JPS62129350A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent moldability, impact resistance and heat resistance and suitable for the interior and exterior trim of automobile, etc., by compounding a polyphenylene ether resin with a polyamide and a specific modified ethylene-alpha-olefin resin. CONSTITUTION:The objective composition is produced by compounding (A) 4-95(wt)%, preferably 10-50% polyphenylene ether resin of formula (R1-R4 are alkyl, aryl, etc.), (B) 95-4%, preferably 85-40% polyamide (e.g. nylon 6,6) and (C) 1-50%, preferably 5-25% ethylene-alpha-olefin (e.g. propylene) copolymer modified with one or more compounds selected from unsaturated acid (e.g. acrylic acid) and unsaturated acid anhydride (e.g. maleic anhydride).

Description

DETAILED DESCRIPTION OF THE INVENTION a. J-mouth UW Ice Spoon The present invention relates to a thermoplastic resin composition having excellent processability, impact resistance, and heat resistance.

b. Conventional technology Polyphenylene ether resin has excellent mechanical properties, electrical properties, and heat resistance, as well as good dimensional stability, so it is attracting attention as a resin suitable for a wide range of applications. However, its major drawbacks are poor moldability and impact strength. In order to improve the moldability of polyphenylene ether resin, it has been proposed in Japanese Patent Publication No. 45-997, but polyphenylene ether resin and polyamide have very poor compatibility and cannot be obtained. The resin composition obtained by injection molding of the resin composition has poor mechanical properties (particularly when the polyamide content exceeds 20%, the mechanical properties are significantly inferior).
The impact resistance was very low.6 In addition, in order to improve the impact resistance of the resin composition, an ethylene-propylene copolymer (hereinafter referred to as E'PR) was added as an Elas 1 hemer component. but.

Impact resistance was hardly improved.

Problems to be Solved by the C0 Invention The inventors of the present invention have conducted intensive studies to obtain a resin composition that has excellent processability, impact resistance, and heat resistance and can be used in a wide range of applications. Based on this knowledge, it was discovered that by further blending ERR modified with at least one selected from unsaturated acids and unsaturated acid anhydrides to polyamide, a resin composition with unprecedented performance can be obtained. Based on these findings, the present invention has been achieved.

Means to solve the d1 problem That is, the present invention.

1. A composition comprising (a) 4 to 95% by weight of a polyphenylene ether resin, (b) 95 to 4% by weight of a polyamide, and (c) 1 to 50% by weight of an ethylene-α-olefin copolymer, The present invention relates to a thermoplastic resin composition characterized in that component (c) is an ethylene-α-olefin copolymer modified with at least one selected from unsaturated acids and unsaturated acid anhydrides.

The polyphenylene ether resin as component (a) used in the present invention is a polymer represented by the general formula (1), and a specific example thereof is poly(2,6-dimethylphenylene-1°4-ether )
, poly(2,6-diethylphenylene-1,4-ether), poly(2,6-dipromophenylene-1,4-ether), poly(2-methyl-6-nitylphenylene-1゜4) -ether), poly(2-chloro-6-methylphenylene-1,4-ether), poly(2-methyl-6
isopropylphenylene-1,4-ether), poly(
2,6-di-n-propylphenylene-1,4-ether), poly(2-chloro-6-propylphenylene-1,
4-ether), poly(2-chloro-6-ethylphenylene-1,4-ether), poly(2-methylphenylene-1,4-ether), poly(2-chlorophenylene-1,4-ether) , poly(2-phenylphenylene-1,4-ether), poly(2-methyl-6-phenylphenylene-1,4-ether), poly(2-bromo-6-phenylphenylene-1,4-ether) , poly(2,4'-methylphenylphenylene-1,4-
ether), their copolymers, and their styrenic compounds Graph 1 - copolymers.

The blending amount of the polyphenylene ether resin in the thermoplastic resin composition of the present invention is 4 to 95% by weight, preferably 8 to 60% by weight, and more preferably 10 to 50% by weight.
It is. 4% by weight of polyphenylene ether resin
If it is less than 95% by weight, no significant effect on improving heat resistance will be observed, and if it exceeds 95% by weight, processability will be poor.

