JPS5924751A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To provide the titled resin compsn. having excellent flow characteristics, low-temperature impact resistance, etc., by blending a hindered phenol compd. and/or an arom. amine with a mixture of a polyamide and a modified polyolefin having functional groups. CONSTITUTION:95-50wt% polyamide is mixed with 5-50wt% modified polyolefin having functional groups selected from carboxyl, carboxylate metal salt, carboxylate ester, anhydride, and epoxy groups, such as an ethylene/acrylic acid copolymer. 0.02-3pts.wt. hindered phenol compd. such as 3,5-di-t-butyl-4- hydroxytoluene and/or arom. amine such as N,N'-di-beta-naphthyl-p-phenylenediamine are/is blended with 100pts.wt. above mixture to obtain the desired polyamide resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a mixture of polyamide and modified polyolefin.
The present invention relates to a polyamide resin composition that has improved flow characteristics during molding, low-temperature impact resistance after heat treatment, etc. by adding this specific compound.

Recently, molding materials made of mixtures of polyamide and various polyolefins have been developed in order to improve the impact strength of polyamide resins when dry or at low temperatures, and to obtain materials that can withstand harsh usage conditions. Polyolefins that have been proposed so far as effective for improving the impact strength of polyamide include ethylene and α, β.
- Copolymers with unsaturated luponic acid (for example,
No. 2-12546), so-called ethylene-based ionomer resins made by adding metal ions such as sodium, magnesium, and zinc to copolymers of ethylene and α, β-unsaturated carboxylic acid derivatives (for example, Third
845163, Japanese Patent Publication No. 54-4745) and modified polyolefins into which acid anhydrides and epoxy compounds are grafted (e.g., Japanese Patent Publication No. 55-44108, Japanese Patent Publication No. 57-22347, Japanese Patent Publication No. 57-22347, Japanese Patent Publication No. 55-9)
No. 661, JP-A-55-165952). The polarity and reactivity of these modified polyolefins change depending on the various functional groups introduced into them, and as a result, they exist as a fine dispersed phase in the polyamide matrix phase and play the role of absorbing impact energy. The reaction between the functional groups of the modified polyolefin and the polyamide increases the viscosity of the mixture, which often causes a problem of deterioration of fluidity during molding, particularly during injection molding. Furthermore, mixtures of polyamide and various modified polyolefins as mentioned above certainly exhibit excellent impact resistance not only at temperatures above room temperature but also at low temperatures below 0°C.
It has become clear that the material has a serious drawback in that the low-temperature impact strength is significantly reduced when heat treated at 0-1'50°C for about 50-500 hours. This shows that when a molded product made of a mixture of polyamide and modified polyolefin is used for a long time in a high-temperature environment, its impact strength gradually decreases, and at low humidity it becomes extremely brittle. This is one of the problems that needs to be improved in order to apply it to

Therefore, the present inventors investigated the purpose of improving the fluidity during injection molding and the low-temperature impact strength after heat treatment of a composition made of polyamide and modified polyolefin, and found that the addition of a specific compound is extremely effective. They discovered this and arrived at the present invention.

That is, the present invention (~polyamide: 95-50
Modified polyolefin having at least one functional group selected from t% and (Bll carboxylic acid group, carbonic acid metal base, carboxylic acid ester group, acid anhydride group, and evoquine group: from 5 to 50% by weight) A mixture of 100
The present invention provides a polyamide resin composition containing 0.02 to 6 parts by weight of C) a hindered phenol compound and/or an aromatic amine compound.

The characteristics of the present invention are to improve the fluidity of a mixture consisting of polyamide and modified polyolefin during injection molding, and to prevent a decrease in low-temperature 1aj:131 strength after heat treatment by adding a specific amount of a hindered phenolic compound and/or an aromatic amino compound. It has been found that the addition of these compounds has an extremely effective effect, and in the absence of these hindered phenol compounds and aromatic amino compounds, even if other compounds are added, there is almost no improvement effect. unacceptable. In other words, among the copper compounds, hindered phenol compounds, aromatic amine compounds, and phosphorus compounds that have been conventionally known as heat-resistant agents and antioxidants, only hindered phenol compounds and aromatic amine compounds are modified with polyamides. Although the polyolefin mixture has the specific effects of improving fluidity during injection molding and suppressing the decrease in low-temperature impact strength after heat treatment, the addition of a copper compound does not cause any decrease in low-temperature impact strength after heat treatment. In addition, phosphorus compounds generally promote thickening of the resin mixture, rather worsen fluidity during molding, and have a relatively small effect on improving low-temperature impact strength after heat treatment.

