JPH0376754A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which does not corrode coexistent metals, such as copper (alloy), in a high temperature environment and has excellent heat resistance by incorporating a copper halide, an alkali metal halide, and a specified thiazole compound each in a specified amount into a polyamide resin. CONSTITUTION:The title composition is prepared by mixing 100 pts.wt. polyamide resin (e.g. polyhexamethyleneadipamide) with 0.001-1 pt.wt. copper halide (e.g. CuI), 0.01-5 pts.wt. alkali metal halide (e.g. KI), and 0.005-5 pts.wt. thiazole compound selected from compounds of formulas I to IX [wherein R1 to R7 are each H, phenyl, benzyl, alkyl, nitro, (alkyl)amino, carboxyl (except N- substituted carboxyl), hydroxyl, alkoxy, aryl, phenoxy, halogen, anilino, tolyl or benzyloxy; A is a single bond or a group of any one of formulas X to XII].

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyamide resin composition having excellent heat resistance. More specifically, the present invention relates to a heat-resistant polyamide resin composition that has an excellent antirust effect on polyamide resin molded products used in high-temperature environments and metal materials coexisting therewith.

<Prior Art> Polyamide resins are used in various fields such as automobile parts and mechanical parts due to their good mechanical properties, moldability, and chemical resistance.

Among these, electrical and electronic components used in the automobile field are often used in high-temperature environments, such as connectors in engine compartments, and are therefore required to have heat resistance.

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-50-84).
61, JP-A-56-4651), and it is also known to add hindered phenol compounds and thiazole compounds (for example, JP-A-50-87447).
No. 1, JP-A-49-53944, JP-A-53-
88857], it is also known to add a thiazole compound for another purpose (for example, Japanese Patent Application Laid-Open No. 52-3204).
Publication No. 6).

<Problem to be solved by the invention> However, when using conventional heat-resistant polyamide resin to which copper halide and potassium halide are added as a material for connectors, which are one of the electrical and electronic parts for automobiles, the environment in which it is used is When the connector is at high temperature, the metal materials used in the connector and pair, especially the connection terminals made of copper and prepared alloys, are corroded by the corrosive gas generated from the polyamide resin, which not only causes poor contact but also shortens the life of the terminals. It became clear that it would be significantly shorter. In today's highly developed electronic control equipment, incorrect display and malfunction due to poor contact are commonplace! This is a very serious safety problem in 1IitL applications.

Therefore, the present inventors conducted intensive studies to obtain a heat-resistant polyamide resin that has excellent heat resistance stability and does not corrode metal materials, especially copper and copper alloys, even when used in high-temperature environments. The present invention was accomplished by discovering that the above object can be achieved by adding an organic compound in combination with copper halide and alkali halide.

Means for Solving the Problems> That is, the present invention provides (a) halogenated f! with respect to 100 parts by weight of polyamide resin. 40.001 to 1 part by weight, (b)
The object of the present invention is to provide a polyamide resin composition containing 0.01 to 5 parts by weight of an alkali halide and (c) 0.005 to 5 parts by weight of a thiazole compound selected from the following general formulas (1) to 0.

(V) (Vl) (I> (If) (■) (■> (IV) [Formula ■, ■, O, ■, ■, ■, 0.@, R+, R2 in ω
, R3, R4, R5, R6, R7 are hydrogen atoms, phenyl groups, benzyl groups, alkyl groups, nitro groups, amino groups, carboxyl groups (excluding N substitution), hydroxyl groups, alkoxy groups, aryl groups, phenoxy groups, alkyl A group such as an amino group, no\rokene, anilino group, tolyl group, benzyloxy group, and R1, R2, R3, R4, Rs, R
6. R7 may be the same group or different groups, and groups other than hydrogen atoms may be substituted with other groups.

The polyamide used in the present invention is a polyamide whose main components are an amino acid, a lactam or a diamine, and a dicarboxylic acid. Specific examples of the components include lactams such as ε-caglolactam, enantlactam, and ε-laurolactam, amino acids such as ε-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, tetramethylene diamine, hexamethylene diamine. ,
undecamethylene diamine, dodecamethylene diamine,
2.2.4- / 2.4.4 Trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, P-xylylenediamine, 1.3-
Bis-aminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane,
Diamines such as inphorondiamine, adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, 1
．． Dicarboxylic acids include 4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and dimer acid. These components are subjected to polymerization either alone or in the form of a mixture of two or more, and both the polyamide homopolymer and copolymer thus obtained can be used in the present invention. Polyamides particularly useful in the present invention include polycapramide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (
Nylon 610), polyundecaneamide (Nylon 1
1), polydodecanamide (nylon 12), polyhexamethylene adipamide/hexamethylene terephthalamide copolymer (nylon 66/6T), polycapramide/
Polyhexamethylene adipamide copolymer (nylon 6/66) and mixtures of these polyamides.

