NEW POLYAMIDES RESIN COMPOSITION FOR AUTOMOBILE EXTERIOR

Abstract: This invention relates to a new polyamide resin composition for preparing automobile exterior, in particular which is prepared by mxing crystalline polyamide with amorphous polyamide, thermoplastic elastomer and fluoropolymer, and shows excellent impact strength, thermal stability, light-weight and paintability.

Description: NEW POLY AMIDES RESIN COMPOSITION FOR AUTOMOBILE EXTERIOR BACKGROUND OF THE INVENTION This invention relates to new polyamide compositions for automobile exterior, more particularly, to polyamide compositions showing excellent impact strength, good thermal stability, light weight and good paintability, which are prepared by mixing crystalline polyamide with amorphous polyamide, thermoplastic elastomer and fluoropolymer. In recent, the automobile parts tend to switch over from metals to plastics in order to reduce the body weight, design freely, simplify manufacturing process and so forth. In particular, as polyamide resins (in general, polyamide-6 and polyamide-66) not only have superior mechanical properties such as strength, modulus, toughness and abrasion resistance, but also show good thermal stability, oil resistance, chemical resistance and excellent moldability, polyamide resins are applied to automotive parts such as radiator tank, engine cover, heater tank, gear shift housing, canister, radiator fan and the like. And the trend accelerated more, besides the interior or engine functional parts aforementioned, plastics tend to be applied to automotive large exterior parts such as fender, door panel, spoiler, wheel cover, bumper and the like. However, these large exterior parts require to have the following properties : the impact strength resistable the change of outside circumstances factors (temperature, humidity, outside impact or collision and etc.) ; the thermal stability resistable painting process of high temperature and/or heal occurred by high speed driving ; the moldability able to flow and mold till mold of 2mm thickness cavity ; the good dimensional & mechanical stability by low moisture absorption in wet condition (low dimensional, mechanical properties's fluctuation) ; and so forth. Us Patent No. 4988764, Japan Patent Publication No. 60-49018, -86161, - 86162, -179455, -262853 and -210660 disclose polymer compositions consisting of polyamides and polyolefins. The above patents have been claimed good dimensional stability by control of moisture absorption, but those have worse thermal stability. British Patent No. 387903 & No. 327978 and German Patent No. 3827668 5 disclose crystalline polyamide and polylefin compositions reinforced by inorganic filler, which have relatively better thermal stability, modulus and dimensional stability. However, those patents have insufficient impact strength, surface gloss and moldability, and relatively heavy weight by increased density. US Patent No. 4923924, British Patent No. 295103 and German Patent No. ι o 3834912 disclose the modified polyphenylene oxide or the modofied polyphenylene ether compositions having relatively good impact strength, paintability and thermal stability, but they have very poor flowability, light stability and worse chemical resistance. Therefore, they have limits to apply to exterior materials of automotive. US Patent No. 2696482 discloses amorphous polyaamides prepared by 15 condensation of bis(4-aminocyclohexyl)-methane with isophthalic acid, and US Patent No. 3597400 discloses amorphous polyamides consisting of bis(4-aminocyclohexyl methane, hexamethylene diamine, isophthalic acid and terephthalic acid. However, due to very high melt viscosity, those amorphous polyamides have very poor flowability and moldability. 