KR100501764B1 - Wiper blade - Google Patents

Abstract

A water repellent component is contained in the wiper blade body and the coating layer made of a natural rubber composition through a water repellent carrier, so as to be slippery with the glass surface (that is, slidability). It is an object of the present invention to provide a water repellent performance over a long period of time by gradually oozing water repellent components from the wiper blade on the glass surface while improving the mechanical properties.

As a solution, the natural rubber composition obtained by kneading a water repellent carrier containing a water repellent component is used as a wiper blade body. The water repellent component is selected from silicone oil based, pullulor (fluorine) oil based and silane based components. The water repellent carrier is a powder selected from silicone rubber, silicone, fluorine and fluorine-based rubber. The coating layer containing the water repellent component is held on the surface of the lip portion of the wiper blade body.

Description

WIPER BLADE {WIPER BLADE}

The present invention provides a water repellent component from a wiper blade on a vehicle glass surface while improving slipperiness with a functional wiper blade, specifically a vehicle glass surface (hereinafter, simply referred to as a "glass surface"). The present invention relates to a wiper blade having a function of gradually exuding water and imparting water repellent performance.

Conventional wiper blades form a thin film of water at the interface between the glass surface and the wiper blade to provide slipperiness to the wiper blade as a film of water and to obtain a good field of view through the glass surface. In recent years, however, more people are applying water repellents to glass surfaces. Even if the wiper blade slides on the glass surface coated with the water repellent agent, a thin film of water cannot be formed at the interface with the glass surface. Thus, various wiper blades have been devised and functionalized to improve this. As one of them, in recent years, a method has been proposed in which a silicone water repellent component is exuded directly from a wiper blade to coat on a glass surface.

However, in terms of physical properties, silicone rubber has the disadvantage that mechanical strength is lower than natural rubber, and in particular, the tear strength is poor. In addition to the drawbacks in the formulation, but also easy to generate compression permanent deformation, there is a drawback is poor fatigue resistance and wear resistance.

In other words, if the silicone water-repellent component is extruded from the wiper blade molded with the silicone rubber composition, the silicone-based water repellent component is homogeneous with the composition of the wiper blade, so even if it is easy to exude on the glass surface, In the point that the water droplets on the glass surface, which is the original function, are smoothly removed while the edge part of the lip part of the wiper blade is easily crushed, the neck part is easily cut off, and the pressing force is continued by the wiper arm part for a long time. When it is applied, there are disadvantages such as crushed marks, which actually lose rubber elasticity. And if it is used continuously for a long time, the edge part of the lip part wears out, and the wiper performance is deteriorated or slipperiness is reduced, and the original function of the wiper blade is not sufficiently exhibited. In this respect, the above method is not suitable to clean up the water droplets on the glass surface.

On the other hand, in the silicone rubber compound, a silicone oil-based or silane-based water repellent component is mixed and vulcanized to manufacture a molded body, since the silicone rubber and the water repellent component are in the same system, so that the mixing is simple. It is also easy to make.

However, since the silicone rubber and the water repellent component are the same system, the silicone oil-based or silane-based water repellent component easily disperses inside. Specifically, the wiper blade will be described. Since the water repellent component easily leaks out of the wiper blade body, the water repellent component can seep out of the surface of the wiper blade at once and cannot continuously ooze this water repellent component. Therefore, even if it is possible to water-repellent glass surface by oozing out the water repellent component in a moment, even if a year or two years, a small amount of water repellent component can not continue to ooze out. However, the required property of the wiper blade is to keep the small amount of water repellent component continuously and oozing out for a longer time.

In addition, in the wiper blade formed with the silicone rubber composition, when a large amount of water repellent component is added to allow it to ooze out for a long time, it begins to bleed out at once, and water droplets adhere to the surface of the wiper blade, which is bad to see and is not good. . In addition, a bending motion generated when the wiper blade is slid on the glass surface is applied to the lip portion, so that the tendency of the water repellent component to bleed out is accelerated. In addition, even if a large amount of water-repellent ingredients are oozed out at once, the water-repellent ingredients that ooze out on the glass surface are often washed away with water and become useless. Furthermore, if it is allowed to ooze out at once, the water repellent component is applied and spread on the glass surface at once, and thus a stain is formed on the glass surface. Rather, the clock becomes poor and safety cannot be secured.

On the other hand, since the wiper blade made of the silicone rubber composition has the disadvantages described above, it is considered to make the wiper blade composition into a molded body of a natural rubber (NR rubber) composition which is advantageous over the silicone rubber in terms of mechanical properties. However, when a wiper blade made of a natural rubber composition is molded by directly adding a water repellent component of silicone oil, fluorine oil, and silane to the rubber compound before molding, the obtained wiper blade does not exude any water repellent component. Therefore, even if the holding performance of the water repellent component is good, the water repellent component does not exude, and thus the effect of forming a water repellent film on the glass surface cannot be obtained.

As described above, when the wiper blade body is made of the silicone rubber composition, even though the water repellent component is leaked out, the water repellent component of the silicone oil or silane system is the same system, so it tends to leak out at a short time, and thus it is difficult to ooze out stably for a long time. . In the silicone rubber compound as a raw material, even if the raw silicone rubber, a low molecular weight silicone oil component is inevitably present, which is unavoidable in terms of composition.

Therefore, if you want to use a water repellent component other than the same system, such as a fluorine oil system, the low-molecular-weight silicone oil powder and the fluoro oil-based water repellent component of the system different from it do not mix with each other (both solubility in the other party None), rather, white turbidity is formed or soiled, and slipping the wiper blades causes the turbidity to be applied onto the glass surface, which is a problem in terms of safety due to visibility.

In addition, the wiper blade body made of a silicone rubber composition has poor mechanical properties, in particular, poor tear strength, so that the edge portion of the lip portion of the wiper blade is liable to be distorted. Moreover, there is a drawback in that the neck portion connecting the lip portion and the fuselage portion is thin and particularly prone to rupture.

