JPH0376752A - 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 triazole compound each in a specified amount into a specified polyamide resin. CONSTITUTION:The title composition is prepared by mixing 100 pts.wt. polyamide resin (e.g. polyhexamethyleneadipamide) having a terminal amino group content of at most 6X10<-5>mol/g of the polymer 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. triazole compound (e.g. benzotriazole).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyamide resin composition having excellent heat resistance and improved coloration. More specifically, the present invention relates to a heat-resistant polyamide resin composition with improved coloring and excellent antirust effect on polyamide resin molded bodies 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, electric and electronic parts 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-50-1484).
No. 61, JP-A-56-4651).

It is also known to add a hindered phenol compound (e.g., JP-A-50-87447), and it is also known to add a triazole compound for another purpose (e.g., JP-A-51-66342). .

<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 by the polyamide resin, which not only causes poor contact but also shortens the life of the terminals. It has been found that the length can be significantly shortened. Nowadays, electronic control equipment is highly developed, and erroneous display and malfunction due to poor contact are extremely serious safety problems especially in automobile 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 has been achieved 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) for 100 parts by weight of a polyamide resin whose amino end group concentration is smaller than 6X10-5 (mol 7g polymer), (b) from 1 to 1 weight part of copper halide 01OO. (c) 0.01 to 5 parts by weight of an alkali halide; and (d) a triazole compound in an amount of 5 to 5 parts by weight of O, OO.

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 constituent components include lactams such as ε-caglolactam, enantlactam, and ω-laurolactam, amino acids such as ε-amitsukagulonic 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-bisaminomethylcyclohexane, 1.4 -Diamines such as bis-aminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, inphorondiamine, adipic acid, superric 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), and polytetramethylene adipamide (nylon 66).
Nylon 46>, polyhexamethylene adipamide (nylon 610), polyundecaneamide (nylon 11)
, polydodecaneamide (nylon 12), polyhexamethylene adipamide/hexamethylene terephthalamide copolymer (nylon 66/6T), polycabramide/polyhexamethylene adipamide copolymer (nylon 6/6)
6) and a mixture 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. Furthermore, it is desirable that the terminal amino group concentration of these polyamides is less than 6X10-5 (mol 7g polymer), and JP-A-51-66342 states that the terminal amino group concentration is 6X10-5 (mol 7g polymer) or more. Certain cases are described and methods for obtaining colored polyamide resins are described.

In applications, colored polyamide resin is undesirable because it significantly reduces the commercial value.
In order to reduce the size and improve the coloration, if necessary, one or more monocarboxylic acid compounds and/or dicarboxylic acid compounds can be easily added to the polyamide at any stage. Examples of carboxylic acid compounds include the following.

#Acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, isostearic acid, pelargonic acid, undecanoic acid, myristic acid, arachidic acid, behenic acid, Crotonic acid, lignoceric acid, oleic acid, elaidic acid, linoleic acid, linuric acid, monochloroacetic acid, cerotic acid, montanic acid, melisic acid, benzoic acid, oxalic acid,
Malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, citric acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, Terephthalic acid, isophthalic acid, hemimellitic acid, trimellitic acid, homophthalic acid, o, m and p-phenylene diacetic acid, 0-phenylene acetic acid-propionic acid, naphthalene dicarboxylic acid, dimer acid, monobromoacetic acid, monofluoroacetic acid, glycol Acid, lactic acid, pyruvic acid, oxalic acid, malic acid, tartaric acid, chiracolaic acid, naphthenic acid, toluic acid, phenylacetic acid, pt-butylbenzoic acid, cinnamic acid, chlorobenzoic acid, brombenzoic acid, ethoxybenzoic acid vP acid , mandelic acid, protocatechuic acid, vanillic acid, resorcinic acid, naphthoic acid, pyromellitic acid, and other carboxylic acids.

The copper halide used in the present invention includes iodized steel,
#1 bromide, cupric bromide, 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, and the amount of copper halides added is 0.001 to 1 part by weight per 100 parts by weight of the polyamide resin.
Preferably it is 5 to 0.5 parts by weight of O, OO.