20 Also, polymer blends (alloy) prepared by mixing and extruding the above amorphous polyamide with thermoplastic elastomer have relatively poor flowability and moldability. Therefore, the inventors of this invention put an effort to solve these problems of the old technology, and as a result of thai, finished the preferred compositions of this 25 invention which show wonderful impact strenth, thermal stability, flowability, surface gloss, paintability, light stability, chemical resistance, light weight, and so forth, which are prepared by mixing crystalline polyamide with amorphous polyamide, thermoplastic elastomer, fluoropolymer. SUMMARY OF THE INVENTION An objective of this invention is to provide polyamide compositions for automotive exterior materials, showing wonderful impact strenth, thermal stability, flowability, surface gloss, paintability, light stability, chemical resistance, light weight, and so forth. The preferred compositions of this invention are polyamide compositions for automotive exterior materials comprising, in percent by weight(wt%) ; (a) 30 to 90 wt% crystalline polyamide ; (b) 3 to 50 wt% amorphous polyamide ; (c) 5 to 30 wt% thermoplastic elastomer ; and (d) 0.1 to 10 wt% fluoropolymer, based on a total of 100wt% for components (a) through (d). DETAILED DESCRIPTION OF THE INVENTION The polyamide compositions of this invention comprise, in percent by weight : (a) 30 to 90wt% crystalline polyamide ; (b) 3 to 50wt% amorphous polyamide ; (c) 5 to 30wt% thermoplastic elastomer ; and (d) 0.1 to 10wt% fluoropolymer, based on a total of 100wt% for components (a) through (d ), which are used for automotive exterior materials, showing excellent impact strength, thermal stability, flowability, surface gloss, paintability, light stability, chemical resistance, light weight, and so forth. The crystalline polyamides suitable for use in the compositions of this invention are those polymers commonly known by the generic term, nylon, characterized by the presence of recurring amide groups as an integral part of the polymer chain. Included are the various polyamide hom polymers, copolymers, and the like as well as blends thereof, containing more than 80wt% by weight hexamethylene diamine and adipic acid of total crystalline polyamide components, prepared by condensation of one or more components selected from C -C π aliphatic diamine & aliphatic dicarbonic acid mixture, C fι -C^ lactam or amino acid. The crystalline polyamides are used in the range of 30 lo 90wt%, for increasing moldability, flowability and thermal stability. In case of less than 30wt% cystalline polyamide, poor moldability due to low melt viscosity and in case of more than 90wt%, the impact strength and the dimensional stability are reduced. Typically used is polyamide-66 (nylon-66) derived by condensation of hexamethylene diamine with adipic acid, but to improve more flexibility, toughness, and moldability, it is possible to use polyamide copolymers by condensation of hexamethylene diamine & adipic acid with less than 20wl% ε -caprolactam, or polyamide blends of polyamide-66 with less than 20wt% polyamide-6 ; to use polyamide copolymers by condensation of more lhan 80wt% hexamethylene diamine & adipic acid mixture with less than 20wt% of another components : for example, C 6 -C 15 aliphatic diamines such as octameihylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, or dodecamethylene diamine and C 6 -C I5 aliphatic dicarbonic acid such as azelaic acid, sberic acid, sebacic acid, dodecanoic acid, or C f ,-C,, lactam (or amino acid) such as <o -laurolactam, 11- aminoundecanic acid, 12-aminododecanic acid. The above crystalline polyamide may be typically listed as follows : polyamide-66 (or nylon-66) prepared by condensation of hexamethylene diamine and adipic acid in equimolar ratio ; polyamide-66 copolymers such as polyamide-66/6, polyamide-66/610, polyamide-66/612, polyamide-66/1 1 , polyamide-66/12, polyamide- 