JPS6079053A - Perfluoroalkoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. having excellent melt molding and improved physical properties, by blending a heat-resistant polyether resin with a perfluoroalkoxy resin filled with heat-resistant fiber powder. CONSTITUTION:40-130pts.vol. heat-resistant fiber powder and 0.5-30pts.vol. heat-resistant polyether resin are blended with 100pts.vol. perfluoroalkoxy resin. The term ''heat-resistant'' used herein is intended to means that the additives can withstand the molding temp. (usually 330-400 deg.C) of the perfluoroalkoxy resin. The fiber power is pref. a powder having a fiber length of 5mm. or below from the viewpoint of easy melt molding such as extrusion and injection molding. Examples of the heat-resistant polyether resins are heat-resistant thermoplastic resins contg. an ether linkage in the main polymer chain, such as polyether etherketone, polyether imide, polyether sulfone, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a river fluoroalkoxy resin composition containing Nh, fibrous filler wood powder, which has excellent melt moldability and improved physical properties.

Perfluoroalkoxy resins have the outstanding and unique properties of fluororesins, such as excellent heat resistance, chemical resistance, electrical insulation resistance, low coefficient of friction, and non-adhesion, and are suitable for extrusion molding and injection molding. It is a true thermoplastic resin that can be melt-molded.

On the other hand, this resin is relatively soft and has the disadvantage of poor wear resistance and creep resistance, so it is recommended to add fillers to improve these properties. 'It will be done. However, even if perfluoroalkoxy resin is mixed with, for example, plus #& fiber powder, melt-kneaded, and coextruded, many pores remain in the extruded strand, especially when the fiber filling cost increases. There was a problem that poor dispersion of the #& fiber powder occurred and the strands were broken during crimp coextrusion, making it impossible to produce a good molded product.

As a result of research aimed at solving this problem, the present inventors have developed a heat-resistant polymer containing ether bonds in the main chain of a polymer such as polyethersulfone resin, which is a perfluoroalkoxy resin filled with fibrous powder. When a synthetic resin is added, good extrusion molding can be performed, and
It was also found that the properties of the molded products obtained were also mixed.

Thus, according to the present invention, a perfluoroalkoxy resin containing 100 parts by volume of a perfluoroalkoxy resin, 40 to 130 parts by volume of a heat-resistant I-fiber powder, a part J-position, and 0.5 to 30 parts by volume of a heat-resistant polyether resin is prepared. A fluoroalkoxy O (fattening composition) is provided.

In the present invention, perfluoroalkoxy resin is a chain fluorocedar resin having perfluoroalkoxy side chains, and is a copolymer containing tetrafluoroethylene and a comonomer capable of providing such side chains as essential components. 372±
A resin having a specific melt viscosity at 1"C in the range of 1 x 103 to 106 poise.

Typical comonomers that can provide a perfluoroalkoxy side chain are: CF3(CF2)nOCX, =CX2X- (n is 0 to ?
, X3, ×2 and X:l are F or perfluoroalkylfluorovinyl polyethers represented by the formula [1], Rf CF:1(CFx)++(OCFCF2)mOcX1=
cXzX3 (n is 0 to 7, m is 1 to 5, Rf is F or C
Examples include perfluoroalkylfluorovinyl polyethers represented by the following formula: F3, x1, x2, and X is F or H). Typical brands of such copolymers include "Teflon" PFA-J (manufactured by Mitsui 70 Rochemical Co., Ltd.) and "Neoflon" PFA (manufactured by Daikin Industries, Ltd.).

The perfluoroalkoxy resin referred to in the present invention may also be one obtained by copolymerizing fluoroolefins such as hexafluoropropene, vinylidene fluoride, and chlorotho+7 fluoroethylene in addition to the essential components,
Typical brands of such resins include °'Teflon'E.
PE-J [manufactured by Mitsui 70 Rochemical Co., Ltd.] and the like.

In the present invention, heat resistance means being able to withstand the molding temperature (usually 330 to 4.00°C) of perfluoroalkoxy resin. As heat-resistant fibers, we use glass fibers 44L, carbon fibers, graphite fibers, inorganic fibers and whiskers such as potassium titanate whiskers, silicone carbide whiskers, sapphire voice cars, steel wires, copper wires, stainless steel wires, etc. metal fibers,
Examples include so-called boron fibers in which boron, silicon carbide, etc. are deposited on tungsten core wire or carbon fibers, composite fibers such as silicon carbide fibers, and heat-resistant fibers such as aromatic polyamide fibers. mMF.

From the viewpoint of ease of melt molding such as extrusion and injection, it is desirable that the powder has a fiber length of 10 mm or less, preferably 5+n+n or less. It is also desirable to treat the fibers with a treatment agent such as a silane coupling agent in order to increase the affinity between the fibers and the resin.

