is 300r / min-400r / min.

[0063] The following are typical but non-limiting embodiments of the present invention:

[0064] In the following examples, the PBT used was 1100-211M (Chang Chun Chemical Co., Ltd., Taiwan), the ASA powder was Royaltuf 960A (Chemtura), the POK was M330A (Hyosung, South Korea), the glass fiber was GF (T187 NEG), the compatibilizer SAN-g-GMA (SAG-002) was purchased from Nantong Rizhisheng, the PS-g-MAH was purchased from Polyscope, Netherlands, the antioxidant 245 was purchased from BASF, the antioxidant 1076 was purchased from Lianlong, the antioxidant 168 was purchased from Lianlong, the antioxidant P-EPQ was purchased from Songyuan Industry Co., Ltd., and the POK-g-GMA was a self-made product, which was produced by mixing 90wt%-98wt% of POK (M330A (Hyosung, South Korea)), 0.1wt%-0.5wt% of peroxide (dicumyl peroxide, DCP, AkzoNobel), and glycidyl methacrylate (GMA, Shandong Jiaxu Chemical Co., Ltd.). 2wt%-8wt% were reactive extruded using a twin-screw extruder. The extruder temperature settings for each zone were: 190℃, 200℃, 200℃, 215℃, 225℃, 225℃, 220℃, 220℃, 220℃, 225℃ (die head). The twin-screw speed of the extruder was 280 r / min. PETS lubricant was purchased from Iterate; the metal salt ionomer A-C295 of ethylene-acrylic acid copolymer was purchased from Honeywell; and EBS was purchased from Shanghai Lianren Chemical. Example 1

[0065] This embodiment provides a PBT / ASA / POK alloy material and its preparation method. The raw material composition of the alloy material is as follows: PBT: 43.6 parts by weight; ASA: 10 parts by weight; POK: 10 parts by weight; compatibilizer SAN-g-GMA (SAG-002): 5 parts by weight; glass fiber GF (T187 NEG): 30 parts by weight; antioxidant 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; lubricant PETS and ethylene acrylic acid copolymer metal salt ionomer A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0066] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min. Example 2

[0067] This embodiment provides a PBT / ASA / POK alloy material and its preparation method. The raw material composition of the alloy material is as follows: PBT: 43.6 parts by weight; ASA: 10 parts by weight; POK: 10 parts by weight; POK-g-GMA (self-made): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0068] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min. Example 3

[0069] This embodiment provides a PBT / ASA / POK alloy material and its preparation method. The raw material composition of the alloy material is as follows: PBT: 33.6 parts by weight; ASA: 15 parts by weight; POK: 15 parts by weight; SAN-g-GMA (SAG-002): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0070] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min. Example 4

[0071] This embodiment provides a PBT / ASA / POK alloy material and its preparation method. The raw material composition of the alloy material is as follows: PBT: 33.6 parts by weight; ASA: 15 parts by weight; POK: 15 parts by weight; POK-g-GMA (self-made): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0072] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min. Example 5

[0073] This embodiment provides a PBT / ASA / POK alloy material and its preparation method. The raw material composition of the alloy material is as follows: PBT: 33.6 parts by weight; ASA: 20 parts by weight; POK: 10 parts by weight; POK-g-GMA (self-made): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0074] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min. Example 6

[0075] This embodiment provides a PBT / ASA / POK alloy material and its preparation method. The raw material composition of the alloy material is as follows: PBT: 33.6 parts by weight; ASA: 10 parts by weight; POK: 20 parts by weight; POK-g-GMA (self-made): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0076] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min. Example 7

[0077] This embodiment provides a PBT / ASA / POK alloy material and its preparation method. The raw material composition of the alloy material is as follows: PBT: 33.6 parts by weight; ASA: 10 parts by weight; POK: 20 parts by weight; PS-g-MAH: 5 parts by weight; GF(T187NEG): 30 parts by weight; 1076 and 168 (in a 1:1 ratio): 0.8 parts by weight; EBS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0078] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min.

[0079] Comparative Example 1:

[0080] Comparative Example 6: A PBT / ASA / POK alloy material and its preparation method are provided. The raw material composition of the alloy material is as follows: PBT: 53.6 parts by weight; ASA: 10 parts by weight; POK: 0 parts by weight; SAN-g-GMA: 5 parts by weight; GF(T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0081] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min.

[0082] Comparative Example 2:

[0083] Comparative Example 6: A PBT / ASA / POK alloy material and its preparation method are provided. The raw material composition of the alloy material is as follows: PBT: 51.6 parts by weight; ASA: 10 parts by weight; POK: 2 parts by weight; POK-g-GMA (self-made): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0084] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min.

[0085] Comparative Example 3:

[0086] Comparative Example 6: A PBT / ASA / POK alloy material and its preparation method are provided. The raw material composition of the alloy material is as follows: PBT: 23.6 parts by weight; ASA: 10 parts by weight; POK: 30 parts by weight; POK-g-GMA (self-made): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0087] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min.

