Thermoplastic resin composition

Abstract: The present invention provides resin compositions containing thermoplastic resins. Thermoplastic resins employable for the compositions are polyolefin resins, polyester resins, polystyrene resins, polyamide resins and polyphenylene ether resins. The present invention can be particularly effected by using polyamide, particularly, specific aromatic polyamides. In the present invention, the resin compositions can be improved in various chemical and physical properties such as flame-retardance, moldability, color tone, heat stability, mechanical strength by the use of other resin component and stabilizers such as halogenated organic compounds, modified polyolefins, antimony compounds, phosphorus-containing compounds, amine- or phosphorus-type stabilizers.

Description: FIELD OF THE INVENTION The present invention relates to thermoplastic resin compositions. More particularly, the invention relates to thermoplastic resin compositions which are remarkably improved in various chemical and physical properties such as flame-retardance, granulation properties, molding properties, color tone, heat resistance, heat aging characteristics, heat stability, abrasion resistance and strength. BACKGROUND OF THE INVENTION In recent days, resin materials have been widely employed in various fields, and for the purpose of satisfying physical and chemical properties required for the resin materials, there have been developed various resin compositions by incorporating additives, fillers, reinforcing agents, etc. to various resins. For example, in accordance with the integration of electronic components, physical and chemical properties (specifically, heat resistance and flame retardance) of extremely high level have been required for the resin materials used in this electronic art. The resin materials are utilized as printable circuit boards, semiconductor packages, etc. of electric or electronic parts. As is well known, the electric or electronic components work upon application of an electric current, and in this stage a heat is generated. As the electronic machines have been used in more various surroundings or the electric circuits have been made more integrated recently, the printable circuit boards or the semiconductor packages are used continuously and at extremely high temperatures, and hence heat resistance and flame retardance of much higher level are eagerly required for the resin materials used therefor. As an organic material having high heat resistance and high flame retardance, a flame-retardant resin composition obtained by adding a halogenated organic compound and an antimony-containing compound to a thermoplastic resin is employed. Among thermoplastic resins, polyamides are known as engineering plastics being excellent in mechanical and chemical properties, and a representative example of polyamides is nylon. In the practical use, various additives can be added to the polyamides depending on the purpose. Most of the polyamide resins have a melting point higher than that of other resins such as polyphenyl sulfide. Further, these polyamide resins have a high crystallinity, and they are excellent in other properties such as heat distortion resistance of the resin without reinforcement, sliding properties and fatigue resistance. Among the polyamide resins, aliphatic polyamides represented by nylon 6 and nylon 66 are utilized in the art of synthetic fibers. It is known that a copper-containing compound is added to the aliphatic polyamides to obtain compositions which are hardly oxidized even when exposed to high temperatures for a long period of time to be inhibited from the lowering of the mechanical properties. Further, it has been recently known that the aromatic polyamides are excellent in various properties such as abrasion resistance, strength, chemical resistance, heat resistance and molding properties. Therefore, the aromatic polyamides are utilized as engineering plastics employable as resin materials for automobile industry and for electrical industry. However, those conventional resin compositions still have various problems. For example, the above-mentioned flame-retardant resin composition comprising a thermoplastic resin, a halogenated organic compound and an antimony-containing compound often brings about strand-foaming in the granulation stage or coloring of pellets. Further, when the flame-retardant polyamide resin, that is one of the thermoplastic resins, is subjected to continuous injection molding for a long period of time, a mold of the molding machine might be little by little deposited with a decomposition product of the resin (this deposition is referred to hereinafter as "mold-staining"). If the mold-staining occurs, the transfer efficiency of the mold tends to lower or the decomposition product of the resin is easily introduced into the resulting molded product. Moreover, a gas bent is choked up with the decomposition product of the resin to cause burn marks of the resin. For these reasons, the mold is generally cleaned at regular intervals to remove stains from the mold. For cleaning the mold, the molding operation is compelled to be stopped, and as a result, the production of the molded products is stopped. From the viewpoint of productivity, therefore, eagerly desired are flame-retardant polyamide resins which hardly bring about mold-staining. In the art of electronic parts, there has been recently employed a method comprising fitting electronic components having a part formed from the polyamide resin (such as hausing thereof) onto a printable wiring board and then firmly fixing the electronic