JP2002105306A - Polyether aromatic ketone resin composition and film and sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the sliding properties of a polyether aromatic ketone resin and produce a resin molded product without damage and abrasion in both itself and others and excellent in moldability. SOLUTION: This resin composition comprises 100 pts.wt. of a polyether aromatic ketone resin and 1-100 pts.wt. of spherical carbon particles having 0.1-100 μm average particle diameter. The film and sheet comprise the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent properties as a sliding resin material based on polyether aromatic ketone. For example, electrical and electronic equipment, aviation equipment, space equipment, automobile equipment, transportation equipment,
The present invention relates to sliding materials such as gears, cams, pulleys, sleeves, bearings, washers, sealing materials, cushion seats, valve parts, and protective covers, which are parts of office equipment, general industrial equipment, and other various equipment.

[0002]

2. Description of the Related Art Hitherto, polyether aromatic ketone resins are well known as engineering plastics having excellent mechanical, chemical, thermal and abrasion resistance. The polyether aromatic ketone resin alone has a high friction coefficient, but the addition of the fluororesin significantly improves the slidability and lowers the friction coefficient (Japanese Patent Laid-Open No. 6-1).
No. 36255) is well known. However, while the self-lubricating properties are improved, the amount of wear increases when used under high load conditions or when the frictional contact speed is extremely high due to the decrease in the mechanical strength and load resistance of the molded product. was there.

[0003] By adding a solid lubricant such as glass fiber, aramid fiber, carbon fiber, molybdenum disulfide or the like to a polyether aromatic ketone resin, the mechanical strength and slidability thereof are remarkably improved and the amount of wear is reduced ( JP-A-1-282
252, JP-A-1-282253). However, when the sliding partner material is a relatively soft metal, particularly an aluminum alloy or a stainless steel material, the added fibrous reinforcing material is liable to be worn, and in a remarkable case, abnormal wear occurs. is there.

[0004] The cause of such abnormal wear is mainly that the tip of a relatively hard fibrous reinforcing material such as glass fiber or carbon fiber attacks the surface of the soft metal, and the abrasion powder generated at that time causes abrasive action. Is a phenomenon that performs

When a fibrous reinforcing fiber material is used, the obtained resin molded product has a large anisotropy in shrinkage, and the dimensional stability when the ambient temperature increases due to the use environment and the generation of frictional heat increases. descend. It is difficult to use in applications that require high dimensional accuracy.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems, to provide excellent wear resistance, a low coefficient of friction, and a sliding condition against a soft metal material such as an aluminum alloy. Another object of the present invention is to provide a sliding resin material which is not damaged by itself and others. As means for forming the sliding resin material into a desired shape, various molding methods such as injection molding, melt extrusion molding, casting molding, compression molding, sintering molding, powder coating and the like are made possible.

[0007]

Means for Solving the Problems As a result of intensive search for solving the above problems, the present inventors have found that spherical or granular carbon particles obtained by heat-treating spherical or granular phenolic resin to polyether aromatic ketone resin. A polyether aromatic ketone resin composition (hereinafter referred to as "carbon particle-containing polyether aromatic ketone material" in the text) characterized by having excellent wear resistance and a low friction coefficient. It has been found that a low sliding resin material can be provided.

The polyether aromatic ketone resin used in the present invention is a thermoplastic resin composition having a repeating unit represented by the formula (1) or (2). I having the structure of 1)
There is CIEK (trade name) manufactured by CI.

[0009]

Embedded image

[0010]

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Incidentally, in addition to the repeating units (1) and (2), the following repeating units can be included.

[0012]

Embedded image (In the formula, A represents a direct bond, O, S, SO ₂ , CO or a divalent hydrocarbon group, and Q and Q ′ each represent S
O ₂ or CO, Ar ′ is a divalent aromatic group, and m is 0, 1, 2, or 3. )

The resin composition according to the present invention contains 1 to 100 parts by weight of carbon particles with respect to 100 parts by weight of a polyether aromatic ketone resin, so that heat resistance and abrasion resistance can be obtained at low cost. Thus, a slidable resin composition having excellent chemical resistance and excellent moldability can be obtained.

In the present invention, the carbon particles are added in an amount of 1 to 100 parts by weight based on 100 parts by weight of the polyether aromatic ketone resin. Preferably 3 parts by weight to 5 parts by weight
0 parts by weight.

When the amount of the carbon particles in the present invention is less than 1 part by weight based on the polyether aromatic ketone resin, the effect of improving the abrasion resistance of the obtained resin composition is not easily exhibited, which is not preferable. On the other hand, when the amount is more than 100 parts by weight, the moldability of the resin composition deteriorates, which is not preferable.

The polyether aromatic ketone resin has excellent heat resistance, abrasion resistance, chemical resistance, and mechanical strength, and has excellent melting properties that enable injection molding and melt extrusion molding. I have.

