JPH09296136A - Coating composition for repairing wiper blade rubber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing a specific binder and silicone rubber powder, capable of repairing cracks of a wiper blade rubber due to its deterioration with the lapse of time and of improving its wiping ability through coating it with the composition. SOLUTION: This coating composition is obtained by incorporating a solution prepared by dissolving (A) a highly flexible one-pack normal temperature-drying type resin or one-pack normal temperature-curing type resin as binder in a petroleum-based aliphatic solvent (pref. mineral spirit) with (B) silicone resin powder. The component A is pref. an oil-modified polyurethane resin, moisture- curable urethane resin, lacquer-type urethane resin, lacquer-type acrylic resin or a copolymer of fluoroolefin and alkyl vinyl ether. This composition is pref. further incorporated with (C) a solid lubricant selected from polytetrafluoroethylene, molybdenum disulfide, graphite, baron nitride etc. The amount of the component B to be used is about 20-130 pts.wt. based on 100 pts.wt. of the component A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to the surface of a wiper blade rubber to repair the lack of wiping property due to cracks generated when the wiper blade rubber deteriorates with time, and to reduce the sliding resistance with the glass surface. The present invention relates to a coating composition that suppresses squeaking and chattering of glass by reducing the amount.

[0002]

2. Description of the Related Art Wiper blade rubbers are affected by ultraviolet rays from the sun, infrared rays, ozone in the atmosphere, sand, mud, and dust. It will deteriorate. The wiper blade rubber that has deteriorated under these conditions increases the sliding resistance due to the abrasion of the surface treatment layer such as halogen treatment or molybdenum disulfide coating that is originally treated for the purpose of reducing the sliding resistance, and wipes it off due to the occurrence of cracks. Loss of properties occurs, resulting in squeaking and chattering of the wiper blade rubber, and poor visibility. Conventionally, in order to solve these problems, there is a coating composition in which molybdenum disulfide is used as a lubricant, cellulose is used as a binder, and ethyl acetate is used as a solvent, but it is possible to temporarily suppress squeaking and chattering of glass. However, it is not durable and cannot be said to have solved the problem. Much more
There is no example of a coating composition for repairing a wiper blade rubber that has deteriorated with time and has cracks.

The wiper blade rubber may be treated with a coating composition containing molybdenum disulfide or graphite at the manufacturing stage for the purpose of reducing sliding resistance.
These use a two-part curing type binder that cures by the reaction of various polyols and polyisocyanates, and an organic solvent with a strong dissolving power is used, and it is necessary to solve problems such as poor workability and safety and health problems. Many problems remain.

[0004]

The present invention solves the above-mentioned drawbacks of the prior art, and improves the wiping property by repairing the cracks caused by the deterioration of the wiper blade rubber over time. , And the wiper blade rubber to have slidability with respect to glass, to improve workability and to use a low-pollution solvent.

The present inventors have arrived at the present invention as a result of studying various methods for achieving such an object. The present invention is a one-liquid room-temperature-drying resin or A one-part room temperature dry or curable coating composition for repairing a wiper blade rubber, characterized in that a liquid room temperature-curable resin is used as a binder, and a silicone rubber powder is added to a dissolved product of the petroleum-based aliphatic solvent.

That is, a one-liquid room-temperature-drying resin binder or a one-liquid room-temperature-curing resin binder (hereinafter, both are simply referred to as a resin) having excellent flexibility and soluble in a petroleum-based aliphatic solvent, which is a low-pollution solvent, and silicone rubber By applying a coating composition obtained by adding a powder to the surface of the wiper blade rubber, repairing cracks generated due to deterioration of the wiper blade rubber over time, improving the wiping property thereby and sliding property to the wiper blade rubber It was found that it could be granted.

The silicone rubber powder used in the present invention is an organopolysiloxane polymer having a siloxane bond, and is a spherical fine powder having rubber elasticity in a wide range of -70 ° C to 250 ° C. The average particle size of the silicone rubber powder is preferably 20 μm or less, and particularly preferably 1 to 5 μm.

