JPH04258663A - Aromatic polyetherketone resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in abrasion resistance and sliding properties and showing a low molding shrinkage by compounding an aromatic polyetherketone resin, a fluororesin, and an aluminum borate whisker each in a specified amt. CONSTITUTION:100 pts.wt. aromatic poyetherketone resin pref. having repeating units of formula I or II, 3-60 pts.wt. fluororesin (e.g. a tetrafluoroethylene resin), and 3-10 pts.wt. aluminum borate whisker are compounded.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition based on polyether aromatic ketone having excellent properties as a sliding material.

0002

BACKGROUND OF THE INVENTION Polyether aromatic ketone is an engineering plastic with excellent mechanical, chemical and thermal properties, and also has excellent wear resistance, and is expected to be applied to various sliding materials.

However, polyether aromatic ketone alone cannot be used as a sliding material because of its high coefficient of friction.

[0004] In general, methods for improving the sliding properties such as self-lubricating properties and wear resistance of plastics include blending solid lubricants, blending tetrafluoroethylene resins, blending lubricating oils, etc. JP-A-56-61458, JP-A-55-135163, JP-A-47-4261
This technique is disclosed in Japanese Patent Publication No. 5, Japanese Patent Publication No. 46-5321, and the like. However, when a solid lubricant is added, hardly any improvement in load resistance can be expected. In addition, products containing resins with a low coefficient of friction such as tetrafluoroethylene resin can be expected to have a considerable effect on improving self-lubricating properties, but on the other hand, the mechanical strength and load bearing capacity of the molded product will inevitably decrease. Abrasion resistance is also not sufficient. Furthermore, even if lubricating oil is dispersed therein, if it is used by adhering or coating it on other objects, it may have an adverse effect because it is oil-impregnated.

[0005] Also, tetrafluoroethylene resin and glass fiber,
A method of improving mechanical strength and abrasion resistance by jointly using fibrous reinforcing materials such as carbon fibers and aramid fibers is known (JP-A-58-109554, JP-A-58-179262). ), but when these reinforcing materials are used, there is a problem that the anisotropy of the shrinkage rate is large and the dimensional stability is reduced.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sliding material composition that has excellent wear resistance and a low coefficient of friction. Furthermore, it is an object of the present invention to provide various precision sliding material compositions that have a small molding shrinkage rate and require high precision when used as molded materials.

[0007]

[Means for Solving the Problems] As a result of various studies to achieve the above object, the present inventors completed the present invention by using a fluororesin and aluminum borate whiskers in combination with polyether aromatic ketone. reached.

That is, the present invention is a polyether aromatic ketone resin composition comprising 100 parts by weight of polyether aromatic ketone, 3 to 60 parts by weight of fluororesin, and 3 to 100 parts by weight of aluminum borate whiskers.

The polyether aromatic ketone used in the present invention is typically a thermoplastic crystalline resin having a repeating unit represented by formula (I) (Chemical formula 3) or (II) (Chemical formula 4). Can be mentioned.

0010

[Chemical formula 3]

[0011]

[Chemical 4] For example, PE manufactured by ICI as having the structure of formula (I)
There is EK (trade name), and PEK (trade name) manufactured by ICI Corporation has the structure of formula (II).

In addition to the repeating units (I) and (II), the following repeating unit (formula 5) can also be included.

[0013]

[Chemical formula 5] (However, in the formula, A is a direct bond, oxygen, sulfur, -SO2 -
, -CO- or a divalent hydrocarbon group, the oxygen atom in the unit represented by the following formula (Chemical formula 6) is at the ortho or para position with respect to Q or Q', and Q and Q' are the same or different -CO- or SO2, Ar' is a divalent aromatic group, and m is 0, 1, 2 or 3. )

[0014]

