JP2003073542A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition which has a high strength and rigidity such as high creep characteristics and develops an excellent effect also on surface appearance. SOLUTION: This polyamide resin composition comprises (A) 100 pts.wt. of a polyamide containing polyhexamethylene adipamide as a main constituent, (B) 0.05 to 30 pts.wt. of a swelling laminar silicate, (C) 0.001 to 0.5 pt.wt. of a copper compound, (D) 0.01 to 0.5 pt.wt. of a compound selected from aliphatic amides, fatty acids and their derivatives, and (E) 0.01 to 0.5 pt.wt. of a higher fatty acid metal salt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyamide resin composition having excellent mechanical strength, especially creep resistance and surface appearance.

[0002]

2. Description of the Related Art Conventionally, in order to improve the mechanical properties of polyamide resins, it has been practiced to incorporate glass fibers and inorganic fillers into the resins. However, simply melting and kneading these inorganic fillers causes problems such as poor dispersion of the inorganic filler in the resin and poor interfacial adhesion, low impact resistance, and poor surface appearance. Therefore, there is a method of improving the dispersion of the filler in the resin by subjecting the surface of the inorganic filler to a coupling treatment such as an organic silane compound in order to enhance the affinity or the binding force between the thermoplastic resin and the inorganic filler. The method only improves the compatibility between the resin and the inorganic filler, and has not been sufficiently improved. Further, with a normal filler, it is necessary to increase the filling amount in order to obtain sufficient strength, and there is a problem that the obtained resin composition has a high specific gravity.

On the other hand, clay minerals, which are a type of inorganic layered compound, have been used for a long time as fillers, but in ordinary mixing and kneading, secondary agglomeration occurs and they are uniformly dispersed in the resin. Was difficult. JP-A-8-12881
In the publication, by using an intercalation compound having a layered silicate as a host and a specific quaternary ammonium ion as a guest,
Attempts have been made to obtain a uniform dispersion. Also,
JP-A-8-151449 and JP-A-9-48856
The publication discloses an attempt to swell a clay mineral with a solvent, melt-knead it with a resin, and remove the solvent by holding a vent port provided in an extruder at a reduced pressure to obtain a uniform dispersion. There is.

[0004]

These techniques show some improvement in mechanical properties such as strength and elastic modulus. To obtain higher rigidity, the amount of the layered silicate added should be increased. As a result, there is a problem in that the moldability and surface appearance are degraded.

An object of the present invention is to obtain a polyamide resin composition having high mechanical strength, especially creep resistance, without deteriorating the surface appearance.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors have found that a polyamide containing polyhexamethylene adipamide as a main constituent is
The present inventors have found that a polyamide resin composition containing a swelling layered silicate, a compound selected from a copper compound, a fatty acid amide, a fatty acid and a derivative thereof, and a higher fatty acid metal salt can solve the above-mentioned problems, and completed the present invention.

That is, in the present invention, (1) (A) 100 parts by weight of polyamide containing polyhexamethylene adipamide as a main constituent, (B) swellable layered silicate of 0.1.
05 to 30 parts by weight, (C) copper compound 0.001 to 0.5
Parts by weight, 0.01 to 0.5 parts by weight of a compound selected from (D) an aliphatic amide, a fatty acid and a derivative thereof,
(E) A polyamide resin composition containing 0.01 to 0.5 part by weight of a higher fatty acid metal salt, and the present invention further provides (2) the copper compound (C) is a monovalent copper halide compound. The polyamide resin composition according to (1) above, wherein the compound of (3) (D) is an aliphatic amide, and the polyamide resin composition according to (1) or (2) above. (4) (E) The higher fatty acid metal salt is a stearic acid metal salt, wherein (1) to
The polyamide resin composition according to any one of (3), (5)
A molded product obtained by molding the polyamide resin composition according to any one of (1) to (4) above.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The polyamide resin (A) having polyhexamethylene adipamide as a main component used in the present invention means a polycondensation having an amide bond obtained by using at least 50 mol% or more of hexamethylene diamine and adipic acid as main raw materials. Say the body. A small amount of other copolymerization component may be added to the polyamide resin of the present invention as long as the object of the invention is not impaired. Typical examples of the copolymerization component include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetra Methylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, (2,2,4- or 2,4,4-)
Trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3- Aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (amino Propyl) piperazine, aminoethylpiperazine and other aliphatic, alicyclic and aromatic diamines, and speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2
-Chloroterephthalic acid, 2-methylterephthalic acid, 5-
Examples thereof include aliphatic, alicyclic and aromatic dicarboxylic acids such as methyl isophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid and hexahydroisophthalic acid.

