JPS6317967A - Lubricating resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent sliding property and moldability while keeping original mechanical properties of base resin and suitable as a bearing material, etc., by compounding a base resin with specific amounts of an organopolysiloxane having (iso)cyanate group and an organopolysiloxane having amino group, etc. CONSTITUTION:100pts.(wt.) of a synthetic resin (e.g. phenolic resin) is compounded with (A) 0.5-20pts., preferably 1-15pts. of an organopolysiloxane having a unit containing isocyanate group or cyanate group [e.g. the compound of formula I or formula II (R is alkylene, etc.; m is 5-10,000; n is 2-100), etc.] and (B) 0.5-20pts., preferably 1-15pts. of an organopolysiloxane having a unit containing one or more kinds of groups selected from amino group, carboxyl group, alcoholic hydroxyl group and mercapto group (e.g. the compound of formula III).

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 and are very expensive. It has the following drawback. Therefore, measures have been taken to improve the sliding characteristics by adding solid lubricants to other synthetic resins, but this method does not sufficiently improve the sliding characteristics 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 create a so-called oil-impregnated plastic. Specific methods include 1) simply mixing lubricating oil into the resin, and 2) retaining lubricating oil. Add the available carrier together with lubricating oil, 3) 1) above.
In addition to 2), there are also those in which a fibrous filler is added as an oil conductor. These oil-impregnated plastics are intended to have sliding properties by leaching lubricating oil, but (1) the coefficient of friction is low and unstable, and (2) the oil leaches out when heated. (3) Poor formability; (4) The carrier scrapes the mating material during sliding; (5)
) Oil tends to separate during molding or when wires are crossed, (6) Material properties deteriorate, (7) Sliding surfaces tend to get oil and dust, etc., (8) - Abnormal wear occurs when oil runs out. There were various problems such as

[Problem that the invention seeks to solve]

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 (
In particular, 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
00 parts (parts by weight, same hereinafter), 0.5 to 20.0 parts of organopolysiloxane having an isocyanate group or a unit containing a cyanate group, and further an amino group,
Adopts a means to create a lubricating resin composition by blending with 0.5 to 20.0 parts of organopolysiloxane having a unit containing at least one type of group selected from carboxyl group, alcoholic hydroxyl group, and mercapto group. This is what I did.

The details are 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, ureaguanamine co-condensation resin,
Amino resin, acetoguanamine resin, melamine anamine 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 or ultra-high molecular weight), chlorinated polyolefin, polypropylene, Modified polyolefin, water-crosslinked polyolefin, ethylene-
Vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polystyrene, ABC 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, fully aromatic polyester, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester elastomer,
Examples include blends of various polymeric substances.

Next, the organopolysiloxane having a unit containing an isocyanate group, a cyanate group, an amino group, a carboxyl group, an alcoholic hydroxyl group, and a mercapto group in this invention is an organopolysiloxane such as dimethylsiloxane, methylphenylsiloxane, and trimethylfluoropropylsiloxane. Isocyanate groups, cyanate groups, amino groups, carboxyl groups, alcoholic hydroxyl groups, and mercapto groups are introduced into homopolymers or copolymers of two or more of these, examples of which are as follows. It is. That is, isocyanate group-containing organopolysiloxane CH3CH3CH3C)13CH3C2H4NHCaH6(CH3)NCO
etc. Organopolysiloxane containing a cyanate group Organopolysiloxane containing an amino group CH3CH3C3H6NHC2H4NH2 Organopolysiloxane containing a carboxyl group Organopolysiloxane containing an alcoholic hydroxyl group Organopolysiloxane containing a mercapto group [here, k
is an alkylene group, m=5-10000, n=2-1
It is 00. ] can be mentioned.

In addition, in this invention, the reason why 0.5 to 20.0 parts of organopolysiloxane having an isocyanate group or a unit containing a cyanate group is blended with respect to 100 parts of the synthetic resin is that a small amount below this lower limit deteriorates the sliding properties. The improvement effect is insufficient, and on the other hand, if the amount exceeds the upper limit, the mechanical properties of the synthetic resin will significantly deteriorate, which is undesirable, and the amount is preferably in the range of 1.0 to 15.0 parts. Furthermore, an organopolysiloxane having a unit containing at least one type of group selected from an amino group, a carboxyl group, an alcoholic hydroxyl group, and a mercapto group is 0.5 to 2
The reason for adding 0.0 part is that if the amount is less than this lower limit, the reaction with the organopolysiloxane having the isocyanate group or cyanate group-containing unit will not be sufficient and it will not be possible to bind it inside the synthetic resin. ,
This is because it exhibits the drawbacks of ordinary oil-containing plastics, and conversely, if the amount exceeds the upper limit, the mechanical properties of the synthetic resin will significantly deteriorate, which is undesirable.
The range is 0 to 15.0 parts. Here, the organopolysiloxane having a unit containing at least one type of group selected from an amine group, a carboxyl group, an alcoholic hydroxyl group, and a mercapto group has a blending ratio of 2
More than one type may be used in combination. Further, in order to advance the reaction, a catalyst such as amines or a tin compound may be appropriately added depending on the case. Further, isocyanate groups can be introduced by reacting an alcoholic hydroxyl group-containing organopolysiloxane with a diisocyanate compound, but this reaction may also be carried out during mixing with the synthetic resin. In other words, an organopolysiloxane containing an alcoholic hydroxyl group-containing organopolysiloxane, diisocyanates such as toluene diisocyanate and ethylene diisocyanate, and at least one group selected from an amino group, a carboxyl group, an alcoholic hydroxyl group, and a mercapto group is used as a synthetic resin. Siloxane may also be blended.