66/6/610, polyamide-66/6/612 and the like ; polyamide mixtures such as polyamide-66/ polyamide-11, polyamide-66/polyamide-12, polyamide-66/polyamide-69, polyamide- 66/polyamide-66/6, polyamide-66/polyamide-66/612 and the like, and then the crystalline polyamide must comprise more than 80wt% hexamethylene diamine & adipic acid, or more than 80wt% polyhexamethylene adipamide (polyamide-66, nylon- 66) polymerized from hexamethylene diamine & adipic acid. If it is less than 80wt%, the thermal stability and the mechanical properties are reduced. Used in this invention are amorphous polyamides for improving the thermal stability, the impact strength, the low moisture absorption and dimensional stability and the like, which are polymerized from the alicyclic diamines of the following structural formula(I), isophthalic acid, terephthalic acid, and C f ,-C,*- aliphatic diamines & dicarbonic acids, C f ,-C 15 lactams or amino acids, and included is more than 5mole% of one or more components selected from the alicyclic diamines of formula(I), isophthalic acid, terephthalic acid, in the amorphous polyamide of this invention. wherein, R, = R j or R, ≠ R 2 ; R, and R 2 can be hydrogen or C,- C 3 alkyl group. Recommended in this invention is to use the amorphous polyamides in the range of 3 - 50wt%, base on a total of 100wt% for all components. As amorphous polyamides have high melt viscosity and high material cost, when the amorphous polyamides are more than 50wt%, the flowability and moldability of the composition is reduced rapidly and the material cost is increased. Also, when the amorphous polyamide is less than 3wt%, the adding effect could not be expected. The alicyclic diamines of the above formula(l) are illustrated as follows : Bis(4-Aminocyclohexyl)methane, Bis(4-Amino-2-methylcyclohexyl)methane, Bis(4-Amino-3-methylcyclohexyl)methane, Bis(4-Amino-2-ethylcyclohexyl)methane, Bis(4-Amino-3-ethylcyclohexyl)methane, Bis(4-Amino-2-propylcyclohexyl)methane, Bis(4-Amino-3-propylcyclohexyl)methane, Bis(4-Amino-2-isopropylcyclohexyl)methane, Bis(4-Amino-3-isopropylcyclohexyl)methane, Bis(4-Aminocyclohexyl)propane, Bis(4-Amino-2-methylcyclohexyl)propane, Bis(4-Amino-3-methylcyclohexyl)ρropane, Bis(4-Amino-2-ethylcyclohexyl)propane, Bis(4-Amino-3-ethylcyclohexyl)propane, Bis(4-Amino-2-propylcyclohexyl)propane, Bis(4-Amino-3-propylcyclohexyl)propane, Bis(4-Amino-2-isopropylcyclohexyl)propanc, Bis(4-Amino-3-isopropylcyclohexyl)propane. Usually, the alicyclic diamines are obtained as the mixture of geometric isomers such as trans-trans, cis-trans, cis-cis, which are formed between amino group and carbon atom in 1,4-position of cyclohexane ring produced by the addition of hydrogen to the aromatic ring. Usually, the more the amount of trans-trans structure in the alicyclic diamines, the higher the glass transition temperature(Tg) and the thermal stability of the amorphous polyamide, but the more the amount of cic-cis stiucture, the lower is the glass transition te perature(Tg) and the thermal stability. Therefore, the ratio of isomers may be controlled preferably, depending on requirements of usage. The above alicyclic diamines may be applied dependently or indepentdently in this invention. For example, il can be used as mixed mixture with one or more monomer(s) sselected from C ή -C ls aliphatic diamine monomers such as hexamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and also, to control the glass transition temperature, flowability, transparency, chemical resistance and the like, may be used as mixed with small quantity of another alicyclic or aromatic diamine monomers such as 3-aminomethyl-3,3,5-trimethylcyclohexyl amine, 2,5-bis(aminomethyl)novonane, isophorone diamine, 1 ,4-diaminomethylcyclohexane, m-xylene diamine, p-xylene diamine and the like. The dicarbonic acid monomers