JPS62174258A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which has excellent smoothness and uniformity in appearance and ell-balanced physical properties with regard to rigidity and resistance to impact, heat and chemicals, consisting of a polyamide resin and a specified modified ethylene copolymer. CONSTITUTION:50-90wt% ethylene (a) is reacted with 5-49wt% alkyl ester of an alpha,beta-unsaturated carboxylic acid (b) (e.g., ethyl acrylate) and 0.5-10wt% maleic anhydride (c) in the presence of a metal ion forming agent selected from among metal salts of 10-21C fatty acids or amino acids (e.g., sodium stearate) to obtain a modified ethylene copolymer (B) having an MI of 1-100g/10min and contg. partially ionized component (C). 50-97wt% polyamide resin (A) is blended with 50-3wt% component B and optionally a reinforcing fiber, an inorg. filler, a flame retardant aid, a lubricant, etc. (C).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel thermoplastic resin composition G that can be used as an RLI-shaped article, sheet, or film by injection molding or extrusion molding.

More specifically, it is made by blending a polyamide resin with two parts of a modified ethylene copolymer containing publicly ionized acid anhydride groups. Alternatively, an ethylene copolymer containing an acid anhydride group and a metal ion generating agent were blended into a polyamide resin, and at the same time, the acid anhydride group was partially ionized. The present invention relates to a novel thermoplastic resin composition with an excellent balance of physical properties and an excellent appearance.

[Conventional technology]

This polyamide resin is generally rigid and wear resistant.

Due to its excellent chemical resistance, heat resistance, and electrical properties, it is widely used as an engineering plastic.

However, it has drawbacks or points that require improvement in terms of impact resistance, molding stability, etc., and these are obstacles to the development of practical applications.

Various methods have been proposed to date to improve the impact resistance, which is a drawback of such polyamide resins.

For example, as representative methods, Japanese Patent Publication No. 54-4743, Japanese Patent Publication No. 55-44108, and Japanese Unexamined Patent Publication No. 58-2
Examples include a method of adding a modified ethylene copolymer type polymer having rubber elasticity and an active group capable of reacting with a polyamide resin, as described in Japanese Patent No. 3850.

However, according to the results of studies conducted by the present inventors, although it is possible to obtain a molded article with relatively improved impact resistance using the above-mentioned prior art, it is still not sufficient. Furthermore, it was found that the material was not satisfactory from the viewpoint of physical property balance between rigidity and impact resistance.

That is, its somewhat improved impact resistance and flexibility than the polyamide resin itself has poorer mechanical properties such as stiffness and tensile strength.

This is offset by hardness, etc. Furthermore.

There are problems in that molded products that are colored and have a poor appearance are often obtained, and that their applications are limited.

Therefore, it is important to select a modified ethylene copolymer type polymer to be added to the polyamide resin that does not cause the above-mentioned problems, and its development is strongly desired.

[Problem that the invention seeks to solve]

The present invention aims to improve impact resistance, which is a drawback of polyamide resins, by applying a modified ethylene copolymer with a specific structure, without impairing mechanical properties such as rigidity.
This is an attempt to solve the above problems, and its purpose is to use polyamide resin as the main component. The object of the present invention is to provide a thermoplastic resin composition having excellent impact resistance and mechanical properties such as rigidity.

[Means for solving problems]

From this perspective, the present inventors conducted a wide and detailed search for polymers that are effective in modifying polyamide resins, and found that a modified ethylene copolymer with a specific structure has particularly good impact resistance and rigidity. It was found that it has a good balance and is excellent in terms of molding processability and the shape of the molded product.
We have arrived at the present invention.

That is, the present invention.

■ Polyamide resin 50-97% by weight.

(B) 50-90% by weight of etyleno, 5-49% by weight of α,β-unsaturated carboxylic acid alkyl ester.

and 1.0% partially ionized maleic anhydride.
Modified ethylene copolymer consisting of 50 to 10% by weight
3% by weight of the thermoplastic resin composition.

The component (g) polyamide resin in the present invention is as follows:
It is possible to use polyamides obtained by polycondensation of lactams having three or more membered rings, polymerizable ω-amino acids, dibasic acids, and noamines.