When used alone, the compounding ratio of the above silicone rubber powder is 2 with respect to 100 parts by weight of the resin.
It is preferably from 0 to 130 parts by weight. If it is less than 20 parts by weight, the slidability and crack repair effect may not be obtained, and if it exceeds 130 parts by weight, the adhesion to the wiper blade rubber may be reduced and the sliding durability may be reduced. is there. When used in combination with a solid lubricant, resin 100
10 to 120 parts by weight is preferable with respect to parts by weight. If it is less than 10 parts by weight, the slidability and crack repair effect may not be obtained, and if it exceeds 120 parts by weight, the adhesion to the wiper blade rubber may be reduced and the sliding durability may be reduced. is there.

The solid lubricant used in the present invention includes:
One or more are selected from the group consisting of polytetrafluoroethylene, molybdenum disulfide, graphite, boron nitride and the like, and polytetrafluoroethylene is particularly preferable.

The above-mentioned polytetrafluoroethylene is
It is well known that it can be easily produced by polymerizing by a conventionally known method and has a very low friction coefficient. The average particle size is preferably 20 μm or less, and particularly preferably 0.5 μm to 5 μm. The blending ratio is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the resin, and if it is less than 10 parts by weight, satisfactory slidability cannot be obtained, and if it exceeds 200 parts by weight, the adhesion to the wiper blade rubber is deteriorated. Or the sliding durability may be reduced.

The above molybdenum disulfide, boron nitride and graphite each have a hexagonal crystal structure, and it is considered that shearing occurs between the layers due to the weak bonding force between the layers of the layered structure and low friction characteristics are exhibited. Has been.

The average particle size of the above molybdenum disulfide is 1
It is preferably 0 μm or less, particularly preferably 0.5 μm to 5 μm. The compounding ratio is 20 to 200 with respect to 100 parts by weight of the resin.
Parts by weight are preferred. If it is less than 20 parts by weight, satisfactory slidability cannot be obtained, and if it exceeds 200 parts by weight, the adhesion to the wiper blade rubber may be reduced or the sliding durability may be reduced.

The average particle size of the above graphite is 40 μm.
m or less is preferable, and 2 to 15 μm is particularly preferable. The mixing ratio is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the resin. If it is less than 10 parts by weight, satisfactory slidability cannot be obtained, and if it exceeds 200 parts by weight, the adhesion to the wiper blade rubber may be reduced, or the sliding durability may be reduced.

The average particle size of the boron nitride is 15 μm.
The following is preferable, and 1 to 8 μm is particularly preferable. The mixing ratio is preferably from 10 to 150 parts by weight based on 100 parts by weight of the resin. If it is less than 10 parts by weight, satisfactory slidability cannot be obtained,
If it exceeds 150 parts by weight, the adhesion to the wiper blade rubber may be reduced and the sliding durability may be reduced.

As the resin used in the present invention, an oil-modified polyurethane resin which is a one-part room temperature dry type or a one-part room temperature cure type and is soluble in a petroleum-based aliphatic solvent, a moisture-curable urethane resin, a lacquer-type urethane resin, Lacquer type acrylic resins, copolymers of fluoroolefin and alkyl vinyl ether, and the like. Among them, the performance required for wiper blade rubber is abrasion resistance, weather resistance, water resistance, flexibility and toughness, heat resistance, A copolymer of a fluoroolefin and an alkyl vinyl ether, which is excellent in adhesion and washer liquid resistance, is preferable.

The oil-modified polyurethane resin used in the present invention is a one-liquid room temperature dry type resin in which phthalic anhydride of alkyd resin is replaced by diisocyanate, and is dried by oxidative polymerization of (semi) dry oil. The molecular weight is 20
000 to 70,000.

The moisture-curable urethane resin used in the present invention is a one-liquid room temperature-curable type, contains NCO in the molecule,
After coating, moisture (moisture) in the air reacts with the isocyanate groups to cure and form a coating film. The molecular weight is 20
000 to 70,000.

The lacquer type urethane resin used in the present invention is a one-liquid room temperature dry type and is a thermoplastic resin obtained by reacting a hydroxyl group-terminated polyester or polyether and a long chain glycate with diisocyanate. The molecular weight is 30
000 to 70,000.

The lacquer type acrylic resin used in the present invention is a one-liquid room temperature dry type, and is a thermoplastic resin obtained by copolymerizing acrylic acid and methacrylic acid derivatives, styrene and the like as main components. The molecular weight is 100
It is 00 to 100,000.

