JP2003073540A - Polyether aromatic ketone resin composition and film and sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyether aromatic ketone resin composition which improves the slidableness of a polyether aromatic ketone resin to prevent the damage and abrasion of both the resin composition itself and other counter materials, and has excellent moldability. SOLUTION: This polyether aromatic ketone resin composition comprises 100 pts.wt. of a polyether aromatic ketone resin and 1 to 100 pts.wt. of spherical alumina particles having an average particle diameter of 0.1 to 100 μm. The polyether aromatic ketone resin preferably has repeating units of represented by formula (1) or (2). The alumina particles are preferably spheres having an average particle diameter of 0.1 to 100 μm. Films or sheets obtained from the resin compositions.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent properties as a sliding resin material based on polyether aromatic ketone. For example, electrical / 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 various other equipment.

[0002]

2. Description of the Related Art Conventionally, polyether aromatic ketone resins are well known as engineering plastics having excellent mechanical, chemical and thermal properties and abrasion resistance. The polyether aromatic ketone resin alone has a high friction coefficient, but the addition of the fluororesin significantly improves the slidability thereof and reduces the friction coefficient (Japanese Patent Laid-Open No. 6-1).
No. 36255) is more well known than before. However, the self-lubrication property is improved, but the mechanical strength and load bearing property of the molded product are reduced, so that the wear amount is increased when used under high load conditions or conditions where the frictional contact speed is extremely high. was there.

By adding a solid lubricant such as glass fiber, aramid fiber, carbon fiber or molybdenum disulfide to a polyether aromatic ketone resin, its mechanical strength and slidability are remarkably improved and the amount of wear is reduced ( Japanese Patent Laid-Open No. 1-282
252, Japanese Patent Laid-Open No. 1-282253). However, when the sliding mating material is a relatively soft metal such as an aluminum alloy or a stainless steel material, the added fibrous reinforcing material easily wears them, and in a remarkable case, abnormal wear occurs. is there.

The cause of such abnormal wear is mainly due to the fact that the tip of the 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 the polishing action. Is a phenomenon to do.

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

[0006]

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

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, the polyether aromatic ketone resin is characterized by containing spherical alumina. It has been found that a resin composition (hereinafter referred to as "carbon particle-containing polyether aromatic ketone material" in the text) can provide a sliding resin material having excellent abrasion resistance and a low friction coefficient.

The polyether aromatic ketone resin used in the present invention is a thermoplastic resin composition characterized by having a repeating unit represented by the formula (1) or (2). I having the structure of 1)
CIEK PEEK (trade name) and the like are available.

[0009]

[Chemical 3]

[0010]

[Chemical 4]

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

[0012]

[Chemical 5] (In the formula, A represents a direct bond, O, S, SO ₂ , CO or a divalent hydrocarbon group, and Q and Q ′ are S respectively.
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 part by weight to 100 parts by weight of alumina particles with respect to 100 parts by weight of the polyether aromatic ketone resin, so that the heat resistance and abrasion resistance can be reduced at low cost. Thus, it becomes possible to obtain a slidable resin composition having excellent chemical resistance and excellent moldability.

The amount of carbon particles added in the present invention is 1 to 100 parts by weight based on 100 parts by weight of the polyether aromatic ketone resin. Preferably 1 part by weight to 2
0 parts by weight.

When the amount of carbon particles added 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 difficult to be exhibited, which is not preferable. On the other hand, if the amount is more than 100 parts by weight, the moldability of the resin composition is deteriorated, which is not preferable.

The polyether aromatic ketone resin has excellent heat resistance, abrasion resistance, chemical resistance, mechanical strength, and excellent melting characteristics that enable injection molding and melt extrusion molding. There is.

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

In the present invention, carbon particles having an average particle diameter of 0.1 μm to 100 μm are used. Preferably 1
μm to 50 μm.

When the average particle diameter of the alumina particles in the present invention is smaller than 0.1 μm, the workability during hot melt processing is poor with respect to the polyether aromatic ketone resin, and there is a risk of classification and the like.

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

The granular alumina particles in the present invention can greatly improve the slidability of the slidable resin composition. Since the alumina particles have the effect of receiving a load on the sliding surface, the wear resistance can be improved.

Since the granular alumina particles in the present invention are spherical, they are excellent in dispersibility in the base resin and can be uniformly dispersed in the polyether aromatic ketone resin. Therefore, the slidable resin composition as a whole can be obtained. It is possible to evenly impart good wear resistance.

Since the granular alumina particles in the present invention are spherical, when added to the resin, a smooth surface can be obtained after various molding.

As the method for producing the above-mentioned granular alumina particles, a method obtained by firing and synthesizing metal powder in an oxidizing gas stream is desirable.

In the resin composition of the present invention, it is desirable that the polyether aromatic ketone resin and the granular alumina particles are uniformly mixed.

Fiber reinforcements (glass fibers, carbon fibers, potassium titanate fibers, ceramic fibers, aramid fibers, boron fibers, etc.), granular reinforcements (calcium carbonate, calcium carbonate, Clay, talc, silica, mica, carbon particles, etc., conductivity improver (carbon, zinc oxide, titanium oxide etc.), thermal conductivity improver (powdered metal oxide etc.), antioxidant, heat stabilizer, Antistatic agents, UV absorbers, lubricants, release agents, dyes, pigments, other thermoplastic resins (polyamide-based, polycarbonate-based,
Polyacetal type, PET type, PBT type, polyarylate type, polyphenylene sulfide type, polyether sulfone type, polysulfone type, polyarylate type, polyetherimide type, polyimide type, fluorine type, polyether nitrile type, liquid crystal polymer type, etc. ), And a thermosetting resin (phenolic resin, epoxy resin, polyimide resin, silicon resin, polyamideimide resin, etc.) may be used in combination.

