JP3063394B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, and more particularly, to a resin composition having excellent blow properties, comprising polyphenylene ether and polyamide reinforced with glass fibers as main constituent resin components.

[0002]

2. Description of the Related Art Polyphenylene ether is a resin having excellent mechanical and electrical properties and high heat resistance. However, polyphenylene ether has drawbacks of poor moldability and solvent resistance. There is a situation where the range is greatly restricted. Polyamide, on the other hand, has excellent moldability and mechanical properties, and is a useful thermoplastic resin that is widely used, but has the drawback of large water absorption and poor dimensional stability, and comes in contact with salts such as calcium chloride. This has the disadvantage of causing cracks and the like. Under such circumstances, it is industrially valuable to blend a polyphenylene ether and a polyamide each having excellent characteristics to produce a resin composition having both advantages, and proposals have already been made. Yes
No. 997). In addition, resin compositions having enhanced compatibility between polyphenylene ether and polyamide are also disclosed in JP-B-60-11966, JP-B-61-10494, JP-A-59-66452 and JP-A-56-49753. Is disclosed. However, these compositions are not sufficient in terms of rigidity,
Use for structural materials and the like that require high rigidity is limited.

As a means for increasing the rigidity, a filler such as glass fiber is generally used. As a composition comprising such polyphenylene ether and polyamide, aliphatic polyamide, polyphenylene ether and fibrous reinforcing material are used. (Japanese Patent Application Laid-Open No. 63-35652), polyphenylene ether, polyamide having a crystalline melting point of 265 to 320 ° C., a copolymer of a styrene compound and an α, β-unsaturated carboxylic anhydride. Resin composition comprising polymer and fibrous, flake or powdery reinforcing agent (JP-A-61-204263), polyphenylene ether, polyamide having many terminal amino groups, saturated aliphatic polycarboxylic acid, rubber-like Resin composition comprising substance and filler (JP-A-62-240354); polyphenylene ether; Resin composition comprising amide, alkenyl aromatic compound-conjugated diene copolymer, compound having both unsaturated group and polar group in the same molecule and glass fiber (JP-A-63-101452), polyamide, polyphenylene ether And a resin composition comprising a styrene-maleic anhydride copolymer, a modified polyolefin and glass fiber (Japanese Patent Application Laid-Open No. 3-177454). However, these conventionally proposed glass fiber reinforced polyphenylene ether / polyamide compositions have insufficient mechanical properties, or have poor plasticizing properties and drawdown properties when subjected to blow molding, and thus are not necessarily industrial. Is not satisfactory.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a glass fiber reinforced polyphenylene ether / polyamide composition having excellent mechanical properties and blow moldability.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a combination of a specific compatibilizing agent and a specific polyolefin, and polyphenylene ether, polyamide, glass fiber, The present inventors have found that the specific composition of the compatibilizer and the polyolefin is a decisive factor in obtaining a desired resin composition, and have completed the present invention. That is, the present invention relates to a composition 10 comprising (A) 10 to 65% by weight of polyphenylene ether and (B) 90 to 35% by weight of polyamide.
0 parts by weight (C) 5 to 100 parts by weight of glass fiber, (D) modified ethylene and α-olefin which is a monoene
And (E) a carbon-carbon double bond or a carbon-carbon triple bond and (b) a carboxyl group, an acid anhydride in a molecule as a compatibilizer. Substance group, amino group, acid amide group, imide group, epoxy group, carboxylic ester group, isocyanate group,
A resin composition comprising 0.01 to 10 parts by weight of an unsaturated polar monomer compound having a methylol group or a hydroxyl group at the same time. (A) used in the present invention
Polyphenylene ethers are represented by the general formulas [I] and [II] (wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are the same or different
-Butyl group

[0006]

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[0007] alkyl group having 1 to 4 carbon atoms, excluding an aryl group, a halogen, residues monovalent, such as hydrogen, R _3, R ₅
Are not hydrogen at the same time. ) Is a repeating unit, and the structural unit is [I] or a homopolymer or a copolymer comprising [I] and [II], or a mixture of both, or a mixture of the polymer and polystyrene, or as the polymer. It is a graft copolymer obtained by grafting styrene.

