JPH0717828B2 - 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]

Polyarylene sulfide resin and aromatic polyetherketone resin are all excellent in heat resistance, chemical resistance, electrical property, mechanical property, etc. It is used in the field. However, these resins are not satisfactory in terms of lubricity and non-tackiness. Generally, in order to improve lubricity and non-adhesiveness, liquid or solid lubricants such as tetrafluoroethylene resin, graphite, molybdenum disulfide, metal soap and other solid lubricants, mineral oil, grease and wax are added. However, the composition in which these lubricants are mixed not only significantly lowers the creep resistance, rigidity or impact resistance, but also cannot be said to have sufficient lubricity and non-adhesiveness.

Further, the fluorinated polyether polymer has excellent lubricity and non-adhesiveness, and has recently attracted particular attention as a lubricant or non-adhesive. Regarding a separating claw for a copying machine in which this fluorinated polyether polymer is coated with a heat resistant resin,
The applicant of this invention has already disclosed it in Japanese Patent Application No. 60-78699. However, the surface of the molded article made of either or both of the polyarylene sulfide resin and the aromatic polyether ketone resin and the fluorinated polyether polymer have poor affinity and do not always adhere firmly. However, even if the lubricity and the non-adhesiveness are improved, if the sliding time is long, the coating film formed at the corners will also be peeled off, which causes many troubles.

[Problems to be solved by the invention]

As described above, a heat resistant resin such as a polyarylene sulfide resin or an aromatic polyether ketone resin is coated with a fluorinated polyether polymer in order to improve lubricity and non-adhesiveness. However, there was a problem in that the adhesiveness was insufficient and peeling was easy, and stable sliding was not possible for a long time.

[Means for solving problems]

In order to solve the above problems, the present invention provides a resin composition obtained by adding and mixing a thermosetting resin to one or both of a polyarylene sulfide resin or an aromatic polyether ketone resin, a compound represented by the general formula -CxF ₂ x -O- [x is an integer of 1 to 4] is used as a main structural unit and a means for producing a lubricating resin composition coated with a fluorinated polyether polymer having an isocyanate group as a terminal functional group is adopted. is there. The details will be described below.

First, the polyarylene sulfide resin in the present invention is a polymer represented by the general formula Ar-Sn. Here, -Ar- in the formula is a divalent aromatic residue containing at least one carbon 6-membered ring, for example, And each of these aromatic rings has F, Cl, Br,
A substituent such as CH ₃ may be introduced. A particularly typical polyarylene sulphide has the general formula Is a polyphenylene sulphide (hereinafter abbreviated as PPS), and a commercially available product is Ryton (trademark) manufactured by US Phillips Petroleum Co., Ltd.

Next, the aromatic polyether ketone resin in the present invention, as a repeating unit, Alone or with this repeating unit and other repeating units,
For example And the like are polymers which coexist to such an extent that the original properties of the polyetherketone resin are not lost, and Udel-PEEK (trademark) manufactured by UK ICI Co., Ltd., which is a commercial product, may be mentioned as an example. Although it is possible, it is a resin (hereinafter abbreviated as PEEK) that has excellent heat resistance, flame resistance, and mechanical properties.

Further, the thermosetting resin of the present invention is preferably one having a hydroxyl group, a carboxyl group, a methylol group, and an amino group which show reactivity with a fluorinated polyether polymer described later, and among them, a thermosetting resin having a hydroxyl group. Resins such as phenol resin and epoxy resin having a hydroxyl group are particularly preferable resins. Here, it is desirable that the phenol resin does not undergo thermal deterioration even at the molding temperature of the above-mentioned polyarylene sulfide resin and aromatic polyether ketone resin, and for example, a phenol / alkyl resin or a phenol / formaldehyde resin is preferable. The phenol / alkyl resin is As a resin having a chemical structure represented by, a commercially available product such as Millex (trademark) XL-225 manufactured by Mitsui Toatsu Chemicals, Inc. can be exemplified. The phenol / formaldehyde resin is, for example, a phenol / aldehyde resin which is a condensation product of phenols and aldehydes, or a nitrogen-containing phenol / aldehyde copolymer resin which is a condensation product of phenols, nitrogen-containing compounds and aldehydes. is there. Here, as the phenols, phenol, cresol,
Examples include xylenol, alkylphenol, resorcinol, and the like, aldehydes such as formalin, paraformaldehyde, and trioxane, and nitrogen-containing compounds such as urea, aniline, melamine, and compounds having at least two active hydrogens such as guanidine. can do. A number of methods for producing such a phenol resin are already known, for example, in JP-A-57-17701, JP-A-58-17114 and others, but as a commercial product, Bell Pearl (trademark) manufactured by Kanebo Co., Ltd. And the like. Further, the epoxy resin having a hydroxyl group is particularly preferably a modified epoxy resin composed of polyhydroxyphenylene ether, and examples of commercially available products include T-resin manufactured by Mitsui Petrochemical Co., Ltd.

