JPH0762223A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in fluidity' and thermal stability in molding and useful for electrical and electronic parts, etc., by adding an impact resistance improver, a specific substituted succinic acid and a thermal stabilizer to a blend of a polyphenylene ether resin and a polyamide. CONSTITUTION:This composition is obtained by adding (C) 0-20 pts.wt. of an impact resistance improver (e.g. polybutadiene), (D) 0.1-5 pts.wt. of a substituted succinic acid of the formula HO2CCHXCHYCO2H (X is a halogen, an alkyl or arylacyloxy; Y is a halogen, an alkyl, arylacyloxy or H) and (E) 0-3 pts.wt. of a thermal stabilizer [e.g. tetrakis(2,4-di-tertiary-butylphenyl)4,4'- biphenylenephosphanite] to 100 pts.wt. of a blend of (A) 30-70 pts.wt. of a polyphenylene ether resin and (B) 70-30 pts.wt. of a polyamide. The composition has excellent thermal stability when used in a high-temperature atmosphere and weld strength as well as good solvent-resistance and oil resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The resin composition of the present invention can be used without impairing the appearance of molded articles, mechanical properties, heat resistance and dimensional accuracy.
Particularly, the present invention relates to a PPE / PA resin composition having excellent fluidity during molding (hereinafter abbreviated as fluidity) thermal stability, thermal stability when used in a high temperature atmosphere, and weld strength, and having significantly improved solvent resistance and oil resistance. It can be used in a wide range of fields such as electrical and electronic parts, automobile parts, machine parts, construction parts and sundries.

[0002]

2. Description of the Related Art Conventionally, a composition comprising PPE and a styrene resin has excellent electrical properties, mechanical properties, heat resistance, hot water resistance, dimensional accuracy, moldability, etc. It is used in a wide range of fields such as parts, machine parts, and miscellaneous goods. However, a composition comprising PPE and a styrenic resin has insufficient solvent resistance and oil resistance, and therefore improvement has been strongly desired.

Japanese Patent Publication No. 59-33614 includes PPE, P
A thermoplastic resin composition having good heat resistance, which comprises a copolymer of A and a styrene compound and an α / β unsaturated dicarboxylic acid anhydride, is disclosed. However, this method does not always improve heat resistance. However, there is a problem that mechanical properties are further deteriorated. Further, Japanese Patent Publication No. 60-11966 discloses that in order to improve solvent resistance and oil resistance, P
Although a method of melt-kneading A, PPE and a specific unsaturated compound is disclosed, the effect is not always sufficient even when the disclosed compound is used.

[0004]

The problem to be solved by the present invention is to prevent the appearance, mechanical properties, heat resistance and dimensional accuracy of a molded product from being impaired, and in particular, to improve fluidity and thermal stability during molding, and high temperature. PPE with excellent thermal stability and weld strength when used in an atmosphere and with significantly improved solvent resistance and oil resistance
And to provide a resin composition containing PA as a main component.

[0005]

In order to solve the above problems, the present inventors have added various third substances to PPE and PA at various ratios and have conducted repeated studies. As a result, PPE and P
The present invention was completed by discovering a resin composition obtained by adding a specific substituted succinic acid to the composition of A and melt-kneading.

That is, the present invention relates to (A) PPE30-
70 parts by weight, (B) 70 to 30 parts by weight of PA, and a total of 100 parts by weight of both, (C) 0 to 20 parts by weight of impact modifier, (D) 0 substituted succinic acid represented by the following general formula 1 .1
To 5 parts by weight, and (E) a heat stabilizer 0 to 3 parts by weight.

HOOC-CHX-CHY-COOH (where X represents a halogen atom or an alkyl or arylacyloxy group, and Y represents a halogen atom, an alkyl or arylacyloxy group, or hydrogen)

The (A) 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-phenol copolymer and a graft copolymer obtained by graft-polymerizing styrene to the former two are used in the present invention.
Preferred as PE. The intrinsic viscosity of PPE suitable for the present invention is 0.35 dl / g 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 0.35 dl / g
When it is lower, the mechanical strength is largely lowered and the value as a practical molded product is impaired, so that it cannot be used in the resin composition of the present invention.