The polyamide of component (b) used in the present invention usually has the formula H
2N (cH2)X N Hz (wherein, X is 4 to
is an integer between 12 and 12. ) and a linear carboxylic acid of the formula HOzC(cH= )yCO2H, where y is an integer between 2 and 12. things and
112 produced by ring-opening polymerization of lactam can be used. Preferred examples of these polyamides include nylon 6.6. Nylon 6.9. nylon 6.10
, nylon 6.12, nylon 6, nylon 12, nylon 11, nylon 4.6, etc.

Also, nylon 6/6.6, nylon 6/6.10, nylon 6/12. Nylon 6/6.12, Nylon 6/6.
Copolyamides such as 6/6.10 and nylon 6/6°6712 are also 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 diammine, and metaxylene diamine and the above linear carboxylic acids. The resulting polyamides include polyesteramides, polyetheramides, and polyesteretheramides. Note that polyamide may be used alone, or two or more types of polyamide may be used in combination.

The amount of component (b) used is 95 to 4% by weight, preferably 90 to 35% by weight, and more preferably 4 to 85 to 40% by weight. If the amount of component (b) exceeds 95% by weight, no significant effect on improving heat resistance will be observed, and if it is less than 4% by weight, processability will be poor.

Component (c) of the present invention is ethylene-α-modified with at least one selected from unsaturated acid anhydrides and unsaturated acids.
Olefin copolymers, particularly preferred among these are ethylene-α-olefin copolymers, and particularly preferred among these are ethylene-α-olefin copolymers containing unsaturated acids and unsaturated acids. It is a polymer formed by copolymerization, especially graft polymerization, of at least one selected from saturated acid anhydrides.

The α-olefin used here is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and specific examples include propylene, butene-1, pentene-1, and hexene-1.
Examples include 1,heptene-1,4-methylbutene-1,4-methylpentene-1, but propylene is particularly preferred. Although it is possible to copolymerize the component (c) of the present invention with a polyene compound, it is preferable from the viewpoint of processability that a polyene compound is not copolymerized. The polyene compounds used here include 1,4-pentadiene,
1,5-hexadiene, 2-methyl-1,5-hexadiene.

3.3-dimethyl-1,5-hexadiene, 1゜7-octadiene, 1,9-decadiene, 6-methyl-1,5
-hexadiene, 1,4-hexadiene, 7-methyl-
1,6-octadiene, 9-methyl-1,9-undecane, isoprene, ], 3-pentadiene, 1,4.9-
Decatriene, 4-vinyl-1-cyclohexane, cyclopentadiene, 2-methyl-2,5-norbornadiene, 5-methyl-2-norbornene, 5-ethylidene-
Examples include 2-norbornene, 5-isopropylidene-2-norbornene, 5-impropenyl-2-norbornene, dicyclopentadiene, tricyclopentadiene, and the like.

The weight ratio of ethylene and α-olefin is 95:5 to 5:9.
5, preferably 95:5 to 20:80, more preferably 92:8 to 60:40, particularly preferably 85:15 to 7
0:30.

Weight ratio of ethylene and α-olefin is 20; 8o to 30
: Particularly good workability in the range of 70.

Weight ratio of ethylene and α-olefin is 80:20-70
: Particularly good wI @ resistance in the range of 25.

When the above polyene compound is used, the iodine value is 2 to 40.
Component (c) within the range of is used.

Mooney viscosity of ethylene-α-olefin copolymer (
MLx+4,100℃) is 5 to 20 in terms of impact resistance.
0, preferably 5 to 100. More preferably, it is 5-50. Impact resistance is particularly good when the Mooney viscosity is in the range of 10 to 30.

Furthermore, the amount of cyclohexane-insoluble ethylene-α-olefin copolymer is 50% by weight or less, preferably 5% by weight, since it affects the processability and impact resistance of the thermoplastic resin composition of the present invention.
% by weight or less.

