JPH0726136A - Thermally stabilized polyphenylene ether/polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having extremely excellent thermal stability during molding and thermal deterioration resistance in the case of use in a high-temperature atmosphere without impairing appearance of molded article, mechanical properties, dimensional accuracy, fluidity in molding, solvent resistance and oil resistance. CONSTITUTION:This resin composition comprises (A) 20-80 pts.wt. of a polyphenylene ether resin, (B) 80-20 pts.wt. of a polyamide resin, (C) 0.1-10 pts.wt. of a compatibilizing agent, (D) 0.05-3 pts.wt. of N,N'-hexamethylenebis(3,5- di-t-butyl-4-hydroxy-hydrocinnamide) and (E) 0.05-3 pts.wt. of tetrakis(2,4-di-t- butylphenyl) 4,4'-biphenylenediphosphonate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The resin composition of the present invention impairs the appearance of molded articles, mechanical properties, heat resistance, dimensional accuracy, fluidity during molding (hereinafter abbreviated as fluidity), solvent resistance and oil resistance. The PPE / polyamide resin composition, in which the thermal stability during molding and the heat deterioration resistance when used in a high temperature atmosphere are remarkably improved.
It can be used in a wide range of fields such as machine parts and sundries.

[0002]

2. Description of the Related Art Conventionally, a composition comprising PPE and a styrene resin is excellent in electrical properties, mechanical properties, hot water resistance, dimensional accuracy, moldability, etc.
It is used in a wide range of fields such as automobile parts, machine parts, and sundries. However, the composition comprising PPE and styrene resin has a heat deterioration resistance when used in a high temperature atmosphere,
Since the solvent resistance and oil resistance are insufficient, improvement has been strongly desired.

Japanese Patent Publication No. 59-33614 discloses that styrene compounds 60 to 9 are added to 100 parts by weight of polyamide.
A method of adding 5 parts by weight or more of a copolymer composed of 9% by weight and an .alpha..beta. Unsaturated dicarboxylic acid anhydride 1 to 40% by weight is disclosed. Even in this method, since the content of the styrene compound is high, there is a problem that the thermal stability during molding and the heat deterioration resistance when used in a high temperature atmosphere are deteriorated. Further, in JP-A-60-15453, in order to improve solvent resistance and oil resistance, a sterically hindered phenol or phosphite compound is added as a stabilizer to a composition comprising PPE and PA. Is disclosed as good.
Certainly, when a sterically hindered phenol or phosphite compound is added to a composition composed of PPE and PA, the thermal stability can be improved to some extent. However, PPE and P
Even if a sterically hindered phenol or a phosphite compound is simply added to the composition of A, the thermal stability during molding and the heat deterioration resistance when used in a high temperature atmosphere are not always satisfactory.

[0004]

The problem to be solved by the present invention is to achieve a high degree of molding at the time of molding without impairing the appearance, mechanical properties, dimensional accuracy, solvent resistance, oil resistance and fluidity of the molded product. It is an object of the present invention to provide a PPE / PA resin composition having significantly improved thermal stability and heat deterioration resistance when used in a high temperature atmosphere. Such a PPE / PA resin composition can be used in a wider range of fields such as electric / electronic parts, automobile parts, machine parts and sundries.

[0005]

In order to solve the above-mentioned problems, the present inventors added two or more kinds of various heat stabilizers to a resin composition comprising PPE, PA and a compatibilizer at various ratios. However, the research was repeated to obtain a synergistic effect. As a result, P
By adding a specific organophosphorus stabilizer and a specific sterically hindered phenolic compound to a resin composition consisting of PE, PA and a compatibilizer at the same time and melt-kneading, high thermal stability at the time of molding and high temperature atmosphere The present invention has been completed by finding out a PPE / PA resin composition having significantly improved heat deterioration resistance when used in.

That is, the present invention relates to (A) PPE 20-
80 parts by weight, (B) 80 to 20 parts by weight, (C) compatibilizing agent 0.1 to 10 parts by weight, (D) N, N'-hexamethylenebis (3,5-di-t-butyl-4) -Hydroxy-
Hydrocinnamide) 0.05-3 parts by weight and (E)
Tetrakis (2,4-ditertiarybutylphenyl)-
A resin composition comprising 0.05 to 3 parts by weight of 4,4'-biphenylenediphosphonite.