The fluoroolefin-alkyl vinyl ether copolymer used in the present invention is a one-liquid room temperature dry type, and the main basic skeleton is an alternating copolymer of fluoroolefin and alkyl vinyl ether. The molecular weight is 10,000 to 40,000. In general, a copolymer of fluoroolefin and alkyl vinyl ether often contains a hydroxyl group, but the presence or absence of the hydroxyl group is not critical in the present invention. However, the fluoroolefin and the alkyl vinyl ether copolymer having some hydroxyl groups have good dispersibility of the solid lubricant.

The coating composition of the present invention is produced by dissolving a resin in a petroleum-based aliphatic solvent, mixing the silicone rubber powder and the solid lubricant in the solution, and dispersing the mixture.

When the coating composition of the present invention is used,
After applying the present coating composition by a coating method such as spray coating, dipping, brush coating, etc., the petroleum-based aliphatic solvent is volatilized and dried or cured. The coating after drying or curing is 3
-30 μm is preferable, and 5-10 μm is particularly preferable.
As the thickness of the coating increases, the ability to follow the wiper blade rubber, which is the base material, deteriorates, causing cracks in the coating itself, which may lower the wiping performance.

The material of the wiper blade rubber which is the article to be coated with the coating composition of the present invention includes natural rubber and ethylene-
Examples thereof include propylene rubber, nitrile rubber, chloroprene rubber and the like. Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

[0024]

[Examples and Comparative Examples]

Example 1 100 parts by weight of a copolymer of fluoroolefin and alkyl vinyl ether (resin A) was added to Mineral Spirit 300.
A coating composition was produced by dissolving in 1 part by weight, and 70 parts by weight of silicone rubber powder was mixed and dispersed in the solution.

Examples 2 to 37 Resins A to E were dissolved in a solvent, and silicone rubber powder and solid lubricant A to solid lubricant D were mixed and dispersed in the solution to paints shown in Tables 1 to 3. A composition was produced.

The outline of various raw materials used in Examples and Comparative Examples is as follows. It should be noted that all of these are examples of the raw materials used in this test, and the present invention is not limited to these. -Resin A: copolymer of fluoroolefin and alkyl vinyl ether, fluoroethylene alkyl vinyl ether alternating copolymer, molecular weight of about 30,000-Resin B: oil-modified polyurethane resin, oil-linseed oil (5
2%), molecular weight about 40,000. Resin C: Moisture curable urethane resin, NCO content 2.
7-3.8%, molecular weight about 40,000 ・ Resin D: lacquer type urethane resin, molecular weight about 5,000
0-Resin E: lacquer type acrylic resin, acid value = 1 to 3, molecular weight of about 30,000-Silicone rubber powder: spherical fine powder of silicone rubber having a structure in which linear dimethylpolysiloxane is cross-linked, average particle size 5 μm, Particle size distribution 1 to 20 μm Solid lubricant A: Polytetrafluoroethylene, average particle size 3 to 5 μm Particle size distribution 1 to 20 μm Solid lubricant B: Molybdenum disulfide, average particle size 0.5 to
1.2 μm Solid lubricant C: Graphite, average particle size 9.5 to 1
0.5 μm, particle size distribution 1.5 to 40 μm Solid lubricant D: boron nitride, average particle size 1 to 2 μm Solvent: mineral spirit, component C9 to C12 paraffin 60 to 70%, C9 to C10 alkylbenzene 20 to 30%