components to the board utilizing infrared rays reflow-soldering. However, the conventional polyamide resin compositions are unsuitable for this method, because they are insufficient in the heat resistance and the flame retardance. The infrared rays reflow-soldering is a method for fixing electronic components onto the circuit board. The method comprises temporarily fixing the electronic components onto the predetermined portions of a circuit board which has been beforehand provided with solder dots on the portions, and melting the solder under irradiation of the board with infrared rays to firmly fix the electronic components onto the circuit. In the conventional method for fixing the electronic components onto the circuit board using a solder bath, it is difficult to fit the electronic components on the board with a high denseness, so that the above-mentioned infrared rays reflow-soldering has been employed instead of the conventional method, to improve the denseness. However, a problem still resides in the infrared rays reflow-soldering. That is, infrared rays are applied from the upper side of the board in this method, and the electronic part-forming materials using conventional polyamide resin compositions have a low melting point as well as ABS resin, polycarbonate and polybutylene terephthalate, so that the temperature for the infrared rays reflow-soldering cannot be sufficiently raised. Japanese Patent Provisional Publication No. 36(1961)-317552 discloses nylon 46 containing a brominated crosslinking aromatic polymer as the flame-retardant resin composition formed by using brominated compounds of polyvinyl aromatic compounds (e.g., divinylbenzene and divinylxylene) or brominated compounds of crosslinking aromatic polymers synthesized by forming a crosslinking structure in liner polyvinyl compounds such as polystyrene, polyvinyltoluene, polymethylstyrene and polyvinyltoluene in addition to monovinyl aromatic compounds (e.g., styrene, methylstyrene and vinyltoluene) are employed in the publication. The above publication describes that the flame-retardants are effectively employed for nylon 46, but not describe any relationship between the flame-retardants and other polyamides. The present inventors have found that the aromatic polyamides are excellent in mechanical properties and in heat resistance of a short term, but they markedly deteriorate in the mechanical properties because of oxidation thereof when exposed to high temperatures for a long period of time. For improving the mechanical properties of the aromatic polyamides, a method of adding copper-containing compounds to the aromatic polyamides can be thought as in the aforementioned aliphatic polyamides. However, if the copper-containing compounds are added to the aromatic polyamides, any satisfactory effects cannot be obtained. The present inventors have earnestly studied to solve the above-described problems existing in the prior arts, and as a result, they obtained the following findings and accomplished the invention. That is, the resin compositions comprising a thermoplastic resin, a halogenated organic compound and an antimony-containing compound can be remarkably improved in granulation properties and color shades of pellets, by adding a phosphorus-containing compound thereto. In addition, other properties of the compositions such as heat resistance and flame retardance are never marred even by adding the phosphorus-containing compound. Moreover, thus obtained resin compositions (i.e., flame-retardant resins) can reduce occurrence of the aforementioned mold-staining by adding thereto at least one of an amine-type stabilizer and a phosphorus-type stabilizer. In the case of using polyamide as the thermoplastic resin, if a brominated compound of a polymer formed from an aromatic vinyl compound and a specific carboxylic acid is introduced into a resin composition, the resulting resin composition can be provided with an extremely high flame retardance. Further, if an aromatic amine-type stabilizer and an organic phosphite-type stabilizer are added to a specific aromatic polyamide, there can be obtained a resin composition having high heat aging characteristics and showing high heat stability in the molding stage. OBJECTS OF THE INVENTION It is the first object of the invention to provide a thermoplastic resin composition which is remarkably improved in granulation properties and color shades of pellets and is not lowered in heat resistance or flame retardance. It is the second object of the invention to provide a thermoplastic resin composition capable of reducing occurrence of mold-staining in the molding stage. It is the third object of the invention to provide a resin composition which is excellent in heat resistance and heat stability as well as in the flame retardance and is suitably employable for electronic components which are fixed to a circuit board through infrared rays reflow-soldering. It is the fourth object of the invention to provide a polyamide resin composition which is very excellent not only in the heat aging characteristics and molding stability but also in the mechanical, chemical and physical properties. SUMMARY OF THE INVENTION The thermoplastic resin composition of the invention is a flame-retardant resin composition comprising polyamide, a halogenated organic compound, an antimony-containing compound, a phosphorus-containing compound not being a phosphorus-type stabilizer, and an amine-type stabilizer and/or a phosphorus-type stabilizer. The polyamide resins employable in the resin composition of the invention are linear polymers having an amide bond, and examples