The resin composition according to the present invention comprises 1 part by weight to 100 parts by weight of carbon particles having an average particle size of 0.1 μm to 100 μm per 100 parts by weight of the polyether aromatic ketone resin.
By containing parts by weight, it becomes possible to obtain a slidable resin composition having excellent heat resistance, abrasion resistance, chemical resistance and excellent moldability at low cost.

The average particle diameter of the carbon particles in the present invention is from 0.1 μm to 100 μm. Preferably 1
μm to 50 μm. More preferably, 3 μm to 30 μm
μm.

When the average particle diameter of the carbon particles in the present invention is smaller than 0.1 μm, the wear resistance of the polyether aromatic ketone resin cannot be improved.

In the present invention, the average particle diameter of the carbon particles is 1
When it is larger than 00 μm, the appearance of the molded product is not preferable, and it is difficult to obtain smoothness of the surface.

The spherical or granular carbon particles obtained by heat-treating the spherical or granular phenolic resin in the present invention can dramatically improve the slidability of the slidable resin composition. Since the carbon particles have an effect of receiving a load on the sliding surface, the wear resistance can be improved.

The spherical or granular carbon particles obtained by heat-treating the spherical or granular phenolic resin in the present invention are spherical, so that they have excellent dispersibility in the base resin and can be uniformly dispersed in the polyether aromatic ketone resin. Since the resin composition can be dispersed, it is possible to uniformly impart good abrasion resistance to the entire slidable resin composition.

Since the spherical or granular carbon particles obtained by heat-treating the spherical or granular phenolic resin in the present invention are spherical, when added to the resin, a smooth surface can be obtained after various moldings.

As a method of heat-treating the spherical or granular carbon particles obtained by heat-treating the spherical or granular phenol resin, a method in which the carbon particles are calcined in a nitrogen atmosphere and at a high temperature of 500 ° C. or more is preferable.

In the resin composition of the present invention, it is preferable that spherical or granular carbon particles obtained by heat-treating a polyether aromatic ketone resin and a spherical or granular phenol resin are uniformly mixed.

As long as the effects of the present invention are not impaired, fiber reinforcing materials (glass fibers, carbon fibers, potassium titanate fibers, ceramic fibers, aramid fibers, boron fibers, etc.) and granular reinforcing materials (calcium carbonate, Clay, talc, silica, mica, etc.), conductivity improver (carbon, zinc oxide, titanium oxide, etc.), thermal conductivity improver (powder metal oxide, etc.), antioxidant, heat stabilizer, antistatic agent , UV absorbers, lubricants, mold release agents, dyes, pigments, other thermoplastic resins (polyamide, polycarbonate, polyacetal, PET, PBT, polyarylate, polyphenylene sulfide, polyether sulfone) ,
Polysulfone type, polyarylate type, polyetherimide type, polyimide type, fluorine type, polyether nitrile type, liquid crystal polymer type, etc., thermosetting resin (phenol type, epoxy type, polyimide type, silicon type, polyamide imide type etc.) ) May be used together.

The method of adding, mixing and kneading the carbon particle-containing polyether aromatic ketone material in the present invention is not particularly limited, and various mixing and kneading means are used. For example,
Each of them may be separately supplied to a melt extruder and mixed.Also, only the powder raw material is dry-preliminarily kneaded using a mixer such as a Henschel mixer, a ball mixer, a blender, a tumbler, etc. Can be melt-kneaded. As a molding method, an appropriate molding method can be applied to a resin serving as a base material. For example, there are various molding methods such as injection molding, melt extrusion molding, casting molding, compression molding, sintering molding, and powder coating. In a preferred embodiment, the carbon particle-containing polyether aromatic ketone material is preferably formed into a film sheet by melt extrusion, but the extrusion method and take-off method are not particularly limited. The method for producing a sheet made of the above-mentioned material of the present invention is preferably a method of cooling and solidifying with a cooling roll immediately after melt extrusion. By making the surface of the cooling roll smooth, it is possible to transfer the smoothness of the roll surface to the sheet surface when the molten PEEK is solidified. When the resulting PEEK sheet having high smoothness is punched and used as a thrust bearing material, the occurrence of wear can be prevented.

In the cooling and solidifying step, besides a method using a cooling roll, there is a method using a belt conveyor type take-up belt. By keeping the surface of the take-off belt smooth, it is possible to transfer the smoothness of the belt surface to the sheet surface when the molten PEEK is solidified. When a cooling roll is used, there are a method of cooling one side of a sheet and a method of simultaneously cooling and solidifying both surfaces of the sheet using two or more rolls. When picking up by belt conveyor type,
There is a method of pulling one side of the sheet by belt conveyance, and a method of carrying out cooling and solidification while sandwiching both surfaces of the sheet by using two or more belts.