Conventionally well-known methods can be used to mix the composition of the present invention described above. For example, the synthetic resin and the above-mentioned compounded components may be mixed individually or with an appropriate solvent (
For example, fluorochloronolambda hydrocarbon, etc.) is mixed in a mixer such as a Henschel mixer, ball mill, or tumbler mixer, then the solvent is removed and the mixture is fed to an injection molding machine or melt extruder with good melt-mixability. Alternatively, the mixture may be melt-mixed in advance using a heated roller, kneader, Banbury Mixer 1 melt extruder, or the like. Alternatively, an organopolysiloxane having a unit containing an isocyanate group or a cyanate group and an organopolysiloxane having a unit containing at least one type of group selected from an amino group, a carboxyl group, an alcoholic hydroxyl group, and a mercapto group may be separately prepared. It is also possible to prepare pellets (1α) mixed with a synthetic resin, mix the two types of pellets in a predetermined ratio immediately before molding, and supply the mixture to an injection molding machine.

In addition, the method for molding the composition of this invention is not particularly limited, but compression molding, extrusion molding, injection molding, etc. are practical methods. This mixture can be pulverized using a jet mill, a freezing pulverizer, etc., and the powder can be used as it is or after being classified into a desired particle size as a powder coating for fluidized dip coating, electrostatic powder coating, etc.

In addition to the above-mentioned lubricating compounding agent, i.e., organopolysiloxane, the composition of the present invention contains additives that can be widely incorporated into synthetic resins in an appropriate amount that does not reduce the properties of the lubricating resin composition. You can also do that. 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 with a lubricating compounding agent. Furthermore, it is of course possible to use conventionally known and publicly used lubricants in combination with the above additives, such as tetrafluoroethylene resin powder, graphite, graphite fluoride, talc, boron nitride, and other industrial lubricants. They can be selected and used as appropriate depending on the purpose of use.

In addition, glass fiber, carbon fiber, which is known as a reinforcing agent,
Fibrous materials such as alumina fibers, asbestos, rock wool, wollastonite, potassium titanate whiskers,
Alternatively, inorganic fillers such as glass powder, talc, clay, calcium carbonate, etc. can also be used. 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 composition of the present invention is not impaired.

[Effect]

In the lubricating resin composition of the present invention, the isocyanate group or the functional group of the cyanate group-containing organopolysiloxane reacts with the functional group of the other organopolysiloxane to improve the lubricity of the organopolysiloxane in the synthetic resin. A three-dimensional network is formed, and because the network is finely dispersed, the coefficient of friction is small.Moreover, the lubricating substance remains within the structure without being extracted from the base material, so the coefficient of friction is stable. In addition, since the base material is reinforced by the mesh, there is little wear and no decrease in mechanical strength (all of the drawbacks of conventional oil-impregnated plastics are thought to be eliminated).

〔Example〕

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

■Polyethylene (manufactured by Mitsui Petrochemicals: HIZEX 13
00J) [PE], ■12 Nylon [Manufactured by Daicel Chemical Co., Ltd.: Diamid L16
40P) [PA12], ■66 nylon (manufactured by Toshisha: Amiran CM3001N)
[PA661, ■Polyacetal (manufactured by Polyplastics: Duracon M90-02) CPOM), ■Polybutylene terephthalate (manufactured by Mitsubishi Chemical Industries, Ltd.: Novadwool 5010) C
PBTI, ■Polyphenylene sulfide (manufactured by Phillips Petroleum, USA: Ryton P-4 powder)
[PPS], ■Polyetherimide (manufactured by U.S. General Electric Co., Ltd.: Ultem 1000) [PEI], ■Polyimide resin (manufactured by West German Technoshimie Co., Ltd.: Polyamide Bismaleimide C183) [PABMI, 0 Silicone oil containing hydroxyl groups at both terminals (Shin-Etsu Chemical Co., Ltd.) Kogyo-sha silicone oil X22-
Isocyanate group-containing organopolysiloxane obtained by blending 5 g of 160C (molecular weight 5600) and 3.5 g of 2.4-)luene diisocyanate and mixing at room temperature for 1 hour, [phase] amino group-containing organopolysiloxane) Siloxane (Niamin modified silicone oil KF861 manufactured by Shin-Etsu Chemical Co., Ltd.)
), ■Carboxyl group-containing organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.: Carboxyl-modified silicone oil X-2
2-3701E), 0 alcoholic hydroxyl group-containing organoborisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.: Silicone diol X-22-160
0), [Phase] Mercapto group-containing organopolysiloxane (dimercapto-modified silicone oil X-2 manufactured by Shin-Etsu Chemical Co., Ltd.
2-980), (2) non-functional organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.: silicone oil KF96 3000).