In component (c) of the present invention, unsaturated acids used for modification, for example grafting, include, for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, etc., and preferably acrylic acid, methacrylic acid, etc. It is an acid. These unsaturated acids may be used alone or in combination of two or more.

Examples of unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride,
Examples include butenyl succinic anhydride, tetrahydrophthalic anhydride, etc., and a particularly preferred unsaturated acid anhydride is maleic anhydride.

These unsaturated acid anhydrides may be used alone or in combination of two or more.

The above-mentioned unsaturated compounds used for modifying the ethylene-α-olefin copolymer may be used in combination.

Component (c) of the present invention is a mixture of an ethylene-α-olefin copolymer, the unsaturated compound or the unsaturated compound mixture, and a peroxide, such as lOO'C-300''.
C (preferably 150-250°C) for 0.5-30 minutes (
It can be obtained by heat treatment (kneading), preferably for 1 to 10 minutes.

These reactions are carried out using extruders, kneaders, and Banbury mixers.
etc. can be done.

Alternatively, it can also be obtained by dissolving the ethylene-α-olefin copolymer, the unsaturated compound, and the organic peroxide in an organic solvent and heating the solution. As the solvent used at this time, a hydrocarbon having 6 to 12 carbon atoms, a halogenated hydrocarbon having 1 to 12 carbon atoms, tetrahydrofuran, or the like is used. The heating temperature varies depending on the type of organic peroxide used, but is usually 40 to 30.
The temperature is 0°C, preferably 50 to 200°C, and the heating time is 1 minute to 10 hours, preferably 5 minutes to 5 hours. After the reaction is completed, the polymer is poured into a solvent in which the polymer, such as alcohol, is insoluble, or it is solidified by being ripped in a steam bath and then dried. Further, other vinyl monomers copolymerizable with the unsaturated dicarboxylic acid anhydride or the unsaturated acid described in r6i can be used.

Examples of copolymerizable vinyl monomers include vinyl cyanide compounds such as acroni-1-lyl and methacrylonitrile.

Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-
Acrylic acid alkyl esters such as ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate-1-, octadecyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate-1-, amyl methacrylate-1 Hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate-1, phenyl methacrylate, benzyl methacrylate-1, etc., methacrylic acid alkyl esters, styrene, α- methylstyrene,
Methylstyrene, vinylxylene, monochlorostyrene, diclostyrene, monobromstyrene, dibromstyrene.

Aromatic vinyl compounds such as P-tert-butylstyrene, ethylstyrene, vinylnaphthalene, maleimide,
There are maleimide-based compounds such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-phenylmaleimide, and N-(P-bromophenyl)maleimide, which can be copolymerized. Other vinyl monomers may be used alone or in combination of two or more.

The other copolymerizable vinyl monomer may be mixed with the unsaturated compound and subjected to a modification reaction according to the polymerization method in graph 1, or the other copolymerizable vinyl monomer may be mixed with the unsaturated compound. A copolymer with the unsaturated metal material may be polymerized, and the polymer may be subjected to a modification reaction according to the graft polymerization method or the like.

The peroxide used in the production of component (c) is:
All known organic peroxides may be used.

For example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-
Di(t-butylperoxy)hexane, 2,2' bis(t-butylperoxy)-P-diisopropylbenzenedicumylperoxy 1-, di-butylperoxide, 1-butylperoxybenzoate, 1 ,1-
Bis(butylperoxy)-3,3,5-trimethylcyclohexane, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, p-butylbenzoyl peroxide, azobisisobutyroni-1-lyl, etc. and preferably 2,5-dimethyl-2,5-di(
1-Butylperoxy)hexane, 2,5-dimethyl-
2,5-di(butylperoxy)hexyne-3. The amount of organic peroxide used here is 4 ethylene = α
-0.05 per 100 parts by weight of olefin copolymer
-2 parts by weight, preferably 0.1-part by weight.