As the polyamide of the present invention, it is possible to use a mixture of polyhexamethylene adipamide resin (nylon 66 resin) with a small amount of another polyamide resin. Polyamide resins that can be mixed and used include polycaproamide (nylon 6), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polytetramethylene adipamide (nylon 46), polycaproamide Hexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 6)
12), polyhexamethylene terephthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (Nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene terephthalamide De / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / poly (2-methyl pentamethylene) terephthalamide copolymer (nylon 6T /
M5T), polyhexamethylene terephthalamide / polyhexamethylene sebacamide / polycaproamide copolymer (nylon 6T / 610/6), polyhexamethylene terephthalamide / polydodecane amide / polyhexamethylene adipamide copolymer (nylon 6T / 12/6
6), polyhexamethylene terephthalamide / polydodecane amide / polyhexamethylene isophthalamide copolymer (nylon 6T / 12 / 6I), polyxylylene adipamide (nylon XD6) and the like.

There is no particular limitation on the degree of polymerization of the polyamide resin, but it may be added in a 1% by weight 98% concentrated sulfuric acid solution at 25 ° C.
The relative viscosity measured in 1. is preferably in the range of 2.0 to 7.0.

The swellable layered silicate (B) used in the present invention is described in "Clay Handbook" p. Nos. 41 to 43 (edited by The Clay Society of Japan, Gihodo (issued on January 15, 1942)), the tetrahedral silicate sheet is overlaid on top and bottom of the octahedral sheet containing an element selected from aluminum, magnesium, lithium and the like. It has a 2: 1 type structure in which a single plate-shaped crystal layer is formed, and has exchangeable cations between the layers of the plate-shaped crystal layer. The size of the single plate crystal is usually 0.05 to 0.5 μm in width and 6 to 6 in thickness.
It is 15 angstroms. The cation exchange capacity of the exchangeable cation is 20 to 300 meq / 100 g.
It is preferable to use those of
It is in the range of 150 meq / 100 g.

Specific examples of such layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and various clays such as vermiculite, halloysite, kanemite, kenyaite, zirconium phosphate and titanium phosphate. Minerals, swelling fluoromica such as Li-type fluoro-teniolite, Na-type fluoro-teniolite, Na-type tetrasilicon-fluorine mica, Li-type tetra-silicon-fluorine mica, etc. may be mentioned, and even natural ones are synthesized. May be. Among these, smectite-based clay minerals such as montmorillonite and hectorite and swelling fluoromica such as Na-type tetrasilicon fluoromica and Li-type fluoroteniolite are preferable, and smectite-based clay minerals such as montmorillonite are more preferable.

For the swellable layered silicate (B) of the present invention, it is preferable to use a layered silicate containing an organic onium ion between the layers of the plate crystal layer.

Examples of the organic onium ion include ammonium ion, phosphonium ion and sulfonium ion. Among these, ammonium ion and phosphonium ion are preferable, and ammonium ion is particularly preferably used. As ammonium ion,
It may be any of primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, and quaternary ammonium ion.

Examples of the primary ammonium ion include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

Examples of secondary ammonium ions include methyldodecyl ammonium and methyl octadecyl ammonium.

Examples of the tertiary ammonium ion include dimethyldodecyl ammonium and dimethyl octadecyl ammonium.

Examples of the quaternary ammonium ion are benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium and the like, trioctylmethylammonium, trimethyloctylammonium, trimethyldodecylammonium. , Alkyl trimethyl ammonium ions such as trimethyl octadecyl ammonium, dimethyl dioctyl ammonium, dimethyl didodecyl ammonium,
Examples thereof include dimethyldialkylammonium ions such as dimethyldioctadecyl ammonium.

In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6
-Aminocaproic acid, 11-aminoundecanoic acid, 12
Examples also include ammonium ions derived from aminododecanoic acid, ethanolamine derivatives, diethanolamine derivatives and the like.

