JPH07126417A - Surface treatment method for rubber article and rubber article treated by the method - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] To provide a method for forming a silicone resin film having excellent adhesion and abrasion resistance on a rubber article by using an aqueous silicone-based treating agent. [Structure] An aqueous emulsion comprising the following first to third components is applied to the surface of a rubber article and cured. First component: specific organohydrogenpolysiloxane, specific diorganopolysiloxane having hydroxyl groups at both terminals,
Nonionic surfactant and specific amount of water Second component: Hydrolytic condensate of specific dialkoxysilane having aminoalkyl group, specific amount of water-soluble organic compound with respect to nitrogen in the hydrolytic condensate Acid and / or inorganic acid,
And specific amounts of water and third component: organometallic salt compound, nonionic surfactant,
And each specific amount of water

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a surface treatment method for imparting abrasion resistance to the surface of a rubber article.
In particular, a rubber article suitable for a weather strip for automobiles can be obtained by treating with the surface treatment method of the present invention.

[0002]

2. Description of the Related Art Conventionally, various rubber materials have been used for weather strips. This weather strip is used for automobile doors, windshields, rear windshields, trunks, etc., but its surface is rubbed by the door, glass, or trunk lid, so that the surface is required to have abrasion resistance. Therefore, various surface treatment methods have been proposed so far. For example, a method of surface treatment with a urethane resin composition (Japanese Patent Laid-Open Nos. 3-20376 and 3-21675).
No. 3, No. 3-21676, No. 3-86774, No. 3-252477, No. 4-8
778, 4-8779, 4-25580, 4-25581, 4
-31474) or a method of surface-treating with a silicone resin composition (Japanese Patent Publication No. 56-47864, Japanese Patent Laid-Open No. 54-9).
No. 0369 and Japanese Patent Publication No. 4-80072).

[0003]

However, the urethane resin film has poor weather resistance, and therefore the durability of the film is poor, and although the method using a silicone resin composition can impart some properties, in terms of abrasion resistance, etc. Further quality improvement is desired. In addition, since it is a solvent-diluted treatment agent,
There are environmental and safety issues. The present invention has been made to provide a method for treating the surface of a rubber article with an organopolysiloxane composition which has improved the above problems, and a rubber article treated by this method.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific organopolysiloxane having a hydrogen atom directly bonded to a silicon atom,
A first component containing a diorganopolysiloxane having a terminal hydroxyl group, a nonionic surfactant and water, a hydrolyzed condensate of a specific dialkoxysilane having an aminoalkyl group, a water-soluble organic acid and / or an inorganic acid, and The surface of a rubber article is an aqueous organopolysiloxane emulsion obtained by mixing a second component containing water, and an organic metal salt compound, a nonionic surfactant and a third component containing water. The present invention has been completed by finding that a film having excellent characteristics is formed by applying the composition onto a substrate and curing the composition.

That is, the gist of the present invention is to apply a water-based organopolysiloxane emulsion obtained by mixing the following first to third components to the surface of a rubber article and cure it. The surface treatment method, as well as the treated rubber article. First component (A) General formula (1) R ¹ _a H _b SiO _{(4-ab) / 2} (1) (wherein R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms and A hydrogen atom directly bonded to a silicon atom represented by 1 <a <2.2 and 0.1 <b <1 which is one or more groups selected from halogenated hydrocarbon groups. Organopolysiloxane having 1 to 90% by weight (B) the following general formula (2) HO- (R ² ₂ SiO) _m -H ... (2) (wherein R ² has 1 to 20 carbon atoms). 1 to 90% by weight of 1 or 2 or more groups selected from the monovalent hydrocarbon group and halogenated hydrocarbon group, and 10 ≦ m ≦ 3000. (C) Nonionic surfactant 0.1 to 50% by weight (D) Water balance Second component (a) General formula (3) R ³ R ⁴ N (CH ₂ ) _p [NR ⁵ (CH ₂ ) _q ] _{^{r SiR 6 (OR 7) 2}} ··· (3) ( wherein, R ^3, R ⁴ R ⁵ are each hydrogen or a monovalent hydrocarbon group and halogenation hydrocarbon group group selected from, R ^6, R ⁷ are each monovalent hydrocarbon radicals and halogen 1 to 6 carbon atoms having 1 to 6 carbon atoms Of a dialkoxysilane having an aminoalkyl group represented by the formula 1 ≦ p ≦ 6, 1 ≦ q ≦ 6, and 0 ≦ r ≦ 3. 1 to 90% by weight (b) 0.1 to 2 equivalents of water-soluble organic acid and / or inorganic acid to 1 atomic equivalent of nitrogen of component (a) represented by the general formula (3) (c) water Remaining third component (I) Organometallic salt compound 1 to 90% by weight (II) Nonionic surfactant 0.1 to 50% by weight (III) Water remaining