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

The coating compositions of the examples are evaluated for wiping performance and friction tests by the following methods. The results are shown in Tables 4-8. Evaluation of wiping performance 1. Manufacture of test pieces (1) Items to prepare ・ Automobile wiper blade rubber (commercially available Honda Automobile length: 500 mm, material: natural rubber (halogenated product)) ・ Muddy water (blending content JIS dust type 1: JIS dust 2)
(Type: Water = 1: 3: 12) (2) Manufacturing procedure An automobile wiper blade rubber was attached to an automobile, and 50 cc of muddy water was dropped onto the glass of the sliding portion of the wiper blade rubber at an initial stage and every 1000 times of sliding, 10,000
Slid once to deteriorate the wiper blade rubber. Then, the coating compositions of Examples and Comparative Examples were sprayed to give a film thickness of 1
It is coated with 0 μm and left at 25 ° C. for 6 hours. 2. Test method According to JIS D5710, 4.2 Wiping performance, 7.2 Wiping performance test, perform the test. Evaluation items are
The number of smooth operation, presence or absence of remarkable chatter and abnormal noise, and wiping performance (water drop remaining line (initial and after 500,000 times endurance)). Whether or not smooth operation is possible =
○, no = x, and presence / absence of chatter = yes, no =
X, presence / absence of abnormal noise is set as yes = no, x =
For the wiping performance, see Note 1 of JIS D 5710 4.2.
Based on ~ 3, M zone (the wiping area of the wiper blade reciprocating from the center point of the wiper blade rubber to the both ends by 1/4) and S zone (wiping range other than M zone) ), The number of hair lines (extremely thin strip-like wipes with a width of 0.5 mm or less), heavy lines (fine strip-like wipes with a width of 1 mm or less) and wide lines (strip-like wipes with a width of approximately 1 to 20 mm). Is represented by a number as [number of M zones / number of S zones]. Friction test 1. Preparation of test piece Natural rubber sheet (hardness JIS A 60 thickness 2m
m) is subjected to a halogen treatment, and the coating compositions of Examples and Comparative Examples are spray-coated to a film thickness of 10 μm.
Leave at ℃ for 6 hours. 2. Test method Using a reciprocating motion tester, under conditions of a sliding speed of 6000 mm / min, a load of 100 g, and a sliding distance (stroke) of 100 mm, the initial and 10 times with respect to the mating material 1/4 inch glass ball
Measure the friction coefficient after enduring 10,000 times.

[0031]

[Table 4]

[0032]

[Table 5]

[0033]

[Table 6]

[0034]

[Table 7]

[0035]

[Table 8]

Comparative Example 1 The coating composition of the present invention was tested without coating. The test results are shown in Table 9.

[0037]

[Table 9]

Comparative Examples 2 to 6 The coating compositions shown in Table 10 were produced by changing the compounding ratio of the coating compositions of the examples. The test results are shown in Table 11.

[0039]

[Table 10]

[0040]

[Table 11]

[0041]

EFFECT OF THE INVENTION Silicone rubber powder is added to the one-part room temperature dry type resin or one-part room temperature curing type resin soluble in petroleum-based aliphatic solvent having excellent flexibility of the present invention, or silicone rubber powder and solid lubricant. The coating composition obtained by adding to the wiper blade rubber is used to repair cracks caused by deterioration of the wiper blade rubber over time, thereby improving wiping properties and imparting slidability to the wiper blade rubber. effective. In addition, since the resin is a one-liquid room temperature dry type resin or a curable resin, it has excellent workability, and the inclusion of a petroleum-based aliphatic solvent as a solvent makes it safer than the inclusion of a general organic solvent. There is a nature.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 175/04 PHM C09D 175/04 PHM (72) Inventor Masahito Shimada 714 Yabata, Chigasaki City, Kanagawa Prefecture ) Inventor Masa Makino 116 Higashikawa, Aoyama, Toyoyama-cho, Nishikasugai-gun, Aichi Prefecture

Claims (5)

[Claims] 1. A wiper comprising a one-liquid room-temperature-drying resin or a one-liquid room-temperature-curing resin, which has excellent flexibility, as a binder, and a silicone rubber powder added to a dissolved product of the petroleum-based aliphatic solvent. A one-part room temperature dry or curable coating composition for repairing blade rubber. 2. The room-temperature-drying or curable resin is any of oil-modified polyurethane resin, moisture-curable urethane resin, lacquer type urethane resin, lacquer type acrylic resin, and copolymer of fluoroolefin and alkyl vinyl ether. The coating composition described. 3. The coating composition according to claim 1, wherein a solid lubricant is added. 4. The coating composition according to claim 3, wherein the solid lubricant is one or more selected from the group consisting of polytetrafluoroethylene, molybdenum disulfide, graphite, boron nitride and the like. 5. The coating composition according to claim 1, wherein the solvent is mineral spirits.