JPS58201845A - Polyamide resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a polyamide resin composition.

In particular, the present invention relates to polyamide resin compositions having improved ductility, toughness and impact resistance.

Polyamide resin (hereinafter abbreviated as MX nylon), which is synthesized from xylylene diamine whose main component is meta-xylylene diamine and α,ω-linear aliphatic dibasic acid, is a high elastic modulus fiber or biaxially stretched film. It is attracting attention industrially. However, in the unstretched state, it has the property of brittle fracture at room temperature and has poor impact resistance, so hot-stretched products have not been of industrial value for a long time.

Kanmoto et al., by blending glass fiber etc. with MX nylon, the above drawbacks are greatly improved and the chemical properties, thermal properties,
It was discovered that a molding material or molded product with excellent mechanical properties could be obtained (Japanese Patent Publication No. 54-32458). Because of its excellent physical properties, MX nylon reinforced with glass fiber is used as an engineering plastic. As such, there are high expectations for its future. However, its ductility and toughness are still not sufficient.

Generally, various methods have been proposed to improve the impact resistance of polyamide resins. For example, British patent 998,4
No. 39 is a thermoplastic resin comprising a mixture of 50 to 99% linear polyamide and 1 to 50% olefin copolymer particles, and in which the olefin copolymer contains 0.1 to 10 mol% of acid groups. A composition is disclosed. In addition, U.S. Pat. No. 3,845,163 discloses a copolymer of an α-olefin and an α,β-ethylenically unsaturated carboxylic acid in which at least 10% of the acid groups are formed by metal ions in order to improve the toughness of molded products. It has been shown to form a resin composition with a neutralized ionic copolymer. However, the compositions shown in Patent V (the composition shown in this patent are still insufficient in terms of the impact resistance of molded articles, and the moldability of the compositions are not sufficient. When fillers are contained, there are problems with moldability and fluidity, and improvements have long been desired.

MX nylon differs greatly in basic physical properties, crystallization behavior, etc. from general-purpose polyamide resins such as nylon 6 and nylon 66, so it is different from α-olefin.

To obtain a molding material with excellent performance and workability that could not be achieved by techniques conventionally applied to general-purpose polyamide resins, such as adding a copolymer with β-unsaturated carboxylic acid or a copolymer similar thereto. I can't. MX nylon is a material that has a relatively slow crystallization rate and an extremely low mold shrinkage rate, so it may be difficult to release the molded product from the mold.

Furthermore, the time required for crystallization or solidification of the molded product becomes longer, resulting in many disadvantages such as a significantly longer molding cycle.

The present inventors have arrived at the present invention as a result of intensive research to obtain an MX nylon molding material with excellent moldability and impact resistance.

Therefore, the present invention is characterized by the following: 1 to 99 parts by weight, preferably 50 to 99 parts by weight, of a polyamide resin obtained from xylylene diamine and an α,ω-linear aliphatic dibasic acid, and 6699 to 1 part by weight of nylon. , preferably 50 to 1 N parts, 1 part by weight of 100 parts, (0) an α-olefin and/or conjugated diolefin compound, and an α, β-unsaturated carboxylic acid and/or a metal salt thereof. A copolymer having a structural unit derived from α-olefin and/or a conjugated diolefin, optionally further having a structural unit derived from α,β-unsaturated carboxylic acid ester. A modified α-olefin and/or conjugated diene copolymer in which the structural units derived from the system compound are present in a proportion of 75 to 98 mol%, preferably 80 to 98 mol%.
It is a polyamide-based resin composition consisting of il'H5-.

The MX nylon used in the present invention is composed of meta-xylylene diamine alone or a diamine mixture containing 60% by weight or more of metaxylylene diamine and 40% by weight or less of para-xylylene diamine, and a carbon number of 6 to 12 expressed by the general formula %. α of (n=4-10)
, a polyamide resin synthesized by a polycondensation reaction with an ω-linear aliphatic dibasic acid, such as adipic acid, sebacic acid, superric acid, undecane dioic acid, dodecane diacid, etc. Considering the balance of moldability, molded product performance, etc., the above α.