The amount of the unsaturated compound reacted with the ethylene-α-olefin copolymer is preferably 0.01 to 50% by weight, more preferably 0.1 to 10% by weight based on the ethylene-α-olefin copolymer. %, particularly preferably 0.2-5
Weight%. Is it resistant if the amount of denaturation is too much or too little? aI-impactability is poor.

The amount of the component (c) used in the thermoplastic resin composition of the present invention is 1 to 50% by weight, preferably 2 to 30% by weight,
More preferably, it is 5 to 25% by weight. If it is less than 1% by weight, no effect of improving impact resistance will be observed, and if it exceeds 50% by weight, processability will be poor.

In obtaining the thermoplastic resin composition of the present invention, various extruders,
It can be obtained by kneading with a Banbury mixer, kneader, roll, etc.

During the above kneading, the composition of the present invention may be obtained by mixing all of the components of the present invention, or after mixing and kneading one or more of the components and a portion of each component, Furthermore, the remaining components may be blended and further kneaded to obtain the thermoplastic resin composition of the present invention.

In addition, from the viewpoint of impact resistance and processability, it is better to first knead the components (a) and (c), and then add the component (b) and knead them further. Similarly preferred is a method in which 50% by weight or less of component (b) is first added to component (a)/component (c) and kneaded, and then the remaining component (b) is added and further kneaded. Get results.

When using the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, asbestos,
Fillers such as walrus night, calcium carbonate, talc, and barium sulfate can be used alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. It is preferable that these fillers are contained in an amount of 5 to 150 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

Additionally, known additives such as flame retardants, antioxidants, plasticizers, colorants, and lubricants may be added. Preferred flame retardants and antioxidants are phosphorus compounds.

Polyamides 1 to 1 in which other polymers, such as polyesters such as PBT and I)ET, are used in the thermoplastic resin composition of the present invention
By using less than 50% by weight of the carbon dioxide, a product with excellent impact resistance can be obtained. Furthermore, other polymers may be used depending on the required performance, such as polyethylene, polypropylene, BRlNBR, 'SBR, 5-B-S block copolymers.

Water l7fSs-13-3. Polystyrene, AS resin, I
-1 piece PS, ABS resin, AES resin, polysulfone,
Polyether sulfone, N-phenylmaleimide copolymerized styrenic resin, MBS, methyl methacrylate-styrene copolymer, 5-I-S block copolymer, polyimide, pps, polyetheretherketone, vinylidene fluoride polymer, etc. can be blended as appropriate.

The thermoplastic resin composition of the present invention can be used as various molded products by injection molding, extrusion into a sheet 1, vacuum molding, irregular molding, foam molding, and the like.

Various molded products obtained by the above molding method.

Utilizing its excellent properties, it can be used for automobile exterior and interior parts, various electrical and electronic related parts, housing, etc.

d. Example 1 Next, the present invention will be explained in more detail with reference to Production Examples and Examples; however, 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.

The polyphenylene ethers used in Examples and Comparative Examples are as follows.

■) Weight A-1 (53.6 g of cupric bromide after sufficiently purging the interior of the stainless steel reactor equipped with an oxygen blower, a cooling coil, and a stirrer at the bottom of the polyphenylene ether reactor with nitrogen) , di-n-butylamine LL10g,
Furthermore, 1-luene4. 2,6-xylenol 8 in OQ
．． 75 kg was dissolved and added. After stirring to make a homogeneous solution, polymerization was carried out for 90 minutes while rapidly blowing oxygen into the reaction vessel. During the polymerization, water was circulated through a cooling coil to maintain the internal temperature at 30°C. After polymerization,
30Q of toluene was added, and a 20% aqueous solution of 430 g of disodium ethylenediaminetetraacetate dissolved in water was added to stop the reaction.

The polymer solution phase was removed from the resulting product mixture by centrifugation. While stirring the polymer solution phase vigorously, methanol was gradually added to form a slurry. After being separated by filtration, Polymer 1 was thoroughly washed with methanol, further separated by filtration, and then dried to obtain Polymer A-1.

