JP2623789B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a resin composition. Specifically, the present invention relates to a resin composition containing a polyphenylene ether resin and a copolyamide resin.

More specifically, a thermoplastic aromatic copolyamide and / or an aromatic nucleated hydrogenated copolyamide are blended in a certain ratio to a resin composition comprising a polyphenylene ether, an aliphatic polyamide, and a specific compatibilizer to provide mechanical properties. The present invention relates to a novel thermoplastic resin composition which has a small decrease in physical properties, particularly, a flexural modulus when absorbing water, and is excellent in processability.

The composition of the present invention can be used as molded articles, sheets and the like by injection molding, extrusion molding and the like.

<Related Art> A resin composition comprising a polyphenylene ether resin and a polyamide resin such as nylon 6 or nylon 66 is known. (JP-B-45-997, JP-B-53-47390, JP-A-56-16525, JP-A-56-26918, U.S. Patent No. 4,315,086, JP-A-61-66452, (See JP-A-62-151456, JP-A-62-129350, JP-A-62-250050, and the like.) These resin compositions are disadvantageous of both component resins, for example, the former has difficulty in processing and has low processability. It is known that it is a useful resin composition having improved solvent resistance, the latter low heat resistance and high water absorption, etc. In recent years, electric parts, machine parts, sporting goods, automobile parts, especially exterior materials, etc. Application to is expanding.

<Problems to be Solved by the Invention> However, a resin composition composed of polyphenylene ether, an aliphatic polyamide having a relatively high amide group concentration such as nylon 6, nylon 66, and nylon 46, and polyphenylene ether is a component of the polyamide itself. Although the superabsorbency is considerably improved, there are problems in practical physical properties. For example, the amount of water absorption changes relatively depending on the polyamide content in the resin composition, and there is a serious drawback that physical properties are reduced due to a small amount of water absorption of about 1% based on the composition, and particularly the bending elastic modulus is significantly reduced. Have.

Although such a resin composition has a lower coefficient of thermal expansion than the polyamide itself, which is a constituent, it is larger than a metal material and also polyphenylene ether, which is another main constituent, and has a high thermal expansion coefficient at a high temperature. There is a disadvantage that deformation due to expansion is large.

An object of the present invention is to provide a polyphenylene ether-polyamide resin composition in which the remarkable decrease in rigidity during water absorption is remarkably improved.

Another object is to provide a polyphenylene ether / polyamide resin composition having a lower coefficient of thermal expansion.

Aliphatic polyamides, particularly nylon 46, nylon 6, nylon 66, which are one of the main components of the resin composition according to the present invention, have relatively high crystallinity, excellent oil resistance, heat resistance,
Has toughness and the like.

On the other hand, thermoplastic aromatic copolyamides such as polyhexamethylene isophthalamide (nylon 6I) have characteristics such as higher thermal deformation temperature under high load than aliphatic polyamides, but generally have low crystallinity. Therefore, there is a drawback that deformation due to hot water and a large amount of alcohol absorption are caused.

<Means for Solving the Problems> Accordingly, the present inventors have developed a significant disadvantage of a resin composition containing polyphenylene ether and an aliphatic polyamide, which is a serious drawback, without impairing other properties, and a significant decrease in flexural modulus at the time of water absorption. As a result of intensive research on resin compositions containing polyphenylene ether and polyamide for the purpose of improvement and further reduction of the coefficient of thermal expansion, thermoplastic polyamide copolyamide and / or aromatic nucleus were added to aliphatic polyamide. The present inventors have found that a resin composition containing a polyphenylene ether and a polyamide having an excellent balance of physical properties can be obtained by using a polyamide in which a hydrogenated copolyamide is blended in a specific range, thereby completing the present invention.

That is, the present invention relates to (A) 10 to 70 parts by weight of a polyphenylene ether, a mixture of polyphenylene ether and polystyrene, or 10 to 70 parts by weight of a graft copolymer of polyphenylene ether and styrene;
-7.5% by weight of a thermoplastic aromatic copolyamide and / or an aromatic nucleated hydrogenated copolyamide;
90 to 30 parts by weight of a mixture comprising 9.5 to 92.5% by weight of a thermoplastic aliphatic polyamide, and (C) a compatibilizer for a total of 100 parts by weight of the above components (A) and (B) as a compatibilizer. (A) a carbon-carbon double bond or a carbon-carbon triple bond, and (b) a carboxyl group, an acid anhydride group, an amino group, an acid amide group, an imide group, an epoxy group, a carboxylic acid ester group, or an isocyanate group. ,
A compound containing at least one functional group selected from a methylol group, an oxazolidine and a hydroxyl group, and at least one compound selected from oxazoline (hereinafter abbreviated as "compatibilizer") in an amount of 0.01 to 30 parts by weight; It relates to a plastic resin composition.