which can be applied in equimolar ratio with the diamine monomers, are listed as the followings : the C 6 -C 15 aliphatic dicarbonic acids such as adipic acid, azelaic acid, sberic acid, sebacic acid, decanoic acid, undecanoic acid, 2,2,4-trimethyladipic acid, 2,4,4,- trimethyladipic acid, and the like ; aromatic dicarbonic acids such as isophthalic acid, terephthalic acid, etc. And it may be possible to use together with the small quantity of another alicyclic dicarbonic acids such as 1,3-cyclohexanedicarboxylic acid, 1,4- cyclohexanedicarboxylic acid, and the like, to control the glass transition temperature, flowability, transparency or chemical resistance. And also, it is possible to use together with another components such as C 6 -C 1S lactams or amino acids : £ -caprolactam, <-<■ -laurolactam, 6-aminocapronic acid, 11- aminoundecanic acid, 12-amonododecanic acid, and the like. According to this invention, included is more than 5mole% of one or more components selected rom the alicyclic diamines of the foιτnula(I), isophthalic acid, terephthalic acid, base on the amorphous polyamide component. When it is less than 5mole%, the thermal stability of the amorphous polyamide is not effective. The thermoplastic elastomer is used in this invention to increase the impact strength against physical collision or flying gravel at low temperature (-30 - -40T. ) and includes ethylene thermoplastic elastomer grafted with a β -unsaturated acid unhydride or its derivative(s) : the compounds obtained by the addition polymerization of ehtylene with one or more monomers selected from the group consisting of C 3 -C 3 of olefins, acrylic acids or their derivatives, vinyl monomers and less than 10 mole% of diene monomers. Recommended is to use the thermoplastic elastomers in the range of 5 ~- 30wt%. When the amount of the thermoplastic elastomer is less than 5wt%, the increasing effect of the impact resistance at low temperature is very low, and when it is more than 3()wt%, the thermal stability is reduced suprisingly and the moldability is 5 also reduce, because of the reduced flowability. The above C 3 -C 8 olefins may include propylene, butylene, butadiene, 1-pentene, isobutylene, 4-m ethyl- 1-pentene, isoprene, 1-hexene, 1 ,3-hexadiene, 1 ,4-hexadiene or 1-heptene, and the acrylic acids & their derivatives may include methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, methyl ι o methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, hydro xyethyl metha- crylate, aminoethyl methacrylate, glycidyl methacrylate, acrylic acid, methacrylic acid and metal salts of acrylate and metacrylate. And, the above vinyl monomers may include stylene, -*>■ -methylstylene, acrylonitrile, vinyl chloride, etc., and the above diene monomers may include 1,3- 15 cyclohexadiene, 1,4-cyclohexadiene, butadiene, cyclopentadiene, 1 ,3-pentadiene, 2,4- hexadiene, 2,5-novonadiene, 2-ethyl-2,5-novonadiene, 2-(l'-propenyl)-2-novonene, etc. As described, the well-known thermoplastic elastomer may be illustrated generally as the followings : for example, ethylene-propylene copolymer, ethylene- propylene-diene copolymer, styrene-ethylene-butylene-styrene copolymer, ethylene- 0 ethylacrylate copolymer, etc. ; in particular copolymer elastomers, from ethylene, propylene and diene monomer, grafted with « β -unsaturated acid anhydride. The above <* β -unsaturated acid anhydride, a β -unsaturated acid or their derivatives may be illustrated typically as maleic anhydride, itaconic anhydride, citraconic anhydride, acrylic acid, methacrylic acid, maleic acid, methylmaleic acid, 25 fumalic acid, methylfumalic acid, ethylfumalic acid, dimethyl malate, diethyl malate, etc. In this invention the fluoropolymer is used for improving the surface gloss and the paintability. The fluoropolymers are obtained by addition polymerization with