CN103073877A - Low water absorption polyamide composition and products thereof - Google Patents
Low water absorption polyamide composition and products thereof Download PDFInfo
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- CN103073877A CN103073877A CN2012103453305A CN201210345330A CN103073877A CN 103073877 A CN103073877 A CN 103073877A CN 2012103453305 A CN2012103453305 A CN 2012103453305A CN 201210345330 A CN201210345330 A CN 201210345330A CN 103073877 A CN103073877 A CN 103073877A
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Abstract
The present invention discloses a low water absorption polyamide composition and products thereof. Main components of the low water absorption polyamide composition comprise: (a) polyamide, wherein an intrinsic viscosity of the polyamide is 2.0-3.2 dl/g; (b) a fire retardation agent, wherein the fire retardation agent comprises a phosphorus fire retardation agent and a nitrogen fire retardation agent; (c) a fire retardation synergist; (d) glass fibers; (e) an optional cross-linking agent; and (f) optionally other substances. The products are prepared by using the low water absorption polyamide composition. The low water absorption polyamide composition is used in electrical and electronic fields. The low water absorption polyamide composition has characteristics of good fire retardation, good mechanical property, and low water absorption, and is a halogen-free, red phosphorus-free and environmental-friendly material.
Description
Technical field
The present invention relates to the Polymer Synthesizing field, particularly a kind of low water absorption polyamide composite and goods thereof.
Background technology
Polyamide (PA) is commonly called as nylon, make by the lactan ring-opening polymerization or by dicarboxylic acid monomer and diamine monomer polymerization, it has good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, be easy to processing, be widely used as metal, the traditional material surrogates such as timber, be widely used in especially field of electronics, along with the development of field of electronics, to the low water absorbable of electric element higher requirement can be arranged, because the water-absorbent of polymeric amide has hindered its development and application.In recent years, constantly have new modification technology to attempt to solve this technical problem, traditional method is to add fiber or other inorganics in polymeric amide, to reduce its water-intake rate.
Summary of the invention
In sum, the present invention is necessary to provide a kind of low water absorption polyamide composite, and its flame retardant properties is good, and water-absorbent is low.
In addition, also be necessary to provide a kind of goods of above-mentioned low water absorption polyamide composite.
In addition, also be necessary to provide a kind of application of above-mentioned low water absorption polyamide composite.
A kind of low water absorption polyamide composite, its main component comprises:
(a) polymeric amide, the limiting viscosity of described polymeric amide are 2.0dL/g ~ 3.2dL/g;
(b) fire retardant, described fire retardant comprises phosphorus flame retardant and nitrogenated flame retardant;
(c) fire retarding synergist;
(d) glass fibre;
(e) optional linking agent;
(f) other optional material.
A kind of low water absorption polyamide composite, its main component is for comprising by weight:
(a) polymeric amide 25 ~ 70 weight parts, the limiting viscosity of described polymeric amide is 2.0dL/g ~ 3.2dL/g;
(b) fire retardant 5 ~ 25 weight parts, described fire retardant comprises phosphorus flame retardant and nitrogenated flame retardant;
(c) fire retarding synergist 0.5 ~ 10 weight part;
(d) glass fibre 10 ~ 45 weight parts;
(e) optional linking agent 0 ~ 5 weight part;
(f) other optional material 0.5 ~ 1 weight part.
A kind of low water absorption polyamide composite is made of by weight following composition:
(a) polymeric amide 25 ~ 70 weight parts, the limiting viscosity of described polymeric amide is 2.0dL/g ~ 3.2dL/g;
(b) fire retardant 5 ~ 25 weight parts, described fire retardant comprises phosphorus flame retardant and nitrogenated flame retardant;
(c) fire retarding synergist 0.5 ~ 10 weight part;
(d) glass fibre 10 ~ 45 weight parts;
(e) optional linking agent 0 ~ 5 weight part;
(f) other optional material 0.5 ~ 1 weight part.
