JPH0596637A - Manufacture of component for internal combustion engine - Google Patents

Abstract

(57) [Summary] (Correction) [Purpose] To obtain a method of manufacturing an internal combustion engine part made of a fiber-reinforced resin material having excellent heat resistance and mechanical strength. [Structure] 95-60% by weight is a polyether resin, 5
Polyetherimide resin is used in an amount of up to 40% by weight, and a resin formed by blending carbon fibers in either one or both resins in an amount of 25 to 45% by weight based on the total amount of the resin and carbon fibers. The etherketone resin pellets and the polyetherimide resin pellets are heated above the flow start or melting start temperature of the polyetherimide resin, and the polyetherketone resin is contained in the plasticized and melted polyetherimide resin, Subsequent heating by a temperature above the flow starting temperature or the melting starting temperature of the polyetherketone resin to obtain a state in which the polyetherketone resin, the polyetherimide resin and the carbon fibers are uniformly mixed. A method of manufacturing a component for an internal combustion engine, the method comprising molding an internal combustion engine component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a component for an internal combustion engine, such as an impeller for an integrated centrifugal compressor, from a fiber reinforced resin material having excellent heat resistance and mechanical strength.

[0002]

2. Description of the Related Art Polyethersulfone (hereinafter abbreviated as PES), polyetherimide (hereinafter abbreviated as PEI), polyamideimide (hereinafter abbreviated as PAI), polyimide (hereinafter abbreviated as PI), Polyphenylene sulfide (hereinafter abbreviated as PPS), polyetheretherketone (hereinafter abbreviated as PEEK),
Polyether ketone (hereinafter abbreviated as PEK), polyether nitrile (hereinafter abbreviated as PEN), polyallyl ether ketone (hereinafter abbreviated as PAEK), polyether ketone ketone (hereinafter abbreviated as PEKK)
Such heat-resistant resins are called super engineering plastics because they are significantly superior to general-purpose engineering plastics in terms of heat resistance and mechanical strength, and are used in various applications such as electrical and electronic machinery, machinery, automobiles, etc. ing. However, due to recent technological advances, properties having these heat-resistant resins, particularly those having improved mechanical strength, have been required. Therefore, a method of improving mechanical strength and heat resistance by incorporating a fibrous reinforcing material, particularly carbon fiber, into these heat resistant resins has been implemented.

Since carbon fibers are often used in carbon fiber reinforced plastics having an epoxy resin as a matrix, epoxy resins are used as a sizing agent for carbon fibers.

Since carbon fibers are often used in carbon fiber reinforced plastics having an epoxy resin as a matrix, epoxy resins are used as a sizing agent for carbon fibers. However, the epoxy resin sizing agent is effective when the thermosetting resin such as epoxy resin is the matrix, but the adhesiveness to the heat resistant resin is poor, and a resin composition having good mechanical strength is obtained. I can't. Therefore, as seen in JP-A-53-106752, it has been attempted to use a polyamide resin as a carbon fiber sizing agent for a thermoplastic resin.

Further, Japanese Unexamined Patent Publication No. 56-120730 discloses the use of carbon fibers bundled with an aromatic polysulfone resin, and Japanese Laid-Open Patent Publication No. 2-269766 discloses a carbon fiber bundled with a polysulfone resin. Containing polyetherketone (PEK) and polyetherimide (PEI)
A resin composition consisting of is proposed.

Furthermore, PE having an extremely high melting temperature
Use of carbon fiber that has been condensed with a polyethersulfone resin as a means for reducing the thermal decomposition of the sizing agent that occurs when using K, PEEK, liquid crystal polymer (hereinafter abbreviated as LCP), etc. as the carbon fiber reinforced resin composition Is disclosed in Japanese Patent Laid-Open No. 1-175972.

As a conventional component for an internal combustion engine, for example, a fiber reinforced resin impeller, for example, Japanese Patent Publication No. 52-48684.
JP-A No. 57-119105 and JP-A No. 57-119105, and the resin material constituting these fiber-reinforced resin impellers is characterized in that carbon fibers are used as a reinforcing material for the resin. In particular, JP-A-57-119
Japanese Patent Laid-Open No. 105 describes that a carbon fiber reinforced resin using a heat-resistant thermoplastic resin or thermosetting resin as a matrix resin is used for an impeller.

[0008]

As the resin impeller material, a PES resin using carbon fiber as a reinforcing material, which has been subjected to a converging process using a PES resin in JP-A-1-7890, is specifically mentioned. Also, JP-A 1-22
Japanese Patent No. 9523 discloses a PAI resin that uses carbon fibers that have been subjected to a converging process using a PES resin as a reinforcing material.
Furthermore, in Japanese Unexamined Patent Publication No. 1-271176, P
A method of using a polyketone sulfide (hereinafter abbreviated as PKS) resin in which carbon fibers subjected to a converging process using an ES resin are used as a reinforcing material is disclosed.

Further, in an example of using a polyetherketone resin material, which is superior in strength and toughness as the material disclosed in the above-mentioned published patent publication, as a matrix resin, JP-A-63-236598 describes P
Japanese Patent Application Laid-Open No. 1-175972 discloses an example of using an EEK resin, and a resin having a relatively low glass transition temperature, which is promising as a resin material for a high supercharge type turbocharger having a high maximum operating temperature, is disclosed. As a means to improve the heat resistance of etherketone resin, PK is added to PEK resin.
A resin composition prepared by blending an EI resin is disclosed in JP-A-2-269.
No. 765, and the carbon fiber reinforced resin composition is disclosed in JP-A-2-269764. By the way, the above-mentioned JP-A-2-269764 and JP-A-2-269764.
Japanese Patent No. 269765 has a low glass transition temperature (158
℃) PEK resin has a high glass transition temperature (217
C) PEI resin is mixed in a predetermined mixing ratio to improve mechanical properties at high temperature.