The present invention will be described in detail below.
The first component of the aqueous emulsion, which is the surface treatment agent used in the method of the present invention, comprises (A) to (D) as described above, and the first component is an aqueous emulsion. (A) in the first component is an organopolysiloxane having a hydrogen atom directly bonded to the silicon atom represented by the general formula (1). R ¹ in the formula is one or more groups selected from monovalent hydrocarbon groups having 1 to 20 carbon atoms and halogenated hydrocarbon groups. Examples of R ¹ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group,
Decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups, cyclopentyl group, cyclohexyl group and other cycloalkyl groups, phenyl group, tolyl group and other aryl groups, trifluoropropyl group,
Examples include halogenoalkyl groups such as chloropropyl group, chlorophenyl group, nonafluorohexyl group, heptadecafluorodecyl group, and halogenophenyl groups,
It is particularly desirable that 90 mol% or more of R ¹ is a methyl group.

The values of a and b in the formula are 1 <a <2.2,
0.1 <b <1, but if a is less than 1, the final cured film will be too hard and will not follow the deformation of the rubber substrate. Become too soft and have poor wear resistance,
1 <a <2.2. More preferably 1.1 ≦ a ≦ 1.8
Is. If b is less than 0.1, the cured film will be too soft, and if it is more than 1, it will be too hard. Therefore, 0.1 <b <1 is preferable for the same reason as above. More preferably, 0.30 ≦ b ≦ 0.95.

The viscosity of (A) at 25 ° C. is preferably 10,000 to 10,000 centistokes. When the viscosity is lower than 1 centistokes, the cured film becomes too hard, it is difficult to follow the deformation of the rubber article, and peeling easily occurs. On the other hand, when it is higher than 10,000 centistokes, the cured film is too soft and wear resistance is poor. More preferably, it is 10 to 1000 centistokes.

When the amount of (A) in the first component is less than 1% by weight, the film finally obtained on the surface of the rubber article is too soft and has poor abrasion resistance, and more than 90% by weight. The coating on the surface of the rubber article is too hard to easily follow the deformation of the rubber article, and cracks easily occur, resulting in poor durability.
The viscosity of the component becomes high, and it becomes difficult to mix with other second component and third component. From this, (A) is 1 in the first component
It is set to 90% by weight, and more preferably 10 to 50% by weight.

(B) in the first component is a diorganopolysiloxane having a terminal hydroxyl group represented by the above general formula (2). R ² in the formula is one or more groups selected from monovalent hydrocarbon groups having 1 to 20 carbon atoms and halogenated hydrocarbon groups. Examples of R ² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Octyl group, decyl group, dodecyl group, tetradecyl group,
Hexadecyl, octadecyl, and other alkyl groups, cyclopentyl, cyclohexyl, and other cycloalkyl groups, phenyl, tolyl, and other aryl groups, trifluoropropyl, chloropropyl, chlorophenyl, nonafluorohexyl, heptadeca Examples thereof include a halogenoalkyl group such as a fluorodecyl group and a halogenophenyl group, and it is particularly preferable that 90 mol% or more of R ² is a methyl group.

The value of m in the formula is 10≤m≤3000. m is
When it is less than 10, the resulting cured film is too hard to follow the deformation of the rubber article, and peels easily. On the other hand, if it is more than 3000, the cured film is too soft and wear resistance is poor. More preferably, it is 100 or more and 1000 or less.

