JPH02269766A - Internal combustion engine part and auxiliary machinery part - Google Patents

Abstract

PURPOSE:To prepare an internal combustion engine part and an auxiliary machinery part which are light and excellent in durability with little degradation in strengths and rigidity even at a high temp. by molding said parts from a fiber reinforced resin obtd. by mixing a resin compsn. comprising an arom. polyetherketone and a polyetherimide with a specific carbon fiber in a specified ratio. CONSTITUTION:An internal combustion engine part and an auxiliary machinery part are molded from a fiber-reinforced resin obtd. by mixing 75-55wt.% resin compsn. comprising 95-60wt.% arom. polyetherketone having the repeating units of formula I and 5-40wt.% polyetherimide having the repeating units of formula II with 25-45wt.% carbon fiber which has been thermally treated at 300-400 deg.C after having been covered with an arom. polysulfone resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to internal combustion engine parts and auxiliary parts made of fiber-reinforced resin, particularly impellers, power transmission gears, etc. used in centrifugal compressors.

[Prior Art] Conventional fiber-reinforced resin impellers include, for example, Japanese Patent Publication Nos. 52-48684, 135132/1982, 119105/1980, 18296/1980, and There are impellers described in Japanese Patent No. 61-283797, but the resin materials that make up these impellers are
It is characterized by using carbon fiber as a reinforcing material for the resin. In particular, JP-A-57-119105 describes that a carbon fiber reinforced resin using a heat-resistant thermoplastic resin or a thermosetting resin as a matrix resin is used for an impeller.

[Problem to be solved by the invention] However, the operating conditions of a centrifugal compressor impeller are
℃ to 200℃ (maximum temperature during regular use is 165℃)
The maximum rotation speed is 13X 10' rpm, and the stress generated at maximum rotation is approximately 20 kg/mm" for the current product (made of aluminum alloy, outer diameter 60 mm), and the blade attachment is approximately 10 kg 7/+++ m" at the root. It will also happen. By using a fiber-reinforced resin with a low specific gravity, the maximum stress during one rotation can be reduced to about 100 lbs. In this way, from the current usage conditions, heat resistance, strength (tensile, bending,
When materials are selected taking into account factors such as elastic modulus (tensile, bending), durability and fatigue properties (tension, bending), creep properties (tension, compression), etc., the thermal resistance disclosed in JP-A-57-119105 Plastic resins or thermosetting resins cannot be used as is for impellers.

Fiber-reinforced resin compositions that satisfy these conditions include:
Polyethersulfone (PES), polyetherimide (PEI), polyetheretherketone (PEEK)
, polyetherketone (PEK), polyetherketoneketone (PEKK), polyketone sulfide (PKS)
), polyallyletherketone (PAE), aromatic polyamide (PA), polyamideimide (PAI), polyimide (PI), and other heat-resistant resins, and carbon fibers, glass fibers, whiskers, etc., are combined into composite compositions. is possible.

However, since the above-mentioned resin has a high melting temperature, it is necessary to mold the resin at a considerably high melting temperature of 350°C to 430°C. In addition, currently commercially available carbon fibers for resin reinforcement use polyamide resins (decomposition temperature 280"C) for thermoplastic resins as binding agents,
Epoxy resin for thermosetting resin (decomposition temperature 30
At the resin melting temperature (350°C to 430°C) mentioned above during molding, these binding agents are likely to decompose, resulting in a decrease in interfacial strength due to insufficient wetting between the carbon fiber and matrix resin. Moreover, variations in strength tend to occur, and when used as an impeller material for a centrifugal compressor made of fiber-reinforced resin, there is a problem in that the reinforcing effect of carbon fibers is not effectively utilized and the strength is low. Furthermore, matrix resins created by maximizing the wettability of carbon fibers and matrix resins have a low glass transition temperature and lack of rigidity when used at the maximum temperature of 165°C during normal use. There was also.

The purpose of the present invention is to have high heat resistance, even in high temperature areas.
An object of the present invention is to provide internal combustion engine parts and auxiliary machine parts made of fiber-reinforced resin with little reduction in strength and rigidity.

