JP2002284980A - Aromatic polyether ketone-based resin molded product and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber-reinforced aromatic polyether ketone-based resin molded product useful for a slide member or the like and having a reduced coefficient of dynamic friction. SOLUTION: This aromatic polyether ketone-based molded product is characterized in that a lubricating oil is impregnated into a molded product comprising 20-98 mass % aromatic polyether ketone-based resin, 2-50 mass % fibrous reinforcing material and 0-30 mass % oil-absorbing component. The method for producing the aromatic polyether ketone-based resin molded product is characterized in that the method comprises a molding step for molding the resin composition, and an impregnating step for impregnating the molded product obtained by the molding step with the lubricating oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polyether ketone resin molded article having a reduced dynamic friction coefficient, and a method for producing the same.

[0002]

2. Description of the Related Art Aromatic polyetherketone resins are thermoplastic crystalline resins and have excellent properties such as high impact properties, heat resistance, hydrolysis resistance, radiation resistance and chemical resistance. It is widely used in applications such as parts, machine parts, aircraft parts, and electric / electronic parts.

On the other hand, when a sliding portion is formed of a fiber-reinforced resin molded product in an automobile part, a machine part, an aircraft part, or the like, the resin used is required to have a particularly low coefficient of friction and wear resistance. Therefore, various engineering plastics satisfying such performance have been used for the sliding portion, and aromatic polyetherketone resin is one of them. That is, an aromatic polyetherketone resin reinforced with a fibrous reinforcing material such as carbon fiber is known as a material that can be used for sliding parts.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a molded article of the above-mentioned fiber-reinforced aromatic polyetherketone resin, while maintaining excellent various characteristics and further reducing the dynamic friction coefficient, thereby improving the sliding property. It is intended to make a molded product more suitable for applications such as moving parts.

That is, an object of the present invention is to provide an aromatic polyetherketone resin molded article having excellent mechanical strength, heat resistance and fluidity, and having a reduced dynamic friction coefficient, and
It is to provide a manufacturing method thereof.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above-mentioned object, and as a result, after manufacturing a molded article comprising at least an aromatic polyetherketone resin and a fibrous reinforcing material. By impregnating the molded product with lubricating oil, it was found that the coefficient of kinetic friction was extremely reduced, and the present invention was completed.

That is, according to the present invention, an aromatic polyetherketone resin is used in an amount of 20 to 98% by mass and a fibrous reinforcing material of 2 to 50%.
A molded article of an aromatic polyetherketone resin, which is obtained by impregnating a molded article made of a resin composition containing an oil-absorbing component with 0 to 30% by mass with a lubricating oil.

Further, the present invention provides a molding method for molding a resin composition containing 20 to 98% by mass of an aromatic polyetherketone resin, 2 to 50% by mass of a fibrous reinforcing material, and 0 to 30% by mass of an oil absorbing component. A method for producing an aromatic polyether ketone resin molded article, comprising: a step of impregnating a molded article obtained by the molding step with a lubricating oil.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic polyetherketone resin used in the present invention is a thermoplastic resin having a repeating unit in which a phenyl group is bonded by an ether group and a ketone group.

As a typical method for producing an aromatic polyetherketone resin, dialkali metal salts of various bisphenols and a ketone group in which two halogen atoms are in the ortho or para position, preferably para position, or Depending on the method, a method of performing a polycondensation reaction with an aromatic dihalite substituted and activated by a sulfonyl group in the presence of, for example, an aromatic sulfone as a solvent may be mentioned. Specifically, for example, Japanese Patent Application Laid-Open No. 50-27897,
JP-A-51-119797, JP-A-52-380
No. 00, JP-A-54-90296, JP-B-5
It can be produced by the methods described in JP-A-5-23574 and JP-B-56-2091.

Examples of the aromatic polyetherketone resin include polyetheretherketone, polyetherketone, polyetherketoneetherketoneketone, and the like. These can be used alone or in combination of two or more. Particularly preferred is a resin having a repeating unit represented by the following formula (I), (II) or (III).

[0012]

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[0013] Among the commercially available aromatic polyetherketone resins, typical ones include a polyetheretherketone manufactured by Victrex, comprising a repeating unit represented by the above formula (I), and a compound represented by the above formula (II) Victrex polyether ketone comprising a repeating unit represented by the formula (I)
II) BASF Ultratrapek consisting of repeating units
(Product name).

As the fibrous reinforcing material used in the present invention, for example, carbon fiber, glass fiber, potassium titanate fiber,
Various materials such as ceramic fibers, boron fibers, silicon carbide fibers, silicon nitride fibers, asbestos fibers, rock wool fibers, aramid fibers, alumina fibers, and stainless steel fibers can be used. Of these, carbon fibers are particularly preferred. Carbon fibers are fibers obtained by firing organic fibers. Specific examples thereof include acrylic carbon fibers, rayon carbon fibers, lignin carbon fibers, pitch carbon fibers, and the like.