The PPE used in the present invention can be produced, for example, according to the method described in JP-A-63-286464. In particular, poly (2,6-dimethyl-1,
4-phenylene) ether, 2,6-dimethyl-1,4
-Phenol / 2,3,6-trimethyl-1,4-enol copolymer and a graft copolymer obtained by graft-polymerizing styrene to the former two are used in the present invention.
Preferred as E. PPE suitable for the present invention has an intrinsic viscosity of 0.30 when measured with a chloroform solution at 25 ° C.
It is preferably in the range of ˜0.60 dl / g. If the intrinsic viscosity is higher than 0.60 dl / g, the melt viscosity of the composition will be high, and the bar flow value will be low, making it particularly difficult to mold a large-sized thin-walled molded product. Conversely, the intrinsic viscosity is 0.30 dl / g
If it is lower, the mechanical strength is greatly reduced and the value as a practical molded article is impaired, so that it cannot be used in the PPE / PA resin composition of the present invention.

PAs used in the present invention are PA4 and PA.
6, aliphatic PAs such as PA66, PA610, PA11, PA12, polyhexadiamine terephthalamide,
One or more kinds of PAs selected from aromatic PAs obtained from polyhexadiamine isophthalamide, metaxylene diamine and adipic acid can be preferably used.

The compatibilizer used in the present invention is a carboxyl group, an acid anhydride group, a carboxylic acid ester group,
1 selected from amino group, imino group, amide group, isocyanate group, epoxy group, hydroxyl group and oxazoline ring
A compound having one or more functional groups, preferably a compound having a carboxyl group, an acid anhydride group, an amino group, an imino group, an isocyanate group, an epoxy group, a hydroxyl group or an oxazoline ring in the molecule can be used. Further, a polymer containing at least one carboxyl group, acid anhydride group, amino group, imino group, epoxy group, amide group, isocyanate group, hydroxyl group in the molecule, preferably a carboxyl group,
Polymers containing an acid anhydride group, amino group, imino group, epoxy group, isocyanate group or hydroxyl group can also be used. Particularly preferred compatibilizers used in the present invention are maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, methylnadic acid anhydride, dichlorosuccinic anhydride, dibromosuccinic anhydride, citraconic acid and itaconic acid. Of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, polymers or copolymers of unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides, and unsaturated oxazolines. Further, saturated carboxylic acids such as malic acid and citric acid, isocyanates such as toluene diisocyanate and methylene diphenyl diisocyanate, epoxy resins and precursors thereof can also be suitably used as the compatibilizer.

The sterically hindered phenol compound used in the present invention is N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide).
Is. The organophosphorus stabilizer used in the present invention is tetrakis (2,4-di-tert-butylphenyl) 4,
It is 4'-biphenylene diphosphonite. N, N'-
Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and tetrakis (2,4
-Di-tert-butylphenyl) 4,4'-biphenylene diphosphonite. That is, the PPE / PA resin composition, which is the object of the present invention and has a significantly improved thermal stability at the time of molding, and the heat deterioration resistance when used in a high temperature atmosphere, is N, N'-hexamethylenebis ( 3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and tetrakis (2,4-ditertiarybutylphenyl) 4,4'-biphenylenediphosphonite can be obtained only in combination. .

(A) PPE, (B) PA of the present invention,
(C) Compatibilizer, (D) N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and (E) tetrakis (2,4-ditertiarybutyl) The amount ratio of phenyl) 4,4'-biphenylene diphosphonite is as described above.

In the present invention, if the amount of the compatibilizing agent is less than 0.1 parts by weight, the dispersed state of PPE and PA will not be stable and the mechanical strength will be low, such being undesirable. If the amount of the compatibilizer is more than 10 parts by weight, the thermal stability at the time of molding and the mechanical deterioration due to thermal deterioration when used in a high temperature atmosphere will be severe.
Must be avoided.

In the present invention, when the content of N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) is less than 0.05 parts by weight, thermal stability during molding is improved. Also, when used in a high temperature atmosphere, deterioration of mechanical strength becomes large due to thermal deterioration, which is not preferable. On the other hand, if the amount is more than 3 parts by weight, the load deflection temperature is lowered, which is not preferable.