of such polymers include a polymer obtained by polycondensation of an organic diamine and an organic dicarboxylic acid, a polymer obtained by polycondensation of an aminocaproic acid, and a polymer obtained by ring-opening of lactams. Concretely examples thereof are polymers having a constituent unit represented by the following formula (E) or (F). In the formula (E) or (F), each of p and q is a positive integer, and each of R 1 , R 2 and R 3 is an aliphatic, alicyclic or aromatic hydrocarbon or its derivative. As the polyamide, there can be more concretely mentioned aliphatic polyamides such as ring-opened polymers of lactams, namely cyclic amides, (e.g., polycapronamide produced by ε-caprolactam: nylon 6), polycondensates of aminocarboxylic acids (e.g., polyundecanamide produced by ω-aminoundecanoic acid: nylon 11; polydodecanamide produced by ω-aminododecanoic acid: nylon 12), polycondensates of aliphatic dicarboxylic acids and aliphatic diamines (e.g., polyhexamethylene adipamide produced by adipic acid and hexamethylenediamide: nylon 6,6; polyhexamethylene sebacamide produced by sebacic acid and hexamethylenediamine: nylon 6,10; polyhexamethylene dodecamide produced by dodecane diacid and hexamethylenediamine: nylon 6,12; polyundecamethylene adipamide produced by adipic acid and undecamethylenediamine: nylon 11,6; polytetramethylene adipamide produced by adipic acid and tetremethylenediamine: nylon 4,6); aromatic polyamides, namely, polycondensates of aromatic dicarboxylic acids and aliphatic diamines; and all aromatic polyamides such as polycondensates of aromatic dicarboxylic acids and aromatic diamines (e.g., polyhexamethylene terephthalamide: nylon 6T; polyhexamethylene isophthalamide: nylon 6I; and polymethaxylylene adipamide: MXD6). Also employable are copolycondensation polyamides (e.g., nylon 6/nylon 66, nylon 6/nylon 610, nylon 6/nylon 12, nylon 6/nylon 66/nylon 610, nylon 66/nylon 46, nylon 6/nylon 46, nylon 6/nylon 6T, nylon 6/nylon 6I, nylon 6T6, nylon 6TI, nylon 6T10 and nylon 6T12); polyester amides; and polyether amides. In the invention, the above-mentioned polyamide resins can be employed singly or in combination of two or more kinds. The thermoplastic resin composition of the invention contains the above polyamide as a host resin component. Further, in the thermoplastic resin composition of the invention, preferably employed is an aromatic polyamide [I] composed of a specific dicarboxylic acid constituent unit [X] and a specific alkylenediamine constituent unit [Y]. The aromatic polyamide [I] is described below in detail. The specific dicarboxylic acid constituent unit [X] contained in the aromatic polyamide [I] contains a terephthalic acid constituent unit (a) as an essential constituent unit. The polyamide recurring unit containing the terephthalic acid constituent unit (a) is represented by the following formula [I-a]: wherein R 1 is an alkylene group having 4 - 25 carbon atoms. The specific dicarboxylic acid constituent unit constituting the aromatic polyamide may contain a dicarboxylic acid constituent unit other than the above-mentioned terephthalic acid constituent unit (a). As the dicarboxylic acid constituent unit other than the terephthalic acid constituent unit, there can be mentioned an aromatic dicarboxylic acid constituent unit (b) other than the terephthalic acid and an aliphatic dicarboxylic acid constituent unit (c). Examples of the aromatic dicarboxylic acid constituent unit (b) other than the terephthalic acid include constituent units derived from an isophthalic acid (IA), a phthalic acid, a 2-methylterephthalic acid, a naphthalenedicarboxylic acid and a diphenyldicarboxylic acid. If the polyamide used for the resin composition according to the invention contains the aromatic dicarboxylic acid constituent unit (b) other than the terephthalic acid, preferred examples of the constituent unit (b) are an isophthalic acid constituent unit and a naphthlenedicarboxylic acid constituent unit, and particularly preferred is an isophthalic acid constituent unit. A recurring unit having a most preferred isophthalic acid constituent unit among the aromatic dicarboxylic acid constituent units (b) other than the terephthalic acid is represented by the following formula [I-b]: wherein R 1 is an alkylene group having 4 - 25 carbon atoms. There is no specific limitation on the aliphatic acid constituent unit (c), but preferably the constituent unit (c) is derived from an aliphatic dicarboxylic acid constituent unit having 4 - 20 (preferably 6 - 12) carbon atoms. Examples of aliphatic dicarboxylic acids used for deriving the aliphatic dicarboxylic acid constituent unit (c) include a succinic acid, an adipic acid (AA), an azelaic acid, a sebacic acid, a decanedicarboxylic acid, a undecanedicarboxylic acid and a dodecanedicarboxylic acid. If the aromatic polyamide according to the invention contains the aliphatic dicarboxylic acid constituent unit (c), a preferred example of the constituent unit (c) are an adipic acid constituent unit and a sebacic acid constituent unit. A recurring unit containing the aliphatic dicarboxylic acid constituent unit (c) is represented by the following formula [I-c]: wherein n is an integer of 2 to 20, preferably 2 to 18, more preferably 4 to 12, particularly 4 to 10, and R 1 is alkylene group having 4 - 25 carbon atoms. As the dicarboxylic acid constituent unit [X], a polycarboxylic acid constituent unit can be contained in the polyamide in a small amount (e.g., approx. not more than 10 % by mole), in addition to the above-described terephthalic acid constituent unit (a) and the above-described