JPH0414140B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyamide resin composition that has excellent rigidity, low-temperature impact resistance, salt water resistance, and moldability. Polyamide resins are expected to be in great demand as engineering plastics due to their excellent physical properties. However, low temperature impact resistance, water resistance,
Performance such as salt water resistance is not sufficient, and improvements are desired. For example, as a method of improving impact resistance such as Izotsu impact strength,
Publication No. 12546, Japanese Patent Publication No. 1983-44108, Japanese Patent Publication No. 1983
In prior art documents such as JP-A-9661 and JP-A-55-9662, there are A method of compounding an elastomeric polymer has been proposed. The compositions proposed in these prior art documents all have improved impact resistance such as Izot impact strength.
The rigidity is greatly reduced, and furthermore, the falling weight impact strength at low temperatures is insufficient, and these compositions have the disadvantage that it is difficult to obtain actual molded products with high rigidity and high impact resistance. Furthermore, these compositions often have excessively low melt fluidity, and depending on the molding method, they also have the disadvantage of low molding processability. Furthermore, these compositions have poor water resistance, especially hydrolysis resistance, under conditions of contact with salt water such as various alkali metal salts or alkaline earth metal salts, and are therefore used in fields where such performance is required, particularly in automobile parts, etc. Its use was also restricted. In addition, as a method to improve water resistance such as hygroscopicity or salt water resistance of polyamide resin,
53-80014, JP-A-56-167751, JP-A-56-109247, and JP-A-56-157451 disclose that polyamide resin contains ethylene as one component.
A method of blending a neutralized α/β-unsaturated monocarboxylic acid copolymer (ionomer resin) has been proposed. Although the compositions proposed in these prior art documents can improve water resistance such as water absorption and salt water decomposition resistance, they have a drawback in that they are inferior in the effect of improving low-temperature impact resistance. Furthermore, as a method for improving the decrease in rigidity of the polyamide resin composition mentioned above, JP-A-57-8246 discloses a graft modified product of a composition such as a crystalline polyolefin and an ethylene/α-olefin elastic copolymer. A method of blending has been proposed. However, with this method, it is difficult to control the melt fluidity of the modified polyolefin and modified ethylene/α-olefin elastic copolymer in the graft modified product due to crosslinking, and as a result, a polyamide composition with good dispersibility cannot be obtained. The temperature range for improving impact resistance becomes significantly narrower, and the improvement effect is also small. In particular, the low-temperature isot impact strength and falling weight impact strength at -20°C or lower are significantly reduced, and the melt fluidity of the composition is also reduced. There is a drawback. Furthermore, in the prior art document, JP-A-55-
Publication No. 36279 discloses that when blending a modified ethylene/α-olefin elastomeric copolymer to improve the impact resistance of polyamide, an unmodified ethylene/α-olefin elastomeric copolymer is further added to the polyamide. A polyamide composition with excellent appearance and color tone can be obtained by blending with
It is also described that the method has excellent economic effects because the proportion of the α-olefin elastic copolymer used can be reduced. However, according to the description of the publication, especially the description of Examples and Comparative Examples, it is clear that a modified ethylene/α-olefin elastomeric copolymer and an unmodified ethylene/α-olefin elastomeric copolymer are blended into polyamide. Considering the effect of improving the impact resistance of polyamide compositions obtained by changing the composition of Although the effect of improving impact resistance is recognized compared to that of modified ethylene/α-
Compared to the experiment (reference example) in which the olefin elastic copolymer was blended alone, the impact resistance was improved in proportion to the blending ratio of the modified ethylene/α-olefin elastic copolymer. It is merely an economical effect achieved by reducing the amount of the modified ethylene/α-olefin elastomeric copolymer used. As a result of studying the development of polyamide compositions with excellent performance, the present inventors found that modified ethylene
- By blending an olefin-diene elastic copolymer and a polar vinyl monomer-containing ethylene random copolymer with a polyamide in a specific range to form a composition, the impact resistance of the polyamide composition can be improved. With regard to the improvement effect of the modified ethylene/α-olefin/diene elastic copolymer and the polar monomer-containing ethylene random copolymer, there is a synergistic effect;
The inventors have discovered that the present invention is not only effective in reducing the amount of the α-olefin/diene elastic copolymer used, and have arrived at the present invention. According to the present invention, the polyamide composition of the present invention has improved impact resistance such as isot impact strength and falling weight impact strength at low temperatures, stress crack resistance, and water absorption and salt water decomposition resistance under salt water conditions. The water resistance of the composition has been significantly improved, and furthermore, this composition has excellent moldability because there is little decrease in melt flowability. To summarize the present invention, the present invention comprises polyamide
(A), a modified ethylene/α-olefin/diene elastic copolymer (B), and a polar vinyl monomer-containing ethylene random copolymer (C), the polyamide composition comprising: The composition of the components is the modified ethylene α based on 100 parts by weight of the polyamide (A).