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 NH4
, la, metal elements of Tl'a, mb, la, ■a, Va
, Via is a compound of an amphoteric metal element and a halogen element, and contains NH4, potassium, calcium, strontium,
Cesium, sodium, barium, beryllium, magnesium, lithium, rubidium, zinc, aluminum,
Chloride, iodide, fluoride, bromide, etc. of gallium, indium, thallium, germanium, antimony, bismuth, boronium, and lead 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. . If the amount added is less than O or Oi parts by weight, the heat resistance effect due to the synergistic effect with the halogenated steel will be insufficient, which is undesirable. Heat resistance is not further improved.

The triazole compound used in the present invention is 1.2
．． 3-triazole, 2H-1,2,3-triazole, 4H-1,2,4-1 riazole, IH-1,2,
4-triazole, 1.2.3.4-oxatriazole, 1.2.4.5-oxatriazole, 1,2.3
．． 4-thiatriazole, 1,2,4.5-thiatriazole, a triazole compound represented by the following general formula (■), Olo, 0 [wherein R-1R'', R'' is H, 7/l/#/l / group, cycloalkyl group, arylalkyl group, phenyl group, hydroxyl group, amino group, imino group, benzamide group,
A group selected from anilino group, carboxyl group, mercapto group, acyl group, halogen (alkyl group and phenyl group may be substituted with other groups), etc., and R'', R
"R" may be the same group or groups selected separately. Examples of compounds represented by 2〇, ■ include 1-methyl-1,2,3-) lyazole , 2-methyl-1,2,3
-triazole, 4-methyl-1,2゜3-triazole, 4,5-dimethyl-1,2,3-triazole, 1
-phenyl-1,2,3-triazole, 2-7enyl-1,2,3-triazole, 4-phenyl-1,2,
3-triazole, 4-methyl-2-phenyl-1,2
, 3-triazole, 1-benzyl-1,2,3-triazole, 4,5-dimethyl-2-phenyl-1,2,
3-triazole, 1,5-diphenyl-1,2,3-
Triazole, 2.4.5-triphenyl-1,2,3
-) Riazole, 4-oxy-1,2,3-triazole, 5-oxy-1-7enyl-1,2,3-triazole, 5-oxy-4-methyl-1-phenyl-1,2
, 3-triazole, 5-oxy-1,4-diphenyl-1,2,3-triazole, 1-phenyl-1゜2,
3-triazol-4-ylcarbinol, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 1-benzamide-4
-Methyl-1,2,3-triazole, 1-benzalamino-4-methyl-1,2°3-triazole, 2-amino-4,5-dimethyl-1,2,3-triazole,
1-amino-4,5-diphenyl-1,2,3-triazole, 5-amino-1-7enyl-1.2.3-)riazole, 5-methylamino-1-phenyl-1,2,
3-triazole, 5-amino-1,4-diphenyl-
1,2,3-triazole, 1.2.3-triazol-4-ylethylamine, 4-acetyl-5-methyl-
1,2,3-triazole, 4-acetyl-5-oxy-1,2,3-)lyazole, 1,2,3-triazole-4-carboxylic acid, 2-methyl-1,2,3-)lyazole -4-carboxylic acid, 1-methyl-1,2,3-)
Riazole-5-carboxylic acid, 5-methyl-1,2,3
-triazole-4-carboxylic acid, 2-ethyl-5-methyl-1,2゜3-triazole-4-carboxylic acid, 1
-Phenyl-1,2,3-triazole-4-carboxylic acid, 2-phenyl-1,2,3-triazole-4-carboxylic acid, 1-phenyl-1,2,3-triazole-