[Chemical 6] The fluororesin used in combination with the polyether aromatic ketone in the present invention is a synthetic polymer containing fluorine atoms (F) in its molecules, and generally has higher heat resistance than other synthetic resins. ,
It has excellent chemical resistance and electrical properties (especially high frequency properties), as well as unique low friction and non-adhesive properties. For example, typical examples include those having the following specific structural formulas, and at least one kind or a mixture of two or more of these can be used. (1) [-CF2CF2-]n: Polytetrafluoroethylene (hereinafter referred to as PTFE) (2) [-CF2CF2CF(CF3)CF2-]n
: Tetrafluoroethylene-hexafluoropropylene copolymer resin (hereinafter referred to as FEP) (3) [-(CF2CF2)
m -(CF(OR1)CF2)-]n: Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (hereinafter referred to as PFA) (However, R1 represents a fluorinated alkyl group CnF2n+1.) (4) [- CF2CF2CF(CF3)CF2-CF
-(OR2)CF2-]n: Tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer resin (hereinafter referred to as EPE) (However, R2
represents a fluorinated alkyl group Cn F2n+1. )
(5) (-CH2CH2CF2CF2-)n: Tetrafluoroethylene-ethylene copolymer resin (hereinafter referred to as ETFE) (6) (-CH2CH2CFClCF2-) n:
Trifluorochloroethylene resin (hereinafter referred to as ECTFE) (7) (-CF2CH2-)n: Vinylidene fluoride resin (hereinafter referred to as PVDF) (8) (-CFClCF2-) n: Polychlorotrifluoroethylene (hereinafter referred to as PCTFE) ( 9) (-CH2CHF-)n: Polyvinyl fluoride (hereinafter referred to as PVF) Among the above-mentioned fluororesins, completely fluorinated tetrafluoroethylene resin (P
TFE) has particularly excellent properties and is most preferably used in the present invention. The amount of these fluororesins added in the present invention is as follows:
The amount ranges from 3 to 60 parts by weight. If the amount of the fluororesin added is less than 3 parts by weight, the effect of improving the friction coefficient of the resulting resin composition will be small, which is not preferable. Moreover, if the amount of the fluororesin added is more than 60 parts by weight, it is not preferable because the wear resistance will conversely decrease.

Further, a typical aluminum borate whisker used in the present invention is 2Al2 O3 .B2
O3 or 9Al2 O3 ・2B2 O3, for example, 2Al2
O3 ・B2 O3 Aluminum borate whiskers having the composition expressed include at least one aluminum supply component selected from aluminum hydroxide and aluminum inorganic salts, and boron oxides, oxyacids, and alkali metals thereof. at least one boron-supplying component selected from salts in the presence of at least one melting agent selected from alkali metal chlorides, alkali metal sulfates, and alkali metal carbonates. It is obtained by heating to a temperature of 1000°C to react and grow.

[0016] Also, 9Al2 O3 .2B2 O3
Aluminum borate whiskers have a composition represented by: aluminum hydroxide, at least one aluminum supplying component selected from aluminum inorganic salts, and boron oxide, oxygen acid, and alkali metal salt thereof. at 900 to 1200°C in the presence of at least one melting agent selected from alkali metal chlorides, alkali metal sulfates, and alkali metal carbonates. React by heating to temperature,
It is obtained by growing it and is commercially available, for example, under the trade name Arborex (manufactured by Shikoku Kasei Co., Ltd.).

[0017] The aluminum borate whiskers obtained by these methods have a fiber diameter of 0.05 to 5 μm and a fiber length of 2 to 100 μm, which are significantly smaller than glass fibers, so they can also be used to reinforce products with small shapes. Therefore, the filler material is not exposed on the surface of the product.

The amount of aluminum borate whiskers added in the present invention is 10% of the above-mentioned polyether aromatic ketone.
The amount ranges from 3 to 100 parts by weight relative to 0 parts by weight. If the amount of aluminum borate whiskers added is less than 3 parts by weight, the effect of improving the abrasion resistance of the resulting resin composition will be undesirable. Furthermore, if the amount of aluminum borate whiskers added is more than 100 parts by weight, the moldability of the resin composition will deteriorate, which is not preferable.

In the resin composition according to the present invention, it is desirable that the polyether aromatic ketone, the fluororesin, and the aluminum borate whiskers are uniformly mixed.

[0020] The addition and mixing method is not particularly limited, and various means can be employed. For example, they can be separately supplied to a melt extruder and mixed, or they can be pre-kneaded in advance using a mixer such as a Henschel mixer, a ribbon blender, or a tumbler, and then supplied to a melt mixer. It is also possible to adopt a method in which the components are dispersed in an aqueous medium or an organic medium and mixed by a wet mixing method.

Fiber reinforcing materials (eg, glass fibers, carbon fibers, potassium titanate fibers, aramid fibers, ceramic fibers, etc.) may be added as necessary, as long as they do not impede the effects of the present invention.
Granular reinforcements (e.g. calcium carbonate, clay, talc,
Silica, etc.), antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, dyes, pigments, as well as other thermoplastic resins (e.g. polyamide, polycarbonate, polyphenylene sulfide, polyetherimide, PET, PBT, (polyacetal, polysulfone, polyether sulfone, polyether ether ketone), thermosetting resin (for example, phenol resin, epoxy resin, silicone resin, polyimide resin, polyamideimide resin, etc.) may be used in combination.

The resin composition of the present invention described above can be molded into a predetermined molded article by a molding method such as an injection molding method, an extrusion molding method, or a compression molding method.

