JPS63264672A - Lubricative resin composition - Google Patents

Abstract

PURPOSE:To obtain a lubricative resin composition which is good in moldability and can give a molding which has excellent sliding characteristics and retains the mechanical properties essential to a synthetic resin, by mixing the synthetic resin with a polyfluoroether having specified groups and a fluororubber. CONSTITUTION:A lubricative resin composition prepared by mixing synthetic resin (e.g., PE, nylon 12 or polyacetal) with 0.5-20.0pts.wt. polyfluoroether containing at least one kind of groups selected from among carboxyl groups, ester group, epoxy groups, amino groups and mercapto groups [e.g., a compound wherein the main structure unit containing any one kind of said groups is repersented by the formula (wherein x is 1-40)] and 0.5-20pts.wt. fluororubber (e.g., a binary copolymer comprising a tetrafluorothylene/propylene copolymer). A molding obtained from this composition retains the mechanical properties essential to the synthetic resin itself and has excellent sliding properties and good moldability, so that it is suitable as a material for sliding parts such as bearing materials.

Description

[Detailed description of the invention] [Industrial application field] This invention relates to a lubricating resin composition.

[Conventional technology]

In recent years, as machines have become lighter, synthetic resin products have come to be used in large numbers as machine parts, and synthetic resins with excellent sliding properties are required for bearings. Conventionally, polyamide, polyacetal, polyethylene, fluororesin, etc. have been used as synthetic resins with good sliding properties. These can function without lubrication at low loads and low speeds, but as the loads and high speeds increase, they seize or flow due to frictional heat, making them unusable. Fluororesins, especially tetrafluoroethylene resins, show excellent sliding properties by adding fillers to improve wear properties, but these can only be molded by compression molding.
It also has the disadvantage of being very expensive. Therefore, measures have been taken to improve the sliding properties by adding solid lubricants to other synthetic resins, but this method does not sufficiently improve the sliding properties under high speed and high loads. In addition, in order to solve the above problem, there is a method of adding lubricating oil to synthetic resin to make so-called oil-impregnated plastic.The specific methods are (1) simply mixing lubricating oil into the resin, (2) adding lubricating oil to the resin. (3) adding a carrier that can hold the lubricant together with the lubricating oil; (3) the above (
In addition to 1) and (2), there are also those in which a fibrous filler is added as an oil conductor. Such oil-impregnated plastics are intended to have sliding properties by leaching lubricating oil, but 1) the Fj friction coefficient is unstable at a low value, and 2) oil seeps out when heated. 3) Poor formability, 4) The assembly scrapes the mating material during sliding, 5)
Oil tends to separate during molding or kneading, 6) material properties deteriorate, 7) oil tends to adhere to sliding surfaces and dust, etc. tend to adhere, 8) abnormal wear occurs once the oil runs out, and many other problems. There was a problem.

[Problem to be Solved by the Invention 1] As mentioned above, in the conventional technology, the friction coefficient is stable at a low value, the wear coefficient is small, and the mechanical properties (
There is a problem in that it is not possible to obtain a material that does not cause a decrease in strength, and even synthetic resins that have many 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 proposes a synthetic resin 1
0.00 parts by weight, 0.5 to 20.0 parts by weight of polyfluoroether containing any one of carboxyl group, ester group, isocyanate i, alcoholic hydroxyl group, epoxy group, amino group and mercapto group. This method employs a method of blending 0.5 to 20.0 parts by weight of fluorine-containing rubber to form a lubricating resin composition. The details will be described below.