In the present invention, when the amount of tetrakis (2,4-ditertiarybutylphenyl) 4,4'-biphenylenediphosphonite is less than 0.05 parts by weight, the thermal stability during molding and the use in a high temperature atmosphere can be improved. However, thermal deterioration causes a large decrease in mechanical strength, which is not preferable. Also, 3
When the amount is more than the weight part, the load deflection temperature is lowered, which is not preferable.

In the case of the present invention, the ratio of PA in the ratio of the two components PPE and PA is preferably 20 to 80% by weight. When PA is less than 20% by weight, fluidity, solvent resistance and oil resistance are poor, and when PA is more than 80% by weight, thermal properties such as load deflection temperature are deteriorated, which is not preferable.

In the present invention, an impact strength improver may be added if necessary. That is, as an impact strength improver,
Polybutadiene, SBR, EPDM, EVA, polyacrylic acid ester, polyisoprene, hydrogenated isoprene, acrylic elastomer, polyester / polyether co-elastomer, PA elastomer (for example, Toray Industries, Inc., trade name Pebax, Dainippon Ink) Chemical Co., Ltd.
Manufactured by Grelax A), ethylene / butene 1 copolymer, styrene / butadiene block copolymer, hydrogenated styrene / butadiene block copolymer, ethylene / propylene copolymer, ethylene / propylene / ethylidene norbornene Copolymer, thermoplastic polyester elastomer, hydrogenated SEBS elastomer (for example, Shell Chemical Co., Ltd., trade name Clayton G), ethylene-α olefin copolymer (for example, Mitsui Petrochemical Co., Ltd., trade name Tuffmer), Propylene-α-olefin copolymer, ethylene methacrylic acid-based special elastomer (for example, Mitsui DuPont Polychemical Co., Ltd., trade name Tufflit T3000), core-shell type elastomer in which the core layer is made of rubber and the shell layer is made of hard resin (For example, Takeda Pharmaceutical Co., Ltd. Manufactured by STAFLOY, trade name Mitsubishi Rayon Co., Ltd., trade name Metabrene S), acrylic (reaction type) elastomer (for example, Kureha Chemical Co., Ltd., trade name Paraloid EXL), MBS elastomer and Kureha BTA. Elastomer or the like can be added.

Other thermoplastic resins, such as PC, PBT, PET, PE, P, within the range not impairing the object of the present invention.
P, maleic acid modified PP, POM, PMMA, MS,
AS, AAS, AES, AMBS, PS, HIPS, styrene-maleic acid copolymer resin (for example, USA.
Arco Chemical Co., Ltd., trade name Dailark), polyphenylene sulfide, polyether ether ketone, polysulfone, etc. can also be added.

In order to improve the mechanical strength, rigidity and dimensional stability of the heat-stabilized PPE / PA resin composition of the present invention, glass fiber, glass beads, glass flakes, glass fiber cloth, glass fiber mat, graphite, carbon fiber. , Carbon fiber cloth, carbon fiber mat, carbon black, carbon flakes, aluminum, stainless steel, metal fibers and flakes made of brass and copper, metal powder, organic fibers, acicular potassium titanate, mica, talc, clay, ( Needle-shaped)
One or more reinforcing agents selected from titanium oxide, wollastonite and calcium carbonate may be added. rigidity·
In order to increase the strength and further improve the appearance and smoothness of the molded product, the fiber diameter may be reduced. As a glass fiber having a small fiber diameter, E-FMW-8 manufactured by Nippon Inorganic Co., Ltd.
00 (average fiber diameter 0.8 μm) and E-FMW-1700
(Average fiber diameter of 0.6 μm) can be exemplified.

The surface of the above-mentioned reinforcing agent is a known surface treatment agent such as vinylalkylsilane, methacryloalkylsilane, epoxyalkylsilane, aminoalkylsilane,
The surface treatment may be performed with a titanate coupling agent such as mercaptoalkylsilane, chloroalkylsilane, isopropyltriisostearoyl titanate, or a zircoaluminate coupling agent. Further, as a sizing agent for fibers, a known sizing agent such as epoxy type, urethane type, polyester type, styrene type sizing agent may be used for sizing.