The component that a kind of low water absorption polyamide composite comprises comprises (a) polymeric amide 25 ~ 70 weight parts by weight, (b) fire retardant 5 ~ 25 weight parts, (c) fire retarding synergist 0.5 ~ 10 weight part; (d) glass fibre 10 ~ 45 weight parts; (e) optional linking agent 0 ~ 5 weight part; (f) other optional material 0.5 ~ 1 weight part.
Further, the component that above-mentioned low water absorption polyamide composite comprises comprises by weight: (a) kymene 0 ~ 65 weight part, (b) fire retardant 6 ~ 20 weight parts, (c) fire retarding synergist 1 ~ 8 weight part; (d) glass fibre 10 ~ 45 weight parts; (e) optional linking agent 1 ~ 4 weight part; (f) other optional material 0.5 ~ 1 weight part.
Further, the component that low water absorption polyamide composite comprises can comprise by weight: (a) polymeric amide 45-60 weight part, (b) fire retardant 12-18 weight part, (c) fire retarding synergist 3-7 weight part; (d) glass fibre 15-40 weight part; (e) optional linking agent 2-4 weight part; (f) optional other material 0.5-1 weight part.
Wherein, the limiting viscosity of described polymeric amide is preferably 2.2dL/g ~ 2.8dL/g.
Wherein, the degree of crystallinity of described polymeric amide is 35% ~ 50%.
Wherein, described (d) glass fibre is through pretreated glass fibre, described preprocessing process is with the terpolymer EP rubber (MEPDM) of the maleic anhydride graft of molten state or/and the ethylene-octene copolymer of maleic anhydride graft (MPOE) carries out the surface infiltration processing to glass fibre, carries out drying after the infiltration.
Wherein, described phosphorus flame retardant is selected from the dialkylphosphinic salts with following general formula:
Wherein, described nitrogenated flame retardant comprises melamine polyphosphate and/or melamine cyanurate.
Wherein, described fire retarding synergist is one or more composition of antimonous oxide, talcum powder, zinc borate, borax, hydrotalcite etc.
Wherein, described (e) linking agent is selected from least a in Resins, epoxy, styrene maleic anhydride copolymer and the ethene-maleic anhydride copolymer.
Wherein, other optional material of described (f) comprises tertiary amine and/or quaternary amine material, and described tertiary amine material can be diethylenetriamine, and described quaternary amine material can be triethylene tetramine.
Wherein, described (f) optional other material also further comprises at least a in antioxidant, the lubricant.
Wherein, described oxidation inhibitor can be selected from Hinered phenols antioxidant, phosphite ester kind antioxidant or the composition of the two, such as Hinered phenols antioxidant Ingranox1098, and phosphite ester kind antioxidant P-EPQ.Described oxidation inhibitor also can be selected from N, N'-pair-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (oxidation inhibitor 1098), four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), three ［ 2, the 4-di-tert-butyl-phenyl ］ phosphorous acid ester (irgasfos 168), Triethylene glycol two [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] (oxidation inhibitor 245), 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide (antioxidant 3114), 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxybenzene methyl) benzene (oxidation inhibitor 1330), 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone (oxidation inhibitor 1790), 1,3, the combination of one or more in 5-three (3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide (antioxidant 3114) and the mantoquita composite antioxidant; Preferred oxidation inhibitor 1098, antioxidant 1010, one or more combinations of mantoquita composite antioxidant; And most preferably be the two the combination of oxidation inhibitor 1098 and mantoquita composite antioxidant.Described mantoquita composite antioxidant can be selected the mixture of 50-90% potassiumiodide and 10-40wt% cuprous iodide, or the mixture of 50-90% Potassium Bromide and 10-40wt% cuprous iodide.
The combination of one or more in the optional autoxidation polyethylene wax of described lubricant, ethylene vinyl acetate, ethylene acrylic acid co polymer, montanin wax, Poly Propylene Wax, the pentaerythritol stearate, preferential oxidation polyethylene wax, montanin wax, pentaerythritol stearate, and most preferably be pentaerythritol stearate.