- The olefin-diene elastic copolymer (B) is in the range of 1 to 100 parts by weight, and the polar vinyl monomer-containing ethylene random copolymer (C) is in the range of 1 to 100 parts by weight, [] The modified ethylene/α-olefin/diene elastic copolymer (B) has a base ethylene/α-olefin/diene elastic copolymer having a diene component unit content of more than 0.5 mol% and 10 mol% or less. It is obtained by graft copolymerizing an unsaturated carboxylic acid or its derivative component unit in the range of 0.01 to 10 parts by weight to 100 parts by weight of the polymer, and the crystallinity is in the range of 40% or less, and at 190 ° C. Melt flow rate [MFR 190℃] is 0.01
and [] the polar vinyl monomer-containing ethylene random copolymer (C) contains vinyl acetate, (meth)acrylic acid ester,
At least one selected from the group consisting of (meth)acrylic acid and neutralized salts of (meth)acrylic acid
A polyamide containing ethylene component units as a main component, and having a melt flow rate at 190°C [MFR 190°C] of 0.01 to 100 g/10 min. The gist of the invention is a composition. The polyamide (A) used in the polyamide composition of the present invention is of sufficient molecular weight to produce molded articles, and is composed of a saturated organic dicarboxylic acid having 4 to 12 carbon atoms and a saturated organic dicarboxylic acid having 2 to 13 carbon atoms. It can be produced by condensing equimolar amounts of organic diamines having atoms. Here, if necessary, diamine can be used in the polyamide so that the amino group ends are in excess compared to the carboxyl group ends, or conversely, dicarboxylic acid can be used so that the carboxyl groups are in excess. can. These polyamides can also be produced from the amine and acid-forming derivatives and amine-forming derivatives, such as esters, acid chlorides, amine salts, and the like. Typical dicarboxylic acids used to make polyamides include adipic acid, pimelic acid, suberic acid, sebacic acid and dodecanedioic acid. On the other hand, typical diamines include hexamethylene diamine and octamethylene diamine. Furthermore, polyamides can also be produced by self-condensation of lactams. Examples of polyamides include polyhexamethylene adipamide (6.6 nylon), polyhexamethylene azelamide (6.9 nylon), polyhexamethylene sebaamide (6.10 nylon) and polyhexamethylene dodecanoamide (6.12 nylon), There are polybis(4-aminocyclohexyl)methandodecanamides, or polyamides prepared by ring opening of lactams, namely polycaprolactam (6nylon), polylauritulactam or poly-11-aminoundecanoic acid. It is also possible to use polyamides produced by polymerization of at least two amines or acids used to produce the polyamides mentioned above, for example polymers made from adipic acid and isophthalic acid and hexamethylene diamine. be. It is also possible to use blends of polyamides such as nylon 6.6 and mixtures of nylon 6. The condensation polyamides used in the present invention are preferably polyhexamethylene adipamide (nylon 6.6) or polyhexamethylene azeramide (nylon 6.9) and polycaprolactam (nylon 6). Modified ethylene/α-olefin/diene elastic copolymer (B) blended into the polyamide composition of the present invention
The content of diene component units exceeds 0.5 mol%,
Unsaturated carboxylic acid or its derivative component unit per 100 parts by weight of the base ethylene/α-olefin/diene elastic copolymer in a range of 10 mol% or less.