The polyphenylene ether used in the present invention has a general formula (Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are the same or different and have 1 to 4 carbon atoms, excluding tert-butyl, alkyl, aryl,
It is a monovalent residue such as halogen or hydrogen, and R ₃ and R ₅ are not simultaneously hydrogen. ) Is a repeating unit, and the structural unit is a homopolymer or a copolymer consisting of [I] or [I] and [II], a mixture of both, a mixture of the polymer and polystyrene, or styrene as the polymer. And the like.

Representative examples of homopolymers of polyphenylene ether include poly (2,6-dimethyl-1,4phenylene) ether,
Poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-npropyl-1,4-phenylene) Ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-
6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-)
Examples include homopolymers such as phenylene) ether and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether.

Polyphenylene ether copolymer is ortho-cresol or general formula (Where R ₃ , R ₄ , R ₅ , and R ₆ each have 1 carbon atom excluding the tert-butyl group)
To 4 are monovalent residues such as an alkyl group, an aryl group, halogen, and hydrogen, and R ₃ and R ₅ are not hydrogen at the same time. )), And a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure obtained by copolymerization with an alkyl-substituted phenol such as 2,3,6-trimethylphenol.

The thermoplastic aromatic copolyamide (B) (i) used in the present invention is a copolyamide containing an aromatic component such as polyhexamethylene isophthalamide (nylon 6I). The thermoplastic copolyamide containing such an aromatic component is prepared by melt polymerization of an aromatic amine acid and / or an aromatic dicarboxylic acid such as paraaminomethylbenzoic acid, paraaminoethylbenzoic acid, terephthalic acid and isophthalic acid as main components. Means a possible polyamide.

Diamines which are other constituents of polyamide include hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, meta-xylylenediamine, para-xylylenediamine , Bis (p-aminocyclohexyl) methane, bis (p-aminocyclohexyl) propane, bis (3-methyl, 4-aminocyclohexyl) methane, 1,3-
Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like can be used. Isocyanates can be used instead of diamines. The copolymerization component used as required is not particularly limited, and examples thereof include 4,4'-diphenylmethane diisocyanate and tolylene diisocyanate. Lactams or units of ω-amino acids with 4 to 12 carbon atoms, or compounds derived from aliphatic dicarboxylic acids with 4 to 12 carbon atoms and aliphatic diamines with 2 to 12 carbon atoms, for example ε-caprolactam Lactams such as ω-lacrolactam, 11-aminoundecanoic acid and 12-aminododecanoic acid, or amino acids, and equimolar salts of the above-mentioned various diamines with adipic acid, azelaic acid and sebacic acid.

Representative examples of thermoplastic aromatic copolyamides composed of these components include copolymerized polyamides of para-aminomethylbenzoic acid and ε-caprolactam (nylon AMBA / 6),
2,2,4-−2,4,4-trimethylhexamethylenediamine
Polyamide based on terephthalate (nylonTM
DT, TMDT / 6I), hexamethylenediamine, isophthalate and / or hexamethylenediamine terephthalate as the main component, bis (paraaminocyclohexyl)
Methane isophthalate and / or terephthalate or bis (3-methyl, 4-aminocyclohexyl) methane isophthalate and / or terephthalate or bis (paraaminocyclohexyl) propaneisophthalate and / or bis (paraamino) Polyamide (Nylon 6I / PACM I, Nylon 6I / DMPACM I, Nylon 6I / PACP I, Nylon 6I / 6T / PACM I / PACM T, Nylon 6I) Copolymer of cyclohexyl) propane terephthalate
/ 6T / DMPACM I / DMPACM T, nylon 6I / 6T / PACP I / PACP
T), hexamethylenediamine, isophthalate or hexamethylenediamine terephthalate as the main component, ε-caprolactam, 12-aminododecanoic acid, hexamethylenediamine adipate, bis (paraaminocyclohexyl) methane adipate Polyamide (Nylon 6I, 6I / 6) containing a salt, bis (3-methyl, 4-aminocyclohexyl) methane / adipate as a copolymer component
T, 6I / 12,6T / 6,6T / 66,6I / PACM6,6I / DMPACM6), bis (paraaminocyclohexyl) methane / isophthalate or bis (3-methyl, 4-aminocyclohexyl) methane, isophthalate (Nylon PACM I / 612, Nylon DMPACM I / 12) and the like, and a copolysynthesis compound such as hexamethylenediamine dodecane diacid salt and 12-aminododecanoic acid.

(B) The aromatic nuclear hydrogenated copolyamide of (i) refers to cyclohexane 1,4-dicarboxylic acid or cyclohexane 1,3-dicarboxylic acid obtained by nuclear hydrogenation of terephthalic acid or isofudaric acid. These are alicyclic copolyamides that can be obtained by using terephthalic acid and isophthalic acid, respectively, which are acid components. In addition, diamines, diisocyanates, and nuclear hydrogenated products of (4,4'diphenylmethane diisocyanate, tolylene diisocyanate, etc.) can also be used as monomers.

