JPS6356559A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition suitable as exterior automotive trim, etc., having improved heat resistance, chemical resistance, impact resistance, etc., by blending specific amounts of polytetramethylene adipamide, polyarylene sulfide and a specific modified rubber-like polymer. CONSTITUTION:(A) 96-39wt%, preferably 95-45wt% polytetramethylene adipamide resin which is a polyamide consisting of a repeating constituent unit shown by formula I and has >=1.5 relative viscosity is blended with (B) 3-60wt%, preferably 5-50wt% polyarylene sulfide comprising a constituent unit shown by formula II (R is >=6C aromatic group) as a main component and (C) 1-47wt%, preferably 5-25wt% modified rubber-like polymer (e.g. styrene-butadiene copolymer, etc.) modified with a functional group selected from carboxyl group, acid anhydride group, epoxy group and hydroxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a polyamide resin composition having excellent heat resistance, chemical resistance, impact resistance, and mechanical strength.

b. Prior art polytetramethylene adipamide resin (hereinafter referred to as nylon 4.
6) has excellent heat resistance and toughness, and is expected to be put into practical use as a structural material for various purposes. However, nylon 4.6 has the drawback of poor solvent resistance and impact resistance.

Problems to be Solved by the C0 Invention The inventors of the present invention have conducted intensive studies to improve the above-mentioned drawbacks of nylon 4.6, and as a result, they have modified nylon 4.6 with a specific proportion of polyarylene sulfide and a specific functional group. By blending rubbery polymers, nylon 4,6
It has been found that the crystallinity of polyarylene sulfide is increased and the chemical resistance and impact resistance are improved. Surprisingly, it was unexpected that the heat resistance and mechanical strength were further improved. The present invention was achieved based on this knowledge.

Means for solving the d0 problem, that is, the present invention is: (A) Polytetramethylene adipamide resin 96-3
9% by weight (B) 3-60% by weight of polyarylene sulfide and (C) carboxyl group, acid anhydride group, epoxy group,
The present invention provides a polyamide resin composition comprising 1 to 47% by weight of a modified rubbery polymer modified with at least one functional group selected from amino groups and hydroxyl groups.

Nylon 4,6 (A) used in the present invention has the following formula %
It is a polyamide consisting of a repeating structural unit represented by the formula
Publication No. 30, Publication No. 56-149431, Publication No. 58-8
This is described in Japanese Patent Publication No. 3029, Japanese Patent Publication No. 60-28843, etc.

Further, the preferable molecular weight of the nylon 4.6 used in the present invention is the relative viscosity (η-at: 30'C and the polymer 1
g in 100ml of 97% sulfuric acid)
．． 5 or more, more preferably in the range of 2.5 to 5.0.

The amount of nylon 4,6 used in the polyamide resin composition of the present invention is 96 to 39. % by weight, preferably from 95 to 45% by weight. If the amount used exceeds 96% by weight, chemical resistance and mechanical strength will be poor. Also, if it is less than 39% by weight,
Heat resistance and mechanical strength decrease.

The polyarylene sulfide (B) used in the present invention has as a main component a structural unit represented by the general formula %), where R represents an aromatic group having 6 or more carbon atoms. Typical examples of the above aromatic group include p-phenylene, m-phenylene, 2,6-naphthalene, 4,4'-biphenylene, p,p'-bibenzyl, and nuclear substituted products thereof; It is a thermally substituted p-phenylene nucleus, that is, it is represented by the structural unit of the general formula %. Among these, poly p-phenylene sulfide is most preferred in terms of moldability, ease of handling, and the like. Here, the main component is one containing at least 70 mol% or more of the above structural units. If this main component is less than 70 mol %, undesirable results will occur, such as decreased crystallinity of the resulting polymer, low transition temperature, and poor physical properties when molded. As long as it is less than 30 mol%, it may contain an aromatic group having a trivalent or higher bond, such as a 1,2,4-bonded phenylene nucleus, an aliphatic group, a petero atom-containing group, etc.

The method for producing the polyarylene sulfide (B) used in the present invention includes a condensation reaction between a dihalogenated aromatic compound and a dithiol aromatic compound or a monohalogenated aromatic thiol, or a dihalogenated aromatic compound and an alkali sulfide or Examples include, but are not limited to, a method utilizing a desalination condensation reaction between an alkali hydrosulfide and an alkali or hydrogen sulfide and an alkali compound.

The amount of the polyarylene sulfide used is 3 to 60% by weight, preferably 5 to 50% by weight. If the amount used is less than 3% by weight, chemical resistance and mechanical strength will be poor.

