JPH068428B2 - 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, a means for improving the sliding characteristics by adding a solid lubricant to other synthetic resins is adopted, but this method does not sufficiently improve the sliding characteristics under high speed and high load. In order to solve the above problems, there is a method of adding lubricating oil to synthetic resin to make so-called oil-containing plastic, and concrete methods are 1) simply mixing the lubricating oil with the resin, 2) retaining the lubricating oil. A possible carrier is added with the lubricating oil. 3) above 1) and 2)
Besides, a fibrous filler may be added as an oil conductor. Such oil-impregnated plastics try to give the sliding characteristics by leaching the lubricating oil, but (1) the friction coefficient is not stable at a low value, and (2) the oil soaks when heated. (3) Poor moldability, (4) Carrier scrapes the mating material during sliding, (5) Oil easily separates during molding or kneading, (6) Physical properties of material deteriorate, (7) There were various problems such as oil on the sliding surface, which was likely to cause dust, and (8) Abnormal wear, which occurred once the oil was cut off.

[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 wear coefficient is small, and the mechanical properties (especially strength) are not deteriorated.
There is a problem that even synthetic resins having 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 provides a synthetic resin 1
0.5 to 100 parts (parts by weight, the same applies hereinafter) of organopolysiloxane having a unit containing a carboxyl group
20.0 parts and 0.5 to 20.0 parts of an organopolysiloxane having a unit containing at least one kind of group selected from an amino group and an alcoholic hydroxyl group are mixed to obtain a resin composition having lubricity. The means is adopted. The details are given 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), chlorinated polyolefin, polypropylene, Modified polyolefin, water-crosslinked polyolefin, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polystyrene, ABS resin, polyamide,
Methacrylic resin, polyacetal, polycarbonate,
Cellulosic 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.

Next, the organopolysiloxane having a unit containing a carboxyl group, an amino group, and an alcoholic hydroxyl group in the present invention is a homopolymer of organopolysiloxane such as dimethylsiloxane, methylphenylsiloxane, trimethylfluoropropylsiloxane, or two or more kinds of A copolymer having a carboxyl group, an amino group, and an alcoholic hydroxyl group introduced therein. Examples of these are as follows. That is, a carboxyl group-containing organopolysiloxane Amino group-containing organopolysiloxane Organopolysiloxane containing alcoholic hydroxyl groups [Here, R is an alkylene group or the like, m = 5 to 1000
0 and n = 2 to 100. ] Can be mentioned.

In the present invention, the reason why 0.5 to 20.0 parts of the organopolysiloxane having a unit containing a carboxyl group is blended with 100 parts of the synthetic resin is because a small amount less than the lower limit value improves the sliding property. Is insufficient, and conversely, if the amount exceeds the upper limit, the mechanical properties of the synthetic resin are significantly deteriorated, which is not preferable.
The range is from 15.0 parts. Further, 0.5 to 2 of an organopolysiloxane having a unit containing at least one kind of group selected from an amino group and an alcoholic hydroxyl group is further added.
The reason for blending 0.0 parts is that if the amount is less than the lower limit, the reaction with the organopolysiloxane having a unit containing a carboxyl group is not sufficient and it cannot be bound to the inside of the synthetic resin. This is because it exhibits the drawback of plastics, and conversely, when the amount exceeds the upper limit, the mechanical properties of the synthetic resin are significantly deteriorated, which is not preferable, and it is preferably in the range of 1.0 to 15.0 parts. Here, the organopolysiloxane having a unit containing at least one kind of group selected from an amino group and an alcoholic hydroxyl group may be used in combination of two kinds within the range of the mixing ratio. In addition, a catalyst may be optionally added to promote the reaction.

For mixing the composition of the present invention described above, a conventionally well-known method can be used. For example, the synthetic resin and each of the above-mentioned components are dissolved individually or in an appropriate solvent (for example, fluorochlorohydrocarbon) and mixed with a mixer such as a Henschel mixer, a ball mill, a tumbler mixer, and then the solvent is removed. Then, it may be 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 or the like may be used in advance. Moreover, an organopolysiloxane having a unit containing a glycidyl group and an organopolysiloxane having a unit containing at least one type of group selected from an amino group and an alcoholic hydroxyl group are separately mixed with a synthetic resin to prepare a pellet. Alternatively, a method may be used in which two types of pellets are mixed at a predetermined ratio immediately before molding and supplied to an injection molding machine. Further, the method of molding the composition of the present invention is not particularly limited, but compression molding, extrusion molding, injection molding and the like are possible, and the composition of the present invention is melt-mixed. After that, this mixture can be pulverized by a jet mill, a freeze pulverizer, or the like, and can be used as it is or pulverized to have a desired particle size as a powder coating material for fluid immersion coating, electrostatic powder coating, or the like.

In the composition of the present invention, in addition to the above-mentioned lubricating compounding agent, that is, organopolysiloxane, additives that can be widely compounded in general synthetic resins can be appropriately used in an amount within a range that does not deteriorate the properties of the composition. . Examples of such an additive include a release agent, a flame retardant, a weather resistance improver and the like. These additives are added and compounded at the same time as the lubricating compounding agent of the present invention. A method of blending with a lubricity compounding agent can be adopted. Furthermore, it is of course possible to use publicly known lubricants conventionally known in the above additives, and tetrafluoroethylene resin powder, graphite, fluorinated graphite, talc, boron nitride, other industrial lubricants, etc. Also, it can be appropriately selected and used according to the purpose of use. Further, glass fiber known as a reinforcing agent, carbon fiber, alumina fiber, asbestos, rock wool, wollastonite, fibrous substances such as potassium titanate whiskers, or inorganic substances represented by glass powder, talc, clay, calcium carbonate and the like. Fillers and the like can also be used.
In any case, it is needless to say that the intermediate or 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. .

