JP2952294B2 - Polyetherketone resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyetherketone resin composition having excellent properties as an engineering plastic material.

[Conventional technology]

Conventionally, polyetherketone resin is heat-resistant, flame-retardant,
As an engineering plastic material excellent in chemical resistance and the like, it has been used particularly in the fields of electric and electronic devices, vehicle devices such as automobiles, and the like. However, this resin is not satisfactory in non-adhesiveness, sliding characteristics, and high-temperature rigidity, and cannot be applied in the field of office equipment such as a copying machine in which these characteristics are required. Also,
Polytetrafluoroethylene, polytetrafluoroethylene-hexafluoropropylene copolymer, polytetrafluoroethylene-
Attempts have been made to improve non-adhesion and sliding properties by adding a fluororesin such as a perfluoropropylene copolymer. In this case, in order to impart sufficient non-adhesiveness and sliding characteristics to the resin composition, it is necessary to add a considerably large amount of the above-mentioned fluororesin. Cannot maintain the mechanical strength to be provided, in particular, the high-temperature rigidity. It is also conceivable to use a fibrous reinforcing agent such as glass fiber or carbon fiber in combination to compensate for this drawback, but in order to maintain the above-mentioned sufficient strength, it is necessary to add a considerable amount of these. In this case, anisotropy or warpage based on the orientation of the fibrous reinforcing agent is generated, and the mating material is easily damaged during sliding, and a sufficient lubricity cannot be obtained.

[Problems to be solved by the invention]

As described above, in the conventional technology, in addition to excellent heat resistance, flame retardancy, chemical resistance, etc., it is excellent in non-adhesion, has high mechanical strength at high temperatures, and has excellent sliding characteristics. There is a problem that a resin composition has not been obtained, and solving these problems has been an issue.

[Means for solving the problem]

To solve the above problem, the present invention relates to 3,3,3-trifluoro-
In this method, 10 to 90 parts by weight of a copolymer of 2-trifluoromethylpropene and 1,1-difluoroethylene is added to obtain a polyetherketone resin composition. The details are described below.

First, polyetherketone resin used in the present invention have the general formula _{-CO-Ar 1 -CO-Ar 2} ( wherein, Ar ₁ and Ar _2, at least a diaryl ether linkage forming part of the polymer backbone Ar ₁ and Ar ₂ are covalently bonded to a carbonyl group through an aromatic carbon atom.) Or a repeating unit represented by the following formula: , And other repeating units represented by the following formulas, specifically, a polymer coexisting in an amount of less than about 50 monomer% within a range that does not lose the inherent properties of the polyetherketone resin. And
Suitable polyetherketone resins include: And those having a repeating unit such as
These are available, for example, from ICI of the United Kingdom, from VICTREX-PEEK or VICTREX (V
It is commercially available as (ICTREX) -PEK. The method for producing polyetherketone is disclosed in, for example, JP-A-54-90296.

Next, the copolymer of 3,3,3-trifluoro-2-trifluoromethylpropene and 1,1-difluoroethylene used in the present invention has the formula (I) The repeating unit represented by the formula (I) is used alone or together with the repeating unit represented by CH ₂ CF ₂ in a proportion of less than 20 monomer% so that the inherent properties of the copolymer of the formula (I) are not lost. It is a coexisting copolymer. A method for producing a co-union of 3,3,3-trifluoro-2-trifluoromethylpropene and 1,1-difluoroethylene is disclosed in
As disclosed in JP-A-32785 and the like, 3,3,3-trifluoro-2-trifluoromethylpropene and 1,1-
It is produced by copolymerizing difluoroethylene with a predetermined solvent, in which case the molar ratio of the two substances is in the range of 1: 9 to 9: 1 and in the temperature range of about -15 ° C to about 80 ° C. Copolymerize. As such a copolymer, for example,
Manufactured by Ausimont, USA: CM-X.

The polyether ketone resin described above and 3,3,3-trifluoro-2-trifluoromethylpropene and 1,1-
When compounding a copolymer of difluoroethylene,
The copolymer is blended in an amount of 10 to 90 parts by weight based on 100 parts by weight of the polyether ketone resin. This is because if the amount is less than 10 parts by weight, excellent non-adhesiveness and sliding properties cannot be obtained, and if the amount is more than 90 parts by weight, high-temperature rigidity and mechanical strength are extremely low.

In the resin composition of the present invention, a general-purpose filler that can be mixed with a general synthetic resin can be appropriately mixed in an amount that does not impair the object of the present invention. Specific examples of such a filler include heat-resistant polymer materials such as silicone resin, polyether sulfone resin, aromatic polyester resin, and polyimide resin, and heat-resistant fiber reinforcing materials (for example, glass fiber, carbon fiber, graphite, and the like). Fibers, potassium titanate whiskers, wollastonite, ceramic fibers, magnesium whiskers, aluminum borate whiskers, steel wires, copper wires, stainless copper wires, silicon carbide fibers, other heat-resistant organic fibers such as inorganic fibers or aromatic amides Fiber), thermal conductivity improver (graphite,
Metals such as zinc and aluminum or magnesium oxide,
Powders of inorganic compounds such as zinc oxide), heat-insulating properties (glass beads, silica balloons, diatomaceous earth, magnesium carbonate powder, asbestos, etc.), lubricating properties (molybdenum disulfide, graphite, carbon, mica, talc, etc.) Lubricants) and coloring materials (iron oxide, cadmium sulfide, cadmium selenide and other inorganic pigments, carbon black, etc.).

