JPH0415254A - Polyether ketone resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent heat resistance, flame retardancy, chemical resistance and nonstickiness, high mechanical strengths at high temperatures, and excellent sliding properties by adding a specified copolymer to a polyether ketone resin. CONSTITUTION:A resin composition prepared by adding 10-90 pts.wt. copolymer of 3,3,3-trifluoro-2-trifluoromethyl-propene with 1,1-difluoroethylene to 100 pts.wt. polyether ketone resin. A molding obtained from the above resin composition by injection molding or other techniques has nonstickiness, excellent lubricity and abrasion resistance presumably because a fluororesin which is the copolymer of 3,3,3-trifluoro-2-trifluoromethylpropene with 1,1-difluoro-ethylene is highly concentrated on its surface. By virtue of the strength and rigidity of this fluororesin, the molding has excellent strengths and high-temperature rigidity as a whole.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyetherketone resin composition having excellent properties as an engineering plastic material.

[Prior art] Polyetherketone resin has traditionally been used as an engineering plastic material with excellent heat resistance, flame retardance, and chemical resistance, especially in fields such as electrical and electronic equipment and vehicle equipment such as automobiles. I've been However, this resin does not have satisfactory non-adhesive properties, sliding properties, and high temperature rigidity, and cannot be applied in the field of office equipment such as copying machines, which require these properties. In addition, non-stick properties can be achieved by adding fluororesins such as polytetrafluoroethylene, polytetrafluoroethylene-hexafluoropropylene copolymer, and polytetrafluoroethylene-perfluoropropylene copolymer to polyetherketone resin. Attempts have also been made to improve the sliding properties.

In this case, in order to impart sufficient non-adhesion and sliding properties to the resin composition, it is necessary to add a considerable amount of the fluororesin described above, but if too much fluororesin is added, the resin composition Mechanical strength, especially high-temperature rigidity, which should be maintained cannot be maintained. In order to compensate for this drawback, it may be possible to use fibrous reinforcing nets such as glass fibers or carbon fibers, but in order to maintain the above-mentioned sufficient strength, it is necessary to add a considerable amount of these. In that case, new problems arise such that anisotropy and warpage occur due to the orientation of the fibrous reinforced side, and the mating material is easily damaged during sliding, making it impossible to obtain sufficient lubricity.

[Problem to be solved by the invention]

In this way, in conventional technology, in addition to excellent heat resistance, flame retardance, and chemical resistance, polyetherketone-based materials have excellent non-adhesive properties, high mechanical strength at high temperatures, and excellent sliding properties. There is a problem that a resin composition has not been obtained, and it has been a challenge to solve these problems.

[Means to solve the problem]

In order to solve the above problem, the present invention adds a copolymer of 3,3,3-trifluoro-2-trifluoromethylpropene and 1゜1-difluoroethylene to 100 parts by weight of polyetherketone resin. This method employs a method of adding 10 to 90 parts by weight to form a polyetherketone resin composition. The details will be described below.

First, the polyetherketone resin used in this invention has the general formula -CO-^r, -Co-^r2 (in the formula, Ar+
and Arg are aromatic residues at least one of which has a diarylether bond forming part of the polymer main chain, and Ar+ and ^rt are covalently bonded to the carbonyl group via the aromatic carbon atom. ) The repeating unit represented by () alone, or this repeating unit and other repeating units represented by () may be used in an amount of 50 monomers (1%) to the extent that the original properties of the polyetherketone resin are not lost. The polymers coexisted in an amount of approximately . Suitable polyetherketone resins include those having repeating units such as,
These are commercially available, for example from ICI UK as VrCTREX-PEEK or VICTREX-PEK. Incidentally, a method for producing polyetherketone is disclosed in JP-A-54-90296 and the like.