Moreover, if it exceeds 60% by weight, heat resistance and mechanical strength will decrease.

The modified rubbery polymer (C) used in the present invention has a carboxyl group, an acid anhydride group, an epoxy group,
It is modified with at least one functional group selected from amino groups and hydroxyl groups.

Examples of methods for modifying rubbery polymers include (1) a method of copolymerizing an unsaturated compound having the above-mentioned functional group during polymerization of the rubbery polymer;

■ Rubbery polymers, unsaturated compounds having the above functional groups,
A method of grafting by heating using a kneader in the presence of peroxide and optionally an anti-aging agent.

(2) A method in which a rubbery polymer is dissolved in a solvent and then heated and grafted in the presence of an unsaturated compound having the above functional group and a peroxide.

(2) A method in which an unsaturated compound having the above-mentioned functional group and a peroxide are present when kneading nylon 4,6, polyarylene sulfide, and a rubbery polymer using an extruder or the like.

and so on.

Among these methods, methods ① and ① above are industrially advantageous, and especially from the viewpoint of impact resistance and chemical resistance,
The method is preferred.

When the polyamide resin composition of the present invention is obtained by the method (2) above, the amount of the unsaturated compound used is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the rubbery polymer.

The rubbery polymers used here include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, diene rubber such as polyisoprene, ethylene-α-olefin copolymer, ethylene-
Examples include non-diene rubbers such as α-olefin-polyene copolymers and polyacrylic esters, and these may be used alone or in combination of two or more.

Further, there are styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, ethylene-based ionomer resins, and the like. The above-mentioned styrene-butadiene block copolymers include AB type, AHA type, ABA tapered type, radial teleblock type, etc., and these can be used alone or in combination of two or more types.

In terms of impact resistance, preferred rubbery polymers and thermoplastic elastomers include styrene-butadiene copolymers, ethylene-α-olefin copolymers, polyacrylic esters, styrene-butadiene block copolymers, and hydrogenated Styrene-butadiene block copolymers, etc., more preferably styrene-butadiene copolymers, ethylene-butadiene block copolymers, etc.
These include α-olefin copolymers, styrene-butadiene block copolymers, and the like.

In the above ethylene-α-olefin copolymer, the weight ratio of ethylene and α-olefin is 95:5 to 5:95,
Preferably 95:5 to 20780, more preferably 9
2:8-60:40. Particularly preferably 85:1
5-70:30. When the weight ratio of ethylene and α-olefin is in the range of 20:80 to 30:TO, the processability of the resulting resin composition is particularly good.

In addition, the weight ratio of ethylene and α-olefin was 80:2.
When the ratio is in the range of 0 to 70:25, the resulting resin composition has particularly good impact resistance.

Furthermore, the Mooney viscosity (MLI, 1...℃) of the ethylene-α-olefin copolymer is 5 to
200, preferably 5-100, more preferably 5-100
It is 50. The impact resistance of the resulting resin composition is especially good when the Mooney viscosity is in the range of 10 to 30.

The cyclohexane-insoluble content of the ethylene-α-olefin copolymer affects the processability and impact resistance of the polyamide resin composition of the present invention, and is 50% by weight or less, preferably 5% by weight or less.

The α-olefin of the ethylene-α-olefin copolymer is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, such as propylene, butene-11pentene-1, hexene-1, heptene-1,4- Methyl butene-1,4
-Methylpentene-1 and the like. Particularly preferred is propylene.

Examples of the carboxyl group-containing unsaturated compound that modifies the rubbery polymer include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid, with acrylic acid and methacrylic acid being preferred. these are,
It can be used alone or in combination of two or more.

Examples of unsaturated compounds containing acid anhydride groups include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenyl succinic anhydride, and tetrahydrophthalic anhydride. Particularly preferred unsaturated acid anhydrides are Maleic anhydride. These can be used alone or in combination of two or more.

Furthermore, the epoxy group-containing unsaturated compound is a compound having an epoxy group and an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound in the molecule.

For example, unsaturated epoxy compounds such as unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes, and p-glycidyl styrenes represented by the following general formulas (I), (n), and (III). .

R1(■) R-C-C)h Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxylic acid esters, allyl glycidyl ether, 2-
Methyl allyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-
Examples include 1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, and p-glycidylstyrene. These can be used alone or in combination of two or more.

Furthermore, the hydroxyl group-containing unsaturated compound is a compound that has at least one unsaturated bond (double bond, triple bond) in the molecule and also contains a hydroxyl group. Typical examples thereof include alcohols having double bonds, alcohols having triple bonds, and esters of -valent or divalent unsaturated carboxylic acids and unsubstituted polyhydric alcohols.