If the content of (B) in the first component is less than 1% by weight, the cured film finally obtained on the surface of the rubber article is too hard to follow the deformation of the rubber article and cracks occur. If it is more than 90% by weight, the cured film obtained is too soft and has poor wear resistance and is easy to peel off. At the same time, the viscosity of the obtained first component is high and the second component is high. , It becomes difficult to mix with the third component. Therefore, the blending amount of (B) is 1 to 90% by weight in the first component, and more preferably 10 to 50% by weight.

(C) in the first component is a nonionic surfactant for emulsifying and dispersing (A) and (B) in water of (D), and examples thereof include polyoxyethylene higher alcohols. Ether, polyoxyethylene alkyl phenyl ether, sorbitan monoalkylate, sorbitanial chelate, polyoxyethylene sorbitan monoalkylate, polyoxyethylene sorbitanial chelate, polyoxyethylene sorbitan tetraalkylate, glycerol monoalkylate, etc. are exemplified. These can be used alone or in combination of two or more, and in addition to these general nonionic surfactants, fluorine-based nonionic surfactants or silicone nonionic surfactants can be used. Agents can also be used, but this nonionic Those surfactants having an HLB in the range of 1.5 to 20, particularly preferably in the the range of 7.0 to 19.0.

The blending amount of the first component (C) is
It is desirable that the amount is the minimum amount necessary to stably emulsify and disperse (A) and (B), but if it is less than 0.1% by weight, the stability of the first component becomes poor and 50% by weight is obtained.
If the amount is larger, the flexibility of the finally obtained cured film will be reduced, and therefore the abrasion resistance will be poor. From this, the content of (C) in the first component is 0.1 to 50% by weight, more preferably 1 to 10% by weight.

To prepare the first component consisting of these (A) to (D), emulsification and dispersion may be carried out according to a conventionally known method. For example, (C) may be dissolved or dispersed in (D) to prepare an aqueous solution or dispersion, and (A) and (B) may be premixed and added together or separately without mixing. Good. Alternatively,
The components (A), (B) and (C) are stirred to form a uniform dispersion liquid, and part of the water (D) is added thereto with mechanical stirring to carry out phase inversion emulsification dispersion. Adding the remaining (D) is also an effective method. As a stirring device in these methods, a generally known device such as a homomixer, a paddle type stirrer, or an anchor type stirrer can be used.

The second component is composed of (a) to (c) as described above, and is an aqueous solution or aqueous dispersion obtained by mixing (a) to (c). (A) in the second component is a hydrolysis-condensation product of a dialkoxysilane having an aminoalkyl group represented by the general formula (3).
In the formula, R ³ , R ⁴ , and R ⁵ are each hydrogen or a group selected from a monovalent hydrocarbon group having 1 to 6 carbon atoms and a halogenated hydrocarbon group, and R ⁶ and R ⁷ are each 1 carbon atoms. To 6 monovalent hydrocarbon groups and halogenated hydrocarbon groups. Also, 1 ≦ p ≦ 6, 1 ≦ q ≦ 6, and 0 ≦ r ≦ 3,
When p and q are 0, the desired hydrolyzed condensate cannot be obtained because the Si-N bond undergoes hydrolysis, and when it is greater than 6, the property imparting effect as the component (a), that is, the rubber of the cured film is obtained. Since the effect of improving the adhesion to the base material decreases, 1 ≦ p and q ≦ 6. More preferably p, q =
2 or 3. When r is larger than 3, it is industrially difficult to synthesize and therefore it is set to 3 or less, more preferably r = 0 or 1.

When R ³ , R ⁴ and R ⁵ are hydrocarbon groups, examples of these groups include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and hexyl group, cyclopentyl group and cyclohexyl group. And the like, and a halogenoalkyl group such as a phenyl group and a trifluoropropyl group, and the like. In the component (a), the hydrocarbon group is preferably 10 mol% or less and the hydrogen is 90 mol% or more. .
Examples of R ⁶ and R ⁷ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and hexyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, halogenoalkyl groups such as phenyl group and trifluoropropyl group. And the like, and particularly preferably a methyl group or an ethyl group.