(B) PA which can be used in the present invention is PA
4, PA6, PA66, PA610, PA11, PA1
One or more kinds of PAs selected from aliphatic PAs such as 2, polyhexadiamine terephthalamide, polyhexadiamine isophthalamide, and aromatic PAs obtained from metaxylene diamine and adipic acid can be preferably used.

Examples of the (C) impact strength improver used in the present invention include the following polymers. That is, polybutadiene, SBR, EPDM, EVA, polyacrylic acid ester, polyisoprene, hydrogenated polyisoprene,
Acrylic elastomer, diblock or triblock copolymer consisting of polystyrene phase and hydrogenated polyisoprene phase (for example, Kuraray Co., Ltd., trade name Septon), polyester / polyether coelastomer, P
A-based elastomer (for example, Toray Industries, Inc., trade name Pebax), PA-based elastomer (for example, Dainippon Ink and Chemicals, Inc., trade name Grelax A), ethylene-butene 1 copolymer, styrene-butadiene Block copolymers, hydrogenated styrene / butadiene block copolymers, ethylene / propylene copolymers, ethylene / propylene / ethylidene norbornene copolymers, thermoplastic polyester elastomers, hydrogenated SEBS elastomers (for example Shell Chem ), Trade name Kraton G), ethylene-α olefin copolymer and propylene-α
Olefin copolymer (for example, Mitsui Petrochemical Co., Ltd.)
Manufactured by Tufmer, a special ethylene methacrylic acid-based elastomer (for example, Mitsui DuPont Polychemical Co., Ltd., trade name Tufflit T3000), a core-shell type with a rubber core layer and a hard resin shell layer. Elastomer (for example, Takeda Yakuhin Co., Ltd., trade name Stafroid), acrylic (reaction type) elastomer (for example, Kureha Chemical Co., Ltd., trade name Paraloid E)
XL), MBS elastomer, Kureha BTA elastomer, core / shell type elastomer (for example,
Mitsubishi Rayon Co., Ltd., trade name Metabrene S), core / shell type elastomer whose core is silicon rubber and shell is acrylic rubber or acrylic resin (for example, Mitsubishi Rayon Co., Ltd. grade name S2001 or RK120). Etc. may be added.

The (D) substituted succinic acid used in the present invention is a mono- or di-substituted succinic acid represented by the above-mentioned general formula 2, preferably 1 to 2 Cl or B.
Substituted succinic acid substituted with r and substituted succinic acid substituted with one lower alkylacyloxy group. 1 to
Specific examples of the substituted succinic acid substituted with two Cl or Br include monochlorosuccinic acid, dichlorosuccinic acid, monobromosuccinic acid and dibromosuccinic acid. Examples of the substituted succinic acid substituted with one lower alkylacyloxy group include formyloxysuccinic acid, acetoxysuccinic acid, propionyloxysuccinic acid and butyryloxysuccinic acid. These substituted succinic acids are 2
You may use together 1 or more types.

The resin composition of the present invention may contain one or more heat stabilizers (E). Preferred heat stabilizers are tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenephosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite. , Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and other phosphorus-based heat stabilizers, N, N'-hexamethylenebis (3,5-di-t-
Butyl-4-hydroxy-hydrocinnamide), 1,
3,5-Trimethyl-2,4,6-tris (3,5-
Di-t-butyl-4-hydroxybenzyl) benzene,
2,2-thio-diethylenebis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate], 2,2'-methylene-bis (4-methyl-6-t
-Butylphenol), tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, and other phenolic heat stabilizers, amine heat stabilizers, zinc oxide,
Examples include zinc sulfide. A particularly preferred heat stabilizer is tetrakis (2,4-di-t-butylphenyl) 4,4'-
Biphenylene phosphonite, N, N'-hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide, zinc oxide and zinc sulfide.