Among the ω-linear aliphatic dibasic acids, adipic acid is particularly preferred.

In the present invention, useful modified α-olefin and/or conjugated diene copolymers added to improve the impact resistance of the polyamide resin composition include ethylene/isobutyl acrylate/methacrylic acid, ethylene/acrylic Methyl 6-acid/methacrylic acid, ethylene/methyl methacrylate/methacrylic acid, ethylene/propylene/1°4 hexadiene/maleic anhydride or maleic acid monoester, ethylene/propylene/norbornadiene/maleic anhydride or maleic acid monoester, ethylene/propylene/1
, 4-hexadiene/fumaric acid, ethylene/acrylic acid, ethylene/methacrylic acid, ethylene/maleic anhydride or maleic acid monoester copolymers, and some or all of the carboxylic acid moieties of the copolymers are metal salts. It is a copolymer etc., and the structural units are present in a ratio of 75 to 98% from an α-olefin and/or a conjugated diene compound.

In addition, as is clear from these examples, in the present invention, α, β
-Unsaturated carboxyl alcohols shall also include acid anhydrides and dibasic acid monoesters.

The composition of the present invention is produced by melt-mixing the copolymer described above with a polyamide resin M4 composition consisting of MX nylon and nylon 66.

Addition of a copolymer effective for imparting impact resistance to polyamide resin compositions is effective for imparting impact resistance to polyamide resin compositions.
The amount is 3 to 100 parts by weight per 0 weight IsK, and these resins are mixed in advance in a mixer and then manufactured in a screw type extruder or similar equipment. The extrusion temperature is preferably in the range of 5 to 50°C higher than the melting point of the polyamide resin.The composition of the present invention may contain one or more conventional additives, such as oxidation, thermal Also included are embodiments modified with stabilizers, inhibitors, nucleating agents, plasticizers, flame retardants, antistatic agents, lubricants, etc. against deterioration due to ultraviolet rays and the like.

Further, in the polyamide resin composition of the present invention, inorganic fillers such as glass fiber and calcium carbonate are added to 5 to 100 repaired parts.
The polyamide resin composition prepared by adding 1 part by weight of 150% has significantly improved physical properties, and is also excellent in moldability and fluidity.

The following examples and comparative examples will be used to explain Example 1 Ethylene/methyl methacrylate/methacrylic acid/sodium methacrylate copolymer (molar ratio 95/1.5/I
, 8/1.7 + modified hydrocarbon A), 90 parts of nylon MXD 6 (linear polyamide resin obtained from xylylene diamine and adipic acid, the same applies hereinafter), and 665 parts of nylon were mixed and After melt-mixing at a cylinder temperature of 270°C using a single-screw extruder, the polyamide-based resin composition was formed into water-cooled pellets.The pellets were used to mold test pieces and subjected to physical property tests. . The test piece molding conditions, test piece shape, and test method are as follows.

Test piece forming conditions Mold temperature 130℃ Resin temperature 255℃ Injection time: 15 seconds.

Cooling time: 15 seconds.

Test method Tensile strength ASTM D 63B 9- Elongation ASTM D 638 Tensile modulus ASTM D 658 Bending strength ASTM D 79[1 Flexural modulus ASTM D 790 Izot impact ASTM D 256 Heat distortion temperature AS'l'MD 64B test results are shown in Table 1.

Examples 2 to 5 and Comparative Example 1.2 In the same manner as in Example 1, polyamide resin compositions were obtained based on the formulations shown in Table 1. Test pieces were molded using these molding materials and subjected to physical property tests. Table 1 shows these results.
It was shown to.

In Comparative Example 1, nylon MXD6 was evaluated as a molding material, and in Comparative Example 2, a molding material obtained by melt-mixing nylon MXD695 and nylon 665 parts by weight was evaluated.

Example 6 Ethylene/methacrylic acid/methyl methacrylate/magnesium methacrylate (molar ratio 82/7/4/
7. Modified hydrocarbon B) 10 parts by weight, nylon MXD6
45iiH: After mixing 66511" parts of nylon and 40 parts by weight of glass [41 (3, chopped strand) in a mixer, using a shore screw extruder,
The mixture was melt-mixed at a cylinder temperature of 270°C, cooled with water, and pelletized to obtain a polyamide resin composition. A test piece was formed using this pellet and subjected to physical property measurements.

