JPH0940915A - Lustering agent for rubber article and lustering method for rubber article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agent and to provide a both method for lustering rubber articles whereby a nonsticky film excellent in luster can be formed on the surface of a rubber article such as an automotive tire. SOLUTION: This lustering agent comprises an amino-modified silicone oil, a water-reactive silicone which reacts with the amino-modified silicone oil to cure it in the presence of water, and a hydrophobic volatile org. solvent. The lustering method comprises spraying the agent onto the surface of a rubber article, evaporating the solvent, and causing the amino-modified silicone oil to be reacted and cured with the water-reactive silicone in the presence of water at room temp. within 30min to form a cured lustrous film on the surface.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polish for a rubber product and a method for polishing a rubber product.

[0002]

2. Description of the Related Art Conventionally, a silicone-based compound as a main raw material has been used as a polishing agent for automobile tires. For example, a polish having a silicone oil as a main component such as dimethyl silicone has been used for a long time.

However, the glossing agent containing silicone oil as a main component remains sticky on the tire surface forever when applied to the tire surface, and mud and dust adhere to it to lose the gloss on the tire surface. There was a problem that the aesthetics were spoiled. Moreover, a tire coated with a polish containing silicone oil as the main component loses its gloss in a short time because the polish is easily washed away from the surface when exposed to rainwater or washed. Sisters,
There was also a problem with the durability of the gloss effect.

Further, as an agent for improving adhesion to tires, durability, etc., a polishing agent in which silicone resin is dispersed in silicone oil, or one in which silicone oil and modified silicone oil are dispersed in water (JP-A-1 -20
7369) and the like are also known. However, the effect of the silicone oil containing these polishing agents is strong, and the stickiness when applied to the tire was not so different from the conventional polishing agents mainly containing silicone oil.

On the other hand, a polishing agent obtained by dispersing and emulsifying a polyacrylate compound or a polyurethane compound in water can form a clean film without stickiness, but since the film has no flexibility, it is a tire during running. The phenomenon that the film could not be expanded and contracted and the film cracked and whitened was observed. On the other hand, a room temperature curable silicone rubber-based glazing agent for tires has an excellent film flexibility, and therefore, like a glazing agent obtained by dispersing and emulsifying a polyacrylate compound or a polyurethane compound in water. Although there is no risk of whitening, the dryness, glossiness and durability when applied to the tire surface were not sufficient.

[0006] As described above, all of the conventional polishing agents used for tires satisfy all the characteristics such as the drying property for forming a dry film in a short time, the gloss of the film, and the durability. Was not.

[0007] The present invention has been made in view of the above points,
Gloss for rubber products that can form a film with excellent luster without stickiness in a short time on the surface of rubber products such as automobile tires, and with excellent flexibility etc. An object of the present invention is to provide a polishing agent and a method for polishing a rubber product.

[0008]

Means for Solving the Problems That is, the polishing agent for rubber products of the present invention comprises an amino-modified silicone oil, water-reactive silicones that react and cure with the amino-modified silicone oil in the presence of water, and a hydrophobic agent. And a volatile organic solvent. In the polish of the present invention, the amino-modified silicone oil is preferably a side-chain amino-modified amino-modified silicone oil. In addition, it is preferable that it contains substantially no water.

In the method for polishing a rubber product according to the present invention, the above-mentioned polishing agent is sprayed on the surface of the rubber product to volatilize the volatile organic solvent, and the amino-modified silicone oil and the water-reactive silicones are present in the presence of water. It is characterized in that it is reacted and cured at room temperature within 30 minutes to form a cured glossy coating on the surface of a rubber product.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the amino-modified silicone oil is a compound represented by the following general formula (1) having an amino group on the side chain and / or terminal of dimethylpolysiloxane.

[0011]

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The amino-modified silicone oil preferably has an amino equivalent of 1000 to 4000, particularly 1500 to 2500. The kinematic viscosity is an index of the degree of polymerization of the amino-modified silicone oil, and in the present invention, the amino-modified silicone oil having a kinematic viscosity of 10 to 10000 cst, particularly 50 to 5000 cst, is preferable. The amino-modified silicone oil has different properties depending on whether it has an amino group as a side chain of the dimethylpolysiloxane main chain (side-chain amino-modified) or an amino group at the end (terminal amino-modified). In the present invention, side chain amino-modified ones are preferable in terms of reaction curing rate with a water-reactive silicone compound, which will be described later, and gloss of a cured film. The amino-modified silicone oil can be used alone or in combination of two or more.

Water-reactive silicones are compounds that react and cure with amino-modified silicone oils in the presence of moisture. Examples of such water-reactive silicones include, for example, a silicone resin having a relatively low molecular weight and a silanol group at the terminal, a silicone resin having a silanol group at the terminal as a main component, and generally a room temperature curable silicone resin, What is called a room temperature curable silicone rubber can be used.

