JP2903709B2 - Surface coating member - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a surface covering member, and particularly to a wiper blade, a seal packing, an O-ring, a weather strip,
The present invention relates to a surface covering member in which a surface of rubber or plastic such as a glass run, a timing belt, a rubber bellows, a gear, and a door catch is lubricated. The present invention relates to a surface covering member suitable for a surface covering sliding member whose surface slides with another member, such as a wiper blade, a glass run, a weather strip, and an O-ring.

BACKGROUND ART Conventionally, molded products such as natural rubber and synthetic rubber have been used as wiper blade rubber. However, this type of wiper rubber has the following drawbacks, and is not always satisfactory.

That is, during semi-dry or cold weather, an adhesion phenomenon occurs between the wiper blade rubber and the glass surface, and the so-called “lock phenomenon” in which the operation of the wiper is stopped, and the speed dependence of the friction coefficient shows a negative characteristic, which is a self-locking phenomenon. Excitation vibration, so-called "chatter phenomenon" occurs, poor wiping, abnormal wear of the blade rubber surface, shortened life of each part of the wiper system connection, increased power consumption of the operating motor, "chatter phenomenon"
There are problems such as discomfort and eyestrain.

To solve these problems, Japanese Patent Application Laid-Open No. 55-15873
It has been proposed to cover a wiper blade rubber surface with a silicone composition containing molybdenum disulfide.

However, it has been found that the durability of the coating layer is insufficient in the wiper blade rubber of JP-A-55-15873 having this coating. This is the same problem for weather strips and glass runs.

In addition, there is the following defect between the metal surface and the rubber material, and it does not always have satisfactory characteristics.

That is, the oil seal and the gasoline cap seal stick to each other between the rubber and the metal surface, resulting in a high torque at the time of opening and closing. O-rings, packings, timing belts and the like may cause abnormal wear, stick slip, and squeal due to high sliding resistance between the rubber and the metal surface. Holes also occur in rubber bellows due to abnormal wear. Also,
Gears such as polyacetal and nylon resin, door catches, and the like generate abnormal wear, squeal, and squeak.

These are also treated by applying grease or the like to solve the problem, but it has been found that durability is insufficient.

DISCLOSURE OF THE INVENTION An object of the present invention is to solve the above problems and to provide a surface covering member having extremely good slidability and high durability of a covering layer.

The surface-coated member of the present invention is a surface-coated member having a coating layer containing a solid lubricant and a resin matrix formed on a surface thereof, and is a thermosetting resin cured by the curing agent; The resin is a fluoroolefin vinyl ether vinyl ester copolymer resin.

The rubber or plastic constituting the main body of the surface covering member of the present invention is not particularly limited, and various rubbers and plastics can be employed. The rubber may be either natural rubber or synthetic rubber. Examples of synthetic rubber include styrene butadiene rubber, butadiene rubber, isoprene rubber, ethylene propylene rubber (EPM, EPDM), acrylonitrile butadiene rubber, chloroprene rubber, isobutylene isoprene rubber, alphin rubber, polyether rubber, polysulfide rubber, Silicone rubber, acrylic rubber,
Examples include fluorine rubber, halogenated polyethylene rubber, urethane rubber, ethylene vinyl acetate rubber, high styrene rubber, acrylonitrile isoprene rubber, and the like. Of these, EP
DM is preferred.

As the plastic, either a thermosetting resin or a thermoplastic resin may be used.

Examples of plastics include ABS resin, ABS blend, acetal resin (homopolymer), acrylic resin, ACS resin, alkyd resin, amino resin, ASA resin, cellulosic resin, chlorinated polyether, diallyl phthalate resin, and epoxy. Resin, ethylene vinyl acetate copolymer, fluororesin, ionomer, methylpentene polymer, phenolic resin, polyamide (nylon), polyallyl ether, polyallyl sulfone, polybutene-1,
Polycarbonate, unsaturated polyester resin, polyethylene, polyethylene terephthalate (tetron), polyimide, polyamide imide, polyphenylene oxide, polyphenylene sulfide, polypropylene, polystyrene, polysulfone, polyether sulfone, polyurethane, vinyl chloride resin, and polyarylate.