Accordingly, the inventors of the present invention have completed the present invention by earnest research and development in order to eliminate the above-described drawbacks when the wiper blade body containing the water repellent component is formed as a natural rubber composition by focusing on natural rubber.

Specifically, the wiper blade body made of a natural rubber composition has excellent mechanical properties, excellent resilience required for sliding of the wiper blade, and a tensile strength, elongation rate, compressive permanent deformation, Since the tear strength, fatigue resistance, and abrasion resistance are excellent, it is difficult to reduce the wiping performance due to the edge portion of the lip portion being easily broken, the neck portion being easily cut, or the press marks being formed. And even if it is used continuously for a long time, the advantage that it is difficult to wear.

In addition, when using the water repellent component of silicone oil, fluorine oil, and silane, the type of the natural rubber and the water repellent component is different, so that once the water repellent component enters the molded body of the natural rubber composition, the water repellent component is less likely to bleed out. Thus, the holding performance of the water repellent component is maintained high. In addition, the fluorine water repellent component cannot be used like the silicone rubber composition.

In the present invention, as a mechanism for oozing out the water repellent component from the wiper blade body made of a natural rubber composition for a long time, a material carrying the water repellent component is mixed in the natural rubber composition and the substance [water repellent agent]. It was possible to let the water repellent component slowly bleed out from the carrier.

In the present invention, by coating the surface of the lip portion of the wiper blade body made of a natural rubber composition, the coating layer contributes to the sliding property, and also contains a water repellent carrier in the coating layer, silicone oil-based, fluorine oil The water-repellent component of the system and the silane system was allowed to exude from the coating layer.

The wiper blade according to the present invention is characterized by comprising a natural rubber composition obtained by kneading a water repellent carrier containing a water repellent component as a wiper blade body, wherein the water repellent component is silicone oil-based or pullulor (fluorine). It is preferably selected from oil-based and silane-based components, and the water-repellent carrier is preferably a powder selected from silicone rubber, silicone, fluorine and fluorine-based rubber.

The most preferable among the above water repellent carriers is silicone rubber powder. This silicone rubber powder is not a raw rubber of silicone. When silicone rubber powder is used as the water repellent carrier, the water repellent component and the water repellent carrier are made of a combination of the same system or materials having low surface tension, so that the water repellent component is easily supported. In the present invention, the water repellent carrier also serves as a storage tank of the water repellent component.

The weight% of the water repellent carrier kneaded into the natural rubber composition is 1 to 40% by weight, preferably 1 to 20% by weight, relative to 100% by weight of the natural rubber composition. If the weight percentage of the water repellent carrier kneaded to the natural rubber composition is less than 1% by weight, the water repellent carrier is stuck in the natural rubber composition, so that the passage of the water repellent component is not formed in the wiper blade body made of the natural rubber composition. And when the weight of the water repellent support material kneaded to a natural rubber composition exceeds 40 weight%, the natural rubber composition will not show the physical property as a wiper blade.

The water repellent carrier must be impregnated with a water repellent component of silicone oil, fluorine oil and silane. The amount of the water repellent component to be impregnated in the water repellent carrier is preferably in the range of 1 to 4 times the weight of the water repellent carrier, although it is possible in the range of 0.5 to 5 times the weight of the water repellent carrier. If the impregnated amount of the water repellent component is less than 0.5 times, even if the water repellent carrier is sufficiently kneaded in the natural rubber composition, the water repellent component does not exude. And when the impregnation amount of a water repellent component exceeds 5 times, a natural rubber composition will not show the physical property as a wiper blade. If the amount of impregnated water repellent is set within the above range, the amount of seepage can be controlled as the amount of impregnated water is large and small.

When the above water repellent carrier is further dispersed during kneading in the natural rubber composition, a fine connection of the water repellent carrier occurs in the natural rubber composition, and the water repellent component is exuded to the surface of the wiper blade body through the fine path. As described above, since the water repellent carrier serves as a storage tank of the water repellent component, it is possible to contain a large amount of water repellent component in the natural rubber composition by including the water repellent component in the water repellent carrier. Therefore, when the wiper blade is slid on the glass surface, pressure is applied to the inside of the wiper blade main body by the elastic movement of the wiper blade main body and the lip portion, so that the water repellent component easily leaks out from the inside of the wiper blade main body.

As described above, when the silicone oil-based, fluoro-oil-based, or silane-based water-repellent components are added directly to the natural rubber composition without passing through the water-repellent carrier, the water-repellent components are dispersed in the natural rubber composition and do not ooze out to the surface. do. That is, since the system of the water repellent component is not very similar to natural rubber, it does not diffuse. On the other hand, if the combination of the silicone rubber and the water-repellent component of the silicone- or silane-based component is the same, the silicone rubber and the fluoro-oil-based component are combined even if the silicone rubber can easily disperse in the silicone rubber. As for the raw silicone rubber itself, it is a high-polymerized product of silicone oil, and since it contains a low molecular weight oil component in the system, the silicone oil and fluorine oil are mixed with each other without dissolving each other to form a cloudy liquid. Of liquid makes the glass face bad. Therefore, the combination of silicone rubber and fluorine oil is impossible.

 In this invention, the coating layer containing the said water repellent component may be hold | maintained on the surface of the lip | rip part of the said wiper blade main body. The water repellent carrier containing the water repellent component may be kneaded with a binder component that holds the coating layer and the coating layer bonded to the wiper blade body. As the water repellent carrier, a powder selected from silicone rubber, silicone, fluorine and fluorine-based rubber may be used. In addition, a solid lubricant powder may be used as the water repellent carrier.

However, in recent years, even if a coating layer is formed on the lip of the wiper blade, in particular, a method of improving sliding performance and wiping performance has been proposed, there is no function to exude the water repellent component from the coating layer.