Among these ammonium ions, the total number of carbon atoms in the molecule of ammonium ion is 11 to 30.
The quaternary ammonium ions of are particularly preferred. Specific examples include trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyldodecylammonium, and benzyldimethyloctadecylammonium.

The layered silicate containing the organic onium ion between the layers in the present invention can be produced by reacting the layered silicate having an exchangeable cation between the layers and the organic onium ion by a known method. Specific examples thereof include a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol or a method by directly reacting a layered silicate with a liquid or molten ammonium salt.

In the present invention, the amount of the organic onium ion relative to the layered silicate is such that the layered silicate is dispersed in terms of dispersibility, thermal stability during melting, gas during molding, and suppression of odor generation. Preferred for cation exchange capacity,
It is in the range of 0.4 to 2.0 equivalents. More preferably,
It is 0.8 to 1.2 equivalents.

In addition to containing the above-mentioned organic onium salt, the layered silicate may be pretreated with a coupling agent having a reactive functional group before use in order to obtain better mechanical strength. Is preferred. As such a coupling agent, an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound,
Examples thereof include epoxy compounds.

Organosilane compounds (sometimes referred to as silane coupling agents hereinafter) are particularly preferred, and specific examples thereof include γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane. Epoxy group-containing alkoxysilane compounds such as ethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane ,
Ureido group-containing alkoxysilane compounds such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- Isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyl Isocyanato group-containing alkoxysilane compounds such as trichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, .gamma.-hydroxypropyl trimethoxysilane, .gamma.
Hydroxyl group-containing alkoxysilane compound such as hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N
Carbon-unsaturated group-containing alkoxysilane compounds such as -β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane-hydrochloride are mentioned.
Particularly, a carbon-carbon unsaturated group-containing alkoxysilane compound is preferably used.

Treatment of the layered silicate with these silane coupling agents is carried out by a method in which the layered silicate is adsorbed to the layered silicate in a polar solvent such as water, methanol or ethanol, or a mixed solvent thereof, or a Henschel mixer. A method of adding layered silicate to a high-speed stirring mixer such as, and adsorbing it by dropping in the form of a silane coupling agent or an aqueous solution containing an organic solvent while stirring, and further directly adding silane coupling agent to the layered silicate. And a method of adsorbing them by mixing them in a mortar or the like, and any method may be used. When the layered silicate is treated with a silane coupling agent, water, acidic water, or water in order to accelerate the hydrolysis of the alkoxy group of the silane coupling agent,
It is preferable to mix alkaline water and the like at the same time. Also,
In order to increase the reaction efficiency of the silane coupling agent, water such as methanol or ethanol and an organic solvent that dissolves both the silane coupling agent may be mixed in addition to water.
The reaction can be further promoted by heat-treating the layered silicate treated with such a silane coupling agent. A so-called integral blending method may be used in which, when the layered silicate and the thermoplastic polyester are melt-kneaded without previously treating the layered silicate with the coupling agent, these coupling agents are added.

The order of the treatment of the layered silicate with the organic onium ion and the treatment with the coupling agent is not particularly limited, but it is preferable to first treat with the organic onium ion and then with the coupling agent.

In the present invention, the content of the (B) swellable layered silicate is preferably 0.05 to 30 parts by weight as an inorganic ash content based on 100 parts by weight of the polyamide resin of the present invention. It is more preferably 0.1 to 20 parts by weight, and particularly preferably 0.2 to 10 parts by weight. The content is 0.
If it is less than 05 parts by weight, the effect of improving the physical properties is small, and if the content exceeds 30 parts by weight, the toughness decreases. The amount of the inorganic ash is obtained by ashing 2 g of the polyamide resin composition in an electric furnace at 500 ° C. for 3 hours and measuring the mass before and after ashing.

The (C) copper compound used in the present invention is a copper compound, such as a copper halide, sulfate, acetate or fatty acid salt. As a specific example, cuprous chloride,
Cupric chloride, cuprous bromide, cupric bromide, cuprous iodide,
Cupric iodide, cupric sulfate, cupric nitrate, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and the aforementioned inorganic halogens. Examples thereof include complex compounds of copper oxide with xylylenediamine, 2-mercaptobenzimidazole, benzimidazole and the like. Of these, monovalent copper compounds, especially monovalent copper halide compounds, are preferable, and cuprous acetate, cuprous iodide and the like can be exemplified as particularly preferable copper compounds.

