JPH02247253A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition suitable for electrical parts, automobiles, etc., having excellent heat-resistant aging properties, mechanical characteristics, heat resistance and chemical resistance by blending nylon 46 with specific amounts of CuI and KI. CONSTITUTION:Nylon 46 is blended with CuI and KI in such a way that content of CuI is 0.16-2wt.%, ratio of content of CuI and KI is CuI/KI=(1/4-1/20) and total amounts of CuI and KI are <=15wt.%.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a resin composition with excellent heat aging resistance, and more specifically, a resin composition with excellent heat aging resistance consisting of nylon 46, Cul, and 1. The present invention relates to a resin composition.

The resin composition of the present invention is expected to be applied to a wide range of uses such as electricity, automobiles, and machinery due to its excellent heat aging resistance and excellent mechanical properties, heat resistance, and chemical resistance.

(Prior Art) Nylon 46 is already a well-known resin. For example, Japanese Patent Publications No. 60-8248 and Japanese Patent Publication No. 60-28843 disclose a method for manufacturing nylon 46.

Also, E. Roerdink and J. M. M. Warn.
ier introduces the performance of nylon 46 (P.
olymer+ 26e P15! (2 (1985))
. It is also widely known that nylon 46 has excellent properties as an engineering plastic, particularly outstanding mechanical properties, heat resistance, and chemical resistance, and is therefore an extremely promising material as an engineering plastic.

However, the aging properties of nylon 46 are not necessarily satisfactory when viewed as an engineering plastic.

As an attempt to improve the heat aging resistance of nylon 46, only a method disclosed in JP-A-63-142059 is known.

This method combines Cub/KI with nylon 46, and C
u as 120ppm ~ 5.00ppm, ! It is characterized in that it is present in an amount of 100 pp or more per liter.

However, the effect of improving heat aging resistance by this method was not as remarkable as expected from the heat resistance of nylon 46, such as its heat distortion temperature (290'C under small load) and melting point (295'C).

(Problems to be Solved by the Invention) In view of the above circumstances, the purpose of the present invention is to significantly improve the heat aging resistance of nylon 46, and to create a resin composition that has excellent heat aging resistance, mechanical properties, heat resistance, and chemical resistance. The purpose is to provide.

(Means for Solving the Problems) As a result of extensive research aimed at such purposes, the present inventors have found that by blending specific amounts of Cul and XI with nylon 46, the two objects of the present invention can be achieved. This is what led us to the present invention.

That is, the present invention provides a resin composition consisting of nylon 46, Cul, and KI, wherein CuI in the resin composition is
The content is 0.16% to 2% by weight.

The content ratio of Cul and KI (Cul/KT) is 1/4
-1/20, and the total content of Cul and ■ is less than 15% by weight of the resin composition.

As disclosed in Japanese Unexamined Patent Application Publication No. 142059/1983, conventionally, nylon 46 was modified to have a Cu content of 50
It has been pointed out that when 0 ppm or more (0.15% by weight or more as Cu) is added, heat aging resistance deteriorates and discoloration occurs, but the resin of the present invention! II
In the proboscis, the content ratio of Cul to 1 (CuI/
By blending Cu[ and KI with nylon 46 so that KI) takes a specific value, the Cu content can be reduced to 500p.
It is completely surprising that even when the temperature exceeds pm, the heat aging resistance is further improved without decreasing, and the discoloration associated with the addition of Cul is also prevented.

Nylon 46 used in the present invention includes a copolyamide obtained from tetramethylene diamine and adipic acid; and a copolymerized polyamide whose main constituents are ramethylene adivamide and polytetramethylene adipamide units. Furthermore, other polyamides may be included as a mixed component to the extent that the properties of nylon 46 are not affected. The copolymerization component is not particularly limited, and known amide-forming components can be used. As a representative example of the copolymerized component, 6-aminocaproic acid I
I-aminoundecanoic acid, 12-aminododecanoic acid.