The (B) (ii) aliphatic polyamide used in the present invention is known in the art. These have a molecular weight of 10,000 or more and have an equimolar amount of 4 carbon atoms.
Saturated aliphatic dicarboxylic acids containing up to 12 and 2 to 12 carbon atoms
In this case, if necessary, a diamine can be used in the polyamide to give an excess of amine terminal groups over carboxyl terminal groups in the polyamide. Conversely, a dibasic acid can be used to provide an excess of acidic groups. Similarly, these polyamides can be successfully prepared from the acid and amine-forming derivatives of the acids and amines, such as esters, acid chlorides, amine salts, and the like. Typical aliphatic dicarboxylic acids used to produce this polyamide include adipic acid, pimelic acid, azelaic acid, suberic acid,
Sebacic acid and dodecanedioic acid are included, while typical aliphatic diamines include hexamethylene diamine and octamethylene diamine. In addition, these polyamides can be produced by self-condensation of lactams. Examples of polyamides include polyhexamethylene adipamide (nylon 66), polyhexamethylene azeramid,
(Nylon 69), polyhexamethylene sebacamide, (nylon 610), and polyhexamethylene dodecanoamide (nylon 612), poly-bis- (p-aminocyclohexyl) methane dodecanoamide, polytetramethylene adipamide (Nylon 46) or polyamides resulting from ring opening of lactams; polycaprolactam (nylon 6), and polylauryl lactam. Further, polyamides produced by polymerizing at least two kinds of amines or acids used in producing the above polymers, for example, polymers produced from adipic acid, sebacic acid and hexamethylenediamine can be used. . Blends of polyamides, such as blends of nylon 66 and nylon 6, include copolymers such as nylon 66/6. Preferably, the aliphatic polyamide used herein is polyhexamethylene adipamide (nylon 66), or polycaprolactam (ninelo 6), or a blend of polyhexamethylene adipamide (nylon 66) and polycaprolactam (nylon 6). It is.

The (C) "compatibilizing agent" used in the present invention includes (a) a carbon-carbon double bond or a carbon-carbon triple bond, and (b) a carboxyl group, an acid anhydride group, an amino group. A compound containing at least one functional group selected from the group consisting of an amide group, an acid amide group, an imide group, an epoxy group, a carboxylic acid ester group, an isocyanate group, a methylol group, an oxazolidine and a hydroxyl group, and at least one compound selected from oxazolines. is there. Specific examples of the compatibilizer are shown below, but are not limited to the following examples. Maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, a reaction product of maleic anhydride with a diamine, for example, (Where R represents an aliphatic or aromatic group), methylnadic anhydride, dichloromaleic anhydride, maleic amide, soybean oil, tung oil, castor oil, linseed oil, hemp seed, etc. Oil, cottonseed oil, sesame oil, rapeseed oil,
Natural oils such as peanut oil, camellia oil, olive oil, coconut oil, sardine oil, epoxidized natural oils such as epoxidized soybean oil, acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, itaconic acid, methacrylic acid, pentene Acid, angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, α-
Ethyl acrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl- 3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4
-Decenoic acid, 9-undecenoic acid, 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, aicosene Acid, docosenoic acid, erucic acid,
Tetracosenoic acid, mycolipenoic acid, 2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid, geranic acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 9.12
-Hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, elenoic acid Unsaturated carboxylic acids such as stearic acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenoic acid, and traaconthenic acid; Endomethylene tetrahydrophthalic anhydride or esters of these unsaturated carboxylic acids, acid amides, anhydrides, or allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methyl propenyl carbinol, 4-pentene 1-Earl, 10-undecenoic -1
All, propargyl alcohol, 1,4-pentadien-3-ol, 1,4-hexadien-3-ol, 3.
5-hexadiene-2-ol, 2,4-hexadiene-
1-ol of the general formula _{C n H 2n-5 OH,} C n H 2n-7 OH, C n H 2n-9 OH
(Where n is a positive integer) alcohol, 3-butene 1.2-diol, 2.5-dimethyl-3-hexene-2
.Unsaturated alcohols such as 5-diol, 1.5-hexadiene-3.4-diol, 2.6-octadiene-4.5-diol, or such unsaturated alcohols
OH groups, unsaturated amine Tsu replace the -NH ₂ group, or glycidyl acrylate, glycidyl methacrylate, and the like allyl glycidyl ether. Alternatively, maleic anhydride, phenols may be added to low polymerization (such as those having an average molecular weight of about 500 to 10,000) or high molecular weight substances (such as those having an average molecular weight of 10,000 or more) such as butadiene and isoprene, or amino groups, Those into which a carboxylic acid group, a hydroxyl group, an epoxy group, or the like are introduced are exemplified.