In addition, when adding hindered phenol compounds and aromatic amine compounds to polyamide as heat-resistant agents, the amount of addition is -
is usually 0.0111 parts per 100 parts by weight of polyamide.
However, in the present invention, even if such a small amount of I11 is added to the mixture of polyamide and modified polyolefin, the desired effect cannot be obtained, and the amount exceeds the proper amount of addition as a general heat resistant agent. 0.02 parts by weight or more, especially 0.02 parts by weight or more.
．． The addition of the hindered pheno-p compound of the present invention and the aromatic amine compound of the present invention can improve fluidity during molding and improve low-temperature impact resistance after heat treatment only when added in an amount of 0.5 parts by weight or more. It can be said that the effect brought about by compound t is a new and unique effect that cannot be predicted from general heat resistant agents.

The polyamide used in the present invention is not particularly limited, but
Common aliphatic polyamides, such as polycaproamide (
Nylon 6), Polyhexamethylene adipamide (Nylon 66), Polyhexamethylene Sepacamide (Nylon 6)
10), polyundecamethylene adipamide (nylon 116), polyhexamethylene dodecamide (nylon 61)
2), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), copolyamides containing these as main components, mixed polyamides, etc.
It is appropriate. Copolymerized polyamides and mixed polyamides include not only polyamides in which all rR components are aliphatic components, but also aromatic components such as hexamethylene isophthalamide (6I) component, hexamethylene terephthalamide (6T) component, meta Xylylene adipamide (MX
Also included are nylon 6/6 copolymers, nylon 676T copolymers, mixtures of nylon 66 and nylon 6, mixtures of nylon 66 and nylon MXD6, etc., which contain a small amount of component D6). The polyamide used here is usually produced by melt polymerization, and there is no restriction on the degree of polymerization, and any polyamide having a relative viscosity within the range of 2.0 to 5.0 can be selected.

Typical examples of (c) modified polyolefins having at least one functional group selected from carboxylic acid groups, carboxylic acid metal bases, carboxylic ester groups, acid anhydride groups, and epoxy groups used in the present invention include ethylene /acrylic acid copolymer, ethylene/methacrylic acid copolymer,
Ethylene/fumaric acid copolymer, ethylene/methacrylic acid/zinc methacrylate copolymer, ethylene/acrylic acid/sodium methacrylate copolymer, ethylene/isobutyl acrylate/methacrylic acid/zinc methacrylate copolymer Polymer, ethylene/methyl methacrylate/methacrylic acid/magnesium methacrylate copolymer,
Ethylene/ethyl acrylate copolymer, ethylene/a
'PM vinyl copolymer, ethylene/glycidyl methacrylate μ copolymer, ethylene/vinyl acetate/methacrylic acid
Glycidyl phosphate copolymer, ethylene-9-maleic anhydride copolymer ('q' represents graft, the same applies hereinafter),
ethylene/propylene-9-maleic anhydride copolymer,
Ethylene/propylene-couacrylic acid copolymer, ethylene/1-butene-9-fumaric acid copolymer, ethylene/
1-hexene-9-itacone copolymer, ethylene/propylene-9-endobicyclo[2,2,1]-5-hegetene-2,5-dicarboxylic anhydride copolymer, ethylene/propylene-q-meta Grindyl acrylate copolymer, ethylene/propylene/1,4-hexadiene-q-
m-water maleic acid copolymer, ethylene/propylene/zinclopentadiene-Kutsma I-m copolymer, -c-tylene/propylene/norfornadiene-q-maleic acid copolymer, and ethylene/vinifrey acetate 9-1cryl It is also possible to use two or more types of acid corefins in combination.

