JP2717122B2 - Solid lubricant - Google Patents

Description

The present invention relates to water- and oil-repellency, non-adhesion (fouling resistance), chemical resistance, heat resistance, and low friction and friction resistance (sliding properties). The present invention relates to a solid lubricant containing a functional fluorine-containing phenol resin having various characteristics.

2. Description of the Related Art Phenol resins are excellent in electrical insulation, mechanical strength, dimensional stability, heat resistance, etc., so molding materials for electric parts and automobile parts, laminated products such as industrial plates and tubes, It has not only been widely used as a material for shell molds, a material for wood processing adhesives, and the like, but has also been used as a material for brakes and clutches due to its good self-lubricating properties.

However, phenolic resins have the disadvantage that they have poor water resistance due to the presence of phenolic hydroxyl groups (especially they tend to swell or dissolve in alkaline aqueous solutions), and they have better surface properties than fluororesins. And poor slidability.

Problems to be Solved by the Invention The present invention improves such disadvantages of the phenolic resin, and has excellent properties such as excellent water and oil repellency, stain resistance, chemical resistance, heat resistance and slidability. It is intended to provide a solid lubricant containing a fluorine-containing phenol resin.

Means for Solving the Problems That is, the present invention relates to phenol, cresol, xylenol, resorcin, bisphenol A, bisphenol S
And at least a portion of the phenolic OH of the resole-type or novolak-type phenolic resin obtained by a condensation reaction between a phenol component selected from the group consisting of bisphenol AF and an aldehyde component selected from the group consisting of formaldehyde, acetaldehyde and furfural. The present invention relates to a solid lubricant containing a finely divided fluorine-containing phenol resin having an average particle diameter of 500 μm or less substituted by a fluorine-containing ether group represented by the following formula: CF ₃ —CF ＝ CF—O—.

The base resin of the fluorine-containing phenol resin according to the present invention may be appropriately selected from known phenol resins and used.

For example, a resol type or novolak obtained by subjecting a phenol such as phenol, cresol, xylenol, resorcinol and a bisphenol such as bisphenol A, S and AF to an aldehyde such as formaldehyde, acetaldehyde and furfural according to a conventional method. Type phenolic resin.

Although the form of such a base phenolic resin is not particularly limited, from the viewpoint of production and use of a fluorinated phenolic resin as described below, the average particle diameter is 500.
Fine particles of submicron or less, particularly 5 to 30 microns are suitable.

The fluorine-containing phenol resin used in the present invention is a resin in which at least a part of the phenolic hydroxyl group of such a base phenol resin is substituted with a fluorine-containing ether substituent represented by the above formula.

The substitution rate of the phenolic hydroxyl group by the above-mentioned fluorinated ester substituent may be appropriately selected according to the purpose of use of the fluorinated phenol resin, etc., and is not particularly limited. By adjusting this substitution rate, the fluorinated phenol resin is adjusted. Properties such as water repellency, oil repellency, antifouling property, slidability and heat resistance can be appropriately adjusted.

The method for producing the fluorinated phenol resin used in the present invention is not particularly limited, but a preferred production method is the following formula: CF ₃ -CF = CF _{2 in} the presence of the above-mentioned base phenol resin in the presence of a basic catalyst. Is a method of reacting hexafluoropropene represented by the following formula:

The reaction ratio between the base phenolic resin and hexafluoropropene represented by the above formula may be appropriately selected according to the type of the reaction component, the desired fluorination rate, and the like, and is not particularly limited.

Examples of the basic catalyst include tertiary amines such as trimethylamine and triethylamine, inorganic basic salts such as sodium carbonate and potassium carbonate, pyridine, and N, N-dimethylaniline. Particularly, a tertiary amine such as trimethylamine or triethylamine is preferable.

Although the amount of the basic catalyst used is not particularly limited, it is generally used in an amount equivalent to a reaction equivalent.

The above reaction is usually performed in an organic solvent. Examples of the organic solvent include polar solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, diglyme and triglyme, and benzene, toluene, xylene, ether, tetrahydrofuran and acetone. When a phenol resin having a low solubility is used, a polar solvent such as dimethylformamide or dimethylsulfoxide is selected.

The reaction temperature also depends on the type of the reaction components and is not particularly limited, but is usually 0 to 100 ° C.

The fluorinated phenolic resin obtained by the above reaction has an infrared absorption spectrum in the vicinity of 1100 to 1300 cm ^-1 which shows characteristic absorption derived from CF stretching vibration, and thus can be easily identified.

