CN102093707A - Laser-marked and halogen-free flame-retardant polyamide composite material - Google Patents
Laser-marked and halogen-free flame-retardant polyamide composite material Download PDFInfo
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Abstract
The invention relates to a laser-marked and halogen-free flame-retardant polyamide composite material with excellent flame-retardant property and laser marking effect. The polyamide composite material is characterized by comprising the following substances: at least one or more of polyamide resins, at least one or more of inorganic packing materials, at least one or more of halogen-free flame retardants which can provide the excellent flame-retardant property for the composite material, at least one or more of aids which can provide excellent laser marking for the composite material, and other unessential aids such as lubricants, antioxidants, pigments and the like. The composite material has the comprehensive performance of excellent temperature resistance, flame retardance, and dimensional stability, easiness of processing and molding and the like, and also has clear and attractive laser marking effect at the same time. The composite material is widely applied in the fields of household products, electronic appliances, laser handles and the like and has huge market prospect.
Description
Technical field
But the present invention relates to a kind of laser-markable, halogen-free flame-retardant polyamide matrix material, belong to the general engineering plastic polyamide compoiste material and make the field with unusual excellent fire retardant characteristic and splendid laser labelling effect.
Background technology
Polyamide resin is the very excellent thermoplasticity general engineering plastic of a kind of over-all properties, it has excellent temperature tolerance, heat decomposition temperature is usually greater than 350 ℃, can under 80～120 ℃ condition, use continuously, has tensile strength preferably, it is the preferred material of mechanical part, also has excellent impact toughness simultaneously, can be acidproof, alkali, most of inorganic salt solutions, haloalkane, hydro carbons, the ester class, corrosion such as ketone, has good wear resistance, self lubricity, can be widely used in electric, automobile, the functional component in fields such as chemistry and electronic installation is as gear, roller, pulley, roll shaft, impeller in the pump housing, fan blade, high pressure seal is enclosed, valve seat, pad, lining, various handles, bracing frame, electric wire covering etc.Its weak point: the one, though polymeric amide itself has self-extinguishing, flame retardant properties does not reach service requirements; The 2nd, in polymeric amide, add halogen containing flame-retardant, the halide-containing of emitting during the halogen containing flame-retardant burning not only produces injury to the person, and direct contaminate environment; The 3rd, not having can clear laser-marking ability, therefore common way is to adopt silk-screen, printing ink spraying etc. to be used for the sign of thermoplastic product to embody relevant information at present, as manufacturer, date manufactured, quality guaranteed period, anti-counterfeiting mark or the like, but the silk-screen mode causes physical abuse even can produce chemical action product surface inevitably, though surface printing technology such as printing ink spraying are clear, but starting material such as matrix material and printing ink are not only had higher requirement, and its long-term durability can satisfy user's requirement.
Summary of the invention
Purpose of design: avoid the weak point in the background technology, design and a kind ofly both had very excellent fire retardant characteristic energy, but have laser-markable, the halogen-free flame-retardant polyamide matrix material of splendid laser labelling effect again.
Design: in order to realize above-mentioned purpose of design.1, the design that adds other modified component at polymeric amide is one of technical characterictic of the present invention.The purpose of doing like this is: polymeric amide adds other modified component, as glass fiber material, and the glass fibre main component is silicon-dioxide, aluminum oxide, calcium oxide, boron oxide, magnesium oxide, sodium oxide etc., according to what of alkali content in the glass, can be divided into alkali free glass fibre (sodium oxide 0%～2%, the genus aluminium borosilicate glass), medium-alkali glass fibre (sodium oxide 8%～12%, belong to the boracic or the soda lime glass of boracic not) and high alkali glass fibre (sodium oxide more than 13%, genus soda lime glass).The glass fibre of described glass fibre for handling with silane coupling agent, titanate coupling agent, aluminate coupling agent, preferred glass fibre is an alkali free glass fibre, and to add a certain amount of halogen-free flame retardants at above-mentioned matrix material, can guarantee that matrix material not only has excellent flame-retardant, and environmental protection, Halogen, multi-functional.2, halogen-free flame-retardant polyamide matrix material adds the design of specific laser-markable auxiliary agent, is two of technical characterictic of the present invention.The purpose of doing like this is: it not only makes material have laser marking effect clear, attractive in appearance, but also has very excellent heat resistance, flame retardant properties, simultaneously dimensional stability and to be easy to machine-shaping property better.