The amino group-containing unsaturated compound is a vinyl monomer having at least one type of amino group or substituted amino group represented by the following general formula, and specific examples include aminoethyl acrylate, propylaminoethyl acrylate, Alkyl esters of acrylic acid or methacrylic acid such as dimethylaminoethyl methacrylate, aminopropyl methacrylate, phenylaminoethyl methacrylate, and cyclohexylaminoethyl methacrylate = i group,
Vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine derivatives such as allylamine, methacrylamine and N-methylallylamine, acrylamide derivatives such as acrylamide and N-methylacrylamide, p-aminostyrene, etc. Aminostyrenes and the like are used. Among them, allylamine, aminoethyl methacrylate, aminopyrropyl methacrylate, and aminostyrene are economically available on an industrial scale.
It can be used particularly preferably. These amino group- or substituted amino group-containing unsaturated compounds can be used alone or in combination of two or more.

Representative examples of suitable hydroxyl compounds for modifying rubbery polymers with hydroxyl groups include:
3-hydroxy-1-propene, 4-hydroxy-1-
Butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-
Methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, cis-1,4-dihydroxy-2-butene, trans-1
, 4-dihydroxy-2-butene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl crotonate, 2.3,4.5.6- Examples include pentahydroxyhexyl acrylate, 2,3,4.5.6-pentahydroxyhexyl methacrylate, 2.3.4.5-tetrahydroxypentyl acrylate, and 2,3,4.5-tetrahydroxypentyl methacrylate. .

These can be used alone or in combination of two or more.

The amount of the unsaturated compound having the functional group copolymerized and/or grafted to the rubbery polymer, which is the modified rubbery polymer of the present invention, is 0.1 to 100 parts by weight per 100 parts by weight of the rubbery polymer. The amount is 30 parts by weight, preferably 0.5 to 10 parts by weight.

The amount of these unsaturated compounds added can be determined by titration, infrared spectroscopy, or the like.

The peroxide used in the methods (1) to (4) above for modifying rubbery polymers is preferably an organic peroxide, and all known organic peroxides can be used. For example, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert-butylperoxy)
-butylperoxy)hexane, 2,2-bis(ter)
tert-butylperoxy)-p-diisopropylbenzenedicumyl peroxide, di-tert-butyl peroxide, tert-butylperoxybenzoate, 1,1-bis(tert-butylperoxy)-3,
3,5-trimethylcyclohexane, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, p-chlorobenzoyl peroxide, azobisisobutyronitrile, etc., preferably 2.5 -dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-3.

The amount of the organic peroxide added is 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts by weight of the rubbery polymer.
Parts by weight.

The amount of component (C) used in the polyamide resin composition of the present invention is 1 to 47% by weight, preferably 2 to 30% by weight.
, more preferably 5 to 25% by weight. If it is less than 1% by weight, impact resistance will be poor, and if it exceeds 47% by weight, heat resistance and mechanical strength will be poor.

The polyamide resin composition of the present invention can be obtained by kneading a mixture of each component using various extruders, Banbury mixers, kneaders, rolls, etc. A preferred kneading method is a method using an extruder, and among extruders, a method using a twin-screw extruder is particularly preferred in achieving the object of the present invention.

When using an extruder, the melt crosstalk temperature is 220-350℃
The melt kneading temperature is preferably between 2 and more preferably 2.
It is between 50 and 320°C.

Furthermore, it is better to operate under a nitrogen atmosphere in order to prevent deterioration of the resin.

When using the polyamide resin composition of the present invention, fillers such as glass fiber, carbon fiber, metal fiber, glass beads, asbestos, wallasnite, calcium carbonate, talc, and barium sulfate can be used alone or in combination. . It is preferable that these fillers are contained in an amount of 5 to 15011 JL parts based on 100 parts by weight of the polyamide resin composition of the present invention.

Additionally, known additives such as flame retardants, antioxidants, plasticizers, and colorants may be added.

Furthermore, in combination with nylon 4,6 used in the present invention,
Other polyamides can also be used. Preferred examples of other polyamides include nylon 6.6, nylon 6
．． 10, nylon 6.12, nylon 3,4, nylon 6.9, nylon 6, nylon 12, nylon 11, nylon 4, etc. Also nylon 6/6,10, nylon 6/6.12, nylon 6/12, nylon 6/
6°6, nylon 6/6.6/6,10. nylon 6
Copolyamides such as /6.6/6.12 can also be used.

Furthermore, nylon 6/6. T (T: terephthalic acid component), semiaromatic polyamides obtained from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and metaxylene diamine or alicyclic diamine, and semiaromatic polyamides obtained from metaxylene diamine and the above linear carboxylic acids. Mention may be made of polyamides, polyesteramides, polyetheramides and polyesteretheramides.