In the present invention, a binder component is used to bond and hold the coating layer on the wiper blade body. The binder component used for this purpose is urethane cured film, silicone cured film, nylon, RTV rubber, epoxy cured film, imide resin, phenolic resin, and especially curable urethane film and curable silicone film can be preferably used. have. This is because these binder components of the thermosetting type exhibit strong adhesion with natural rubber.

As the water repellent component, components of silicone oil, fluorine oil and silane are preferable.

In addition to the powder selected from silicone rubber, silicone, fluorine, and fluorine-based rubber, a solid lubricant may be used as the water repellent support. Solid lubricants serve to improve the slipperiness and wiping performance of the lip portion. Solid lubricants may employ known materials such as graphite and molybdenum disulfide.

It goes without saying that the coating layer held on the wiper blade body is formed as a thin film, so that the amount of the water repellent component that can be contained in the coating layer cannot be increased by that much. Therefore, the amount of the water repellent component that can bleed out of the coating layer is considerably less than the amount of the water repellent component that oozes out from the wiper blade body containing a large amount of the water repellent component, so that the water repellent component in the coating layer continues to ooze over the long term. I can't get it out. However, since only the lip portion is in contact with the wiper blade glass surface, it can be said that the immediate effect of imparting water repellency to the glass surface is large. The mechanism for specific oozing is similar to that when the water repellent component oozes out from inside the wiper blade body. Silicone oil type, silane type, and fluorine oil type can be used as a water repellent component.

The kind of the water repellent component oozing from the wiper blade body and the water repellent component oozing from the coating layer may be different. For example, the water repellent component oozing from the wiper blade body may be silicone oil-based, and the water repellent component oozing from the coating layer may be fluorine oil-based. Conversely, the water repellent component oozing from the wiper blade body may be fluorine-based, and the water repellent component oozing from the coating layer may be silicone-based. In this manner, any combination of components in the silicone oil system, the fluorine oil system and the silane system may be used. The reason is that the water repellent component in the coating layer oozes out at a time earlier than the water repellent component that oozes out from the wiper blade body, so that both water repellent components do not mix with each other. The liquid does not cover the glass surface and blur the field of view. In addition, the water repellent component in the coating is an extremely thin film thickness of several tens of microns at most, even if the coating layer is thick, and the amount of the water repellent component contained therein is higher than that of the water repellent component contained in the wiper blade body. It is because the water repellent component in the wiper blade main body and the water repellent component in the coating layer do not mix with each other to produce a cloudy liquid because it is so small that it leaks out early as described above.

Among the water repellent components oozing from the wiper blade body or the coating layer, the silicone oil-based components include dimethyl silicone oil, methylphenyl silicone oil, alkyl modified silicone oil, methyl styrene modified silicone oil, olefin modified silicone oil, radical modified silicone oil, and amide modified silicone. Oil, amine modified silicone oil, cyclic silicone oil, fluorine modified silicone oil, mercapto modified silicone oil, epoxy modified silicone oil, higher fatty acid modified silicone oil, carnaba modified silicone oil, trimethylsiloxysilicate dissolved in organopolysiloxane Even if the thing, methylhydrogen silicone oil, etc. are contained, it is not limited to these. Fluoro oil-based components include perfluoropolyether and the like. The silane component (silane compound) includes chlorosilane, alkoxysilane, perfluoroalkylsilane, and the like.

In the present invention, when the coating layer and the binder component are kneaded with a water repellent carrier containing a water repellent component, a powder selected from silicone rubber, silicone, fluorine, and fluorine-based rubber and solid lubricant powder can be preferably used. have. This is because these powders can carry a water repellent component and exhibit lubricity. Powders such as nylon and boron nitride, which mainly exhibit only lubricating performance, can also be employed as solid lubricants.

The powder described above is suitably used in the range of from one third to fifteen times, preferably from one second to 14 times as a weight ratio to the binder component. If the weight ratio of the powder is less than one third, the powder is buried in the binder component, and the water repellent component cannot be held, and the sliding performance of the wiper blade is also reduced. If it exceeds 15 times, the adhesion performance to the wiper blade body of the coating layer itself will be impaired, and sliding durability will not be obtained.

When content of a binder component is a coating agent coating material, 0.01 to 35 weight%, Preferably 0.1 to 20 weight% is suitable. The range of suitable content is irrespective of the kind of binder component, and can apply even what kind of binder component. When binder component content is 0.01 weight% or less, adhesiveness with respect to a wiper blade main body falls, and sliding durability falls. If the weight exceeds 35% by weight, a thick resin layer is formed, thereby lowering the rubber elasticity of the wiper blade body, thereby lowering the wiping performance.

As a solvent of the coating composition which melt | dissolved the binder component, as long as a binder component melt | dissolves, any can be used. For example, alcohols, such as methanol, ethanol, and isopropyl alcohol, aromatic solvents, such as toluene and xylene, ester crab solvents, such as ethyl acetate and butyl acetate, ketone solvents, such as acetone and methyl ethyl ketone, etc. can be used. In consideration of the solvent evaporation rate, two or more solvents may be used in combination.

As for the layer thickness of a coating layer, 3-30 micrometers is preferable, and 5-20 micrometers is especially preferable. As the coating layer of the coating layer becomes thicker, the followability to the wiper blade main body, which is the base material, worsens, causing cracks in the coating layer itself, and thus, the wiping performance may decrease. On the contrary, as the coating film becomes thinner, the amount of the water repellent component may be reduced or the sliding performance may decrease. Therefore, the layer thickness of a coating layer needs to be set in a fixed range. If it is in the said range, a crack will not generate | occur | produce in a coating layer, it will be hard to reduce wiping performance, and a water repellent component of a required amount can be contained, and the fall of slip performance can be prevented.