In the polyamide resin composition of the present invention,
The content of the (C) copper compound is preferably 0.001 to 0.5 part by weight, and more preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the polyamide resin.
When the content of the copper compound is less than 0.001 part by weight,
The creep resistance may be reduced, while the content is 0.
If it exceeds 5 parts by weight, discoloration of the polyamide resin composition due to water absorption becomes remarkable.

In the present invention, it is possible to add an alkali halide compound in the form of being used in combination with a copper compound. Examples of the alkali halide compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide, potassium iodide, Sodium iodide is particularly preferred. It is usually preferable that the amount is 0.01 to 1 part by weight with respect to 100 parts by weight of the polyamide resin, and further 0.05 to 0.8.
A range of parts by weight is particularly preferred.

As the compound (D) used in the present invention, selected from aliphatic amides, fatty acids and their derivatives,
As the aliphatic amide, those having the following general formula are preferably used. R ₂ CONH-R ₁ (1) R ₄ CONH-R ₃ -NHCOR ₅ (2) R ₇ NHCO-R ₆ -CONHR ₈ (3) R ₁₀ CONH-R ₉ -CONHR ₁₁ (4) (in the formula, R is a hydrocarbon group, preferably R ₁ is hydrogen or a hydrocarbon group having _{1 to} 35 carbon atoms, R ₂ , R ₄ ,
_{R 5, R 7, R 8} , R 10, R 11 hydrocarbon group having a carbon number of _{1~35, R 3, R 6,} R 9 is a hydrocarbon group having 1 to 12 carbon atoms. ) Examples of R ₁ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ and R ₁₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group,
n-butyl group, pentyl group, hexyl group, heptyl group,
Octyl group, nonyl group, decyl group, undecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosanyl group, heneeicosanyl group, docosanyl group, tricosanyl group, tetracosanyl group, ethylhexyl group And so on.

Examples of R ₃ , R ₆ and R ₉ are methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group and decamethylene group. Group, undecamethylene group, dodecamethylene group, isopropylidene group, phenylene group, xylylene group and the like.

Examples of the aliphatic amide include lauryl amide, myristyl amide, palmityl amide,
Monoamides such as stearylamide, eicosylamide, behenylamide, oleylamide, N-stearylstearylamide, N-oleyloleylamide, N-
Substituted monoamides such as stearyloleylamide, N-oleylstearylamide, N-oleylpalmitylamide, methylenebisstearylamide, methylenebisoleylamide, ethylenebisstearylamide,
Bisamides such as ethylenebisoleylamide and hexamethylenebisstearylamide are preferably used. Of these, aliphatic bisamides such as ethylenebisstearylamide are particularly preferably used.

The fatty acid and its derivative are an aliphatic carboxylic acid, an ester obtained from an aliphatic carboxylic acid and an aliphatic dihydric alcohol, and a partially saponified product thereof. Examples of the carboxylic acid are lauric acid and myristic acid. , Valmitic acid, stearic acid nonadecanoic acid, arachidic acid,
Behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, laxeric acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassic acid, linoleic acid, linolenic acid, arachidonic acid, stearolic acid, etc. Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol and the like.

Examples of the above-mentioned fatty acid derivatives include montanic acid aliphatic dihydric alcohol ester "Hoechst wax E" manufactured by Hoechst Japan, and partially saponified product "Hoechst wax OP" of montanic acid aliphatic dihydric alcohol ester manufactured by Hoechst Japan. And the like, ethylene glycol ester of melissic acid and its derivative, and the like are preferably used.

The content of the compound (D) selected from fatty acid amides, fatty acids and derivatives thereof is 0.01 to 0.5 parts by weight, preferably 0.05 to 0. 3 parts by weight. 0.0
If it is less than 1 part by weight, the surface appearance may deteriorate,
If the amount is more than 0.5 parts by weight, the amount of gas generated at the time of melting the composition is large, and the smoothness of the surface of the molded product is deteriorated due to silver generation or the like.