Representative examples of the homopolymer of polyphenylene ether include poly (2,6-dimethyl-1,4phenylene) ether and poly (2-methyl-6-ethyl1,4).
-Phenylene) ether, poly (2,6-diethyl-)
1,4-phenylene) ether, poly (2-ethyl-6)
-N-propyl-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, Homopolymers such as 4-phenylene) ether and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether are exemplified. Polyphenylene ether copolymer, orthocresol or the general formula [III]

[0009]

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(Where R _3, R _4, R _{5, and} R ₆ are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, and hydrogen, excluding a tert-butyl group; _3, R ₅ is 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 polyamide (B) used in the present invention is a crystalline aliphatic polyamide, and examples thereof include the following. These have a molecular weight of 10,000 or more and are prepared by combining equimolar amounts of saturated aliphatic dicarboxylic acids containing 4 to 12 carbon atoms with aliphatic diamines containing 2 to 12 carbon atoms. At this time, if necessary, a diamine or the like can be used so as to give an amine terminal group in excess of a carboxyl terminal group in the polyamide. Conversely, dibasic acids can be used to provide excess acid groups. Similarly, these polyamides may be used as the acid- and amine-forming derivatives of the acids and amines,
For example, it can be produced favorably from esters, acid chlorides, amine salts and the like. Representative aliphatic dicarboxylic acids used to produce this polyamide include adipic acid,
Includes pimelic acid, azelaic acid, suberic acid, sebacic acid and dodecanedioic acid, while typical aliphatic diamines include hexamethylene diamine and octamethylene diamine. In addition, these polyamides can be made by self-condensation of lactams. Examples of polyamides include polyhexamethylene adipamide (nylon 66) and polyhexamethylene azeramid (nylon 6
9), polyhexamethylene sebasamide (nylon 61
0), and polyhexamethylene dodecanoamide (nylon 612), poly-bis- (p-aminocyclohexyl) methane dodecanoamide, polytetramethylene adipamide (nylon 46), or a polyamide formed by ring cleavage of lactam; Polycaprolactam (nylon 6) and polylauryl lactam are included. Further, polyamides produced by polymerizing at least two kinds of amines or acids used in producing the above polymer, 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. Of these crystalline polyamides, preferably nylon 4
6, nylon 6, nylon 66, nylon 11, nylon 12, and the like. More preferably, nylon 6,
Nylon 66 or a mixture of nylon 6 and nylon 66 in any ratio is used. As the terminal functional groups of these polyamides, those having many amine terminals, those having many carboxy terminals, those having a balance between them, and mixtures having any ratio thereof are suitably used.

The glass fiber (C) used in the present invention is known in the art, and has a fiber diameter of 15 μm or less and a fiber length of 6 μm.
A chopped strand of not more than mm is preferably used.
When the fiber diameter exceeds 15 μm, the improvement in mechanical strength decreases. Preferably, glass fibers having a diameter of 10 μm or less and a length of 3 mm or less are used. Glass fiber can be used in combination with various coupling agents in order to improve the interfacial adhesion and dispersibility with the polyphenylene ether resin and / or the polyamide resin. The coupling agent usually includes a silane-based or titanium-based coupling agent. Among them, γ-
It is preferable to include a silane coupling agent such as an epoxy silane such as glycidoxypropyltrimethoxysilane, a vinyl silane such as vinyltrichlorosilane, and an aminosilane such as γ-aminopropyltriethoxysilane.

In the present invention, (D) is a modified ethylene
And a copolymer of α-olefin which is a monoene
It is a reolefin. Specific examples of polyolefins include copolymers of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-hexene copolymer and the like, which are reacted with an unsaturated carboxylic acid or a derivative thereof. And a modified product reacted with an active compound. Among these, preferred polyolefins are modified ethylene-butene-1 copolymers.

The (E) compatibilizer used in the present invention contains (a) a carbon-carbon double bond or a carbon-carbon triple bond and (b) a carboxyl group, an acid anhydride group, an amino group, It is an unsaturated polar monomer compound having an acid amide group, an imide group, an epoxy group, a carboxylic ester group, an isocyanate group, a methylol group or a hydroxyl group at the same time. Specific examples thereof include maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, a reaction product of maleic anhydride and a diamine, for example,

[0015]