As already mentioned, a molded product obtained by simply melt-kneading and co-extruding a perfluoroalkoxy resin and a heat-resistant fiber MF powder, such as a glass fiber powder, has poor dispersibility of #& fibrous powder and contains many pores. .

Furthermore, when a product filled with lIi fiber rice powder at a higher concentration, for example, 40% by volume or more, is coextruded in the form of a strand, the strand breaks, making it impossible to perform good molding.

However, by adding 0.5 to 30 volume % of heat resistant polyether resin based on perfluoroalkoxy resin to a mixture of perfluoroalkoxy resin and heat resistant I & navy blue grain powder, the mixture was heated to a temperature of 340 to 380°C. When the mixture described in 1. is melt-kneaded and co-extruded, it is possible to obtain a molded product with good dispersibility of the fiber powder and no pores, and it is also more effective than when no heat-resistant polyether resin is added. Extrusion molded products with high tensile strength, elongation, and creep resistance can be obtained.

As the heat-resistant polyether resin, heat-resistant thermoplastic resins having an ether bond in the main chain of the polymer are used, such as polyetheretherketone, polyetherimide, polyethersulfone, and polysulfone. The heat-resistant polyether resin preferably has a melt viscosity lower than that of the perfluoroalkoxy resin, for example, a melt index value of 10 to 50 as defined later.

The amount of the heat-resistant polyether resin to be added may be relatively small, and may be used in an amount of 5 parts by volume, preferably 1 part by volume or more, per 10 parts by volume of the perfluoroalkoxy resin. The two limit values are not particularly limited from the point of view of improving extrusion properties, but if the amount is too large, for example, exceeding 30 parts by volume, there is a disadvantage that the excellent properties of the perfluoroalkoxy resin will be lost. The amount added is preferably 15 parts by volume or less.

Although the lower limit of the amount of heat-resistant fiber powder filled is not necessarily limited, the amount of heat-resistant fiber powder filled in which the effect of adding heat-resistant polyetherimide fat is effectively exhibited is 40 parts by volume, preferably 50 parts by volume. That's all. As described above, the present invention has the advantage that a high amount of heat-resistant fiber powder can be filled, that is, 40 parts by volume, especially 50 parts by volume or more, which was conventionally difficult to extrude. Not only has it become possible to extrude a perfluoroalkoxy resin composition filled with fiber powder, but the amount that can be filled has been reduced to 1.
It is unique in that it has been dramatically increased to 30 parts by volume. As a result, according to the present invention, the creep resistance of the perfluoroalkoxy resin filled with heat-resistant fiber powder is improved by about 4 to 10 times.

The composition of the present invention has a low coefficient of friction unique to fluororesins.
1; It has +1-trade with Il property, and Il, -,), and its mechanical properties are improved by the addition of heat-resistant fiber powder, so it can be used for various lubrication and non-adhesive applications. Since it has excellent creep resistance, it is particularly suitable for bearing materials where load-bearing properties are expected.

In addition, the melt index (M, 1.) in the present invention is:
Using a melt indexer manufactured by Toyo Seisei Seisakusho Co., Ltd., the preheated and dried sample was placed in a cylinder heated to 360°C, and after preheating for 6 minutes, a load of 5 kg was applied to the orifice (inner diameter 2.095 mm, The amount of sample extruded in 10 minutes is expressed in grams. However, the modified polyphenylene oxide resin in Comparative Example 3 described later had low heat resistance and the sample flowed out, so preheating for 6 minutes could not be performed.

Next, the present invention will be specifically explained using Examples, Comparative Examples, and Reference Examples.

Examples 1 to 3 Perfluoroalkoxy resin pellets (Teflon '341 manufactured by Mitsui 70 Rochemical Co., Ltd., J, melt index (M, I,)==14.2) and glass fiber A
11 (Chopped strand manufactured by Asahi Fiberglass Co., Ltd.)
3MA497, aluminum/silane treatment, average fiber length 3mm)
and polyether sulfone resin powder (manufactured by 1, C, 1 Company)
PES-300P", M, L=25.4)
After tri-blending at the ratio shown in 1, the mixture was fed to a Nitsumugi melt extrusion rock (PCM-3o extrusion rock, manufactured by Ikegai Iron Works) at a treatment temperature of 360 ''C, screw rotation speed of 150 r, p,
While melting and kneading with If+, strand gui (diameter 3mm
, extruded through hole 5), and the extruded strand was continuously cut to obtain pellets.

Next, the above pellets were molded into an injection molding machine (barrel temperature: 320~
380℃, mold temperature 210'C1 injection pressure 800kg
/cm''), and the physical properties of the molded test pieces were measured.

Table 2 shows the observation and evaluation results of the extruded strands and the physical properties of the test pieces.

Example 4 The same procedure as Example 1 was carried out except that the polyether sulfone resin powder was changed to polyether ether ketone resin powder (r, c, r, "'PEEK Natural'" M, L = 18.2, manufactured by Co., Ltd.). extrude the strands to obtain pellets,
A test piece was prepared.