Graft copolymerized in the range of 0.01 to 10 parts by weight, the crystallinity is in the range of 40% or less, and the melt flow rate at 190℃ [MFR B 190℃] is in the range of 0.01 to 50g/10min. Furthermore, the base ethylene α-
It is obtained by graft copolymerizing an unsaturated carboxylic acid or its derivative component unit in a range of 0.05 to 5 parts by weight to 100 parts by weight of an olefin-diene elastic copolymer, and its crystallinity is in a range of 0 to 30%. It is preferable that the melt flow rate at 190°C [MFRB 190°C] is in the range of 0.05 to 20g/10min. Furthermore, the modified ethylene
Other physical properties of the α-olefin/diene elastic copolymer (B) are that the molecular weight distribution (w/n) is usually 1 to 1.
50, preferably in the range of 1 to 20, the melting point is usually below 80°C, preferably below 75°C, and the glass transition temperature is usually below -10°C, preferably -20°C
It is in the following range. The grafting ratio of unsaturated carboxylic acid or its derivative component units in the modified ethylene/α-olefin/diene elastic copolymer is 0.01.
If it is less than 10 parts by weight, the impact strength of the polyamide composition, especially low-temperature impact strength, decreases due to a decrease in compatibility with the polyamide, and if it exceeds 10 parts by weight, the water resistance and impact resistance of the composition decrease. Become. When the crystallinity of the modified ethylene/α-olefin/diene elastic copolymer exceeds 40%, the impact strength of the polyamide composition decreases, and the melt flow rate decreases to 0.01 g/
If it is less than 10 min, the dispersibility with the polyamide will be poor, resulting in a decrease in the impact strength and melt fluidity of the composition, and if it is more than 50 g/10 min, the impact resistance will be decreased. The base polymer constituting the modified ethylene/α-olefin/diene elastic copolymer is a random copolymer of ethylene component units, α-olefin component units other than ethylene, and diene component units,
It is an elastic copolymer with low crystallinity. Its composition is such that the content of ethylene component units is usually 95 to 35 mol%, preferably 90 to 40 mol%, and the content of α-olefin component units is usually 5 to 65 mol%, preferably 10 to 60 mol%. be. The content of diene component units is in the range of more than 0.5 mol% and less than 10 mol%. In addition, its crystallinity is usually 40% or less, preferably 30% or less, and its melt flow rate [MFRB 190℃] is usually 0.01 to 30%.
100g/10min, preferably 0.05 to 20g/
The glass transition temperature is usually -10°C or lower, preferably -20°C or lower. The α-olefin component units other than ethylene constituting the base ethylene/α-olefin/diene elastic copolymer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene,
1-hexene, 1-octene, 1-decene, 1-
Examples include dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene, and a mixture of two or more of these may be used. In addition, as a diene component unit, 1,4
-hexadiene, 1,5-hexadiene, 1,7
-Octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-
Examples include non-conjugated diene components such as norbornene and 2,5-norbonadiene, and conjugated diene components such as butadiene, isoprene, and piperylene, and a mixture of two or more of these components is also acceptable. , is preferably a non-conjugated diene component. Specifically, the base ethylene/α-olefin/diene elastic copolymer includes ethylene/propylene/1,4-hexadiene copolymer, ethylene/propylene/1,7-octadiene copolymer, and ethylene/propylene/1,7-octadiene copolymer. Dicyclopentadiene copolymer, ethylene/propylene/
5-ethylidene-2-norbornene copolymer, ethylene/propylene/5-vinyl-2-norbornene copolymer, ethylene/propylene/5-ethylidene-2-norbornene/5-vinyl-2-norbornene copolymer, ethylene ·propylene·
2,5-norbonadiene copolymer, ethylene/1
-Butene/1,4-hexadiene copolymer, ethylene/1-butene/1,7-octadiene copolymer, ethylene/1-butene/dicyclopentadiene copolymer, ethylene/1-butene/5-ethylidene-2 -Norbornene copolymer, ethylene 1
-Butene・5-ethylidene-2-norbornene・