2) Production of polymer A-2 (polyphenylene ether) In the production of polymer A-1, the phenol compound was
Polymerization was performed in place of 6-xylenol/2,3.6-1 methylphenol=90/10 (molar ratio) to obtain 1 polymer A-2.

Production Example-2 Component (c) of the present invention used in Examples and Comparative Examples was obtained by the following method.

1) Polymer B-1 (anhydrous mylene modified ethylene propylene rubber) 1 Nippon Synthetic Rubber ■ J S RE P02P (ethylene propylene rubber with Mooney viscosity ML, *, (100°C) 24) 100 parts of maleic anhydride, Organic peroxide (Kayahexa AD) 0.3
55 nnφ extruder (1! I
ll, 200°C using a Fully 1-type screw)
, screw rotation speed 3 Orpm (IPEPE opening time approx. 4
Heat treated.

The obtained reaction product was extracted with acetone (boiling point x 2 hours)
The resulting polymer was formed into a film, and as determined by infrared spectroscopic analysis, the grafting rate of maleic anhydride was 0.5 parts by weight per 100 parts by weight of ethylene-propylene rubber.

2) Polymers B-2 to B-8 Under the manufacturing conditions of Polymer B-4, Polymers -B-2 to B-
4 is a variation of maleic anhydride, B-6, B
-7 is one in which the ethylene propylene copolymer species was changed. and B-5 and B-8 are those in which maleic anhydride is replaced with styrene acrylate-maleic anhydride copolymer.

The results are shown in Table-1.

Table-1 Measurement of Mooney viscosity of polymer; at 100'C using a large rotor according to JISK6300? l+++ was determined.

Examples and Comparative Examples The various polymers described above were mixed in the composition ratios shown in Table 2, and melt-kneaded in a twin-screw extruder rotating in the same direction at a barrel temperature of 220°C to 320°C for a residence time of 3 to 5 minutes. A pellet-shaped thermoplastic resin composition was obtained.

After sufficiently drying in a vacuum φ2 dryer, test pieces were prepared using an injection molding machine, and impact resistance, heat resistance, etc. were measured using the following methods. The processability was determined by 4IQ for the above pelletized thermoplastic resin composition. The results are shown in Table-2.

In addition, in Example-13, the kneading method was changed to the composition ratio of Example-1. That is, first, components (a) and (c) were passed through an extruder in a blend of 1<1, and component (b) was added midway through the extruder to obtain a composition with the same composition ratio as in Example-1. It is something.

Shock resistance Dupont type Invac 1 to impact rod tip R = 1 in tester
/2'' was used to determine the falling weight impact strength of a molded product with a thickness of 2.4 m.

Using a heat-resistant UL test piece with a thickness of 1/8", the length of the molded product after being left in an atmosphere of 150° C. for 2 hours was determined as dl, and the heat shrinkage rate was determined according to the following calculation.

Initial length of test piece lOO > i Nozzle diameter I lnφ,
The thickness was 2 on, the temperature was 28.0° C., and the load was 30 kg.

e9 Comparative example 6 of the effect of the invention is a known composition, and although it has excellent moldability and heat resistance, it is a brittle resin with very low impact resistance, and has extremely low industrial utility value A.

The composition of the present invention is a composition in which a specific proportion of component (c) modified with a specific monomer is blended into the composition, and as shown in the examples, the impact resistance is improved, and the impact resistance and heat resistance are improved. It is an excellent resin with highly balanced physical properties such as hardness and moldability.

Therefore, since the composition of the present invention has highly balanced physical properties,
It provides molded products such as L exterior and interior parts, various electric/electronic parts, and housings, and has extremely high industrial value.

Claims (1)

[Claims] 1. Consisting of (a) 4 to 95% by weight of a polyphenylene ether resin, (b) 95 to 4% by weight of a polyamide, and (c) 1 to 50% by weight of an ethylene-α-olefin copolymer. A thermoplastic resin composition, wherein the component (c) is an ethylene-α-olefin copolymer modified with at least one selected from unsaturated acid anhydrides and unsaturated acids. Composition.