Next, the copolymer of 3,3,3-trifluoro-2-trifluoromethylpropene and 1,1-difluoroethylene used in the present invention has a repeating unit represented by formula (1) solely, or with this repeating unit C
It is a copolymer in which the repeating unit represented by HzCPz coexists with less than 1% of 20 monomers so as not to lose the original properties of the copolymer of formula (1). 3,3.3-
) refluoro-2-trifluoromethylpropene and 1.
A method for producing a copolymer with 1-difluoroethylene is disclosed in Japanese Patent Publication No. 49-32785, etc., by combining 3.3.3-trifluoro2-trifluoromethylpropene and 1.3-trifluoro2-trifluoromethylpropene. It is produced by copolymerizing difluoroethylene with ethylene in a predetermined solvent, in which case the molar ratio of both substances is in the range of 1:9 to 9:1, and about -15°
The copolymerization is carried out in a temperature range of about 80°C. An example of such a copolymer is CM-X manufactured by Aujimonoto, USA.

The above-mentioned polyetherketone resin and 3.33-trifluoro-2-trifluoromethylpropene and 1.1
- When blending the difluoroethylene copolymer, lθ to 90 parts by weight of this copolymer are blended to 100 parts by weight of the polyetherketone resin.

Because in small amounts less than 10 parts by weight, excellent non-stick properties,
This is because sliding properties cannot be obtained, and if the amount exceeds 90 parts by weight, high temperature rigidity and mechanical strength will become extremely low.

The resin composition of the present invention may contain general-purpose fillers that can be blended with general synthetic resins in an amount that does not impede the purpose of the present invention. Specific examples include heat-resistant polymeric materials such as silicone resins, polyethersulfone resins, aromatic polyester resins, and polyimide resins, heat-resistant fiber reinforcement materials (e.g., glass fibers, carbon fibers, graphite fibers, potassium titanate whiskers) , wollastonite, ceramic fibers, magfusium whiskers, aluminum borate whiskers, steel wires, copper wires, stainless steel copper wires, silicon carbide fibers and other heat-resistant inorganic fibers or heat-resistant organic fibers such as aromatic amides Ii), Thermal conductivity improving materials (graphite,
Metals such as zinc and aluminum or magnesium oxide,
powder of mI compounds such as zinc oxide), insulation improvers (glass beads, silica balloons, diatomaceous earth, magnesium carbonate powder, asbestos, etc.), lubricity improvers (solids such as molybdenum disulfide, graphite, carbon, mica, talc, etc.) lubricants), colorants (iron oxide, cadmium sulfide, cadmium selenide and other inorganic pigments, carbon black, etc.).

The various operations such as blending, heating, and mixing of the above-mentioned raw materials in this invention are not particularly limited. The melting temperature may be 300 to 400°C, preferably 320°C.
~380°C is suitable. The method for molding the composition of this invention is not particularly limited;
Compression molding, extrusion molding, injection molding, etc. are possible.

The resin composition of the present invention can be melt-mixed and then pulverized using a jet mill, a freezing pulverizer, etc., either as it is or as a powder classified according to the desired particle size. Electro-powder coating etc. can be applied.

[Effect]

The polyetherketone resin composition in this invention is
When molded by injection molding or other methods, on the surface layer of the molded product,
3,3.3-) Fluororesin, which is a copolymer of refluoro-2-trifluoromethylpropene and 1,1-difluoroethylene, is distributed in a high density, resulting in non-adhesion and excellent lubricity. In addition to exhibiting abrasion resistance, it is presumed that due to the strength and rigidity of this fluororesin, the entire molded article exhibits excellent strength and high-temperature rigidity.

〔Example〕

The raw materials used in the Examples and Comparative Examples are listed below. In addition, the abbreviations are written in [ ], and all compounding ratios are parts by weight.