As a means for improving the mechanical properties at high temperatures, a method of mixing a resin material having a higher glass transition temperature is often considered to be an easily presumed technique, but in practice, it is a system of two or more components. However, the glass transition temperature of the mixed system is extremely rarely shifted, and the resin composition described in the above-mentioned Japanese Patent Laid-Open Publication is one of the few examples.

The mixing of PEK resin and PEI resin is described in the above-mentioned JP-A-2-269764 and JP-A-2-26976.
As described in Japanese Patent Publication No. 5, each of them can be separately supplied to and mixed with a melt extruder, or preliminarily mixed with a mixer such as a Henschel mixer, a ribbon blender or a tumbler in advance, and further melt-extruded. May be supplied to the machine.

The resin composition (including the fiber reinforced composition) thus obtained has significantly improved mechanical properties at high temperature as compared with the PEK resin containing no PEI resin. When used for mass production of engine parts, such as fiber reinforced resin impeller, gel deterioration products may occur inside the cylinder of the injection molding machine used for molding, increasing the variation in mechanical strength of injection molded products. In some cases, the quality stability may be deteriorated due to an increase in the defect occurrence rate, etc., so that the inside of the cylinder of the injection molding machine must be frequently cleaned.

An object of the present invention is to clean the inside of a cylinder by reducing gel-like deterioration products which occur when injection molding or extrusion molding is carried out using a fiber reinforced resin composition containing PEK resin and PEI resin. In addition to increasing the interval and improving productivity, it also reduces variations in mechanical strength and defective product rate of internal combustion engine parts such as fiber reinforced resin impellers, and improves the quality of fiber reinforced resin internal combustion engines. It is to provide a method of manufacturing a component for use.

[0014]

Means for Solving the Problems As a result of various studies to achieve the above object, the present inventor has found that when injection molding or extrusion molding is carried out using a PEK resin / PEI resin system or a fiber reinforced resin composition. , The PEK resin and the PEI resin are compounded by a specific compounding method as described below, and under the specific molding conditions enabled by this, it is possible to remarkably reduce the generation of gel-like deterioration products, Further, the compounding, the quality and performance of the fiber-reinforced resin impeller manufactured by using the molding method was found to be clearly superior when compared with the fiber-reinforced resin impeller manufactured by the method not used in the present invention, and the present invention It came to completion.

That is, in the present invention, the polyetherketone resin as the matrix resin and the polyetherimide resin as the matrix resin are contained in an amount of 95 to 60% by weight based on the total amount of both resins.
Is a polyetherketone resin, 5 to 40% by weight of which is a polyetherimide resin, and one or both of the resins has a total of 25 to 45 of the resin and the carbon fiber.
The first step of mixing the polyetherketone resin pellets and the polyetherimide resin pellets formed by blending carbon fibers so that the weight% becomes 1%, and the mixed pellets obtained in the first step, the flow of the polyetherimide resin When the polyetherketone resin is heated to a temperature higher than the start temperature or the melting start temperature, the polyetherketone resin is contained in the plasticized and melted polyetherimide resin, and subsequently heated to a flow start temperature or a melting start temperature or higher of the polyetherketone resin. Then, the polyetherketone resin, the polyetherimide resin, and the carbon fibers are uniformly mixed, and the melt mixing step of the second step is performed, and the melt mixture obtained in the second step is injection-molded or extruded to form an internal combustion engine part. And a third step of molding the same.

The polyetherketone (PEK) resin used as the matrix resin in the present invention has the following general formula:

[Chemical 3] It has a repeating unit represented by

In accordance with the present invention, ASTM D1238
PEK resin having a melt flow index of 5 to 50 g / 10 min, preferably 10 to 25 g / 10 min, measured under the conditions of 380 ° C. and 2.16 kg load is preferably used. Examples of commercially available products include "Pictrex polyetherketone PEK 220P (trademark)" manufactured by British ICI (Imperial Chemical Industries). The polyetherimide (PEI) resin used as the matrix resin in the present invention has the following general formula:

[Chemical 4] It has a repeating unit represented by As a commercially available product, the product name "Ultem" manufactured by GE (General Electric Co.) of England is well known, and can be easily produced by the method described in JP-A-56-826, for example. The melt flow index measured at 320 ° C. under a load of 2.16 kg is 0.3 to 5 g /
The PEI resin is preferably 10 min, preferably 0.5 to 3 g / 10 min.

Since the melting point of PEK resin has a value of 373 ° C., which belongs to the highest temperature class among super engineering plastics, the cylinder temperature during injection molding must be set to about 390 to 400 ° C.
Therefore, the cylinder temperature is 4 for a polymer alloy of PEI resin having relatively poor fluidity and PEK resin having high melting point.
To obtain a molded product with a complicated shape at around 00 ° C, it is necessary to set the cylinder temperature higher than that. By the way, P
It is known that EI resin produces a deteriorated product in the presence of an alkali metal element, and for example, potassium titanate whisker fiber containing a potassium element is known to be not suitable as a reinforcing fiber of PEI resin. There is.