Amino acids such as paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam, hexamethylene diamine 1 undecamethylene diamine, dodecamethylene diamine, 2,2.4-/2.4.4-trimethyl hexa Methylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, baraxylylenediamine, l,3-bis(aminomethyl)cyclohexane 1.4-bis(aminomethyl)cyclohexane 1
-amino-3-aminomethyl-3,5,5h-limethylcyclohexane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine,
Diamines such as aminoethylpiperazine and adipic acid, speric acid, azelaic acid, sebasosic acid, dobucanic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium Dicarboxylic acids such as sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid can be mentioned, and other polyamides used as mixed components can be made of these components.

The method for producing nylon 46 used in the present invention is arbitrary. For example, JP-A No. 56-149430, JP-A No. 5
The method disclosed in JP-A No. 6-149431, JP-A-58-83029, and JP-A-6143631, that is, first, a prepolymer with few cyclic end groups is produced under specific conditions, and then 5 A method of preparing high viscosity nylon 46 by in-phase polymerization 17 in a steam atmosphere, or polar a such as 2-pyrrolidone or N-methylpyrrolidone.
There are methods to obtain it by heating in a solvent. nylon 4
There is no particular restriction on the degree of polymerization of 6, but it is 30°C19
Nylon 46 having a relative viscosity of Ig/cR in the range of 2.0 to 6.0 in 6% sulfuric acid is preferably used.

In the present invention, CuI is used as a heat aging resistance improver for nylon 46. Therefore, in order to obtain a sufficient effect, it is necessary to incorporate CuI in a content of 0.15% by weight or more. Although there is an effect when the amount is less than this, the degree of the effect is not significant. Moreover, when 2% by weight or more of Cul is blended, the melting point and heat distortion temperature of Nylon 46 are greatly lowered, which is not preferable.

In the present invention, KI is used as a heat-aging resistance improving agent for nylon 46 and as a coloring preventive agent for preventing discoloration caused by the addition of Cul to nylon 46. Cul and K
Although a certain degree of heat resistance improvement effect is observed even when each of 1 and 1 is blended alone with nylon+16, when both 1 and 1 are used together in a certain ratio, an extremely remarkable synergistic effect is exhibited. This synergistic effect is due to the content ratio (Cul/KI) of Cu[toni[
This is particularly noticeable when the ratio is within the range of 174 to l/20.

In addition, surprisingly, the ratio of the content of Cul to 1 (C
It is surprising that when uT/XI) is within the above range, discoloration of nylon 46 due to Co11 addition is effectively prevented. The content ratio of Cul and KI (
Even if a large amount of KI is blended so that Cul/N) is 1720 or less, there is no change in the synergistic effect of coloring prevention 1F effect and heat aging resistance improvement.1On the contrary, heat resistance as represented by heat distortion temperature and melting point This is not preferable because it reduces the On the contrary, C
The content ratio of ul and KI (Cu 1/l) is 174
In the above case, discoloration occurs due to the addition of Cu, and the synergistic effect of improving heat aging resistance is also reduced.

The method for producing the resin composition of the present invention is not particularly limited, and includes direct injection molding by blending a predetermined amount of nylon 46, Cul, and KI.
Extrusion molding, blow molding, compression molding Ring 1 It is also possible to use suitable thermoplastic resins for molding.Also, nylon 46, Cul and KI can be mixed in advance and this can be mixed using an extruder etc. The pellets may be melted and kneaded to obtain pellets, and then the pellets may be subjected to the above-mentioned molding.

The resin composition of the present invention may contain other components such as pigments, dyes, reinforcing materials, fillers, heat resistant agents, antioxidants, weathering agents, lubricants, crystal nucleating agents, etc., as long as they do not affect its moldability or physical properties.
Mold release agent, plasticizer, tI refueling agent.

It can contain antistatic agents and other polymers. Filling with reinforcing materials and fillers is especially important; glass fiber,
Fibrous powder or particulate reinforcing materials such as asbestos fibers, carbon fibers, potassium titanate fibers, graphite fibers, wollastonite, talc, calcium carbonate, mica, clay-cured phenolic resins, glass pieces, etc. can be added.