The higher fatty acid metal salt (E) used in the present invention usually has 10 to less than 25 carbon atoms, particularly 12 to 22 carbon atoms.
Fatty acid metal salts obtained from the following fatty acids and metals of Groups I to III of the Periodic Table are preferably used. Examples of fatty acids include stearic acid, balmitic acid, oleic acid, aragic acid, and behenic acid, and examples of metals include zinc, calcium, lithium, and aluminum.
Examples thereof include barium, potassium and magnesium.

Among these, metal salts of stearic acid are preferable, and specific examples thereof include zinc stearate, calcium stearate, lithium stearate, aluminum stearate, barium stearate, magnesium stearate and the like.

The amount of the higher fatty acid metal salt compounded is 0.01 to 0.5 part by weight, preferably 0.02 to 0.3 part by weight, based on 100 parts by weight of the polyamide. 0.0
If it is less than 1 part by weight, good screw biting stability cannot be obtained, and if it is more than 0.5 part by weight, the generated gas at the time of melting the composition is increased and the smoothness of the surface of the molded product is deteriorated due to silver generation or the like. To do.

In the polyamide resin composition of the present invention, it is preferable that the layered silicate is uniformly dispersed in the polyamide resin as the matrix at the level of a single layer.
The state of being uniformly dispersed at the level of a single layer means that the layered silicate is in the state of a single layer to 10 layers and is dispersed in the entire matrix resin without secondary aggregation. This state can be confirmed by cutting a section from the polyamide resin composition and observing it with an electron microscope.

In addition to the above-mentioned swelling layered silicate, the polyamide resin composition of the present invention may further contain an inorganic filler for the purpose of imparting strength and rigidity. The inorganic filler is not particularly limited, and may be a plate-shaped, rod-shaped, spherical, or other non-fibrous inorganic filler, or a fibrous or needle-shaped inorganic filler. Non-fibrous inorganic fillers include wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide. , Metal oxides such as iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, glass beads , Inorganic beads such as ceramic beads, boron nitride, silicon carbide and silica, which may be hollow,
Furthermore, it is possible to use two or more of these inorganic fillers in combination.

The inorganic filler may be pretreated with a coupling agent having a reactive functional group before use.
It is preferable in the sense of obtaining better mechanical strength. Examples of such coupling agents include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

Further, in the polyamide resin composition of the present invention, various known additive components within a range not impairing the object of the present invention, for example, impact modifiers such as various elastomers, crystal nucleating agents, anti-coloring agents and hinders. Antioxidants such as dephenol and hindered amine, epoxy compounds, plasticizers,
Additives such as lubricants, weathering agents and colorants can be added.

The method for producing the polyamide resin composition of the present invention is not particularly limited, and (B) the swelling layered silicate at any time before (A) the polymerization of the polyamide resin, during the polymerization, or after the polymerization. The compound (E) higher fatty acid metal salt selected from the compound (C) copper compound (D) aliphatic amide, fatty acid and its derivative may be added. A particularly preferred method is (A) a high-grade compound (E) selected from the group consisting of (B) a swellable layered silicate after polymerization of a polyamide resin, (C) a copper compound, (D) an aliphatic amide, and a derivative thereof. This is a method of melt-kneading a fatty acid metal salt. In addition,
It is also preferable that the higher fatty acid metal salt (E) is externally added at the time of molding.

The melt-kneading method is not particularly limited as long as mechanical shearing can be performed in a molten state of the polyamide resin. The treatment method may be either a batch method or a continuous method, but a continuous method capable of continuous production is preferable from the viewpoint of productivity. The kneading device used is not particularly limited, but an extruder, particularly a twin-screw extruder is preferably used in terms of productivity. Further, for the purpose of removing water generated during melt-kneading and low-molecular-weight volatile components, it is also preferable to use a melt-kneader equipped with a vent port for suction under reduced pressure. When a twin-screw extruder is used, (A) a polyamide resin, (B) a swellable layered silicate, (C) a copper compound, and (D) a compound selected from aliphatic amides, fatty acids and their derivatives. (E) A method in which the higher fatty acid metal salt is mixed in advance with a blender or the like, and the mixture is fed from the feed port of the extruder, or the components (A) and (C) are fed from the feed port on the upstream side of the extruder. However, there is no particular limitation on the method of supply such as the method of supplying the component (B), the component (D) and the component (E) from the downstream feed port. The screw arrangement of the extruder is also not particularly limited, but a kneading zone is preferably provided in order to finely disperse the layered silicate.