The addition / mixing / kneading method of the carbon particle-containing polyether aromatic ketone material in the present invention is not particularly limited, and various mixing / kneading means may be used. For example,
Each may be separately supplied to the melt extruder and mixed, or only the powder raw material may be preliminarily dry-blended using a mixer such as a Henschel mixer, a ball mixer, a blender, or a tumbler, and then mixed into a melt-kneader. It can be melted and kneaded. As a molding method, an appropriate molding method can be applied to the resin as the base material. For example, various molding methods such as injection molding, melt extrusion molding, cast molding, compression molding, sinter molding, powder coating and the like. As a preferred embodiment, the alumina particle-containing polyether aromatic ketone material is preferably formed into a film sheet by melt extrusion, but the extrusion method and the take-up 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 in which it is cooled and solidified by a take-up 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 PEEK sheet having high smoothness thus obtained is punched and used as a thrust bearing material, abrasion can be prevented.

In the cooling and solidifying step, there is a method of using a belt conveyor type take-up belt in addition to the method of using a cooling roll. By smoothing the surface of the take-up belt, it is possible to transfer the smoothness of the belt surface to the sheet surface when the molten PEEK is solidified. When using a cooling roll, there are a method of cooling the sheet on one side and a method of simultaneously cooling and solidifying both surfaces of the sheet by using two or more rolls. When picking up on a belt conveyor,
There are a method of pulling one side of the sheet by belt conveyance, and a method of cooling and solidifying conveyance while sandwiching both sides of the sheet with two or more belts.

Alumina particle-containing polyether aromatic ketone material used as a thrust bearing material in contact with the rotary shaft is
It is necessary for its wear resistance that its surface be as smooth as possible. Regarding the surface smoothness of the polyether aromatic ketone material sheet containing alumina particles, the center line average roughness (Ra) is preferably 2 μm or less, more preferably 1 μm.
m or less, more preferably 0.5 μm or less.

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

The shape of the alumina particle-containing polyether aromatic ketone material is not particularly limited, but a punched disk-shaped flat plate or a curved plate molded at the time of punching is preferable. The thickness of the polyether aromatic ketone material containing alumina particles is preferably 25 to 1000 μm and is 25 μm.
If it is less than m, the 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 the cost becomes expensive.

[0032]

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 VICTREX PEEK450P (trade name) * 2: Carbon fiber Toho Rayon HTA-C6-X99B * 3: Aluminum borate whisker Shikoku Kasei Arborex Y * 4: Aramid fiber Nippon Aramid Toaron 5011 * 5: Molybdenum disulfide Nippon Graphite Industry Co., Ltd. Mori Powder B * 6: Alumina particles Admatex AO-502

Each material shown in the table was melt-kneaded using a twin-screw kneading extruder to produce pellets. Numerical values in the composition column of each example and comparative example indicate parts by weight. A sheet-like sample was obtained by subjecting the produced pellets to melt extrusion using a single-screw extruder and a T-die, and hot pressing.

Various evaluations were carried out based on the following. (1) Abrasion resistance (1): Using an abrasion wheel abrasion type abrasion tester,
Sliding load 1000 gf, test piece rotation speed 60 rpm, wear distance 245 m Measure test piece wear volume after operation (JIS
(2) Surface hardness: pencil scratch hardness (JIS K 5
400) (3) Abrasion resistance (2): Using a pin-on disc type abrasion tester, sliding load 90 gf, SUS shaft rotation speed 10000
rpm, wear time 100 hours Observe test piece wear marks and shaft tip wear condition after operation. A test piece with little wear and shaft tip wear was evaluated as O, a test piece or shaft tip wear was confirmed as C, and a test piece and shaft tip wear was confirmed as X. (4) Impact resistance: Izod impact strength measurement (JIS K
7110) (5) Formability: The appearance of a sample obtained by carrying out strand processing and sheet processing and molding with a twin-screw kneader and a single-screw kneader is visually evaluated. Good appearances were evaluated as ◯, and those having a large surface roughness or those in which a stable molded product could not be obtained were evaluated as x.

Comparing Examples 1 to 4 of the present invention with Comparative Example 1, as compared with Comparative Example 1 in which the polyether aromatic ketone resin was used alone, the addition of alumina particles did not impair the moldability. It is also understood that the wear resistance is improved without abrading the wear partner material.

In Comparative Examples 9 and 10 of the present invention, if the added amount is small, the effect of improving the slidability cannot be exhibited, and if the added amount is too large, the formability is very poor and the processing is difficult. It turns out that

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

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

With respect to Comparative Examples 6 and 7 of the present invention, it was confirmed that the abrasion resistance was improved, but it is understood that they cannot be excellent sliding materials because the moldability and the appearance after molding are deteriorated.

[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 it is possible to produce a resin molded product which is free from damage and abrasion of itself and others.

Claims (4)

[Claims] 1. A polyether aromatic ketone resin composition comprising 1 part by weight to 100 parts by weight of alumina 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). [Chemical 1] [Chemical 2] 3. Alumina particles having an average particle size of 0.1 to 1
The polyether aromatic ketone resin composition according to claim 1 or 2, which is a sphere having a diameter of 00 µm. 4. A film or sheet made of the polyether aromatic ketone resin composition according to claim 1, 2 or 3.