JPS62129349A - 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 with a polyamide and specific two kinds of resins at specific ratios. CONSTITUTION:The objective composition is produced by compounding (A) 3.5-95(wt)%, preferably 10-50% polyphenylene ether resin of formula (R1-R4 are alkyl, aryl, etc.), (B) 95-3.5%, preferably 80-35% polyamide (e.g. nylon 6,6), (C) 1-50%, preferably 5-25% ethylene-alpha-olefin copolymer modified with one or more compounds selected from unsaturated acid anhydride (e.g. maleic anhydride) and unsaturated acid (e.g. acrylic acid) and (D) 0.5-90%, preferably 0.5-40% copolymer of a styrene monomer and 0.1-30% one or more unsaturated compounds selected from unsaturated carboxylic acid anhydride, unsaturated acid, epoxy group-containing unsaturated compound, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a thermoplastic resin M1 composition having excellent processability, impact resistance, and heat resistance.

"Conventional technology" Polyphenylene ether resin has excellent mechanical properties, electrical properties, heat resistance, and good dimensional stability, so it has been attracting attention as a resin suitable for a wide range of applications. 1], but its major disadvantage is that its moldability and impact resistance are poor. 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 the resulting The resin composition has poor mechanical properties (especially when the polyamide content exceeds 20%, it is significantly poor).
It had very low impact resistance. In addition, the resin M1
Even if an attempt is made to improve the impact resistance of the product (addition of a polymer (hereinafter referred to as EPR) to the ethylene-propylene system as an elastomer component), the impact resistance remains unchanged.

"Problems to be Solved by the Invention" The present inventors have developed a resin composition that has excellent processability, impact resistance, and heat resistance and can be used in a wide range of applications (1)
・As a result of one study, it was discovered that by blending two specific resins in a specific ratio with polyphenylene ether and polyamide, a thermoplastic resin composition with unprecedented performance can be obtained.Based on this knowledge, the present invention was made. reached.

"Means for Solving the Problems" That is, the present invention provides (a) polyphenylene ether-based ml11-13,5
~95% by weight (b) Polyamide 95-3.5% by weight (c)
Ethylene-α-olefin co-ffi (1 to 50% by weight) styrenic polymer (0.5 to 90% by weight), wherein component (c) is an unsaturated acid anhydride and an unsaturated an ethylene-α-olefin copolymer modified with at least one selected from acids; (d)
The components are a combination of a styrenic compound and at least one unsaturated compound selected from an unsaturated dicarboxylic acid anhydride, an unsaturated acid, an epoxy group-containing unsaturated compound, and an amine 7-based vinyl intermediate. A thermoplastic resin composition characterized by being a polymer.

The present invention will be explained in detail below.

The polyphenylene ether resin as component (a) used in the present invention has the general formula represents a polymer represented by ), and examples thereof include poly(2,6-dimethylphenylene-1,4-ethyl)J? (2,6-
danitylphenylene-1,4-ether), poly(2,
6-dipromephenylene-1,4-ether), poly(
2-methyl-6-ethylphenylene-1,4-ether), poly(2-chloro-6-methylphenylene-1,4
-ether), poly(2-methyl-6-imbropylphenylene-1,4-ether), poly(2,6-di-n
-propylphenylene-1゜4-ether), poly(2
-chloro-6-promphenylene-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-from-6-phenylphenylene-1,4-ether), poly(2,4'-methylphenylphenylene-1,4-ether), and their copolymers and It is a graft copolymer of these styrene compounds.

The blending amount of the polyphenylene ether resin in the thermoplastic/W resin composition of the present invention is 3.5 to 95% by weight, preferably 8 to 60% by weight, more preferably 10 to 5% by weight.
The percentage is 0.

When the amount of polyphenylene ether-based needles in one finger is less than 3.5% by weight, WJ does not have a significant effect on improving heat resistance, and 95m
If it exceeds bk%, workability will be poor.

The polyamide component (b) used in the present invention is:

Usually, the formula H7N-(cH2)X-NH2 (in the formula.