The coating layer covering the rubber or plastic comprises a solid lubricant and a resin matrix.

The resin matrix is a thermosetting resin cured by a curing agent, and a fluoroolefin vinyl ether vinyl ester copolymer resin is used as the thermosetting resin.

As the solid lubricant, sulfides such as molybdenum disulfide and tungsten disulfide, fluorine compounds such as polytetrafluoroethylene and fluorinated graphite, graphite, silicone powder and the like can be used. These solid lubricants may be used alone or in combination of two or more. In the present invention, a combination of a sulfide, a fluorine compound and graphite is preferred because of excellent lubrication durability, conformability, and feeling. In this case, the compounding ratio of sulfide and fluorine compound, graphite, sulfide 10 to 1500 parts by weight of graphite 100 parts by weight
It is preferable to use 100 parts by weight and 3000 parts by weight of a fluorine compound.

Solid lubricants have an average particle size of 10 μm or less, especially 5 μm.
m or less, particularly preferably 3 μm or less. The mixing ratio of the solid lubricant to the resin matrix is 50 to 95 for the solid lubricant.
Parts by weight, preferably 50 to 5 parts by weight of a resin matrix, particularly preferably 70 to 90 parts by weight of a solid lubricant and 30 to 10 parts by weight of a resin matrix.

In the present invention, in order to provide the coating on the surface of rubber or plastic, the above-mentioned solid lubricant, thermosetting resin and curing agent may be dispersed or dissolved in an organic solvent and applied.

As the curing agent, polyisocyanate, melamine resin, and the like can be used.

Organic solvents include methyl ethyl ketone, toluene,
Xylene, isopropyl alcohol, isobutanol,
Preferred are n-butanol, butyl acetate, MIBK, cellosolve acetate and the like.

Various methods such as brushing, spraying, and dipping can be adopted as a method of applying. Prior to performing this coating, the surface of rubber or plastic may be washed, or a surface treatment may be applied to improve compatibility with the resin matrix. Examples of such a surface treatment include a primer treatment.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic side view illustrating an experimental method.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, examples and comparative examples of the present invention will be described.

The following [Comparative Example 1] to [Comparative Example 4] and [Example 1] to
By spraying the composition shown in [Example 9]
Spray on the surface of the rubber piece, cure this composition under the respective curing conditions (heating conditions), and apply a thickness to the surface of the rubber piece.
A coating layer of 10 μm was formed. 10mm × 6mm × 2
The test piece was cut out into a size of mm. The above coating layer is formed on a 10 mm × 6 mm surface of this test piece.

This test piece is used for FALEX NO.1 tester (Faville-Lev
ally CORPORATION), and the durability of the coating layer was examined.

FIG. 1 is a schematic side view showing the state of this test. A test piece 1 is held by a test piece holder 2 and a load of 9.06 kg is applied to the outer peripheral surface of a ring 3 having a diameter of 35 mm.
(20LBS). The material of the outer peripheral surface of the ring 3 is SAE4620 steel, and the surface roughness is 6-12 rms
It is. The ring 3 was reciprocated around its axis at a rate of 100 cycles / min in a 90 ° rotation range as shown by the arrow.

The number of cycles until the friction coefficient reached 0.2 was measured as life sioul. When the coating layer was worn out before the coefficient of friction reached 0.2 and the rubber layer was exposed, the number of cycles up to that point was regarded as the life cycle.

Table 1 shows the life cycle of each comparative example and example. Table 1 also shows the measurement results of the static friction coefficient and the dynamic friction coefficient of the surface of the coating layer of each test piece before sliding with the ring 3.

From Table 1, it is apparent that the test pieces of Examples 1 to 9 of the present invention have a small coefficient of friction and a remarkably high durability of the coating layer.

Each of the solid lubricants used below has an average particle size of 5 μm or less.