[0023] The present invention will be explained in detail below with reference to Examples, but these are merely illustrative and the present invention is not limited thereto.

[0024]

[Example] Examples 1 to 4 PEE manufactured by ICI as polyether aromatic ketone powder
K450P (product name), fluororesin powder made by Kitamura Co., Ltd., tetrafluoroethylene resin Teflon KTL-610
(product name) and Alborex (product name) manufactured by Shikoku Kasei Co., Ltd. as aluminum borate whiskers, respectively in Table-1.
After dry blending with the composition described in 1., uniform pellets were obtained by extruding while melt-kneading using a 40 mm diameter extruder (extrusion temperature 340 to 400° C.).

[0025] Next, the above uniform pellets were molded into test pieces using a normal injection molding machine under temperature conditions of a cylinder temperature of 370 to 400°C and a mold temperature of 150 to 180°C.
The friction coefficient and wear coefficient were measured as sliding properties, and the molding shrinkage rate was also measured, and the results shown in Table 1 were obtained.

[0026] The friction coefficient was measured at room temperature using a Suzuki type friction tester with a mating material of stainless steel under the conditions of a surface pressure of 10 kg/cm2 and a speed of 6 m/min. Measurement was performed at room temperature using a cylindrical abrasion tester at a speed of 100 m/min.

[0027] Also, the molding shrinkage rate is 75mm x 75mm x
A 2 mm flat plate is molded, and the flow direction of the melt is set in MD (Ma
(chine Direction), the right angle direction is TD
(Transvrse Direction),
Each measurement value was determined.

Comparative Examples 1 to 5 The same tests as in Examples 1 to 3 were conducted except that the composition of the resin composition was changed as shown in Table 1.

The results are shown in Table 1.

Examples 5 to 7 PEK manufactured by ICI as polyether aromatic ketone powder
220P (product name), fluororesin powder made by Mitsui Fluorochemical Co., Ltd., tetrafluoroethylene resin Teflon KTL-6
10 (trade name) and Alborex (trade name) manufactured by Shikoku Kasei Co., Ltd. as aluminum borate whiskers were dry blended with the compositions listed in Table 2, respectively, and then Examples 1 to 1 were prepared.
The test was conducted using the same procedure as in 3.

[0031] The results are shown in Table-2.

Comparative Examples 6-10 The same tests as in Examples 4-5 were conducted except that the composition of the resin composition was changed as shown in Table 2.

The results are shown in Table 2.

From Tables 1 and 2, the resin composition according to the present invention has a small coefficient of friction and a small coefficient of wear, and also has a small mold shrinkage rate, making it an extremely excellent composition as a sliding material.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

Effects of the Invention The sliding material composition according to the present invention has greatly improved sliding properties and molding shrinkage rate, and is useful as various sliding materials that require high precision.

Claims (4)

[Claims] 1. A polyether aromatic ketone resin composition comprising 100 parts by weight of polyether aromatic ketone, 3 to 60 parts by weight of a fluororesin, and 3 to 10 parts by weight of aluminum borate whiskers. 2. The polyether aromatic ketone has the formula (I
) (Chemical formula 1) or formula (II) (Chemical formula 2). [Chemical formula 1] [Chemical formula 2] [Claim 3] The fluororesin is one of the following (1) to (9):
The polyether aromatic ketone resin composition according to claim 1, wherein the polyether aromatic ketone resin composition is at least one resin selected from resins having a structure represented by: (1) [-CF2CF2-]n: polytetrafluoroethylene (2) [-CF2CF2CF(CF3)C
F2-]n: Tetrafluoroethylene-hexafluoropropylene copolymer resin (3) [-(CF2CF2) m-(CF(OR1
)CF2)-]n: Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (However, R1 represents a fluorinated alkyl group CnF2n+1.) (4)
[-CF2CF2CF(CF3)CF2-CF-(OR
2) CF2-]n: Tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer resin (R2 is a fluorinated alkyl group Cn F
2n+1 is shown. ) (5) (-CH2CH2CF
2CF2-)n: Tetrafluoroethylene-ethylene copolymer resin (6) (-CH2CH2CFClCF2-)n:
Trifluorochloroethylene resin (7) (-CF2CH2-
)n: Vinylidene fluoride resin (8) (-CFClC
F2-) n: polychlorotrifluoroethylene (9
) (-CH2CHF-)n: polyvinyl fluoride Claim 4: 9 aluminum borate whiskers
Al2 O3 ・2B2 O3 and/or 2Al
The polyether aromatic ketone resin composition according to claim 1, characterized in that it has a composition represented by 2 O3 .B2 O3.