JPH0778162B2 - Polyamide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a polyamide resin composition having excellent heat resistance. More specifically, the present invention relates to a polyamide resin molded product used in a high temperature environment and a heat resistant polyamide resin composition having an excellent rust preventive effect on a metal material coexisting therewith.

<Prior Art> Polyamide resins are used in various fields such as automobile parts and machine parts because of their good mechanical properties, molding processability, and chemical resistance. Among them, in the electric / electronic parts used in the automobile field, the environment used, such as the connector in the engine room, is often high temperature, and heat resistance is required.

It is known to add copper halides and potassium halides for the purpose of improving the heat resistance of polyamide resins (for example, JP-A-49-53944, JP-A-50-8461 and JP-A-56-56). 4651 publication). It is also known to add a hindered phenol compound and a thiazole compound (for example, JP-A-50-87447 and JP-A-49-539).
44, JP-A-53-88857). It is also known to add a thiazole compound for another purpose (for example, JP-A-52-32046).

<Problems to be Solved by the Invention> However, when a conventional heat-resistant polyamide resin to which copper halide and potassium halide are added is used as a material for a connector which is one of electric and electronic parts for automobiles, its working environment is When the temperature is high, the metallic materials used in pairs with the connector, especially the connecting terminals made of copper and copper alloys, are corroded by the corrosive gas generated from the polyamide resin, which not only causes contact failure but also prolongs the life of the terminals. It became clear that it would be significantly shortened. At present, when electronic control devices are highly developed, erroneous display and malfunction due to poor contact are extremely serious safety problems in automobile applications.

Therefore, the present inventors have conducted extensive studies to obtain a heat-resistant polyamide resin that does not corrode metal materials, particularly copper and copper alloys even under use conditions in a high-temperature environment, which are excellent in heat resistance stability. The inventors have found that the above object can be achieved by adding an organic compound together with a copper halide and an alkali halide, and reached the present invention.

<Means for Solving the Problems> That is, the present invention relates to (a) 0.001 to 1 part by weight of copper halide, (b) 0.01 to 5 parts by weight of alkali halide, and (c) with respect to 100 parts by weight of polyamide resin. Another object of the present invention is to provide a polyamide resin composition containing 0.005 to 5 parts by weight of a thiazole compound selected from (I) to (IX) in the following general formula.

[Formulas (I), (II), (III), (IV), (V), (V
I), (VII), (VIII), (IX) in R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ and R ₇ are hydrogen atom, phenyl group, benzyl group, alkyl group, nitro group, amino group, carboxyl group (excluding N-substituted) hydroxyl group, alkoxy group, aryl group,
A group such as a phenoxy group, an alkylamino group, a halogen, an anilino group, a tolyl group, and a benzyloxy group, which is R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be the same group or different groups. Other groups except a hydrogen atom may be substituted with another group.

A is a single bond, -CH ₂ -, Is a bonding group represented by. The polyamide used in the present invention is a polyamide containing amino acids, lactams or diamines and dicarboxylic acids as main constituent components. Specific examples of the constituents include ε-caprolactam, enantolactam, lactams such as ε-laurolactam, ε-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and other amino acids, tetramethylenediamine, hexamethylenediamine. , Undecamethylenediamine, dodecamethylenediamine, 2,2,
4- / 2,4,4-trimethylhexamethylenediamine, 5-
Methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p
-Aminocyclohexylpropane, diamine such as isophoronediamine, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalene Dicarboxylic acid,
There are dicarboxylic acids such as dimer acid. These constituents are subjected to the polymerization in the form of a single kind or a mixture of two or more kinds, and any of the polyamide homopolymer and the copolymer thus obtained can be used in the present invention. Polyamides particularly useful in the present invention include polycapramide (nylon 6) and polyhexamethylene adipamide (nylon 6).
6), polytetramethylene adipamide (nylon 46),
Polyhexamethylene sebacamide (nylon 610), polyundecane amide (nylon 11), polydodecane amide (nylon 12), polyhexamethylene adipamide / hexamethylene terephthalamide copolymer (nylon 66/6)
T), polycapramide / polyhexamethylene adipamide copolymer (Nye copolymer (nylon 6/66) and mixtures of these polyamides.