The average particle size of such a thermosetting resin is preferably 50 μm or less, and 80% by weight or more is preferably 150 μm or less. This requires a high temperature of 250 ° C or higher when melt-mixing with either or both of the polyarylene sulfide resin and the aromatic polyetherketone resin, and the thermosetting resin compounded at such temperature. This is because the curing time is extremely short and it is difficult to obtain a mixture in which the thermosetting resin having a large particle size is uniformly dispersed in small units.
And the addition amount of the thermosetting resin is preferably 10 to 90 parts by weight with respect to 100 parts by weight of either or both of the polyarylene sulfide resin and the aromatic polyether resin, which is 10 parts by weight. If the amount is less than less than 100 parts, the reactivity with the fluorinated polyether polymer cannot be expected, and if it exceeds 90 parts by weight, mechanical properties such as polyarylene sulfide resin and aromatic polyetherketone resin are inherently possessed. Is damaged. A small amount of a curing accelerator or the like may be added in order to adjust the curing rate of the thermosetting resin, and the composition is characterized by its heat resistance, mechanical strength or reactivity with a fluorinated polyether polymer. Various fillers may be added as long as they do not adversely affect the above. Specific examples of the filler include polyamideimide resin, polyetherimide resin, aromatic polyester resin, polyimide resin, silicone resin, fluorine resin, and other heat-resistant polymer materials, glass fiber, carbon fiber,
Graphite fiber, wollastonite, potassium titanate whiskers, silicon carbide whiskers, sapphire whiskers, heat-resistant inorganic single fibers such as steel wire, copper wire, stainless wire, tungsten core wire or carbon fiber, etc., boron or silicon carbide Heat-resistant inorganic composite fibers such as so-called boron fibers or silicon carbide fibers, etc., heat-resistant organic fibers such as aromatic amide fibers, graphite or metals such as zinc, aluminum, magnesium, etc., or for improving thermal conductivity of oxides, etc. Inorganic powder, glass beads, silica balloon, diatomaceous earth, asbestos, inorganic powder for improving heat insulation such as magnesium carbonate, molybdenum disulfide,
There are many examples such as inorganic powders for improving lubricity such as graphite, carbon, mica and talc, and inorganic pigments for coloring such as iron oxide, cadmium sulfide, cadmium selenide and carbon black.

The method of mixing the above polyarylene sulfide resin, aromatic polyether ketone resin, thermosetting resin, and further filler if necessary is not particularly limited, but polyarylene sulfide resin, aromatic Since the melting temperature of the group polyetherketone resin is quite high, the raw materials except the thermosetting resin are preliminarily dry-mixed and then heat-melted using, for example, a twin-screw extruder, and the thermosetting property near the cylinder exit Extrude and granulate by supplying resin, or make thermosetting resin into B-stage (prepolymerization) by using a kneader etc. and add other raw materials to it, mix well, and biaxially melt. A method of heating and melting with an extruder and extruding and granulating may be adopted.

Further, the fluorinated polyether polymer of the present invention is a polymer having a general formula —CxF ₂ x —O— [x is an integer of 1 to 4] as a main structure and having an isocyanate group as a terminal functional group. The number average molecular weight is preferably about 1000 to 5000. For example As the fluorinated polyether polymer as shown in, a commercially available product such as FOMBLIN (trademark) Z-DISCO (average molecular weight of 2000) manufactured by Monte-Dison of Italy can be exemplified. The coating method of such a fluorinated polyether polymer may be a general coating method. Among them, the spray method, the dipping method and the like are simple and practical, but the dipping method is the most suitable in terms of the yield of the coating liquid. preferable. Further, the fluorinated polyether polymer can be dissolved in a highly fluorinated organic solvent to prepare an appropriate solution, but in the usual case, the concentration of this polymer is 0.3 to 10% by weight, especially when performing thin film coating. Is preferably 0.5 to 3% by weight. The reason for this is that a thick liquid with a concentration of more than 10% by weight thickens the coating film, and as a result, it has many free reactive end groups that do not participate in the reactivity with the thermosetting resin in the composition. This is because there is a risk that the adhesiveness and non-adhesiveness will be inferior. After painting,
Dry to remove organic solvents in the coating (eg 50 ° C
It may be subjected to a heat treatment at a high temperature, which also serves to accelerate the reaction between the terminal functional group of the polymer in the coating film and the thermosetting resin (using a moderate hot air drying oven, etc.) .

[Action]

Thermosetting resin added and mixed in the composition of the present invention impairs excellent properties such as heat resistance and mechanical properties originally possessed by polyarylene sulfide resin, aromatic polyetherketone resin and the like. Without it, it chemically binds strongly to the coating film of the fluorinated polyether polymer and exerts the effect of preventing the coating film from peeling off even when it is slid for a long time.

〔Example〕

The raw materials used in Examples and Comparative Examples are summarized below.