As shown in Chemical formula 3, the PEK resin does not have an alkali metal atom in its molecular structure. However, since a catalyst containing an alkali metal is added in the manufacturing process, the PEK resin may not be contained in the pellet. Alkali metal elements such as potassium and sodium are contained in the range of several ppm to about 100 ppm, which is one of the factors causing the problem to be solved by the present invention. However, it is also known that when the resin temperature is low, the amount of deterioration products generated in the presence of an alkali metal is relatively small. The second factor that promotes the generation of gelled substances is that the PEI resin, which has poor heat resistance, is oxidatively deteriorated in the presence of high temperature oxygen because the cylinder temperature is set to around 400 ° C. during injection molding or extrusion molding as described above. It is also possible that the polyetherimide adheres to the inside of the cylinder and begins to accumulate due to a crosslinking reaction. As a result of thermal analysis, the gel-like deteriorated product generated due to the above-mentioned cause did not have a melting point at least within the range of the resin temperature reached during injection molding or extrusion molding. Therefore, with the lapse of time, that is, as the production quantity of molded products increases, the diameter of the parts that accumulate inside the cylinder and through which the resin flows during molding gradually decreases, and it is as if molding is repeated while gradually reducing the nozzle diameter. Produces results like.

For internal combustion engine parts, especially for fiber-reinforced resin impellers, the technology of orienting the fibers so that the direction in which the centrifugal stress is large becomes strong is particularly important, and defective products (those with internal defects) are minimized during mass production. It is also necessary to limit it. For this reason, it is essential to perform molding within the molding conditions that balance the mechanical characteristics and the yield rate, but the accumulation of deteriorated materials as described above increases the production quantity even if the set value of the control system of the molding machine is kept constant. At the same time, it will deviate from the initial setting value. Such a decrease not only lowers the yield rate, but also increases and decreases the variation of mechanical properties, which is the most important cause of lowering the reliability of durability. This is a problem that must be solved in order to provide a fiber-strength resin impeller.

The mixing of PEK resin and PEI resin is described in the above-mentioned JP-A-2-269764 and JP-A-2-26976.
From the viewpoint of homogenization as described in Japanese Patent Publication No. 5, the PEK resin and the PEI resin are blended, and pellets of a polymer alloy of the PEK resin and the PEI resin are obtained using an extruder, and then the pellets are obtained. It is desirable to obtain a molded product by injection molding or extrusion molding using. However, in order to pelletize the polymer alloy, it is necessary to raise the resin temperature at least above the melting temperature of the PEK resin. Further, since the resin temperature is raised to around 400 ° C. in the subsequent molding step, the heat resistance is poor. The PEI resin has extremely severe conditions.

Therefore, the present inventor has tried a method of reducing the heat history of the PEI resin once in order to reduce the deterioration of the PEI resin. That is, rather than using PEK resin and PEI resin to form polymer alloyed pellets,
We decided to use the method of directly charging EK resin pellets and PEI resin pellets from the hopper of an injection molding machine or an extrusion molding machine. To obtain a molded product using fiber-reinforced PEK resin / PEI resin, PEK resin pellets or P
It is necessary to add the reinforcing fiber to one or both of the pellets of the EI resin, but in this case, there is no great difference in suppressing the generation of the deteriorated product by using either method. However, as can be seen from the examples described below, the raw material and molding method described in the present invention have the effect of reducing gel-like deteriorated products under certain conditions, and in addition to the above-mentioned JP-A-2-269764.
It is possible to obtain a molded product having a higher strength than in the case of manufacturing by the method described in Japanese Patent Laid-Open No. 2-269765 and in the case of expecting this secondary effect, reinforcing fiber is possible. As long as it is contained in the pellet of PEK resin, it is efficient and desirable.

Next, since the PEK resin / PEI resin pellets, not the PEK resin / PEI resin polymer alloy pellets, are directly charged from the hopper of the molding machine, the temperature of the cylinder of the injection molding machine is set as shown in FIGS. 1 and 2. As shown, change the temperature of the zone from the hopper to PEK resin / PE
Set much lower than when using polymer alloy pellets of I resin. That is, FIG. 1 shows an injection molding machine and a P
FIG. 6 is a diagram showing an example of temperature setting during injection molding when injection molding is performed using EK pellets and PEI pellets, in which the temperature during injection molding when injection molding is performed using an injection molding machine and PEK / PEI alloy pellets. It is a figure showing a setting example, 1 is a nozzle, 2 is a heater, 3 is a screw, 4 is a cylinder, 5 is a hopper, 6a is PEK pellets and PE.
I pellet, 6b is PEK / PEI alloy pellet, 7
Is a hydraulic cylinder, and 8 is a hydraulic motor.

For example, when using pellets of a polymer alloy of PEK resin / PEI resin, an example of temperature setting of the cylinder temperature is 400 ° C./400° C./390° C. /
370 ° C. (when divided into four zones from the nozzle side to the hopper side) can be mentioned. On the other hand, when PEK resin pellets and PEI resin pellets are added, for example, 390 ° C./380° C./340° C. / Very low temperature in the zone above the hopper, such as 330 ° C. Such a temperature setting cannot be established for PEK resin / PEI resin polymer alloy pellets. The reason for this is that when pellets in the state of polymer alloy are used, the melting start temperature is PE
Since it is much higher than that of I resin, even in the coldest zone as in the above example, 3
This is because the pellets do not plasticize unless the temperature is set to around 70 ° C. On the other hand, when pellets of PEK resin and PEI resin are used, the temperature of the zone where the temperature is lower than the hopper may be higher than the melting start temperature of the PEI resin. When the temperature is set in this way, the PEI resin pellets having a low melting start temperature start to melt first in the two zones from the hopper. Then, in the zone from the nozzle, the melting of the PEK resin pellets dispersed in the molten PEI resin is started. In this zone, the PEI resin has already been sufficiently melted and the resin temperature is likely to rise due to shearing heat generation, and plasticization begins at a lower temperature than when using polymer alloy pellets. Therefore, even if the temperature of the zone from the nozzle is set lower than that when polymer alloy pellets are used, there is no disadvantage in molding. The molding machine used for such a molding method preferably has a long cylinder length from the viewpoint of compatibility, but no problem occurs even if a standard cylinder is used for the molding machine.