X is an integer between 4 and 12. ) and a linear carbon dioxide represented by the formula HO2C-(cH2)y-CO2H, where y is an integer between 2 and 12. ,
Those produced by ring-opening polymerization of lactams can be used. Preferred examples of these polyamides include nylon 616, nylon 6.9, nylon 6.10, nylon 6.12. Nylon 6, -J-1t:In12,
Nylon 11. There are 4, 6, etc.

Also nylon 6/6.6, nylon 6/6. to.

Nylon 6/12, nylon 6/6, 12. nylon 6
/6, 6/6, 10. Su Iron 6/6.6/12
Copolymerized polyamides such as the following are also used.

Furthermore, nylon 6/6, T, (T, terephthalic acid component)
, semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as terephthalic acid and inphthalic acid and metaxylene diamine, or alicyclic diamines, polyamides obtained from metaxylene diamine and the above-mentioned linear carboxylic acids,
Mention may be made of 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 3.5% by weight, preferably 90 to 25% by weight, and more preferably 80 to 35% by weight.

If the amount of component (b) exceeds 95% by weight, no significant effect on improving heat resistance will be seen, and if it is less than 3.5% by weight, processability will be poor.

The uninvented component (c) is ethylene-α modified with at least one selected from unsaturated acid anhydrides and unsaturated acids.
-It is an olefin-based co-enzyme.

Among these, particularly preferred is ethylene-α-olefin/
In system copolymerization, unsaturated acids and unsaturated acid anhydrides copolymerize,
In particular, it is a graft-polymerized polymer.

The α-olefin used here is an unsaturated carbide ice accumulation compound having 3 to 20 carbon atoms, and specific examples include propylene, butene-1, pentene-1, hexene-1
, heptene-1,4-methylbutene-1,4-methylpentene-1, etc., but propylene is particularly preferred.

Although it is also 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, ■, 7-octadiene, 1,9-decadiene,
6-Methyl-1,5-hexadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 9-methyl-1,9-undecane, isoprene, 1,3-pentadiene, 1,4.9- decatriene, 4-vinyl-1-cyclohexane, cyclopentadiene, 2-methyl-2,
5-norbornadiene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, 5-impropylidene-2-norbornene, 5-impropenyl-2-
Examples include fulbornene, dicyclopentadiene, tricyclopentadiene, and the like.

The weight ratio of ethylene and α-olefin is 95:5 to 5:9.
5. Preferably 95:5 to 2o:.8o, more preferably 92:8 to 60:40. Particularly preferably 85:15~
70:30.

The heavy h1 ratio of ethylene and α-olefin is 20:80
Workability is particularly good in the range of ~30 near 0.

Ethylene and α-olefin! T! 'Quantity ratio is 80=20
~70:1 Impact resistance is particularly good in the range of 25.

- When the polyene compound described in - is used, the iodine value is 2 to 4.
A component (c) in the range of 0 is used.

11-di-viscous f(ML +
-4, +00°C) is 5 to 2 degrees from the viewpoint of impact resistance.

The range is preferably 5 to 10O1, more preferably 5 to 50. Impact resistance is particularly good when Mooney clay is in the range of 10 to 30.

Moreover, the cyclohexane insoluble content IJ of the ethylene-α-olefin copolymer affects the processability and impact resistance of the thermoplastic resin composition of the present invention! Yes, 50% by weight, +1
7 or less than 5% IIY%.

In component (c) of the present invention, unsaturated acids used for modification, for example grafting, include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, etc., and preferably acrylic acid and methacrylic acid. It is. 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, citracone anhydride,
Examples include butenyl succinic anhydride, tetrahydrophthalic anhydride, etc., and a particularly preferred unsaturated acid anhydride is maleic anhydride. These unsaturated compounds may be used alone or in combination of two or more.

2. These ethylene-α-olefin copolymers and the above-mentioned The unsaturated compound or the unsaturated compound mixture and the peroxide are mixed and heat treated (kneading) at, for example, 100 to 300°C (preferably 150 to 250°C) for 0.5 to 30 minutes (preferably 1 to 10 minutes). You can get it by doing

These reactions can be carried out using an extruder, kneader, Banbury mixer, or the like. Alternatively, it can also be obtained by dissolving the ethylene-α-olefin copolymer and the organic peroxide in an organic solvent and heating the solution.