The above-mentioned modified polyolefin can be produced by known methods, for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 46-2752.
Publication No. 7, Special Publication No. 50-2650, Special Publication No. 52-
It can be produced according to the methods disclosed in Japanese Patent Publication No. 46677, Japanese Patent Publication No. 5716-1982, Japanese Patent Publication No. 19037-1983, Japanese Patent Publication No. 41173-1983, Japanese Patent Publication No. 9925-1987, and the like. As for ethylene ionomers, various commercially available grades such as Surlyn, Himilan, and Copolene are generally available. The degree of polymerization of the modified polyolefin used in the present invention is not particularly limited, but
Usually melt index is 0.01~50 g/l
Anything within the range of 0 min can be arbitrarily selected.

In addition, in the present invention, it is also possible to mix a small amount of other polyolefins with the above-mentioned modified polyolefin, and the polyolefins include polyethylene, polypropylene, ethylene/9-propylene copolymer, ethylene/puden-1 typical polymer,
Ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene 15-ethylidene norbornene copolymer Oyohiko-f L/7/7"ropylene/
A 1,4-hexadiene copolymer or the like can be used.

The mixing ratio of (A) polyamide and modified polyolefin is polyamide = 95 to 50% by weight, preferably 90 to 50% by weight.
60% by weight and modified polyolefin = 5 to 50 weight φ, preferably 10 to 40 weight φ. If the amount of modified polyolefin used is less than 5% by weight, the impact strength improvement effect will be small, while if the amount of modified polyolefin used exceeds 50% by weight, the strength and heat resistance of the mixture will decrease, etc. is not achieved, and the original purpose of the polyamide resin composition cannot be achieved, which is not preferable.

The q-hindered phenol compound used in the present invention is, for example, 3,5-G-butyl Jv-4-
Hydroxytoluene, 2,2'-methylenebis-(4-
10-Methyl-6-t-buty)v7xnorlv), 4.4
'-Methylenebis(2,6-di-t-butylpheno-J
v), 4.4'-butylidenebis-6-t-buty/l/
-l11-cresol, 2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4
-Methylphenol, 1.1.3-tris(2'-methyl-5'-1-buty/I/-4'-hydroxyphenylene/
I/) Butane, 1.6,5-trimethyl-2,4,6-tris (6',
5'-di-t-butyl-4'-hydroxybenzyl)
Benzene, 4.4'-thiobis(2'-methyl-6'-
t-butylpheno-)v), 2,2'-thiobis(4
'-Methi/L/-6'-1-butyphlepheno-t+z
), 4,4'-thiobis(3-methyl-6-t-butylpheno-)V), ophtadeV) Lt-6-(6,5
-di-t-butyl-4-hydroxyphenyl)propionate, 1.1.1.1-tetrakis[methy/L/
-5-(3,5-di-t-buty)v-4-hydroxyphenyl)gropionate]methane, N1N'-hexamethylenebis(3,5-di-t-butyl-4-hydrocinnamamide), 2.2'-thiodiethylbis-(3
-(5,5-di-t-butyl-4-hydroxyphenyl)-furopione-)), N-lauroyl-p-aminophenol and N-stearoyl-p-aminophenol, commonly known as "Irganox" Compounds of each 111i, which are commercially available under part names such as 111i, can be used.

A typical example of the aromatic amino compound used in the present invention is 4,4'-bis(4-α,α'-dimethylbenzyl)diphenylamine, N,N'-cyβ-naphthyl-p-phenylenediamine. etc.

Cholera's hindered phenolic compounds and aromatic amine compounds can be added in combination of two or more, and the amount used is 10-+ the total amount of polyamide and modified polyolefin.
0.02 to 3 parts, more preferably 0.02 to 3 parts per part.
It is appropriate to add 0.3 to 1 part by weight. When the amount of the hindered pheno-p compound and/or aromatic amine compound added is less than 0.02 parts by weight, it is unique in that it improves fluidity during injection molding and prevents a decrease in low l-crystalline AB+4 strength after heat treatment. On the other hand, if the amount of these compounds added exceeds the sextet, it is undesirable because there is a risk that they will precipitate on the surface of the molded product, impairing the outer IN t'' or causing a decrease in physical properties.The present invention (a compound commonly called a peroxide decomposer, used in combination with a hindered phenol compound and/or an aromatic amine compound,
For example, it is also possible to add dilaurylthiodipropionate, laurylstearylthiodipropionate and dilaurylthiodipropionate. These compounds are hindered phenolic compounds and/or
Alternatively, if an aromatic amine compound is not present, even if added, the effect of improving fluidity and preventing a decrease in low-temperature impact strength after heat treatment will not be exhibited.