As described above, in the case of molding using the polymer alloy composition of PEK resin / PEI resin, the effect of heat deterioration in the kneading step is removed by not forming pellets of the polymer alloy, and further polymer alloying is performed. Taking advantage of not being used, the temperature of the zone from the hopper is set to the melting start temperature of the PEI resin or higher and the melting temperature of the PEK resin or lower, preferably to the melting start temperature of the PEI resin as much as possible to suppress thermal deterioration of the PEI resin. It is effective to minimize the thermal deterioration by setting the temperature close to each other. Furthermore, since the PEI resin is melted first, it is easy to plasticize the PEK resin.
Since the temperature on the nozzle side can be lowered, the deterioration reaction is further suppressed, which is an advantage of the present material and the present molding method.

The present invention is not limited to the polymer alloy of PEK resin / PEI resin, but in a polymer alloy or polymer blend of two or more components, the melting start temperature of the resin material constituting the polymer alloy or polymer blend is When the temperature is higher than the deterioration starting temperature, it is effective because it has the effect of suppressing the thermal deterioration reaction. The present invention also has the above-mentioned side effects. That is, in the fiber-reinforced resin composition, there is no great difference in the effect of suppressing thermal deterioration even if the reinforcing fibers are added to either or both of the PEI resin pellets and the PEK resin pellets. However, in the molding method as described above, since the PEI resin pellets are melted first, the PEK resin pellets containing as many reinforcing fibers as possible, preferably all the reinforcing fibers are blended as much as possible. Since pellets are melted in molten PEI resin, fiber breakage is extremely small, and mechanical properties are such that reinforcing fibers are blended in PEI resin pellets or blended in both PEK resin pellets and PEI resin pellets. Much better than if you are. Therefore, in the present invention, the pellets containing reinforcing fibers are more effective than the short fiber pellets by the long fiber pellets produced by pultrusion and the like. Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.

Example 1 "Pictrex Polyether Sulfone P" from ICI (Imperial Chemical Industries)
A polyether sulfone solution was prepared using 20% by weight of ES 5003P ™, 40% by weight of dichloromethane and 40% by weight of 1,1,2-trichloroethane. A surface of acid-treated acrylic carbon fiber (trade name HTA, manufactured by Toho Rayon Co., Ltd.) roving was continuously dipped in a polyether sulfone solution at a speed of 60 m / Hr, dried to remove the solvent, and then 3 mm long. It was cut into pieces and made into chopped strands. This chopped strand was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C., and heat-treated in an air atmosphere for 10 hours. The carbon fiber chopped strands thus obtained and "Victrex polyetherketone PEK 220P (trademark)" manufactured by ICI as aromatic polyetherketone (PEK)
The ratio of fiber weight to fiber weight + PEK resin weight is 6
After dry blending to 6.6: 100,
Extruding while melting and kneading at an extrusion temperature of 380 ° C. with a 5 mm diameter extruder, and about 40% by weight carbon fiber reinforced PE
K resin pellets were obtained. Next, the pellets and Ultem 1000 (trademark) manufactured by CE (General Electric Co.) of the United States used as the polyetherimide resin (PEI) were melted at a temperature of 34.8 wt% carbon fiber reinforced PEK.
The resin / PEI resin was dry-blended and charged from the hopper of the injection molding machine. As the injection molding machine, JSW J-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. is used, and the resin temperature setting is 390 ° C / 380 ° C /
340 ° C./330° C. (temperature setting was shown in order from the nozzle side to the hopper side; the same applies below), injection pressure: primary 50%, secondary 90%, tertiary 60%, pressure retention time: primary 4.0 Second, second 5.0 seconds, third 30.0 seconds, mold temperature:
A fiber reinforced resin impeller 9 as shown in FIG. 4 was manufactured using the mold shown in FIG. 3 under molding conditions of 220 ° C. In FIG. 3, 10 is a mold gate, 11 is an upper mold, 12 is an assembly mold, 13 is an impeller-shaped portion, 14 is a lower mold, 15
Indicates a pin.

Example 2 The same chopped strands as used in Example 1 were placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C., and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) is dry-blended so that the ratio of the fiber weight to the fiber weight + PEK resin weight is 66.6: 100, and then extruded with a 65 mm extruder at an extrusion temperature of 380 ° C. while melt-kneading. Was carried out to obtain PEK resin pellets reinforced with about 40% by weight of carbon fiber. Next, GE Corp. (General
Pel resin pellets of about 20% by weight of carbon fiber based on Ultem 1000 ™ manufactured by Electric Co., Ltd., using the same carbon fiber and treatment method as used to manufacture the PEK resin pellets described above. 65
It was obtained at an extrusion temperature of 320 ° C. using an mm diameter extruder. The PEK resin pellets and PEI resin pellets thus obtained were melted at 36.8 wt% carbon fiber reinforced PEK resin /
It was dry-blended so as to be a PEI resin and charged from a hopper of an injection molding machine. As an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. is used, and a resin temperature setting is 390 ° C / 380 ° C / 340 ° C /
330 ° C. (temperature setting was shown in order from the nozzle side to the hopper side, the same applies hereinafter), injection pressure: primary 50%,
Secondary 90%, tertiary 60%, pressure holding time: primary 4.0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 220 ° C., using the mold shown in FIG. A fiber-reinforced resin impeller as shown in FIG. 4 was manufactured.