First, the synthetic resin in this invention is not particularly limited, and may be either thermosetting or thermoplastic resin, such as 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-guanamine resin, polyester resin, diallyl phthalate resin, xylene resin, epoxy resin, epochine acrylate resin, silicone resin, urethane resin, tetrafluoroethylene resin, chlorotrifluoroethylene resin,
Tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, vinylidene fluoride resin, ethylene/tetrafluoroethylene copolymer, vinyl chloride resin, vinylidene chloride resin, polyethylene resin (low density) , high density, ultra-high polymer, chlorinated polyolefin resin, polypropylene resin, modified polyolefin resin, water-crosslinked polyolefin resin, ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, polystyrene resin, ABS resin, polyamide resin , methacrylic resin, polyacecool resin, polycarbonate resin, cellulose resin, polyvinyl alcohol resin, polyurethane elastomer, polyimide resin, polyetherimide resin, polyamideimide resin, ionomer resin, polyphenylene oxide resin, methylpentene polymer,
Polyallyl sulfone resin, polyallyl ether resin, polyether ketone resin, polyphenylene sulfide resin, polysulfone resin, wholly aromatic polyester, polyethylene terephthalate resin, polybutylene terephthalate resin, thermoplastic polyester elastomer, blends of various other polymeric substances, etc. can be exemplified, and then the carboxyl group, ester group,
Isocyanate group, alcoholic hydroxyl group, epoxy group,
A polyfluoroether containing either one of an amino group and a mercapto group is -CxFtxO [x is 1
~4 integer] as the main structural unit, and the average molecular weight is approximately 50
0 to 50,000 polymers into which functional groups such as carboxyl groups, ester groups, isocyanate groups, alcoholic hydroxyl groups, epoxy groups, amino groups, and mercapto groups are introduced, such as the following. That is, the carboxyl base: +1 (E-CM + C1F, 0÷1÷CFzO)1α
Those containing ester groups such as 2■open: H,C00C-CP, O(-C,F,0-)r+cFt
Ohal+), etc., containing an isocyanate group: containing an alcoholic hydroxyl group: containing an epoxy group: containing an amine group: containing a mercapto group: where m in the formula and n is an arbitrary integer.

Furthermore, the fluorine-containing rubber in the present invention is preferably an elastic polymer containing a small number (one kind) of polymerized units of a fluorine-containing olefin, and two or more kinds of polymerized units. Examples of fluororubber-like elastomers include binary copolymers made of tetrafluoroethylene/propylene copolymers and ternary tetrafluoroethylene/propylene copolymers made of units containing glycidyl ether groups as reaction sites. Copolymers can be mentioned.

Furthermore, tetrafluoroethylene/perfluoroalkyl perfluorovinylether copolymer, vinylidene fluoride,
Propylene hexafluoride polymer, vinylidene fluoride/propylene pentafluoride copolymer, vinylidene fluoride/ethylene trifluoride chloride polymer, ethylene tetrafluoride/ethylene/isobutylene copolymer, ethylene/6 Examples include fluorinated propylene copolymers, tetrafluoroethylene/butene-1 copolymers, and tetrafluoroethylene/ethyl vinyl ether copolymers. The content ratio of each of the above components in such a fluorine-containing rubber-like elastic body is as follows:
As long as it is an elastic copolymer, it can be selected from a wide range, such as copolymers consisting of 40 to 70 mol% tetrafluoroethylene and 60 to 30 mol% propylene, 50 to 90 mol% fluorinated copolymers, etc. Liden and 50-10
A copolymer consisting of mol% hexafluoropropylene and 0 to 30 mol% tetrafluoroethylene; a copolymer consisting of 30 to 90 mol% tetrafluoroethylene and 70 to 10 mol% perfluoroalkyl perfluorovinyl ether; Polymer, 50-90 mol% vinylidene fluoride and 10-90 mol% vinylidene fluoride
A copolymer consisting of 50 mol% of propylene pentafluoride can be exemplified. Of course, the above-mentioned fluorine-containing rubber-like elastic body has, in addition to the above-mentioned component units and reaction sites, other units (for example, a tetrafluoroethylene/propylene copolymer containing vinylidene fluoride, ethylene, isobutylene, acrylic acid, Units such as its alkyl ester, hexafluoropropylene, trifluorochlorinated ethylene, chloroethyl vinyl ether, perfluoroalkyl vinyl ether, etc.) may be appropriately contained in the tetrafluoroethylene/propylene copolymer. The reaction site consists of a unit containing a glycidyl vinyl ether group, and among them, glycidyl vinyl ether is preferred, but in addition, glycidyl acrylate, acrylic acid, methacrylic acid, 2-
Examples include chloroethyl vinyl ether.