The surface of the polyether aromatic ketone material containing carbon particles used as a thrust bearing material in contact with the rotating shaft needs to be as smooth as possible for abrasion resistance. Regarding the surface smoothness of the carbon particle-containing polyether aromatic ketone material sheet, the center line average roughness (Ra)
Is preferably 2 μm or less, more preferably 1 μm or less,
More preferably, it is 0.5 μm or less.

In order to obtain a carbon particle-containing polyether aromatic ketone material sheet having excellent surface smoothness, it is necessary that no foreign matter is mixed into the sheet. When processing into a melt-extruded sheet, it is possible to remove kneaded foreign substances and the like by filtering the molten polyether aromatic ketone material containing carbon particles. The type and condition of the foreign matter removing filter used for filtration are not particularly limited.

The shape of the carbon particle-containing polyether aromatic ketone material is not particularly limited, but is preferably a punched disk-shaped flat plate or a curved plate formed at the time of punching. The thickness of the carbon particle-containing polyether aromatic ketone material is preferably from 25 to 1000 μm. If the thickness is less than 25 μm, workability such as punching and the stability at the time of assembly are poor, and if it exceeds 1000 μm, it is difficult to punch or costly. It becomes something.

[0032]

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

The raw materials used in the examples are as follows. * 1: Polyether aromatic ketone resin PEEK450P (trade name) manufactured by VICTREX * 2: Carbon fiber HTA-C6-X99B manufactured by Toho Rayon * 3: Aluminum borate whisker Alvorex Y manufactured by Shikoku Chemicals * 4: Aramid fiber manufactured by Nippon Aramid Toaron 5011 * 5: Molybdenum disulfide Nippon Graphite Industries Mori Powder B * 6: Carbon particles Kanebo Bellpearl C-800

Each material shown in the table was melt-kneaded using a twin-screw kneading extruder to produce pellets. The numerical values in the composition column of each Example and Comparative Example indicate parts by weight. A sheet-shaped sample was obtained from the produced pellets by melt extrusion using a single screw extruder and a T-type die or the like, or by hot pressing.

Various evaluations were performed based on the following. (1) Wear resistance (1): Using a wear wheel wear type wear tester,
Measure the wear volume of the test piece after running with a sliding load of 1000 gf, a test piece rotation speed of 60 rpm, and a wear distance of 245 m (JIS
(2) Surface hardness: Pencil scratch hardness (JIS K5)
400) (3) Abrasion resistance (2): Using a pin-on-disk abrasion tester, sliding load 90 gf, SUS shaft rotation speed 10000
Observation of test piece abrasion marks and abrasion at the shaft tip after operation at 100 rpm for 100 hours. ○ indicates that the test piece and the tip wear were small, △ indicates that the test piece or tip wear was confirmed, and x indicates that the test piece and tip wear were confirmed. (4) Impact resistance: Izod impact strength measurement (JIS K
(Based on 7110) (5) Formability: The appearance of a sample obtained by performing strand processing and sheet processing with a twin-screw kneader and a single-screw kneader was visually evaluated. A sample having good appearance was marked with "O", and a sample with large surface roughness, or a sample for which a stable molded product could not be obtained, was marked with "x".

When Examples 1 to 4 of the present invention and Comparative Example 1 are compared, as compared with Comparative Example 1 using only the polyether aromatic ketone resin, the addition of carbon particles does not impair the moldability. It can be seen that the abrasion resistance is improved without abrading the wear partner.

In Comparative Examples 9 and 10 of the present invention, when the amount of addition is small, the effect of improving the slidability cannot be exerted, and when the amount of addition is too large, the moldability is extremely poor and processing is difficult. It turns out that it becomes.

In Comparative Examples 2 and 3 of the present invention, the effect of reducing the amount of wear can be confirmed, but it can be seen that the sliding material cannot be an excellent sliding material because it wears the mating material.

In Comparative Examples 4, 5, and 8 of the present invention, it can be seen that wear of the mating material and / or self-wear occurred, and the material could not be an excellent sliding material.

In Comparative Examples 6 and 7 of the present invention, the improvement of the abrasion resistance was confirmed, but it was found that the moldability and the appearance after the molding were deteriorated, so that an excellent sliding material could not be obtained.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

As described above, the resin composition of the present invention is excellent in abrasion resistance and moldability, and makes it possible to produce a resin molded article free from damage and wear by itself and others.

Claims (4)

[Claims] 1. A polyether aromatic ketone resin composition comprising 1 to 100 parts by weight of carbon particles based on 100 parts by weight of a polyether aromatic ketone resin. 2. The polyether aromatic ketone resin composition according to claim 1, wherein the polyether aromatic ketone resin has a repeating unit represented by the formula (1) or (2). Embedded image Embedded image 3. The carbon particles are spherical or granular carbon particles obtained by heat-treating a spherical or granular phenolic resin, and are spherical carbides having an average particle diameter of 0.1 to 100 μm. The polyether aromatic ketone resin composition according to the above. 4. A film or sheet comprising the polyether aromatic ketone resin composition according to claim 1, 2 or 3.