The polyamide resin composition of the present invention can be molded into a molded product by a known method. At that time, the polyamide resin composition of the present invention may be used in the form of a masterbatch. That is, as an example, (A) a part of polyamide resin, (B) swelling layered silicate, (C) copper compound, (D) compound selected from aliphatic amide, fatty acid and its derivative, and (E) Examples thereof include a method in which a master batch pellet made of a higher fatty acid metal salt and the rest of the pellets of the polyamide resin (A) are mixed and melt-molded to form a directly molded product. Specific examples of the molding method include known molding methods such as injection molding, extrusion molding and blow molding. The obtained molded product exhibits a high flexural modulus with a small amount of filler and is particularly excellent in creep resistance, and is suitable for various engineering parts and structural materials.

Examples of its specific use are various gears, various cases, sensors, connectors, sockets, resistors,
Relay case switch coil bobbin, housing, electrical and electronic parts such as computer related parts,
Households represented by VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, lighting equipment, refrigerators, air conditioners, typewriters, word processors, office electrical appliance parts, oilless bearings, stern bearings, underwater bearings. Various bearings, motor parts, lighters, typewriters, various bolts and nuts, electric tool housings, mechanical parts such as wheels for bicycles, tricycles, snowmobiles, alternator terminals, alternator connectors, IC regulators, light deer Potentiometer base, various valves such as exhaust gas valves, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body Carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, air conditioner thermostat base, heating warm air flow control valve, radiator holder brush holder. , Water pump impeller, Turbine vane, Wiper motor related parts, Dust distributor, Starter switch, Starter relay, Wire harness connector, Window washer nozzle, Air conditioner panel switch board, Fuel related electromagnetic valve coil, Fuse connector, Horn terminal , Electric component insulation board, step motor rotor, lamp socket, lamp reflector, lamp housing Automobile / vehicle-related parts such as gears, brake pistons, solenoid bobbins, engine oil filters, ignition cases, relay boxes, junction boxes, wheel caps, clips, fasteners, engine covers, cylinder head covers, timing belt covers, radiator tanks, housing, etc. Interior and exterior parts, structural materials, underfloor supports, building materials such as sash parts, and furniture related parts such as chair legs.

[0048]

The present invention will be described in more detail with reference to the following examples. Evaluation items and measurement method Polymerization degree of polyamide resin: Determined as relative viscosity measured at a concentration of 1% by weight at 25 ° C in 98% concentrated sulfuric acid.

Flexural Modulus: Evaluated according to ASTM D790. The test piece size was a 1/2 inch × 5 inch × 1/4 inch rod-shaped test piece.

Creep property test: ASTM No. 1 test piece with a thickness of 1/8 inch was used at 100 ° C. and a load of 20 M.
The amount of tensile creep strain after 100 hours at Pa was measured.

Surface appearance: A 80 mm × 80 mm × 3 mm square plate was molded by injection molding, and the surface of the molded product was visually observed to give the surface appearance. Judgment is that the fluorescent lamp on the ceiling is copied on the surface of the square plate, the shape of the fluorescent lamp can be clearly observed as `` ○ '', the shape of the outline is observable `` △ '', no observation at all, Alternatively, a product having silver or a flow mark on the surface of the molded product was marked with "x".