Examples include 5-vinyl-2-norbornene copolymer and ethylene/1-butene/5-vinyl-2-norbornene copolymer. Examples of the unsaturated carboxylic acid or its derivative component unit of the graft monomer component constituting the modified ethylene/α-olefin/diene elastic copolymer (B) include acrylic acid, methacrylic acid, α-ethyl acrylic acid, and maleic acid. , fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid,
Methyltetrahydrophthalic acid, endocis-bicyclo[2.2.1]hept-5-ene-2,3-
Dicarboxylic acid (nadic acid), methyl-endocys-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (methyl nadic acid)
Examples include unsaturated carboxylic acids such as unsaturated carboxylic acids, and derivatives of unsaturated dicarboxylic acids such as acid halides, amides, imides, acid anhydrides, and esters of unsaturated carboxylic acids. Specifically, maleyl chloride, maleimide, maleic anhydride, etc. , citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred. To produce the modified ethylene/α-olefin/diene elastic copolymer by graft copolymerizing the graft monomer selected from the unsaturated carboxylic acid or its derivative onto the ethylene/α-olefin/diene elastic copolymer, Various conventionally known methods can be employed. For example, ethylene α
- There is a method in which the olefin/diene elastic copolymer is melted and a graft monomer is added thereto to perform graft copolymerization, or a method in which the olefin/diene elastic copolymer is dissolved in a solvent and a graft monomer is added therein to perform graft copolymerization. In either case, a radical initiator may be used to efficiently graft copolymerize the graft monomer. Grafting reactions are usually 60
It is carried out at a temperature between 350°C and 350°C. The ratio of radical initiator used is usually 0.01 to 100 parts by weight of the ethylene/α-olefin/diene elastomeric copolymer.
In the range of 10 parts by weight. As the radical initiator, organic peroxides, organic peresters, azo compounds, etc. can be used. Polar vinyl monomer-containing ethylene random copolymer (C) blended into the polyamide composition of the present invention
contains at least one component unit selected from the group consisting of vinyl acetate, (meth)acrylic acid ester, (meth)acrylic acid, and neutralized salts of (meth)acrylic acid as a polar vinyl monomer, and contains an ethylene component. It is an ethylene-based random copolymer whose main component is ethylene units, and its melt flow rate at 190°C must be in the range of 0.01 to 100 g/10 min, and furthermore, it must be in the range of 0.05 to 100 g/10 min.
Preferably, it is in the range of 50g/10min. The melt flow rate of the polar vinyl monomer-containing ethylene random copolymer (C) at 190°C is 0.01.
When the impact strength of the polyamide composition becomes smaller than 100g/10min, the impact strength of the polyamide composition decreases.
If the heating time exceeds 10 min, the impact strength, tensile strength, and bending strength of the polyamide composition will decrease. When the polar vinyl monomer-containing ethylene random copolymer (C) is an ethylene random copolymer containing vinyl acetate component units, the content of the ethylene component units is usually 70 to 99.5 mol%,
The ethylene/vinyl acetate random copolymer is preferably in the range of 75 to 99 mol%, and the content of vinyl acetate component units is usually in the range of 1 to 30 mol%, preferably 2 to 25 mol%. Its crystallinity is usually in the range of 0 to 60%, preferably 0 to 50%, its melting point is usually in the range of 105°C or less, preferably 100°C or less, and its density is usually 0.92 to 1.20 g/cm ³ , preferably 0.93
and 1.10 g/cm ³ . The ethylene/vinyl acetate copolymer may contain carbon monoxide as the third monomer component. When the polar vinyl monomer-containing ethylene random copolymer (C) is an ethylene random copolymer containing (meth)acrylic acid or its neutralized salt component units, the content of the ethylene component units is usually The content of neutralized salt component units of (meth)acrylic acid is usually in the range of 0.05 to 10 mol%, preferably 0.1 to 8 mol%. be. The ethylene random copolymer containing neutralized salt component units of (meth)acrylic acid is usually [1] ethylene.