The (C) compatibilizer in the present invention also includes a compound containing two or more double or triple bonds in the group (a), two or more functional groups in the group (b) (same or different). What is done
Of course, it is also possible to use more than one compound.

Among them, maleic anhydride, maleic acid, fumaric acid, itaconic acid, glycyl acrylate, glycidyl methacrylate, and allyl glycidyl ether are preferred.

In the present invention, (D) an elastomer and / or a polyolefin resin having a low flexural modulus (hereinafter abbreviated as a rubber-like substance) and / or a modified rubber-like substance can be used as the impact resistance improving agent.

Specifically, ethylene propylene rubber, ethylene propylene non-conjugated diene rubber, ethylene butene rubber, propylene butene rubber, isoprene butylene rubber, polyisoprene, polybutadiene, styrene butadiene rubber, styrene butadiene styrene block copolymer, partially hydrogenated styrene butadiene block copolymer, Styrene isoprene block copolymer, partially hydrogenated styrene isoprene block copolymer, linear low-density polyethylene, or the like, or a mixture thereof is used.

The modified rubber-like substance is obtained by modifying the rubber-like substance with (C) a “compatibilizer”. For example, maleic anhydride grafted ethylene propylene rubber, maleic anhydride grafted styrene butadiene styrene block copolymer, maleic anhydride grafted partially hydrogenated styrene butadiene block copolymer, glycidyl methacrylate grafted ethylene propylene rubber and the like can be used.

Ethylene-acrylate-maleic anhydride copolymers, ethylene-acrylate-glycidyl methacrylate copolymers, ethylene-vinyl acetate-glycidyl methacrylate copolymers obtained by copolymerizing a compatibilizer, or blends thereof are also used as rubber-like substances. . Among them, ethylene propylene rubber, ethylene butene rubber, styrene butadiene block copolymer, partially hydrogenated styrene butadiene block copolymer, styrene isoprene block copolymer, partially hydrogenated styrene isoprene block copolymer, density 0.885 to 0.935 g / cm
³ , preferably linear low density polyethylene in the range of 0.885 to 0.925 g / cm ³ and graft polymers obtained by grafting (C) a compatibilizer on these polymers. Also,
Also suitable are ethylene-methyl acrylate-maleic anhydride copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl acrylate glycidyl methacrylate copolymer or blends thereof.

The amount of component (D) is not particularly limited, but is preferably 3 to 60 parts by weight based on the total composition (100 parts by weight of (A) + (B) + (C)).

In the present invention, the method of compounding the rubber-like substance and / or the modified rubber-like substance (D), which is the component (A), (B), (C) and the impact strength improver, is not particularly limited, and a known melt kneading method is used. Can be used. As the melt-kneading apparatus, an extruder, a kneader, a roll and the like can be used, and an extruder is particularly preferable. There is no particular limitation on the order of constituting each component at the time of melt-kneading. That is, component (A),
A method in which (B) and (C) are added all at once and melt-kneaded at the same time. Components (A) and (C) are melt-kneaded in advance in the presence or absence of a radical initiator, and then component (B) is added. In the method of melt-kneading and adding the component (D) as an impact resistance improver, the component (D) is added together with the components (A), (B) and (C), A method in which the components (D) and (A) and (C) are melt-kneaded in advance in the presence or absence of a radical initiator, and then a component (B) is added and melt-kneaded, Alternatively, components (A) and (C) are melt-kneaded with components (A) and (C) in the presence or absence of a radical initiator, and then components (B) and (D) are added and melted. A method of kneading, or the components (D) and (C) are previously added in the presence of a radical initiator. Melt kneading and then, component (A)
And the method of adding and mixing (C) and melt-kneading may be used.

In the present invention, the mixing ratio of the components (A), (B) and (C) is 10 to 70 parts by weight of the component (A), 90 to 30 parts by weight of the component (B), and the total of the components (A) and (B) is 100. Component (C) is 0.01 to 30 parts by weight relative to parts by weight. If the amount of the component (C) is less than 0.01 part by weight, the mechanical strength of the thermoplastic resin composition of the present invention decreases, and the intended effect of the present invention cannot be obtained. If the amount exceeds 30 parts by weight, the appearance deteriorates.