Specifically, ε-caprolactam, aminocaproic acid,
Enantholactam, 7-aminoheptanoic acid, 11-7
Polymers such as minoundecanoic acid, or hexamethylenediamine/nonamethylenediamine, undecachilenediamine.

Polymers obtained by polycondensing noamino acids such as dodecamethylene diamine and metaquinone diamine with dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, cepatic acid, dodecane dibasic acid, and geltaric acid, or polymers thereof. Examples include copolymers of

Specific examples include polyamide 6, polyamide 6.6. Polyamide 6.10. Polyamide II, Polyamide +2. Polyamide 6, +2. Aliphatic polyamide resins such as polyhexamethylene diamine terephthalamide, polyhexamethylene isophthalamide,
Aromatic polyamide resins such as ren group-containing polyamides may be mentioned.

Among these, polyamide 6 and polyamide 6.6 are particularly important industrially.

In a thermoplastic resin composition according to the present invention.

Bo1j amide resin as a constituent component (g) is 50 to 97
The content is preferably 60 to 92% by weight, more preferably 70 to 90% by weight.

Therefore, the modified ethylene copolymer as component (1) is contained in an amount of 3 to 50% by weight, preferably 8 to 40% by weight, and more preferably 10 to 30% by weight.

If the polyamide resin component (g) is less than 50% by weight.

Rigidity and heat resistance are insufficient, and if the content exceeds 97% by weight, favorable results cannot be obtained in terms of impact resistance.

The component that is one of the constituent components of the resin composition according to the present invention (
B) A modified ethylene copolymer whose monomer components consist of ethylene, α, β-unsaturated carboxylic acid alkyl ester, and partially G-ionized maleic anhydride, and the ethylene copolymer contains 50 to 90% by weight of ethylene. %, preferably 60-8
5% by weight.

α, β-unsaturated carboxylic acid alkyl ester is 5 to 49
% by weight, preferably 7-45% by weight, and 0.5-10% by weight of partially ionized maleic anhydride,
Preferably it is 1 to 8% by weight.

The α,β-unsaturated carboxylic acid alkyl ester is an alkyl ester of an unsaturated carboxylic acid having 3 to 8 carbon atoms, such as acrylic acid, methacrylic acid, etc. Specific examples include ethyl acrylate, acrylic acid, etc. n-propyl,
Isopropyl acrylate, n-butyl acrylate, Ac IJ) t-butyl chloride, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-tutaacrylate
-propyl, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate, and among these, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are particularly preferred.

Metal species suitable for partial metal ionization of maleic anhydride include IA and IB in the periodic table of single elements.

nA, IIB, IIIA, and metals of the fourth period of groups 1, such as Na, K, Cu, Mg
, Ca, Ba.

These include Zn, Cd, AI, Fe, Co, and N1, and among these, the special numbers include Na, Ni, Mg.
, Ca, Ba, and Zn are preferred.

As a metal ion generating agent, each intercalated organic acid salt is used.

Examples include oxides, hydroxy/carbonates, free metals, metal hydrides, metal alkoxides, and organic metals, but among these, organic carboxylates or amino acid salts are preferred. is a metal salt of a higher aliphatic carboxylic acid having 10 to 24 carbon atoms, such as capric acid, lauric acid, myristic acid, bartimic acid, stearinoic acid, behenic acid, lignoceric acid, or

Examples include metal salts of various amino acids such as aspartic acid and glutamic acid. Among these, gold salts of stearic acid or glutamic acid are preferred.

There are no particular limitations on the method for the neutralization reaction between the generating agent and the ethylene copolymer containing maleic anhydride groups, but one example is a Banbury mixer-2 extruder.

Alternatively, it is convenient to melt and knead directly in a colander such as a roll.

Component IB) modified ethylene copolymer used in the present invention is:
Its constituent monomer is maleinoic anhydride.

Resin composition Q in the present invention, component B) may be partially metal ionized in advance.
It is not necessarily important whether or not the is ionized beforehand.

That is, component IB) modified ethylene copolymer is component (~
A resin composition formed by directly kneading an ethylene copolymer and a metal ion generating agent together in the presence of a polyamide resin also achieves the object of the present invention,
It is also of great industrial significance.