A terminal silanol silicone resin or terminal silanol silicone oil to which a crosslinking agent, a polymerization catalyst or the like is added can also be used. Examples of the cross-linking agent include silanes such as alkoxysilane, acetoxysilane, ketoxime silane, isopropenoxysilane, aminosilane, and amidosilane. As the polymerization catalyst, an organometallic compound catalyst containing zinc, iron, cobalt, titanium, tin, lead, boron or the like, an acid, an alkali, an amine, or the like is used. These crosslinking agents and polymerization catalysts can be used alone or in combination of two or more. The cross-linking agent is 0.1 to 1 of the total amount of amino-modified silicone oil and water-reactive silicones.
It is preferable to add about 0% by weight, and it is preferable to add about 0.01 to 10% by weight of the total amount of the amino-modified silicone oil and the water-reactive silicone compound as the polymerization catalyst.

Water-reactive silicones are generally preferred to have a relatively low molecular weight in view of compatibility with other components and workability during spraying. For example, in the case of a room temperature curable silicone resin, a 50% volatile organic compound is used. Solvent diluent (eg Isopar E
A diluent having a viscosity of about 1 to 30 cps is preferable. In addition, the water-reactive silicones have a film formed by a curing reaction with an amino-modified silicone oil, which cures in a short time, has no stickiness, has a smooth and glossy surface, resists expansion and contraction of rubber, cracks, Those which do not cause whitening and have excellent gloss durability are preferable. As the water-reactive silicones, one kind or a mixture of two or more kinds can be used similarly to the amino-modified silicone oil. The water-reactive silicones used in the present invention are not limited to those described above as long as they can be cured by reaction in the presence of amino-modified silicone oil and water.

In the present invention, the amino-modified silicone oil and the water-reactive silicones are generally in a weight ratio of water-reactive silicones: amino-modified silicone oil =
It is preferably used in a ratio of 1: 8 to 1: 0.2.
The more preferable mixing ratio of the both depends on the kind of the water-reactive silicones and, in the case of a mixture of two or more water-reactive silicones, also on the difference in the mixing ratio thereof.
When the water-reactive silicones are, for example, the above-mentioned room temperature curable silicone resin, a more preferable mixing ratio is room temperature curable silicone resin: amino-modified silicone oil = 1: 5 to 1: 1 by weight ratio. When the polymerizable silicone is a room temperature curable silicone rubber, a more preferable mixing ratio is a weight ratio of room temperature curable silicone rubber: amino-modified silicone oil = 1: 3 to 1: 1. When a mixture of a room temperature curable silicone resin and a room temperature curable silicone rubber is used, the mixing ratio of these mixture and the amino-modified silicone oil is room temperature curable silicone resin +
Room temperature curable silicone rubber: amino-modified silicone oil = 1: 3 to 1: 1.

As the water-reactive silicone, it is preferable to select one that reacts and cures with the amino-modified silicone oil within 30 minutes in the presence of water in order to shorten the curing time. However, the cure time also depends on other factors. For example, in room temperature curing type silicone rubber,
In some cases, the curing reaction with the amino-modified silicone oil is slow, and in such a case, the reaction curing time can be shortened by using it in combination with a room temperature curable silicone resin.
Further, the curing reaction rate can be increased by adding a polymerization catalyst of amino-modified silicone oil and water-reactive silicones.

Since the amino-modified silicone oil and the water-reactive silicones undergo a curing reaction in the presence of moisture, the contact with moisture is cut off during storage and the curing reaction is caused by contact with moisture during use. It is necessary to do so. Therefore, as the solvent in the polishing agent of the present invention,
It is necessary to use a hydrophobic volatile organic solvent that does not easily contain water and is excellent in solubility or dispersibility of amino-modified silicone oil or water-reactive silicones.

Since the hydrophobic volatile organic solvent is less likely to contain water, the use of the hydrophobic volatile organic solvent as a solvent reduces the risk of a curing reaction of both components during storage. When the polish is sprayed on the surface of rubber products, the volatile organic solvent in the polish evaporates in a short time, and the volatilization of the solvent causes the amino-modified silicone and water-reactive silicones to come into contact with the moisture in the air. As a result, a curing reaction occurs between both components, and both components are concentrated to increase the concentration, whereby the curing reaction is further accelerated. As such a hydrophobic volatile organic solvent, a solvent that does not swell and corrode rubber materials is selected and used. Examples of preferable hydrophobic volatile organic solvent include petroleum hydrocarbons such as n-paraffin, isoparaffin, and cycloparaffin, and HCFC. The volatile organic solvent generally has a content of the organic solvent of 20 to 9 in the polishing agent of the present invention.
It is added so as to be 5% by weight, preferably 50 to 90% by weight.