In the PPE / PA heat-stabilized resin composition of the present invention, if necessary, a flame retardant such as triphenyl phosphate, tricresyl phosphate, a polycondensate thereof, or red phosphorus can be used. Known phosphorus compounds can be added. Further, a halogen compound such as decabromodiphenyl ether, brominated polystyrene, low molecular weight brominated polycarbonate, or brominated epoxy compound can be added as a flame retardant. Flame retardant aids such as antimony trioxide, antimony tetraoxide, zirconium oxide can also be used in combination with the halogen compound.

In the heat-stabilized PPE / PA resin composition of the present invention, if necessary, an antistatic agent, a plasticizer, a lubricant, a release agent, a dye, a pigment, an ultraviolet absorber, a light stabilizer, etc. It can be added.

The heat-stabilized PPE / PA resin composition of the present invention can be produced by the equipment and method generally used for producing a thermoplastic resin composition. For example, PPE
You may manufacture the pellet for shaping | molding by mixing the components which comprise a PA resin composition collectively by a mixer, such as a tumbler, melt-kneading using a uniaxial or biaxial extruder, and extruding.
Alternatively, PPE, impact strength improver and compatibilizer are melt-kneaded first, and then polyamide, N, N'-hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) Alternatively, tetrakis (2,4-ditertiarybutylphenyl) 4,4′-biphenylenediphosphonite may be added, melt-kneaded, and extruded to produce molding pellets.

As is clear from the above description, the heat-stabilized PPE / PA resin composition of the present invention has a molded article appearance, mechanical properties, heat resistance, dimensional accuracy, fluidity during molding, solvent resistance and The thermal stability during molding and the heat deterioration resistance when used in a high temperature atmosphere have been significantly improved without impairing oil resistance, so electrical and electronic parts, automobile parts, machine parts,
It can be used in a wide range of fields such as sundries.

[0024]

EXAMPLES The present invention will be specifically described with reference to the following examples and comparative examples, but the present invention is not limited to these. The molding method and test method of the test piece in the examples and comparative examples are as follows.

(1) Raw materials used PA is Amylan CM1017 (abbreviated as PA6) manufactured by Toray,
PPE used was manufactured by Mitsubishi Gas Chemical Co., Ltd. and had an intrinsic viscosity in chloroform at 25 ° C. of 0.45 dl / g. Maleic anhydride was used as the compatibilizer. As a highly sterically hindered phenolic compound, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) is commercially available from Ciba Geigy Corporation as Irganox 1
The one sold under the trade name of 098 (abbreviated as stabilizer 1) was used. For comparison, as a highly sterically hindered phenolic compound, tetrakis [methylene-3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] methane (abbreviated as stabilizer 2), 2,4-bis-
(Octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (abbreviated as stabilizer 3) is commercially available from Ciba Geigy Inc. as Irganox 1010 and Irganox 565, respectively. I used the one sold under the product name. Tetrakis (2,4-di-tertiarybutylphenyl) 4,4'-biphenylene diphosphonite as an organic phosphorus stabilizer is sold by Ciba Geigy under the trade name of Irgafoss P-EPQ (Stabilizer 4). I used the one that has been used. Also,
Styrene ・ made by Shell Chemical Co., Ltd. as an impact resistance improver
An ethylene / butylene / styrene type block copolymer, trade name Kraton G1651 (abbreviated as SEBS) was used.

(2) Kneading conditions of composition Among the components constituting the heat-stabilized PPE / PA resin composition of the present invention, first, PPE, a compatibilizer and SEBS are shown in Table 1,
After mixing in the ratios shown in Table 2, at a cylinder set temperature of 280 ° C,
Pellets were produced by melt-kneading with a twin-screw extruder having a screw diameter of 30 mm. The remaining components shown in Tables 1 and 2 were mixed with the pellets, melt-kneaded with a twin screw extruder having a screw diameter of 30 mm at a cylinder setting temperature of 290 ° C. to produce pellets, which were used for molding Izod impact test pieces in the next section. .

(3) Molding conditions for Izod impact test pieces After drying the pellets manufactured by the above method at 100 ° C. for 5 hours, the mold temperature is 100 ° C. and the cylinder set temperature is 300 ° C. by an SG125 type injection molding machine manufactured by Sumitomo Heavy Industries. , Injection pressure 9
8 MPa, 1 cycle 50 seconds, 63.5 × 12.7
A 3.2 mm Izod impact test piece was molded for 20 shots using a mold capable of molding 8 pieces in one shot, the first 15 shots were discarded, and the subsequent 5 shot test pieces were used to determine the Izod impact strength. The measurement was performed, and Table 1 and Table 2 indicated Impact 1.