dicarboxylic acid constituent unit (b), (c) other than the terephthalic acid constituent unit. Concrete examples of the polycarboxylic acid constituent units are constituent units derived from tribasic acids (e.g., a trimellitic acid) and polybasic acids (e.g., a pyromellitic acid). There is no specific limitation on the diamine constituent unit [Y] constituting the aromatic polyamide together with the above-mentioned dicarboxylic acid constituent unit [X], but in general, it is derived from aliphatic alkylenediamine and/or alicyclic alkylenediamine, particularly, aliphatic alkylenediamine having 4 - 25 (preferably 6 - 25, more preferably 4 - 18) carbon atoms and/or alicyclic alkylenediamine having the same carbon atoms. The aliphatic diamine constituent unit may be an alkylenediamine constituent unit of straight chain or that of branched form. Examples of the aliphatic diamine constituent unit are as follows. Constituent units derived from the following alkylenediamines of straight chain: 1,4-diaminobutane 1,6-diaminohexane 1,7-diaminoheptane 1,8-diaminooctane 1,9-diaminononane 1,10-diaminodecane 1,11-diaminoundecane 1,12-diaminododecane Constituent units derived from the following alkylenediamines of branched form: 1,4-diamino-1,1-dimethylbutane 1,4-diamino-1-ethylbutane 1,4-diamino-1,2-dimethylbutane 1,4-diamino-1,3-dimethylbutane 1,4-diamino-1,4-dimethylbutane 1,4-diamino-2,3-dimethylbutane 1,2-diamino-1-butylethane 1,6-diamino-2,5-dimethylhexane 1,6-diamino-2,4-dimethylhexane 1,6-diamino-3,3-dimethylhexane 1,6-diamino-2,2-dimethylhexane 1,6-diamino-2,2,4-trimethylhexane 1,6-diamino-2,4,4-trimethylhexane 1,7-diamino-2,3-dimethylheptane 1,7-diamino-2,4-dimethylheptane 1,7-diamino-2,5-dimethylheptane 1,7-diamino-2,2-dimethylheptane 1,8-diamino-1,3-dimethyloctane 1,8-diamino-1,4-dimethyloctane 1,8-diamino-2,4-dimethyloctane 1,8-diamino-3,4-dimethyloctane 1,8-diamino-4,5-dimethyloctane 1,8-diamino-2,2-dimethyloctane 1,8-diamino-3,3-dimethyloctane 1,8-diamino-4,4-dimethyloctane 1,6-diamino-2,4-diethylhexane 1,9-diamino-5-mehylnonane As the diamine constituent unit [Y], particularly preferred are constituent units derived from aliphatic alkylenediamines of straight chain, and examples of such aliphatic alkylenediamines of straight chain include 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminoctane, 1,10-diaminodecane, 1,12-diaminododecane and a mixture thereof. Of these, most preferred is 1,6-diaminohexane. The alicyclic alkylenediamine constituent unit is a constituent unit derived from diamine generally having 6 - 25 carbon atoms and containing at least one alicyclic hydrocarbon ring. As the alicyclic alkylenediamine constituent unit, there can be mentioned those derived from for example the following alicyclic alkylenediamines: 1,3-diaminocyclohexane 1,4-diaminocyclohexane 1,3-bis(aminomethyl)cyclohexane 1,4-bis(aminomethyl)cyclohexane isophoronediamine piperazine 2,5-dimethylpiperazine bis(4-aminocyclohexyl)methane bis(4-aminocyclohexyl)propane 4,4'-diamino-3,3'-dimehtyldicyclohexylpropane 4,4'-diamino-3,3'-dimethyldicyclohexylmethane 4,4'-diamino-3,3'-dimehtyl-5,5'-dimethyldicyclohexylmethane 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylpropane α-α'-bis(4-aminocyclohexyl)-p-diisopropylbenzene α-α'-bis(4-aminocyclohexyl)-m-diisopropylbenzene α-α'-bis(4-aminocyclohexyl)-1,4-cyclohexane α-α'-bis(4-aminocyclohexyl)-1,3-cyclohexane Among the alicyclic alkylenediamine constituent units, preferred are constituent units derived from alicyclic alkylenediamines such as bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, and more preferred are constituent units derived from alicyclic alkyelendiamines such as bis(4-aminocyclohexyl)methane, 1,3-bis(aminocyclohexyl)methane and 1,3-bis(aminomethyl)cyclohexane. As the alkylenediamines used for deriving the diamine constituent unit [Y], aliphatic alkylenediamines or alicyclic alkylenediamines can be employed singly or in combination. The aromatic polyamide [I] can be prepared by known processes. For example, as described in Polymer Reviews, 10 , Condensation Polymers by Interfacial and Solution Methods (by P.W. Morgan), Inter-Science Publishers (1965) or Markromol. Chem., 47, 93-113, (1961), diacidic halide of an aromatic dicarboxylic acid capable of deriving the aforementioned constituent unit of the aromatic polyamide [I] is subjected to polycondensation with diamine through a solution method to prepare an aromatic polyamide [I]. Otherwise, the aromatic polyamide [I] can be prepared by utilizing interfacial polymerization. Further, the aromatic polyamide [I] can be also obtained by subjecting an aromatic dicarboxylic acid corresponding to the aromatic dicarboxylic acid constituent unit and diamine corresponding to the diamine constituent unit, or the salt of the aromatic dicarboxylic acid and the diamine to polycondensation through a fusion method in the presence or absence of a solvent such as water. Moreover, the aromatic polyamide [I] can be also obtained by producing an oligomer utilizing the above solution method and then subjecting the oligomer to polycondensation through solid phase polymerization. The diamine constituent unit which forms the aromatic polyamide employable in the invention may contain an aromatic diamine constituent unit in addition to the aforementioned alkylenediamine constituent unit. As the aromatic diamine constituent unit, there can be mentioned constituent units derived from aromatic diamines such as m-xylylenediamine and p-xylylenediamine. These aromatic diamines can be employed singly or in combination. The polyamide employable in the invention may be a polyamide