The amount of the water repellent component contained in the water repellent carrier (powder) to be kneaded in the coating layer is appropriately in the range of 1/20 to 4 times the weight of the powder, preferably 1 to 3/10 times Range. If the weight of the water repellent component is less than one-twenty the weight of the powder, the water repellent will not evenly adhere to the glass surface when the wiper blade is slipped. If it exceeds four times, the powder will not retain the water-repellent component, and the water-repellent component will leak like sweating. As the coating method of coating coating on the surface of these wiper blade main bodies, any well-known methods, such as a spray method, a dipping method, and a brush application method, can be used.

The vulcanizing agent, vulcanization aid, vulcanization conditions (temperature and time), etc. which are used when manufacturing the wiper blade of this invention may be suitably determined, and there is no limitation in particular. As sulfur-based vulcanizing agents, powdered sulfur, precipitated sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide and the like can be used. In addition, well-known components added to the conventional rubber composition, such as a vulcanization adjuvant, a reinforcing agent, a softener, a coloring agent, an extender, an anti-aging agent, and a ultraviolet absorber, can be added suitably.

EXAMPLE

Next, an Example and a comparative example are demonstrated. In order to obtain the seven types of wiper blades of Examples 1 to 7 according to the present invention, the molding process of the wiper blade body as described below, the surface treatment process of the wiper blade body, and the formation of a coating layer on the wiper blade body are necessary. The process was carried out.

And Examples 1 to 6 have a coating layer and Example 7 does not have a coating layer.

<Molding of the wiper blade body>

After the water-repellent component powder was mixed well with the water-repellent carrier powder, it was mixed with the natural rubber composition, thoroughly kneaded, and vulcanized at 150 ° C. for 15 minutes to form an uncoated wiper blade body.

For the water repellent carrier powder, for example, 100 parts of fluorine rubber G801 (Dier, Daikin Industries Co., Ltd.) and 20 parts of MT carbon black (Thermax N-900, manufactured by CANCARB LTD) are used. And 4 parts of triallyl isocyanate (TAIC, manufactured by Nippon Chemical Co., Ltd.) and 1.5 parts of peroxide (Pha-hekki Co., Ltd., 25B, manufactured by Nippon Chemical Co., Ltd.). The water-repellent carrier was kneaded on a roller to extrude the sheet to a thickness of 2 mm, and then 160 Press vulcanization at 10 ° C. for 10 minutes, and then oven vulcanization at 180 ° C. for 4 hours to produce a sheet of water repellent carrier, cut the sheet into small chip shapes of 5 × 5 mm, and freeze grinder (JFC-300; Freeze-milling was carried out using Nippon Bunkyo Co., Ltd.) to obtain a water repellent carrier powder having a size of 50 μm or less.

Tables 1 and 7 show the types and blending amounts of the water repellent carrier and the components of the water repellent. Likewise, the types and compounding amounts of the components of the natural rubber composition are shown in Table 2.

<Surface Treatment>

Dissolve 50 g of bleach and 50 ml of 12 prescribed hydrochloric acid in 100 g of water. The wiper blade main body shape | molded at the shaping | molding process of the wiper blade main body was immersed in this solution for 3 minutes, and the surface was chlorinated.

<Formation of coating layer>

Subsequently, after coating the coating material shown in Table 3 on the surface of the lip portion of the wiper blade body after the chlorination treatment, it was cured and dried at 80 ° C. for 30 minutes.

This step yielded a wiper blade whose surface of the lip portion was coated with a layer thickness coating layer shown in Table 3.

For Examples 1 to 6, Table 3 shows the kinds and compounding amounts of the components of the coating coating, the coating method of the coating coating, and the layer thickness (film thickness) of the coating layer after curing drying.

[Comparative Example]

In order to obtain the seven types of wiper blade main bodies of Comparative Examples 1-7, the shaping | molding process of the wiper blade main body below, the surface treatment process of the wiper blade main body, and the coating process of the coating layer with respect to the wiper blade main body were performed as needed. .

Comparative Examples 1 to 5 molded the wiper blade main body with the natural rubber composition, and Comparative Examples 6 and 7 formed the wiper blade main body with the silicone rubber composition.

Comparative Example 1 contains no water repellent carrier and a water repellent component, and does not have a coating layer.

In Comparative Example 2 and Comparative Example 4, the water repellent component was mixed directly with the natural rubber without using the water repellent carrier. It does not have a coating layer. And the comparative example 2 makes the quantity of a water repellent component into a normal amount, and the comparative example 4 makes it more than the normal amount of a water repellent component.

In Comparative Example 3 and Comparative Example 5, the water repellent carrier component (using talc) in which the water repellent component was mixed was mixed with natural rubber. Comparative Example 3 does not have a coating layer. Comparative Example 5 has a coating layer.

Comparative Example 6 and Comparative Example 7 kneaded the water repellent component directly into the silicone rubber without using a water repellent carrier. Comparative Example 6 does not have a coating layer. Comparative Example 7 has a coating layer.

A. Comparative Examples 1 to 5 using a natural rubber composition

<Molding of the wiper blade body>

In Comparative Example 1, the natural rubber was kneaded and vulcanized at 150 ° C. for 15 minutes to form an uncoated wiper blade body.

In Comparative Example 2 and Comparative Example 4, when the natural rubber composition was kneaded, the water repellent component was kneaded directly.

In Comparative Examples 3 and 5, the water repellent component was kneaded well in the water repellent carrier and then mixed when the natural rubber composition was kneaded.

And the vulcanization temperature and time are the same with respect to Comparative Examples 1-5.

The kind and compounding quantity of the water repellent support body and the component of a water repellent agent are shown in Table 4 about the comparative examples 1-5. Likewise, the types and compounding amounts of the components of the natural rubber composition are shown in Table 5.

<Surface Treatment>

Dissolve 50 g of bleach and 50 ml of 12 prescribed hydrochloric acid in 100 g of water. In this solution, the molded wiper blade main body was immersed for 3 minutes, and the surface was chlorinated, and the wiper blade main body was obtained.