Wherein, described polymeric amide is selected from polycaprolactam, poly-(11-aminoundecanoic acid), nylon 12, polyhexamethylene adipamide, poly-azelaoyl hexanediamine, polyhexamethylene sebacamide, nylon 612, poly-hexamethylene terephthalamide, nylon 46, polycaprolactam/poly-hexamethylene terephthalamide multipolymer, polyhexamethylene adipamide/poly-hexamethylene terephthalamide multipolymer, polyhexamethylene adipamide/poly-6I hexamethylene isoterephalamide multipolymer, poly-hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide multipolymer, poly-hexamethylene terephthalamide/nylon 12 multipolymer, polyhexamethylene adipamide/poly-hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide multipolymer, the poly hexamethylene adipamide Ursol D, poly-hexamethylene terephthalamide/poly-paraphenylene terephthalamide-2 methyl pentamethylenediamine multipolymer, nylon 10T/1012, poly-paraphenylene terephthalamide's nonamethylene diamine, poly-paraphenylene terephthalamide's decamethylene diamine, polymeric amide 11T, polymeric amide 12T, their multipolymer, perhaps their composition.
A kind of low water absorption polyamide composite goods, described goods use aforesaid low water absorption polyamide composite.
A kind of application of aforesaid low water absorption polyamide composite, described low water absorption polyamide composite is applied in field of electronics.
Compare prior art, low water absorption polyamide composite of the present invention, its flame retardant properties is good, is the environment-friendly material of Halogen no red phosphorus, and good mechanical property, and the low water absorption performance is good.
Embodiment
Be described further below in conjunction with the application of some embodiments to composition, preparation method and the described matrix material of PC matrix material of the present invention.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
Used material among the present invention is can be from the material of having bought on the market.
The detection method that the present invention uses has:
Degree of crystallinity
Measure the degree of crystallinity of polymkeric substance with X-ray diffractometer.The model of X-ray diffractometer is the D/Max-IIIA type.The polymkeric substance of melting is used the amorphous sample of the sudden cold preparation sample of liquid nitrogen, the X-ray diffraction peak area of amorphous sample and polymer samples is respectively S
1And S
2, pass through Xc=(S
2-S
1)/S
2* 100 calculate degree of crystallinity.
Wherein Xc represents degree of crystallinity (%), S
1The X-ray diffraction peak area of expression amorphous sample, S
2The X-ray diffraction peak area of expression sample.
Limiting viscosity [η]
In 25 ℃ 98% vitriol oil, measure concentration and be 0.05,0.1,0.3 and the logarithmic viscosity number η of the polymeric amide of 1g/dL
Inh
η
inh=[ln(t
1/t
0)]/C
Wherein, η
InhExpression logarithmic viscosity number (dL/g), t
0The blank time of expression solvent, t
1The flushing time of expression sample solution, C represents the concentration (g/dL) of sample solution.
With η
InhData Extrapolation to concentration be 0, obtain the limiting viscosity [η] of sample.
Tensile strength is measured according to ISO527-2, and test condition is 23 ℃ and 10mm/min.
Flexural strength and modulus in flexure are measured according to ISO178, and test condition is 23 ℃ and 2mm/min.
The Izod notched Izod impact strength is measured according to ISO180, and test condition is 23 ℃, and the breach type is A type breach.
Heat-drawn wire: according to ISO75-2 standard test, test condition 0.45MPa.
Shrinking percentage: according to the ISO2577 standard test.
Water-intake rate: according to the ISO62 standard testing, 23 ℃/50%R.H of test condition.
The testing method of flame retardant properties: according to UL-94 vertical combustion testing standard test, wherein V-0 level and the one-tenth-value thickness 1/10 thereof of test polymer are during its one-tenth-value thickness 1/10 is listed in the table below, one-tenth-value thickness 1/10 is larger, its flame retardant properties is poorer, is lower than the V-0 rank such as its UL grade, then represents with Fail.