Technical scheme: the preparation of laser-markable, halogen-free flame-retardant polyamide, it comprises following component (weight meter):
A) at least a or several polyamide resins and
B) at least a or several inorganic filling materials and
C) at least a or several halogen-free flame retardantss that the matrix material excellent fire-retardancy can be provided and
D) at least a or several provide the excellent laser-markable auxiliary agent of matrix material and
F) other processing aids
Above-mentioned laser-markable, halogen-free flame-retardant polyamide matrix material, comprise one or more polyamide resins, this type of polymeric amide is meant that those have the various polymkeric substance of amino and hydroxy-acid group by polymerization, " CO-NH-" is the general group of this base polymer, according to the availability and the special suitability of this material, preferred polymeric amide is poly-(hexamethylene adipamide) (hereinafter referred to as " nylon 66 ") and poly-(hexanolactam) (hereinafter referred to as " nylon 6 ").
Above-described nylon 66, the relative viscosity scope should be 2.40～2.80, and preferred range of viscosities should be 2.55～2.70, and melt flow rate (MFR) preferably can be greater than 9.5g/10min.
Above-described nylon 66, wherein, based on the gross weight meter of composition, the consumption of preferred nylon 66 is about 30～70 parts.
Above-described nylon 6 can be import nylon 6 or homemade nylon 6, and they are having advantage separately, and preferably those monomer content are less than 0.5%, and tensile strength is greater than the nylon 6 of 70MPa.
Above-described nylon 6 wherein, can be the 1013B of Ube chemical industry, perhaps can be the M2400 that newly understands Meida Company, and preferred scheme is that in composition total weight, the consumption of nylon 6 is about 25～75 parts.
Above-mentioned laser-markable, halogen-free flame-retardant polyamide matrix material, composition comprise at least a or several inorganic filling materials.The filler that is fit to comprises glass fibre, aluminum oxide, talcum powder, carbon black, kaolin, wilkinite, synthetic magnesium silicate, zinc oxide, calcium sulfate wood powder etc., or their mixture.
Above-described inorganic filling material, in the gross weight of composition, preferred consumption is about 8～55 parts, and preferred consumption is about 15～35 parts.
Above-described inorganic filling material, after adding a certain proportion of inorganic filling material, mixing material has excellent mechanical property, can also have better dimensional stability simultaneously, according to the alternative and the suitability of material, preferred inorganic materials is a glass fibre.
Above-described glass fibre, preferably those use the short glass fiber that silane coupling agent, titanate coupling agent, aluminate coupling agent were handled, and short glass fiber length is about 2～12 millimeters, and preferred length is 3～7 millimeters.
The single fiber diameter of glass fibre preferably is preferably 8～15 microns, can be long glass fibres or short glass fiber, and the preferred short glass fiber of the present invention in the gross weight of composition, comprises be about 15.0～35.0 parts that this staple fibre accounts for composition.
Above-mentioned laser-markable, halogen-free flame-retardant polyamide matrix material, composition also should comprise at least a or several halogen-free flame retardantss that the matrix material excellent fire-retardancy can be provided.
Above-described halogen-free flame retardants can be inorganic filling class, as Al (OH)
3, Mg (OH)
2, red phosphorus, expansible black lead etc., also can be organic class, as ammonium polyphosphate (abbreviating APP as), phosphoric acid ester, phosphorus oxide, melamine cyanurate (abbreviating MCA as), Melamine Polyphosphate, melamine pyrophosphate salt, melamine pyrophosphate (MPP), hypophosphite etc.
Above-described halogen-free flame retardants, preferably MPP class and hypophosphite based flame retardant, wherein, in the gross weight of composition, the consumption of fire retardant is approximately 8～30 parts.
Above-mentioned laser-markable, halogen-free flame-retardant polyamide matrix material, necessary, will add at least one or several in the composition can provide matrix material excellent laser-markable auxiliary agent, and in the gross weight of composition, preferred mark agent consumption is about 0.1～2 part.