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(Where R represents an aliphatic or aromatic group), methylnadic anhydride, dichloromaleic anhydride, maleic amide, soybean oil, drill oil, castor oil, flaxseed oil Oil, hemp seed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil,
Natural oils such as sardine oil, epoxidized natural oils such as epoxidized soybean oil, acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, tipric acid, 2-pentenoic acid, 3 -Pentenoic acid,
α-ethylacrylic 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-tetradecene Acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic 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, eleostearic acid, oleic acid, eicosapentaenoic acid,
Unsaturated carboxylic acids such as erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenic acid, and traacontenic acid, or esters of these unsaturated carboxylic acids, Acid amide, anhydride, or allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol,
Methylpropenylcarbinol, 4-penten-1-ol, 10-undecene-1-ol, propargyl alcohol, 1,4-pentadien-3-ol, 1,4-
Hexadiene-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) represented by Alcohol, 3-butene-1,2-diol, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-3,4-
Diol, 2,6-octadiene-4,5-unsaturated alcohol such as a diol, or an OH group of such unsaturated alcohols, unsaturated amines Tsu replace the -NH ₂ group or glycidyl acrylate, glycidyl methacrylate And allyl glycidyl ether.

The compound used as a compatibilizer in the present invention includes two or more functional groups of the group (a),
It goes without saying that a compound containing two or more (same or different) functional groups of the group is also included, and it is also possible to use two or more compounds. Among them, maleic anhydride, maleic acid, fumaric acid, itaconic acid, -hymic acid anhydride, glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether are preferred.

The mixing ratio in the resin composition of the present invention is as follows:
(A) 10-65 parts by weight of polyphenylene ether and (B) 90-35 parts by weight of polyamide [(A) +
(B)] 100 parts by weight of (C) glass fiber 5
100 parts by weight, (D) 1 to 35 parts by weight of a polyolefin and (E) 0.01 to 10 parts by weight of a compatibilizer, preferably 25 to 60 parts by weight of (A) a polyphenylene ether and 75 to 40 parts of a polyamide (B). (C) 5 to 65 parts by weight of glass fiber and (D) 3 to 25 parts of polyolefin with respect to 100 parts by weight of the total amount [(A) + (B)] by weight.
Parts by weight and 0.1 to 5 parts by weight of the (E) compatibilizer. To the resin composition of the present invention, if necessary, an inorganic filler, a pigment, an ultraviolet absorber, a heat stabilizer, an antioxidant, other resins such as polystyrene, and a plasticizer can be added.

In the present invention, the method of compounding the polyphenylene ether (A), the polyamide (B), the glass fiber (C), the polyolefin (D) and the compatibilizer (E) is not particularly limited. 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 are no particular restrictions on the order in which the components are added during melt kneading. That is, a method in which the components (A), (B), (C), (D) and (E) are added all at once and simultaneously melt-kneaded, and the components (A), (D) and (E) are used as radical initiators. Melt kneading in the presence or absence of the components, and then the components (B) and (C)
And melt kneading by adding additional components (A), (C),
A method in which (D) and (E) are previously melt-kneaded in the presence or absence of a radical initiator, and then melt-kneaded by additionally adding (B), components (A), (D) and (E) ) Is melt-kneaded in advance, then (B) is additionally kneaded, and the component (C) is further added, followed by melt-kneading. However, at least before the polyamide is kneaded, the polyphenylene ether may be used. And the compatibilizer are desirably kneaded.

[0020]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples, and the present invention is not limited thereto. The test methods in the examples were performed by the following methods. Parison characteristics: A parison is extruded at 270 ° C. and 170 g / min using a blow molding machine manufactured by Nippon Steel Works at 270 ° C., and the length of the parison immediately before the descent speed of the parison starts to rapidly increase due to its own weight (critical parison length) is determined. Was. The longer the critical parison length, the better the parison characteristics in blow molding. Plasticization properties: Sumitomo Nestal injection molding machine Cycap 1
Using 10/50 (manufactured by Sumitomo Heavy Industries), the cylinder set temperature at which the measuring time was stable under the following conditions was determined. The lower the set temperature, the better the plasticization characteristics. Screw torque: 13 Kgfm Screw rotation speed: 50 rpm Measuring stroke: 68 mm Cylinder set temperature: Temperature was raised from 225 ° C at 5 ° C intervals. (However, the nozzle temperature was kept constant at 260 ° C.) Mechanical properties: Test pieces were prepared with an IS220E injection molding machine by Toshiba Machine Co., Ltd. Flexural modulus: implemented according to ASTM D790. Flexural strength: Same as above Izod impact strength: Performed according to ASTM D256. (However, the thickness of the test piece is 3.2 mm and is notched.)