Example 3 The same chopped strand used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C., and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) is dry-blended so that the ratio of the fiber weight to the fiber weight + PEK resin weight is 53.8: 100, and then extruded with a 65 mm diameter extruder at an extrusion temperature of 380 ° C. while melt-kneading. Was carried out to obtain PEK resin pellets reinforced with about 35% by weight of carbon fiber. Next, GE Corp. (General
Pel resin pellets of carbon fiber reinforced PEI resin of about 10% by weight, based on Ultem 1000 (trademark) manufactured by Electric Co., Ltd. and using the same carbon fiber and treatment method as used for manufacturing the PEK resin pellets described above. 65
It was obtained at an extrusion temperature of 320 ° C. using an mm diameter extruder. The PEK resin pellets and PEI resin pellets thus obtained were melted to obtain 29.6% by weight of carbon fiber reinforced PEK resin /
It was dry-blended so as to be a PEI resin and charged from a hopper of an injection molding machine. As an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. is used, and a resin temperature setting is 390 ° C / 380 ° C / 340 ° C /
330 ° C. (temperature setting was shown in order from the nozzle side to the hopper side, the same applies hereinafter), injection pressure: primary 50%,
Secondary 90%, tertiary 60%, pressure holding time: primary 4.0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 220 ° C., using the mold shown in FIG. A fiber-reinforced resin impeller as shown in FIG. 4 was manufactured.

Example 4 The same chopped strand as used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C., and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) is dry-blended so that the ratio of fiber weight to fiber weight + PEK resin weight is 42.8: 100, and then extruded with a 65 mm diameter extruder at an extrusion temperature of 380 ° C. while melt-kneading. Then, about 30 wt% carbon fiber reinforced PEK resin pellets were obtained. Next, GE Corp. (General
Pel resin pellets of carbon fiber reinforced PEI resin of about 40 wt% based on Ultem 1000 ™ manufactured by Electric Co., Ltd. and using the same carbon fiber and treatment method used to make the PEK resin pellets described above. 65
It was obtained at an extrusion temperature of 320 ° C. using an mm diameter extruder. The PEK resin pellets and PEI resin pellets thus obtained were melted at 32.3 wt% carbon fiber reinforced PEK resin /
It was dry-blended so as to be a PEI resin and charged from a hopper of an injection molding machine. As an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. is used, and a resin temperature setting is 390 ° C / 380 ° C / 340 ° C /
330 ° C. (temperature setting was shown in order from the nozzle side to the hopper side, the same applies hereinafter), injection pressure: primary 50%,
Secondary 90%, tertiary 60%, pressure holding time: primary 4.0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 220 ° C., using the mold shown in FIG. A fiber-reinforced resin impeller as shown in FIG. 4 was manufactured.

Example 5 The same chopped strand as used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C. and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) is dry-blended so that the ratio of fiber weight to fiber weight + PEK resin weight is 42.8: 100, and then extruded with a 65 mm diameter extruder at an extrusion temperature of 380 ° C. while melt-kneading. Then, about 30 wt% carbon fiber reinforced PEK resin pellets were obtained. Next, GE Corp. (General
Pel resin pellets of carbon fiber reinforced PEI resin of about 45 wt% based on Ultem 1000 ™ manufactured by Electric Co., Ltd. and using the same carbon fiber and treatment method used to produce the PEK resin pellets described above. 65
It was obtained at an extrusion temperature of 320 ° C. using an mm diameter extruder. The PEK resin pellets and PEI resin pellets thus obtained were melted at 33.6 wt% carbon fiber reinforced PEK resin /
It was dry-blended so as to be a PEI resin and charged from a hopper of an injection molding machine. As an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. is used, and a resin temperature setting is 390 ° C / 380 ° C / 340 ° C /
330 ° C. (temperature setting was shown in order from the nozzle side to the hopper side, the same applies hereinafter), injection pressure: primary 50%,
Secondary 90%, tertiary 60%, pressure holding time: primary 4.0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 220 ° C., using the mold shown in FIG. A fiber-reinforced resin impeller as shown in FIG. 4 was manufactured.

Example 6 The same chopped strand as used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C., and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) is dry-blended so that the ratio of the fiber weight to the fiber weight + PEK resin weight is 66.6: 100, and then extruded by melt-kneading at an extrusion temperature of 380 ° C. with a 65 mm diameter extruder. Was carried out to obtain PEK resin pellets reinforced with about 40% by weight of carbon fiber. Then the above-mentioned pellets and US GE used as polyetherimide resin (PEI)
Ultem 100 manufactured by General Electric Co., Ltd.
0 (trademark) was dry blended so as to be a carbon fiber reinforced PEK resin / PEI resin of 28.6% by weight when melted, and charged from a hopper of an injection molding machine. As an injection molding machine, JSW J-75SSII manufactured by Japan Steel Works, Ltd.
Using A injection molding machine, resin temperature setting: 390 ° C / 38
0 ° C / 340 ° C / 330 ° C (temperature setting was shown in order from the nozzle side to the hopper side, the same shall apply hereinafter), injection pressure: primary 50%, secondary 90%, tertiary 60%, dwell time:
Using the mold shown in FIG. 3 under the molding conditions of primary 4.0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, and mold temperature: 220 ° C., FIG.
A fiber-reinforced resin impeller as shown in was produced.