In the present invention, (A) 30 to 70 parts by weight of PPE and (B) 70 to 30 parts by weight of PA are added to 100 parts by weight in total, and (C) an impact modifier is added in an amount of 0 to 20 parts by weight and (D) is substituted. A resin composition comprising 0.1 to 5 parts by weight of succinic acid and 0 to 3 parts by weight of (E) heat stabilizer. In the ratio of PPE and PA, if PA is less than 30 parts by weight, fluidity, solvent resistance,
Oil resistance and weld strength are inferior, and when PA is higher than 70 parts by weight, thermal properties such as load deflection temperature are deteriorated, which is not preferable. In the present invention, if the amount of the impact modifier exceeds 20 parts by weight in the above-mentioned mixing ratio, the elastic modulus and the deflection temperature under load are greatly lowered, which is not preferable. The addition rate of the impact resistance improver is preferably 1 to 10 parts by weight, more preferably 5 to 10.
8 parts by weight.

Further, when the addition ratio of the substituted succinic acid acting as a compatibilizer is lower than 0.1 part by weight, the dispersed state of PPE and PA is not stable, the impact strength and the elongation at break are low and the dispersion is large, which is preferable. Absent. On the other hand, when the addition ratio of the substituted succinic acid exceeds 5.0 parts by weight, the molecular weight is drastically reduced, and the mechanical properties, thermal properties, solvent resistance and oil resistance are low, and further, the melt kneader and the injection molding machine are used. It is not preferable because it causes corrosion of the mold. The addition rate of the substituted succinic acid is preferably 0.2 to 3 parts by weight, more preferably 0.3 to 1 part by weight. If the amount of the heat stabilizer exceeds 3 parts by weight, the deflection temperature under load and the impact resistance are greatly lowered, which is not preferable. The addition rate of the heat stabilizer is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight.

Used as the compatibilizer of the present invention (D)
When the substituted succinic acid is a halogenated dicarboxylic acid,
It is preferable to blend one or more of (F) a halogen scavenger. As a halogen scavenger, metal soap such as zinc stearate, dibutyltin malate, dibutyltin malate polymer, organic tin salt compound such as dibutyltin laurate,
Examples thereof include acidic phosphoric acid esters such as stearyl acid phosphate and metal salts thereof. The amount of the halogen scavenger used is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight.

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

The mechanical strength and rigidity of the resin composition of the present invention,
To improve dimensional stability, 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 needle titanate, mica, talc One or more reinforcing materials selected from clay, clay, (acicular) titanium oxide, wollastonite and calcium carbonate may be added. In order to increase the rigidity and strength and further improve the appearance and smoothness of the molded product, it is preferable to use one having a small fiber diameter. Examples of the glass fiber having a small fiber diameter include E-FMW-800 (average fiber diameter 0.8 μm) and E-FMW-1700 (average fiber diameter 0, manufactured by Nippon Inorganic Co., Ltd., described in Japanese Patent Application No. 02-177585. ．
6 μm) can be exemplified.

The surface of the reinforcing material 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, the reinforcing material may be bundled with a known epoxy-based, urethane-based, polyester-based or styrene-based sizing agent.

In the resin composition of the present invention, if necessary,
As a flame retardant, triphenyl phosphate, tricresyl phosphate, a polycondensate thereof, or a known phosphorus compound such as red phosphorus 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.

If necessary, an antistatic agent, a plasticizer, a lubricant, a release agent, a dye, a pigment, an ultraviolet absorber, a light stabilizer and the like can be added to the present invention.