The mixing ratio of the thermoplastic aromatic copolyamide and / or the aromatic nucleated hydrogenated copolyamide and the aliphatic polyamide in the component (B) used in the present invention is 0.5 to 0.5 with respect to the total polyamide present in the composition. 7.5% by weight, the latter being 99.5 to 92.5% by weight complementarily. When the blending ratio of the thermoplastic aromatic copolyamide and / or the aromatic nucleated hydrogenated copolyamide is less than 0.5% by weight, the effect of improving rigidity reduction upon water absorption is remarkably reduced. The oil resistance of the composition is significantly reduced. Preferably, the blending ratio of both is from 0.5 to 50% by weight of a thermoplastic aromatic copolyamide and / or an aromatic nucleated hydrogenated copolyamide, and 99.5 to 50% by weight of an aliphatic polyamide in a complementary manner.
0.5 to 25% by weight, the latter complementarily 99.5 to 75% by weight.

The polyphenylene ether of the component (A) used in the present invention is 0.5 g / dl in chloroform solution.
Reduced viscosity (ηsp / c) measured at 5 ° C is 0.25 ~ 0.65dl / g,
Preferably it is in the range of 0.35 to 0.60 dl / g.

If it is less than 0.25 or more than 0.65 dl / g, the mechanical strength of the thermoplastic resin composition of the present invention, particularly the impact strength, is lowered, and the intended purpose is not achieved. If it exceeds 0.65 dl / g, the fluidity decreases, which is not preferable.

If necessary, the resin composition may further contain ordinary fillers such as glass fiber, glass flake, talc, mica, etc., dyes, pigments, UV deterioration inhibitors, heat stabilizers, flame retardants, antioxidants and plasticizers. Can be included.

The molded article obtained from the thermoplastic resin composition of the present invention is suitably used for automobile parts, electric / electronic parts and the like.

Molded parts for automobile parts include bumpers, fenders, aprons, food panels, fascias, rocker panels, rocker panel reinforces, floor panels,
Exterior articles such as rear quarter panels, door panels, door supports, roof tops, trunk lids, instrument panels, console boxes, glove boxes,
Interior parts such as shift knob, pillar garnish, door trim, handle, armrest, wind louver, carpet, headrest, seat belt, seat, etc., distributor cap, air cleaner, radiator tank, battery case, radiator shroud, washer tank, cooling fan, heater Examples include parts in an engine room such as a case, a mirror body, a wheel cover, a trunk trim, a trunk mat, a gas tank, and the like.

<Examples> Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the examples. The reduced viscosity (ηsp / c) of the polyphenylene ether in the examples is a value measured at 25 ° C. for a 0.5 g / dl chloroform solution. The heat distortion temperature (HDT), notched Izod impact strength (NI), and flexural modulus of the resin composition were D648 and D25 of the ASTM method, respectively.
According to 6 and D790.

All resin compositions used for injection molding of test pieces are 120
It was used by vacuum drying at ℃ for 6 hours. Measurement of physical properties of test pieces is 23
The sample was left for 48 hours in an air atmosphere at 50 ° C. and a relative humidity of 50%, and then subjected to measurement. However, the measurement of bending elastic modulus and water absorption rate at the time of water absorption is 23
7 days (168 hours) in an air atmosphere at 50 ° C and 50% relative humidity
It was measured after standing.

The water absorption was measured using a Karl Fischer moisture meter (CA-05 moisture vaporizer VA-05 manufactured by Mitsubishi Kasei Corporation).

The coefficient of thermal expansion was measured by subjecting a test piece (HDT) injection molded under the conditions described above to an air atmosphere at 23 ° C and 50% relative humidity.
After standing for 5 hours, 5 mm x 5 mm in the resin composition flow direction (MD direction)
A test piece having a size of mm × 5 mmt was cut out, and the coefficient of thermal expansion in the MD direction was measured in a temperature range from −40 ° C. to 80 ° C.

The measuring instrument used was a thermal analyzer DT manufactured by Shimadzu Corporation.
-40 was used.

All injection molding conditions were as follows: ASTM standard dumbbell specimens were molded under the conditions of a cylinder temperature of 290 ° C and a mold temperature of 80 ° C. The injection molding machine used was Toshiba Machine's IS150E.

Reference Example 1 (preparation of the polyphenylene ether resin. Pursuant to the method of JP-B-60-46129 JP.) To reactor 1.5 m ³ 2,6-dimethylphenol 122.2Kg, xylene 366.5Kg, methanol 122.2Kg, Sodium hydroxide 2.
4kg, Eriochrome Black T (Hanai Chemical Co., Ltd.)
0.55 kg, 1.49 kg of 2-pipecoline and 0.099 kg of manganese chloride tetrahydrate were charged, and air was blown at a rate of 300 Nl / min for 10 hours while stirring to carry out oxidative polymerization. During this time, the temperature of the reaction mixture was maintained at 30 ° C., and the pressure of the reaction system was maintained at 8 kg / cm ² G. After completion of the reaction, post-treatment is carried out according to a conventional method, and poly (2,6-dimethyl-1,4-phenylene) oxide 119 kg
I got The reduced viscosity of the obtained poly (2,6-dimethyl-1,4-phenylene) oxide was 0.535 dl / g.