Example 7 The same chopped strand as used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C., and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) is dry-blended so that the ratio of fiber weight to fiber weight + PEK resin weight is 25.0: 100, and then extruded with a 65 mm diameter extruder at an extrusion temperature of 380 ° C. while melt-kneading. Was carried out to obtain PEK resin pellets reinforced with about 20% by weight of carbon fiber. Next, GE Corp. (General
Pel resin pellets of carbon fiber reinforced PEI resin of about 45 wt% based on Ultem 1000 ™ manufactured by Electric Co., Ltd. and using the same carbon fiber and treatment method used to produce the PEK resin pellets described above. 65
It was obtained at an extrusion temperature of 320 ° C. using an mm diameter extruder. The PEK resin pellets and the PEI resin pellets thus obtained were melted to obtain 32.5% by weight of carbon fiber reinforced PEK resin /
It was dry-blended so as to be a PEI resin and charged from a hopper of an injection molding machine. As an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. is used, and a resin temperature setting is 390 ° C / 380 ° C / 340 ° C /
330 ° C. (temperature setting was shown in order from the nozzle side to the hopper side, the same applies hereinafter), injection pressure: primary 50%,
Secondary 90%, tertiary 60%, pressure holding time: primary 4.0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 220 ° C., using the mold shown in FIG. A fiber-reinforced resin impeller as shown in FIG. 4 was manufactured.

Example 8 The same chopped strand as used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C. and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) is dry-blended so that the ratio of the fiber weight to the fiber weight + PEK resin weight is 81.8: 100, and then extruded by melt-kneading with a 65 mm diameter extruder at an extrusion temperature of 380 ° C. Was carried out to obtain PEK resin pellets reinforced with about 45% by weight of carbon fiber. Next, GE Corp. (General
Pel resin pellets of about 20% by weight of carbon fiber based on Ultem 1000 ™ manufactured by Electric Co., Ltd., using the same carbon fiber and treatment method as used to manufacture the PEK resin pellets described above. 65
It was obtained at an extrusion temperature of 320 ° C. using an mm diameter extruder. The PEK resin pellets and PEI resin pellets thus obtained were melted at 37.1 wt% carbon fiber reinforced PEK resin /
It was dry-blended so as to be a PEI resin and charged from a hopper of an injection molding machine. As an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. is used, and a resin temperature setting is 390 ° C / 380 ° C / 340 ° C /
330 ° C. (temperature setting was shown in order from the nozzle side to the hopper side, the same applies hereinafter), injection pressure: primary 50%,
Secondary 90%, tertiary 60%, pressure holding time: primary 4.0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 220 ° C., using the mold shown in FIG. A fiber-reinforced resin impeller as shown in FIG. 4 was manufactured.

Example 9 The same chopped strand as used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C., and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) is dry-blended so that the ratio of fiber weight to fiber weight + PEK resin weight is 42.8: 100, and then extruded with a 65 mm diameter extruder at an extrusion temperature of 380 ° C. while melt-kneading. Then, about 30 wt% carbon fiber reinforced PEK resin pellets were obtained. Next, GE Corp. (General
Pel resin pellets of carbon fiber reinforced PEI resin of about 45 wt% based on Ultem 1000 ™ manufactured by Electric Co., Ltd. and using the same carbon fiber and treatment method used to produce the PEK resin pellets described above. 65
It was obtained at an extrusion temperature of 320 ° C. using an mm diameter extruder. The PEK resin pellets and PEI resin pellets thus obtained were melted at 36.9 wt% carbon fiber reinforced PEK resin /
It was dry-blended so as to be a PEI resin and charged from a hopper of an injection molding machine. As an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. is used, and a resin temperature setting is 390 ° C / 380 ° C / 340 ° C /
330 ° C. (temperature setting was shown in order from the nozzle side to the hopper side, the same applies hereinafter), injection pressure: primary 50%,
Secondary 90%, tertiary 60%, pressure holding time: primary 4.0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 220 ° C., using the mold shown in FIG. A fiber-reinforced resin impeller as shown in FIG. 4 was manufactured.

Comparative Example 1 The same chopped strand as used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C. and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) "and polyetherimide (PEI) manufactured by GE (General Electric Co.), USA, Ultem 1
After 000 (trademark) was dry-blended in the ratio shown in Table 1, the mixture was extruded with a 65 mm diameter extruder at an extrusion temperature of 380 ° C. while melt-kneading to obtain a uniform blended pellet. Next, using the above-mentioned uniformly compounded pellets as an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. was used, and a resin temperature setting was 400 ° C / 400 ° C / 3.
90 ° C./370° C. (temperature setting is shown in order from the nozzle side to the hopper side; the same applies hereinafter), injection pressure: 50% primary, 90% secondary, 60% tertiary, pressure holding time: primary 4.
0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 22
A fiber reinforced resin impeller as shown in FIG. 4 was manufactured using the mold shown in FIG. 3 under molding conditions of 0 ° C.

Comparative Example 2 The same chopped strand as used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C. and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) "and polyetherimide (PEI) manufactured by GE (General Electric Co.), USA, Ultem 1
After 000 (trademark) was dry-blended in the ratio shown in Table 1, the mixture was extruded with a 65 mm diameter extruder at an extrusion temperature of 380 ° C. while melt-kneading to obtain a uniform blended pellet. Next, using the above-mentioned uniformly compounded pellets as an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. was used, and a resin temperature setting was 400 ° C / 400 ° C / 3.
90 ° C./370° C. (temperature setting is shown in order from the nozzle side to the hopper side; the same applies hereinafter), injection pressure: 50% primary, 90% secondary, 60% tertiary, pressure holding time: primary 4.
0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 22
A fiber reinforced resin impeller as shown in FIG. 4 was manufactured using the mold shown in FIG. 3 under molding conditions of 0 ° C.