<Formation of coating layer>

Subsequently, after coating the coating material shown in Table 6 to the surface of the lip portion of the wiper blade main body after the chlorination treatment, it was cured and dried at 80 ° C. for 30 minutes.

This step yielded a wiper blade whose surface of the lip portion was coated with a layer thickness coating layer shown in Table 6.

For Comparative Examples 1 to 5, the types and amounts of components of the coating coating, the coating method of the coating coating, and the layer thickness (film thickness) of the coating layer after curing drying are shown in Table 6.

B. Comparative Example 6 and Comparative Example 7 Using Silicone Rubber Composition

<Molding of the wiper blade body>

After adding the vulcanizing agent to the silicone rubber compound, the water-repellent component was added, the sheet was extruded to a thickness of 4 mm on the roller, first vulcanized at 165 ° C for 15 minutes, and then secondary vulcanization at 200 ° C for 4 hours. To form a wiper blade made of a silicone rubber composition.

For Comparative Example 6 and Comparative Example 7, the types and compounding amounts of the silicone rubber composition and the water repellent component are shown in Table 4 or Table 5.

<Formation of coating layer>

The coating chart shown in Table 6 of the surface of the lip section and the wiper blade body was then applied and then cured and dried at 80 ° C. for 30 minutes.

This step yielded a wiper blade whose surface of the lip portion was coated with a coating layer of the layer thickness shown in Table 6.

For Comparative Example 7, Table 6 shows the kinds and compounding amounts of the components of the coating chart, the coating method of the coating chart, and the layer thickness (film thickness) of the coating layer after curing drying.

[Table 1] Water repellent carrier and water repellent component

Example One 2 3 4 5 6 7 Water repellent Carrier Silicone rubber powder wt% Torefiiru E604Torefiiru E500KMP594 10.0-- --18.0 --- -1.0- -3.0- --- -20.0- Silicone Resin Powder wt% Tos Paaru 120 - - 1.0 - - - - Fluorine Resin Powder wt% KTL-500F - - 4.0 1.0 - - - Fluoro rubber powder wt% G801 vulcanizate - - - - - 15.0 - Water repellent ingredient Silicone oil wt% KF96-1000csKF96-500000csFL-5KP-359 10.0 --- -10.010.0- 3.01.8-0.5 ---- ---- 10.010.0-- 10.010.0-- Fluorooil wt% Honburin Y-04 - - - 6.0 - - - Silane wt% KBM-7803 - - - - 10.0 - -

[Table 2] Natural rubber composition

Example One 2 3 4 5 6 7 Natural rubber wt% 100.0 80.0 100.0 90.0 100.0 100.0 80.0 Biz stearic acid wt% SBR 1500 wt% IR 2 200 wt% 1.0-- 1.020.0- 1.0-- 1.0-10.0 1.0-- 1.0-- 1.020.0- Galvanized No. 3 wt% 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Process oil wt% 10.0 10.0 9.0 9.0 10.0 10.0 10.0 Carbon Black (FEF) wt% 50.0 - 50.0 50.0 50.0 50.0 - Carbon Black (GPF) wt% - 50.0 - - - - 50.0 Paraffin155 wt% 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Nokurak B wt% 2.0 - 2.0 - 2.0 2.0 - Nokurak AW wt% - 2.0 - 2.0 - - 2.0 Nokushera DM wt% 1.8 - - - 1.8 1.8 - Nokushera PX wt% - 1.8 1.8 1.8 - - 1.8 Powder Sulfur (vulcanizer) wt% 2.0 2.0 2.0 2.0 2.0 2.0 2.0

[Table 3] Coating Coating

Example One 2 3 4 5 6 7 Film thickness of coating layer μm   15   20   12   18   13.5   16  -       Application method Spray gun Spray gun Spray gun Brush application Spray gun Spray gun  - Topic wt% BF-8AA Powder KMP600KMP590CLAYTON APAYSR3022ZX-007C 25.53-2.33-0.107.16--135.7--37.72-0.52.5 ----- -25.532.33-0.10-4.33--69.37-104.05 --- 4.03.0 --- 25.53--2.330.10--1.81-70.64-105.97 --- 2.0--1.5- 11.55-1.00-0.10-4.33 --- 35.4853.214.00 ------ 1.33 11.55--2.330.1--1.8134.00-36.4820.7320.732.5 --- 0.5-- 25.52-2.33-0.107.16--135.7--37.72-0.52.5 ----- -------------------- Curing agent wt% YC6831E405-80THLXLtoluene 0.72 --- 9.5 -0.98--9.02 --1.18-8.82 -0.98--9.02 --- 1.188.82 0.72 --- 9.5 -----

[Table 4] Water repellent carrier and water repellent component

Comparative example One 2 3 4 5 6 7 Water repellent carrier Talc wt% Talc GTA - - 5.0 - 5.0 - - Water repellent ingredients Silicone oil wt% KF96-100csKF96-1000csKF96-10000csKF96-500000csFL-5KP-359 ------ -3.0-3.0-- -2.0-6.0-- -10.0-15.0-- -2.0-6.0-- 5.0 ----- --5.05.0--

[Table 5] Natural rubber composition or silicone rubber composition

Comparative example One 2 3 4 5 6 7 Natural rubber wt% 100.0 100.0 100.0 80.0 100.0 - - Biz stearic acid wt% SBR wt% 1.0- 1.0- 1.0- 1.020.0 1.0- - - Galvanized No. 3 wt% 5.0 5.0 5.0 5.0 5.0 - - Process oil wt% 10.0 9.0 10.0 10.0 10.0 - - Carbon Black (FEF) wt% 50.0 50.0 - - - - - Carbon Black (GPF) wt% - - 50.0 50.0 50.0 - - Paraffin155 wt% 1.5 1.5 1.5 1.5 1.5 - - Nokurak B wt% 2.0 2.0 - - - - - Nokurak AW wt% - - 2.0 2.0 2.0 - - Nokushera DM wt% 1.8 1.8 - - - - - Nokushera PX wt% - - 1.8 1.8 1.8 - - Powder Sulfur (vulcanizer) wt% 2.0 2.0 2.0 2.0 2.0 - - Silicone Rubber Compound wt% KE-961-u KE-9611-u - - - - - 100.0- -100.0 C-8 (vulcanizing agent) - - - - - 2.0 2.0