Comparative Example-3 15 parts by weight of polyphenylene ether having an intrinsic viscosity of 0.57 measured at 30 ° C. in a chloroform solution having a concentration of 0.5 g / dl, 15 parts by weight of maleic anhydride (MAH) as a compatibilizer, and polyolefin A continuous twin-screw kneader (Toshiba TEM5) was prepared by mixing 3.5 parts by weight of anhydrous maleated polypropylene resin (m-PP) and 14 parts by weight of polypropylene resin (PP).
0) from the first hopper, and 35 parts by weight of polyamide (Unitika nylon registered trademark A1030BRT) and 30 parts by weight of glass fiber (Nippon Glass Fiber RESO3TP64) from the second hopper provided between the first hopper and the vent hole. The mixture was charged using a weight feeder, the cylinder temperature was set to 260 ° C., and the mixture was melt-kneaded at a screw rotation of 330 rpm to perform granulation. The mechanical properties of the composition were measured.

Comparative Example-4 35 parts by weight of polyphenylene ether having an intrinsic viscosity of 0.57 measured at 30 ° C. in a chloroform solution having a concentration of 0.5 g / dl, 35 parts by weight of maleic anhydride as a compatibilizer, and Japanese Patent Publication No. Sho 44 as a polyolefin Ethylene-butene-1 copolymer (EBR) having a butene-1 content of 18% by weight and a Mooney viscosity at 100 ° C of ML _{1 + 4} 100 of 30 obtained by a homogeneous solution method with reference to the method described in JP-A-9390 5 parts by weight are charged from the first hopper of the continuous twin-screw kneader (TEM50 Toshiba Machine), and the second hopper is provided between the first hopper and the vent hole.
Polyamide (Unitika nylon registered trademark A
1030BRT) 45 parts by weight, glass fiber (Nippon Glass Fiber RES)
O3TP64) 15 parts by weight were put in using a weight feeder, the cylinder temperature was set to 260 ° C, and the screw rotation was 330 rp.
The mixture was melt-kneaded and granulated. The mechanical properties and parison and plasticizing properties of the composition were measured.

Example 1 Maleic anhydride graft amount obtained by modifying ethylene-butene-1 copolymer with maleic anhydride in Comparative Example 4 1.0
A resin composition was manufactured and evaluated under the same blending ratio and the same extrusion conditions as in Example 2 except that wt% (relative to rubber) (m-EBR) was used.

Comparative Example 1 The same compounding ratio as in Example 1 except that the compatibilizing agent in Example 1 was replaced by 3.5 parts by weight of a styrene-maleic anhydride copolymer (Sekisui Chemical Co., Ltd., Dairak 232) A resin composition was manufactured and evaluated under the same extrusion conditions.

Comparative Example 2 A resin composition was prepared and evaluated under the same mixing ratio and the same extrusion conditions as in Example 2 except that the ethylene-butene-1 copolymer was not added in Example 2.

Example-2 In Comparative Example-4 , the polyolefin was converted to a maleic anhydride-modified ethylene-propylene copolymer (Sumitomo Esplen® E120P, maleic anhydride graft amount 1.5 wt% (vs. rubber), m-EPR). Example except for replacement-
A resin composition was produced and evaluated under the same blending ratio and the same extrusion conditions as in Example 2.

[0027]

【table 1】

[0028]

The resin composition of the present invention thus obtained can be formed into various parts by blow molding and supplied to the world. Automotive parts such as air ducts and resonators are expected to be applied.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 23:00) (56) References JP-A-63-199754 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (3)

(57) [Claims] 1. A polyphenylene ether (A)
Parts by weight, (B) 90 to 35 parts by weight of polyamide and [(A) +
(B)] 100 parts by weight, (C) 5 to 100 parts by weight of glass fiber, (D) modified ethylene and α-olefin which is a monoene
And (E) a carbon-carbon double bond or a carbon-carbon triple bond and (b) a carboxyl group, an acid anhydride in a molecule as a compatibilizer. Substance group, amino group, acid amide group, imide group, epoxy group, carboxylic ester group, isocyanate group,
A thermoplastic resin composition comprising 0.01 to 10 parts by weight of an unsaturated polar monomer compound having a methylol group or a hydroxyl group at the same time. 2. The polyolefin (D) monoene α
The resin composition according to claim 1, wherein the olefin is butene-1 . 3. The compounding ratio of the polyolefin (D) is as follows:
The resin composition according to claim 1, wherein the amount is 3 to 20 parts by weight based on 100 parts by weight of ((A) + (B)).