Here, in this invention, the reason why polyfluoroether having a functional group and fluorine-containing rubber having a functional group are mixed in the synthetic resin is that it is impossible to form a network structure due to the mutual reaction of different functional groups with either one of the compounds. This is because the polyfluoroether cannot be retained within the synthetic resin structure and exhibits the same drawbacks as ordinary lubricant-containing synthetic resins, and two or more types of polyfluoroethers with different functional groups The network structure becomes stronger than when mixing
This is because it can be better retained within the structure of the synthetic resin. The reason for adding 0.5 to 20.0 parts by weight of both polyfluoroether and fluorine-containing rubber is that if the amount is less than the lower limit, the effect of improving the sliding properties is insufficient; This is because the mechanical properties of the synthetic resin are significantly deteriorated, which is not preferable.Among these, the particularly preferable range is 1.0 to 15.0 parts by weight.

To mix such synthetic resins, polyfluoroethers, and fluorine-containing rubbers, conventional methods (known methods may be used; for example, synthetic resins and the above-mentioned compounding components may be mixed individually, or fluorochlorohydrocarbons may be mixed together). or the like, and mixed with a mixer such as a Henschel mixer, a ball mill, or a tumbler mixer, and then the solvent is removed and supplied to an injection molding machine or a solvent extruder with good melt-mixability, or Melt mixing may be carried out in advance using a heated roller, kneader, Banbury Mixer-1 melt extruder, etc.Also, when molding these compositions, the method is not particularly limited, but compression molding, In addition to practical methods such as extrusion molding and injection molding,
The powder of the molten mixture finely pulverized by a jet mill, freezing pulverizer, etc. is used as it is, or after being classified to the desired particle size,
It can also be used for fluidized dip coating, electrostatic powder coating, etc.

The lubricating resin composition of the present invention includes, in addition to the above-mentioned lubricating compounding agents, such as a fluorine-containing rubber-like elastomer, polyfluoroether, etc., additives that can be widely blended with synthetic resins in -i.
They can also be used in combination as appropriate in amounts that do not reduce the properties of the lubricating resin composition. Examples of such additives include mold release agents, flame retardants, weather resistance improvers, etc. These additives may be added and blended simultaneously with the lubricity compound of the present invention, but they may be mixed with the additives in advance. It is possible to adopt a method of blending a mixture with a lubricating compounding agent or a graft copolymerized elastomer. Furthermore, it is of course possible to use conventionally known and publicly used solid or liquid lubricants in combination with the above additives, such as tetrafluoroethylene resin powder, graphite, graphite fluoride, talc, boron nitride, fluorinated oil, Silicone oil and other industrial lubricants can also be selected and used as appropriate depending on the purpose of use. In any case, it is of course possible to modify the intermediate or final product to improve its properties by chemical or physical treatment, as long as the lubricity of the lubricating resin composition of the present invention is not impaired.

[Operation] In the lubricating resin composition of the present invention, the functional groups of the polyfluoroether and the functional groups of the fluorine-containing rubber react with each other, so that the polyfluoroether having lubricating properties and the fluorine-containing rubber are formed in the resin structure. A three-dimensional network structure containing rubber is formed, and because the network is finely dispersed, the coefficient of friction is small.Moreover, this lubricating substance remains firmly within the tissue without falling off, so the coefficient of friction remains long. It is presumed that it will remain stable for a long period of time, and at the same time the synthetic resin structure of the base material will be reinforced, resulting in little wear and no decrease in mechanical strength, solving all of the drawbacks of conventional oil-containing plastics.

〔Example〕

First, the raw materials used in the Examples and Comparative Examples shown below are as follows. Abbreviations are shown in brackets.