[Means to solve the problem]

As a result of various studies to achieve the above object, the present inventors discovered that excellent internal combustion engine parts and auxiliary parts can be obtained by using a specific fiber-reinforced resin,
This led to the completion of the present invention.

That is, the present invention provides internal combustion engine parts and auxiliary parts made of fiber-reinforced resin, in which the fiber-reinforced resin contains (a) 95 to 60% by weight of an aromatic polyether ketone having a repeating unit represented by the following formula (1). % and the following (2
75 to 55% by weight of a resin composition consisting of 5 to 40% by weight of polyetherimide having repeating units represented by the formula (3)
The present invention is an internal combustion engine part and an auxiliary machine part characterized by being an aromatic polyetherketone resin composition comprising 25 to 45% by weight of carbon fiber heated at 00 to 400°C.

Generally, matrix resins include polyethersulfone (PES), polyetherimide (PEI), polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK),
Polykedone sulfide (PKS), polyallyletherketone (PAEK), aromatic polyamide (PA),
Polyamideimide (PAI), polyimide (PI
) etc. are used. However, the so-called polymer alloy resin made of polyetherketone and polyetherimide used in the present invention is effective as it is easy to mold and has high heat resistance strength.

The polyether ketone constituting the polymer alloy resin used as the matrix resin is as follows - Formula % Formula % In the present invention, 380
°C, 2. The melt flow index measured under l6kg load condition is 5 to 50 g/l0m1n, preferably I
Botetherketone within the range of O to 25 g/IO+nin is preferably used.

A commercially available product is "Pictrex Polynyderketone IIEK 22 (trademark)" manufactured by Imperial Chemical Industries Ltd. in the UK.

The polyetherimide used in the present invention has a structure represented by the following formula (2). Commercially available products include the product name "
"Ultem" is widely known, for example, published in Japanese Patent Application Publication No. 58-8
It can be easily produced by the method described in Japanese Patent No. 26.

In the present invention, the melt flow index measured at 320°C and a load of 2.16 kg is 0.3 to 5 g/
l0m1n, preferably 0.5-3 g/l0nin
Polyetherimides in the range of are preferably used.

The blending ratio of aromatic polyetherketone and polyetherimide is 95 to 70% by weight of aromatic polyetherketone,
A suitable amount is 65 to 30% polyester waste. If the amount of aromatic polyetherketone exceeds 95% by weight and the amount of polyetherimide is less than 5% by weight, the desired effect of improving the mechanical strength of the resin composition at high temperatures will be insufficient; When the ketone content is less than 70% by weight and the polyetherimide content exceeds 30% by weight, the resulting resin composition loses the excellent chemical properties possessed by aromatic polyetherketones.

In the present invention, the aromatic polysulfone resin used as a sizing agent to coat the surface of carbon fibers is a linear polymer having arylene bonds, ether bonds, and sulfone bonds as bonding units, for example, as shown in the following formula. It is known to consist of repeating units. Among these, especially formula (3)
The following resins are preferred.

+31-+O-@-3O□()ushi H3 (ri) 斗0tsu15Obe)0-0-〇(God- +71 Ju0sha SO□-ku8men(÷ fllll -f-0tsu-SO□ (b)SO□()0
() f? l -+0-C)SO□-000℃■1□-
@+ These aromatic polysulfone resins can be produced, for example, by the methods described in Japanese Patent Publication No. 10067/1980, Japanese Patent Publication No. 7799/1982, and Japanese Patent Publication No. 617/1989, etc., and at least these One or a mixture of two or more of these can be used. Typical examples of commercially available products shown by Formula 5 (3) include "Pictrex Polyethersulfone (trademark)" by Imperial Chemical Industries Ltd. in the United Kingdom, "Sumibroi S (trademark)" by Susumu Kagaku ■, Also, Mitsui Toatsu Chemical
[Polyether sulfone (PES) J is mentioned,
A typical example represented by formula (2) is "Needel Polysulfone (trademark)" manufactured by Amoco Chemical Company, USA.