The above-mentioned fluorine-containing phenol resin used in the present invention may be used as a homopolymer, but usually various additives depending on the use, for example, a curing agent (for example, ammonia having an amine bond, hexamethylenetetramine, etc.), modified (Eg, rosin, ester gum, drying oil, synthetic rubber, etc.), filler (eg, linter, wood flour, paper, asbestos, whisker, glass fiber, metal fiber, polyamide,
A synthetic fiber such as polyester and polyvinyl chloride, alumina, mica, talc, molybdenum disulfide, etc.), a plasticizer, a release agent, a colorant, a diluent, a heat-resistant auxiliary and the like are appropriately blended to be used as a composition.

 Hereinafter, the present invention will be described with reference to examples.

Example 1 Dimethylformamide 2 was placed in a three-necked flask (100 ml) equipped with a thermometer, a stirrer, a reflux condenser and a gas inlet tube.
5 g and 2.0 g of triethylamine were added, and 10 g of a finely particulate phenol resin was added thereto, and the temperature of the system was increased to 80 ° C. while stirring and dispersing. Then, hexafluoropropene was bubbled with stirring for 2 hours (5 ml / Min), and the reaction was further carried out at 80 ° C. for 3 hours.

The reaction mixture was sufficiently washed with acetone to obtain 12 g of spherical and finely divided fluorine-containing phenol resin.

Confirmation of the product, C near the reduced and 1100～1300Cm ^-1 of OP stretching vibration absorption around 3500 cm ^-1 in the IR spectrum
-F was performed by generation of stretching vibration absorption.

The resulting finely divided fluorine-containing phenolic resin exhibits strong water repellency and excellent fluidity, and is particularly suitable as a solid lubricant to be blended in plastics and the like.

In order to examine the suitability of the fluorinated phenol resin obtained as described above as a solid lubricant, the resin and nylon 6 were melt-kneaded at a weight ratio of 1: 9 using a twin-screw kneading extruder. An annular test piece 1 was prepared from the obtained composition using an injection molding machine (75 tons).

For comparison, test pieces 2 and 3 were similarly prepared from a 1: 9 (weight ratio) blend of untreated particulate phenolic resin and nylon 6 and nylon 6, respectively.

The friction coefficient and the amount of wear of the test pieces 1 to 3 were measured using a Suzuki-type friction and wear measuring device (manufactured by ORIX Corporation) according to a conventional method.

The measurement conditions are as follows: Surface pressure: 1.42 kg Surface peripheral speed: 200 mm / sec Running time: 2 hours Relative ring: Stainless steel S45C Temperature: 25 ° C Temperature: 65% The measurement results are shown in Table 1 below. As is apparent from Table 1, the friction and wear characteristics of the test piece 1 containing the above-mentioned fluorine-containing phenol resin are clearly smaller than those of the test pieces 2 and 3, and the lubrication characteristics are significantly improved.

Effect of the Invention The fluorine-containing phenol resin used in the present invention has excellent water and oil repellency, antifouling properties, chemical resistance, heat resistance, sliding properties, and the like, and its use is extremely diverse,
Among them, it exhibits excellent functions as a solid lubricant,
For example, slidable plastic, lubricating rubber, high slit paint or coating agent (eg, magnetic tape coating agent), high lubricating grease, etc. can be obtained by blending with plastic, rubber, paint, coating agent, lubricating oil, etc. Can be

The above properties of the fluorinated phenolic resin can be freely adjusted by appropriately selecting the type of the fluorinated ether substituent and the substitution ratio of the phenolic hydroxyl group by the substituent.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-57632 (JP, A) JP-A-2-34621 (JP, A) JP-A-1-121352 (JP, A) JP-A-1- 141942 (JP, A) JP 47-33044 (JP, B1)

Claims (1)

(57) [Claims] 1. A phenol, cresol, xylenol,
Phenol of a resole or novolac phenolic resin obtained by a condensation reaction of a phenol component selected from the group consisting of resorcin, bisphenol A, bisphenol S and bisphenol AF with an aldehyde component selected from the group consisting of formaldehyde, acetaldehyde and furfural. Solid lubricant containing a fine-particle fluorinated phenolic resin having an average particle size of 500 μm or less in which at least a part of the OH is substituted by a fluorinated ether group represented by the following formula: CF ₃ —CF = CF—O— .