Embodiment 1-6
The terpolymer EP rubber (MEPDM) of glass fibre with the maleic anhydride graft of molten state soaked, dry after stirring.With will add in the reactor by its weight part except other material of glass fibre shown in the table 1, carry out that homogenizer mixes or enter premixing machine by the metering feeding device separately.The said mixture material is sent in the twin screw extruder, regulating the feeding rotating speed is 250-350rpm, in twin screw extruder, add above-mentioned glass fibre of anticipating, the temperature of each of dual-screw-stem machine section extruder temperature from the charging opening to the head is respectively 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃, screw speed 250-350rpm, the length-to-diameter ratio of twin screw extruder is 75, under the conveying and shearing action of twin screw extruder, abundant fusion plastification, mediate mixing, extrude through head, tie rod, cooling, pelletizing, dry, obtain low water absorption polyamide composite, measure the performance of gained polymeric amide according to above-mentioned testing method, and with the results are shown in Table 1.
Embodiment 7-9
The ethylene-octene copolymer (MPOE) of glass fibre with the maleic anhydride graft of molten state soaked, dry after stirring.With will add in the reactor by its weight part except other material of glass fibre shown in the table 1, carry out that homogenizer mixes or enter premixing machine by the metering feeding device separately.The said mixture material is sent in the twin screw extruder, regulating the feeding rotating speed is 250-350rpm, in twin screw extruder, add above-mentioned glass fibre of anticipating, the temperature of each of dual-screw-stem machine section extruder temperature from the charging opening to the head is respectively 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃, screw speed 250-350rpm, the length-to-diameter ratio of twin screw extruder is 75, under the conveying and shearing action of twin screw extruder, abundant fusion plastification, mediate mixing, extrude through head, tie rod, cooling, pelletizing, dry, obtain low water absorption polyamide composite, measure the performance of gained polymeric amide according to above-mentioned testing method, and with the results are shown in Table 1.
Comparative Examples 1-9
With reference to each embodiment, the embodiment that sequence number is the same is corresponding with Comparative Examples.To add in the reactor by its weight part by the material shown in the table 2, carry out that homogenizer mixes or enter premixing machine by the metering feeding device separately, wherein embodiment 7-9 does not add fire retarding synergist.The said mixture material is sent in the twin screw extruder, regulating the feeding rotating speed is 250-350rpm, in twin screw extruder, add glass fibre, above-mentioned glass fibre be do not pass through pretreated, the temperature of each of dual-screw-stem machine section extruder temperature from the charging opening to the head is respectively 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃, screw speed 250-350rpm, the length-to-diameter ratio of twin screw extruder is 75, under the conveying and shearing action of twin screw extruder, abundant fusion plastification, mediate mixing, extrude through head, tie rod, cooling, pelletizing, dry, obtain polymeric amide, measure the performance of gained polymeric amide according to above-mentioned testing method, and with the results are shown in Table 2.
Table 1
Table 2
Compare and to find out with Comparative Examples 1-6 by embodiment 1-6, glass after treatment can significantly reduce the water-absorbent of material, simultaneously for guaranteeing good flame retardant properties, the embodiment 7-9 explanation of comparing with Comparative Examples 7-9 needs to add the fire retarding synergist that this patent declares and just can reach fire-retardant purpose in this composition.
Following embodiment is for the impact on low water absorption polyamide composite performance of the present invention of the limiting viscosity that further specifies used polymeric amide, degree of crystallinity.