Further, the carbon fibers used in the present invention include acrylic, rayon, lignin, and pitch type carbon fibers, and although any of them can be used, in the present invention, acrylic fibers, which have the highest fiber strength, are most preferably used. The form of carbon fiber is chopped strand.

It may be roving, woven fabric, etc., but preferred is one obtained by firing polyacrylonitrile filament, rayon filament, or petroleum pitch.
Particularly suitable are those made from acrylonitrile filaments. It is more preferable that the surface of these carbon fibers is previously oxidized by ozone or electrolytic oxidation. As a method for coating these carbon fibers with aromatic polysulfone resin, aromatic polysulfone resin is coated with dichloromethane.

Chloroform, 1.2 dichloroethane, 1.1. l, 2
．． 2-tetrachloroethane, dimethyl sulfoxide,
Normal methyl benkune, methyl ethyl ketone, 1.1
．． In a solution dissolved in a solvent such as 2-trichloroethane,
Carbon fibers are soaked and then dried to remove the solvent to obtain carbon fibers coated with aromatic polysulfone resin.

Usually, the coating amount of the aromatic polysulfone resin on the carbon fiber is preferably 0.1 to 10 parts by weight per 100 parts by weight of the carbon fiber, and the effect of the present invention cannot be obtained if it is less than 0.1 part by weight.
Further, even if 10 parts by weight or more is coated, no improvement in mechanical strength can be expected and it is meaningless.

The carbon fiber coated with the aromatic polysulfone resin as described above is heat-treated by exposing it in air to a temperature of 300 to 400°C, particularly preferably 340 to 380°C. The heat treatment time is 3 to 20 hours, particularly preferably 5 hours.
~15 hours.

Various methods can be adopted for mixing the carbon fiber coated with the aromatic polysulfone resin thus obtained and the resin composition of aromatic polyetherketone and polyetherimide. For example, 3 to 6 mm of coated and heat-treated carbon fiber
It is also possible to cut it into lengths and feed it and the resin composition of aromatic polyetherketone and polyetherimide individually into a melt extruder for mixing. It can also be preblended in a mixer and then fed to a melt extruder. Furthermore, the coated and heat-treated carbon fiber roving can be directly fed to a melt extruder and mixed with a resin composition of aromatic polyetherketone and polyetherimide. i.e. carbon fiber, polyetherketone,
There are no restrictions on the mixing order or mixing method of the three components of polyetherimide, as long as they finally have the composition ratio of the present invention.

In the present invention, the blending ratio of carbon fiber coated with aromatic polysulfone resin, aromatic polyetherketone, and polyetherimide resin composition is 25 to 45% by weight of carbon fiber, aromatic polyetherketone, and polyetherimide. The mixture is 75-55% by weight. If the amount of carbon fibers is 25% by weight without grooves, the resulting resin composition will have low mechanical strength, which is not preferable. If more than 45% by weight of carbon fiber is blended, it will be difficult to uniformly melt and mix the resulting resin composition, and the melt fluidity will also drop significantly, impairing processability in injection molding and the like. The resin composition may contain fillers such as talc, lucium carbonate, mica, and glass peas, fibrous reinforcing materials such as glass fiber, potassium titanate fiber, aramid fiber, and ceramic fiber, stabilizers, and coloring. Agents may be mixed within the range that does not impair the quality and performance of the resin composition.

A polymer alloy resin composition of carbon fiber-reinforced polyetherketone and polyetherimide is usually subjected to an injection molding process as a pellet-shaped molding material that is easy to handle.
For example, these are made by blending polyetherketone resin, polyetherimide resin, and carbon fiber using a known single-screw or twin-screw extruder, and at a cylinder temperature of 360°C to 420°C.
It is obtained by extrusion shaping at a temperature of 370°C to 390°C, preferably 370°C to 390°C, with a compression ratio of 2 to 3 in the screw of an extruder. Injection molding is carried out using a normal injection molding machine, with a cylinder temperature of 360°C to 420°C, preferably 380°C to 420°C.
00℃, the mold temperature is 150℃ to 230℃, preferably 180℃ to 200℃, and it is easy to manufacture complex-shaped carbon fiber reinforced resin centrifugal compressor impellers, power transmission gears, etc. can be obtained.