The degree of polymerization of the polyamide used here is not particularly limited, and the relative viscosity of a 1% concentrated sulfuric acid solution at 25 ° C is 1.
Any material within the range of 5 to 5.0 can be used. The polyamide resin has a terminal group whose terminal group concentration is adjusted by adding one or more of a monocarboxylic acid compound and / or a dicarboxylic acid compound or a monoamine compound and / or an amine compound to the polyamide at any stage. Good.

Examples of the copper halide used in the present invention include copper iodide,
Cuprous breath, cupric breath, cuprous chloride, cupric chloride, cuprous fluoride, cupric fluoride and the like are preferably used.
These copper halides may be used alone or in combination of two or more. The amount of copper halide added is 0.001 to 1 part by weight, preferably 100 parts by weight of the polyamide resin.
It is 0.005 to 0.5 parts by weight. If the addition amount is less than 0.001 part by weight, the heat resistance effect becomes insufficient, which is not preferable, and even if the addition amount is more than 1 part by weight, the heat resistance of the obtained polyamide resin composition will not be further improved.

The alkali halide used in the present invention includes NH4, I
a, IIa metal element, IIb, IIIa, IVa, Va, a compound of an amphoteric metal element of Vla and a halogen element, NH4, potassium, calcium, strontium, cesium, sodium, barium, beryllium, magnesium, lithium,
Rubidium, zinc, aluminum, gallium, isodymium, thallium, germanium, antimony, bismuth,
Polonium, lead chloride, iodide, fluoride and bromide are preferably used. These alkali halides may be used alone or in combination of two or more.
The amount of alkali halide added is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight. If the addition amount is less than 0.01 parts by weight, the heat resistance effect due to the synergistic effect with copper halide becomes insufficient, which is not preferable. Even if the addition amount is more than 5 parts by weight, the heat resistance of the obtained polyamide resin composition is No further improvement.