(c)) The method of mixing polyamide, (g) modified polyolefin, and (Q hindered phenol compound and/or aromatic amine compound) is not particularly limited, and a commonly known method can be adopted. That is, polyamide,
A method in which modified polyolefin pellets, powder, pieces, etc. and additives are uniformly mixed with a high-speed stirrer, and then melt-kneaded in a single-screw or multi-screw extruder with sufficient cross-mixing capacity. A method of kneading a modified polyolefin containing/or an aromatic amine compound in an extruder, first melt-kneading the polyamide and modified polyolefin in an extruder, and then adding a hindered pheno-p compound and/or an aromatic amine compound during molding. Any of the following methods can be used: a method in which polyamide, modified polyolefin, and additives are triblended during molding, and molding is performed by injection or extrusion.

The resin composition of the present invention may contain other components such as pigments, dyes, reinforcing agents, etc., as long as they do not impair its moldability and physical properties.
Fillers, mold release agents, lubricants, crystal nucleating agents, ultraviolet absorbers, plasticizers, antistatic agents, other polymers, and the like can be added and introduced. In particular, it is important to add commonly known mold release agents and crystal nucleating agents to improve moldability. For example, N%
Addition of N'-ethylenebisstearylamide, N%N'-methylenebisstearylamide, calcium stearate, lithium stearate, barium stearate, aluminum stearate, montanic acid wax, talc, RiV-, Kaori, etc. It is possible to do so. Addition of plasticizers is also an effective method for obtaining extremely flexible materials, such as N-butylbenzenesulfonamide, N-methylbenzenesulfonamide, N-ethyl-〇, p-toluene! Lefonamide, p-oxygen
Compounds such as benzoic acid-2-ethylhexyl ester can be utilized. In addition, by adding and blending fibrous or powder reinforcing agents and fillers such as glass fiber, asbestos fiber, carbon fiber, wollastenite, talc, calcium carbonate, and potassium titanate whiskers, the composition has high rigidity and high impact strength. can get things.

The composition of the present invention can be used for general injection molded products, hoses, tubes,
It is useful for various applications such as films, monofilaments, TSVT coverings, blow molded products, and laminates.

The present invention will be explained in more detail with reference to Examples below.

The physical properties of the test pieces described in Examples and Comparative Examples were measured and evaluated using the following method.

(1) Relative viscosity = JIS K6810 (2)
Melt index: ASTM D123
8(6) Tensile properties: ASTM D65B (
4) Bending properties: ASTM D790 (5)
Isot impact strength 1. Ac: ASTM D2
56(6) Fluidity of injection molding; So-called spiral flow test using a spiral mold Example 1 Relative viscosity obtained by melt polymerizing ε-caprolactam 1i2.
70 parts by weight of nylon 6 and 500 parts by weight of ionomer resin "HIMILAN" 1706 manufactured by Mitsui Polychemicals (melt index: 0.7, ethylene/methacrylic acid/zinc methacrylate copolymer) 100 parts by weight of mixture To this, 0.2 parts by weight of "Irganotsukunu" 1098 manufactured by Chipa Geigy was added and mixed uniformly with a high-speed stirrer, then melt-kneaded with an extruder having a diameter of 65 mm and pelletized.

After vacuum-drying the pellets, a spiral flow test was conducted using an injection molding machine under the conditions of a cylinder temperature of 250°C and a mold temperature of 70°C, with varying injection pressures and three successive thicknesses. It showed excellent fluidity with a flow length of 80 cm at kg/cAO. In addition, Izotsu impact test pieces prepared by injection molding under the same conditions were heat treated in air at 120°C for 50 hours, and then 25°C to -
When impact strength was measured in a temperature range of 40°C and the values before and after heat treatment were compared, it was found that there was almost no change in Izot impact strength and excellent low-temperature impact strength was maintained even after heat treatment.

Izot impact strength before heat treatment: 23°C 40 kg. cmAm/20°C 23 -40°C 17 Izot impact strength after heat treatment 23°C 40 kg-cm/cm Notch -20°C 22 -40tE 17 In addition, tensile strength molded at the same time as the impact test piece The physical properties of No. 23 when absolutely dry were measured using a test piece and a bending test piece, and were as follows.