It is preferable that the polish of the present invention contains substantially no water. Therefore, although a hydrophobic organic solvent is used in the present invention, a trace amount of water is also contained in the hydrophobic organic solvent. May be included. It is preferable to add a water adsorbent to capture such a small amount of water.

In the polish of the present invention, waxes used in general polishes (for example, ester wax, acid wax,
Carnauba wax, etc.), various silicone oils (dimethyl silicone oil, methylphenyl silicone oil, various modified silicone oils, etc.), non-reactive silicone resin, non-reactive silicone rubber, etc., or various additives can also be added.

The polish of the present invention is generally manufactured by sealing it in a spray can or the like. The method for polishing a rubber product with the polishing agent of the present invention comprises spraying the polishing agent of the present invention on the surface of a rubber product to volatilize a volatile organic solvent and form a cured film on the surface of the rubber product within 30 minutes at room temperature. It is a method of forming.
In the method of the present invention, moisture in the air is used for the curing reaction between the amino-modified silicone oil and the water-reactive silicone. The volatile organic solvent in the polishing agent is volatilized in a short time, and the volatilization of the organic solvent causes the amino-modified silicone oil and the water-reactive silicones to come into contact with moisture in the air to cause a curing reaction between the two. As described above, the water-reactive silicones themselves also undergo a crosslinking reaction in the presence of water, but the curing reaction is further accelerated depending on the combination with the amino-modified silicone oil.

Therefore, in the method of the present invention, in order to form a cured film within 30 minutes, water-reactive silicones which form a cured film within 30 minutes at room temperature in the presence of amino-modified silicone oil and water are selected. Or by adjusting the mixed composition of water-reactive silicones, selecting the catalyst, etc.
The formulation is adjusted to form a cured film within 0 minutes.
In the method of the present invention, the time for forming the cured film is preferably within 15 minutes. To form a cured film within the above preferable curing time, or particularly preferable curing time,
In the same manner as described above, it is sufficient to select water-reactive silicones that react and cure with an amino-modified silicone oil within a target time, or to select a compounding composition and a catalyst.
In the present invention, all of the water-reactive silicones may not be cured and reacted with the amino-modified silicone oil, and some of them may be reaction-cured by the water-reactive silicones.

The method of the present invention is not limited to the case of polishing the surface of an automobile tire, but can be applied to the surface polishing of general rubber products such as footwear and rubber gloves.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.

Examples 1 to 9 and Comparative Examples 1 to 3 For each polishing agent having the composition shown in Table 1, the drying property,
A gloss and gloss durability test was conducted. In Comparative Example 1, Comparative Example 2 and Comparative Example 3, a commercially available product mainly containing silicone oil, a commercially available product mainly containing silicone oil and a silicone resin, and a commercially available product mainly containing polyurethane were used. The results of these tests are also shown in Table 1. The amino-modified silicone oil, water-reactive silicones, and organic solvent shown in Table 1 are as follows. In addition, the compounding amounts shown in Table 1 are all wt%, and those containing an organic solvent and the like are shown in terms of effective component amount conversion values.

Amino-modified silicone oil FZ3710: A side-chain amino-modified silicone oil manufactured by Nippon Unicar Co., Ltd. Amino equivalent 1800, Kinematic viscosity 1000c
st KF869: Side chain amino-modified silicone oil manufactured by Shin-Etsu Silicone Co., Ltd. Amino equivalent 3800, Kinematic viscosity 1400c
st X22-161C: Terminal-modified silicone oil manufactured by Shin-Etsu Silicone Co., Ltd. Amino equivalent 2300, Kinematic viscosity 72cst

Water-Reactive Silicones Water-Reactive Silicones No. 1: Room temperature curable silicone resin (product name: SR2316) manufactured by Toray Dow Corning Silicone Co., Ltd. Contains 77% organic solvent. Water-reactive silicones No. 2: Room temperature curable silicone resin (product name: SD8000) manufactured by Toray Dow Corning Silicone Co., Ltd. Contains 50% organic solvent. Water-reactive silicones No. 3: Silicone resin manufactured by Toray Dow Corning Silicone Co., Ltd. (Product name: B
Y15-701A, containing 30% of organic solvent) 2 parts by weight of methyltriisopropenoxysilane as a crosslinking agent and 0.5 parts by weight of cobalt naphthenate as a catalyst per 100 parts by weight of Y15-701A. Water-reactive silicones No. 4: Silicone resin manufactured by Toray Dow Corning Silicone Co., Ltd. (Product name: B
Y15-701A, containing 30% of an organic solvent) 100 parts by weight, 2 parts by weight of methyltriisopropenoxysilane as a crosslinking agent, and 0.5 parts by weight of tetrabutoxytitanium as a catalyst. Water-reactive silicones No. 5: To 100 parts by weight of terminal silanol silicone oil (product name: PRX-413) manufactured by Toray Dow Corning Silicone Co., Ltd.
Blended with 0.5 parts by weight of tetrabutoxy titanium. Water-reactive silicones No. 6: Room temperature curable silicone rubber manufactured by Toray Dow Corning Silicone Co., Ltd. (Product name: PRX-305). Contains 50% organic solvent. Water-reactive silicones No. 7: Room temperature curable silicone resin manufactured by Shin-Etsu Chemical Co., Ltd. (Product name: X61-429)
K).