The thiazole compounds represented by the general formulas (I) to (IX) used in the present invention include thiazole, isothiazole, benzothiazole, 1,2,3-thiodiazole, 1,2,5
-Thiadiazole, 1,3,4-thiadiazole, 1,2,4-thiadiazole, 2,2'-bithiazolyl, 4,4'-dimethyl-2,2'-bithiazolyl, benzothiazole, 1,2-benzothiazole, 2,1-benzothiazole, 1,2,3-oxathiazole, 2,1,3-benzoxathiazole, 2-methylthiazole, 4-methylthiazole, 5-methylthiazole, 2,4-dimethylthiazole, 2, 5-dimethylthiazole, 4,5-dimethylthiazole, 2,4,5-trimethylthiazole, cyclohexenothiazole, 1,4-bis (4-methyl-2-thiazolyl) benzene, p, p'-bis (4- Methyl-2-thiazolyl) biphenyl), 2-
Benzylaminothiazole, 2-benzoyl-5-methylthiazole, ole, bis (4-methyl-2-thiazolyl) sulfide, 2- (p-aminobenzenesulfonamide) thiazole, 2-acetamidothiazole, 2-
Acetamide-4-methylthiazole, naphtho [1,2]
Thiazole, 2,2'-dithiobis-benzothiazole,
2-ethylthiazole, 2-phenylthiazole, 4-
Phenylthiazole, 5-phenylthiazole, 5-
(P-Chlorophenyl) thiazole, 2-methyl-4-
Phenylthiazole, 4-methyl-5-phenylthiazole, 5-methyl-4-phenylthiazole, 4,5-diphenylthiazole, 2-methyl-4,5-dimethylthiazole, 4-methyl-2-styrylthiazole, 2- Methylcyclohexenothiazole, 2,3,4-trimethylthiazolium chloride, N-benzyl-2,4-dimethylthiazolium bromide, 4-methyl-N-phenylthiazolium iodide, N-ethyl iodide -4-methylthiazolium, 2,
2'-bithiazolyl, 4,4'-dimethyl-2,2'-bithiazolyl, 5,5 '-(β-oxyethyl) -4,4'-dimethyl-2,2'-bithiazolyl, biazolyl, bis (2- Thiazolyl) alkanes, 4,4'-bithiazolyls, bis (4-thiazolyl) methane, 2,4'-bithiazolyl, 2,
5'-bithiazolyl, 4,5'-bithiazolyl, 5,5-bithiazolyl, polythiazoles, 2-chlorothiazole,
2-bromothiazole, 2-bromo-5-methylthiazole, 2-bromo-4,5-dimethylthiazole, 2,5-dibromothiazole, 5-bromothiazole, 2-chloro-4-methylthiazole, 4-chloro Methylthiazole, 4-chloromethyl-2-methylthiazole, 4-chloromethyl-2-phenylthiazole, 2-oxy-4
-Methylthiazole, 2-methoxy-4-methylthiazole, 2-oxy-5-methylthiazole, 5-ethoxy-2-methylthiazole, 5-methoxy-4-methylthiazole, 2-oxy-4-methyl-5- Thiazolecarboxylic acid, 2-oxy-4,5-diphenylthiazole, 2-oxymethyl-4-methylthiazole, 5-oxymethylthiazole, 5-oxymethyl-4-methylthiazole, 5- (α-oxyethyl) -4 -Methylthiazole, 5- (β-oxyethyl) -4-methylthiazole, 5- (γ-oxypropyl) -4-methylthiazole, 2-nitrothiazole, 4-methyl-2-nitrothiazole, 5-methyl-2 -Nitrothiazole, 5
-Brom-2-nitrothiazole, 2-bromo-5-nitrothiazole, 2-aminothiazole, 2-amino-
4-methylthiazole, 2-amino-5-methylthiazole, 2-amino-4,5-dimethylthiazole, 2-amino-4-phenylthiazole, 2-amino-5-phenylthiazole, 2-amino-4,5 -Diphenylthiazole, 2-anilino-4-methylthiazole, 2-anilino-4,5-, diphenylthiazole, 2-amino-4
-Chlorothiazole, 2-amino-5-chlorthiazole, 2-aminomethylthiazole, 4-aminomethylthiazole, 2-hydrazino-4-phenylthiazole,
2-amino-5- (p-aminophenyl) thiazole,
2,4-diamino-5-phenylthiazole, 5-acetamidothiazole, 5-amino-2-oxy-4-phenylthiazole, 5-amino-2-methylaminothiazole, 2-acetylthiazole, 2-thiazolecarboxylic acid, 4-methyl-2-thiazolecarboxylic acid, 2,4-
Thiazoledicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, thiazoline derivative, thiazolone derivative, thiazolidine derivative, thiazolidone derivative, 2-methylbenzothiazole, 3-ethyl-2-iodide Methylbenzothiazolium, 2-methylbenzothiazole, 2-phenylbenzothiazole, 2- (p-aminophenyl) -6-methylbenzothiazole, 2-chlorobenzothiazole, 2-
Oxybenzothiazole, 2-ethoxybenzothiazole, 2-oxy-5-methylbenzothiazole, 3,5-
Dimethyl-2-benzothiazolone, 3-ethyl-2-benzothiazolone, 3-phenyl-2-benzothiazolone, 4-oxybenzothiazole, 5-oxy-2-methylbenzothiazole, 6-oxybenzothiazole,
2-nitrobenzothiazole, 5-nitrobenzothiazole, 2-aminobenzothiazole, 2-amino-6-
Methylbenzothiazole, 2-anilinobenzothiazole, 5-aminobenzothiazole, 2,5-diaminobenzothiazole, 2-benzothiazolecarboxylic acid, 4-
Methyl-2-benzothiazolecarboxylic acid, 2,2'-dibenzothiazolyl sulfide, benzothiazoline, 2-
Phenylbenzothiazoline, 3-methyl-2-methylenebenzothiazoline, isothiazole, 2,1-benzisothiazole, benzoselenazole, 2-methylbenzoselenazole, 2-phenylbenzoselenazole, 2,2 '
-Dithio-bis-benzenazole, N-cyclohexylbenzothiazolylsulfenamide, N-oxydiethylenebenzothiazylsulfenamide and the like.

Particularly, a benzothiazole derivative is preferably used.

The thiazole compounds may be used alone or in combination of two or more. Addition amount of thiazole compound is 0.00
It is 5 to 5 parts by weight, preferably 0.05 to 3 parts by weight. If the addition amount is less than 0.005 parts by weight, it is not preferable because the anticorrosion effect of metal materials, particularly copper and copper alloys is insufficient.
Even if the added amount is more than 5 parts by weight, the rust preventive effect obtained is not improved.

The copper halide, alkali halide, and thiazole compound of the present invention can be added as they are to the polyamide resin. Further, the copper halide may be added after forming a complex salt with the thiazole compound in advance, and the thiazole compound and the other thiazole compound used for the complex salt and the complex salt of the copper halide and the thiazole compound are used in combination, The addition of further heat-resistant agents (eg phenol derivatives) is included in a preferred embodiment of the invention. The timing of adding the copper halide, the alkali halide and the thiazole compound is not particularly limited. That is, it can be added before the polymerization, during the polymerization, or at any time after the polymerization. As the addition method after the polymerization, dry blending and melt kneading by an extruder can be effectively used.