Example 1 Na-type montmorillonite (cation exchange capacity (hereinafter CE
It may be abbreviated as C) 85 meq / 100 g) 100 g
Was stirred and dispersed in 10 liters of warm water, and 36 g of benzyldimethylstearyl ammonium chloride (BDMS: carbon number 27) (1.0 to the cation exchange capacity was added thereto).
2 liters of warm water in which 2 times) was dissolved was added and stirred for 1 hour. The generated precipitate was filtered off and washed with warm water. The washing and filtering operations were repeated 3 times, and the obtained solid was vacuum dried at 80 ° C. to obtain a dry swellable layered silicate. This swellable layered silicate was added to 100 parts by weight of nylon 66 resin having a relative viscosity of 2.9 so that the amount of inorganic ash was 0.5 parts by weight, and 0.02 part by weight of cuprous iodide and After blending 0.03 parts by weight of potassium iodide and 0.3 parts by weight of ethylenebisstearylamide with a tumbler mixer, melt kneading with a PCM-30 type twin-screw extruder (Ikegai) having a cylinder temperature of 280 ° C. Then, a resin composition was obtained.
The obtained composition was pelletized, vacuum dried at 80 ° C. for 10 hours, and calcium stearate was added and mixed in an amount of 0.03 parts by weight with respect to 100 parts by weight of the polyamide resin at the time of molding. Injection molding was performed at 280 ° C and a mold temperature of 80 ° C to obtain a test piece. Table 1 shows the evaluation results of mechanical properties and surface appearance.

Example 2 Nylon 66 and a swellable layered silicate, a fatty acid compound and a higher fatty acid metal salt were melt-kneaded in the same manner as in Example 1 except that the compounding amount of the swellable layered silicate was 1 part by weight. Then, after obtaining the resin composition, molding and evaluation were performed. The results are shown in Table 1.

Example 3 A polyamide resin composition was obtained in the same manner as in Example 2 except that the addition amount of cuprous iodide was 0.05 parts by weight, and then molding and evaluation were performed. The results are shown in Table 1.

[0055]

[Table 1] Comparative Example 1 Nylon 66 and a swelling layered silicate, a copper compound, and a higher fatty acid metal salt were melt-kneaded in the same manner as in Example 2 except that the fatty acid compound was not added, and a resin composition was obtained, followed by molding and An evaluation was made. The results are shown in Table 2.

Comparative Example 2 Nylon 66 was melt-kneaded with a copper compound, a fatty acid compound and a higher fatty acid metal salt in the same manner as in Example 2 except that the swelling layered silicate was not added, and a resin composition was obtained. Molding
An evaluation was made. The results are shown in Table 2.

Comparative Example 3 Nylon 66 and a swelling layered silicate, a fatty acid compound, and a higher fatty acid metal salt were melt-kneaded in the same manner as in Example 2 except that a copper compound was not added, to obtain a resin composition. , Molding and evaluation were performed. The results are shown in Table 2.

Comparative Example 4 Nylon 66 and a swelling layered silicate, a copper compound, and the like as in Example 2 except that the higher fatty acid metal salt was not added.
The fatty acid compound was melt-kneaded to obtain a resin composition, which was then molded and evaluated. The results are shown in Table 2.

[0059]

[Table 2]

[0060]

EFFECTS OF THE INVENTION According to the present invention, a resin composition having excellent mechanical properties can be easily obtained, and even if the amount of inorganic ash is small, the flexural modulus and creep properties are excellent in rigidity, and the surface appearance of a molded product is excellent. It is suitable for molded products such as automobile parts, electric / electronic parts, building materials, furniture, daily sundries, etc.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/20 C08K 5/20 F term (reference) 4F071 AA54 AB15 AB26 AC04 AC09 AF13 AF52 AH03 AH12 AH17 AH19 4J002 CL031 DD077 DG057 DH047 DJ006 EG039 EG047 EG049 EG077 EP018 FA016 FB086 FB096 FD016 FD207 FD208 FD209 GM00 GQ00

Claims (5)

[Claims] Claims: (A) 100 parts by weight of polyamide containing (A) polyhexamethylene adipamide as a main constituent,
(B) 0.05 to 30 parts by weight of swellable layered silicate, (C)
0.001 to 0.5 part by weight of a copper compound, 0.01 to 0.5 part by weight of a compound selected from (D) an aliphatic amide, a fatty acid and a derivative thereof, and (E) a higher fatty acid metal salt.
A polyamide resin composition comprising 01 to 0.5 part by weight. 2. The polyamide resin composition according to claim 1, wherein the copper compound (C) is a monovalent copper halide compound. 3. The polyamide resin composition according to claim 1 or 2, wherein the compound (D) is an aliphatic amide. 4. The polyamide resin composition according to claim 1, wherein the higher fatty acid metal salt (E) is a stearic acid metal salt. 5. A molded product obtained by molding the polyamide resin composition according to any one of claims 1 to 4.