the following fluoro compounds and oletins : 40 ~ 100 wt% of fluoro compounds which come from the following formula(II) ; 0 - 60 wl% of C 2 -C,, olelins of one or more selected from the group consisting of ethylene, propylene, hutylene, butadiene, 1 - pentene, isobutylene, 4-methyl-l -pentene, isoprene, 1 -hexene, 1 ,3-hexadiene, 1,4- hexadiene and 1-heptene. In this invention, recommended is to used the fluoropolymers in the range of 0.1 ~ 10 wt%. If the fluoropolymer is less than 0.1 wt%, it is hard to expect the addition effect, and if it is more than 10 wt%, the material cost is increased and the flowability & moldability are reduced. wherein, R,, R 2 and R 3 are H or F ; R 4 is F, Cl, CF 3 or CF 2 CF 3 ; and at least, one should be a fluoro group among the R, , R 2 , R 3 and R 4 . The said fluoropolymer may be illustrated typically as the followings : polytetrafluoroethylene(PTFE) ; the copolymer(FEP) from tetrafluoroethylene(TFE) and hexafluoropropylene(HFP) ; polychloiOtrifluoroethylene(PCTFE) ; polyvinylidenefluoride(PVDF) ; the copolymer(ETFE) from tetratluoroethylene(TFE) and ethylene ; the copolymer(ECTFE) from chlorotrifluoroelhylene(CTFE) and ethylene ; the copolymer(VDF/HFP) from vinylidene fluoroide(VDF) and hexafluoropropylene(HFP) ; the copolymer(VDF/PFP) from VDF and pentafluoropropylene(PFP) ; the copolymer(VDF/HFP/PFP) from VDF, HFP and PFP ; the copolymer(VDF/HFP/TFE) from VDF, HFP and TFE ; the copolymer(NDF/PFP/ TFE) from VDF, PFP and TFE ; the copolymer(VDF/CTFE) from VDF and CTFE ; and the copolymer from TFE and propylene and the like. The polyamide compositions of this invention can comprise another plastic- additives : aromatic amine stabilizer, nickel stabilizer, hindered phenol stabilizer, phosphorous stabilizer and sulfur stabilizer as processing stabilizer, thermal stabilizer, light stabilizer and ageing stabilizer, and plastic additives such as pigment, dye, nucleating agent, inorganic filler, surfactant, dispersing agent, lubricant, mold releasing agent, plasticizer, polishing agent, etc.. The polyamide compositions prepared by this invention have excellent impact strength, thermal stability, moldability, surface gloss, paintability and light weight(reducing the body weight). Therefore, this composition is very useful in a wide variety of exterior plastic material for automobiles. This invention is illustrated in detail as the following examples. Also, the inventors of this invention want to indicate that this invention is nol restricted only to those Examples. The crystalline polyamide, the amorphous polyamide and the thermoplastic elastomer used on the following Examples and comparisons are as the followings : A. Crystalline Polyamide (a-1) Crystalline polyamide I (C-PAI) ; This polymer consists of hexamethylene diamine and adipic acid in equimolar ratio, and its relative viscosity is 2.6 in 95% sulfuric acid at 25 . and melting point is 26 1 . (a-2) Crystalline polyamide II (C-PAI1) ; This polymer consists of 90 wt% of mixture of hexamethylene diamine and adipic acid in equimolar ratio and 10 wt% of £ -caprolactam, and its relative viscosity is 2.7 in 957« sulfuric acid at 2513 and melting point is 240T. . B. Amorphous Polyamide (b-1) Amorphous polyamide I (A-PAI) ; This polymer consists of 40 mole% bis(4-aminocyclohexyl)propane, 15 mole% isophthalic acid, 5 mole% terephthalic acid, and 30 mole% azelaic acid. The melt viscosity(28() _ , 5000 sec "1 ) is 5600 poise and the glass transition temperature(Tg) is 180T. . (b-2) Amorphous polyamide II (A-PAI1) ; This polymer consists of 40 mole% bis(4-amino-3-methyl-cyclohexyl)-methane, 40 mole% adipic acid and 20 mole% of «■ -laurolactam. The melt viscosity (2801 , 5000 sec "1 ) is 7500 poise and the glass transition temperature is 1461. . (b-3) Amorphous polyamide III (A-PAIII) ; This polymer consists of 35 