Examples 1 to 18 Organopolysiloxane was blended with synthetic resin as 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. , granulate and feed the pellets to an injection molding machine,
Under the injection molding conditions shown in Table 2, the inner diameter is 14 mm and the outer diameter is 2 mm.
A ring-shaped test piece of 3 mm and 13 plates in length, and ASTM-D
(A 53g type ■ dumbbell test piece was molded.A friction and wear test was conducted using the ring-shaped test piece.The friction test was performed using a thrust type friction tester at a sliding speed of 10 m/min and a load of 1.
The friction coefficients shown in Table 1, Table 2, and Table 3 of the tube were measured 1 minute after the start of operation and 60 minutes later under the condition of 0 kg/cm2. The wear test was carried out using a thrust type wear tester at a sliding speed of 32 m/min and a load of 3.1 kg/cm.
This was carried out under the following conditions. In both tests, the mating material was bearing steel 5.
UJ2 (hardened, ground finish) was used. Further, using a dumbbell test piece, tensile strength was determined under the conditions of an atmosphere of 23±2° C., a distance between chucks of 54 mm, and a tensile speed of 5 mm/min. The results are summarized in Table 3.

Comparative Examples 1 to 14: Test pieces similar to Examples 1 to 18 were prepared using the compounding composition, mixing conditions, and molding conditions shown in Tables 4 and 5, and
Similar measurements were made. The results are summarized in Table 6. In Comparative Examples 2.3.4 and 7, the molded bodies were separated during molding and were non-uniform, and the surfaces of the mating materials in these Comparative Examples after sliding were sticky.

Comparing the above Examples 1 to 18 and Comparative Examples 1 to 14, as is clear from the measured values shown in Tables 3 and 6, the friction coefficient and wear coefficient in the Comparative Examples are relatively small; Table 4 Tensile strength decreases significantly (for example, Comparative Example 5.7), the friction coefficient is unstable (Comparative Example 2.3.4), or the friction coefficient and wear coefficient are large compared to the Examples (Comparative Example 5.7). Example 1.6.8-1
4), and the expected properties shown in Table 5 have not been obtained in either case. In contrast, Examples 1 to 18
All of these had low friction coefficients and low wear coefficients without decreasing tensile strength, had good moldability, and were extremely preferable without exhibiting the disadvantages of ordinary oil-impregnated plastics. Furthermore, since the objective of low friction and low wear is 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 described above, the molded article made of the lubricating resin composition of the present invention retains the mechanical properties inherent to synthetic resins, has excellent sliding properties, and has good moldability compared to conventional ones. Because it is a material that simultaneously satisfies the three properties of slidability, formability, and economic efficiency that have never been possible before, it can be said to be optimal for bearing materials. Therefore, the significance of this invention is extremely large.

Patent applicant: Western Bear Rulon Industrial Co., Ltd. Agent: Kama 1) Text - Date of amendment - Procedural amendment (voluntary) March 1988 288 1, Indication of case Patent Application No. 164428 of 1988 2, Name of the invention: Lubricating resin composition 3. Relationship with the case of the person making the amendment. Patent applicant address: 7-22-17 Nishigotanda, Parts Ward, Tokyo. Name (
Name) Western Bear Rei Rulon Kogyo Co., Ltd. 5゜Showa Year Month Day (Delivery date) 6, Number of inventions increased by amendment 1, Specification page 14, lines 10-11, ``Silicone oil X22-160C (molecular weight 5600) and 5g of silicone diol X-22-160C (molecular weight 56
Corrected to 00))56g.

2. On page 14, line 18, "Orgacubo 1-nosiloxane)" is corrected to "organopolysiloxane."

Claims (1)

[Claims] Based on 100 parts by weight of the synthetic resin, 0.5 to 20.0 parts by weight of an organopolysiloxane having an isocyanate group or a unit containing a cyanate group, and at least one selected from amino groups, carboxyl groups, alcoholic hydroxyl groups, and mercapto groups. 1. A lubricating resin composition comprising 0.5 to 20.0 parts by weight of an organopolysiloxane having units containing various types of groups.