There is no particular restriction on the degree of polymerization of the polyamide used here, and any polyamide having a relative viscosity of 1% concentrated sulfuric acid solution at 25° C. within the range of 1.5 to 5.0 can be used. In addition, the polyamide resin has terminal groups of monocarboxylic acid compounds and/or dicarboxylic acid compounds, or monoamine compounds and/or diamine compounds. ! The terminal group concentration may be adjusted by adding the above to the polyamide at any stage.

The copper halide used in the present invention includes copper iodide,
Cuprous chloride, cupric chloride, cupric chloride, cupric chloride, cupric 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 halides added is 0.001 to 1 part by weight per 100 parts by weight of the polyamide resin, preferably O, OO5 to 0.5 parts by weight.

If the amount added is less than 0.001 part by weight, the heat resistance effect will be insufficient, which is undesirable, and even if the amount added is more than 1 part by weight, the heat resistance of the resulting polyamide resin composition will not be further improved. do not have.

The alkali halide used in the present invention is N P
I4, Ia, Ila metal elements, Ilb, l11a,
It is a compound of amphoteric metal elements IVa, Va, and Vla and halogen elements, and includes NH4, potassium, calcium, strontium, cesium, sodium, barium, beryllium, magnesium, lithium, rubidium, zinc, aluminum, gallium, isodium, thallium, germanium. , antimony, bismuth, boronium, and lead chlorides, iodides, fluorides, and bromides are preferably used.

These alkali halides may be used alone or in combination of two or more.The amount of alkali halides added is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight!
I! It is a quantity part. If the amount added is less than 0.01 part by weight, the heat resistance effect due to the synergistic effect with copper halide will be insufficient, which is not preferable, and even if the amount added is more than 5 parts by weight, the heat resistance of the polyamide resin composition obtained will be reduced. There is no improvement in gender.

The thiazole compounds represented by the general formulas 〇 to ① used in the present invention include thiazole, isothiazole, benzothiazole, 1,2.3-thiadiazole, 1,2.
5-thiadiazole, 1,3゜4-thiadiazole, 1
, 2.4-thiadiazole, 2.2-monobithiazolyl,
4.4-1dimethyl-2゜2-1bithiazolyl, 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-
Benzyl aminothiazole, 2-benzoyl-5-methylthiazole, -l, bis(4-methyl-2-thiazolyl) sulfide, 2-(p-aminobenzenesulfonamido)thiazole, 2-acetamidothiazole, 2-
Acetamido-4-methylthiazole, naphtho(1,2
) Thiazole, 2.2-1 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, chloride 2°3,4
-) dimethylthiazolium, N-benzyl-2 bromide,
4-dimethylthiazolium, 4-methyl-N-phenylthiazolium iodide, N-ethyl-4-methylthiazolium iodide, 2,2-1bithiazolyl, 4,4゛-dimethyl-2,2 -bithiazolyl, 5.5--(β-oxyethyl>-4,4°-dimethyl-2,2-bithiazolyl, biazolyl, bis(2-thiazolyl)alkanes,
4.4-1-bithiazolyl, 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-chloromethylthiazole, 4-
Chlormethyl-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-bromo-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-
Chlorthiazole, 2-amino-5-chlorothiazole, 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
-thiazole dicarboxylic acid, 4.5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic 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-benziisothiazole, benzoselenazole, 2-methylbenzoselenazole, 2 -phenylbenzoselenazole, 2,2-1 dithiobis-benzothiazole, N-cyclohexylbenzothiazolylsulfenamide, N-oxydiethylenebenzothiazylsulfenamide, and the like.

In particular, benzothiazole derivatives are preferably used.

The thiazole compound may be used alone or in combination of two or more kinds.The amount of the thiazole compound added is 0.
0.05 to 5 parts by weight, preferably 0.05 to 3 parts by weight. If the amount added is less than 0.005 parts by weight, the rust preventive effect on metal materials, especially copper and copper alloys, will be insufficient, which is undesirable, and even if the amount added is more than 5 parts by weight, the rust preventive effect obtained will be improved. It will not be done.