The solvent used at this time is a hydrocarbon having 6 to 12 carbon atoms, a halogenated hydrocarbon having 1 to 12 carbon atoms, tetrahydrofuran, or the like. The heating temperature varies depending on the type of organic peroxide used, but is usually 40 to 300.
'C, preferably 50 to 200°C, and heating time is 1 minute to 10 hours, preferably 5 minutes to 5 hours. After the reaction path r, a polymer such as alcohol is solidified in an insoluble solvent f1 or solidified by steam stripping and then dried.

Other vinyl monomers copolymerizable with the unsaturated acid anhydride and unsaturated acid may also be used.

Other copolymerizable vinyl monomers include vinyl cyanide compounds such as acrylonitrile and methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
Hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate-1, octadecyl acrylate
1. Acrylic acid alkyl esters such as phenyl acrylate and benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate,
Cyclohexyl methacrylate-1, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate.

Methacrylic acid alkyl esters such as benzyl methacrylate. Styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromstyrene.

Dibromustyrene, p-tert-butylstyrene,
Aromatic vinyl compounds such as ethylstyrene and vinylnaphthalene; maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-phenylmaleimide, and N-(p-plumophenyl)maleimide; There are system compounds, etc.
These other copolymerizable vinyl monomers may be used alone or in combination of two or more.

Other vinyls capable of forming a nail base 71j 1.1 may be mixed with the unsaturated compound and subjected to a modification reaction using the graft polymerization method, etc., or the other vinyls capable of copolymerization IIf' A co-polymer of the l'-jlk body and the unsaturated compound may be polymerized, and the polymer may be subjected to a modification reaction according to the graft polymerization method or the like described above.

The peroxide used in the production of component (c) is:
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)hexane, 2
．． 2'-bis(tert-butylperoxy)-p-cyinpropylhenzendicumylperoxysite, t
ert-butyl peroxyside, tert-butyl peroxyhennoate, 1,1-bis('t er
(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,4-dichlorobenzoylperoxyi, benzoyl peroxide, p-chlorobenzoyl peroxide, azobisisobutyronitrile, etc. , preferably 2,5-dimethyl-2,5-di(ter
t-butylperoxy)hexane, 2,5-dimethyl-
2゜5-di(tert-butylperoxy)hexyne-
It is 3.

The amount of organic peroxide used here is 0.05 to 2 parts by weight per 100 parts of the ethylene-α-olefin copolymer.
Parts by weight, preferably 0.1-1 parts by weight.

The amount of the unsaturated compound reacted with the ethylene-α-olefin copolymer is preferably 0.01-50% by weight, more preferably 0.1-10% by weight based on the ethylene-α-olefin copolymer. % by weight, particularly preferably from 0.2
It is 5% by weight. If there is too much or too little denaturing liquid, the impact resistance will be poor. The amount of the component (c) used in the thermoplastic resin composition of the present invention is 1 to 50? [4% by weight, preferably 2 to 30% by weight, more preferably 5 to 25% by weight. 1 layer j cutting%
If it is less than 50% by weight, no improvement in impact resistance will be observed, and if it exceeds 50% by weight, processability will be poor.

The uninvented component (d) is a styrene-based l1ltimer, an unsaturated dicarboxylic acid anhydride, an unsaturated acid, an epoxy group-containing unsaturated compound, and an amino group-containing vinyl system; at least one member selected from 11 members. The unsaturated compound is preferably copolymerized in an amount of 0.1 to 30%.

As the unsaturated dicarboxylic anhydride and unsaturated acid used here, the unsaturated dicarboxylic acid anhydride and unsaturated acid mentioned above are used.

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 one 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 (II), (m), and (■). .

(R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond.) Su (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond. x is -CH2-0- 1-()-〇- or 10-.) W' (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond. R' is hydrogen or a methyl group.) Specific 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-l-hexene, vinylcyclohexene monoxide, p-glycidylstyrene, and the like. These can be used alone or in combination of two or more.