Embodiment 10-15
The terpolymer EP rubber (MEPDM) of glass fibre with the maleic anhydride graft of molten state soaked and drying.With will mix or enter the well that feeds intake by the metering feeding device separately by homogenizer by its weight part except other material of glass fibre shown in the table 3, wherein the viscosity of polymeric amide and degree of crystallinity are as shown in table 3.The said mixture material is sent in the twin screw extruder, regulating the feeding rotating speed is 250-350rpm, in twin screw extruder, add above-mentioned glass fibre of anticipating, the temperature of each of dual-screw-stem machine section extruder temperature from the charging opening to the head is respectively 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃, screw speed 250-350rpm, the length-to-diameter ratio of twin screw extruder is 75, under the conveying and shearing action of twin screw extruder, abundant fusion plastification, mediate mixing, extrude through head, tie rod, cooling, pelletizing, dry, obtain low water absorption polyamide composite, measure the performance of gained polymeric amide according to above-mentioned testing method, and with the results are shown in Table 3.
Comparative Examples 10-13
The terpolymer EP rubber (MEPDM) of glass fibre with the maleic anhydride graft of molten state soaked and drying.With will mix or enter the well that feeds intake by the metering feeding device separately by homogenizer by its weight part except other material of glass fibre shown in the table 3, wherein the viscosity of polymeric amide and degree of crystallinity are as shown in table 3.The said mixture material is sent in the twin screw extruder, regulating the feeding rotating speed is 250-350rpm, in twin screw extruder, add above-mentioned glass fibre of anticipating, the temperature of each of dual-screw-stem machine section extruder temperature from the charging opening to the head is respectively 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃, screw speed 250-350rpm, the length-to-diameter ratio of twin screw extruder is 75, under the conveying and shearing action of twin screw extruder, abundant fusion plastification, mediate mixing, extrude through head, tie rod, cooling, pelletizing, dry, obtain low water absorption polyamide composite, measure the performance of gained polymeric amide according to above-mentioned testing method, and with the results are shown in Table 3.
Table 3
Compare with Comparative Examples 10,11 from embodiment 10-12, the viscosity of polymeric amide is lower than 2.0dL/g or is higher than 3.2dL/g, further be lower than 2.2dL/g or be higher than 2.8dL/g, its flame retardant properties meeting is on the low side and its water-intake rate also raises, embodiment 15-17 compares with Comparative Examples 12,13, when the degree of crystallinity of polymeric amide is lower than 35% or when being higher than 50%, its flame retardant properties can be on the low side and its water-intake rate also raise.The viscosity of polyamide resin and degree of crystallinity all affect the final water-intake rate of material and flame retardant properties.
Following Comparative Examples further specifies linking agent to the impact of described low water absorption polyamide composite performance
Comparative Examples 14-22
The terpolymer EP rubber (MEPDM) of glass fibre with the maleic anhydride graft of molten state soaked and drying.With will mix or enter the well that feeds intake by the metering feeding device separately by homogenizer by its weight part except other material of glass fibre shown in the table 4.The said mixture material is sent in the twin screw extruder, regulating the feeding rotating speed is 250-350rpm, in twin screw extruder, add alkali-free glass fiber, the temperature of each of dual-screw-stem machine section extruder temperature from the charging opening to the head is respectively 220 ℃, 230 ℃, 240 ℃, 250 ℃, 240 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃, screw speed 250-350rpm, the length-to-diameter ratio of twin screw extruder is 75, under the conveying and shearing action of twin screw extruder, abundant fusion plastification, mediate mixing, extrude through head, tie rod, cooling, pelletizing, dry, obtain low water absorption polyamide composite, measure the performance of gained polymeric amide according to above-mentioned testing method, and with the results are shown in Table 4.
Table 4
After Comparative Examples 14-22 and the embodiment 1-9 contrast, after finding to add linking agent, its water-intake rate of the daiamid composition for preparing has obvious reduction.
The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (10)
1. low water absorption polyamide composite, its main component comprises:
(a) polymeric amide, the limiting viscosity of described polymeric amide are 2.0dL/g ~ 3.2dL/g;
(b) fire retardant, described fire retardant comprises phosphorus flame retardant and nitrogenated flame retardant;
(c) fire retarding synergist;
(d) glass fibre;
(e) optional linking agent;
(f) other optional material.
