JPH0759669B2 - Lubricating resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a lubricating resin composition.

[Conventional technology]

In recent years, as the weight of machines has been reduced, synthetic resin products have been widely used as machine parts, and synthetic resins having excellent sliding characteristics are required for those used in bearings. Conventionally, polyamide, polyacetal, polyethylene, fluorine resin and the like have been used as synthetic resins having good slidability. These can be used even in the low load and low speed region even without lubrication, but as the load and speed increase, they become seized or flow due to frictional heat and become unusable. Fluorine resin, especially tetrafluoroethylene resin shows excellent sliding characteristics by adding a filler to improve wear characteristics, but this can be molded only by compression molding,
It also has the drawback of being very expensive. Therefore,
Means for adding a solid lubricant to other synthetic resins to improve the sliding characteristics have been adopted, but this method does not sufficiently improve the sliding characteristics under high speed and high load. To solve the above problem, there is a method of adding a lubricating oil to a synthetic resin to form a so-called oil-impregnated plastic. Specific methods are 1) simply mixing the lubricating oil with the resin and 2) retaining the lubricating oil. A possible carrier is added together with a lubricating oil, 3) In addition to 1) and 2) above, a fibrous filler is added as an oil conductor. Such oil-impregnated plastics try to have sliding characteristics by allowing the lubricating oil to exude, but (1) the friction coefficient is not stable at a low value, and (2) the oil exudes when heated. (3) Poor formability, (4) Carrier scrapes the mating material during sliding,
(5) Oil easily separates during molding or kneading,
There are various problems such as (6) physical properties of the material are deteriorated, (7) oil is easily attached to the sliding surface to cause dust, etc. (8) Abnormal wear occurs once the oil runs out.

[Problems to be solved by the invention]

As described above, in the prior art, it is not possible to obtain a material in which the friction coefficient is stable at a low value, the friction coefficient is small, and the mechanical characteristics (simply strength) are not deteriorated.
There has been a problem that many synthetic resins having excellent properties are not suitable for sliding materials that require low friction and wear resistance.

[Means for solving problems]

In order to solve the above problems, the present invention provides a synthetic resin 10
0.5 to 20.0 parts by weight of at least two kinds of polyfluoroethers selected from the group consisting of polyfluoroethers having a carboxyl group, an ester group, an isocyanate group or an alcoholic hydroxyl group as a functional group are mixed with 0 parts by weight, A means for producing a lubricating resin composition in which a three-dimensional network structure of polyfluoroether is formed by a reaction between functional groups is adopted. The details will be described below.

First, the synthetic resin in the present invention is not particularly limited, and may be any of thermosetting or thermoplastic resins, for example, phenol resin, urea resin,
Melamine resin, melamine / phenol co-condensation resin, xylene-modified phenol resin, urea / guanamine co-condensation resin, amino resin, acetoguanamine resin, melamine anamin resin, polyester resin, diallyl phthalate resin, xylene resin, epoxy resin, epoxy acrylate resin, Silicone resin, urethane resin, polytetrafluoroethylene, chlorotrifluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, vinylidene fluoride resin, ethylene / tetrafluoroethylene Copolymer, ethylene / chlorofluoroethylene copolymer, vinyl chloride resin, vinylidene chloride resin, polyethylene (low density, high density, ultra high molecular weight), chlorination Riorefuin, polypropylene, modified polyolefin, water crosslinking polyolefin, ethylene
Vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, polystyrene, ABS resin, polyamide,
Methacrylic resin, polyacetal, polycarbonate,
Cellulose resin, polyvinyl alcohol, polyurethane elastomer, polyimide, polyetherimide, polyamideimide, ionomer resin, polyphenylene oxide, methylpentene polymer, polyallyl sulfone, polyallyl ether, polyether ketone, polyphenylene sulfide, polysulfone , Wholly aromatic polyester, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester elastomers, blends of various polymer substances, and the like.