[Table 6] Coating Coating

Comparative example One 2 3 4 5 6 7 Film thickness of coating layer μm - - - - 16 - 16 Application method - - - - Spray gun - Spray gun Topic wt% BF-8AKMP600CLAYTON APAYSR3022Xylene TolueneKF96-1000csKF96-10000cs -------- -------- -------- -------- 25.532.330.107.16138.737.72-- -------- 25.532.330.107.16135.737.720.52.5 Curing agent wt% YC6831 Toluene - - - - 0.729.5 - 0.729.5

Each sample name (article name), provider name, and property used in Examples 1-7 and Comparative Examples 1-7 are listed. In addition, the marking was made in principle as a sample name (provider name).

Torrefiiru E604

(Toray, Dow Corning, Silicon, Japan) spherical shape, average particle size 2㎛

                                         Silicone rubber powder

Torrefiiru E500

(Toray, Dow Corning, Silicon, Japan) spherical shape, average particle size 3㎛

                                         Silicone rubber powder

KMP594 (Japanese chemical company of Japan) spherical shape, average particle size 5 ㎛

                                         Silicone rubber powder

Tos Paaru 120 (Tokyo Silicone Co., Ltd., Japan)

                                         Silicone resin powder

Daier G801 (Daikin Industries, Ltd.) Fluoro rubber

KTL-500F [Japan, Co., Ltd.] PTFE Powder

KF96-100cs (Japan Shinshin Chemical Co., Ltd.) Dimethyl Silicone Oil

KF96-1000cs (Japan Shinshin Chemical Co., Ltd.) Dimethyl Silicone Oil

KF96-500000cs (Japan Shinshin Chemical Co., Ltd.) Dimethyl Silicone Oil

KE961-u (Japan Shinshin Chemical Co., Ltd.) silicone rubber compound

FL-5 (Japanese chemical company) Fluorine modified silicone oil

KP-359 (Japan Shinshin Chemical Co., Ltd.) Amino Modified Silicone Oil

KBM-7803 (Japanese chemical company) heptadecatrifluorodecyl tree

                                          Methoxysilane

Honburin Y-04 (Aujimontosa) Fluorinated Oil

Natural rubber (RSS No. 3)

SBR1500 (Japan Synthetic Rubber) SBR Rubber

IR2200 (Japan Synthetic Rubber) IR Rubber

Talc GTA (Kunimine Industries) hydrous magnesium silicate,

                                           Particle size 300 mesh, more than 97%

C-8 (Japan Shinshin Chemical Co., Ltd.) 2,5-dimethyl-2,5-bis (t-butyl

                                           Peroxide) -hexane

Biz Stearic Acid (Japan Branch)

Galvanization No. 3

Process oil (出 光 石油 CHEMISTRY)

旭 Carbon black (FEF) (旭 Carbon company)

Carbon Black (GPF)

Paraffin 155 (日本 精 蠟)

Nokurak B (Japan Daishin Chemical Co., Ltd.) Antioxidant

Nokurak AW (Japanese Chemical Industry)

Nokucera DM (vulnerable to vulcanization)

Nokusera PX (vulcanization accelerator)

Powder Sulfur (Japanese 鍊 井 澤 精鍊 所)

BF-8A (Japan's Fukuyama Black Co., Ltd.) natural scales graphite,

                                             Average particle size 8 ㎛

A powder (Japan's 大阪 造船 所 company) molybdenum disulfide

KMP600 (Japanese chemical company) spherical silicone composite powder

                                             Average particle size 5 ㎛

KMP590 (Japan Shinshin Chemical Co., Ltd.) silicone resin powder, spherical,

                                             Average particle size 2.0 ㎛

CLAYTON APA (SOUTHERN CLAY PRODUCTS.INC) Anti-Sedimentation Agent

YSR3022 (Tokyo Silicone Co., Ltd., Japan) Concentration 30% hardening silicone

ZX-007C (Japan Fukushima Chemical Co., Ltd.) concentration 35.7%, OH value 21.42,

                                             Silicone modified polyols

Desmotte 670BA (Japan Bayer Urethane Co., Ltd.) concentration 80%, OH value 112.2,

                                                Polyester polyol

xylene

Cyclohexane

Cyclohexanone

toluene

EMS-1 (Japan Co., Ltd.) Fluorine (solid)

KF96-10000cs (Japan Shinshin Chemical Co., Ltd.) Dimethyl Silicone Oil

KF-354 (Japan Shinshin Chemical Co., Ltd.) Polyether Modified Silicone Oil

KE9611-u (Japan Shinshin Chemical Co., Ltd.) silicone rubber compound

KF99 (Japanese chemical company) Methylhydrogenpolysiloxane

KF393 (Japanese chemical company) Amino modified silicone oil

KF9901 (Skin Chemical Co., Ltd. of Japan) Methylhydrogenpolysiloxane

YC6831 (Tokyo Silicon, Japan) concentration 25%, organic tin,

E405-80T concentration 80%, NCO% = 7.1,

                                            Isocyanate

HL (Japan Urethane) Concentration 80%, NCO% = 12.9,

                                            Isocyanate

XL (Japan urethane company) concentration 75%, NCO% = 12.9,

                                            Isocyanate

Test Methods:

Testing was performed using the apparatus of FIG. 3 of "7.2 Wiping Performance Test" using the items of JIS D-5710 "4.2 Wiping Performance" and the same "7.2 Wiping Performance Test". The glass surface of the apparatus was treated with Soft99 Co., Ltd. to completely remove the oil film and stains before operating the respective test articles (wiper blades obtained in Examples 1 to 7 and Comparative Examples 1 to 7). The test was then started.