Examples of such silanes include γ- (N
-Β-aminoethyl) aminopropylmethyldimethoxysilane, γ- (N-β-aminoethyl) aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane and the like are typical. It is mentioned as a thing. Hydrolysis of these silanes may be performed according to a known method. That is, the dealcoholization condensation reaction proceeds easily by adding water to these silanes. Then, the produced alcohol may be distilled off.

If the content of the component (a) in the second component is less than 1% by weight, the adhesion of the cured coating to the surface of the rubber article will be low and the abrasion resistance will be poor.
If the amount is larger, the cured film will be too soft and the abrasion resistance will be poor as well. It is more preferably 10 to 50% by weight.

(B) in the second component decomposes when (a) in the first component is dissolved or stably dispersed in (c) water and (A) in the first component is mixed with the second component. It is added and blended in the second component in order to improve the stability during mixing so as not to cause a reaction. Examples of the organic acid used as (b) include formic acid, acetic acid, propionic acid, malonic acid, maleic acid, salicylic acid and the like. Further, examples of the inorganic acid include hydrochloric acid, phosphoric acid, sulfuric acid and the like.

When the content of the second component (b) in the second component is less than 0.1 equivalent to 1 atomic equivalent of the nitrogen atom contained in (a), the component (a) is solubilized or stably dispersed in water. The effect is not sufficient and the effect of improving the stability at the time of mixing with the first component and the third component is poor, and if it is more than 2 equivalents, the stability at the time of mixing is also lowered. More preferably 0.5 to 1.5 equivalents, even more preferably
It is in the range of 0.8 to 1.2 equivalents.

As a method for preparing the second component containing (a) to (c), (a) is dissolved or dispersed in water (c), and then (b) is added. The method of adding (a) after dissolving or dispersing b) in water of (c) can be easily prepared.

The third component is composed of (I) to (III) as described above, and the organometallic salt compound of (I) is dispersed in the water of (III) by the nonionic surfactant of (II). It has been done. The organometallic salt compound (I) is an organometallic salt that can act as a catalyst for curing the treating agent composition used in the method of the present invention, and includes, for example, zinc octylate, iron octylate and octylate. Organometallic salts such as cobalt and tin octylate, dibutyltin diacetate,
Dibutyltin dioctoate, dibutyltin dilaurate,
Examples thereof include tin salts containing alkyl groups such as dioctyltin diacetate, dioctyltin dioctoate, and dioctyltin dilaurate.

When the amount of the component (I) in the third component is less than 1% by weight, the amount of the third component to be blended with the first component and the second component is sufficient to exert a sufficient catalytic action. It is inefficient because it has to be increased, and if it exceeds 90% by weight, the viscosity of the third component becomes too high and the mixing property with the first and second components decreases, so it is set to 1 to 90% by weight. . It is more preferably 10 to 50% by weight.

The nonionic surfactant of (II) is for emulsifying and dispersing the organometallic salt compound of (I) in the water of (III) as described above, and examples thereof include polyoxyethylene. Examples include higher alcohol ethers, polyoxyethylene alkyl phenyl ethers, sorbitan monoalkylates, sorbitan trichelates, polyoxyethylene sorbitan monoalkylates, polyoxyethylene sorbitan trichelates, polyoxyethylene sorbitan tetraalkylates, and glycerol monoalkylates. These may be used alone or in combination of two or more. Further, in addition to these general nonionic surfactants, fluorine-based nonionic surfactants or silicone nonionic surfactants may be used. Surfactants can also be used, The nonionic surfactant HL
It is preferable that B is in the range of 1.5 to 20, particularly 7.0 to 19.0.

The compounding amount of (II) in the third component is as follows.
If it is less than 0.1% by weight, the stability will be poor,
If it exceeds 50% by weight, the flexibility of the cured film finally obtained will be lowered, so it is set to 0.1 to 50% by weight.
It is more preferably 1 to 10% by weight.