Table 2 shows the observation evaluation results of the strands and the physical properties of the test pieces.

Comparative Example 1 A strand was extruded in the same manner as in Example 1 except that a heat-resistant polyether resin was mixed, but a large number of strand breakages occurred (for example, 4 to 5 times per 10 m). For this reason, an extrusion test was conducted in the same manner by raising the processing temperature from 360°C to 380°C, but as in the case of 360°C, many strand breakages occurred.

Table 2 shows the observation and evaluation results of the extruded strands.

Comparative Example 2 Poly7-enyl-7-eyed resin powder (manufactured by Phillips Petroleum Co., Ltd.) was used instead of heat-resistant polyether resin.
The test was conducted in the same manner as in Example 1, except that Rydon PPS P-4''M, ■, = 37°9) was used.During extrusion, strand breakage occurred approximately once per 10M of strand. The surface of the obtained strand was rough and unsuitable for commercial use.

Physical properties such as compression creep resistance, bending strength, tensile strength, and elongation of the prepared test pieces were lower than those of Examples 1 and 4 in which the same amount of glass fiber was mixed. The evaluation results and physical properties of the strands are shown in Table 2.

Comparative Example 3 Modified polyphenylene oxide resin with low heat resistance (manufactured by Engineering Plastics Co., Ltd. "Noryl 731J-802゛, M, I = 15" was used instead of heat-resistant polyether resin)
Strands were extruded in the same manner as in Example 1 except that 9°3) was used, but many strand breaks occurred. For this reason, the treatment temperature was changed from 360°C to 340°C and 380°C, but many strand breaks occurred in each case.

Examples 5-6 “Teflon” 134 as perfluoroalkoxy resin
In Example 5, aromatic Polyamide fiber (
"Kevlar 49" manufactured by DuPont Co., Ltd., fiber role: about 1τ), potassium titanate whisker (manufactured by Daikyu Chemical Co., Ltd. "Teismo D", j!IiMt艮O, (',
+ 2-0, (13nun and graphite powder (“ACP-10+10” manufactured by Nippon Graphite Co., Ltd., natural flaky graphite,
The above components were triblended using a powder with an average particle size of 6 μm. -I: The mixing ratio of the components listed above is shown in Table-1.

Preparation and evaluation of extruded strands and pellets and measurement of physical properties of test pieces were carried out in the same manner as in Example 1, and the results are shown in Table 2.

Example 7 Perfluoroalkoxy resin (Teflon '350-JM, manufactured by Mitsui 70 Chemical Co., Ltd., !, = 1.8) and carbon M
& Tsutsugi (M-1047 manufactured by Hane Kagaku Co., Ltd., M&it length approx. 0
, 4 mto) and polyetheretherketone resin (1
After tri-blending "PEEK" (manufactured by Company 1), extruded strands and pellets were obtained in the same manner as in Example 1. Next, the pellets were heated at a temperature of 340°C.
A test piece was prepared by compression molding at a pressure of 18 mm and 5 kg/cm2, and its physical properties were measured.

The evaluation results and physical properties of the strands are shown in Table 2.

Comparative Example 4 A strand was extruded in the same manner as in Example 7 except that no heat-resistant polyether resin was used, but many strand breaks occurred. For this reason, extrusion molding was carried out in the same manner by increasing the processing temperature from 360°C to 380°C and 4()0°C, but many strand breakages occurred.

Comparative Example 5 A strand was extruded in the same manner as in Example 7, except that polyphenylene sulfide resin (Rydon'PPS P-4) was used in place of the heat-resistant polyether resin, and the amount of carbon fiber used was changed. However, many strands broke.

Reference example perfluoroalkoxy resin (“Teflon” 34 (1-
, J) Injection molding 8! (Barrel temperature 320-380℃
, mold temperature 210℃, injection pressure 30 ('l kg/c
m2) to prepare a test piece, and its physical properties were measured.

The measurement results are shown in Table-2.

^　-- Ax Chi

Claims (1)

[Claims] 1. A perfluoroalkoxy resin composition containing 100 parts by volume of perfluoroalkoxy resin, 40 to 130 parts by volume of heat-resistant fiber powder, and 0.5 to 30 parts by volume of heat-resistant polJ ether resin as essential components. thing. 2. The composition according to claim 1, wherein the heat-resistant polyether resin is a polyether sulfone resin, a polyetherimide resin, or a polyether ether ketone resin. 3. The composition according to claim 2, wherein the amount of heat-resistant polyether resin added is 1 to 15 parts by volume.・1. The composition according to claim 3, wherein the heat-resistant fiber powder has a #& fiber length of 5111111 or less. 5. The composition according to claim 4, wherein the amount of heat-resistant fiber powder filled is 50 to 120 parts by volume. 6. The composition for melt molding according to claim 5. 7. The composition for sliding members according to claim 5.