5-carboxylic acid, 1.5-diphenyl-1,2゜3-triazole-4-carboxylic acid, 1.2.3-triazole-4,5-dicarboxylic acid, 1-methyl-1,2,3-
Triazole-4,5-dicarboxylic acid, 1-phenyl-
1,2,3-) Riazole-4゜5-dicarboxylic acid, 2
-Phenyl-1,2,3-triazole-4,5-dicarboxylic acid, 4-oxy-1,2,3-triazole-5
-carboxylic acid, 5-oxy-1,2,3-triazole-4-carboxylic acid amide, 5-oxy-1-methyl-1
, 2,3-triazole-4-carboxylic acid ester, 5
-oxy-1,2,3-1 lyazol-1-yl acetic acid,
5-oxy-1-phenyl-1,2,3-1 riazole-4-carboxylic acid, 1-oxy-1,2゜3-triazole-4,5-dicarboxylic acid, 5-amino-1-phenyl-1 , 2,3-triazole-4-carboxylic acid, 5-
Ethyl anilino-1,2,3-triazole-4-carboxylate, 1-methyl-1,2,4-triazole, 3-
Methyl-1,2゜4-triazole, 3.5-dimethyl-1,2,4-triazole, 3.5-diethyl-1,
2,4-triazole, 1-phenyl-1,2,4-)
Riazole, 3-phenyl-1,2,4-1 riazole, 1゜5-diphenyl-1,2,4-triazole, 1
,3-diphenyl-1,2,4-)riazole,3,5
-diphenyl-1,2,4-triazole, 1.3.5
-triphenyl-1,2,4-triazole, 3-lylor-3-bromo and 3-iodo-1,2,4-triazole, 3-chloro-1-phenyl-1,2,4-triazole, 3 -chloro-4-methyl-1,2,4-triazole, 5-chloro-3-methyl-4-phenyl-1
, 2,4-triazole, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole,
5-amino-3-methyl-1,2,4-) lyazole,
4-amino-1,2,4-) lyazole, 4-amino-
3,5-dimethyl-1,2,4-)riazole, 3-(
β-aminoethyl)-1,2,4-triazole, 3-
Mercapto-1,2,4-triazole, 4-ethyl-
3-mercapto-1,2,4-)riazole, 3-mercapto-1-phenyl-1,2,4-triazole, 5
-Mercapto-1-phenyl-1,2゜4-triazole, 4-amino-3-mercapto-1,2,4-triazole, 3-mercapto-1,5-diphenyl-1,2
, 4-triazole, 5-(p-aminophenyl)-3
-Mercapto-1,2,4-triazole, 1.2.4
-triazole-3(5)-carboxylic acid, 1-phenyl-1,2,4-triazole-3-carboxylic acid, 5-methyl-1-7enyl-1,2,4-triazole-3-
Carboxylic acid, 1.2.4-triazol-1-yl acetic acid, 1.2.4-triazol-3-yl acetic acid, 1-phenyl-1,2,4-1 riazole-3,5-dicarboxylic acid, 1 -(p-aminophenyl)-5-oxy-1,2
, ethyl 4-triazole-3-carboxylate, 5-amino-1,2,4-triazole-3-carboxylic acid, 4-
Amino-1,2,4-triazole-3,5-dicarboxylic acid, 5-amino-1,2,4-triazolyl-3-thione, 3-mercapto-4-phenyl-1,2,4-triazole-5 -one, 3,5-dimercapto-1,2
, 4-triazole, 3.5-dimercapto-1-phenyl-1,2,4-)riazole, 3.5-dimercapto-1,4-diphenyl-1,2,4-triazole,
Examples include 3,5-diimino-1,2,4-)riazole and 4-amino-3,5-diimino-1,2,4-triazole.

[In the formula, n represents an integer of 0 to 4, R, R2 is H, alkyl group, cycloalkyl group, arylalkyl group, phenyl group, hydroxyl group, amino group, anilino group, halogen (alkyl group, phenyl The group may be substituted with another group), and R1 and R2 may be an atom group or may be groups selected separately.] Formula ■, Formula Examples of compounds represented by O include benzotriazole, 1-methyl-benzotriazole, 5.6-
Examples include dimethylbenzotriazole, 2-phenylbenzotriazole, -oxybenzotriazole, and 1-oxymethylbenzotriazole.