The third component consisting of these (I) to (III) may be prepared by a conventionally known emulsification dispersion method. For example, a method of mixing (I) in an aqueous solution or an aqueous dispersion of (II) dissolved or dispersed in (III) with mechanical stirring, or alternatively, (I) and (II) are uniformly stirred. Phase inversion emulsification dispersion was carried out by adding a part of (III) to the product with mechanical stirring, and the remaining (I) was added.
There is a method of adding II). When (I) is a solid substance, it may be optionally dissolved in a solvent or dispersed as liquid paraffin or petrolatum.

The first to third components obtained as described above
The components are mixed at the time of use, but the first component
The third component is preferably compounded in the mixed solution so that each component has the following compounding amount. That is, the first component (A) is 1 to 50% by weight, the first component (B) is 1 to 90% by weight, the second component (a) is 1 to 90% by weight, and the third component (I ) Is 0.01 to 20% by weight.

If the content of the first component (A) is less than 1% by weight, the cured film obtained will be soft and the abrasion resistance will be poor, and if it is more than 50% by weight, it will be harder and the rubber article will be deformed. As a result, the followability is poor and the rubber article is easily peeled off. Therefore, the amount of (A) in the mixed liquid of the first component to the third component is preferably 1 to 50% by weight, and more preferably 2 to 20% by weight.
The first component (B) is added to give the cured film proper flexibility, but this is 90% by weight.
If the amount is larger, the flexibility of the cured film will exceed a suitable range and the abrasion resistance will be poor, and the viscosity of the first to third component liquid mixtures will be high, making application difficult. On the contrary, when the amount of (B) is less than 1% by weight, the cured film becomes hard and the followability to the deformation of the rubber article becomes poor, and the rubber article easily peels off. Therefore, the first
The amount of (B) in the mixed liquid of the third component is 1 to 90% by weight.
However, it is more preferably 5 to 50% by weight.
Is the range.

When the content of the second component (a) is less than 1% by weight, the adhesion of the obtained cured film to the rubber substrate becomes insufficient and the abrasion resistance becomes poor. If it is more than 90% by weight, the cured film becomes soft and the abrasion resistance also becomes poor, and the viscosity of the mixed solution of the first component to the third component becomes high, which makes application difficult. Therefore, the amount of (a) in the mixed liquid of the first component to the third component is preferably 1 to 90% by weight, more preferably 2 to 50% by weight.

The third component (I) serves as a curing reaction catalyst for the treating agent composition used in the method of the present invention.
If the amount is less than 01% by weight, the catalytic action is poor, the curing reaction does not occur sufficiently and the film becomes soft, and if the amount is more than 20% by weight, not only the curing reaction is not significantly promoted, but also the film is plasticized. On the contrary, it may become soft. From this, the amount of (I) in the mixed liquid of the first component to the third component is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.

Examples of rubber materials to which the surface treatment method of the present invention can be applied include natural rubber, EPDM, SBR, chloroprene rubber, isoprene-isobutylene rubber and nitrile rubber. The rubber article made of these rubber materials may have a sponge shape, a solid shape or the like.

As a surface treatment method for a rubber article, a mixed solution of the first to third components is applied by brush coating, spray coating, roll coating, dip coating, knife coating, etc., and then at room temperature or at room temperature. The film may be cured by warm drying. As a result, the intended surface-treated rubber article is obtained. The surface-treated rubber article obtained in this manner is particularly used for weather strips for automobiles, but since it has excellent wear resistance, it is used as a sealing material such as O-rings, gaskets and various packings, Widely applicable as a hose material.

If necessary, carbon black, fluororesin powder, melamine resin powder, acrylic resin powder, polycarbonate resin powder, silicone resin powder, nylon resin powder, graphite powder, etc. may be used as long as the effects of the present invention are not impaired. It is optional to add various organic or inorganic pigments, paraffin wax, polyethylene wax, silicone oil and the like to the composition.