The oil-absorbing component used as required in the present invention refers to a component capable of promoting the impregnation of the molded product with the lubricating oil at least in the lubricating oil impregnation step. Specific examples thereof include activated carbon, porous silica, graphite, and carbon powder.

In the present invention, a resin composition containing 20 to 98% by mass of the aromatic polyether ketone resin described above, 2 to 50% by mass of a fibrous reinforcing material, and 0 to 30% by mass of an oil absorbing component is used. Prepare. The blending amount of the aromatic polyetherketone resin is particularly preferably 50 to 95% by mass,
60-90 mass% is more preferable. The amount of the fibrous reinforcing material is particularly preferably 5 to 40% by mass, more preferably 10 to 30% by mass. The compounding amount of the oil absorbing component is, in particular, 0.1.
It is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 3% by mass.

The resin composition may contain other fillers in an appropriate amount, if desired. The fillers include, for example, a wear resistance improving material, an electric property improving material, a tracking resistance improving material, an acid resistance improving material, a thermal conductivity improving material, a metal oxide, a coloring agent, a release agent, various types of stable Agents, plasticizers and the like. In addition, other thermoplastic resins and thermosetting resins can be added in an appropriate amount according to the purpose within a range that does not impair the purpose of the present invention.

In producing this resin composition, conventionally known methods for producing various resin compositions can be applied.
In particular, it is preferable to manufacture by the following methods (1) and (2).

(1) aromatic polyetherketone resin,
Fibrous reinforcement and, if desired, oil-absorbing and other ingredients, mortar, Henschel mixer, drum blender,
Premixing is performed using a tumbler blender, a ball mill, a ribbon blender, and the like, and then kneaded with a usual melt extruder, melt mixer, hot roll, or the like, and then pelletized or powdered.

(2) aromatic polyether ketone resin,
And if desired, the oil-absorbing component and other components are dissolved or suspended in an organic solvent in advance, the fibrous reinforcing material is immersed in this solution or suspension, and then the solvent is removed in a hot-air oven, and then pelletized or Make powder.

As the organic solvent used in the above method (2), for example, N, N-dimethylformamide, N, N
N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxy Ethane, bis (2-methoxyethyl) ether,
1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethylsulfoxide, dimethylsulfone , Tetramethylurea, hexamethylphosphoramide and the like. These organic solvents can be used alone or in combination of two or more.

The pellet or powdery resin composition obtained as described above is molded by various conventionally known molding methods such as an injection molding method, an extrusion molding method, a compression molding method and a transfer molding method. To obtain an aromatic polyether ketone resin molded article having the following shape. Since this molded product is mainly composed of an aromatic polyetherketone resin and a fibrous reinforcing material, it has excellent physical properties such as heat resistance and mechanical properties, and is suitable for use in, for example, structural members, mechanical parts, and automobile parts. Very useful. In addition, mechanical properties, heat resistance, and the like can be further improved by subjecting the molded article to a heat treatment at an appropriate temperature for the purpose of removing or crystallizing residual stress.

In the present invention, the molded article is further impregnated with a lubricating oil to reduce the dynamic friction coefficient of the molded article. This impregnation step can be performed, for example, by immersing the molded article in heated lubricating oil.

The lubricating oil used here may be any lubricating oil capable of impregnating an aromatic polyetherketone resin molded article in a desired amount, and the specific type thereof is not particularly limited. However, when the molded article of the present invention is used for a sliding portion, it is particularly preferable to use a lubricating oil used for the sliding. The amount of the lubricating oil impregnated is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and particularly preferably 0.1 to 1 part by mass, per 100 parts by mass of the molded article.

The temperature in the impregnation step is from 30 ° C. to 200
C is preferable, and 50C to 180C is more preferable. The pressure of the system in the impregnation step is preferably atmospheric pressure, reduced pressure, or reduced pressure, and particularly preferably −200.
It is more preferable to reduce the pressure from mmHg (7.47 × 10 ⁴ Pa) to a vacuum. The time of the impregnation step is preferably 0.1 to 24 hours, more preferably 10 to 24 hours.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 A resin composition was prepared by mixing 80 parts of an aromatic polyetheretherketone (PEEK, trade name, manufactured by Victrex) and carbon fiber (Vesfite, trade name, manufactured by Toho Rayon Co., Ltd.). Then, a plate-shaped molded product having a size of 50 mm × 50 mm × 3 mm was obtained by injection molding.