Comparative Example 3 The same chopped strand as used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C. and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) "and Polyetherimide (PEI) as Ultem 1 manufactured by GE (General Electric Co.), USA
After 000 (trademark) was dry-blended in the ratio shown in Table 1, the mixture was extruded with a 65 mm diameter extruder at an extrusion temperature of 380 ° C. while melt-kneading to obtain a uniform blended pellet. Next, using the above-mentioned uniformly compounded pellets as an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. was used, and a resin temperature setting was 400 ° C / 400 ° C / 3.
90 ° C./370° C. (temperature setting is shown in order from the nozzle side to the hopper side; the same applies hereinafter), injection pressure: 50% primary, 90% secondary, 60% tertiary, pressure holding time: primary 4.
0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 22
A fiber reinforced resin impeller as shown in FIG. 4 was manufactured using the mold shown in FIG. 3 under molding conditions of 0 ° C.

Comparative Example 4 The same chopped strand as used in Example 1 was placed in a stainless steel pad and placed in an electric furnace heated to 370 ° C. and heat-treated in an air atmosphere for 10 hours. Carbon fiber chopped strands thus obtained,
Aromatic Polyetherketone (PEK) manufactured by ICI as "Victrex Polyetherketone PEK 220P"
(Trademark) "and polyetherimide (PEI) manufactured by GE (General Electric Co.), USA, Ultem 1
After 000 (trademark) was dry-blended in the ratio shown in Table 1, the mixture was extruded with a 65 mm diameter extruder at an extrusion temperature of 380 ° C. while melt-kneading to obtain a uniform blended pellet. Next, using the above-mentioned uniformly compounded pellets as an injection molding machine, a JSWJ-75SSIIA injection molding machine manufactured by Japan Steel Works, Ltd. was used, and a resin temperature setting was 400 ° C / 400 ° C / 3.
90 ° C./370° C. (temperature setting is shown in order from the nozzle side to the hopper side; the same applies hereinafter), injection pressure: 50% primary, 90% secondary, 60% tertiary, pressure holding time: primary 4.
0 seconds, secondary 5.0 seconds, tertiary 30.0 seconds, mold temperature: 22
A fiber reinforced resin impeller as shown in FIG. 4 was manufactured using the mold shown in FIG. 3 under molding conditions of 0 ° C.

In Examples 1 to 9 and Comparative Examples 1 to 4 described above, the influence of deterioration appears as a change in the mechanical properties and the rate of non-defective products.
The test piece 16 (w ₁ = 2) shown in FIG. 5 (c) was obtained by continuously molding 0 pieces and inspecting internal defects by X-rays and cutting out from the part A shown in FIGS. 5 (a) and 5 (b) of the molded product impeller 9. .6 mm, w
₂ = 3.5 mm, L = 15.0 mm, t = 2.0 mm) tensile strength of 1st, 100th, 200th, 250th,
The measurement was performed using the 300th molded impeller made of fiber reinforced resin. Further, this cut-out test piece was dissolved with concentrated sulfuric acid to measure the length of the carbon fiber. The tensile test has a test speed of 0.
It was carried out at 5 m / min and 150 ° C. Examples 1 to 9 in Table 1
Regarding the fiber content of PEK resin pellets and PEI resin pellets, the weight mixing ratio of PEK resin pellets and PEI resin pellets, and PEK resin and PEI when melted
The weight ratio of the resin and the weight fraction of the carbon fiber at the time of melting are shown. For Comparative Examples 1 to 4, the weight ratio of the PEK resin and the PEI resin and the weight fraction of the carbon fiber are shown. Table 2 shows the results of each test described above.

[Table 1]

[Table 2] As is clear from the test results of the examples and the comparative examples shown in Table 2, the frequency of occurrence of defects clearly increases with the increase in the production quantity in the comparative examples, but no such sign is observed in the examples. .. Further, the results of the average fiber length and the tensile strength of the test piece cut out from the impeller made of the fiber reinforced resin proved that the present invention is very effective.

As described above, in the present invention, PE
In order to suppress gel-like deterioration products generated when manufacturing parts for internal combustion engines using the K resin / PEI resin composition, P
After the dry blending of EK resin and PEI resin, thermal deterioration is reduced by omitting the manufacturing process of pelletizing, and from the hopper of the injection molding machine or the extrusion molding machine in the state of PEK resin pellets and PEI resin pellets from the hopper. PEI can be used by making the temperature near the hopper of the cylinder higher than the melting start temperature or the flow start temperature of the PEI resin, making the most of the merit of charging.
The resin was melted first, and the PEK resin contained in the melted PEI resin was plasticized by setting the cylinder temperature near the cylinder to the melting start temperature or the flow start temperature of the PEK resin.

According to the present invention, as described in the examples, the cylinder temperature on the hopper side can be reduced by about 50 ° C. as compared with the case where pellets alloyed in advance are used, which results in fiber reinforced of extremely excellent quality. It is clear from the various test results shown in Table 2 that the resin impeller can be provided. As described above, when the polymer alloyed pellets are used, it is impossible to set the cylinder temperature as shown in the examples, and according to the present invention, the PEI resin is plasticized first. It is also noteworthy that the temperature near the nozzle can also be reduced.