containing a recurring unit having the formula [I-a], a recurring unit having the formula [I-b] and a recurring unit [I-c], or may be a mixture of a polyamide mainly containing a recurring unit having the formula [I-a], a polyamide mainly containing a recurring unit having the formula [I-b] and a polyamide mainly containing a recurring unit having the formula [I-c]. Among mixtures of plural polyamides, preferably employed is a mixture having a composition composed of a polyamide mainly containing a recurring unit having the formula [I-a] and at least one of a polyamide mainly containing a recurring unit having the formula [I-b] and a polyamide mainly containing a recurring unit having the formula [I-c]. In this case, the polyamide mainly containing a recurring unit having the formula [I-a] is generally contained in the composition in an amount of not less than 30 % by weight. Further, a ratio between the polyamide mainly containing a recurring unit having the formula [I-b] and the polyamide mainly containing a recurring unit having the formula [I-c] is generally in the range of 0 : 100 to 40 : 60, preferably 0 : 100 to 30 : 70, by weight. Of the above aromatic polyamides [I], the preferred aromatic polyamide in the third thermoplastic resin composition contains the terephthalic constituent unit (a) in an amount of 30 to 100 % by mole, and the aromatic dicarboxylic acid constituent unit (b) other than the terephthalic acid constituent unit in an amount of 0 to 70 % by mole and/or the aliphatic dicarboxylic acid constituent unit (c) in an amount of 0 to 70 % by mole, in 100 % by mole of the dicarboxylic acid constituent unit [X]. The above-described thermoplastic resins employable in the invention preferably have such a molecular-weight distribution that various molding methods such as extrusion molding, injection molding, blow molding and stamping can be readily conducted. The thermoplastic resin composition of the invention further contains a halogenated organic compound, an antimony-containing compound, a phosphorus-containing compound, and at least one of an aromatic amine-type stabilizer and a phosphorus-type stabilizer, in addition to the above-mentioned polyamide resin. As the halogenated organic compound employable for the thermoplastic resin compositions of the invention, there can be mentioned a brominated crosslinking aromatic polymer as described in Japanese Patent Provisional Publication No. 63(1988)-317552, brominated polystyrene, a brominated polyphenylene ether, a brominated styrene/maleic anhydride copolymer (brominated SMA resin), a brominated epoxy resin, a brominated phenoxy resin, a decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate and perchloropentadecane. Concretely, there can be employed, for example, EBR-370 FK® (trade name of Matsunaga Chemical Co., Ltd.) as the brominated crosslinking aromatic polymer, Pyrocheck 68PB (trade name of Nissan Ferro Organic Chemical Co., Ltd.) as the brominated polystyrene, and PO64P (trade name of Great Lake Co.) as the brominated polyphenylene ether. These halogenated organic compounds can be employed singly or in combination. The bromine content of the halogenated organic compounds preferably is in the range of 15 to 87 %. The above-mentioned halogenated organic compound is used in an amount of 1 to 40 parts by weight, preferably 10 to 30 parts by weight, in terms of halogen atom, per 100 parts by weight of the aforementioned thermoplastic resin. As the antimony-containing compound used as a thermoplastic in the first thermoplastic resin compositions of the invention, there can be mentioned known antimony-containing compounds such as antimony trioxide, antimony pentaoxide, antimony tartrate and sodium antimonate. These antimony-containing compounds can be employed singly or in combination. The antimony-containing compound is used in an amount of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, in terms of antimony atom, per 100 parts by weight of the aforementioned thermoplastic resin. The thermoplastic resin composition of the invention further contains a phosphorus-containing compound in addition to the aforementioned polyamide resin, halogenated organic compound and antimony-containing compound. By addition of the phosphorus-containing compound, the obtained resin composition can be enhanced in the granulation properties, and further a molded product formed from the resin composition can be improved in the color shades. Moreover, even if the phosphorus-containing compound is added, various properties inherently belonging to the resin itself, such as heat resistance and flame retardance, are never lowered. As the phosphorus-containing compound, there can be mentioned various phosphorus-containing compounds such as phosphates, organic phosphates, mixtures of phosphates and organic phosphates, and metal salts synthesized from mixed acids of phosphorus-containing inorganic acids and organic acids. These compounds can be employed singly or in combination. Examples of the phosphates include metal (e.g., Li, Na, K, Mg, Ca, Sr, Zn and Al) salts of phosphoric, phosphorus or hydrophosphorous acids. These phosphates can be employed singly or in combination. Concrete examples of the phosphates are as follows. Sodium salts such as sodium dihydrogenphosphate, disodium hydrogenphosphate, sodium phosphate, sodium hydrogenphosphite, sodium phosphite and sodium hypophosphite; potassium salts such as potassium dihydrogenphosphate, dipotassium hydrogenphosphate, potassium phosphate, potassium hydrogenphosphite, potassium phosphite and potassium hypophosphite; lithium salts such as lithium