Tensile yield stress: 530 kg/cA Bending yield stress: 700 kg/cJ Bending modulus: 17
, 900 kg/c, i Comparative Example 1 The fluidity in injection molding was examined in the same manner as in Example 1 except that Irganosk "109B" was not used, and the spiral flow length was 71 cm. The change in Izod impact strength due to heat treatment was extremely large, and after being treated in air at 120° C. for 50 hours, it was found that the material was extremely brittle at low temperatures.

Izod impact strength before heat treatment 23 tE 39 kglcmA
: m Notch - 20°C 22 - 40°C, 16 Izot impact strength after heat treatment 2 6°C 5 5 kg-cm/cm Notch - 20°C 4 - 40C5kg・ts/m) - f- Comparative Example 2 " in Example 1" The fluidity in injection molding was examined in the same manner as in Example 1, except that cuprous iodide and potassium iodide were added instead of "Irganox" 1098, and the spiral flow length was 72 cm+. Ta. Furthermore, when the Izod impact strength was measured in the low 1N44 range after heat treatment in air at 120° C. for 50 hours, it was found to be an extremely small value, indicating that the material was extremely brittle.

Izot impact strength before heat treatment 26°C 40 kg-cm/-notch-20
°C 23-40 °C 17 Izot impact strength after heat treatment 26 °C 5 6 kg・cm/cmJf-2
01E 4 -40tE 3 Comparative Example 3 All examples except Example 1 were added with 2μ of triphenosulfite instead of 1Irganox 1098 in Example 1.
In the same manner as above, when the fluidity was checked for one injection molding, the viscosity increased significantly and the spiral flow length was 48 cm, which was an extremely poor result.

Further, the Izod impact strength after heat treatment in air at 120° C. for 50 hours was measured in a low temperature region and was as follows.

Izot impact strength before heat treatment: 25°C 42 kg・cm/cm/cm
201Th 25 at -40 18 Izot impact strength after heat treatment 25 p 4 0 kg・cm/cm notch -20℃ 10-40℃ 8 Comparative example 4 89% by weight of ethylene and 1% by weight of methacrylic acid
66% of the methacrylic acid moiety of the copolymer was neutralized and ionized with zinc ions to give a melt index of 1.0.
An ethylene/methacrylic lv9/zinc methacrylate copolymer was prepared. Add 500% of 4,4'-butylidenebis-6-t-butyl-m-cresol to this copolymer.
P, p, m were added and blended.

The thus obtained modified polyolefin containing a hindered pheno-μ compound (20% by weight) and nylon 66 (80% by weight) were melt-kneaded at 280° C. using an extruder and pelletized. This pellet contains a calculated 0.01% by weight of a hindered phenol compound.

Next, after vacuum drying the pellets, Izot impact test pieces were prepared using an injection molding machine under the conditions of a cylinder temperature of 295°C and a mold temperature of 50°C, and this test was carried out in Example 1.
Similarly, when the Izod impact strength was measured in the low temperature region after being heat treated in air at 120° C. for 50 hours, it was found that the following unsatisfactory values were obtained.

Izo impact strength before heat treatment 25℃ 52 kg・cm, km notch
20℃ 20-40℃ 16 Izot impact strength after heat treatment 25℃ 52 to 9・C shoulder notch - 20℃
10-40°C 7 Example 2 A small amount of acetone was dissolved in 1 part of ethylene/propylene copolymer 10011I consisting of 70% ethylene and 30% frohylene.
0.06 parts by weight of /-bis-t-bunalbaroxy-p-diisofolopi7lebenzene and 0.06 parts by weight of maleic anhydride.
After adding 5 parts by weight, the mixture was kneaded at 260° C. using an extruder with a diameter of 40 mm to form a clay. After pulverizing the pellets, unreacted maleic anhydride was extracted with acetone, and then graft-reacted maleic anhydride was analyzed using the infrared absorption spectrum of PVC film.
It was found to contain 65% by weight of maleic anhydride.