Next, the plate-shaped molded product is placed in a closed container, and the temperature is 100 ° C., the pressure is −760 mmHg (vacuum).
Under the conditions described above, the product was immersed in a lubricating oil (manufactured by Nissan Motor Co., Ltd., trade name: Nissanmatic Fluid D) for 24 hours to obtain a molded article of an aromatic polyetherketone resin whose surface was impregnated with the lubricating oil. When the amount of the lubricating oil impregnated in this molded product was measured, it was found that the amount of the lubricating oil impregnated with respect to 100 parts of the molded product was 0.1%.
Three copies.

In order to measure the dynamic friction coefficient of this test piece (aromatic polyetherketone resin molded product), a low-speed thrust friction and wear tester with a furnace was used.
The test time is 4 hours, the lubricating oil is the same as the impregnated lubricating oil, the test surface pressure P is 50 kgf / cm ² (4.9 MPa), and the test speed V is At a setting of 12 m / min, a thrust test with the ring SS-41 was performed. As a result, it was found that the dynamic friction coefficient (μ ′) of this test piece was as low as 0.02.

Example 2 Example 1 was repeated except that the blending amount of carbon fiber was reduced to 10 parts, and 10 parts of porous carbon (manufactured by Kansai Thermochemical Co., Ltd., Maxopoop) was blended instead. Similarly, an aromatic polyetherketone resin molded product having a surface impregnated with a lubricating oil was obtained. When the amount of lubricating oil impregnated in this molded article was measured, it was 0.3 part with respect to 100 parts of the molded article. The coefficient of kinetic friction (μ ′) was as low as 0.02.

Example 3 Except that the blending amount of carbon fiber was reduced to 10 parts, and instead of graphite (manufactured by Nippon Graphite Co., trade name, special CP), 10 parts were blended.
In the same manner as in Example 1, an aromatic polyetherketone resin molded article having a surface impregnated with a lubricating oil was obtained. When the impregnation amount of the lubricating oil in this molded product was measured, the molded product 100
Parts to 0.3 parts. Further, its dynamic friction coefficient (μ ′) was as low as 0.01. Further, the thrust test was performed by increasing the test surface pressure P to 70 kgf / cm ² (6.89 MPa), and the dynamic friction coefficient (μ ′) was 0.0.
It was a low value of 2.

<Examples 4 to 6> The compounding amount of carbon fiber was reduced to 10 parts. Instead, in Example 4, 10 parts of porous silica SiO ₂ (manufactured by Asahi Glass Co., Ltd., trade name: Sunsphere), Example 5 In Example 6, except that phenol-based activated carbon (manufactured by Kanebo Co., trade name: Bellfine) was blended, and in Example 6, granular activated carbon (manufactured by Luck Co., trade name: G activated carbon), the lubricating oil was applied to the surface in the same manner as in Example 1. To obtain an aromatic polyether ketone resin molded article. When the impregnation amount of the lubricating oil in this molded product was measured, Example 4
0.3 parts for 100 parts of each of the molded products Nos. 6 to 6. The dynamic friction coefficient (μ ′) was as low as 0.03.

Example 7 The compounding amount of the aromatic polyetheretherketone was changed to 82 parts and the compounding amount of the carbon fiber was changed to 16 parts.
An aromatic polyetherketone resin molded product having a surface impregnated with a lubricating oil was obtained in the same manner as in Example 1, except that a resin composition containing 2 parts of Ketjen EC (trade name) was used. When the amount of lubricating oil impregnated in this molded article was measured, it was 0.3 part with respect to 100 parts of the molded article. Also,
The coefficient of kinetic friction (μ ′) was as low as 0.02.

Example 8 The amount of the aromatic polyetheretherketone was changed to 70 parts, and carbon fiber (HTA-trade name, manufactured by Toho Rayon Co., Ltd.) was used as a fiber reinforcing material.
(C6-TX) Except that 30 parts were used, an aromatic polyetherketone resin molded article having a surface impregnated with a lubricating oil was obtained in the same manner as in Example 1. The amount of the lubricating oil impregnated in this molded product was measured and found to be 0.4 part with respect to 100 parts of the molded product. The dynamic friction coefficient (μ ') is
It was a low value of 0.02. Furthermore, were subjected to thrust test by increasing the test surface pressure P to 60kgf / cm ² (5.88MPa), the dynamic friction coefficient (mu ') was also 0.02.

<Examples 9 and 10> As fibrous reinforcing materials,
In Example 9, a glass fiber (manufactured by Nippon Sheet Glass Co., Ltd., trade name RE
20 parts of S-TP-78) and 20 parts of potassium titanate fiber (Tismo D, manufactured by Otsuka Chemical Co., Ltd.) in Example 10, except that lubricating oil was applied to the surface in the same manner as in Example 1. An impregnated aromatic polyetherketone resin molded product was obtained. When the impregnation amount of the lubricating oil in this molded article was measured, the amount of the oil impregnated to 100 parts of each molded article of Examples 9 and 10 was 0.1%.
Three copies. The dynamic friction coefficient (μ ′) was as low as 0.02.