 In the following, “parts” means “parts by weight”.

[Comparative Example 1] (Polyurethane resin) Nipporan 5185 100 parts (Nippon Polyurethane Industry Co., Ltd.) (Isocyanate curing agent) 10.0 parts Coronate HL Curing conditions: 80 ° C to 30 minutes [Comparative Example 2] (Polyurethane resin) 26.0 Department Nipporan 5185 (Nippon Polyurethane Industry Co., Ltd.) (Molybdenum disulfide) 30.0 parts Technical grade (Climax Molybdenum) (Polytetrafluoroethylene) 42.0 parts Lubron L-5 (Daikin Industries, Ltd.) (Graphite) ACP1000 2.0 Part (Nippon Graphite Industries Co., Ltd.) (Isocyanate curing agent) Coronate HL 2.6 parts Curing conditions: 80 ° C. for 30 minutes [Comparative Example 3] (corresponding to Example 3 of JP-A-55-15873) 765 45 parts (Silicone content 20% emulsion) (Sumietsu Chemical Co., Ltd.) C-PM-4F (Catalyst Sumitomo Chemical Co., Ltd.) 4.5 parts Molybdenum disulfide (average particle size 4.5 μm) 4.0 parts Water 52 0.0 part Curing conditions: After standing at room temperature for 10 minutes, a cured layer was obtained at 150 ° C. for 10 minutes.

[Comparative Example 4] (fluoroolefin vinyl 100 parts ether vinyl ester copolymer) Fluonate K702 (Dainippon Ink and Chemicals, Inc.) (isocyanate curing agent) 24 parts Burnock DN980 (Dainippon Ink and Chemicals, Inc.) Conditions: 80 ° C. for 10 minutes [Example 1] (Fluoroolefin vinyl 26 parts ether vinyl ester copolymer) Fluonate K702 (Dainippon Ink Chemical Industry Co., Ltd.) (molybdenum disulfide) Technical grade 30 parts (Climax Molybdenum) (Polytetrafluoroethylene) 42 parts Lubron L-5 (Daikin Industries, Ltd.) (Graphite) ACP1000 2 parts (Nippon Graphite Industries, Ltd.) (Isocyanate curing agent) 6.2 parts Burnock DN980 (Dainippon Ink and Chemicals) Curing conditions: 80 ° C. for 10 minutes [Example 2] (28 parts of fluoroolefin vinyl) -Ter vinyl ester copolymer) Fluonate K702 (Dainippon Ink & Chemicals, Inc.) (molybdenum disulfide) Technical grade 10 parts (Climax Molybdenum) (polytetrafluoroethylene) 60 parts Lubron L-5 (Daikin Industries) (Graphite) ACP1000 2 parts (Nippon Graphite Industry Co., Ltd.) (Isocyanate curing agent) 6.7 parts Burnock DN980 (Dainippon Ink and Chemicals, Inc.) Curing conditions: 80 ° C. for 10 minutes [Example 3] (Fluoroolefin vinyl 28 parts ether vinyl ester copolymer) Fluonate K702 (Dainippon Ink & Chemicals, Inc.) (molybdenum disulfide) technical grade 47 parts (Climax Molybdenum) (polytetrafluoroethylene) 23 parts Lubron L -5 (Daikin Industries, Ltd.) (Graphite) ACP1000 2nd Part (Nippon Graphite Industries, Ltd.) ( 6.7 parts Barnock DN980 (Dainippon Ink & Chemicals, Inc.) Curing conditions: 80 ° C-10 minutes [Example 4] (Fluoroolefin vinyl 49 parts ether vinyl ester copolymer) Fluonate K702 (Dainippon Ink) Chemical Industry Co., Ltd. (Molybdenum disulfide) Technical grade 39 parts (Polytetrafluoroethylene) 10 parts Lubron L-5 (graphite) ACP1000 2 parts (Isocyanate curing agent) 6.7 parts Burnock DN980 Curing conditions: 80 ° C-10 minutes [Example 5] (fluoroolefin vinyl 49 parts ether vinyl ester copolymer) Fluonate K702 (molybdenum disulfide) technical grade 47 parts (polytetrafluoroethylene) 2.5 parts Lubron L-5 (graphite) ACP1000 1.5 parts (isocyanate cured 12.0 parts Burnock DN980 Curing condition: 80 ℃ -1 0 minutes [Example 6] (fluoroolefin vinyl 49 parts ether vinyl ester copolymer) Fluonate K702 (molybdenum disulfide) technical grade 49 parts (graphite) ACP1000 2 parts (isocyanate curing agent) 12 parts Burnock DN980 Curing conditions: 80 C-10 minutes [Example 7] (fluoroolefin vinyl 39 parts ether vinyl ester copolymer) Fluonate K702 (molybdenum disulfide) technical grade 59 parts (graphite) ACP1000 2 parts (isocyanate curing agent) 9.4 parts Barnock DN980 Curing conditions : 80 ° C-10 minutes [Example 8] (Fluoroolefin vinyl 28 parts Ether vinyl ester copolymer) Fluonate K702 (Molybdenum disulfide) Technical grade 70 parts (Graphite) ACP1000 2 parts (Isocyanate curing agent) 6.7 parts Barnock DN980 Hardening strip Case: 80 ° C. for 10 minutes [Example 9] (Fluoroolefin vinyl 20 parts Ether vinyl ester copolymer) Fluonate K702 (Molybdenum disulfide) Technical grade 78 parts (Graphite) ACP1000 2 parts (Isocyanate curing agent) 4.8 parts DN980 Curing condition: 80 ℃ -10min INDUSTRIAL APPLICABILITY As described above, the surface-coated member of the present invention has a very low coefficient of friction on the coated surface, and the coating layer has extremely high durability.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ identification code FI C10N 50:08 (58) Fields surveyed (Int.Cl. ⁶ , DB name) C08J 5/00-5/02 C08J 5/12 -5/22 C10M 107/38 C08J 7/04