Above-described laser marking auxiliary agent, this auxiliary agent the inside preferably includes but is not limited to carbon black, graphite, one or several of mica, silicon-dioxide, aluminum oxide, tin-antimony oxide, wherein, in the gross weight of laser marking auxiliary agent, the content of tin-antimony oxide is preferably in 35～60% the scope, and resistance toheat preferably can reach 750 ℃.
Above-described laser marking auxiliary agent, can select those imports, quality is metastable, also can select home-made, more or can be to make by oneself, described laser marking auxiliary agent be self-control and home-made laser marking auxiliary agent in this patent.
Above-mentioned laser-markable, halogen-free flame-retardant polyamide matrix material, matrix material also should add a certain amount of processing aid, can add a certain amount of antioxidant stabilizers in the processing aid of this composition,, improve its heat resistance processability to prevent the matrix material xanthochromia effectively.
Above-mentioned antioxidant stabilizer; N preferably; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (oxidation inhibitor 1098), three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (oxidation inhibitor 168), two (2; the 4-di-t-butyl) season tetrol diphosphites (oxidation inhibitor S-9228), 3; in the 3'-Tyox B (anti-oxidant DLTP) one or more; wherein; in the gross weight of composition, the proportional range of oxidation inhibitor preferably is about 0.1～1.0 part.
Above-mentioned laser-markable, halogen-free flame-retardant polyamide matrix material, also should add one or several dispersion agents in the processing aid of composition, preferred dispersing agent is that one or several are composite for Zinic stearas, calcium stearate, ethylene bis stearic amide, polyethylene wax, oxidized polyethlene wax, ethylene-acrylic acid copolymer, montanic acid wax etc.In the gross weight of composition, the preferred dispersing agent consumption is about 0.1～1.5 part.
The present invention compares with background technology, the one, when having highly stable heat resistance, flame retardant effect, given again that material can be clear, attractive in appearance, laser marking effect easily, enlarged use range and the Application Areas of product; The 2nd, this technology is particularly useful in the thermoplastic articles, major advantage is embodied in and need not contacts, and can not produce unnecessary internal stress, long service life in product, pollution-free, can not produce unfavorable damage to product surface, running cost is lower, the working (machining) efficiency height, the mark of using the laser-marking product is clear, attractive in appearance, the precision height, and have antifalse effect; The 3rd, have the over-all properties of the machine-shaping of being easy to, have a very wide range of applications in fields such as family expenses product, electronic apparatus, laser handles; The 4th, because composition of the present invention is thermoplastic, so be fit to very much with conventional processing mode, by general injection moulding preparation, injecting products of the present invention is applicable to automotive industry, electronic industry, furniture industry and need the Application Areas of product laser-marking, specific product such as keyboard, air switch handle, breaker of plastic casing and alternating current contactor etc.
Embodiment
Embodiment 1: a kind of laser-markable, halogen-free flame-retardant polyamide matrix material include:
A) at least a polyamide resin consumption is 25～80 parts, and preferred version is to be about 45～75 parts or more than one polyamide resin consumption sums, and described polyamide resin is meant nylon 6, nylon 66, perhaps the blend of nylon 6 and nylon 66; The melt temperature scope of described polyamide resin is about 200～280 ℃, and preferred melt temperature scope is controlled at 220～270 ℃, and polyamide resin relative viscosity scope preferably is chosen at 2.15～2.75.
B) at least a or several inorganic filling materials and, described one or several inorganic filling materials and be meant a kind of or its two kinds or three kinds of blends of glass fibre, talcum powder, wollastonite.
C) halogen-free flame retardants of at least a or several flame retardant propertiess and, the halogen-free flame retardants of described one or several flame retardant propertiess and be meant phosphorus system, nitrogen phosphorus system, inorganic filling system, perhaps carry out between them composite, preferred phosphorus flame retardant or nitrogen phosphorus flame retardant; Described halogen-free flame retardants consumption is 8～32 parts.