[0088] Comparative Example 4:

[0089] Comparative Example 6: A PBT / ASA / POK alloy material and its preparation method are provided. The raw material composition of the alloy material is as follows: PBT: 43.6 parts by weight; ASA: 0 parts by weight; POK: 20 parts by weight; POK-g-GMA (self-made): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0090] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min.

[0091] Comparative Example 5:

[0092] Comparative Example 6: A PBT / ASA / POK alloy material and its preparation method are provided. The raw material composition of the alloy material is as follows: PBT: 41.6 parts by weight; ASA: 2 parts by weight; POK: 20 parts by weight; POK-g-GMA (self-made): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0093] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min.

[0094] Comparative Example 6:

[0095] Comparative Example 6: A PBT / ASA / POK alloy material and its preparation method are provided. The raw material composition of the alloy material is as follows: PBT: 13.6 parts by weight; ASA: 30 parts by weight; POK: 20 parts by weight; POK-g-GMA (self-made): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0096] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min.

[0097] Comparative Example 7:

[0098] This comparative example provides a PBT / ASA / POK alloy material and its preparation method. The raw material composition of the alloy material is as follows: PBT: 33.6 parts by weight; ASA: 10 parts by weight; POK: 20 parts by weight; SEBS-g-MAH (Kertene): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0099] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min.

[0100] Comparative Example 8:

[0101] This embodiment provides a PBT / ASA / POK alloy material and its preparation method. The raw material composition of the alloy material is as follows: PBT: 33.6 parts by weight; ASA: 10 parts by weight; POK: 20 parts by weight; BF-7M:E-GMA-MA (Sumitomo): 5 parts by weight; GF (T187 NEG): 30 parts by weight; 245 and P-EPQ (in a 1:1 ratio): 0.8 parts by weight; PETS and A-C295 (in a 1:1 ratio): 0.6 parts by weight.

[0102] The raw materials in the formula are added to a mixer and mixed for 15 minutes. Then, the uniformly mixed material is melted, mixed, and sheared with side-fed glass fiber through a twin-screw extruder. The mixture is then extruded, drawn into strips, and pelletized through the die head to obtain glass fiber reinforced PBT / ASA / POK alloy material. The extruder temperature settings for each section are: 215℃, 225℃, 235℃, 235℃, 245℃, 245℃, 250℃, 250℃, 240℃, 245℃ (die head); the twin-screw speed of the twin-screw extruder is 350 r / min.

[0103] The alloy materials prepared in Examples 1-7 and Comparative Examples 1-8 were injection molded into ISO specimens for testing, and the results are shown in Table 1. The injection molding temperatures were 250℃, 245℃, 240℃, 235℃, and 220℃.

[0104] Among them, (1) tensile strength: ≥110MPa;

[0105] (2) Flexural modulus: ≥7500MPa;

[0106] (3) Notched impact strength: ≥8kJ / m 2 ;

[0107] (4) Tensile strength retention rate (double 85 / 1000h) ≥ 75%;

[0108] (5) Infrared transmittance (2mm): ≥10%.

[0109] Infrared transmittance was measured using equipment from LPKF at 980 nm.

[0110] Table 1: Comparative Examples of Alloy Material Performance Testing in Examples 1-7 and Comparative Examples 1-6

[0111] Tensile strength (MPa) Flexural modulus (MPa) <![CDATA[Izod impact strength (kJ / m 2 )]]> Tensile strength retention rate (double 85 / 1000h) Infrared transmittance (2mm) Warpage (mm) Length 120 mm x Width 120 mm x Degree 2 mm Test standards or test methods ISO 527-1-2012 ISO178-2010 ISO 179-1:2010 ISO 527-1-2012 LPKF TMG3 steel ruler method Example 1 119 8200 7.5 68.9% 10.1 2.2 Example 2 125 7950 8.2 72.8% 10.3 2.15 Example 3 112 7800 9.5 78% 9.2 1.85 Example 4 117 7650 10.8 79.5% 10.7 1.8 Example 5 109 7760 11 75% 10.5 1.75 Example 6 120 7580 12.7 85.8% 11.5 1.8 Example 7 119 7550 10 84.8% 10.9 2.05 Comparative Example 1 128 8500 10 60% 6.8 2.75 Comparative Example 2 127 8460 9.8 63.7% 7.1 2.75 Comparative Example 3 115 7200 11.3 86.9% 11.3 2.55 Comparative Example 4 125 7720 10.8 84.8% 6.9 2.9 Comparative Example 5 123 7698 10.5 85.3% 7.5 2.9 Comparative Example 6 95 7056 6.8 87.4% 9.4 1.5 Comparative Example 7 92 6968 6.4 71.4% 8.4 2.8 Comparative Example 8 90 6872 6.2 69.4% 8.1 2.7

[0112] ISO 527-1-2012 describes a test method for tensile strength; ISO 178-2010 describes a test method for flexural modulus; ISO 179-1:2010 describes a test method for notched impact strength; and ISO 527-1-2012 describes a test method for tensile strength retention.

[0113] Infrared transmittance was measured using an LPKF TMG 3 device, the testing method of which is described in detail in its instruction manual.