dihydrogenphosphate, dilithium hydrogenphosphate, lithium phosphate, lithium hydrogenphosphite, lithium phosphite and lithium hypophosphite; barium salt such as barium dihydrogenphophate, dibarium hydrogenphosphate, barium phosphate and barium hypophosphite; magnesium salts such as magnesium hydrogenphosphate, magnesium dihydrogenphosphate, magnesium phosphate and magnesium hypophosphite; calcium salts such as calcium dihydrogenphosphate, calcium hydrogenphosphite, calcium phosphate and calcium hypophosphite; zinc salts such as zinc phosphite and zinc hypophosphite; and aluminum salts such as aluminium phosphite and aluminum hypophosphite. Examples of the organic phosphates include metal (e.g., Li, Na, K, Mg, Ca, Sr, Zn and Al) salts of alkylphosphoric or alkylphosphorous esters and those of alkyletherphosphoric or alkyletherphosphorous esters. These organic phosphates can be employed singly or in combination. Examples of the metal salts of alkylphosphoric esters include metal salts of monoalkyl esters represented by the formula, PO(OR)(OH) 2 , and metal salts of dialkyl esters represented by the formula, PO(OR) 2 OH. Concrete examples of the monoalkyl esters represented by the formula, PO(OR)(OH) 2 , include ethyllithium phosphate, butylsodium phosphate, 2-ethylhexylbarium and dodecylmagnesium phosphate. Concrete examples of the metal salts of dialkyl esters represented by the formula, PO(OR) 2 OH, include diethylsodium phosphate, dibutylpotassium phosphate, di(2-ethylhexyl)barium phosphate, dioctylmagnesium phosphate, dihexylcalcium phosphate and didodecyllithium phosphate. Examples of the metal salts of alkylphosphorous esters include metal salts of monoalkyl esters represented by the formula, P(OR)(OH) 2 , or metal salts of dialkyl esters represented by the formula, P(OR) 2 OH. Concrete examples of the metal salts of monoalkyl esters represented by the formula, P(OR)(OH) 2 , include ethylsodium phosphite, butylcalcium phosphite, (2-ehtylhexyl)barium phosphite, octylpotassium phosphite and decylmagnesium phosphite. Concrete examples of the metal salts of dialkyl esters represented by the formula, P(OR) 2 OH, include diethylsodium phosphite, dibutylcalcium phosphite, dihexylbarium phosphite, dioctylmagnesium phosphite, di(2-ethylhexyl)barium phosphite and didodecylpotassium phosphite. Also employable as the phosphorus-containing compound in the invention are metal salts synthesized from mixed acids of phosphorus-containing inorganic acids and organic acids: Examples of the phosphorus-containing inorganic acids employable in the invention include hydrophosphorous acid, phosphorus acid and phosphoric acid. Examples of the organic acids employable in the invention include acetic acid, propionic acid, butyric acid, caprylic acid, capric acid, 2-ethylhexoic acid, lauric acid, stearic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, lauryl mercaptopropionic acid, benzoic acid, paratertiarybutyl benzoic acid, dimethyl benzoic acid, aminobenzoic acid, salicylic acid, aminoacetic acid, glutamic acid, oxalic acid, succinic acid, adipic acid, phthalic acid, maleic acid, thiodipropionic acid, fumaric acid, malonic acid, malic acid, tartaric acid and citric acid. In the mixed acid of the phosphorus-containing inorganic acid and the organic acid, the content of the organic acid is in the range of 0.1 to 50 % by weight. Each of the phosphorus-containing inorganic acids and the organic acids can be employed singly or in combination. As the metal or metal compound employable for synthesizing metal salts using mixed acids of the phosphorus-containing inorganic acid and the organic acid, there can be mentioned metals such as Na, K, Mg, Ca, Sr, Ba, Zn, Al and Zr; and metal compounds thereof. Each of these metals and metal compounds can be employed singly or in combination. In the metal salts, the amount of the metal is in the range of 1 to 3 moles per 1 mole of the acid. The metal salt may be a basic acid. The above-described phosphorus-containing compound is employed in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the aforementioned thermoplastic resin. As the amine-type stabilizer, preferably employable are aromatic amine-type stabilizers having the following formula (III-a) or the following formula (III-b): R 1 - NH - R 2 In the formula (III-a) and the formula (III-b), each of R1 to R4 represents an alkyl group (e.g., octyl group), an aromatic group (e.g., phenyl group and naphtyl group), an aromatic group having two or more alkyl groups (e.g., dimethylbenzyl group) or a methacryloyloxy group. Examples of the aromatic amine-type stabilizers having the formula (III-a) include p,p'-dioctyldiphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine and phenyl-α-naphtylamine. Examples of the aromatic amine-type stabilizers having the formula (III-b) include N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p'-phenylenediamine and N,N'-di-β-naphtyl-p-phenylenediamine. Also employable are other amine-type stabilizers such as a 2,2,4-trimethyl-1,2-dihydroquinoline polymer. Those amine-type stabilizers can be employed singly or in combination. As the phosphorus-type stabilizer employable for the second thermoplastic resin composition of the invention, there can be mentioned, for example, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol-di-phosphite, tris(2,4-di-t-butylphenyl)phosphite and tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylenediphosphonite. These phosphorus-type stabilizers can be employed singly or in combination. The thermoplastic resin composition of the invention contains the amine-type stabilizer and/or the phosphorus-type stabilizer in an