D) at least a or several provide the excellent laser-markable auxiliary agent of matrix material and, described at least a or several laser-markable auxiliary agent of matrix material that provides contains tin-antimony oxide with being meant, the proportional range that wherein said tin-antimony oxide accounts for whole laser-markable auxiliary agent is about 25～65%, and preferred range is 32～56%.Described laser-markable assistant packet contains one or several inorganic fillers, and preferred inorganic filler can be a lime carbonate, wollastonite, and mica powder, one or more combinations in the talcum powder, the characteristic of its laser-markable auxiliary agent is at 30～4.0g/m
3Density range, resistance toheat reaches more than 750 ℃ or 750 ℃.
F) at least a or several oxidation inhibitor.Described oxidation inhibitor is four [methyl-β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (antioxidant 1010); β-(3; the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid (antioxidant 1076); N; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine (oxidation inhibitor 1098) propionyl); three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (oxidation inhibitor 168); two (2; the 4-di-t-butyl) season tetrol diphosphites (oxidation inhibitor S-9228); 3; 3'-Tyox B (anti-oxidant DLTP); 4; 4'-thiobis (the 6-tertiary butyl-3-methylphenol) or 4,4'-thiobis (6-tertiary butyl meta-cresol) (antioxidant 300) wherein one or more and composite.Also should add one or several dispersion agents in the described oxidation inhibitor, preferred dispersing agent is wherein one or several such as Zinic stearas, calcium stearate, pentaerythritol stearate, ethylene bis stearic amide, polyethylene wax, oxidized polyethlene wax, ethylene-acrylic acid copolymer, montanic acid wax.
Embodiment 1-1: with nylon 66 (the refreshing horse in tafelberg: EPR27) of 50 weight %; the MPP of 30 weight % (Melapur 200); 0.5 the laser-marking auxiliary agent (self-control) of weight %; 0.25 the N of weight %; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine (middle celebrating chemical industry provides) propionyl); 0.25 three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (Li Anlong company provides) of weight % and the tetramethylolmethane stearate of 0.3 weight % stirred in high-speed mixer 5 minutes; after mixing; drop into the twin screw extruder extruding pelletization; the side feeding adds the short glass fiber (international compound alkali-free short glass fiber) of 20 weight %; the length-to-diameter ratio of twin screw extruder is 40:1; screw speed is 265rpm/min; each subregion temperature of screw rod is; 260 ℃ in first district; 260 ℃ in second district; 260 ℃ in the 3rd district; 260 ℃ in the 4th district; 255 ℃ in the 5th district; 255 ℃ in the 6th district; 255 ℃ of SECTOR-SEVENs; 255 ℃ of Section Eight; 255 ℃ in the 9th district; head temperature is controlled at 275 ℃, and tie rod is crossed the water pelletizing.
Embodiment 1-2: with nylon 66 (the refreshing horse in tafelberg: EPR27) of 35 weight %; the nylon 6 (1013B) of 10 weight %; the MPP of 30 weight % (Melapur 200); 0.5 the laser-marking auxiliary agent (self-control) of weight %; 0.25 the N of weight %; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine propionyl); 0.25 three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid esters of weight % and the tetramethylolmethane stearate of 0.5 weight % stirred in high-speed mixer 5 minutes; after mixing; drop into the twin screw extruder extruding pelletization; the side feeding adds the short glass fiber (international compound alkali-free short glass fiber) of 25 weight %; the length-to-diameter ratio of twin screw extruder is 40:1; screw speed is 265rpm/min; each subregion temperature of screw rod is 260 ℃ in first district; 260 ℃ in second district; 260 ℃ in the 3rd district; 260 ℃ in the 4th district; 255 ℃ in the 5th district; 255 ℃ in the 6th district; 255 ℃ of SECTOR-SEVENs; 255 ℃ of Section Eight; 255 ℃ in the 9th district; head temperature is controlled at 275 ℃, and tie rod is crossed the water pelletizing.