Then, the carboxyl group in the present invention, an ester group, a polyfluoroalkyl ethers containing isocyanate groups, any one alcoholic hydroxyl group, -CxF ₂ x-O-
A polymer having [X is an integer of 1 to 4] as a main structural unit, into which a functional group such as a carboxyl group, an ester group, an isocyanate group, or an alcoholic hydroxyl group has been introduced, is as follows. That, HOOC-CF ₂ OC ₂ those containing a carboxyl group _{F 4 O m CF 2 O n} CF 2 COOH such as those containing an ester group _{H 3 COOC-CF 2 OC 2} F 4 O m CF 2 O n CF ₂ COOCH ₃ etc. containing isocyanate groups OCN-C ₆ H ₃ (CH ₃ ) -NHCOCF ₂ C ₂ F ₄ O _m CF ₂ O _n CF ₂ CONH- (CH ₃ ) C ₆ H ₃ -NCO etc. those containing an alcoholic hydroxyl group HOCH, etc. _{2 2 NHCO-CF 2 OC 2} F 4 O m CF 2 O n CF 2 CONHCH 2 2 OH.

The reason for blending at least two kinds of polyfluoroethers having different functional groups in the present invention is that it is impossible to form a network structure by the reaction of different kinds of functional groups with only one kind of polyfluoroether. This is because it cannot be contained within the synthetic resin structure, and exhibits the same drawbacks as those of ordinary synthetic resin containing lubricant.
In addition, in order to promote the reaction between different polyfluoroethers, a catalyst such as amines may be appropriately added. Here, the compounding amount of the polyfluoroether of the present invention is 10
The reason for limiting the content to 0.5 to 20.0 parts by weight relative to 0 parts by weight is that the effect of improving the sliding properties is insufficient if the amount is less than the lower limit, and conversely if the amount exceeds the upper limit, the mechanical properties of the synthetic resin are This is because the amount is remarkably lowered, which is not preferable, and the range of 1.0 to 15.0 parts by weight is particularly preferable.

The method for mixing the synthetic resin and the polyfluoroether described above may be any conventionally known method, and is not particularly limited. For example, the synthetic resin and the above-mentioned respective components may be individually or appropriately used as a solvent. Dissolve in (fluorochlorohydrocarbon, etc.), Hensiel mixer,
After mixing with a mixer such as a ball mill or a tumbler mixer, the solvent is removed and the mixture is supplied to an injection molding machine or a melt extruder having a good melt mixing property, or a hot roller, a kneader, a Banbury mixer, a melt extruder in advance. And so on. Further, in molding the composition of the present invention, the method is not particularly limited, but compression molding, extrusion molding, injection molding and the like are possible, and after the mixture of the present invention is melt mixed. The mixture can be pulverized by a jet mill, a freeze pulverizer, or the like and used as it is or as a powder having a desired particle size as a powder coating material for fluidized immersion coating, electrostatic powder coating, or the like.

Further, the composition of the present invention may be appropriately combined with additives that are widely mixed with general synthetic resins in an amount within a range that does not deteriorate the properties of the composition. Examples of such additives include mold release agents, flame retardants, weather resistance improvers and the like. These additives may be added and mixed at the same time as the lubricating compounding agent of the present invention, or may be compounded with a lubricating agent. It may be pre-blended with the agent and added to the synthetic resin, and it is also possible to use a publicly known lubricant from the past, of course, tetrafluoroethylene resin powder, graphite, fluorinated graphite,
Talc, boron nitride, other industrial lubricants and the like can be appropriately selected and used according to the purpose of use. Further, well known as a reinforcing agent are glass fiber, carbon fiber, alumina fiber, asbestos, rock wool, wollastonite, fibrous substances such as potassium titanate whiskers, or glass powder, talc, clay, calcium carbonate, etc. Inorganic fillers and the like can also be used. In any case, it is needless to say that the intermediate product or the final product form can be modified by chemical or physical treatment for property improvement as long as the lubricity of the composition of the present invention is not impaired. is there.