mole% of the mixture of 2,2,4- and 2,4,4- trimethylhexa-methylenediamine(equimolar ratio), 15 mole% hexamethylene diamine and 50 mole% terephthalic acid. The melt viscosity (280 T. , 5000 sec "1 ) is 6000 poise and the glass transition temperature is 155 . . C. Thermoplastic Elastomer (c-1) Thermoplastic elastomer (TPE I) ; This is ethyl ene-propylene copolymer grafted with 1.0 wt7 maleic acid anhydride, and its trade name is Exeller 1801, 1803 (Product of Exxon Chemical Co., Belgium). (c-2) Thermoplastic elastomer (TPE II) ; This is a block copolymer, consisting of 72 wt% ethylene/1-butene copolymer and 28 wt% polystyrene, grafted with 2 wt% anhydride. The trade name is Kraton FG-1901 X (Product of Shell Chemical Co., U.S.A.). EXAMPLE 1 - 9 According to mixing ratios of the following Table 1, crystalline polyamide, amorphous polyamide, thermoplastic elastomer and fluoropolymer were dry-mixed in HENSELL mixer, and the mixture was melt-blended in twin-screw extrudert screw diameter 30mm, L/D=30) to obtain resin pellets. Then, ' the melting temperature was 270 ~ 300 . , the rotating rate of screw was 250 RPM, and the extrusion rate of the compositions was 25kg/hr. The resulting pellets were dried in nitrogen sealing oven for 6 hours at 120T. so that the water content was less than 0.1%, and test specimens were made by injection molding method. The various properties of test specimens were measured and listed in Table 2. COMPARISON 10 - 17 The procedures of Example 1 were repealed according to mixing ratios of the following Table 1. The proportion of comparison 16 and 17 were respectively changed to talc and kaoline in return for the amorphous polyamide to compare their characteristics with polyamide composition reinforced by an inorganic filler. COMPARISON 18 Trade name NORYL GTX 901 made by General Electric Co. in U.S.A. was dried for 6 hours in nitrogen sealing oven at 120"C so that the water content was less than 0.03%, and test specimens were made by injection molding method. The resulted test specimen was measured for various properties shown in Table 2. Table 1. Note (1) ETFE is a copolymer of ethylene and tetralluoroethylene(TFE), and its trade name is HALON ET 101 of AUSIMONT CO. in U.S.A. (2) FEP is a copolymer of TFE and hexafluoropropylene(HFP) prepared by Mitsui FLUOROCHEMICAL CO. in Japan. Table 2. Note (1) Impact strength : Izod Notched impact strength was measured by ASTM D256. (2) Heat distorsion temp. : This was measured by ASTM D648. (3) Vicat softening temp. : This was measured by ASTM D1525. 5 (4) Melt index(MI) : This was measured by ASTM 1238 (5) Surface gloss : This was examined with the naked eye. (6) Paintability : (D Heat cyclic resistance ; One cycle consists of 80 Tj x 3hrs — -- room temp, x 1 hr → -30T. x 3hrs -→ t o room temp, x l hr → 50t. , 98% RH x 15hrs → room temp, x lhr. After test 5 cycles, no coat defect(colorless, gloss reduction, crack, swelling, releasing, elusion, hardness change, adhesivity) must be found. (|) Alkaline resistance ; The prepared test piece was dropped 0.2ml of (UN sodium hydroxide, and 15 left for 24hrs at 20 ±2t , 0.5 ± 5% humidity. After washing the test piece with water and blowing the air, it was left for lhr. After the above process, no coat defect must be found by appearance examination. (3) Wax remover resistance ; The test piece (about -f-size) was investigated under the following 0 conditions and observed the appearance change, and then no coat defect must be found. - Temperature : 40± 2"C Time : 30 minutes Method : Soaking 5 © Painting scalle resistance ; A urethane piece(25g, 1cm size) using sheet material was put in 3 / bottle having wide entrance with a cap, and test piece (40 x 50 mm) was put into the bottle so as not to contact with the urethane piece and to be able to see the painting surface. After standing for 