The amine group-containing vinyl monomer is expressed by the general formula (wherein R+ represents hydrogen, methyl group, or ethyl group, and R
2 is hydrogen, alkyl group having 1-12 carbon atoms, 2-1 carbon atoms
(2) alkanoyl group having 6 to 12 carbon atoms, phenyl group having 6 to 12 carbon atoms, cycloalkyl group having 6 to 12 carbon atoms, or derivatives thereof; Specific examples include aminoethyl acrylate, propylaminoethyl acrylate, dimethylamino/ethyl methacrylate,
Alkyl ester derivatives of acrylic acid or methacrylic acid, such as aminopropyl methacrylate, phenylaminoethyl methacrylate, and cyclohexylaminoethyl methacrylate, and vinylamine derivatives, such as N-vinyldiethylamine and N-acetylvinylamine. , allylamine, allylamine derivatives such as methacrylamine and N-methylallylamine, acrylamide and N-
Acrylamide derivatives such as methylacrylamide and 7-minostyrenes such as p-7 minostyrene are used. Among them, allylamine, aminoethyl methacrylate, amino/propyl methacrylate, aminostyrene, etc. are particularly preferably used because they can be obtained economically on a commercial scale. These unsaturated compounds containing a 7-mino group or an a-substituted amino group may be used alone or in combination of two or more.

All of the above-mentioned aromatic vinyl compounds are used for the styrene-based single stitched body.

In addition to the above-mentioned essential components, component (d) of the present invention can be copolymerized with other vinyl monomers that can be copolymerized with these.

Other vinyl monomers used here include the vinyl cyanide compound, the acrylic acid alkyl ester, the methacrylic acid alkyl ester, and the maleimide compound. These ili :,'1 body is 1
Used in one species or two or more species.

Component (d) of the present invention is emulsion polymerization, which is a known combination method,
It can be obtained by bulk polymerization, solution polymerization, suspension polymerization, etc.

The amount of component (d) used in the present invention is 0.5 to 9
0% by weight, preferably 0.5-60% by weight
, more preferably 0.5 to 40% by weight. If it is less than 0.5% by weight, the impact resistance will be poor, and if it exceeds 90% by weight, the heat resistance will be poor.

The thermal n(%) resin composition of the present invention can be obtained by kneading with a six-type extruder, Banbury mixer, kneader, roll, etc. During the above kneading, each of the final IJI The composition of the present invention may be obtained by mixing all the components, or by mixing and kneading one or more of each component and - parts of each component, and then further blending the remaining components. Then, the thermoplastic resin m-acid of the present invention may be obtained by further kneading.

From the viewpoint of impact resistance and workability, it is better to first knead the components (a), (c), and (d), and then add the component (b) and knead further.

In addition, first, in the (a) component / (c) component / (d) component, (
A method in which 50% by weight or less of component (b) is added and kneaded, and then the remaining component (b) is added and further kneaded can also yield favorable results.

When using the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, asbestos,
Fillers such as wallasnite, calcium carbonate, talc, and barium sulfate can be used alone or in combination. Among these fillers, the shape of glass fiber and carbon ia fiber is 6 to 60 μm in H & fiber diameter and 30 gm or more!
Those having an I length are preferred.

These fillers are preferably contained in an amount of 5 to 150 parts by weight per 100 parts by weight of the thermoplastic resin composition.

Additionally, known additives such as flame retardants, oxidation inhibitors, oxidizing agents, W agents, coloring agents, and lubricants may be added. fif
Preferred flame retardants and antioxidants are phosphorus compounds.

By using other polymers, such as PBT and pEry polyesters, in an amount of less than 50% by weight of the polyamide used in the heat of +'ffj composition of the present invention, excellent resistance can be achieved. i
You can get something with inertia.

Furthermore, other polymers may be used depending on the required performance, such as polyethylene, polypropylene, BR, NBR, SBR, 5
-B-S block copolymer, hydrogenated 5-B-3, polystyrene, AS tree 11H, H [PS, ABS resin, AES
Resin, polysulfone, polyether sulfone, N-phenylmaleimide copolymerized styrene resin, MBS, methacrylic methyl-styrene copolymer, 5-I-S block copolymer, polyimide, PPS, polyether ether ketone, fluoride A vinylidene polymer or the like can be appropriately blended.