The resin composition of the present invention can be produced by the equipment and method generally used for producing a thermoplastic resin composition. For example, the components that make up the PPE / PA resin composition are mixed together in a mixer such as a tumbler,
The pellets for molding may be manufactured by melt-kneading using a uniaxial or biaxial extruder and extruding. Preferably, PPE and the substituted succinic acid are melt-kneaded first, and then PA, an impact modifier and a heat stabilizer are additionally added, melt-kneaded, and extruded to produce molding pellets. More preferably, PPE, impact modifier and substituted succinic acid are melt-kneaded first, and then PA
A method of manufacturing pellets for molding is employed by adding a heat stabilizer and a heat stabilizer, melt-kneading, and extruding.

[0021]

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: Polyamide 6 manufactured by Toray Industries, Inc. (trade name: Amilan CM1017, abbreviated as PA6) and PPE manufactured by Mitsubishi Gas Chemical Co., Inc. have an intrinsic viscosity of 0.4 in chloroform at 25 ° C.
The one used was 5 dl / g. As the impact modifier, a core-shell type elastomer (made by Takeda Yakuhin Co., Ltd., trade name: STAFLOY IM-301, abbreviated as IM) having a rubber core layer and a hard resin shell layer was used. As the substituted succinic acid, acetoxysuccinic acid (abbreviated as compound 1), dibromosuccinic acid (abbreviated as compound 2), succinic acid (abbreviated as compound 3) and tartaric acid (abbreviated as compound 4) were used for comparison. As a heat stabilizer, tetrakis (2,4
-Di-t-butylphenyl) 4,4'-biphenylenephosphonite (abbreviated as thermal stabilizer 1), N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinna Mide (abbreviated as heat stabilizer 2) and dibutyltin malate (abbreviated as heat stabilizer 3) were used.

(2) Kneading conditions of composition and molding conditions of test piece Among the components constituting the resin composition of the present invention, PPE, SEBS, substituted succinic acid and succinic acid and tartaric acid used for comparison are After mixing in the ratios shown in Tables 1 and 2, the pellets were manufactured by melt-kneading with a twin screw extruder having a screw diameter of 30 mm at a cylinder setting temperature of 310 ° C. To the pellets, the remaining components shown in Tables 1 and 2 were added, and the mixture was melt-kneaded at a cylinder setting temperature of 290 ° C. with a twin screw extruder having a screw diameter of 30 mm to produce pellets. 1 of the obtained pellets
SG125 manufactured by Sumitomo Heavy Industries, Ltd. after drying at 00 ° C for 5 hours
Using a mold injection molding machine, the mold temperature is 100 ° C., the cylinder setting temperature is 280 ° C., the injection pressure is 98 MPa, and ASTM-D6
Using a mold that has gates at both ends of the long axis of a 3.2 mm thick tensile test piece of 38 standard type 1, the welded tensile test piece is molded for 10 shots and discarded, and the next 10 shots are molded and used as a tensile test piece. did. Under the same conditions as the tensile test piece, an Izod impact test piece of 63.5 × 12.7 × 3.2 mm was molded for 10 shots (40 pieces) and discarded.
0 shots (40 shots) were molded, and Izod impact strength was measured with 5 shots out of the shots, which was designated as Impact 1. The other five test pieces were annealed in a 160 ° C. oven for 100 hours, and then the Izod impact strength was measured and designated as Impact 2. As described above, after molding the Izod impact test piece for 10 shots + 10 shots, the molding is interrupted for 30 minutes while maintaining the cylinder temperature of the injection molding machine at 280 ° C., after which one shot is discarded, and the next two shots are Izod impacted. The strength was measured and designated as Impact 3.

(3) Tensile breaking elongation According to ASTM-D638, five tests were carried out at a pulling speed of 5 mm / min and a test temperature of 23 ° C., and an average of five breaking elongations with weld (abbreviated as entering elongation, unit:%). ) Was asked.

(4) Izod impact strength measurement method (unit: J / m) According to ASTM-D256, a notch of 0.25R is cut into a test piece having a thickness of 3.2 mm by cutting,
Five pieces were measured at 23 ° C., and the average value of the five pieces was 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.

[0028]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention is improved in fluidity, solvent resistance and oil resistance without impairing the appearance of molded products, mechanical properties, heat resistance and dimensional accuracy, and is used in injection molding and extrusion. Molding and blow molding are also possible, electrical and electronic parts,
It can be used in a wide range of fields such as automobile parts, machine parts and household sundries.

[0029]

[Table 1]Example 1 2 3 4 5 6 7 8 (Blending ratio) PPE 35 35 35 35 35 55 55 55 55 55 PA6 65 65 65 65 65 45 45 45 45 45 IM 5 5 5 5 5 5 5 5 5 Compound 1 0.3 0.5 1.0 1.0 0.5 Compound 2 0.5 0.3 0.5 1.0 Stabilizer 1 0.4 0.2 0.4 0.4 0.4 0.4 0.2 Stabilizer 2 0.4 0.2 0.2 0.2 0.4 0.4Stabilizer 3 0.4 0.4 0.2 0.4 0.4 0.4 (Physical Properties) Impact 1 320 360 340 330 330 430 450 420 420 440 Impact 2 270 280 260 260 250 350 360 360 370 360 Impact 3 260 280 240 240 250 320 340 330 330 310 Expansion 35 35 38 39 43 29 25 23 28

[0030]

[Table 2]Comparative Example 1 2 3 4 5 6 7 8 (Blending ratio) PPE 15 85 35 35 35 55 55 55 55 55 PA6 85 15 65 65 65 45 45 45 45 45 IM 5 5 5 5 5 5 5 5 5 Compound 1 0.3 0.5 Compound 3 0.5 1.0 1.0 1.0 1.0 Compound 4 0.5 1.0 Stabilizer 1 0.4 0.2 0.4 0.4 0.4 0.4 0.2 Stabilizer 2 0.4 0.2 0.2 0.2 0.4 0.4Stabilizer 3 0.4 0.4 0.2 0.4 0.4 0.4 (Physical properties) Impact 1 60 50 65 65 40 55 55 50 40 25 Impact 2 55 45 60 35 35 50 45 40 25 Impact 3 60 40 55 55 35 30 30 40 35 20 Set elongation 12 2 1 2 1 2 1 1

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Hajime Sentoku 5-6-2 Higashi-Hachiman, Hiratsuka City, Kanagawa Sanryo Gas Chemical Co., Ltd. Plastics Center

Claims (5)

[Claims] 1. A total of 10 to 70 parts by weight of (A) polyphenylene ether resin (hereinafter abbreviated as PPE) and 30 to 70 parts by weight of (B) polyamide (hereinafter abbreviated as PA).
0 parts by weight to (C) an impact resistance improver of 0 to 20 parts by weight, and (D) a substituted succinic acid represented by the following general formula 1 0.1 to 0.1 parts by weight.
A resin composition comprising 5 parts by weight and (E) 0 to 3 parts by weight of a heat stabilizer. HOOC-CHX-CHY-COOH (where X represents a halogen atom or an alkyl or arylacyloxy group, and Y represents a halogen atom, an alkyl or arylacyloxy group, or hydrogen) 2. The resin composition according to claim 1, wherein the (D) substituted succinic acid is a substituted succinic acid substituted with 1 to 2 Cl or Br. 3. The resin composition according to claim 1, wherein (D) the substituted succinic acid is a substituted succinic acid substituted with one lower alkylacyloxy group. 4. The (E) heat stabilizer is tetrakis (2,4-).
Di-t-butylphenyl) 4,4'-biphenylenephosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl) Phenyl) pentaerythritol diphosphite, N, N'-hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,2-thio-diethylenebis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,2'-methylene-bis (4-methyl-6-t-butylphenol, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, zinc oxide, zinc sulfide. The resin composition according to claim 1, which is one or more kinds. 5. An additional 0.05% of (F) a halogen scavenger.
The resin composition according to claim 2, which is added in an amount of 2 parts by weight.