The test items include the smooth operation, the presence of noticeable tremor and abnormal noise, the wiping performance (the number of lines remaining after wiping the droplets), and the water repellency of the glass. It was set as the endurance test after 100,000 times, 200,000 times, 300,000 times, 400,000 times, and 500,000 times after the initial sliding.

For the smooth operation (mainly shaking at the lower end of the blade), o (,), o (x), o (with or without), o (no), o (with or without abnormal sound), None was shown as (circle).

Wiping performance was investigated in accordance with JIS D-5710 "4.2 Wiping performance".

In addition, the item of JIS D-5710 "4.2 Wiping Performance" specifies the wiping performance of blades and arms, and it works smoothly, without noticeable tremor and abnormal noise, and wiping water droplets. We assume thing of pass.

<Number in M zone>

                          Hairline Hevia Line Wide Line

Initial Wiping Performance 3 1 0

Wiping performance after durability test 5 2 0

<Number in S zone>

                          Hairline Hevia Line Wide Line

Initial Wiping Performance 5 2 0

Wiping Performance after Endurance Test 7 3 2

And according to the remarks of JIS D-5710 "4.2 Wiping performance", "M zone" means the wiping area of the quarter part from the center point of the blade to the both ends of the area formed by the wiper blade reciprocating. `` S zone '' means the wiping range other than M zone, `` hair line '' means the wiping of extremely thin tendon shape of width 0.5 mm or less, and `` heavy line '' means width 1 It is prescribed that a thin tendon-shaped wipe of less than or equal to mm and a "wide line" means a band-shaped wipe remaining of about 1 to 20 mm in width. And it is prescribed that it includes several hair line and hevia line gathered, and the thing which remained after wiping of thin film | membrane. In addition, after endurance test in "wiping performance after endurance test" shows 500,000 times of reciprocation operation (sliding operation).

As a test method of the water repellent agent, the glass of the water repellent component exuded from the wiper blade body or the coating layer (coating layer) by reciprocating (sliding) the wiper blade on the glass surface of the apparatus of FIG. 3 of JIS D-5710 "7.2 Wiping Performance Test". The fixation state for was observed by looking at the water repellent state of the water, and the results are shown in Tables 7 to 12.

For the evaluation items, in the M and S zones of the wiper blades, the water repellent conditions of the wiper blade sliding were observed 100,000 times, 200,000 times, 300,000 times, 400,000 times, and 500,000 times after the sliding of the wiper blades. (Circle) and the thing which become a distorted water droplet (triangle | delta) and what does not become a water droplet were represented by x, and it was set as water-repellent performance.

The evaluation of the wiping performance based on JIS D-5710 is expressed as XY with the number X of M zones and the number Y of S zones arranged horizontally. For example, when the number X of the M zones is 0 and the number Y of the S zones is 0, "00" is shown as "00", when the number X of the M zones is 0, and the number Y of the S zones is 1, "01" and the like.

The wiper glides smoothly as a whole and the water-repellent state of the glass is clean, and it is indicated by? That the sufficient safety can be secured.

TABLE 7

Early

Example Comparative example One 2 3 4 5 6 7 One 2 3 4 5 6 7 Works smoothly ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ shiver ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ An abnormal sound ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ Glass Water Repellent Performance ○ ○ ○ ○ ○ ○ △ × × × × × ○ ○ Wiping performance Hair line 00 00 01 01 00 01 01 12 12 12 11 00 13 11 Hevia lines 00 00 00 00 00 00 00 01 11 11 11 00 11 11 Wideline 00 00 00 00 00 00 00 00 00 00 00 00 00 00 Overall safety ◎ ◎ ◎ ◎ ◎ ◎ × × × × × × × ×

Note 1) In Example 7, glass water repellency was slightly weak at the beginning of operation.

Note 2) In Comparative Examples 1 to 7, the glass water repellency was poor even at the beginning of operation, and the wiping performance was also poor compared with the Examples.

Note 3) In Comparative Example 6 and Comparative Example 7, the clock was bad because the oil that had leaked out even during the initial operation.

TABLE 8

100,000 times

Example Comparative example One 2 3 4 5 6 7 One 2 3 4 5 6 7 Works smoothly ○ ○ ○ ○ ○ ○ ○ × × × × ○ × ○ shiver ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ ○ × ○ An abnormal sound ○ ○ ○ ○ ○ ○ ○ × × × × ○ × ○ Glass Water Repellent Performance ○ ○ ○ ○ ○ ○ ○ × × × × × ○ ○ Wiping performance Hairline 01 02 01 01 01 01 02 23 23 13 12 11 23 23 Hevia lines 00 00 00 00 00 00 00 12 12 12 12 00 12 21 Wideline 00 00 00 00 00 00 00 00 00 00 00 00 00 00 Overall safety ◎ ◎ ◎ ◎ ◎ ◎ ◎ × × × × × × ×

Note 1) In Comparative Examples 1 to 7, the glass water repellency was poor, and the wiping performance was also poor compared with the examples.

TABLE 9

200,000 times

Example Comparative example One 2 3 4 5 6 7 One 2 3 4 5 6 7 Works smoothly ○ ○ ○ ○ ○ ○ ○ × × × × ○ × ○ shiver ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ ○ × ○ An abnormal sound ○ ○ ○ ○ ○ ○ ○ × × × × ○ × × Glass Water Repellent Performance ○ ○ ○ ○ ○ ○ ○ × × × × × △ ○ Wiping performance Hairline 11 12 12 11 12 01 12 35 33 33 23 12 33 34 Hevia lines 01 00 01 00 01 00 01 33 23 23 22 01 23 22 Wideline 00 00 00 00 00 00 00 01 00 00 00 00 01 10 Overall safety ◎ ◎ ◎ ◎ ◎ ◎ ◎ × × × × × × ×

Note 1) In Comparative Examples 1 to 7, the glass water repellency was poor, and the wiping performance was also poor compared with the examples.