The thermoplastic resin M1 composition of the present invention can be used as various molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, etc.

(Various molded products obtained by the two-legged molding method utilize their excellent properties to create automobile exteriors, interior parts, interior materials, etc.)
It can be used for various child-related parts, housing, etc.

"Examples" The present invention will be described in more detail below with reference to Examples and Production Examples, but these are merely illustrative and do not limit the scope of the present invention.

Incidentally, in each of the following F, parts and % indicate parts and weight %, respectively.

Production Example 1 The polyphenylene ethers used in Examples and Comparative Examples are as follows:
obtained by the method.

l) After filling and replacing the inside of a stainless steel reactor equipped with an oxygen blowing device, a cooling coil, and a stirrer at the bottom of the steel-making reactor for polymer A-1 (polyphenylene ether), 453.6 g of 2tI bromide was added. , 1110 g of di-n-butylamine, and 8.75 kg of 2.6=xylenol dissolved in 40 g of toluene were added. After stirring to obtain a homogeneous solution, 9-part polymerization was carried out while rapidly blowing oxygen into the reaction vessel. During Togane, wood was circulated through a cooling coil to maintain the internal temperature at 30°C. After the end of Togane, 30 toluene! ; L was added, and a 20% aqueous solution of 430 g of disodium ethylenecyaminetetraacetate dissolved in ice was added to stop the reaction.

A polymer solution phase was taken out from the resulting product mixture by centrifugation, and methanol was gradually added to the polymer solution phase while stirring vigorously to form a slurry. After filtering and drying, Polymer A-1 was obtained.

2) ff
Togane was performed in place of 6-xylenol/2,3,6-)limethylphenol=90/10 (molar ratio) to obtain Polymer A-2.

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

1) jR combination-1 (maleic anhydride modified ethylene propylene rubber) Ethylene propylene rubber (JSREP manufactured by Nippon Gosei Co., Ltd.)
O2F, Mooney viscosity M L +, 4 (+011'C)
24) 1 part of maleic anhydride and 0.0 parts of organic peroxide (Kayahexa AD manufactured by Kayaku Nuri Co., Ltd.) per 100 parts.
Three parts were premixed in advance and heat treated using a 55 mmφ extruder (1 car, full-flight type screw) at 200° C. and a screw rotation speed of 30 rpm (residence time of about 4 minutes).

After extracting 77 tons of the obtained reaction product (boiling point x 2 hours), the polymer was formed into a film and the maleic anhydride graft I5 was determined by infrared spectroscopic analysis. The grafting rate of maleic anhydride was 0.5ii parts per 100 parts of ethylene propylene.

2) Polymers B-2 to B-8 Polymers B-2 to B-4 under the manufacturing conditions of Polymer B-1
is a modified form of water maleic acid 4'L. B-6
, B-7 are ethylene propylene co-Togane type. B-5 and B-8 are maleic anhydride in place of acrylic styrene-maleic anhydride copolymer. The results are shown in Table-1.

Table-1 Ethylene-malesic anhydride polymer Propylene rubber type 11) 3 Raft amount (parts) B-2JSREP-02P L
, IB-3JSREP-02P
2B-4JSREP-02P 0
, IB-5JSREP-02P
O, 5 (7 acrylic acid) B-6JSREP-911P
O, 5(Mooney viscosity ML and 4(loo')
c) :15)B-7JSREP-912P
0, 5 (Mooney viscosity ML 4 (100 nits): 10) B-8JSR
EP-Q2P 2
, 0 (Styrene-Maleic Anhydride Copolymer Skewer) Production Example-3 The (d) I& portion of the present invention used in Examples and Comparative Examples was obtained by the method F below.