2. low water absorption polyamide composite as claimed in claim 1 is characterized in that:
Its main component is for comprising by weight:
(a) polymeric amide 25 ~ 70 weight parts, the limiting viscosity of described polymeric amide is 2.0dL/g ~ 3.2dL/g;
(b) fire retardant 5 ~ 25 weight parts, described fire retardant comprises phosphorus flame retardant and nitrogenated flame retardant;
(c) fire retarding synergist 0.5 ~ 10 weight part;
(d) glass fibre 10 ~ 45 weight parts;
(e) optional linking agent 0 ~ 5 weight part;
(f) other optional material 0.5 ~ 1 weight part.
3. low water absorption polyamide composite is made of by weight following composition:
(a) polymeric amide 25 ~ 70 weight parts, the limiting viscosity of described polymeric amide is 2.0dL/g ~ 3.2dL/g;
(b) fire retardant 5 ~ 25 weight parts, described fire retardant comprises phosphorus flame retardant and nitrogenated flame retardant;
(c) fire retarding synergist 0.5 ~ 10 weight part;
(d) glass fibre 10 ~ 45 weight parts;
(e) optional linking agent 0 ~ 5 weight part;
(f) other optional material 0.5 ~ 1 weight part.
4. such as claim 1,2 or 3 described low water absorption polyamide composites, it is characterized in that:
Described (d) glass fibre is through pretreated glass fibre, described preprocessing process is with the terpolymer EP rubber (MEPDM) of the maleic anhydride graft of molten state or/and the ethylene-octene copolymer of maleic anhydride graft (MPOE) carries out the surface infiltration processing to glass fibre, carries out drying after the infiltration.
5. low water absorption polyamide composite as claimed in claim 4 is characterized in that:
The degree of crystallinity of described polymeric amide is 35% ~ 50%.
6. low water absorption polyamide composite as claimed in claim 4 is characterized in that:
Described phosphorus flame retardant is selected from the dialkylphosphinic salts with following general formula:
Described nitrogenated flame retardant comprises melamine polyphosphate and/or melamine cyanurate.
7. low water absorption polyamide composite as claimed in claim 4 is characterized in that:
Described fire retarding synergist is one or more composition of antimonous oxide, talcum powder, zinc borate, borax, hydrotalcite.
8. low water absorption polyamide composite as claimed in claim 4 is characterized in that:
Other optional material of described (f) comprises tertiary amine and/or quaternary amine material, and described tertiary amine material comprises diethylenetriamine, and described quaternary amine material comprises triethylene tetramine; Other material that described (f) is optional also further comprise at least a in antioxidant, toughner, the lubricant.
9. low water absorption polyamide composite as claimed in claim 4 is characterized in that:
Described polymeric amide is selected from polycaprolactam, poly-(11-aminoundecanoic acid), nylon 12, polyhexamethylene adipamide, poly-azelaoyl hexanediamine, polyhexamethylene sebacamide, nylon 612, poly-hexamethylene terephthalamide, nylon 46, polycaprolactam/poly-hexamethylene terephthalamide multipolymer, polyhexamethylene adipamide/poly-hexamethylene terephthalamide multipolymer, polyhexamethylene adipamide/poly-6I hexamethylene isoterephalamide multipolymer, poly-hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide multipolymer, poly-hexamethylene terephthalamide/nylon 12 multipolymer, polyhexamethylene adipamide/poly-hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide multipolymer, the poly hexamethylene adipamide Ursol D, poly-hexamethylene terephthalamide/poly-paraphenylene terephthalamide-2 methyl pentamethylenediamine multipolymer, nylon 10T/1012, poly-paraphenylene terephthalamide's nonamethylene diamine, poly-paraphenylene terephthalamide's decamethylene diamine, polymeric amide 11T, polymeric amide 12T, their multipolymer or their composition.
10. low water absorption polyamide composite goods, it is characterized in that: described goods use such as each described low water absorption polyamide composite of claim 1-9 and make.
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