amount of 0.05 to 7 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 pars by weight, per 100 parts by weight of the aforementioned polyamide resin. By adding the amine-type stabilizer and/or the phosphorus-type stabilizer to the resin composition composed of the above-mentioned polyamide resin, halogenated organic compound, antimony-containing coumpound and phosphorus-containing compound, the resin composition can be prevented from decomposition thereof, whereby occurrence of mold-staining can be remarkably reduced even when the resin composition is continuously subjected to injection molding for a long period of time. The essential components of the thermoplastic resin composition of the invention has been described. However, the thermoplastic resin composition of the invention may further contain a fibrous reinforcing agent in addition to the aforementioned components, namely, polyamide thermoplastic resin, halogenated organic compound, antimony-containing compound, phosphorus-containing compound, and, amine-type stabilizer and/or phosphorus-type stabilizer. When the fibrous reinforcing agent is added to the resin composition, the resulting composition can be sometimes much more enhanced in various properties such as heat resistance, flame retardance, tensile rigidity strength, flexural strength and impact strength. As the fibrous reinforcing agent employable in the thermoplastic composition of the invention, there can be employed inorganic fibrous reinforcing agents such as glass fibers, potassium titanate fibers, metal-coated glass fibers, ceramic fibers, wollastonite, carbon fibers, metal carbide fibers and hardened metal fibers. These fibrous reinforcing agents may be beforehand treated with silane compounds such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane and 2-glycidoxypropyltrimethoxysilane. The inorganic fibrous reinforcing agents are preferred from the viewpoint of the heat resistance, and among them, glass fibers are particularly preferred because of excellent reinforcing effect. The fibrous reinforcing agent is used in an amount of 0.5 to 300 parts by weight, preferably 10 to 150 parts by weight, per 100 parts by weight of the aforementioned thermoplastic resin composition. The thermoplastic resin compositions of the invention may further contain various known additives other than the above-mentioned components, for example, a heat stabilizer, a weather stabilizer, a plasticizer, a thickening agent, an antistatic agent, a parting agent, a pigment, a dye, an inorganic or organic filler, a nucleating agent, and an inorganic compound (e.g., carbon black, talc, clay and mica), provided that those additives do not spoil the objects of the invention. The thermoplastic resin composition of the invention may contain various polymers such as polyethylene, polypropylene, polybutene, polymethylpentene, polystyrene, an acrylonitrile/butadiene copolymer, polybutylene terephthalate, polyethylene terephthalate, a polyphenylene ether, a fluorine resin, a silicone resin, a phenol resin, polyphenylene sulfide and a liquid crystal polymer. The thermoplastic polyamide composition of the invention can be prepared by known processes. For example, the aforementioned components, namely, polyamide, halogenated organic compound, antimony-containing compound, phosphorus-containing compound, and amine-type stabilizer and/or phosphorus-type stabilizer, and other additives if desired, are mixed with each other using an appropriate mixing machine such as Henschel mixer, a V-blender, a ribbon blender and a tumbling blender. Otherwise, the above-components are mixed with each other in the same manner as described above, then the mixture is melted and kneaded using a single screw extruder, a multiple screw extruder, a kneader, Banbury mixer or the like, and the kneadate is subjected to granulation or pulverization. EFFECT OF THE INVENTION The thermoplastic resin composition of the invention is not reduced in the properties inherently belonging to polyamide resin, for example, heat resistance and flame retardance, and further the resin composition can hold degree of the mold-staining brought about in the molding stage to less than 1/2 of that given by the conventional polyamide resin compositions. The present invention is further described by the following examples, but the examples are by no means given to restrict the invention. Example 1 There was kneaded 100 parts by weight of a polyamide (PAGTG;terephthalic acid/adipic acid = 55/45 by molar ratio, Tm = 312 °C, intrinsic viscosity of 1.20 dl/g as measured at 30 °C in concentrated sulfuric acid) together with 38 parts by weight (corresponding to 28.5 parts by weight in terms of bromine atom) of Pyrocheck 68 PB as the halogenated organic compound, 16 parts by weight (corresponding to 10.1 parts by weight in terms of antimony atom) of sodium antimonate Na 2 Sb 2 O 6 as the antimony compound, 1.5 parts by weight of UV-checker AM595 as the phosphorus-containing compound, 0.75 parts by weight of an amine-type stabilizer (A-1: 4,4-bis(α,α-dimethylbenzyl)diphenylamine) and 67.0 parts by weight of glass fiber in a twin-screw extruder set at a cylinder temperature of 320 °C to prepare pellets. The whole amount of the above-described ingredients excluding glass fiber was fed through the main feed opening, and only glass fiber was fed through the side feed opening. The resulting pellets were injection-molded, and the staining of mold was evaluated in the following manner. Evaluation method of mold staining Continuous molding of 2000 shots at a rate of 25 sec/cycle was carried out by using an injection mold for molding a