Reference Example-2 (Thermoplastic aromatic copolyamide-6I / 6T / PACM
Production of I / PACM T (63.5 / 27.2 / 6.5 / 2.8)-. Tokiko Sho 62-
According to the method described in JP-A-28983. 6I means hexamethylenediamine (HMD) and isophthalic acid (I) units, 6T means HMD and terephthalic acid (T)
PACM means unit, PACM I means PACM and I units, and PACM T means PACM and T units. PACM means bis (p-aminocyclohexyl) methane.

In 63.6kg of water, 20.6kg of HMD (concentration 82.03%) and bis (p-
2.38 kg of aminocyclohexyl) methane were added. The mixture was heated and 18.7 kg of isophthalic acid and 8.04 kg of terephthalic acid were added. Next, the pH value was adjusted to 8.6 using a small amount of HMD.
Adjusted to 0. 49 g of sodium phenylphosphinate, 4,4'-butylidenebis (6-t-butyl-
97 g of m-cresol), 20 ml of a 10% emulsion of polydimethylsiloxane and 14 ml of glacial acetic acid were added.

 The temperature of this solution was maintained at 70-80 ° C.

This salt mixture was then filled into an autoclave.
The mixture was heated to 175 ° C. and pressurized to a pressure of 12.7 kg / cm ² . Water is gradually removed and the batch temperature is 226 ℃
Until it reached 12.7 kg / cm ² . The pressure was then gradually reduced to atmospheric pressure and a vacuum was applied. Then the batch temperature was increased to about 270 ° C. When the desired molecular weight was achieved, the autoclave was pressurized with nitrogen gas, the polymer was extruded into a cylindrical strand, quenched in water, and cut into pellets.

For the particular acid and diamine used, the copolyamide is
70% isophthalic acid and 30% terephthalic acid, total 10
Contains 0% acid and 90.5% HMD and 9.5% P
ACM, containing 100% total diamine.

Reference Example-3 (Production of maleic anhydride EPR) EPR manufactured by Sumitomo Chemical Co., Ltd. E-120) 10
1.5 parts by weight of styrene monomer per 0 parts by weight, anhydrous maleic
Acid 1.5 parts by weight, Nippon Yushi Co., Ltd. as a radical initiator
0.1 parts by weight of dicumyl peroxide (DCP)
Mix well with a well mixer and use the same as used in the examples.
It was manufactured using a twin screw extruder manufactured by Japan Steel Works, Ltd. Siri
Temperature is set to 230 ° C and screw rotation speed is 190rp
m.

Reference Example-4 (Maleic anhydride partially hydrogenated styrene butadi
Manufacture of enstyrene block copolymer) Partially hydrogenated styrene butadiene manufactured by Ciel Chemical
Enblock copolymer (Clayton G1650)
Anhydrous maleation was performed in the same manner as in Reference Example 3 except that
Was.

In Examples and Comparative Examples described below, kneading (TEX44, manufactured by Nippon Steel Works Co., Ltd.) was performed using a twin-screw extruder.
This extruder has L / D = 32, and is equipped with a first supply port and a second supply port at the position of L / D = 16.

Examples 1-2 Through Examples 1-2 and Comparative Examples 1-2, manufactured in Reference Example 1.
Polyphenylene ether, anhydrous as "compatibilizer"
Maleic acid, manufactured in Reference Example 3 as an impact strength improver
Maleic anhydride ethylene propylene rubber, dicumyl par
Oxide (Sampelox DCP Sanken Kakosha)
After pre-mixing with a tumbler mixer, first supply
The polyamide was supplied from the second supply port through the supply port.

The cylinder temperature was set at 260 ° C and the screw rotation speed was 360 rpm. The raw material mixing ratio was based on the ratio shown in Table 1. When two or more polyamides were supplied through the second supply port, they were sufficiently mixed in advance with a tumbler mixer and then supplied. A commercially available nylon 6 (manufactured by Unitika Ltd.) as an aliphatic polyamide through Examples 1-2 and Comparative Examples 1 and 2.
A1030BRL) was used.

 In Examples 1 and 2, EMS C was used as a thermoplastic aromatic polyamide.
Grilamide manufactured by HEMIM XE3038 is a reference example in Example 3.
Production of a resin composition using the copolyamide produced in -2
Built.

Comparative Example 1 A resin composition was produced under the same blending ratio and the same extrusion conditions as in Examples 1 and 2, except that all the aromatic copolyamides were replaced with the same nylon 6 used in Examples 1 to 3.

Comparative Example 2 The same blending ratio as in the Example except that the aromatic copolyamide was 10 parts by weight of nylon and the nylon 6 was 30 parts by weight.
A resin composition was produced under the same extrusion conditions.