Embodiment 1-3: with nylon 66 (the refreshing horse in tafelberg: EPR27) of 48 weight %; the MPP of 27 weight % (EPFR-200A); 0.30 the laser-marking auxiliary agent of weight %; the N410 of 5 weight %; 0.25 the N of weight %; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine propionyl); 0.25 three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid esters of weight % and the tetramethylolmethane stearate of 0.3 weight % stirred in high-speed mixer 5 minutes; after mixing; drop into the twin screw extruder extruding pelletization, the side feeding adds the short glass fiber (international compound alkali-free short glass fiber) of 20 weight %.The length-to-diameter ratio of twin screw extruder is 40:1, screw speed is 265rpm/min, each subregion temperature of screw rod is, 260 ℃ in first district, 260 ℃ in second district, 260 ℃ in the 3rd district, 260 ℃ in the 4th district, 255 ℃ in the 5th district, 255 ℃ in the 6th district, 255 ℃ of SECTOR-SEVENs, 255 ℃ of Section Eight, 255 ℃ in the 9th district, head temperature are controlled at 275 ℃, and tie rod is crossed the water pelletizing.
Embodiment 1-4: with nylon 66 (the refreshing horse in tafelberg: EPR27) of 56 weight %; the Exolit OP1312 of 19 weight %; 0.5 the laser-marking auxiliary agent of weight %; 0.3 the N of weight %; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine propionyl); 0.3 two (2 of weight %; the 4-di-t-butyl) the tetramethylolmethane stearate of season tetrol diphosphites (middle celebrating chemical industry provides) and 0.3 weight % stirred in high-speed mixer 5 minutes; after mixing; drop into the twin screw extruder extruding pelletization, the side feeding adds the short glass fiber (international compound alkali-free short glass fiber) of 25 weight %.The length-to-diameter ratio of twin screw extruder is 40:1, screw speed is 265rpm/min, each subregion temperature of screw rod is, 260 ℃ in first district, 260 ℃ in second district, 260 ℃ in the 3rd district, 260 ℃ in the 4th district, 255 ℃ in the 5th district, 255 ℃ in the 6th district, 255 ℃ of SECTOR-SEVENs, 255 ℃ of Section Eight, 255 ℃ in the 9th district, head temperature are controlled at 275 ℃, and tie rod is crossed the water pelletizing.
Embodiment 1-5: with the nylon 6 (1013B) of 40 weight %; the MPP of 30 weight % (Melapur 200); 0.5 the laser-marking auxiliary agent (self-control) of weight %; 0.25 the N of weight %; N '-two-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine propionyl); 0.25 three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid esters of weight % and the tetramethylolmethane stearate of 0.3 weight % stirred in high-speed mixer 5 minutes; after mixing; drop into the twin screw extruder extruding pelletization, the side feeding adds the short glass fiber (international compound alkali-free short glass fiber) of 30 weight %.The length-to-diameter ratio of twin screw extruder is 40:1, screw speed is 265rpm/min, each subregion temperature of screw rod is, 260 ℃ in first district, 260 ℃ in second district, 260 ℃ in the 3rd district, 260 ℃ in the 4th district, 255 ℃ in the 5th district, 255 ℃ in the 6th district, 255 ℃ of SECTOR-SEVENs, 255 ℃ of Section Eight, 255 ℃ in the 9th district, head temperature are controlled at 275 ℃, and tie rod is crossed the water pelletizing.
Comparative Examples 1: with nylon 66 (the refreshing horse in tafelberg: EPR27) of 50 weight %; the N of the MPP of 30 weight % (Melapur 200), 0.25 weight %; N '-two-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl) the tetramethylolmethane stearate of three of hexanediamine, 0.25 weight % ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid esters and 0.3 weight % stirred in high-speed mixer 5 minutes; after mixing; drop into the twin screw extruder extruding pelletization, the side feeding adds the short glass fiber (international compound alkali-free short glass fiber) of 20 weight %.The length-to-diameter ratio of twin screw extruder is 40:1, screw speed is 265rpm/min, each subregion temperature of screw rod is, 260 ℃ in first district, 260 ℃ in second district, 260 ℃ in the 3rd district, 260 ℃ in the 4th district, 255 ℃ in the 5th district, 255 ℃ in the 6th district, 255 ℃ of SECTOR-SEVENs, 255 ℃ of Section Eight, 255 ℃ in the 9th district, head temperature are controlled at 275 ℃, and tie rod is crossed the water pelletizing.