(meth)acrylic acid random copolymer (meth)
A method of converting acrylic acid component units into neutralized salt component units of (meth)acrylic acid by neutralizing them, [2] (meth)acrylic acid by hydrolysis of an ethylene/(meth)acrylic acid ester random copolymer A method of converting an ester component unit into a (meth)acrylic acid component unit and further neutralizing this into a neutralized salt component unit of (meth)acrylic acid, or [3] Ethylene/(meth)acrylic acid It can be produced by any method of converting (meth)acrylic acid ester component units into (meth)acrylic acid neutralization salt component units by directly saponifying the ester random copolymer. . Furthermore, in any of the above methods [1], [2], and [3], vinyl acetate may be contained as a polar vinyl monomer other than (meth)acrylic acid and its derivatives. moreover,
There is no problem even if carbon monoxide is contained as a copolymerization component other than the polar vinyl monomer. The ethylene random copolymer containing (meth)acrylic acid neutralized salt component units contains, in addition to two essential components, ethylene component units and (meth)acrylic acid neutralized salt component units, as is clear from the above manufacturing method. , (meta)
It may contain acrylic acid component units, (meth)acrylic acid ester component units, and/or vinyl acetate component units. The content of the (meth)acrylic acid and/or (meth)acrylic acid ester component units is usually in the range of 0.1 to 15 mol%, preferably 0.5 to 10 mol%. The content of neutralized salt component units of (meth)acrylic acid in the ethylene-based random copolymer is within the above range, and the neutralization rate of (meth)acrylic acid component units is usually 1% or more, preferably It is in the range of 5 to 90%. Further, the content of vinyl acetate component units in the ethylene random copolymer is usually in the range of 1 to 30% by mole, preferably 2 to 20% by mole. The degree of crystallinity of the ethylene random copolymer containing neutralized salt component units of (meth)acrylic acid is usually 0 to 0.
50%, preferably in the range of 0 to 40%, its melting point is usually below 105°C, preferably in the range of 102°C, and its density is usually 0.92 to 1.20 g/cm ³ ,
It is preferably in the range of 0.925 to 1.10 g/cm ³ . When the polar vinyl monomer-containing ethylene random copolymer (C) is an ethylene random copolymer containing neutralized salt component units of the (meth)acrylic acid, specifically as the (meth)acrylic acid component unit, is an acrylic acid or methacrylic acid component unit, and the neutralization salt component unit of (meth)acrylic acid is specifically an ammonium salt or metal salt of acrylic acid or methacrylic acid. Examples of metal salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, calcium salts, strontium salts, and barium salts, zinc salts, cadmium salts, and aluminum salts. is preferably an ammonium salt, an alkali metal salt, a magnesium salt or a zinc salt. In addition, (meth)acrylic acid ester components include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. Examples include acid alkyl esters. In the polyamide composition of the present invention, the modified ethylene/α-olefin/diene elastic copolymer (B)
When blending the polar vinyl monomer-containing ethylene random polymer (C) into polyamide, the ratio of their melt flow rates at 190°C [[MFR 190°C], [[MFRB 190°C]/[[ MFRC 190°C] is usually adjusted to a range of 0.01 to 100, and preferably adjusted to a range of 0.02 to 50. In the polyamide composition of the present invention, the blending ratio of the modified ethylene/α-olefin/diene elastic copolymer (B) to 100 parts by weight of the polyamide (A) must be in the range of 1 to 100 parts by weight. and more preferably in a range of 2 to 80 parts by weight. The blending ratio of the modified ethylene/α-olefin/diene elastic copolymer is 100
If the amount is more than 1 part by weight, the rigidity and melt flowability of the polyamide composition will be reduced, and if it is less than 1 part by weight, the impact resistance, stress crack resistance and water resistance of the polyamide composition will be reduced. Become. Further, the blending ratio of the polar vinyl monomer-containing ethylene random copolymer (C) to 100 parts by weight of the polyamide (A) is 1 to 1.