Note 2) For Comparative Example 2, an abnormal sound appeared during inversion.

TABLE 10

300,000 times

Example Comparative example One 2 3 4 5 6 7 One 2 3 4 5 6 7 Works smoothly ○ ○ ○ ○ ○ ○ ○ × × × × ○ × × shiver ○ ○ ○ ○ ○ ○ ○ × × × ○ ○ × × An abnormal sound ○ ○ ○ ○ ○ ○ ○ × × × × ○ × × Glass Water Repellent Performance ○ ○ ○ ○ ○ ○ ○ × × × × × × △ Wiping performance Hairline 12 22 23 22 23 11 22 56 44 34 24 33 54 54 Hevia lines 01 01 01 01 01 00 02 45 33 24 33 02 44 23 Wideline 00 00 00 00 00 00 00 02 01 00 00 00 11 11 Overall safety ◎ ◎ ◎ ◎ ◎ ◎ ◎ × × × × × × ×

Note 1) In Comparative Examples 1 to 7, smooth operation, shaking, abnormal noise, and glass water repellency were poor, and the wiping performance was also poor compared with the examples.

TABLE 11

400,000 times

Example Comparative example One 2 3 4 5 6 7 One 2 3 4 5 6 7 Works smoothly ○ ○ ○ ○ ○ ○ ○ × × × × ○ × × shiver ○ ○ ○ ○ ○ ○ ○ × × × × ○ × × An abnormal sound ○ ○ ○ ○ ○ ○ ○ × × × × ○ × × Glass Water Repellent Performance ○ ○ ○ ○ ○ ○ ○ × × △ △ × × × Wiping performance Hairline 23 23 24 23 23 22 24 67 45 45 35 44 66 66 Hevia lines 01 11 12 01 01 01 12 46 44 34 44 12 56 33 Wideline 00 00 00 01 00 00 00 03 01 00 01 00 12 11 Overall safety ◎ ◎ ◎ ◎ ◎ ◎ ◎ × × × × × × ×

Note 1) In Comparative Examples 1 to 7, smooth operation, shaking, abnormal noise, and glass water repellency were poor, and the wiping performance was also poor compared with the examples.

Note 2) Water repellency only appeared in Comparative Example 3 and Comparative Example 4.

TABLE 12

500,000 times

Example Comparative example One 2 3 4 5 6 7 One 2 3 4 5 6 7 Works smoothly ○ ○ ○ ○ ○ ○ ○ × × × × × × × shiver ○ ○ ○ ○ ○ ○ ○ × × × × ○ × × An abnormal sound ○ ○ ○ ○ ○ ○ ○ × × × × × × × Glass Water Repellent Performance ○ ○ ○ △ ○ ○ ○ × △ △ △ △ × × Wiping performance Hairline 35 44 45 35 34 23 35 88 66 66 45 45 88 68 Hevia lines 11 11 12 11 01 11 12 56 45 44 45 12 67 44 Wideline 00 00 01 01 00 00 01 13 02 01 11 01 23 21 Overall safety ◎ ◎ ◎ ◎ ◎ ◎ ◎ × × × × × × ×

Note 1) In Comparative Examples 1 to 7, smooth operation, shaking, abnormal noise, and glass water repellency were poor, and the wiping performance was also poor compared with the examples.

Note 2) Water repellency only appeared in Comparative Example 2, Comparative Example 3, Comparative Example 4, Comparative Example 5.

As can be seen from Table 7, in Comparative Example 6, in which only the water repellent component was added to the wiper blade body made of the silicone rubber composition, it was confirmed that the glass water repellent performance was exhibited at the beginning of use, but oil appeared too much on the glass surface. Flashing was confirmed. This tendency also occurred in Comparative Example 7 in which a water repellent component was added to the wiper blade body to form a coating layer, and in Comparative Example 7, it was confirmed that the oil appeared too much on the glass surface and sparkled.

As described above, the wiper blade according to the present invention contains a water repellent component through a water repellent carrier, such as a wiper blade body made of a natural rubber composition, or a coating layer applied to a wiper blade body made of a natural rubber composition, and thus, directly into the natural rubber composition. It does not happen that the water repellent component does not come out as it contains the water repellent component, and it is possible to impart water repellent performance for a long time by gradually seeping the water repellent component from the wiper blade on the glass surface while improving the sliding property with the glass surface. The wiper blade has the advantage that the mechanical strength exerted by the natural rubber, in particular, the tear resistance is high, the compression set is hardly generated, and the fatigue resistance and the wear resistance are also excellent.

In particular, an excellent effect is achieved that a small amount of water repellent component can be steadily oozed out for a longer period of time as compared with exuding the silicone-based water repellent component from the wiper blade formed of the silicone rubber composition.

Claims (7)

A wiper blade comprising a natural rubber composition obtained by kneading a water repellent carrier containing a water repellent component as a wiper blade body. The wiper blade according to claim 1, wherein said water repellent component is selected from silicone oil based, pullulor (fluorine) oil based and silane based components. The wiper blade according to claim 1, wherein the water repellent carrier is a powder selected from silicone rubber, silicone, fluorine and fluorine-based rubber. The wiper blade according to any one of claims 1 to 3, wherein a coating layer containing the water repellent component is held on the surface of the lip portion of the wiper blade body. 5. The wiper blade according to claim 4, wherein the coating layer and a water repellent carrier containing the water repellent component are kneaded in a binder component for bonding the coating layer to the wiper blade body. The wiper blade according to claim 5, wherein the water repellent carrier is a powder selected from silicone rubber, silicone, fluorine and fluorine-based rubber. 6. The wiper blade according to claim 5, wherein said water repellent carrier is a solid lubricant powder.