<Comparative Examples 1-3> In Examples 1-3,
The coefficient of kinetic friction (μ ′) of the plate-shaped molded product before impregnation with the lubricating oil was measured in the same manner. The dynamic friction coefficients of Comparative Examples 1 to 3 were 0.04, 0.03, and 0.03, respectively [P = 50.
kgf / cm ² (4.9 MPa)], which is higher than that of the molded product after impregnation with lubricating oil. Further, for the molded product of Comparative Example 3, the test surface pressure P
Was increased to 70 kgf / cm ² (6.89 MPa). However, the dynamic frictional force increased during the test, and overload occurred 2.3 hours after the start of the test, so that a final measured value could not be obtained.

<Comparative Examples 4 and 5> In Examples 7 and 8, the kinetic friction coefficient (μ ') of the plate-like molded product before impregnation with the lubricating oil was used.
Was similarly measured. The kinetic friction coefficients of Comparative Examples 4 and 5 were 0.03 [P = 50 kgf / cm ² (4.9 MP).
a)], which was higher than that of the molded article after the lubricating oil impregnation. Further, for the molded product of Comparative Example 5, similarly to Example 8, the test surface pressure P was set to 60 kgf / cm ² (5.
When the dynamic friction coefficient when the pressure was increased to 88 MPa) was also measured, the dynamic friction coefficient was 0.04.

Comparative Example 6 The procedure of Example 1 was repeated except that the blending amount of the aromatic polyetheretherketone was changed to 100 parts, the fiber reinforcing material was not blended, and the lubricating oil was not impregnated. A polyetherketone resin molded product was obtained. Its dynamic friction coefficient is 0.04 [P = 50 kgf / cm ²
(4.9 MPa)].

<Comparative Examples 7 and 8> In Examples 9 and 10, the kinetic friction coefficient (μ ') of the plate-like molded product before the impregnation with the lubricating oil was measured in the same manner. The dynamic friction coefficients of Comparative Examples 7 and 8 were both 0.04 [P = 50 kgf / cm ² (4.
9 Pa)], which is higher than that of the molded product after the impregnation with the lubricating oil.

The results of Examples 1 to 10 and Comparative Examples 1 to 8 are summarized in Tables 1 and 2 below.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

As described above, according to the present invention,
A fiber-reinforced aromatic polyetherketone-based resin molded article having excellent mechanical strength, heat resistance, and fluidity and having a reduced dynamic friction coefficient can be obtained. A resin molded product exhibiting such excellent characteristics is industrially very useful as a sliding member in various fields such as an automobile part, a machine part, and an aircraft part.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kayako Yanagihara 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Masayuki Makihara 1-2-9 Shiba Park, Minato-ku, Tokyo Victrex・ F-term in MC Co., Ltd.

Claims (8)

[Claims] 1. An aromatic polyetherketone resin 20 to
An aromatic poly, characterized in that a molded article comprising a resin composition containing 98% by mass, 2 to 50% by mass of a fibrous reinforcing material, and 0 to 30% by mass of an oil absorbing component is impregnated with a lubricating oil. Ether ketone resin molded product. 2. The aromatic polyether ketone resin molded article according to claim 1, wherein 0.01 to 5 parts by mass of lubricating oil is impregnated with respect to 100 parts by mass of the molded article. 3. The aromatic polyetherketone resin according to claim 1, wherein the aromatic polyetherketone resin is at least one resin selected from the group consisting of polyetheretherketone, polyetherketone, and polyetherketoneetherketoneketone. Polyetherketone resin composition. 4. The aromatic polyether ketone resin composition according to claim 1, wherein the fibrous reinforcing material is a carbon fiber. 5. The aromatic polyether ketone resin according to claim 1, wherein the oil absorbing component is at least one component selected from the group consisting of activated carbon, porous silica, graphite and carbon powder. Composition. 6. An aromatic polyether ketone resin 20 to
A molding step of molding a resin composition containing 98% by mass, 2 to 50% by mass of a fibrous reinforcing material, and 0 to 30% by mass of an oil-absorbing component; and impregnating a molded product obtained by the molding step with a lubricating oil. And a method of producing an aromatic polyetherketone-based resin molded product. 7. The method for producing an aromatic polyether ketone resin composition according to claim 6, wherein the impregnation step is performed by immersing the molded article in heated lubricating oil. 8. The aromatic polyether ketone resin according to claim 7, wherein the impregnating step is performed by immersing the molded article in lubricating oil heated to 30 ° C. to 200 ° C. under atmospheric pressure, reduced pressure or vacuum. A method for producing the composition.