[Action]

In the lubricating resin composition of the present invention, the carboxyl group of the carboxyl group-containing organopolysiloxane reacts with the functional group of the other organopolysiloxane,
A three-dimensional network structure with organopolysiloxane lubricity is formed in the synthetic resin, and the network is finely dispersed, resulting in a small coefficient of friction and a lubricating substance that does not fall out of the base material. To stay inside,
It is considered that the friction coefficient is stably maintained, the base material is reinforced by the mesh, the wear is small, and the mechanical strength is not lowered, and all the drawbacks of the conventional oil-impregnated plastic are eliminated.

〔Example〕

First, the raw materials used in the following Examples and Comparative Examples are as follows. The abbreviations are shown in [].

Polyethylene (Mitsui Petrochemical Company; Hijets 13
00J) [PE], 12 nylon (manufactured by Daicel Chemical Co., Ltd .; Daiamide L16)
40P) [PA12], 66 nylon (manufactured by Toray Industries; Amilan CM3001N)
[PA66], polyacetal (manufactured by Polyplastics Co .: Diuracon M90-02) [POM], polybutylene terephthalate (manufactured by Mitsubishi Kasei Kogyo Co., Ltd .; Novadwool 5010) [PBT], polyphenylene sulphide (manufactured by US Philipps Petroleum). Ryton P-4 powder) [PPS], polyetherimide (U.S. General Electric Company; Ultem 1000) [PEI], polyimide resin (Technosimy, West Germany; polyamide bismaleimide C183) [PABM], containing carboxyl group Organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd .; carboxyl-modified silicone oil X-2)
2-3701E), amino group-containing organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd .; amino-modified silicone oil KF861), alcoholic hydroxyl group-containing organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd .; silicone diol X22-160).
C), a non-functional organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd .; silicone oil KF96 3000cst).

Examples 1 to 14: Synthetic resin was blended with organopolysiloxane as shown in Table 1, thoroughly mixed with a Henschel mixer, and then fed to a twin-screw melt extruder, and melt-mixing conditions shown in Table 2 were used. Extruded, granulated, fed the pellets to an injection molding machine, and under the injection molding conditions shown in Table 2, inner diameter 14 mm, outer diameter 23
mm, length 13 mm, ring-shaped test piece, ASTM-D
A 638 Type IV dumbbell specimen was molded. A friction wear test was conducted using a ring-shaped test piece. For the friction test, a thrust type friction tester was used and the sliding speed was 10 m / min and the load was 10
The friction coefficient was measured 1 minute and 60 minutes after the start of operation under the condition of kg / cm ² . Abrasion test Was measured by 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 . In each test, bearing steel SUJ2 (quenched and ground) was used as the mating material. Further, using a dumbbell test piece, the tensile strength was determined under the conditions of an atmosphere of 23 ± 2 ° C., a distance between chucks of 64 mm, and a pulling speed of 5 mm / min. The results are summarized in Table 3.

Comparative Examples 1 to 14: Test pieces similar to those of Examples 1 to 14 were prepared under the compounding compositions, mixing conditions and molding conditions shown in Tables 4 and 5,
The same measurement was performed. The results are summarized in Table 6. In Comparative Examples 2, 3, 4, 6 and 7, the molded body was separated during molding and became non-uniform, and the surface of the mating material after sliding in these Comparative Examples was sticky.

When the above Examples 1 to 14 and Comparative Examples 1 to 14 are compared, as is clear from the measured values shown in Tables 3 and 6, the friction coefficient and the wear coefficient are relatively small in the Comparative Example, Whether the tensile strength is significantly reduced (eg Comparative Examples 5 and 7), Either the friction coefficient is not stable (Comparative Examples 2, 3, 4, 5, 6 and 7) or the friction coefficient and the wear coefficient are larger than those of the Examples (Comparative Examples 1 to 14), and both are expected. Properties have not been obtained. On the other hand, all of Examples 1 to 14 are extremely preferable without lowering the tensile strength, having a low friction coefficient and a low wear coefficient, good moldability, and exhibiting no defects of ordinary oil-impregnated plastics. Atsuta Further, since the object of low friction and low wear is achieved without adding a hard filler which has been widely used in the past, the mating material was not damaged during sliding.

〔effect〕

As described above, the molded body made of the lubricating resin composition of the present invention has excellent sliding properties and good moldability while retaining the original mechanical properties of the synthetic resin. Since it is a material that satisfies all three requirements of slidability, formability, and economic efficiency, it can be said that it is optimal for bearing materials. Therefore, the significance of the present invention is extremely great.

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Claims (1)

[Claims] 1. 0.5 parts of an organopolysiloxane having a unit containing a carboxyl group with respect to 100 parts by weight of a synthetic resin.
To 20.0 parts by weight, and 0.5 to 20.0 parts by weight of an organopolysiloxane having a unit containing at least one type of group selected from amino groups and alcoholic hydroxyl groups. Resin composition.