The ethylene/propylene-9-maleic anhydride copolymer (melt index: 1.5) obtained here: 25% by weight was obtained by melt polymerizing hexamethylene diamine/adhihyophosphate, etc. Nylon 66 with a phase viscosity of 2.60
4.4'-bis(4-a,a'-dimethylbenzi I) per 100 parts by weight of this mixture.
After adding 0.3 parts of diphenylamine, the mixture was melt-kneaded and pelletized using an extruder having a diameter of 65 mm.

Next, after vacuum drying this PVC, a spiral flow test of 3 thicknesses was conducted using an injection molding machine at a cylinder quality of 275°C and a mold temperature of 80°C.
It showed excellent fluidity with a flow length of 93 cm when the injection pressure was 7501 cy/cd. In addition, an Izot impact test piece prepared by injection molding under the same conditions was placed in air at 100%
After heat treatment at ℃ for 150 hours, the impact strength was measured in the temperature range of 25℃ to -40℃ and the values before and after the heat treatment were compared. There was almost no change in the Izotz impact strength, and even after the heat treatment, the impact strength was excellent. It was found that it retains its strength.

Izot impact strength before heat treatment 23°C 70 kg・cm/cm/f=
20°C 23 kg・cm/vm Notch-40
'c 1'8 Izot impact strength after heat treatment 23 °C 6 8 kg・cm/cm notch -20°
tE 27 -40°C 16 Physical properties measured at 23°C and bone dry using a tensile test piece and a bending test piece molded at the same time as the Izot impact test piece were as follows.

Tensile yield stress: 530 Bending yield stress: 720 kg/cJ Flexural modulus;
18,000 kg/cl Comparative Example 5 4.4'-bis(4-α,α'-dimethylbenzi!)
The fluidity in injection molding was examined in the same manner as in Example 2 except that diphenylamine was not used, and the spiral flow length was 8'4 cm.

Furthermore, when the Izot 6ij impact strength was measured in a low temperature range after heat treatment at 100° C. for 150 hours in air, it was found to be an extremely small value, indicating that the material is extremely brittle at low temperatures.

Izot impact strength before heat treatment 26°C 70 kg・cm/cm/Tsuchi-2
0°C 27 -40°C 16 Izot impact strength after heat treatment 23°C 6 5 kg・cm/cm notch
20°C 6 -40°C 6 Examples 3 to 10 Injection was carried out in the same manner as in Example 1, changing the types and blending amounts of polyamide, modified polyolefin, and hindered phe/-/L' compounds as shown in Table 1. The fluidity during molding and the changes in Izod impact strength before and after heat treatment were investigated, and the results shown in Table 1E were obtained.

It was found that in all cases shown in Table 1, materials with excellent fluidity and impact resistance were obtained.

2 a) “/” represents copolymerization. Copolymer composition ratio (weight%)
"/" represents a mixture. Mixing ratio (weight%) b) ``Himilan'' Nimitsui Polychemical ■Ionomer resin.

“Corpolene”: Asahi Dow ionomer resin.

EPDM-"j-MA: ethylene/propylene/1.
4-hexadiene-2-maleic anhydride copolymer. (Manufactured by the method described in Japanese Patent Publication No. 52-45677) KPR-9-AA: Ethylene/propylene-9-acrylic/l/acid copolymer (manufactured by the method described in Example 2) BVA-Q- GMA: x 4- v y / acetic acid pi=tv-9-methacrylic acid Grindi I copolymer. (Manufactured by the method disclosed in Japanese Patent Publication No. 55-12449) EliiA: Nippon Unicar ■Ethylene/acrylate earth chill copolymer.

C) #Irganox”: Manufactured by Chipa Geigy.

“Ionox”: Manufactured by V.L. International.

“Dopanol” = Manufactured by C1 company.

Patent applicant: Toshi Co., Ltd.

Claims (1)

[Claims] (~Polyamide: 95-50 weight ratio and (t)carboxylic acid group, carboxylic acid metal base, carboxylic acid ester group,
(C) a hindered phenol compound and/or an aromatic amine to 100 parts by weight of a mixture consisting of 15 to 50 parts by weight of modified polyolefin 4 having at least one functional group selected from an acid anhydride group and an evoquine group; Compound: Polyamide resin composition 3° prepared by adding and blending 0.02 to 6 parts by weight