Claims (12)

(57) [Claims] 1. A surface-coated member having a coating layer comprising a solid lubricant and a resin matrix formed on a surface thereof, wherein the resin matrix is a thermosetting resin cured by a curing agent, A surface covering member, wherein the resin is a fluoroolefin vinyl ether vinyl ester copolymer resin. 2. The surface-coated member according to claim 1, wherein the solid lubricant is one or more of sulfide, fluorine compound, graphite and silicone powder. 3. The mixing ratio of the solid lubricant and the resin matrix is 50 to 95 parts by weight of the solid lubricant and 50 to 95 parts by weight of the resin matrix.
3. The surface covering member according to claim 1, wherein the amount is 5 parts by weight. 4. The mixing ratio of the solid lubricant and the resin matrix is 70 to 90 parts by weight of the solid lubricant and 30 to 90 parts by weight of the resin matrix.
3. The surface-coated sliding member according to claim 1, wherein the amount is 10 parts by weight. 5. The surface covering member according to claim 2, wherein the sulfide is molybdenum disulfide and / or tungsten disulfide. 6. The surface covering member according to claim 2, wherein the fluorine compound is polytetrafluoroethylene and / or graphite fluoride. 7. A solid lubricant comprising a sulfide, a fluorine compound and graphite in a compounding ratio of 10 to 1500 parts by weight of sulfide and 100 to 3000 parts by weight of a fluorine compound per 100 parts by weight of graphite. 7. The surface-coated member according to any one of items 6 to 6. 8. The surface-coated sliding member according to claim 2, wherein the fixed lubricant has an average particle size of 10 μm or less. 9. The surface-coated sliding member according to claim 2, wherein the fixed lubricant has an average particle size of 5 μm or less. 10. The surface-coated sliding member according to claim 2, wherein the fixed lubricant has an average particle size of 3 μm or less. 11. The surface-coated sliding member according to claim 1, wherein the surface-coated member is a wiper blade rubber. 12. The surface-coated sliding member according to claim 1, wherein the surface-coated member is a seal packing.