■ Polyetherketone resin (manufactured by ICI UK: 450P in Victorenox-PEE) (PEEK)
I■ Polyetherketone resin (manufactured by ICI UK: Victoresox-PEK 220G) [PEK
) ■ Copolymer of 3,3.3-trifluoro-2-trifluoromethylpropene and 1,1-difluoroethylene (manufactured by Aujimonoto, USA: Cl1-X) (CM
-X)■ Polytetrafluoroethylene (manufactured by Mitsui Devon Fluorochemical Co., Ltd.: Teflon 7J) (PTFE)■
Polytetrafluoroethylene-hexafluoropropylene copolymer (Mitsui DuPont Fluorochemical Co., Ltd.: FE
R100) [FEP) ■ Polytetrafluoroethylene-perfluoropropylene copolymer (Mitsui DuPont Fluorochemical Co., Ltd.: PF^-340J) [PFA
)■ Graphite (Nippon Graphite Co., Ltd. 2 ACP) (GR
P) Table 1 Examples 1 to 5: The raw materials blended in the proportions shown in Table 1 and mixed well were supplied to a two-wheel melt extruder (manufactured by Ikegai Tekko Co., Ltd.: PCM-30), and the cylinder temperature was 365°C. , screw rotation speed 11
The mixture was melt-mixed and extruded and granulated at 00 rpm. The obtained pellet was injection molded under the conditions of a cylinder temperature of 380°C, an injection pressure of 1200 kg/d, and a mold temperature of 200°C, and a friction and wear test piece (inner diameter 17 cm, outer diameter 21 cm, length 10 cm) and A bending test piece (based on ASTM-0790), a tensile modulus test piece (width 4 cm, length 251 m, thickness Im), and a contact angle test piece (diameter 10 cm, thickness 3 m) were prepared. The test methods for the obtained test pieces are as follows.

l) Friction and wear test Thrust type wear l! Bearing steel (
SUJ2), sliding speed 32m/min, load 6.25k
Friction coefficient and wear coefficient (i-・
−) was calculated.

2) Bending strong motion test A method according to 157M-0790 was used.

3) Tensile modulus test (retention rate of elastic modulus) Tensile stress was applied at a frequency of 107 using a dynamic viscoelasticity measurement device made by Toyo Seiki Co., Ltd., and the change in tensile modulus with respect to temperature changes was measured at 25°C and 200°C. I asked for it.

4) Non-adhesion (contact angle to water) test The contact angle to water was determined using a goniometer type contact angle measuring instrument G-1 manufactured by Elma Optical Co., Ltd.

Comparative Examples 1 to 5: Test pieces were prepared in the same manner as in Example 1, except that the raw materials were mixed in the proportions shown in Table 1, and the above tests were conducted. It is also listed in Table 1.

As can be seen from this table, Examples 1 to 5 have excellent bending strength and tensile modulus, as well as extremely good non-adhesiveness, and very good sliding properties and abrasion resistance.

On the other hand, in Comparative Example 1 in which CM-X was not added,
Comparative Examples 2 to 4, in which the fluororesin added was PTFE, PEP, and PFA, were inferior in terms of non-adhesiveness, sliding property (*! I coefficient), and abrasion resistance. It has low strength, poor high-temperature rigidity (tensile modulus at 200°C), and poor lubricity and wear resistance.Furthermore, although fluororesin (cM-X) is used, the amount added is excessive. (100 parts by weight) of Comparative Example 5 was inferior in bending strength and high temperature rigidity, and its abrasion resistance was also not very good.

〔effect〕

The polyetherketone resin composition of the present invention exhibits excellent non-adhesive properties without impairing the excellent II mechanical, thermal, and electrical properties inherent to polyetherketone resin, and also exhibits extremely favorable sliding properties. , it is ideal as a sliding member used under high temperatures.

Therefore, its excellent non-adhesive properties can be used for applications that require lubrication and non-adhesive properties, such as bearings in copiers that come into contact with highly adhesive toner, and copying from rotating bodies such as heat rollers and photoreceptors. This invention can be said to be of great significance as it can be used as a suitable material for claw members for peeling off paper.

Claims (1)

[Claims] (1) For 100 parts by weight of polyetherketone resin,
A copolymer of 3,3,3-trifluoro-2-trifluoromethylpropene and 1,1-difluoroethylene
A polyetherketone resin composition characterized in that 0 to 90 parts by weight is added.