Furthermore, the resin composition of the present invention may contain other polymers as long as the properties thereof are not significantly affected.

Examples of such polymers include nylon 6°, nylon 66, nylon 11. Nylon 12. nylon 610,
PE, PP, ^BS, PBT, PET,
Examples include polyarylate PPE.

The resin composition of the present invention can be made into molded articles useful in fields such as electricity, automobiles, and machinery through a molding method used for general thermoplastic resins.

(Examples) The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto. In addition, the evaluation method of measurement method 1 in the examples is as follows.

It was determined from the endothermic peak by heating at a Sakai-temperature speed of 10'C/min using scattered-point DSC.

Hot pickled 110-branch eight STM D648 was blocked and under a small load (18.5kg
/cnl).

■Measurements were made using a No. 1 dumbbell test piece based on STM D63B.

Aging the No. 1 dumbbell test piece in an oven at 170°C and 190°C, and determining the time-dependent change in tensile strength. period.

The surface observation was performed on an ASTM No. 1 dumbbell test piece obtained by negative injection molding.

Examples 1-6. Comparative Examples 1 to 5 Nylon 46 with a relative viscosity of 4.0 in iR/dl, Cul, and KI were blended in the proportions shown in Table 1 in 996% sulfuric acid at 30°C, and
Vacuum dried for hours. These blends were melt-kneaded at 300'C using a twin-screw extruder and cut to obtain pellets.

This pellet was molded using an injection molding machine at a temperature of 300°C to obtain an ASTMI dumbbell test piece, which was used for measurement. The measurement and evaluation results are listed in Table 1.

The resin compositions of the present invention shown in Examples 1 to 6 have a remarkable effect of improving heat aging resistance compared to the nylon 46 alone shown in Comparative Example 1, and in fact, the tensile strength is more than 50 times higher.
Has a strength half-life. Comparative Examples 2 and 3 are examples in which Cul and XI are blended alone, but the resin composition of the present invention has higher heat resistance than these Comparative Examples by containing Cul and XI in a specific ratio. The aging properties are dramatically improved, showing a synergistic effect with CuT and 1.

Furthermore, although Comparative Example 4 shows an example in which the blending amounts of Cul and KI are small, the effect of improving heat aging resistance is extremely small compared to the resin composition of the present invention. Comparative Examples 2 and 5 are C
An example is shown in which the ratio of ul to 1 is other than a specific value, but in this case, discoloration of the molded article occurs, and the effect of improving heat aging resistance is less than that of the resin composition of the present invention.

(Effects of the Invention) In the resin composition of the present invention, by blending a specific amount of Cui and 1 with respect to Nylon 46, the heat aging resistance is significantly improved without impairing the properties of Nylon 46 itself. That is clear.

Patent Applicant Unitika Co., Ltd. Procedural Netti Correction Page ↑ (Spontaneous!), Case Indication Special ■ Uhei 1-68193 No. 2, Name of Invention Resin Composition 3, Person Making Amendment Relationship with Case Patent Applicant Address 1-50 Higashihonmachi, Amagasaki City, Hyogo Prefecture Name (4
50) Unitika Co., Ltd. Address: 4-1-3 Kutabe-cho, Chuo-ku, Osaka 541 Unitika Co., Ltd. Patent Department Telephone: 06-281-5258 (Dial-in) 5
, Contents of the amendment (13 Specification, page 9, lines 11 to 14, ``Examples of such polymers include nylon 6, --------
---・-PPE, etc. "Examples of such polymers include PE, PP, in addition to the polyamides listed above.
, All5. There are PBT, PBT, polyarylate PPB, etc. ” he corrected.

(2) ' (18,5Kg/
cd) Correct J to 1' (4,5Kg/cd) J.

Claims (1)

[Claims] (1) A resin composition consisting of nylon 46, CuI and KI, in which the content of CuI in the resin composition is 0.
．． 16% by weight to 2% by weight, the content ratio of Cul and KI (Cu/K1) is within the range of 1/4 to 1/20, and the total content of Cul and KI is less than 15% by weight of the resin composition.