disc of 70 mm in diameter and 2 mm in thickness, said mold having a specular finished disc-form liner of 70mm in diameter, named of SKD II on the movable platen side, in which gate entered the center of the disc at a right angle. After the completion of the molding, the disc-form liner was taken out and visually examined whether deposit on the surface thereof was observed or not, and the degree of fog was visually examined. The mold temperature during molding was 70 °C, and the cylinder temperature varied depending on the types of the polyamides and was indicated in Table 1. The results are shown in Table 1. Comparative Example 1 The procedure of Example 1 was repeated except that the amine-type stabilizer was omitted. The results are shown in Table 1. Examples 2 to 12 and Comparative Examples 2 and 3 The procedure of Example 1 was repeated except that compounds indicated in Table 1 were used in an amount indicated in Table 1 and the molding of pellets was carried out at a cylinder temperature indicated in Table 1. The results are shown in Table 1. The polyamides, the organohalogen compound, the antimony comounds, the phosphorus-containing compounds, the amine-type stabilizer, the phosphorus-type stabilizer and glass fiber (GF) which were used were the following compounds or products. Polyamide PA 66: CM 3001 N (trade name, a product of Toray Industries, Inc.) PA 46: F5000 (trade name, intrinsic viscosity: 1.67 dl/g as measured at 30 °C in sulfuric acid, a product of Unitika, Ltd.) PA 6T6: A polyamide resin (terephthalic acid/adipic acid = 55/45 by molar ratio, Tm = 312 °C, intrinsic viscosity : 1.20 dl/g as measured at 30 °C in sulfuric acid) Halogenated organic compound Polydibromophenylene oxide (trade name: PO-64P, a product of Great Lakes) Brominated polystyrene (trade name: Pyrocheck 68 PB, a product of Nissan Ferro Organic Chemical KK) Antimony compound Antimony trioxide (trade name: Patox C, a product of Nippon Seiko KK) Sodium antimonate Na 2 Sb 2 O 6 (trade name: Sunepock NA-1075, a product of Nissan Chemical Industries, Ltd.) Phosphorus-containing compound UV-check AM595 (trade name: a product of Nissan Ferro Chemical KK) Amine-type stabilizer (A-1): 4,4-bis(α,α-dimethylbenzyl)diphenylamine (A-2): N,N'-di-β-naphthyl-P-phenylenediamine Phosphorus-type stabilizer (P-1): Tetrakis (2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite (P-2) : Tris(2,4-di-t-butylphenyl) phosphite Glass fiber (GF) Chopped strand (diameter: 13 µm. length: 3 mm)

Claims: A thermoplastic resin composition which comprises polyamide, a halogenated organic compound, an antimony-containing compound, a phosphorus-containing compound not being a phosphorus-type stabilizer, and at least one of an amine-type stabilizer and a phosphorus-type stabilizer. The thermoplastic resin composition as claimed in claim 1, wherein the halogenated organic compound is contained in an amount of 1 to 40 parts by weight in terms of halogen atom, the antimony-containing compound is contained in an amount of 1 to 30 parts by weight in terms of antimony atom, the phosphorus-containing compound is contained in an amount of 0.1 to 10 parts by weight, and at least one of the amine-type stabilizer and the phosphorus-type stabilizer is contained in an amount of 0.05 to 7 parts by weight, per 100 parts by weight of the polyamide. The thermoplastic resin composition as claimed in claim 1 or claim 2, wherein the halogenated organic compound is at least one compound selected from the group consisting of a brominated closs-linking aromatic polymer, brominated polystyrene, a brominated polyphenylene ether, a brominated bisphenol-type epoxy polymer, a brominated styrene-maleic anhydride copolymer, a brominated epoxy resin, a brominated phenoxy resin, a decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate and perchlorocyclopentadecane. The thermoplastic resin composition as claimed in claim 1 or claim 2, wherein the antimony-containing compound is at least one compound selected from the group consisting of antimony trioxide, antimony pentaoxide, antimony tartrate and sodium antimonate. The thermoplastic resin composition as claimed in claim 1 or claim 2, wherein the phosphorus-containing compound is at least one compound selected from the group consisting of phosphate, organic phosphate, a mixture of an inorganic phosphoric acid and an organic phosphoric acid, and a metal salt synthesized from a mixed acid of an inorganic phosphoric acid and an organic acid. The thermoplastic resin composition as claimed in claim 1 or claim 2, wherein the amine-type stabilizer is at least one compound selected from the group consisting of N,N'-diphenyl-p-phenylenediamine, a 2,2,4-trimethyl-1,2-dihydroquinoline polymer, p,p'-dioctyldiphenylamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p'-phenylenediamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, N,N'-di-β-naphtyl-p-phenylenediamine and phenyl-α-naphtylamine. The thermoplastic resin composition as claimed in claim 1 or claim 2, wherein the phosphorus-type stabilizer is at least one compound selected from the group consisting of bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol-di-phosphite, tris(2,4-di-t-butylphenyl)phosphite and tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenediphosphonite.

Inventors: ASO HIROTAKA, IKEJIRI FUMITOSHI, ISHIWATARI KAZUO, SAKAI HIDEKI, YAMAMOTO SANEHIRO, ASO, HIROTAKA, IKEJIRI, FUMITOSHI, ISHIWATARI, KAZUO, SAKAI, HIDEKI, YAMAMOTO, SANEHIRO
Applicants: MITSUI PETROCHEMICAL IND, MITSUI PETROCHEMICAL INDUSTRIES, LTD.
Application year: 1991
Main classification: C08K13
IPC codes: C08K3, C08K5, C08L77, H05K1