[0035]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. [Synthesis Example 1] 500 g of γ-aminopropylmethyldimethoxysilane was charged into a 1 L glass flask, and 170 g of deionized water was added dropwise over 30 minutes with stirring at room temperature. After completion of the dropping, the reaction system was depressurized while raising the temperature, and the produced methanol was distilled off. After continuing the depressurization operation at 55-60 ° C for 30 minutes, the reaction was terminated by cooling and returning to normal pressure. 330 g of the obtained hydrolyzed condensate was added to acetic acid 250 g and water 1620.
Add 3 g glass flask containing g at room temperature, and
The solution was stirred for a minute to obtain an aqueous solution used as the second component. (Named the second component-1)

[Synthesis Example 2] 500 g of γ- (N-β-aminoethyl) aminopropylmethyldimethoxysilane was added to 1 part.
Into an L glass flask, 135 g of deionized water was added dropwise over 30 minutes with stirring at room temperature. After completion of the dropping, the reaction system was depressurized while raising the temperature, and the produced methanol was distilled off. After continuing the depressurization operation at 55-60 ° C for 30 minutes, the reaction was terminated by cooling and returning to normal pressure. 380 g of the obtained hydrolyzed condensate was charged into a 3 L glass flask charged with 203 g of acetic acid and 1950 g of water at room temperature and stirred for 30 minutes to obtain an aqueous solution used as the second component. (Named second component-2)

[Synthesis Example 3] An aqueous solution used as the second component was obtained in the same manner as in Synthesis Example 1 except that 250 g of acetic acid and 1620 g of water were changed to 422 g of hydrochloric acid (36%) and 1448 g of water. (Named second component-3)

[Preparation Example 1] An organopolysiloxane (A-) having an average structural formula shown below in a 500 ml glass beaker was prepared.
1) 66.7 g, diorganopolysiloxane (B-1) 133.
3 g and 20.0 g of polyoxyethylene tridecyl ether (C-1) having 10 moles of ethylene oxide added were mixed by stirring with a homomixer at 6000 rpm, and further deionized water was 40.0 g.
When the mixture was added and stirring was continued at 6000 rpm, phase inversion occurred and thickening was observed. Further, while stirring at 2000 rpm as it was, 140.0 g of deionized water was added to prepare an emulsion to be used as the first component. (Named the first component-1)

Preparation Example 2 In Preparation Example 1 (A-1)
Was replaced by 40.0 g and (B-1) was replaced by 160.0 g to prepare an emulsion in exactly the same manner. (Named First Component-2) [Preparation Example 3] 20.0 g of (A-1) in Preparation Example 1
An emulsion was prepared in exactly the same manner except that (B-1) was changed to 180.0 g. (Named First Component-3) [Preparation Example 4] 61.3 g of (A-1) in Preparation Example 1
(B-1) 122.7g, (A-1), (B-1) and (C-1) when mixed with silicone resin powder (average particle size 7μ
m) An emulsion was obtained in exactly the same manner except that 16.0 g was added. (Named the first component-4)

[Preparation Example 5] 124.0 g of dibutyltin dilaurate, 24.0 g of liquid paraffin and 12.0 g of polyoxyethylene nonylphenyl ether having 10 moles of ethylene oxide added were placed in a 500 ml glass beaker, and the mixture was adjusted to 6000 rpm with a homomixer at room temperature. When the mixture was stirred, and 40.0 g of deionized water was added and the stirring was continued at 6000 rpm, thickening due to phase inversion was observed. Further, 200.0 g of deionized water was added while stirring at 2000 rpm as it was to prepare an emulsion to be used as the third component. (Named Third Component-1)

[0041]

[Chemical 1]

[Examples 1 to 9] The surface treatment agent compositions were prepared by mixing the first to third components in the composition shown in Table 1. This composition is made of EPDM sponge rubber (15 mm × 15
(0 mm × thickness 2 mm) The surface was treated by applying it to the surface with a brush and leaving it for 10 minutes in a hot air circulation type constant temperature bath adjusted to 150 ° C. The obtained surface-treated sponge rubber was subjected to the following friction test, and the number of times of friction until the sponge rubber substrate was exposed was measured. The results are shown in Table 1.
The friction method is reciprocal friction, using a ground glass cell (line contact, line width 5 mm) as a friction cell, applying a thrust load of 350 g, and treating sponge rubber under the conditions of friction speed: 60 reciprocations / min, friction stroke: 70 mm. The surface was tested (Fig. 1
reference).