The amount of metal ions produced is preferably 5 to 80 mol%, more preferably 10 to 80 mol%
It is 70 mol%. If the amount of metal ions produced is less than 5 mol%, cold resistance, especially impact resistance at low temperatures, will be poor;
If it exceeds , the impact resistance will decrease.

In the modified ethylene copolymer (B), ethylene is 50
If it is less than 90% by weight, the stiffness of the composition with the polyamide will be significantly reduced, and if it exceeds 90% by weight, favorable results in impact resistance will not be obtained.

In addition, α, β-unsaturated carboxylic acid alkyl ester is 5
If it is less than 49% by weight or more than 49% by weight, favorable results cannot be obtained in terms of impact resistance.

Also, 1 partially ionized maleinoic anhydride is 0.5
If it is less than 10% by weight, favorable results will not be obtained in terms of impact resistance, and if it exceeds 10% by weight, favorable results will not be obtained in terms of impact resistance and moldability.

Moreover, the melt index (JIS K6760) of the modified ethylene copolymer (B) is 1 to +009/10 minutes.

Preferably it is in the range of 2 to 509/10 minutes.

If the melt index exceeds 1oof/lo minute, it is unfavorable in terms of mechanical properties when used as a composition, and the 1971
If the time is less than 0 minutes, compatibility with polyamide is lacking.

The resin composition of the present invention includes a number other than the above-mentioned formulations.

Additionally, glass fiber and carbon fiber are available as required.

and fibrous reinforced composites such as metal whiskers.

Glue force, alumina, calcium carbonate, talc.

Inorganic photonic agents such as mica, carbon black, TiO2, ZnO, and 5B205, or flame retardant aids, lubricants, nucleating agents, plasticizers, dyes, pigments, antistatic agents, antioxidants, weather resistance. In some cases, it may be preferable to use it as a composite material to which a property-imparting agent is added.

There are no particular limitations on the method for producing the resin composition of the present invention, and any commonly known method can be used. From an industrial standpoint, a method of kneading in a molten state is actually used.

For melt-kneading, commonly used kneading devices such as Bamba's I-mixer, extruder, roll, and various kneaders can be used. (Kneading) W + Here, each resin component is powder or powder.

It is preferable to uniformly mix the pellets in advance using a device such as a tumbler or a Hennon mixer, if necessary.

A method may also be used in which mixing is omitted and the components are individually supplied in fixed quantities to the kneading device.

The kneaded resin composition can be molded by various molding methods such as injection molding, extrusion molding, and the like.

This includes a method in which a molded product is obtained by dry breading during injection molding or extrusion molding and directly kneading it during the melt processing operation without going through a kneading process in advance.

〔Example〕

The present invention will be explained below with reference to examples, but the present invention is not limited by these examples.

In addition, Izot impact strength (sample thickness 3
．． 2MM, measurement temperature 23℃ and -30℃2■-notch) is JIS K7110 *This 1 flexural modulus (sample thickness 32m1, measurement temperature 23℃) is JIS K720
3 i, : , / /l/ t(ndenox (19)
0°C, 2+6Of) were carried out in accordance with JIS K6760i.

In the present examples and comparative examples, the following polyamide resins and ethylene copolymers were used.

1) Polyamide resin PA-1 Ube Industries (Made of meat.

UBE nylon 2020B (polyamide-6,6) PA
-2: Manufactured by Ube Industries ■.

UBE nylon 1013B (polyamide-6) 2) Ethylene copolymer Ethylene copolymers (a), (b),
(c) and (d) are French Patent No. 1,323,
No. 379 and French Patent Application No. 81101,430
It can be produced by the method described in No.

Ethylene copolymer etc.) Made by HINDF ■: 'r
: nt(n0AX8040 (E/BA/MAH=
64.4/33.8/1.8% by weight, MI: 41
F/10 min) Ethylene copolymer ('b) Bodyne 0AX8060 manufactured by Sumika NDF ■ (E/EA
/MAH=70.7/26/3.3% by weight, MI:
40? /10 minutes) Ethylene copolymer (C) Ethylene-ethyl acrylate to maleic acid monomethyl ester copolymer (E/E～～Yoshizheng=67/30.5/2.5% by weight, Ml: 1.09 /10 minutes) ethylene copolymer (d
) Ethylene-butyl acrylate copolymer (E/B
A-70/30% by weight, MI: 9. o r/10
min) where, E: ethylene, BA nibbutyl acrylate)
, EA: ethyl acrylate, MAR maleic anhydride, MAME maleic acid monomethyl ester, M
l Indicates Nortoy/Denox.