Hereinafter, the impeller of the present invention will be explained based on the drawings.

FIG. 1 is a diagram showing an embodiment of the present invention.

First, to explain the configuration, as shown in the figure, the impeller of a centrifugal compressor has a complicated shape and requires precise dimensional accuracy. The impeller 1 is sandwiched between a sleeve 2 and a washer 3, as shown in FIG. 2, and is fixed to a shaft portion 5 with a nut 4.

The impeller of the present invention can be manufactured using the resin composition by a well-known method such as extrusion molding or injection molding. For example, an impeller can be molded using the mold shown in FIG. That is, the pin 7 is attached to the lower mold lO combined with the assembled mold 6 in which the impeller shape is engraved, and then the upper mold 8 is tightly fixed, and the molding material is injected or extruded from six directions through the gate 9 to form the impeller. The shaped portion (cavity portion) 11 is filled and molded.

(Fiber-reinforced resin production example) Production example 1 After coating the surface of polyacrylonitrile carbon fiber (manufactured by Toho Rayon ■, HTA type) that had been surface-treated by electrolytic oxidation with aromatic polysulfone resin, it was cut into 6 mm lengths. The resulting fibers were chopped into chopped carbon fibers, and heat treated at 370° C. for 10 hours in a heat treatment furnace in an air atmosphere.

Next, Table 1 shows the blending ratio of the polymer alloy resin of polyetherketone resin (PEK manufactured by Mitsui Toatsu Chemical Co., Ltd.) and polyetherimide resin (PEI manufactured by GE) as the matrix resin, and The matrix resin and the carbon fiber treated above were blended in such a manner that the carbon fiber content was 30% by weight. This thing L/D=2
3. Using a 65φ shaft vent type extruder with a compression ratio of 3, the extruded strand was cut at a cylinder temperature of 380° C. and a screw rotation speed of 45 rpm to obtain a pellet-shaped molding material. After drying this product with hot air at 150°C for 5 hours, using an 80TON (mold clamping pressure) injection molding machine manufactured by H Seishin Kogyo ■, JIS No. 1 dumbbell test with a cylinder temperature of 380°C and a mold temperature of 180°C with a thickness of 3 mm. Shape the pieces, then 230
Heat treated for 13 hours at room temperature and at high temperature (165℃)
) shown in the tensile test (^STM D-638) and bending test. Looking at the correlation between the blending ratio of polyetherketone and polyetherimide, tensile strength, and flexural modulus, the optimum range is when the blending ratio of polyetherketone resin is 70 to 95% by weight relative to the total amount of matrix resin. Particularly preferred.

Production Example 2 After coating the surface of polyacrylonitrile carbon fiber (manufactured by Toho Rayon ■, HTA type) with surface treatment by electrolytic oxidation with aromatic polysulfone resin, 61nff+
The fibers were cut into lengths to obtain chopped carbon fibers, and heat treated at 370° C. for 10 hours in a heat treatment furnace in an air atmosphere.

Next, polyetherketone resin (
PE manufactured by Mitsui Toatsu Chemical Co., Ltd.) and polyetherimide resin (
A polymer alloy resin with a blending ratio of 80/20 (PEI manufactured by GE) and the carbon fibers treated above were kneaded under the mixing conditions as described in Example 1, and the carbon fiber content was 2.
A pellet-shaped resin composition was prepared by blending the resin compositions in amounts of 0.30, 40.50% by weight. This resin composition was dried with hot air at 1.80°C for 3 hours, and then molded to a thickness of 3+ nm using an 80TON (mold clamping pressure) injection molding machine manufactured by Nissei Jushi Kogyo ■ at a cylinder temperature of 390°C and a mold temperature of 190°C. A JIS No. 1 dumbbell test piece was formed, and then 230
℃ for 3 hours to 45% by weight.

Examples 1 to 3 Fiber-reinforced resin pellets having the compositions shown in Table 2 were produced according to Fuji Production Example 1, and were made using a stiffener.