Comparative Examples 2: with nylon 66 (the refreshing horse in tafelberg: EPR27) of 50 weight %; the MPP of 30 weight % (Melapur 200); 0.5 the laser-marking auxiliary agent EL-201 of weight % (Shanghai should jump Chemical Industry Science Co., Ltd provide); 0.25 the N of weight %; N '-two-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine propionyl); 0.25 three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid esters of weight % and the tetramethylolmethane stearate of 0.3 weight % stirred in high-speed mixer 5 minutes; after mixing; drop into the twin screw extruder extruding pelletization; the side feeding adds the short glass fiber (international compound alkali-free short glass fiber) of 20 weight %; the length-to-diameter ratio of twin screw extruder is 40:1; screw speed is 265rpm/min; each subregion temperature of screw rod is; 260 ℃ in first district; 260 ℃ in second district; 260 ℃ in the 3rd district; 260 ℃ in the 4th district; 255 ℃ in the 5th district; 255 ℃ in the 6th district; 255 ℃ of SECTOR-SEVENs; 255 ℃ of Section Eight; 255 ℃ in the 9th district; head temperature is controlled at 275 ℃, and tie rod is crossed the water pelletizing.
The particle that above-mentioned Comparative Examples and embodiment are finished granulation in 110 ℃ air dry oven dry 4 hours, the moulding of more dried particle being drawn a design on the injection moulding machine of MA600/150, processing temperature is controlled at 245～300 ℃, and the mould temperature control is at 90～115 ℃.
All components and test result are as shown in Table 1 and Table 2, used Elongation test is all tested according to GB GB/T 1040.1-2006 standard, all crooked tests are all tested according to GB GB/T 9341-2000 standard, the shock strength test is tested according to GB/T 1043.1/1eA standard, flame retardant properties is tested according to GB/T 2408-1996 standard, specimen size (mm): (124 ± 0.2) * (13 ± 0.2) * (1.6 ± 0.2) (long * wide * thick).The heat-drawn wire test is tested by GB/T 1634.2-2004 standard; Load is 1.80MPa, and span is 64mm, compares electric trace index (CTI) test and tests by standard GB/T 4207-2003.
Table 1
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 |
| Nylon 66 (wt%) | 50 | 35 | 48 | 56 | / | 50 | 50 |
| Nylon 6,1013B (wt%) | / | 10 | / | / | 40 | / | / |
| Short glass fiber (wt%) | 20 | 25 | 20 | 25 | 30 | 20 | 20 |
| Melapur200(wt%) | 30 | 30 | / | / | 30 | 30 | 30 |
| EPFR-200A(wt%) | / | / | 27 | / | / | / | / |
| ExolitOP1312(wt%) | / | / | / | 19 | / | / | / |
| N410(wt%) | / | / | 5 | / | / | / | / |
| Self-control laser-marking auxiliary agent (wt%) | 0.5 | 0.5 | 0.3 | 0.5 | 0.5 | / | / |
| EL-201(wt%) | / | / | / | / | / | / | 0.5 |
| 1098(wt%) | 0.25 | 0.25 | 0.25 | 0.3 | 0.25 | 0.25 | 0.25 |
| 168(wt%) | 0.25 | 0.25 | 0.25 | 0.3 | 0.25 | 0.25 | 0.25 |
| Tetramethylolmethane stearate (wt%) | 0.3 | 0.5 | 0.3 | 0.3 | 0.5 | 0.3 | 0.3 |
Table 2
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 |
| Tensile strength (MPa) | 109 | 122 | 101 | 135 | 111 | 115 | 112 |
| Notched Izod impact strength (KJ/m 2) | 6 | 8 | 8 | 9 | 6 | 6.5 | 6.2 |
| Non-notched Izod impact strength (KJ/m 2) | 35 | 40 | 40 | 50 | 40 | 38 | 36 |
| Flexural strength (MPa) | 153 | 179 | 140 | 180 | 161 | 160 | 157 |
| Heat-drawn wire (℃) | 230 | 240 | 225 | 240 | 206 | 235 | 232 |
| Compare trace leakage current index (V) | 375 | 350 | 400 | 550 | 400 | 400 | 400 |
| Vertically fire-retardant/1.6mm | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| The mark effect | Clear | Clear | More clear | Clear | Clear | Fuzzy | More clear |
What need understand is: though the foregoing description is to the mentality of designing of the present invention detailed text description of contrasting; but these text descriptions; just the simple text of mentality of designing of the present invention is described; rather than to the restriction of mentality of designing of the present invention; anyly do not exceed mentality of designing of the present invention combination, increase or revise, all fall within the scope of protection of the present invention.