[0114] The steel ruler method involves using a precise 300mm steel ruler against the surface of the material and recording the gap between the steel ruler and the material, which is the degree of warpage.

[0115] The results from Examples 1-7 show that, with different ASA and POK contents and different compatibilizers, higher ASA content leads to increased notched impact strength; higher POK content results in better hydrolysis resistance; and the POK-g-GMA compatibilizer system exhibits superior overall mechanical properties and infrared transmittance compared to the SAN-g-GMA compatibilizer system. Examples 5 and 6 using the POK-g-GMA compatibilizer system further improved hydrolysis resistance and infrared transmittance with increasing POK content, but reduced flexural modulus due to the inherently low flexural modulus of POK. Overall evaluation: All the above examples represent preferred solutions of the present invention. Example 6 exhibits the best overall mechanical properties, optimal hydrolysis resistance, and high infrared transmittance, making it the optimal solution for laser-welded glass fiber reinforced PBT / ASA / POK alloys.

[0116] Comparative examples and Comparative Examples 1-6 show that, with a fixed ASA content, the POK content has a decisive impact on the material's hydrolysis resistance and infrared transmittance. This is because POK has excellent hydrolysis resistance and also disrupts the crystallization of PBT, thereby increasing infrared transmittance. However, with a fixed POK content, excessively high ASA content actually leads to a decrease in overall material performance. This is because the compatibility between amorphous ASA and the crystalline PBT and POK material systems is too poor. Furthermore, it can be seen that using an unsuitable compatibilizer will worsen the overall performance of the material.

[0117] In summary, this invention provides a laser-weldable glass fiber reinforced PBT / ASA / POK alloy material and its preparation method. Through optimized combination and proportioning of PBT, ASA, POK, and a compatibilizer, a laser-weldable glass fiber reinforced PBT / ASA / POK alloy material with excellent comprehensive performance is obtained. Overall evaluation: Through comparative implementation of the examples, Example 6 was selected as the optimal solution for the laser-weldable glass fiber reinforced PBT / ASA / POK alloy material.

[0118] The applicant declares that the detailed process equipment and process flow of this invention are illustrated through the above embodiments, but this invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that this invention must rely on the above detailed process equipment and process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the products of this invention, additions of auxiliary components, and selection of specific methods, all fall within the protection scope and disclosure scope of this invention.

Claims

1. A PBT / ASA / POK alloy material, characterized in that, The alloy material is composed of the following components based on 100 parts by weight of the total alloy material: PBT resin: 30-45 parts by weight; ASA resin: 10-20 parts by weight; POK resin: 10-20 parts by weight; Glass fiber: 28-32 parts by weight; Compatibilizer: 1 part by weight - 10 parts by weight; Antioxidant: 0.2 parts by weight - 2.0 parts by weight; Lubricant: 0.2 parts by weight - 2.0 parts by weight; The compatibilizer includes any one or a combination of at least two of SAN-g-GMA or POK-g-GMA; The infrared transmittance of the alloy material at a 980nm laser wavelength is ≥10%.

2. The alloy material according to claim 1, characterized in that, The viscosity of the PBT resin is 0.8 dl / g to 1.2 dl / g; the acrylate content of the ASA resin is 50 wt% to 60 wt%, and the particle size of the ASA resin is <10 mesh; the melt index of the POK resin is 6 g / 10 min to 60 g / 10 min.

3. The alloy material according to claim 1, characterized in that, The glass fiber is alkali-free reinforced glass fiber.

4. The alloy material according to claim 1, characterized in that, The antioxidants include any one or a combination of at least two of the following: triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[methyl-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hexamethylenediamine, n-octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, tris(2,4-di-tert-butylphenyl) phosphite, dialkyl esters of thiodipropionate, or tetrakis(2,4-di-tert-butylphenyl-4,4'-biphenyl) bisphosphonate.

5. The alloy material according to claim 1, characterized in that, The lubricant comprises any one or a combination of at least two of pentaerythritol stearate, N,N'-ethylenebis-stearamide, metal salt ionomers of ethylene-acrylic acid copolymers, or stearic acid erucamide.

6. A method for preparing an alloy material as described in any one of claims 1-5, characterized in that, The method includes the following steps: After mixing the raw materials according to the formula, the mixture is extruded, drawn into strands, and granulated by a twin-screw extruder to obtain PBT / ASA / POK alloy materials.

7. The preparation method according to claim 6, characterized in that, During the mixing process, the mixing speed is 80 r / min-120 r / min, and the stirring time is 15 min-20 min.

8. The preparation method according to claim 6, characterized in that, The twin-screw extruder has a screw diameter φ of 36 mm and a length-to-diameter ratio L / D of 40.

9. The preparation method according to claim 6, characterized in that, The temperatures of the twin-screw extruder from the feed port to the die outlet are sequentially 180℃-215℃, 200℃-225℃, 210℃-235℃, 210℃-235℃, 220℃-245℃, 220℃-245℃, 230℃-250℃, 230℃-250℃, 215℃-240℃, and 215℃-245℃; the twin-screw speed of the twin-screw extruder is 300r / min-400r / min.