Cylinder temperature 390℃, mold temperature 180℃, injection pressure 2
The product was injected into a mold having a structure as shown in FIG. 3 under molding conditions of 100 kg/cm2 to obtain an impeller-shaped product. After heat treatment of the obtained shape at 230℃ for 3 hours, mechanical processing such as deburring and balance check is performed, and it is fixed to the shaft with the structure shown in Fig. 2, and the temperature range with the air heating device is adjusted. 0~600℃) high speed rotational strength tester (rotation speed 0~2
5X 10' rpm) and the rotation speed is 13X.
A continuous durability test was conducted while adjusting the impeller compressed air outlet temperature to 165°C at 10' rpm. The results obtained are shown in Table 2. Those that withstood 200 hours of continuous durability were judged to be good (O mark).

Example 4 A fiber-reinforced resin pellet having the composition shown in Table 2 (carbon fiber 40 wt%) was produced according to Production Example 1, and the same procedure as that of Examples 1 to 3 was performed except that the mold temperature was 200°C. An impeller-shaped article was produced in the same manner and tested.

The results obtained are shown in Table 2.

Comparative Examples 1 to 3 Impeller-shaped articles were produced and tested in the same manner as Examples 1 to 3, except that fiber-reinforced resin pellets having the compositions shown in Table 2 were used. The results obtained are shown in Table 2.

Comparative Examples 4 and 5 Composition shown in Table 2 (carbon fiber 20wt%, 50wt%)
Example 4 except that a fiber-reinforced resin pellet having
An impeller-shaped article was prepared in the same manner as above and tested. The results obtained are shown in Table 2.

From the results in Table 2, it can be seen that the impellers molded in the Examples are superior in heat resistance strength and creep resistance compared to those in the Comparative Examples.

Table 1 tree and thing Note) Carbon fiber content is constant at 30% by weight.

(Effects of the Invention) As explained above, the parts of the present invention improve the wettability of the carbon fibers and matrix resin in the fiber-reinforced resin used, which improves the strength, and also improves the glass transition temperature. It also has high heat resistance, up to 165℃.
Even in the above high temperature range, there is little decrease in strength and rigidity, so it is possible to achieve the effect of not breaking during high-speed continuous durability. In addition to the above-mentioned common effects, each of the embodiments also has the following effects. Reducing the weight of the impeller improves its ability to follow engine load fluctuations.

In addition, since the precision of the product surface is significantly improved compared to those made of aluminum alloy, it is possible to reduce the phenomenon of separation of intake air from the blade surface during high-speed rotation, and improve intake compression efficiency.

[Brief explanation of drawings]

Fig. 1 is a perspective view of the m-piece inflator of the present invention, Fig. 2 is a cross-sectional view of the impeller attached to the shaft portion, Fig. 3 is a cross-sectional view of the impeller mold, (L:L),
(Fig. 5 is a diagram showing the evaluation results in Example 2 of 1F construction. 1... Impeller 2... Sleeve 3...
Washer 4...Nut 5...Shaft
6...Assembling mold 7...Bin
8... Upper mold 9... Gate 10-
...Lower mold +1...Impeller shape part (cavity) A
...Molding material inlet patent applicant Mitsui Toatsu Chemical Co., Ltd. Nissan Motor Co., Ltd.

Claims (1)

[Scope of Claims] Internal combustion engine parts and auxiliary parts made of fiber-reinforced resin, wherein the fiber-reinforced resin is (a) an aromatic polyether ketone 95-60 having a repeating unit represented by the following formula (1). Weight% and the following (2
) 75 to 55% by weight of a resin composition consisting of 5 to 40% by weight of polyetherimide having a repeating unit represented by the formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ Mathematical formula , chemical formulas, tables, etc. ▼ (b) After coating the surface with aromatic polysulfone resin, 3
Internal combustion engine parts and auxiliary equipment parts, characterized in that they are aromatic polyetherketone resin compositions comprising 25 to 45% by weight of carbon fibers heated at 00 to 400°C.