Polyarylene Sulfide Resin [Ryton P-4 manufactured by American Petroleum International Co., Ltd .: PPS], Aromatic Polyether Ketone Resin [UK UK
Eye: Udel-PEEK150P] (abbreviated as PEEK), phenol resin [Mitsui Toatsu Chemicals: Millex XL
-225] (abbreviated as Millex), phenol resin [Bellpearl H-30 manufactured by Kanebo Co., Ltd.
0], phenol resin [manufactured by the same company: Belpearl C-600], modified epoxy resin [manufactured by Mitsui Petrochemical Co., Ltd .: T-resin], fluorinated polyether polymer [manufactured by Ikoku Montedison Co., Ltd .: Fuombrin Z-DISOC] Humbrin), inorganic filler (potassium titanate whiskers) [Otsuka Chemical Co., Ltd .: Teismo D101] (abbreviation Moismo), inorganic filler (mica) [Canada Mica: Mica S-325] Examples 1 to 1 8: The raw materials other than the thermosetting resin were dry-mixed at the compounding ratio (% by weight, the same applies hereinafter) as shown in Table 1. Then, it was supplied to a twin-screw melt extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.), and a thermosetting resin was fed into the vicinity of the cylinder outlet under the melting conditions shown in Table 1 and extruded. Granulate and injection-mold it under the injection molding conditions shown in the same table. Inner diameter 14 mm, outer diameter 23 mm, length 13 mm cylinder and width
A plate having a size of 12.7 mm, a length of 63 mm and a thickness of 3 mm was obtained. These two types of molded products were made into a fluorine-containing polyether polymer, Fomblin 1.
Approximately remove it by immersing it in a 5% Freon 113 solution
The molded product which had been dried and baked at 150 ° C. for 4 hours and finished with coating was evaluated for adhesion, lubricity and non-tackiness of the coating, and the results are summarized in Table 2. Each of these properties was obtained by the following methods. That is, (1) a plate-shaped molded product coated with an adhesive fluorinated polyether polymer was washed several times with acetone, and the contact angle (degree) with water or styrene before and after the washing was measured by an elma optical goniometer formula. The contact angle was measured by a contact angle tester, and the adhesion was evaluated from the obtained contact angle.

(2) By the contact angle (degree) to water or styrene when the surface of the plate-shaped molded product coated with the non-adhesive fluorinated polyether polymer is lightly wiped with tissue paper and washed with Freon. The non-tackiness was evaluated. The measurement of the contact angle is exactly the same as the adhesion described above.

(3) Using a Matsubara-type thrust-type friction tester for a cylindrical molded body coated with a lubricious fluorinated polyether polymer, bearing steel (SUJ2) as a counterpart material, load of 1 kg / cm ² , per speed A friction test was conducted under the condition of 1 m / min to find the friction coefficient after 30 minutes and 30 hours of sliding, and at the same time, in order to investigate the film state after sliding, the contact angle of water on the sliding surface was the same as above. I asked for it in the way. It is judged that the smaller the contact angle, the worse the condition of the coating.

Comparative Examples 1 to 3: As shown in Table 3, the same operation as in Examples 1 to 8 was performed except that the thermosetting resin was not added and mixed at all, or even if it was added in a small amount of 5% by weight. Cylindrical and plate-shaped moldings were prepared and examined for adhesion, non-adhesion and lubricity. The results obtained are summarized in Table 4.

As is clear from Tables 2 and 4, the examples Nos. 1 to 8 indicate that the adhesiveness and non-tackiness are superior to those of Comparative Examples 1 to 3 as far as the contact angle with respect to water or styrene is concerned, and the lubricity also shows the friction after 30 minutes of sliding. Even if a large difference is not found in the coefficient, a significant difference was found between the contact angles of water between Examples 1 to 8 and Comparative Examples 1 to 3, and After 30 hours of sliding, Comparative Examples 1 to 3 were significantly inferior to Examples 1 to 8 in both the coefficient of friction and the contact angle of water.

〔effect〕

The lubricating resin composition of the present invention retains the excellent thermal, mechanical, electrical and chemical properties inherent in each of the polyarylene sulfide resin and the aromatic polyether ketone resin. In addition, since the thermosetting resin added and mixed chemically bonds strongly to the coating film of the fluorinated polyether having isocyanate groups, it has both lubricity and non-adhesiveness and excellent sliding. It has the advantage of exerting its characteristics.

The lubricating resin composition of the present invention is suitable for use as a material for parts in all technical fields such as automobiles, office equipment, electronic / electrical equipment, general industrial machinery, aerospace equipment, etc., by utilizing the above advantages. It is most suitable for separation claws in copying machines, lens holders for optical disc players, etc. Therefore, it can be said that the significance of the present invention is extremely great.

Claims (4)

[Claims] 1. A resin composition prepared by adding and mixing a thermosetting resin to either or both of a polyarylene sulfide resin and an aromatic polyetherketone resin, and using the following general formula as a main structural unit and isocyanate as a terminal functional group. A lubricating resin composition coated with a fluorinated polyether polymer having a group. Note -CxF ₂ x-O- [x is an integer of 1 to 4] 2. The lubricating resin composition according to claim 1, wherein the thermosetting resin is a thermosetting resin containing at least one of a hydroxyl group, a carboxyl group, a methylol group and an amino group. 3. The lubricating resin composition according to claim 2, wherein the thermosetting resin is a phenol resin. 4. The lubricating resin composition according to claim 2, wherein the thermosetting resin is a modified epoxy resin having a hydroxyl group.