The polyamide resin composition of the present invention can be molded by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, etc. and used as various molded products.

d. Examples Next, the present invention will be explained in more detail with reference to Production Examples and Examples, but these are merely illustrative and do not limit the content of the present invention.

Note that in each side below, parts and % indicate parts by weight and % by weight, respectively.

Modified rubber polymers used in Examples and Comparative Examples were obtained by the following method.

Japan synthetic rubber @JsREP-02P (Mooney viscosity M
L1*a, 1°. °C ethylene-propylene rubber) 10
0 parts to 5 parts of maleic anhydride, organic peroxide: 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (KayahexaAn)
Premix 0.5 parts in advance and use a 55111φ extruder (1
200℃ using full-flight type screwdriver)
Heat treatment was performed at a screw rotation speed of 3 Orpm (residence time of about 4 minutes). The obtained reaction product was extruded into acetone (boiling point x 2
time), the resulting polymer was molded into a film, and the grafting rate of maleic anhydride was determined by infrared spectroscopy to be 2 parts by weight per 100 parts by weight of ethylene-propylene rubber.
．． It was 0 parts by weight.

Other unsaturated compounds were used in place of the maleic anhydride used in the production conditions of the 1-clear polyester polymer R-1 to obtain polymers R-2 to 4 shown in Table-1. Ta.

Table 1 Examples 1 to 16, Comparative Examples 1 to 7 Each component was mixed in the proportions shown in Table 2 and melt-kneaded using a twin-screw extruder to obtain pelletized resin compositions. . The barrel temperature of the twin-screw extruder is 310℃ at the highest point.
The test was carried out at a screw rotation speed of 250 rpsa.

The various polymers, organic peroxides, and glass fibers (GF) shown in Table 2 are as follows.

+11 Nylon 4,6: Relative viscosity 3.5 (2) Nylon 6.6: East side type Amilan CM3006 - Phtadiene-snarene block copolymer Kleint G1650 ■ Unsaturated compounds and organic compounds shown in Table 2 The amount of peroxide used was expressed in parts based on 100 parts of the rubbery polymer.

After thoroughly drying the obtained pellet-shaped polyamide resin composition in a dehumidifying dryer, test pieces were made from this using an injection molding machine, and the heat resistance, chemical resistance, and resistance were evaluated using the following evaluation methods. Impact properties and mechanical strength were measured. The results are shown in Table-2.

According to ASTM 0648, load 18.6 kg/
Measured by csA.

``JA Method■'' Form a flat plate and soak it in a 30% zinc chloride aqueous solution at room temperature.
The appearance after soaking for 8 hours was visually evaluated according to the following evaluation criteria.

O: Good appearance △: Slightly poor appearance ×: Poor appearance ■ Using a VL test piece with a thickness of 1/8 #, the weight increase rate was measured after immersing it in water at 70° C. for 48 hours.

Eye shift impact strength was measured according to ASTM D256 with a thickness of A" and a notch at 23°C.

Bending speed 15 m/s according to ASTM 0790
The bending strength was measured at in.

Comparative example 1 is the result of evaluating each physical property of nylon 4.6 alone, and is inferior in chemical resistance. Comparative example 2 is the result of evaluating each physical property of polyphenylene sulfide alone, and is poor in impact resistance and mechanical strength. is inferior. Furthermore, the composition of Comparative Example 3 is a composition consisting of nylon 4,6 and polyphenylene sulfide, and although the chemical resistance is improving, the impact resistance is poor. Furthermore, as seen in Comparative Example 4, when the rubbery polymer is not modified with a specific functional group as in the present invention, it is inferior in heat resistance, impact resistance, and chemical resistance.

On the other hand, the polyamide resin composition of the present invention shown in Examples is
It can be seen that heat resistance, chemical resistance, impact resistance, and mechanical strength are highly balanced.

f8 Effect of the invention The polyamide resin composition of the invention has heat resistance, chemical resistance,
Because it has a highly balanced impact resistance and mechanical strength, it can be used for molded products such as automobile exterior materials, interior materials, parts, various electric/electronic parts, and housings, and has industrial value. is extremely large.

Claims (1)

[Claims] (A) Polytetramethylene adipamide resin 96-39
Weight% (B) Polyarylene sulfide 3 to 60% by weight and (C) Modified rubber material modified with at least one functional group selected from carboxyl group, acid anhydride group, epoxy group, amino group, and hydroxyl group. A polyamide resin composition comprising 1 to 47% by weight of a polymer.