Claims (10)
1. a laser-markable, halogen-free flame-retardant polyamide matrix material is characterized in that including:
A) at least a polyamide resin consumption is 25～80 parts, and preferred version is to be about 45～75 parts or more than one polyamide resin consumption sums,
B) at least a or several inorganic filling materials and,
C) halogen-free flame retardants of at least a or several flame retardant propertiess and,
D) at least a or several provide the excellent laser-markable auxiliary agent of matrix material and,
F) at least a or several oxidation inhibitor.
2. laser-markable according to claim 1, halogen-free flame-retardant polyamide matrix material is characterized in that: described polyamide resin is meant nylon 6, nylon 66, perhaps the blend of nylon 6 and nylon 66.
3. laser-markable according to claim 1, halogen-free flame-retardant polyamide matrix material, it is characterized in that: the melt temperature scope of described polyamide resin is about 200～280 ℃, preferred melt temperature scope is controlled at 220～270 ℃, and polyamide resin relative viscosity scope preferably is chosen at 2.15～2.75.
4. laser-markable according to claim 1, halogen-free flame-retardant polyamide matrix material is characterized in that: described one or several inorganic filling materials and a kind of or its two kinds or three kinds of blends of being meant glass fibre, talcum powder, wollastonite.
5. laser-markable according to claim 1, halogen-free flame-retardant polyamide matrix material, it is characterized in that: the halogen-free flame retardants of described one or several flame retardant propertiess and be meant phosphorus system, nitrogen phosphorus system, inorganic filling system, perhaps carry out between them composite, preferred phosphorus flame retardant or nitrogen phosphorus flame retardant.
6. laser-markable according to claim 1, halogen-free flame-retardant polyamide matrix material is characterized in that: described halogen-free flame retardants consumption is 8～32 parts.
7. laser-markable according to claim 1, halogen-free flame-retardant polyamide matrix material, it is characterized in that: described at least a or several laser-markable auxiliary agents of matrix material that provide contain tin-antimony oxide with being meant, the proportional range that wherein said tin-antimony oxide accounts for whole laser-markable auxiliary agent is about 25～65%, and preferred range is 32～56%.
8. laser-markable according to claim 7, halogen-free flame-retardant polyamide matrix material, it is characterized in that: described laser-markable assistant packet contains one or several inorganic fillers, preferred inorganic filler can be a lime carbonate, wollastonite, mica powder, one or more combinations in the talcum powder, the characteristic of its laser-markable auxiliary agent is at 30～4.0g/m
3Density range, resistance toheat reaches more than 750 ℃ or 750 ℃.
9. laser-markable according to claim 1; the halogen-free flame-retardant polyamide matrix material; it is characterized in that: described oxidation inhibitor is four [methyl-β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (antioxidant 1010); β-(3; the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid (antioxidant 1076); N; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine (oxidation inhibitor 1098) propionyl); three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (oxidation inhibitor 168); two (2; the 4-di-t-butyl) season tetrol diphosphites (oxidation inhibitor S-9228); 3; 3'-Tyox B (anti-oxidant DLTP); 4; 4'-thiobis (the 6-tertiary butyl-3-methylphenol) or 4,4'-thiobis (6-tertiary butyl meta-cresol) (antioxidant 300) wherein one or more and composite.
10. laser-markable according to claim 9, halogen-free flame-retardant polyamide matrix material, it is characterized in that: also should add one or several dispersion agents in the described oxidation inhibitor, preferred dispersing agent is wherein one or several such as Zinic stearas, calcium stearate, pentaerythritol stearate, ethylene bis stearic amide, polyethylene wax, oxidized polyethlene wax, ethylene-acrylic acid copolymer, montanic acid wax.
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