It is necessary that the amount is in the range of 100 parts by weight, and more preferably in the range of 2 to 80 parts by weight. When the blending ratio of the polar vinyl monomer-containing ethylene random copolymer exceeds 100 parts by weight, the rigidity of the polyamide composition decreases, and when it becomes less than 1 part by weight, the impact resistance and resistance of the polyamide composition decrease. Stress crack resistance and water resistance begin to decline. Furthermore, in the polyamide composition of the present invention, the modified ethylene α-
The blending ratio of the polar vinyl monomer-containing ethylene random copolymer (C) to 100 parts by weight of the olefin-diene elastic copolymer (B) is usually 5 to 2000 parts by weight.
parts by weight, preferably in the range of 10 to 1500 parts by weight. Furthermore, in the polyamide composition of the present invention, the graft copolymerized amount of the modified ethylene-α-olefin-diene elastic copolymer (B) and the polar vinyl monomer-containing ethylene random copolymer (C) The proportion of unsaturated carboxylic acid or its derivative component units is usually 0.02 to 7.
% by weight, preferably in the range 0.05 to 5% by weight. In addition to the above-mentioned three essential components, the polyamide composition of the present invention may optionally contain antioxidants, ultraviolet absorbers, photoprotectants, phosphite stabilizers, peroxide decomposers, basic adjuvants, It is also possible to incorporate fillers such as nucleating agents, plasticizers, lubricants, antistatic agents, flame retardants, pigments, dyes, carbon black, asbestos, glass fibers, carrion, talc, silica, and silica alumina. Furthermore, other polymers can be blended into the composition of the present invention within a range that does not impair its physical properties. The blending ratio of these additives is within an appropriate range. The polyamide compositions of the present invention are prepared by melt mixing in a variety of ways. For example, two essential components may be premixed and then mixed with the remaining other components, or three essential components may be mixed with other remaining components that may be added as needed. Moreover, the above-mentioned additives, such as antioxidants, can be added at any of these stages as necessary. The polyamide composition of the present invention has excellent properties such as rigidity, impact resistance, and water resistance. Among them, when producing the composition, (B) component and (C)
A composition obtained by melt-mixing the polyamide (A) component into a premix obtained by preliminary melt-mixing of the components has particularly excellent performance. The melt flowability [melt flow rate (MFR, 235°C, 1000g load)] of the composition of the present invention is usually 0.1
to 500g/10min, preferably 0.2 to 100
The range is g/10min. The polyamide composition of the present invention can be molded into various shapes by various conventionally known melt molding methods. Examples include methods such as injection molding, extrusion molding, compression molding, and foam molding, and are used for a wide range of applications including automobile parts, electrical appliances, and electrical parts. Next, the present invention will be specifically explained using examples. In addition, in the method of the present invention, the degree of crystallinity and the melt flow rate at 190°C [MFR 190°C] were measured by the following method. Crystallinity: Measured by X-ray diffraction at 23°C. Melt Flare Rate [MFR 190℃]: ASTM D
Measured under -1238-79E conditions (190°C, 2160g). Example 1 Maleic anhydride modified ethylene propylene 5
-ethylidene-2-norbornene copolymer [propylene unit content 36.7 mol%, 5-ethylidene-2
-Norbornene unit content 2.3 mol%, MFR 190℃
0.85g/10min, density 0.87g/cm ³ , crystallinity 10%,
Glass transition point -65℃, molecular weight distribution w/n8]
and Zn-neutralized product of ethylene/methacrylic acid/isobutyl methacrylate ternary random copolymer [methacrylic acid unit content 3.7 mol%, isobutyl methacrylate unit content 2.3 mol%, degree of neutralization with Zn 70