The copper halide, alkali halide, and thiazole compound of the present invention can be added to the polyamide resin as they are, but the copper halide can also be added after forming a complex salt with the thiazole compound in advance. ,
A preferred embodiment of the present invention includes the combined use of a complex salt of halogenated steel and a thiazole compound, the thiazole compound used to form the complex salt, and another thiazole compound, and the addition of another heat-resistant agent (for example, a phenol derivative). It will be done. There are no particular restrictions on the timing of addition of the halogenated steel, the alkali halide, and the thiazole compound. That is, it can be added at any time before, during, or after polymerization, and triblend and melt kneading using an extruder can be effectively used as addition methods after polymerization.

Each additive may be added at the same time at any stage, or may be added separately at any stage.

In addition, the polyamide resin composition of the present invention may contain other additives to the extent that the effects of the present invention are not significantly impaired, such as lubricants, antistatic agents, colorants, crystal nucleating agents, fillers, reinforcing materials, heat resistant agents, A suitable amount of a light stabilizer etc. can be added at any stage.

<Examples> Next, the present invention will be explained in detail by giving Examples and Comparative Examples.

Comparative Example 1 100 parts by weight of hexamethylenediamine adipate,
A mixture consisting of 25 parts by weight of water, 0.03 parts by weight of #1 iodide, and 0.5 parts by weight of potassium iodide was placed in a polymerization kettle, and the atmosphere was replaced with nitrogen. Polymerization was carried out according to the usual polymerization method, and the mixture was spun into strands from the polymerization kettle. It was taken out and cut with a cutter to obtain a pellet-shaped polyamide resin composition. This beret is 80-1
Vacuum drying was performed at 00° C. for 16 hours or more. dried beret 2
0 g was placed in a 50 ml Erlenmeyer flask with a stopper, and a copper plate and a brass plate with degreased surfaces were placed on top of the pellet, and the pellet was tightly stoppered. This Erlenmeyer flask was placed in a gear oven controlled at 150° C., and after continuous heat treatment for 300 hours, it was taken out and the surface condition was compared with that of an untreated copper plate and a brass plate, and the results shown in Table 1 were obtained.

Example 1 0.1 parts by weight of benzothiazole was further added to the composition of Comparative Y41, and polymerization and evaluation were carried out in the same manner as in Comparative Example 1, and the results shown in Table 1 were obtained.

The corrosion resistance of copper and brass was significantly improved compared to 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 changed to 0.3 parts by weight, and the results shown in Table 1 were obtained.

Examples 3 to 5 Polymerization and evaluation were performed in the same manner as in Comparative Example 1, except that benzoic acid, hexamethylene diamine, and adipic acid were added as end group concentration regulators to the composition of Example 1, and the results in Table 1 were obtained. Obtained.

Examples 6 to 17 Mixtures adjusted to the compositions shown in Table 2 were placed in a polymerization pot and polymerized and evaluated in the same manner as in Comparative Example 1 to obtain the results shown in Table 2. It was found that the corrosion resistance of copper and brass was significantly improved compared to the comparative example, and all of these polyamide resin compositions had a high rust prevention effect.

Examples 18-23 The triazole compounds shown in Table 4 were added to the polyamide resin composition obtained in Comparative Example 1 by triblending and melt-kneading, and evaluation was performed in the same manner as in Comparative Example 1, and the results shown in Table 3 were obtained. Obtained.

<Effects of the Invention> A polyamide resin composition obtained by adding one or more thiazole compounds to a polyamide composition consisting of polyamide, copper halide, and alkali halide as in the present invention can be used in a particularly high temperature environment. It has become possible to obtain a polyamide resin composition with good heat resistance and an excellent rust-preventing effect on metal materials, especially copper and copper alloys, which coexist with molded articles formed from the polyamide resin composition. Ta.

Claims (1)

[Scope of Claims] Based on 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) represented by the following general formula. A polyamide resin composition containing 0.005 to 5 parts by weight of a thiazole compound selected from (I) to (IX). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VI) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VII) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼(VIII) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IX) [Formula (I), (II), (III), (IV), (V), (V
I), (VII), (VIII), (IX) R_1, R_2, R
_3, R_4, R_5, R_6, R_7 are hydrogen atoms, phenyl groups, benzyl groups, alkyl groups, nitro groups, amino groups, carboxyl groups (excluding N substitution) hydroxyl groups,
R_1, R_2, R_3, R_
4, R_5, R_6, R_7 may be the same group,
Alternatively, they may be separate groups. Groups other than hydrogen atoms may be substituted with other groups. A is a single bond, -CnH_2n-, a bonding group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ]