JPH05321759A - Car cylinder head cover - Google Patents

Abstract

PURPOSE:To improve the mechanical characteristics and the durability by executing the injection molding of the resin composition by melting and mixing the polyphenylene sulfide resin, the polyphenylene oxide and the fibrous and/or the non-fibrous fillers. CONSTITUTION:The polyphenylene sulfide resin(PPS resin) is the polymer containing more than 70% of repeated unit demonstrated by the constitutional formula I, while the polyphenylene oxide(PPO) is fundamentally composed of the constitutional unit demonstrated by the constitutional formula II. In the formula II, R1-R4 mean the hydrogen atom, the halogen atom, the aromatic hydrocarbon radical. A cylinder head cover for an automobile is obtained by executing the injection molding of the resin composition which is obtained by melting and mixing 100 pt.wt. of the PPS resin, 10-20 pt.wt. of the PPO resin, and 50-400 pt.wt. of the fibrous and/or non-fibrous filler. This secures higher mechanical strength, higher rigidity, the dimensional stability or the like even at high temperature of 100 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automobile cylinder head cover, and more specifically, it retains high strength, rigidity and dimensional stability even at high temperatures and is excellent even in contact with chemicals such as engine oil. The present invention relates to an automobile cylinder head cover obtained by injection molding a durable polyphenylene sulfide resin composition.

[0002]

BACKGROUND OF THE INVENTION It is well known that automobile parts, especially those in the engine compartment, are gradually being replaced by metal from plastic. The main reason for this is that plastic is lighter in weight than metal, has a high degree of freedom in product design, and can be improved in productivity by originally molding a plurality of parts integrally. A cylinder head cover is one of the typical parts in the engine room, and this part is also becoming plastic. Currently, glass fiber reinforced nylon 66 is mainly used, and nylon 66 and more carbon are also used. A cylinder head cover made of a mixture with nylon is also known (JP-A-63-28903).

However, with the recent increase in the number of parts in the automobile engine room, the density of the parts, and the increase in the output of the engine, the cylinder head cover is also exposed to a higher temperature than before during operation, which is essential. With a nylon resin cylinder head cover which is highly water-absorbent and whose rigidity decreases and its dimensions change due to water absorption, this problem becomes particularly apparent at such high temperatures, making it difficult to obtain sufficient durability. Further, the PPS resin becomes a material having high strength by being reinforced especially with a reinforcing material such as glass fiber, and there is no decrease in rigidity due to water absorption, but since the glass transition point is low, the rigidity is not high in the temperature range of 100 ° C or higher. It is sufficient, and the properties alone are insufficient as a cylinder head cover material.

[0004]

SUMMARY OF THE INVENTION Therefore, the present invention provides 10
The subject is to obtain an automobile cylinder head cover that retains high mechanical strength, rigidity, dimensional stability, etc. even at high temperatures of 0 ° C or higher, and has excellent heat resistance and durability against chemicals such as engine oil at high temperatures. ..

[0005]

That is, the present invention is as follows.
(A) 100 parts by weight of polyphenylene sulfide resin,
(B) 10 to 200 parts by weight of polyphenylene oxide and (C) fibrous and / or non-fibrous filler 50 to 4
The present invention provides an automobile cylinder head cover obtained by injection molding a resin composition obtained by melt-kneading 100 parts by weight.

The (A) PPS resin used in the present invention is
The repeating unit represented by the structural formula (I)

[Chemical 1] It is a polymer containing 70 mol% or more, more preferably 90 mol% or more, and if the repeating unit is less than 70 mol%, heat resistance is impaired, which is not preferable. Also PPS
The resin can comprise less than 30 mol% of its repeating unit with a repeating unit having the following structural formula.

[0007]

[Chemical 2] The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible, but is usually 50 to 20,0.
A 00 poise (320 ° C., shear rate 10 sec ⁻¹ ) is used.

Such a PPS resin is generally known in the art, that is, a method for obtaining a polymer having a relatively small molecular weight as described in JP-B-45-3368 or JP-B-52-1224.
It can be produced by the method of obtaining a polymer having a relatively large molecular weight, which is described in JP-A No. 0 or JP-A-61-7332. In the present invention, the PPS resin obtained as described above is crosslinked / polymerized by heating in air, washed with an organic solvent, hot water, an aqueous acid solution, etc., and contains functional groups such as an acid anhydride group, an epoxy group and an isocyanate group. Of course, it is possible to use it after various treatments such as activation with a compound.

The (B) polyphenylene oxide (hereinafter abbreviated as PPO) used in the present invention basically consists of structural units represented by the following structural formula (II),

[Chemical 3] (Here, R1, R2, R3, and R4 are each a hydrogen atom, a halogen atom, an aliphatic group having 1 to 10 carbon atoms, an alicyclic group,
It represents an aromatic hydrocarbon group, and R1 to R4 may be the same or different from each other. ) A homopolymer and / or copolymer having a reduced viscosity (0.5 g / dl chloroform solution, measured at 30 ° C.) in the range of 0.15 to 0.70. Specific examples of such PPO include poly (2,6-dimethyl-1,4-phenylene oxide), poly (2-methyl-6-ethyl-1,4-phenylene oxide), poly (2,6-diphenyl-). 1,
4-phenylene oxide), poly (2-methyl-6-phenyl-1,4-phenylene oxide), poly (2,6
-Dichloro-1,4-phenylene oxide) and the like, and a copolymer such as a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol). An example is coalescence. Among them, poly (2,6-dimethyl-1,4-phenylene oxide), 2,6-dimethylphenol and 2,
A copolymer with 3,6-trimethylphenol is preferable, and poly (2,6-dimethyl-1,4-phenylene oxide) is particularly preferable.

The method for producing PPO is not particularly limited, and those obtained by known methods can be used. For example, it can be easily produced by oxidative polymerization using a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 as a catalyst.
In the present invention, it is of course possible to use the PPO obtained as described above after subjecting it to various treatments such as modification or activation with a compound containing a functional group such as an acid anhydride group, an epoxy group or an isocyanate group. It is possible.

In the present invention, the compounding amount of PPO is 10 to 200 parts by weight with respect to 100 parts by weight of PPS resin.
It is preferably from 0 to 150 parts by weight. If the compounding amount of PPO is less than 10 parts by weight, the strength of the obtained cylinder head cover (especially strength and rigidity at high temperature) becomes insufficient, which is not preferable. On the other hand, if the compounding amount of PPO exceeds 200 parts by weight, the cylinder is covered. This is not preferable because the moldability of the head cover is significantly reduced.

Examples of the (C) fibrous and / or non-fibrous filler used in the present invention include glass fiber, carbon fiber, potassium whisker titanate, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber and asbestos. Fibrous fillers such as fibers, gypsum fibers, metal fibers, wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide , Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and silica Non-fibrous fillers such as Is, they may be hollow, it is also possible to further combination of these fillers 2 or more. Further, it is more preferable to use these fibrous and / or non-fibrous fillers after pretreatment with a coupling agent such as a silane type or titanate type from the viewpoint of mechanical strength and the like.

The compounding amount of the (C) fibrous and / or non-fibrous filler in the present invention is in the range of 50 to 400 parts by weight with respect to 100 parts by weight of PPS resin, and 60 to 35.
Within the range of 0 parts by weight, higher mechanical properties,
It is preferable in the sense of obtaining dimensional stability and the like.

In the cylinder head cover of the present invention, as long as the effects of the present invention are not impaired, antioxidants, heat stabilizers, lubricants, plasticizers, crystal nucleating agents, UV inhibitors, colorants, flame retardants, etc. Additives can be added. Further, the cylinder head cover of the present invention is a polyamide, polysulfone, within a range that does not impair the effects of the present invention.
Tetrafluoropolyethylene, polyetherimide, polyamideimide, polyimide, polycarbonate, polyethersulfone, polyetherketone, polyetheretherketone, epoxy resin, phenol resin, polyethylene, polystyrene, polypropylene, ABS resin, polyester, polyamide elastomer, polyester Resin such as elastomer may be included.

The cylinder head cover of the present invention has the purpose of improving the mechanical strength and the moldability of burrs and the like within a range that does not impair the effects of the present invention. Γ-glycidoxypropyltrimethoxysilane, γ-glycid Xypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyl Trimethoxysisilane and γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanato Propi Methyl diethoxy silane, .gamma.-isocyanatopropyl ethyl dimethoxy silane, .gamma.-isocyanatopropyl ethyldiethoxysilane, may be added to the organic silane compound such as .gamma.-isocyanatopropyl trichlorosilane.

The method for preparing the composition used in the present invention is not particularly limited, but the mixture of raw materials is fed to a commonly known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll. 280-380
A method of kneading at a temperature of ° C can be given as an example. The order of mixing the raw materials is not particularly limited, and PP
A method in which the S resin, PPO and the fibrous and / or non-fibrous filler are dry-blended and then melt-kneaded by the above-mentioned method, or the PPS resin, the fibrous and / or non-fibrous filler and PPO A typical method is to dry-blend two of them and melt-knead them, and then melt-knead the remaining one.

By injection-molding the resin composition thus obtained, high mechanical strength, rigidity, dimensional stability and the like are maintained even at high temperatures of 100 ° C. or higher, and further heat resistance and engine at high temperature are maintained. It is possible to obtain an automobile cylinder head cover excellent in durability against chemicals such as oil.

The present invention will be described in more detail below with reference to examples.

[0019]

EXAMPLES Tensile strength, flexural strength, flexural modulus, Izod impact strength and engine oil resistance of the test pieces described in Examples and Comparative Examples were measured according to the following methods.

Tensile Strength: ASTM-D638 Bending Strength: ASTM-D790 Flexural Modulus: ASTM-D790 Izod Impact Strength: ASTM-D256 Engine Oil Resistance: Tensile dumbbell pieces were treated at 130 ° C./1000 hours in engine oil. The subsequent tensile strength and strength retention were measured and used as a guide for engine oil resistance.

Reference Example 1 (Synthesis Method of Polyphenylene Sulfide) PPS-1: Sodium Sulfide 3.26 in Autoclave
Kg (25 mol, containing 40% of water of crystallization), 4 g of sodium hydroxide, 1.19 Kg of sodium acetate trihydrate (about 8.8 mol) and 7.9 Kg of NMP were charged and gradually heated to 205 ° C. with stirring. After warming, about 1.5 liters of distilled water containing 1.36 kg of water was removed. To the remaining mixture, 3.75 Kg of 1,4-dichlorobenzene (25.5 mol) and 2 Kg of NMP were added and heated at 265 ° C for 3 hours. The reaction product is washed 5 times with hot water at 70 ° C and then at 80 ° C.
After drying under reduced pressure for 24 hours, the melt viscosity is about 600 poise (3
About 2 kg of powdery polyphenylene sulfide (PPS-1) at 10 ° C and a shear rate of 1000 sec ^-1 was obtained.

PPS-2: 3.26 kg of sodium sulfide (25 mol, containing 40% of water of crystallization) in an autoclave,
Sodium hydroxide 4g, sodium acetate trihydrate 1.2
Charge 2 Kg (about 9 mol) and NMP 7.9 Kg,
Gradually raise the temperature to 205 ° C with stirring, and water 1.36K
About 1.5 liters of distilled water containing g was removed. To the residual mixture, 3.75 kg of 1,4-dichlorobenzene (25.5
Mol) and 2 Kg of NMP were added, and the mixture was heated at 265 ° C. for 3.7 hours. The reaction product was washed 5 times with warm water at 70 ° C.,
After drying under reduced pressure at 80 ° C. for 24 hours, about 2 kg of powdery polyphenylene sulfide (PPS-2) having a melt viscosity of about 900 poise (310 ° C., shear rate of 1000 sec ⁻¹ ) was obtained.

As PPS-3, M2900 manufactured by Toray Phillips Petroleum Co. was used.

Example 1 100 parts by weight of PPS resin (PPS-1), 50 parts by weight of PPO (reduced viscosity: 0.45) and 150 parts by weight of glass fiber were dry blended with a Henschel mixer, and then 3
The mixture was melt-kneaded and pelletized by a screw type single-screw extruder set to a cylinder temperature of 20 ° C. After drying the obtained pellets, using an injection molding machine, a cylinder temperature of 320
C. and a mold temperature of 130.degree. C. were injection-molded to obtain predetermined test pieces for property evaluation. The measurement results of the obtained test pieces are summarized in Table 1. The resin composition obtained here had excellent strength and high-temperature rigidity, and exhibited extremely excellent engine oil resistance, and was suitable for automobile cylinder head covers.

The cylinder head cover obtained by injection molding the resin composition obtained here has good appearance and dimensional accuracy, and cracks were observed even in the engine oil resistance test conducted using this molded product. No trouble such as deformation or deformation occurred at all, and it was found to be an automobile part with extremely high practical value.

[0026]

[Table 1] Examples 2 to 6 PPS resin, PPO and various fillers were mixed in the proportions shown in Table 2, melt-kneaded and pelletized by a single-screw extruder having a cylinder temperature of 320 to 340 ° C. The results of injection molding and measurement performed on the obtained pellets in the same manner as in Example 1 are summarized in Table 1. All of them had excellent strength and rigidity, and exhibited extremely excellent resistance to engine oil, and were suitable for automobile cylinder head covers.

All of the cylinder head covers obtained by injection molding the resin composition obtained here have good appearance and dimensional accuracy, and engine oil resistance test conducted using these molded products. Even in the above, no trouble such as cracking or deformation occurred in any of the molded products, and it was proved that the automobile parts had extremely high practical value.

[0028]

[Table 2]

[0029]

The cylinder head cover of the present invention has high mechanical value such as high strength and high temperature rigidity and excellent durability with good engine oil resistance and is of high practical value.

Claims (1)

[Claims] 1. (A) Polyphenylene sulfide resin 1
00 parts by weight, (B) polyphenylene oxide 10 to 20
An automobile cylinder head cover obtained by injection molding a resin composition obtained by melt-kneading 0 parts by weight and 50 to 400 parts by weight of (C) fibrous and / or non-fibrous filler.