%, MFR 190℃ 1.0g/10 minutes, density 0.96g/cm ³ , crystallinity 27%, melting point 85℃] at the ratio shown in Table 1, 30
Premixing was performed using a mmφ extruder (L/D28, set at 230°C). Next, this premix and nylon 6 [manufactured by Toray Industries, Inc., Amiran CM1021XF,
MFR 3.74g/10min, Q conditions] were mixed in the proportions shown in Table 1 to prepare a dry blend consisting of two types of pellets. Furthermore, it is fed to a single screw extruder (L/D28, 30mmφ) set at 260℃,
A melt blend (pellet form) was prepared. The pellets were vacuum-dried at 100° C. for one day and night, and then injection molded under the following conditions to prepare specimens for measuring physical properties. Cylinder temperature: 260°C Injection pressure: 650Kg/cm ² Injection time: 10sec Mold temperature: 80°C Subsequently, physical properties were evaluated using the following method. MFR measurement: ASTM D-1238-79 Q condition MFR
was measured. Bending test: ASTM D using a 1/8″ thick test piece
-790-80 gives flexural modulus FM (Kg/cm ² ),
The bending yield strength FS (Kg/cm ² ) was measured. The test pieces were conditioned for 3 days in a constant temperature and humidity room at 23°C and 50% RH. Falling weight impact strength: A weight of a certain shape is dropped from a height of 90cm onto a test piece (diameter 50mmφ, thickness 1.2mm) placed horizontally at -60℃, and a certain number of pieces are tested by varying the weight of the weight. Falling weight impact strength was evaluated based on the weight (g) of weight required for 50% of the pieces to break. The test pieces were conditioned for 3 days in a constant temperature and humidity room at 23°C and 50% RH. Izotsu impact strength: using a 1/8″ thick test piece,
-40°C notched isot impact strength was measured according to ASTM D-256. The condition of the test piece was adjusted in a constant temperature and humidity room at 23℃ and 50% RH.
I went there today. Water absorption test: According to ASTM D-570, a test piece (2 inches in diameter, 1/8 inch in thickness) was heated at 100℃ for 24 hours.
After drying for an hour, a water absorption test was conducted in water at 50°C for 48 hours, and the water absorption rate (%) was determined from the weight change rate of the test piece. The results are shown in Table 1. Examples 2 to 13 and Comparative Examples 1 to 5 Modified ethylene/α-olefin shown in Table 1
A blend was prepared in the same manner as in Example 1, except that the diene elastic copolymer (B) and the random copolymer containing ethylene/polar vinyl monomer (C) were used in the proportions shown in Table 1, and the physical properties were measured. did. The results are shown in Table 1.

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Claims (1)

[Scope of Claims] 1. A polyamide composition comprising a polyamide (A), a modified ethylene/α-olefin/diene elastic copolymer (B), and a polar vinyl monomer-containing ethylene random copolymer (C), [] The composition of each component in the composition is based on 100 parts by weight of the polyamide (A).
- The olefin-diene elastic copolymer (B) is in the range of 1 to 100 parts by weight, and the polar vinyl monomer-containing ethylene random copolymer (C) is in the range of 1 to 100 parts by weight, [] The modified ethylene/α-olefin/diene elastic copolymer (B) has a base ethylene/α-olefin/diene elastic copolymer having a diene component unit content of more than 0.5 mol% and 10 mol% or less. It is obtained by graft copolymerizing an unsaturated carboxylic acid or its derivative component unit in the range of 0.01 to 10 parts by weight to 100 parts by weight of the polymer, and the crystallinity is in the range of 40% or less, and at 190 ° C. Melt flow rate [MFR 190℃] is 0.01
and [] The polar vinyl monomer-containing ethylene random copolymer (C) contains vinyl acetate, (meth)acrylic acid ester,
It contains at least one component unit selected from the group consisting of (meth)acrylic acid and neutralized salts of (meth)acrylic acid, and has an ethylene component unit as its main component, and its temperature at 190°C Melt flow rate [MFR 190℃] is 0.01
A polyamide composition, characterized in that it is in the range of 100g/10min to 100g/10min.