Each additive may be added simultaneously at any stage or separately at any stage.

Further, the polyamide resin composition of the present invention, other additives to the extent that the effect of the present invention is not significantly impaired, that is, a lubricant, an antistatic agent, a colorant, a crystal nucleating agent, a filler, a reinforcing material,
A heat resistant agent, a light resistant agent, etc. can be added in an appropriate amount at any stage.

<Example> Next, the present invention will be described in detail with reference to Examples and Comparative Examples.

Comparative Example 1 Hexamethylenediamine adipate 100 parts by weight, water 2
A mixture consisting of 5 parts by weight, copper iodide 0.03 parts by weight and potassium iodide 0.5 part by weight is put in a polymerization kettle and after nitrogen substitution, polymerization is carried out according to a usual polymerization method, spun into strands from the polymerization kettle and cut with a cutter. A pelletized polyamide resin composition was obtained. The pellets were vacuum dried at 80-100 ° C for 16 hours or more. 20 g of the dry pellets were put in a 50 ml Erlenmeyer flask with co-columns, and a copper plate and a brass plate whose surface was degreased were placed on the pellets to close the columns. The Erlenmeyer flask was placed in a gear oven controlled at 150 ° C., and heat-treated continuously for 300 hours, and then read out. The surface condition was compared with that of an untreated copper plate and brass plate, and the results shown in Table 1 were obtained.

Example 1 0.1 part by weight of benzothiazole was further added to the composition of Comparative Example 1, polymerization and evaluation were carried out in the same manner as in Comparative Example 1, and the results shown in Table 1 were obtained. Corrosion of copper and brass was remarkably improved as compared with the comparative example.

Example 2 Polymerization and evaluation were carried out in the same manner as in Comparative Example 1 except that the amount of benzothiazole added in Example 1 was 0.3 part by weight, and the results shown in Table 1 were obtained.

Examples 3 to 5 Polymerization and evaluation were carried out in the same manner as in Comparative Example 1 except that benzoic acid, hexamethylenediamine and adipic acid were added to the composition of Example 1 as the terminal group concentration adjusting agent, and the results shown in Table 1 were obtained. Obtained.

Examples 6 to 17 The mixtures adjusted to have the compositions shown in Table 2 were placed in a polymerization kettle and polymerization and evaluation were carried out in the same manner as in Comparative Example 1 to obtain the results shown in Table 2. It was found that the corrosiveness of copper and brass was remarkably improved as compared with the comparative example, and all of these polyamide resin compositions had a high rusting effect.

Examples 18 to 23 To the polyamide resin composition obtained in Comparative Example 1, the triazole compound shown in Table 4 was added by dry blending and melt kneading, and the same evaluation as in Comparative Example 1 was carried out to obtain the results shown in Table 3. Obtained.

<Effects of the Invention> A polyamide resin composition obtained by adding one or more thiazole compounds to a polyamide composition composed of polyamide, copper halide, and alkali halide as in the present invention is used at high temperature. In, it becomes possible to obtain a heat-resistant polyamide resin composition having excellent rusting effect on metal materials coexisting with a molded article molded by the polyamide resin composition, particularly copper and copper alloys. It was

Claims (1)

[Claims] 1. To 100 parts by weight of polyamide resin, (a) 0.001 to 1 part by weight of copper halide, (b) 0.01 to 5 parts by weight of alkali halide, and (c) the following general formulas (I) to (I). A polyamide resin composition containing 0.005 to 5 parts by weight of a thiazole compound selected from IX). [Formulas (I), (II), (III), (IV), (V), (V
I), (VII), (VIII), (IX) in R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ and R ₇ are hydrogen atom, phenyl group, benzyl group, alkyl group, nitro group, amino group, carboxyl group (excluding N-substituted) hydroxyl group, alkoxy group, aryl group,
A group such as a phenoxy group, an alkylamino group, a halogen, an anilino group, a tolyl group, and a benzyloxy group, which is R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be the same group or different groups. Other groups except a hydrogen atom may be substituted with another group. A is a single bond, -CH ₂ -, Is a bonding group represented by. ]