[Action]

In the lubricating composition of the present invention, the different functional groups of at least two kinds of polyfluoroether react with each other to form a three-dimensional network structure of polyfluoroether having lubricity in the synthetic resin structure. Since the mesh is finely dispersed, the friction coefficient is small, and since the lubricating substance stays firmly in the tissue without falling off, the friction coefficient is maintained stably for a long period of time, and at the same time, the synthetic resin of the base material. It is presumed that the structure is reinforced, the wear is small, the mechanical strength is not reduced, and all the drawbacks of the conventional oil-impregnated plastics are solved.

〔Example〕

First, the raw materials used in the following examples and comparative examples are collectively shown as follows. The abbreviations are written in []. Polyethylene [PE] (Mitsui Petrochemical Co., Ltd .: Hijets 1300J), Nylon 12 [PA12] (Daicel Chemical Co., Ltd .: Daiamide)
L1640P), polyacetal [POM] (manufactured by Polyplastics: Diuracon M90-02), polybutylene terephthalate [PBT] (manufactured by Mitsubishi Kasei Co., Ltd .: Novadwool 5010), carboxyl group-containing polyfluoroether [DIAC]
(Ikoku Montefluor Corporation: Carboxyl modified fluorine oil FOMBLIN Z-DIAC), Ester group-containing polyfluoroether [DEAL] (Ikoku Montefluor Corporation: Ester modified fluorine oil FOMBLIN
Z-DEAL2000), isocyanate group-containing polyfluoroether [DISO
C] (Ikoku Montefluo Co .: isocyanate modified fluorine oil FOMBLIN Z-DISOC), alcoholic hydroxyl group-containing polyfluoroether [DO
L] (Ikoku Montefluo Co., Ltd .: alcoholic hydroxyl group-containing fluorine oil FOMBLIN Z-DOL2000). The mixing ratios (parts) of each raw material are all parts by weight.

Examples 1 to 9: Various synthetic resins were mixed with polyfluoroether as shown in Table 1, thoroughly mixed with a Henschel mixer, and then fed to a twin-screw melt extruder under the melt-mixing conditions shown in the same table. The pellets were extruded and granulated, and the pellets were supplied to an injection molding machine to prepare a ring-shaped test piece having an inner diameter of 14 mm, an outer diameter of 23 mm and a length of 13 mm under the injection molding conditions shown in the table. A friction wear test was conducted using a ring-shaped test piece. For the friction test, operation was started using a thrust type friction tester at a sliding speed of 10 m / min and a load of 10 kg / cm ^2.
The coefficient of friction after 0 minutes It was measured. The abrasion test was performed using a thrust type abrasion tester under the conditions of a sliding speed of 32 m / min and a load of 3.1 kg / cm ² . Bearing steel SUJ2 (quenched,
Grinding finish) was used. The obtained results are also shown in Table 1.

Comparative Examples 1 to 9: Test pieces were prepared in the same manner as in Examples 1 to 9 except that the synthetic resin and polyfluoroether were used in the mixing ratios, melt mixing conditions, and injection molding conditions shown in Table 2. A similar friction and wear test was conducted on the obtained test pieces, and the results are also shown in Table 2.

Comparing Table 1 and Table 2, Examples 1 to 9 containing 2 to 3 kinds of polyfluoroethers, Comparative Examples 1 to 8 containing only 1 kind of polyfluoroether, and Polyfluoroethers It is apparent that the friction coefficient and the wear coefficient are much smaller than those of any of Comparative Examples 9 and the hard filler that has been widely used in the related art is not added. It did not damage the sliding surface of the mating material.

[Effects] As described above, the molded product made of the lubricating resin composition of the present invention exhibits a stable low friction coefficient with time, and the synthetic resin structure is reinforced to have abrasion resistance. Since it has excellent sliding characteristics, good moldability, and is optimal for bearing materials, it can be said that the significance of the present invention is extremely great.

Claims (1)

[Claims] 1. 0.5 to 20.0 of at least two kinds of polyfluoroether selected from the group consisting of polyfluoroether having a carboxyl group, an ester group, an isocyanate group or an alcoholic hydroxyl group as a functional group per 100 parts by weight of a synthetic resin. A lubricating resin composition which comprises 3 parts by weight and forms a three-dimensional network structure of polyfluoroether by the reaction of different functional groups.