Example 4 Aliphatic polyamide was converted from nylon 6 to commercially available nylon 66.
(2020B manufactured by Ube Industries, Ltd.)
Amide is Dynamite Nobel Trogamid T 20
Except for replacing with 10, the same compounding ratio as in Example 1,
A resin composition was manufactured according to the extrusion conditions.

Comparative Example 3 A resin composition was produced under the same blending ratio and extrusion conditions as in Example 3 except that all the aromatic copolyamides were replaced with the same nylon 66 used in Example 4.

Example 4 53 parts by weight of polyphenylene ether and 36 parts of nylon 6
The resin composition was manufactured in the same manner as in Example 1 except that the parts by weight and the aromatic copolyamide were changed to 1 part and the maleic anhydride was replaced with fumaric acid.

Comparative Example 4 Except that the aromatic copolyamide was replaced with nylon 6,
A resin composition was produced under the same mixing ratio and the same extrusion conditions as in Example 4.

Example 5 Polyphenylene ether was converted to η manufactured by Nippon Polyether Corporation.
A resin composition was produced under the same blending ratio and the same extrusion conditions as in Example 1 except that poly (2,6-dimethyl 1,4-phenylene ether) having an sp / c of 0.42 dl / g was used.

Comparative Example 5 A resin composition was produced under the same blending ratio and the same extrusion conditions as in Example 5, except that the aromatic polyamide was replaced with nylon 6.

Example 6 A resin composition was produced under the same extrusion conditions as in Example 2 in both the blending ratio and the extrusion conditions except that all the raw materials of the resin composition were supplied from the first supply port.

Example 7 A maleic anhydride partially hydrogenated styrene butadiene styrene block copolymer prepared in Reference Example 4 was used as an impact strength improver in place of maleic anhydride ethylene propylene rubber, and maleic anhydride and dicumyl peroxide were not blended. Except for the above, a resin composition was produced under the same mixing ratio and the same extrusion conditions as in Example 1.

Comparative Example 6 A resin composition was produced under the same blending ratio and the same extrusion conditions as in Example 7, except that the aromatic copolyamide was replaced with nylon 6.

Example 8 Maleic anhydride ethylene propylene as impact modifier
Partially hydrogenated styrene isoprene blow instead of rubber
Copolymer (Quiton G manufactured by Shell Chemical Company) 170
Glycidyl methacrylate using maleic anhydride
The same blending conditions as in Example 2 except that
A resin composition was manufactured under one extrusion condition.

Table 1 shows the results of the examples, and Table 2 shows the results of the comparative examples.

<Effect of the Invention> The thermoplastic resin composition according to the present invention is a molded article when a specific amount of each of polyphenylene ether, aromatic copolyamide and / or aromatic hydrogenated copolyamide, compatibilizer and rubber-like substance is blended. The lowering of the flexural modulus during water absorption reduced the coefficient of thermal expansion, making it possible to use it in a wide range of applications.

According to the present invention, the novel resin composition provided is easily processed into a molded product, a sheet, a film, or the like by a molding method used for a thermoplastic resin, for example, a processing method such as injection molding or extrusion molding. A product with extremely good balance of physical properties such as impact resistance, heat resistance, and bending rigidity is provided.
In particular, a novel resin composition effective for injection molding is provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 25:04 21:00) (C08L 77/00 71:12 25:04 21:00) (72 Inventor Taichi Nishio 5-1 Anesaki Kaigan, Ichihara-shi, Chiba Sumitomo Chemical Industries Co., Ltd. (72) Inventor Hiroomi Abe 5-1 Anesaki Kaigan, Ichihara-shi, Chiba Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Noriyuki Kagawa 2-7-9 Nihonbashi, Chuo-ku, Tokyo Sumitomo Chemical Co., Ltd. (56) References JP-A-63-35652 (JP, A) JP-A-56-26913 (JP, A) JP-A-62-246957 (JP, A) JP-A-63-108056 (JP, A)

Claims (14)