(4) Thermal stability test during molding After the molding in (3), the molding was interrupted for 30 minutes while the cylinder temperature was kept at 300 ° C., and then the Izod impact test was conducted under the molding conditions in (3). The piece was molded for 2 shots, the test piece for the first shot was discarded, and the Izod impact strength was measured for the test piece for the second shot (indicated as Impact 2 in Tables 1 and 2). , PPE / PA
The thermal stability of the resin composition during molding was evaluated.

(5) Izod impact strength after heat treatment at 160 ° C for 100 hours After heat treatment of the Izod impact test piece molded in (3) in an oven at 160 ° C for 100 hours, the Izod impact strength was measured (Table 1 and Table 1). 2 is designated as impact 3), PPE
The thermal stability of the PA resin composition in a high temperature atmosphere was evaluated.

(6) Izod impact strength measuring method According to ASTM-D256, a notch of 0.25R is cut into a test piece having a thickness of 3.2 mm by cutting,
After conditioning for 24 hours in an atmosphere of 23 ° C. and relative humidity of 50 ± 3%, measure 5 Izod impact strengths at 23 ° C.,
The average value (unit: J / m) of 5 lines is shown.

Examples 1 to 8 Table 1 shows the compounding ratios of the constituents and the measurement results. In addition, the compounding ratio of each component which comprises the resin composition of Table 1 is shown by weight part. Comparative Examples 1 to 8 Table 2 shows the compounding ratios of the constituents and the measurement results. In addition, the compounding ratio of each component which comprises the resin composition of Table 2 is shown by weight part.

[0032]

INDUSTRIAL APPLICABILITY The heat-stabilized PPE / PA resin composition of the present invention is used for molding without impairing the appearance of molded products, mechanical properties, dimensional accuracy, fluidity during molding, solvent resistance and oil resistance. Since it has significantly improved thermal stability and heat deterioration resistance when used in a high temperature atmosphere, it can be used in a wide range of fields such as electric / electronic parts, automobile parts, machine parts and sundries.

[0033]

[Table 1]Example number 1 2 3 4 5 6 7 8 (Mixing ratio) PPE 33 33 33 33 53 53 53 43 43 43 43 PA6 60 60 60 40 40 40 43 43 43 Compatibilizer 0.5 0.5 0.5 0.5 1.0 0.5 0.5 0.5 Stabilizer 1 0.1 0.2 0.2 0.4 0.1 0.2 0.4 0.5 Stabilizer 4 0.2 0.2 0.2 0.2 0.2 0.5 0.5 0.5 SEBS 7 7 7 7 7 14 14 14 14 (Physical Properties) Impact 1 270 290 300 320 340 430 430 450 450 Impact 2 230 250 260 260 250 300 380 370 390 Impact 3 220 230 230 250 240 270 390 380 400

[0034]

[Table 2]Comparative example number 1 2 3 4 5 6 7 8 (Compounding ratio) PPE 33 33 33 33 53 53 53 43 43 43 43 PA6 60 60 60 40 40 40 43 43 43 Compatibilizer 0.5 0.5 0.5 0.5 1.0 0.5 0.5 0.5 Stabilizer 2 0.1 0.2 0.4 0.5 0.2 Stabilizer 3 0.2 0.4 0.5 0.3 Stabilizer 4 0.2 0.2 0.2 0.2 0.2 0.5 0.5 0.5 SEBS 7 7 7 7 7 14 14 14 14 (Physical properties) Impact 1 210 210 210 175 220 220 190 310 340 340 Impact 2 105 100 70 70 95 70 140 140 160 170 Impact 3 85 90 90 75 80 65 65 160 160 165

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Claims (1)

[Claims] 1. (A) 20 to 80 parts by weight of a polyphenylene ether resin (hereinafter abbreviated as PPE), (B) polyamide (hereinafter abbreviated as PA) 80 to 20 parts by weight, and (C) a compatibilizer 0.1 to 10 parts. Parts by weight, (D) N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) 0.05-3 parts by weight and (E) tetrakis (2,4-). Ditertiarybutylphenyl) -4,
A resin composition comprising 0.05 to 3 parts by weight of 4'-biphenylenediphosphonite.