The molding conditions and test method for the test were the same as in Example 1. Table 1 shows the formulation and physical property measurement results.

Examples 7 to 9 Polyamide resin compositions were obtained in the same manner as in Example 6,
It was subjected to physical property tests. The formulation, molding conditions, and physical property measurement results are shown in Table 1.

Examples 10 to 12 Polyamide resin compositions were obtained in the same manner as in Example 6 using various modified hydrocarbons.

Modified hydrocarbon C; ethylene/isobutyl acrylate/methacrylic acid/zinc methacrylate = 95/1/2/2 (
Molar ratio) Modified hydrocarbon D; ethylene/propylene/maleic acid monomethyl ester/maleic acid concentration 55/41/2/2
(Molar ratio) Modified hydrocarbon E: Ethylene/methyl acrylate/sodium acrylate = 9515/2 (molar ratio) Table 1 shows the blending recipe and the results of physical property tests of the obtained molded piece of polyamide resin.

Procedural amendment 1. Display of the case 1982 Patent Application No. 60806 2, Name of the invention Polyamide resin composition 3, Person making the amendment Relationship to the case Patent applicant Address 2-5 Marunouchi, Chiyoda-ku, Tokyo February Name Mitsubishi Gas Chemical Co., Ltd. "Claims" column and "Detailed Description of the Invention (2) "Detailed Description of the Invention" column of the specification of the corporation ■ Page 2, line 10 of the specification "Polyamide resin composition ” is corrected to 1. “Polyamide resin composition.”

■ "Polyamide resin composition part" on page 5, lines 8 to 9 of the specification is "polyamide resin composition"
Correct.

- Correct "conjugated diene system" to "conjugated diolefin system" in page 5, line 20 of the specification, page 6, lines 18-19, and page 7, line 12.

■ On page 7, line 13 of the specification, "kara structural unit" is corrected to "kara derived structural euphoria."

■ "Polyamide resin composition" on page 8, line 14 of the specification has been corrected to "polyamide resin composition."

■ On page 9, lines 5-6 of the specification, “xylylenediamine” is changed to “metaxylylenediamine”
Correct.

6. List of attached documents (claims) 1
100 parts by weight of a polyamide resin composition consisting of 1 to 99 parts by weight of a polyamide resin obtained from xylylene diamine and an α, ω-linear aliphatic dibasic acid and 6699 to 1 part by weight of nylon; It has a structural unit derived from an olefin and/or a conjugated diolefin compound and an α,β-unsaturated carboxylic acid and/or a metal salt thereof, and if desired, further α
, a copolymer having a structural unit derived from a β-unsaturated carboxylic acid ester, in which the structural unit derived from an α-olefin and/or a conjugated diolefin compound is 75 to 98 moles. Polyamide resin composition 2 comprising 3 to 100 parts by weight of a modified α-olefin and/or conjugated diolefin copolymer present in a proportion of %, polyamide LiLJ1 according to claim 1
Polyamide resin composition consisting of 1 composition: 100 parts by weight and 5 to 150 parts by weight of an inorganic filler

Claims (1)

[Scope of Claims] 1(a) A polyamide resin composition comprising 1 to 99 parts by weight of a polyamide resin obtained from xylylene diamine and an α,ω-linear aliphatic dibasic acid and nylon 6699 to 1 part by weight. (b) a structural unit derived from an α-olefin and/or a conjugated diolefin compound and an α,β-unsaturated carboxylic acid and/or a metal salt thereof; - A copolymer having a structural unit derived from an unsaturated carboxylic acid ester, the copolymer having α-
A polyamide comprising 3 to 100 parts by weight of a modified α-olefin and/or conjugated diene copolymer in which the structural units derived from an olefin and/or a conjugated diolefin compound are present in a proportion of 75 to 98 mol%. Resin composition 2, a polyamide resin composition comprising 100 parts by weight of the polyamide resin composition according to claim 1 and 5 to 150 parts by weight of an inorganic filler.