22 his at 80T. in closed bottle, their painting surfaces were examined, and scraped with wet material to about 500g of power for 10 times to examine the coating surfaces. (7) Light stability (weather stability) : A test piece was exposed in carbon arc chamber(63 ± 3T. ) for 48min by using acceleration weather resistance tester of ATLAS in U.S.A. After standing for 1200 hrs under the cyclic condition of dispersed water for 12min, colorless, crack and denaturation of the coating surface were observed. (8) Chemical resistance : A test piece was soaked in gasoline in the presence of 20% calcium chloride (CaCl 2 ) at 40T. for 10 days to observe colorless, crack, denaturation and size change. (9) Specific gravity : This was measured by ASTM D792. (10) Tensile strength : This was measured by ASTM D638. (11) Water content : After soaking for 24 hrs in water at 251. , the water content was measured by ASTM D570. (12) Θ : Excellent O : Common (or Fair) x : Poor (or Worse)

Claims: WHAT IS CLAIMED IS 1. The polyamide compositions for exterior material of automobiles comprising, in percent by weight (wt%) ; (a) 30 - 90 wt% of crystalline polyamide, (b) 3 - 50 wt% of amorphous polyamide, (c) 5 - 30 wt% of thermoplastic elastomer and (d) 0.1 ~ 10 wt%- of fluoropolymer, based on a total of l(M)wt% for components (a) through (d). 2. The polyamide compositions defined as the claim 1, wherein the above crystalline polyamide is a polyamide copolymer prepared by condensation of one or more components selected from C ή ~ C 15 aliphatic diamines and C ή ~ C 15 aliphatic dicarboxylic acids and/or ~ C 15 lactam or amino acid, or a mixture of polyamides, and is including more than 80 wt% of hexamethylene diamine and adipic acid. 3. The polyamide compositions defined as the claim 1 to 2, wherein the said amorphous polyamide is obtained by condensation from C 6 - C 15 of aliphatic diamine, alicyclic diamine of the following formula(I), C ή ~ C 15 of aliphatic dicarboxylic acid, isophthalic acid, terephthalic acid and C fi ~ C, 5 of lactam and amino acid, and is included more than 5 mole% the formula(I), isophthalic acid or terephthalic acid. wherein, R, and R 2 are hydrogen or C, - C, alkyl group. 4. The polyamide resin composition defined as the claim 1 to 3, wherein said thermoplastic elastomer is obtained by an addition polymerization of ethylene and one or more selected from the group consisting of ~ C x of olefins or acrylic acids or their derivatives, vinyl monomers and diene monomers corresponding to less than 10 mole%>. 5. The polyamide compositions defined as the claim 1 to 4, wherein the said fluoropolymer is obtained by an addition polymerization from 40 ~ KM) wt% of fluoro compounds of which one or more is selected from the group of the compound of the following structural formula(II), and 60 ~ 0 wt% of olefin compounds of which one or more is selected from the group of C 2 - C g olefins. R, R 2 = - " > R 3 R 4 wherein, R,, R 2 and R 3 are H or F ; R 4 is F, Cl, CF^ or CF 2 CF, ; and at least, one should be a fluoro group among the R,, R 2 , R, and R 4 . 6. The polyamide compositions defined as the claim 5, wherein the said olefin compounds are selected from the group consisting of ethylene, propylene, butylene, butadiene, 1-pentene, isobutylene, 4-methyl-l-pentene, isoprene, 1- hexene, 1,3-hexadiene, 1,4-hexadiene and 1-heptene.

Inventors: JEONG DONG WON, LEE KYUNG YOON, PARK BONG HYUN, SOHN KWANG HO, JEONG, DONG, WON, LEE, KYUNG, YOON, PARK, BONG, HYUN, SOHN, KWANG, HO
Applicants: HYUNDAI MOTOR CO LTD, JEONG DONG WON, LEE KYUNG YOON, PARK BONG HYUN, SOHN KWANG HO, TONG YANG NYLON CO LTD, HYUNDAI MOTOR CO., LTD., JEONG, DONG, WON, LEE, KYUNG, YOON, PARK, BONG, HYUN, SOHN, KWANG, HO, TONGYANG NYLON CO., LTD.
Application year: 1993
Main classification: C08L77
IPC codes: C08L23, C08L27, C08L51, C08L77