Additionally, 2-(2-hydroxy-5″-methylphenyl)-benzotriazole, 2-[2-hydroxy-
3-(3", 4", 5.6"-tetrahydrophthalimidomethyl>-5-methylphenyl)benzotriazole, 2-(2°-hydroxy-3-t-butyl-
5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-15-t-butylphenyl>-benzotriazole, 2-(2″-hydroxy-5-t-octylphenyl)benzo Triazole, salts of tolyltriazole such as potassium, lithium, sodium, magnesium, calcium, barium, strontium, zinc, etc., 2-[2-hydroxy-3,5
-bis(α,α-dimethylbenzyl)phenyl2H
-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, methyl-3-[3-t-butyl-5-(2H-
A condensate of bencytriazol-2-yl)-4-4hydroxyphenyl propionate with polyethylene glycol (molecular weight 300) is preferably used. Particularly preferred are benzotriazole derivatives. These triazole compounds may be used alone or in a mixture of 2N or more.The amount of triazole compound added is 5 to 5 parts by weight of O, OO, 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 triazole compound of the present invention can be added to the polyamide resin as they are. Copper halide can also be added after forming a complex salt with a triazole compound in advance, and a complex salt of copper halide and a triazole compound can be used in combination with the triazole compound used to form the complex salt and other triazole compounds. , and further adding another heat-resistant agent (for example, a phenol derivative) is included in the preferred embodiment R of the present invention.

There are no particular restrictions on the timing of addition of copper halide, alkali halide, and triazole compound, i.e., they can be added at any time before, during, or after polymerization. Tri-blending and melt-kneading using an extruder can be effectively used.

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 agents, 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 copper iodide, and 0.5 parts by weight of potassium iodide was placed in a polymerization kettle, the atmosphere was replaced with nitrogen, the 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 80-10
Vacuum drying was performed at 0° C. for 16 hours or more. 20g dried beret
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 flask was sealed tightly. Place this Erlenmeyer flask in a gear oven controlled at 150℃ for 300 hours! ! Subsequently, after heat treatment, the sample was taken out and the surface condition was compared with that of an untreated copper plate and a brass plate, and results not shown in Table 1 were obtained.

Example 1 0.1 part by weight of benzotriazole was further added to the composition of Comparative Example 1, 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 The amount of benzotriazole added in Example 1 was changed to 0°3fiJ.
Polymerization and evaluation were carried out in the same manner as in Comparative Example 1, except that 1 part was used, and the results shown in Table 1 were obtained.

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

Implementation S6-20 A mixture prepared to have the composition shown in Table 2 was placed in a polymerization pot and polymerized and evaluated in the same manner as in Comparative Example 1, and the results shown in Table 2 were obtained. 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 21 to 25 Mixtures prepared to have the compositions shown in Table 3 were placed in a polymerization kettle, and polymerization and evaluation were carried out in the same manner as in the comparative examples, and the results shown in Table 3 were obtained. Both had high antirust effects on copper and brass.

Examples 26 to 29 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 4 were obtained. Obtained.

<Effects of the Invention> One or more tozoazole compounds are added to the polyamide composition of the present invention, which consists of a polyamide with an amino end group concentration of less than 6 x 1 O-5 (mol 7 g polymer), a copper halide, and an alkali halide. The polyamide resin composition obtained by adding the polyamide resin composition has excellent rust prevention against metal materials, especially copper and copper alloys, which coexist with the molded article formed by the polyamide resin composition, especially in high-temperature usage environments. It has now become possible to obtain a polyamide resin composition with good heat resistance and improved coloration.

Patent application Daitoshi Co., Ltd.

Claims (1)

[Scope of Claims] (a) Amino terminal group concentration is 6×10^-^5 (mol/g
(b) 0.001 to 1 part by weight of copper halide, (c) 0.01 to 5 parts by weight of alkali halide, and (d) 0.005 parts by weight of a triazole compound to 100 parts by weight of a polyamide resin smaller than the polymer. -5 parts by weight of a polyamide resin composition.