After replacing the stainless steel autoclave with a stirrer with nitrogen, 45 parts of styrene, 5 parts of glycidyl methacrylate, and 0.2 parts of tert-dodecyl mercaptan were added in a nitrogen stream.
1.0 parts of sodium dodecylbenzenesulfonate and 140 parts of ion-exchanged water were added. While hot water at 70'C was circulated through the jacket, an aqueous solution of 1.0 part of potassium persulfate dissolved in 20 parts of ion-exchanged water was added at an internal temperature of 60C. After carrying out the combination reaction for 2 hours, 45 parts of styrene, 5 parts of glycidyl methacrylate, 0.2 fi of tert-dodecyl mercaptan, and 1 part of dodecylbenzenesulfonic acid sorter were added.
．． An emulsion consisting of 0 parts of ion-exchanged water and 90 F'B of ion-exchanged water was added, and the polymerization reaction was further carried out for 2 hours. A calcium chloride aqueous solution was added to the obtained polymer latex, and after washing, dehydration, and drying, a polymer D-1 was obtained.

2) Polymers D-2 to D-6 Under the manufacturing conditions of Polymer D-1, the amount of glycidyl methacrylate and glycidyl methacrylate were changed to acrylic acid, p
- Polymerization was performed in place of aminostyrene and allylamine.

Table 2 shows the amount of glycidyl methacrylate, acrylic acid content,
The amounts of p-7 minostyrene and allylamine are shown.

D-215 (glycidyl methacrylate) D-33 (glycidyl methacrylate) D-43 (acrylic acid) D-53 (p-7 minostyrene) [)-63 (allylamine) 3) Polymer D-7 Styrene-maleic anhydride copolymer Coalescing (Dilata ■-ku 232, manufactured by Arcobo Limer) 4) Polymer D-8 ■ Polystyrene (Tobolex 500-51, manufactured by Mitsui Toatsu Co., Ltd.) Examples and Comparative Examples The various polymers described above were subjected to MI in Table 3. The components were mixed at the same proportions and melted and kneaded in a co-rotating twin-screw extruder at a barrel temperature of 220° C. to 280° C. for a residence time of 3 to 5 minutes to obtain a thermoplastic resin composition in the form of pellets.

After sufficiently drying in a vacuum dryer, test pieces were prepared using an injection molding machine, and impact resistance, heat resistance, etc. were measured using the following methods.

The results are shown in Table-3.

In Example-21, the composition ratio was that of Example-1, but the kneading method was changed. First, a blend of components (a), (c), and (d) was passed through an extruder, and while adding component (b) midway through the extruder, the same composition as in Example 1-11 was prepared.
This is the composition of IE).

Impact resistance: Using a DuPont impact tester, the tip of the striking rod R = l/
2", thickness 2.4 mmc7) Falling weight impact strength was determined.

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

Heating number lit rate (%) = (Length of initial test piece - Length of test piece after heating and standing) x
100/(length of initial test piece) Nozzle diameter innΦ, tq
Measurements were made with a diameter of 2 mm, a temperature of 280° C., and a load of 30 kg.

Comparative Example 6 is a known composition, and although it has excellent pre-molding properties and sharpness, it is a brittle resin with very low impact resistance, and its industrial utility value is extremely low.

On the other hand, the composition according to the present invention has significantly improved impact resistance as shown in the examples, and has impact resistance, heat resistance, I&,
The physical properties of formability are highly balanced.

Therefore, since the composition of the present invention has highly balanced physical properties, it can be used in automatic applications where high quality is required.
It can be used for molded products such as 11 exterior and interior parts, various parts related to upper air and air, and housing.

``Effects of the Invention'' As is clear from the following paragraphs, according to the present invention, by blending polyphenylene ether and polyamide with two specific resins in specific ratios, it is possible to improve It has now become possible to provide all types of thermoplastic resins with highly balanced impact resistance, heat resistance, and moldability that are difficult to achieve.

Claims (1)

[Claims] (a) Polyphenylene ether resin 3.5 to 95% by weight (b) Polyamide 95 to 3.5% by weight (c) Ethylene-α-olefin copolymer 1 to 50% by weight
Weight% (d) A composition consisting of 0.5 to 90% by weight of a styrenic polymer, wherein the component (c) is ethylene modified with at least one selected from unsaturated acid anhydrides and unsaturated acids. -α-olefin copolymer, (d)
Ingredients are styrenic monomer and unsaturated dicarboxylic anhydride,
A thermoplastic resin composition characterized in that it is a copolymer with at least one unsaturated compound selected from unsaturated acids, epoxy group-containing unsaturated compounds, and amino group-containing vinyl monomers.