(57) [Claims] (A) polyphenylene ether or (A)
10 to 70 parts by weight of a mixture of polyphenylene ether and polystyrene or 10 to 70 parts by weight of a graft copolymer of polyphenylene ether and styrene, (B) 0.5 to 100 parts by weight based on all the polyamides present
7.5% by weight of a thermoplastic aromatic copolyamide and / or an aromatic nuclei hydrogenated copolyamide, and (ii) 99.5% complementarily based on all polyamides present.
90 to 30 parts by weight of a mixture consisting of 〜92.5% by weight of a thermoplastic aliphatic polyamide, and (C) a total of 100 parts by weight of the above components (A) and (B), And (a) a carbon-carbon double bond or a carbon-carbon triple bond, and (ii) a carboxyl group, an acid anhydride group, an amino group, an acid amide group, an imide group, an epoxy group, a carboxylic acid ester group, and an isocyanate group. A thermoplastic resin composition comprising 0.01 to 30 parts by weight of a compound containing at least one functional group selected from the group consisting of methoxyl, methylol group, oxazolidine and hydroxyl group and at least one compound selected from oxazoline. (2) The polyphenylene ether (A) is poly (2,6 dimethyl-1,4 phenylene ether) and / or
2. The thermoplastic resin composition according to claim 1, which is a copolymer of 2,6 dimethylphenol and 2,3,6 trimethylphenol. 3. The polyphenylene ether (A) is 0.5 g / dl.
Poly (2,2) whose reduced viscosity (ηsp / c) measured at 25 ° C is in the range of 0.25 to 0.65 dl / g
6-dimethyl-1,4-phenylene ether) and / or 2,6
3. The thermoplastic resin composition according to claim 2, which is a copolymer of dimethylphenol and 2,3,6 trimethylphenol. 4. The thermoplastic aliphatic polyamide (B) having a lactam or carbon atom having an average molecular weight of about 10,000 or more.
2. The method according to claim 1, which comprises units of .about.12 .omega.-amino acids or units derived from aliphatic dicarboxylic acids having 4 to 12 carbon atoms and aliphatic diamines having 2 to 12 carbon atoms.
Item 12. The thermoplastic resin composition according to Item 1. 5. The thermoplastic aromatic copolyamide and / or the aromatic nucleated hydrogenated copolyamide is selected from the group consisting of (a) and (b) alone or (a) and (b) as an acid.
(A) terephthalic acid and / or derivatives thereof, (b) isophthalic acid and / or derivatives thereof, and amines as (c), (d), (e), (f),
(G) Polyamide obtained using at least one selected from (g) (c) hexamethylenediamine (d) trimethylhexamethylenediamine (e) bis (p-aminocyclohexyl) methane (f) bis (p-aminocyclohexyl) propane (G) bis (3-methyl, 4-aminocyclohexyl)
Methane or its acids, amines and lactams or carbon atoms 4
2. The method according to claim 1, which comprises units of .about.12 .omega.-amino acids or units derived from aliphatic dicarboxylic acids having 4 to 12 carbon atoms and aliphatic diamines having 2 to 12 carbon atoms.
Item 12. The thermoplastic resin composition according to Item 1. 6. An amine as defined in (c) and (e), (f),
(E), (f) and (g) in a mixture with at least one of (g) and (c) 99.5 to 50 mol%.
The thermoplastic resin composition according to claim 5, wherein the total of the thermoplastic resin composition is 0.5 to 50 mol%. 7. The acid comprises 2 to 60 mol% of (a) terephthalic acid and 40 to 98 mol% of (b) isophthalic acid in 100 mol% of the total acid, and the amine comprises (e), (f) 6. The thermoplastic resin composition according to claim 5, wherein the total of at least one selected from (g) and (g) is 2 to 50 mol% based on 100 mol% of the total amine. 8. An acid comprising 20 to 40 mol% of (a) terephthalic acid and 60 to 80 mol% of (b) isophthalic acid in 100 mol% of total acid, wherein the amine is (C) 94-98 mol% of hexamethylenediamine and (e), (f),
6. The thermoplastic resin composition according to claim 5, which is a mixture with 2 to 6 mol% of at least one selected from (g). 9. An acid mainly comprising (a) terephthalic acid or its dimethyl ester, and an amine mainly comprising (d) 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine. The thermoplastic resin composition according to claim 5, wherein 10. The method according to claim 1, wherein the acid is mainly composed of a mixture of (a) terephthalic acid and (b) isophthalic acid (mixing ratio of 3: 7), and the amine is mainly composed of (c) hexamethylenediamine. 6. The thermoplastic resin composition according to claim 5, wherein 11. The thermoplastic resin composition [(A) + (B) + (C)] according to claim 1 or 5.
A thermoplastic resin composition comprising 3 to 60 parts by weight of (D) a rubber-like substance and / or a modified rubber-like substance as an impact strength improver based on 0 parts by weight. 12. The component (A) according to claim 1.
With respect to 10 to 70 parts by weight, 90 to 30 parts by weight of the component (B), and 100 parts by weight of the components (A) and (B) in total, (D)
A thermoplastic resin composition comprising 3 to 60 parts by weight of a modified rubber-like substance. 13. A molded article for an automobile part, obtained by molding the thermoplastic resin composition according to claim 1, 5, 11, or 12. 14. A molded article for an automobile part may be a cylinder head, a radiator head tank, a spoiler, a bumper,
14. The molded article for automobile parts according to claim 13, which is a fender, a wheel cover, or a side seal garnish.