Volatile organic solvent Isopar E: an isoparaffin organic solvent manufactured by Exxon Chemical Co., Ltd.

[0030]

[Table 1]

The test method and evaluation of the drying property, gloss and gloss durability are as follows. Immediate dryness: 20c from the tire surface with a spray can of polish
m, and the glaze agent was sprayed on the tire surface for 20 seconds, then left at room temperature for 5 minutes, 15 minutes, 30 minutes, and 24 hours, respectively, and then touched with a finger on the sprayed surface of the tire to obtain a solid surface. The presence or absence of feeling was examined. The results were evaluated according to the following criteria. ○: No stickiness. △: A little sticky. X: A solid feeling is strong.

Gloss: The spray can of the polish was separated from the tire surface by 20 cm, the polish was sprayed on the tire surface for 20 seconds and left at room temperature for 24 hours, and then the gloss of the tire surface was compared. The gloss of Example 2 was the best. The results were evaluated according to the following criteria. ⊚ ... has the same gloss as in Example 2. ◯ ... Excellent in gloss, but slightly inferior to that in Example 2. Δ: The gloss is inferior to that of Example 2. × ・ ・ ・ ・ Glossy.

Cracks and whitening: Tires of passenger cars used for daily work are washed with water and dried, and then a spray can of the polish is separated from the tire surface by 20 cm, and the polish is tired for 20 seconds. The surface was sprayed and left at room temperature for 24 hours, and after running for one month from the next day, cracks and whitening of the tire surface were observed. The results were evaluated according to the following criteria. ○ ・ ・ ・ ・ No cracks or whitening. △ ・ ・ ・ ・ There are some cracks. × ・ ・ ・ ・ The entire surface is cracked and the tire looks whitish.

Durability of luster: After washing the tires of passenger cars used for daily work with water and drying, the spray can of the polish is separated from the tire surface by 20 cm and the polish is applied for 20 seconds. The tire surface was sprayed and left at room temperature for 24 hours, and after running for one month from the next day, the gloss of the tire surface was observed. The gloss durability was the highest in Example 1. The results were evaluated according to the following criteria. ⊚ ... has the same gloss as in Example 1. ◯ ... Excellent in gloss, but slightly inferior to that in Example 1. Δ: The gloss is inferior to that of Example 1. × ・ ・ ・ ・ The entire tire is not glossy.

[0035]

As described above, the polish of the present invention comprises an amino-modified silicone oil and water-reactive silicones which react and cure in the presence of water as a main component, and both are reactively cured. By forming a thin coating, the gloss of the coating and the durability of the gloss are excellent. In addition, since a hydrophobic volatile organic solvent that hardly contains water is used as a solvent for dissolving or dispersing these components, the amino-modified silicone oil and the water-reactive silicones may react and cure during storage. Few. For this reason, it is easy to make a one-pack type product that contains both components at the same time, and it is easier to simplify the product form compared to a two-pack type product in which both components must be stored separately, The polishing process is also good. Moreover, since the volatile organic solvent quickly volatilizes when sprayed, the amino-modified silicone oil and the water-reactive silicones are likely to come into contact with moisture in the air, and the sprayed gloss is accompanied by the volatilization of the organic solvent. By increasing the concentrations of both components in the agent, the curing reaction of both components is promoted, and a glossy film having excellent gloss can be formed on the surface of the rubber product in a short time.

Further, according to the method of the present invention, it is possible to form a glossy coating which is not sticky and has an excellent gloss in a short time, so that an efficient treatment can be carried out.

Claims (4)

[Claims] 1. A rubber product comprising an amino-modified silicone oil, water-reactive silicones that react and cure with the amino-modified silicone oil in the presence of water, and a hydrophobic volatile organic solvent. Glazing agent. 2. The polishing agent for rubber products according to claim 1, wherein the amino-modified silicone oil is a side-chain amino-modified amino-modified silicone oil. 3. The polish for a rubber product according to claim 1, which is substantially free of water. 4. A rubber product polish according to any one of claims 1 to 4 is sprayed onto the surface of the rubber product to volatilize a volatile organic solvent and to produce an amino-modified silicone oil and water-reactive silicones. A method for polishing a rubber product, which comprises reacting and curing the mixture in the presence of water at room temperature within 30 minutes to form a cured gloss coating on the surface of the rubber product.