3) Modified ethylene copolymer Ethylene copolymer fa), (b) or (c) is blended with sodium nateate, sodium laurate, or sodium glutamate in the proportions shown in Table 1, and is equipped with a 30mMφ single shaft vent. Using an extruder,
Modified ethylene copolymers A, B, C, D, E, F and G were obtained by pelletizing by melt kneading at a temperature of 230'C.

Examples 1 to 20 and Comparative Examples 1 to 12 Using a 30 rmnφ vented single-screw extruder, a predetermined temperature (280'C for polyamide 6.6,
(in the case of 245°C), various resin compositions as shown in Tables 2 and 3 were obtained.

After drying each resin composition (two pieces) at a temperature of 80℃ for 12 hours, it was used as a molding material in a LO ounce injection molding machine (
Toshiba IS-150E-V type) was used to prepare a test piece for measuring the physical properties of a trowel at a specified temperature (280'C for polyamide 6.6, 245°C for polyamide 6) and a mold temperature of 70'CG. did.

The test results of the Izot impact strength and flexural modulus of the obtained test pieces are as shown in Tables 2 and 3.

A comparison with the comparative example shows that the modification effect of the modified ethylene copolymer of the present invention on the polyamide resin is remarkable.

Examples 21 to 23 Polyamide resin PA-1 or PA-2 was treated with ethylene copolymer (a) and stearic acid l-'J, respectively.
um in the proportions shown in Table 4, and using an extruder with a 30 mm diameter single screw bed, the mixture was heated to a specified temperature (280°C for polyamide-6, 6, 245°C for polyamide-6). Various resin compositions were obtained.

Using each resin composition G, test pieces for measuring physical properties were prepared in the same manner as in Example 1.

The test results of the Izot impact strength and flexural modulus of the obtained test pieces are as shown in Table 4.

From the results in Table 4, it can be seen that even without using a modified ethylene copolymer that has been partially ionized in advance.

It can be seen that a polyamide resin composition having a high Izod impact strength can be obtained by a method of ionizing at the same time when kneading with a polyamide resin.

〔Effect of the invention〕

The thermoplastic resin composition of the present invention not only has good molding processability, but also exhibits remarkable effects in terms of various physical properties of molded products (both of which are good in terms of balanosic properties).

The novel resin composition provided by the present invention can be easily molded by molding methods such as injection molding and extrusion, which are used for conventional polyamide-based thermoplastic resin compositions. / - Processed to provide impact resistance and rigidity.

Provides a product with uniform appearance and smoothness that has an extremely good balance of physical properties such as heat resistance and chemical resistance.

-1 \、

Claims (4)

[Claims] (1) (A) 50-97% by weight of polyamide resin (B) 50-90% by weight of ethylene, 5-49% by weight of α,β-unsaturated carboxylic acid alkyl ester, and partially ionized maleic anhydride 0.5 to 10% by weight of a modified ethylene copolymer, and 50 to 3% by weight of a modified ethylene copolymer. (2) Component (B) modified ethylene copolymer is ethylene 6
0 to 85% by weight of α,β-unsaturated carboxylic acid alkyl ester, 7 to 45% by weight of α,β-unsaturated carboxylic acid alkyl ester, and 1 to 8% by weight of partially ionized maleic anhydride. Resin composition. (3) Component (B) The partially ionized maleic anhydride in the modified ethylene copolymer is partially ionized with a fatty acid having 10 to 24 carbon atoms or a metal salt of an amino acid. Thermoplastic resin composition according to scope 1. (4) Component (B) modified ethylene copolymer is component (A)
In the presence of 50-97% by weight of polyamide resin, ethylene 5
0 to 90% by weight, 5 to 49% by weight of α,β-unsaturated carboxylic acid alkyl ester, 3 to 50% by weight of an ethylene copolymer consisting of 0.5 to 10% by weight of maleic anhydride, and 10 to 24 carbon atoms. 2. The thermoplastic resin composition according to claim 1, which is formed by directly and collectively kneading three fatty acids or a metal ion generating agent represented by a metal salt of an amino acid.