Various operations such as blending, heating and mixing of the above-mentioned various raw materials in the present invention are not particularly limited. For example, after dry-mixing with a mixer such as a Henschel mixer or a tumbler mixer, an injection molding machine or the like may be directly used. It may be supplied to a melt extruder and molded, or may be melt-mixed with a hot roll, kneader, melt extruder or the like. The melting temperature at this time is 300 to 400 ° C, preferably 320 to 380 ° C. In molding the composition of the present invention, the method is not particularly limited, and compression molding,
Extrusion molding, injection molding and the like are possible. Further, the resin composition of the present invention is melt-mixed, then pulverized by a jet mill, a freeze pulverizer, or the like, and powdered as it is or classified according to a desired particle size. Electric powder coating and the like can be performed.

[Action]

When the polyetherketone resin composition of the present invention is molded by an injection molding method, 3,3,3-trifluoro-2-trifluoromethylpropene and 1,1-difluoro The fluororesin, which is a copolymer with ethylene, is distributed at a high density, showing non-adhesion and excellent lubricity and abrasion resistance, and the strength and rigidity of this fluororesin make the whole molded body excellent. It is presumed that the steel shows high strength and high-temperature rigidity.

〔Example〕

Raw materials used in Examples and Comparative Examples are collectively shown as follows. In addition, abbreviations are written in [] and all the mixing ratios are parts by weight.

Polyetherketone resin (manufactured by ICI UK: Victrex-PEEK 450P) [PEEK] Polyetherketone resin (manufactured by ICI UK: Victrex-PEK 220G) [PEK] 3,3, Copolymer of 3-trifluoro-2-trifluoromethylpropene and 1,1-difluoroethylene (manufactured by Ausimont, USA: CM-X) [CM-X] Polytetrafluoroethylene (manufactured by DuPont-Mitsui Fluorochemicals: Teflon) 7J) [PTFE] Polytetrafluoroethylene-hexafluoropropylene copolymer (manufactured by DuPont-Mitsui Fluorochemicals: FER
100) [FEP] Polytetrafluoroethylene-perfluoropropylene copolymer (manufactured by DuPont-Mitsui Fluorochemicals: PFA-
340J) [PFA] Graphite (ACP) [GRP] Examples 1 to 5 The ingredients mixed in the proportions shown in Table 1 and mixed well were supplied to a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.).
The mixture was melt-mixed under the conditions of a cylinder temperature of 365 ° C. and a screw rotation speed of 100 rpm, and was extruded and granulated. The obtained pellets were injection molded under the conditions of cylinder temperature 380 ° C, injection pressure 1200kg / cm ² , mold temperature 200 ° C, friction and wear test pieces (inner diameter 17mm, outer diameter 21mm, length 10mm) and bending test pieces. (ASTM
−D790), tensile modulus test piece (width 4mm, length 25m)
m, thickness 1 mm) and contact angle test piece (diameter 10 mm, thickness 3 mm)
Was prepared. Each test method for the obtained test piece is as follows.

1) Friction and wear test Using a thrust-type friction and wear tester, the mating material is
J2), the friction coefficient and the wear coefficient (cm ³ kg · m) were determined under the conditions of a sliding speed of 32 m / min and a load of 6.25 kg / cm ² .

2) Bending strength test A method based on ASTM-D790 was used.

3) Tensile modulus test (elastic modulus retention) Tensile stress was applied at a frequency of 10 Hz using a dynamic viscoelasticity measuring device manufactured by Toyo Seiki Seisaku-sho, and changes in tensile modulus with temperature were measured at 25 ° C and 200 ° C. I asked.

4) Non-adhesiveness (contact angle to water) test The contact angle to water was determined using a goniometer type contact angle measuring device GI manufactured by Elma Optical Co., Ltd.

Comparative Examples 1 to 5: Except that the raw materials were mixed at the mixing ratios shown in Table 1, a test piece was prepared by performing exactly the same operation as in Example 1, and the above-described tests were performed. Also shown in Table 1.

From this table, Examples 1 to 5 are excellent in bending strength and tensile modulus, extremely excellent in non-adhesiveness, and very excellent in slidability and wear resistance. In contrast, CM
Comparative Example 1, in which -X was not added, was inferior in non-adhesiveness, slidability (coefficient of friction), and abrasion resistance. Comparative Examples 2 to 4 in which the added fluororesins are PTFE, FEP, and PFA, respectively, have low flexural strength and high temperature rigidity (200
Tensile elasticity at ℃) and poor lubricity and wear resistance. Further, Comparative Example 5 in which a fluororesin (CM-X) was used but the amount of addition was excessive (100 parts by weight)
The bending strength and the high-temperature rigidity were inferior, and the wear resistance was not so good.

〔effect〕

The polyetherketone resin composition of the present invention has excellent non-adhesiveness without impairing the excellent mechanical, thermal, and electrical properties of the polyetherketone resin, and exhibits extremely favorable sliding characteristics. Most suitable as a sliding member used under high temperature. Therefore, taking advantage of its excellent non-adhesive properties, applications that require lubrication and non-adhesiveness, such as copying from a rotating body such as a bearing in a copier, a heat roller, or a photoreceptor, which come into contact with strongly adherent toner. It becomes a suitable material such as a nail member for peeling paper, and the significance of the present invention can be said to be extremely large.

Claims (1)

(57) [Claims] 1. A copolymer of 3,3,3-trifluoro-2-trifluoromethylpropene and 1,1-difluoroethylene is added to 10 to 9 parts by weight of 100 parts by weight of a polyether ketone resin.
A polyetherketone-based resin composition characterized by adding 0 parts by weight.