■Polyethylene [P] (manufactured by Mitsui Petrochemical Co., Ltd.: HIZEX 1300J), ■Nylon 12 (PA12) (manufactured by Daicel Chemical Co., Ltd.: Diamid L1640P), ■Nylon 66 (PA66) (manufactured by Toshisha Co., Ltd.: Amilan CM3001N), ■ Polysecool (POM) (manufactured by Polyplastics: Duracon M90-02),
■Carboxyl group-containing polyfluoroether [formerly ^C] (Dicarboxyl-modified fluorocarbon oil manufactured by Montefluo, Italy/ShiroMBLr!i Z-DIAC), ■Ester group-containing polyfluoroether [DI! ^L] Made by Montefluo, Italy: Ester-modified fluorine oil FOMBLI
NZ-DEAL 2000''), ■ Alcoholic hydroxyl group-containing polyfluoroether (DOL) (made by Montefluo, Italy: alcoholic hydroxyl group-containing 7-
/Suoi/L, FOMBLrN Z-[10L 200
0), ■Fluorine-containing rubber (PR) (copolymerized elastomer consisting of 54 moles of tetrafluorinated ethylene, 43 moles of propylene, and 2 moles of glycidyl vinyl ether and exhibiting a MLI viscosity of 60-MLI + 4 (100°C)) ■Polyfluoroether (PFPE@) is an epoxy group-containing polyfluoroether with an average molecular weight of approximately 2000.
Phase] Amino group-containing polyfluoroether 11□N<cH
t: Polyfluoroether with average molecular weight of about 2000 (PFP dark) ■ Polyfluoroether containing mercapto group Its (-Cl1z +-rNttQ)
-CFzO+ CZFaO-)-r+CF, Ok C
FaNII-f CH, with h pieces, the average molecule lv'J2
000 polyfluoroether [Tabari ■ Tertiary amine (N,N-dimethylbenzylamine). Note that all blending ratios (parts) of each raw material are parts by weight.

Examples 1 to 14: Various raw materials were mixed in the proportions shown in Table 1, thoroughly mixed in a Henschel mixer, then fed to a twin-screw melt extruder and extruded under the melt mixing conditions shown in Table 2. The pellets were granulated, and a ring-shaped test piece having an inner diameter of 14mm, an outer diameter of 23++n, and a length of 13III11 was produced using an injection molding machine under the conditions shown in the same table. The friction coefficient and wear coefficient c+j/kg·m were determined for the obtained test piece. The friction test was carried out using a thrust type friction tester at a sliding speed of 1/min.
The friction coefficient was measured 60 minutes after the start of operation under the conditions of 0 m and a load of 10 kg/cta, and the wear test was performed using a thrust type abrasion tester at a sliding speed of 32 m/min and a load of 3.1 kg/c.
It was carried out under the conditions of j. The mating materials in these tests were all bearings fisUJ2 (quenched and ground finished), and the results obtained are also listed in Table 2.

Comparative Examples 1 to 8: Comparative Examples 1 to 8: No. 34, except that various raw materials were blended in the proportions shown in Table 3 without blending fluororubber, and test pieces were produced under the melt mixing conditions and injection molding conditions shown in Table 4. The friction coefficient and wear coefficient of each test piece were measured in exactly the same manner as in Examples 1 to 14. The obtained results are also listed in Table 4.

As is clear from Tables 1 and 2 and Tables 3 and 4, Examples 1 to 14 containing fluororubber are relatively smaller than Comparative Examples 1 to 8 that do not contain fluororubber. The friction coefficient and the wear coefficient of the plastic were extremely favorable, and the plastic did not exhibit the drawbacks of conventional oil-containing plastics. Furthermore, since the objectives of low friction and low wear are achieved without adding hard fillers that have been widely used in the past, there is no damage to the mating material during sliding.

〔effect〕

As is clear from the above, the molded article made of the lubricating resin composition of the present invention has excellent sliding properties while retaining the mechanical properties inherent to synthetic resins, and also has good moldability. Therefore, it is a material that simultaneously satisfies the three properties of slidability, moldability, and economy, which have never been seen before.

Therefore, this composition is most suitable as a material for sliding parts such as bearing materials, and it can be said that the significance of this invention is very large.

Claims (1)

[Claims] 0.5 to 20 parts by weight of polyfluoroether containing any one type of group among carboxyl group, ester group, isocyanate group, alcoholic hydroxyl group, epoxy group, amino group, and mercapto group is added to 100 parts by weight of the synthetic resin. 0
1. A lubricating resin composition comprising 0.5 to 20.0 parts by weight of fluorine-containing rubber and 0.5 to 20.0 parts by weight.