[0043]

[Table 1]

Preparation Example 6 In Preparation Example 1 (A-1)
200.0 g and (B-1) were 0 g to prepare an emulsion in exactly the same manner. (Named First Component-5) [Preparation Example 7] In Preparation Example 1, 0 g of (A-1) and (B-
An emulsion was prepared in exactly the same manner except that 1) was changed to 200.0 g. (Named the first component-6)

[Comparative Examples 1 to 5] The surface treatment agent compositions were prepared by mixing the first to third components in the composition shown in Table 2. The sponge rubber was subjected to a surface treatment and a friction test was conducted in the same manner as in the examples. The results are shown in Table 2.

[0046]

[Table 2]

As described above, in the examples, the adhesion of the film,
While the wear resistance is good, in the comparative example, when the hydrolysis-condensation product of the second component is not added or when the first component (B) is not added, the coating has poor adhesion and wear resistance. However, when the first component (A) is not added, or when the third component is excessive or small, the coating becomes sticky and not suitable for practical use.

[0048]

According to the surface treatment method of the present invention, it becomes possible to form a silicone resin film having excellent adhesion and abrasion resistance on a rubber article by using a water-based treatment agent. The weather strip rubber treated by the surface treatment method of the present invention is suitable for automobiles.

[Brief description of drawings]

FIG. 1 is a diagram for explaining a method of a friction test.

[Explanation of symbols]

 1 Sponge rubber 2 Ground glass cell

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C09D 183/06 (72) Inventor Yoshinori Iguchi 1-person, Hitomi, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Industrial Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor, Satoshi Kuwata 1 Hitomi, Osamu Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (4)

[Claims] 1. A method for treating a surface of a rubber article, which comprises applying an aqueous organopolysiloxane emulsion obtained by mixing the following first to third components to the surface of the rubber article and curing the same. First component (A) General formula (1) R ¹ _a H _b SiO _{(4-ab) / 2} (1) (wherein R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms and A hydrogen atom directly bonded to a silicon atom represented by 1 <a <2.2 and 0.1 <b <1 which is one or more groups selected from halogenated hydrocarbon groups. Organopolysiloxane having 1 to 90% by weight (B) the following general formula (2) HO- (R ² ₂ SiO) _m -H ... (2) (wherein R ² has 1 to 20 carbon atoms). 1 to 90% by weight of 1 or 2 or more groups selected from the monovalent hydrocarbon group and halogenated hydrocarbon group, and 10 ≦ m ≦ 3000. (C) Nonionic surfactant 0.1 to 50% by weight (D) Water balance Second component (a) General formula (3) R ³ R ⁴ N (CH ₂ ) _p [NR ⁵ (CH ₂ ) _q ] _{^{r SiR 6 (OR 7) 2}} ··· (3) ( wherein, R ^3, R ⁴ R ⁵ are each hydrogen or a monovalent hydrocarbon group and halogenation hydrocarbon group group selected from, R ^6, R ⁷ are each monovalent hydrocarbon radicals and halogen 1 to 6 carbon atoms having 1 to 6 carbon atoms Of a dialkoxysilane having an aminoalkyl group represented by the formula 1 ≦ p ≦ 6, 1 ≦ q ≦ 6, and 0 ≦ r ≦ 3. 1 to 90% by weight (b) 0.1 to 2 equivalents of water-soluble organic acid and / or inorganic acid to 1 atomic equivalent of nitrogen of component (a) represented by the general formula (3) (c) water Remaining third component (I) Organometallic salt compound 1 to 90% by weight (II) Nonionic surfactant 0.1 to 50% by weight (III) Water remaining 2. An organopolysiloxane aqueous emulsion obtained by mixing the first component, the second component and the third component, wherein the content of the first component (A) is 1 to 50% by weight, The content of the component (B) is 1 to 90% by weight, the content of the second component (a) is 1 to 90% by weight, and the content of the third component (I) is 0.01.
~ 10% by weight of the first component, the second component and the third component
The surface treatment method for a rubber article according to claim 1, wherein the surface treatment method is a composition containing components. 3. A rubber article treated by the surface treatment method according to claim 1. 4. A rubber article for an automobile weatherstrip treated by the surface treatment method according to claim 1.