Further, as is clear from the measurement results of the average fiber length and the tensile strength of the cut-out test pieces shown in Table 2, the PEI resin is melted first, so that the frequency of breakage of the carbon fibers in the PEK resin pellets is high. It has also been successful in imparting better mechanical properties than when using polymer alloyed pellets to be reduced.

Further, although the fiber-reinforced resin impeller is taken up in the examples, it is not limited to the fiber-reinforced resin impeller, but parts for internal combustion engines, such as valve lifters, valve cotters, valve spring retainers, water pump vanes, water pumps. Housing, gear for oil pump, oil pump housing, rocker cover,
It can also be applied to the manufacture of oil vans, throttle chambers, camshaft drive gears, throttle chambers, air ducts, various pulleys, fuel / water / oil connectors, intake manifolds, connecting rods / piston pins, camshafts, piston skirts, etc. is there.
In this example, the case of carbon fiber reinforcement was taken up, but if necessary, talc, mica, a filler such as glass beads,
Glass fibers, aramid fibers, fibrous reinforcing materials such as ceramic fibers, stabilizers / colorants and the like may be mixed within a range that does not impair the quality of the resin composition and the molded product.

The PEK resin and PEI in the present invention are
The blending range of the resin is aromatic polyether ketone 95-60.
%, Preferably 90-60% by weight, polyetherimide 5-40% by weight, preferably 10-40% by weight, aromatic polyetherketone exceeds 95% by weight, polyetherimide 5% by weight. If it is less than 100%, the improvement in the high temperature strength of the intended resin composition is insufficient, and if the aromatic polyether ketone is less than 60% by weight and the polyetherimide is more than 40% by weight, a resin composition obtained. As described in JP-A-2-269764, the excellent chemical properties of aromatic polyether ketone are lost. When carbon fiber is blended, it is not preferable to blend more than 45% by weight in terms of weight fraction because the fluidity is lowered and it is difficult to be uniform, but when carbon fiber is mainly blended with PEK resin pellets, PEI is not preferable. Since the resin melts first, the carbon fibers in the PEK resin pellets tend to be uniformly dispersed inside the cylinder.
It is also possible in some cases to incorporate up to 0% by weight of carbon fibers. On the other hand, if it is less than 20% by weight, there is no effect. Further, it is preferable that 45% or more of the carbon fibers premixed are contained in the polyetherketone resin pellets. In particular, when expecting an increase in average fiber length and an improvement in tensile strength, which are secondary effects of the present invention, as can be seen from the test results of Example 9 and Comparative Example 4 (see Table 2), carbon fiber At least 4
If 5% or more is not blended in PEK resin pellets,
It is difficult to obtain better tensile strength from the beginning of production than when using polymer alloyed pellets (about 44.0% of carbon fibers are contained in PEK resin pellets in Example 9).

[0046]

EFFECTS OF THE INVENTION According to the present invention, it is possible to minimize the generation of a deterioration product generated during molding of a PEK resin / PEI resin composition, and an internal combustion engine component having excellent quality, for example, a fiber-reinforced resin impeller. And the expansion of the cylinder cleaning cycle. Furthermore, it became possible to obtain mechanical properties superior to those obtained by using polymer alloy pellets.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a main part of an injection molding machine showing an example of temperature setting during injection molding when PEK pellets and PEI pellets are used.

FIG. 2 is a cross-sectional view showing a main part of an injection molding machine showing an example of temperature setting during injection molding when PEK / PEI alloy pellets are used.

FIG. 3 is a cross-sectional view of an injection molding die of a fiber-reinforced resin impeller.

FIG. 4 is a perspective view of a fiber-reinforced resin impeller.

[Figure 5]

[A] is a front view of an injection-molded resin impeller,

[B] is a cross-sectional view of an injection-molded resin impeller,

[C] is a perspective view of a test piece cut out from an injection-molded resin impeller.

[Explanation of symbols]

 1 Nozzle 2 Heater 3 Screw 4 Cylinder 5 Hopper 6a PEK pellet and PEI pellet 6b PEK / PEI alloy pellet 7 Hydraulic cylinder 8 Hydraulic motor 9 Fiber reinforced resin impeller 10 Gate 11 Upper mold 12 Assembly mold 13 Impeller shape part ( Capability) 14 Lower mold 15 Pin 16 Test piece

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number of the agency FI technical display area F02C 7/00 D 7910-3G // B29C 45/00 7344-4F 47/02 7717-4F (C08L 73/00 79:08) 9285-4J B29K 73:00 79:00 105: 06 B29L 31:30 4F

Claims (1)

[Claims] 1. The following formula for forming a matrix resin: A polyetherketone resin having a repeating unit represented by the following formula: The polyetherimide resin having a repeating unit represented by is used so that 95-60% by weight of the total amount of both resins is a polyetherketone resin and 5-40% by weight is a polyetherimide resin. A first step of mixing the polyetherketone resin pellets and the polyetherketone resin pellets, which are formed by blending the resin or both resins with the carbon resin so as to be 25 to 45% by weight of the total of the resin and the carbon fiber, The mixed pellet obtained in the first step is heated to a temperature at which the polyetherimide resin starts to flow or melts, and the polyetherketone resin is contained in the plasticized and melted polyetherimide resin. The polyetherketone resin to a temperature above the flow start temperature or melting start temperature of the polyetherketone resin, A melt mixing step of a second step in which the terimide resin and the carbon fibers are uniformly mixed, and a third step of molding an internal combustion engine part by injection molding or extrusion molding of the melt mixture obtained in the second step. ,
A method for manufacturing a component for an internal combustion engine, comprising: