JP2007332165A - Tire-coating agent set and tire-coating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tire-coating that imparts black gloss on the black surface of a tire, a black bumper or the like for automobiles, causes neither stickiness nor adhesion of stains nor cracks of a film, and can be washed using a general car shampoo. <P>SOLUTION: The tire-coating agent set is constituted of a first liquid comprising black matter dispersed in a dispersant and a second liquid comprising a silicone-grafted acrylic resin dissolved in a solvent. The tire-coating method comprises applying the first liquid comprising the black matter dispersed in the dispersant and applying on the thus-formed black film the second liquid comprising the silicone-grafted acrylic resin dissolved in the solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a tire coating agent set and a tire coating method for polishing a black surface of a tire such as an automobile, a bicycle, a motorcycle, or a black bumper.

JP-A-8-239629 JP 2000-144038 A JP 2002-256225 A Japanese Patent Laid-Open No. 5-230161 JP-A-7-196975

  Conventionally, several protective polishes have been proposed that give a beautiful appearance to the surfaces of tires and black bumpers used in vehicles such as automobiles, bicycles, motorcycles, etc., and maintain a clean feeling. Among them, as a tire polishing agent, those mainly composed of silicone oil and those mainly composed of wax are already known.

  Silicone oil as the main component is generally used because it has a high gloss on the finished surface, but most of it is a fluid with a high boiling point, so it has poor drying properties after being applied to a tire. In addition, the finished surface will remain sticky, making it more difficult for contaminants to adhere to it and not exhibiting its anti-staining effect (anti-stain properties), and a detergent that contains a surfactant to remove the attached contaminants Even if it is attempted to wash with water, etc., there is a problem that due to silicone oil or contaminants, the detergent does not foam, and the sponge, which is a cleaning tool, is stained black.

  Therefore, Patent Document 1 proposes a tire polish that is obtained by emulsifying and dispersing wax, organosiloxane oil, carbon black, and polyurethane resin in water. This tire polish can suppress the stickiness of the finished surface, but it requires wiping after application, and the gloss after finishing is inferior to that of the main component of silicone oil. .

  Patent Document 2 proposes a tire polishing agent in which a plasticizer is blended with an acrylic ester polymer and / or a methacrylic ester polymer having a glass transition temperature of 0 to 50 ° C. In order to improve the water resistance and durability, this tire polish agent forms a water-insoluble coating film on the tire surface. When the coating film deteriorates due to changes over time, it is difficult to remove it easily by washing, and it is difficult to completely remove it. As a result, a new paint is applied on the old coating film. In addition to the problem that the appearance is gradually damaged, on the other hand, there is also a problem that the gloss cannot be easily lowered when it is desired to reduce the gloss. .

  Further, Patent Document 3 includes a water-dispersible or water-soluble resin component and a modified silicone having a hydrophilic group as a plasticizer component compatible with the resin component, and forms a water-washable film. Protective polishes for tires have been proposed.

  However, since the tire polishing agent disclosed in Patent Document 3 does not contain black matter such as carbon black, the black polishing effect is poor.

  Therefore, the present invention has been made in view of the above-mentioned problems of the prior art, and the problem to be solved by the present invention is to impart a black glossy gloss to black surfaces of automobile tires, black bumpers, etc. It is an object of the present invention to provide a tire coating that can be cleaned with a general car shampoo without causing stickiness, adhesion of dirt, and cracking of the film.

  As a result of diligent study, the present inventors have formulated a tire coating agent by separating it into a first liquid in which a black product is dispersed in a dispersion medium and a second liquid for polishing, and the second liquid. As a result, it was found that these problems can be solved by using a liquid obtained by dispersing a silicone graft acrylic resin in a dispersion medium, and the present invention was completed.

  That is, the tire coating agent set of the present invention comprises a first liquid obtained by dispersing a black product in a dispersion medium, and a second liquid obtained by dissolving a silicone graft acrylic resin in a solvent. .

  In the tire coating method of the present invention, a first liquid obtained by dispersing a black material in a dispersion medium is applied, and a silicone graft acrylic resin is dissolved in a solvent on the black film formed thereby. The second liquid is applied.

  By applying the first liquid, a black film is formed on the black surface of automobile tires, black bumpers, etc., and by applying the second liquid on it, it is glossy and non-sticky and prevents adhesion of dirt. Performance can be imparted. The film can be cleaned with a general car shampoo without causing cracks in the film.

  In the present invention, the silicone graft acrylic resin refers to a resin containing a component obtained by grafting silicone onto an acrylic resin, an acrylic ester resin, a methacrylic resin or a methacrylic ester resin.

（Ｒ¹は水素又はメチル基、Ｒ²は酸素原子により中断されてもよい炭素数１〜12の２価炭化水素基、Ｒ³は炭素数１〜６の１価炭化水素基、ｍは１、２又は３で、ｎは３〜200の整数を表わす。）
の構造を有することが好ましい。 In the present invention, the silicone graft acrylic resin is represented by the following general formula (1):

(R ¹ is hydrogen or a methyl group, R ² is a C 1-12 divalent hydrocarbon group which may be interrupted by an oxygen atom, R ³ is a C 1-6 monovalent hydrocarbon group, m is 1 2 or 3, n represents an integer of 3 to 200)
It is preferable to have the following structure.

（Ｒ¹は水素又はメチル基、Ｒ²は酸素原子により中断されてもよい炭素数１〜12の２価炭化水素基、Ｒ³は炭素数１〜６の１価炭化水素基、Ｒ⁴は水素又はメチル基、ｍは１、２又は３で、ｎは３〜200の整数を表わす。）
の構造を有することが好ましい。 In the present invention, the silicone graft acrylic resin is represented by the following general formula (2):

(R ¹ is hydrogen or a methyl group, R ² is a C 1-12 divalent hydrocarbon group which may be interrupted by an oxygen atom, R ³ is a C 1-6 monovalent hydrocarbon group, R ⁴ is Hydrogen or methyl group, m is 1, 2 or 3, n represents an integer of 3 to 200)
It is preferable to have the following structure.

（Ｒ¹は水素又はメチル基、Ｒ²は酸素原子により中断されてもよい炭素数１〜12の２価炭化水素基、Ｒ³は炭素数１〜６の１価炭化水素基、Ｒ⁴は水素又はメチル基、Ｒ⁵は水素又はメチル基、Ｒ⁶は他のアルキル基又は官能基含有アルキル基、ｍは１、２又は３で、ｎは３〜200の整数を表わす。）
の構造を有することが好ましい。 In the present invention, the silicone graft acrylic resin is represented by the following general formula (3):

(R ¹ is hydrogen or a methyl group, R ² is a C 1-12 divalent hydrocarbon group which may be interrupted by an oxygen atom, R ³ is a C 1-6 monovalent hydrocarbon group, R ⁴ is (Hydrogen or methyl group, R ⁵ is hydrogen or methyl group, R ⁶ is another alkyl group or functional group-containing alkyl group, m is 1, 2 or 3, and n is an integer of 3 to 200)
It is preferable to have the following structure.

（Ｒ¹は水素又はメチル基、Ｒ²は酸素原子により中断されてもよい炭素数１〜12の２価炭化水素基、Ｒ³は炭素数１〜６の１価炭化水素基、ｍは１、２又は３で、ｎは３〜200の整数を表わす。）
又は下記一般式（２）

（Ｒ¹は水素又はメチル基、Ｒ²は酸素原子により中断されてもよい炭素数１〜12の２価炭化水素基、Ｒ³は炭素数１〜６の１価炭化水素基、Ｒ⁴は水素又はメチル基、ｍは１、２又は３で、ｎは３〜200の整数を表わす。）
の構造を有するシリコーングラフトアクリル系樹脂と、下記一般式（４）の構造を有する樹脂とを混合・分散して構成することもできる。

（Ｒ⁴は水素又はメチル基、Ｒ⁵は水素又はメチル基、Ｒ⁶は他のアルキル基又は官能基含有アルキル基を表わす。） In the present invention, the second liquid has the following general formula (1):

(R ¹ is hydrogen or a methyl group, R ² is a C 1-12 divalent hydrocarbon group which may be interrupted by an oxygen atom, R ³ is a C 1-6 monovalent hydrocarbon group, m is 1 2 or 3, n represents an integer of 3 to 200)
Or the following general formula (2)

(R ¹ is hydrogen or a methyl group, R ² is a C 1-12 divalent hydrocarbon group which may be interrupted by an oxygen atom, R ³ is a C 1-6 monovalent hydrocarbon group, R ⁴ is Hydrogen or methyl group, m is 1, 2 or 3, n represents an integer of 3 to 200)
A silicone graft acrylic resin having the following structure and a resin having the structure of the following general formula (4) may be mixed and dispersed.

(R ⁴ represents hydrogen or a methyl group, R ⁵ represents hydrogen or a methyl group, and R ⁶ represents another alkyl group or a functional group-containing alkyl group.)

  According to the present invention, black surfaces such as automobile tires and black bumpers are imparted with a black luster and reproduced in the same way as new tires, without causing stickiness, adhesion of dirt, cracking of the coating, A tire coating can be provided that can be cleaned with a common car shampoo.

  In this invention, a black pigment or a black dye is mentioned as a black thing contained in a 1st liquid. Black pigments include carbon black, aniline black, synthetic iron oxide (TAROX, etc., manufactured by Titanium Industry Co., Ltd.), ivory black (bone charcoal), peach black (vegetable charcoal), temp black (oil charcoal), bitumen (asphalt), etc. In particular, inexpensive and non-toxic carbon black is preferable. Examples of black dyes include orthoaminophenol and paraphenylenediamine.

In the present invention, the dispersion medium contained in the first liquid may be any liquid that disperses a black pigment at room temperature or a liquid that dissolves a black dye and has volatility. Examples thereof include a dispersion medium, a petroleum dispersion medium, a glycol dispersion medium, and an aqueous dispersion medium. Examples of the alcohol-based dispersion medium include methanol, ethanol, 1-propanol, 2-propanol, and the like, and examples of the silicone-based dispersion medium include dimethyl silicone having a kinematic viscosity at 25 ° C. of 0.65 to ² mm ² / s, 4 to 6 Examples of petroleum-based dispersion media include paraffinic hydrocarbons such as pentane, hexane, and heptane, industrial gasoline, kerosene, mineral split, isoparaffin, and cycloparaffin. Examples of the system dispersion medium include ethylene glycol, propylene glycol, trimethylene glycol, triethylene glycol, 1,4-butanediol, and 1,5-pentanediol. As the aqueous dispersion medium, water may be used for hydrophilic carbon black, and water containing a dispersant for each of anionic, cationic, nonionic and amphoteric surfactants can be used for ordinary hydrophobic carbon black. Water containing a nonionic activator dispersant is preferred in terms of ease of use. Here, as the dispersant for the nonionic activator, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene isocetyl ether, polyoxyethylene isostearyl ether, Polyoxyethylene octyldodecyl ether, polyoxyethylene behenyl ether, polyoxyethylene decyl tetradecyl ether, polyoxyethylene cholesteryl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene isodecyl ether, polyoxyethylene tridecyl ether, polyoxy Ethylene oxide added higher alcohols (AE) such as ethylene lanolin alcohol ether, polyoxyethylene poly Xylpropylene decyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl amine ether, polyoxyethylene allyl ether, polyoxyethylene alkyl allyl ether, alkyl glyceryl ether, etc. Ether based nonionic activator, polyoxyethylene glycol fatty acid ester, polyoxyethylene hydrogenated castor oil, ethylene oxide-added alkylphenol (APE), polyoxyethylene-added polyoxypropylene glycol, glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester , Polyoxyethylene sorbitan fatty acid ester, tetraoleic acid Polyoxyethylene sorbitol, alkanolamine - fatty acid condensates, alkanolamides, alkylpolyglycosides, etc., further can be suitably used a nonionic surfactant such as a fluorinated hydrocarbon group contained in these active agents. In particular, those that do not adversely affect the tire, such as cracks, are preferred, and 2-propanol, the above silicone dispersion medium, heptane, water containing the above ether nonionic activator, and the like are preferred.

  In the present invention, the first liquid can be made into an O / W type or W / O type emulsion by adding various binder components such as wax and resin and an emulsifier.

In the present invention, specific silicone graft acrylic resins contained in the second liquid include, for example, the following monomers and other radical polymerizable monomers as disclosed in Patent Document 4 and Patent Document 5: It can be obtained by radical polymerization.

In the present invention, examples of the solvent contained in the second liquid include an alcohol dispersion medium, a silicone dispersion medium, a petroleum dispersion medium, a glycol dispersion medium, and an aqueous dispersion medium. Examples of the alcohol-based dispersion medium include methanol, ethanol, 1-propanol, 2-propanol, and the like, and examples of the silicone-based dispersion medium include dimethyl silicone having a kinematic viscosity at 25 ° C. of 0.65 to ² mm ² / s, 4 to 6 Examples of petroleum-based dispersion media include paraffinic hydrocarbons such as pentane, hexane, and heptane, industrial gasoline, kerosene, mineral split, isoparaffin, and cycloparaffin. Examples of the system dispersion medium include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, and 1,5-pentanediol. The aqueous dispersion medium may be water or water containing a dispersant for each of anionic, cationic, nonionic and amphoteric surfactants. Among these, water containing a nonionic activator dispersant is preferable in terms of ease of use. Here, as the dispersant for the nonionic activator, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene isocetyl ether, polyoxyethylene isostearyl ether, Polyoxyethylene octyldodecyl ether, polyoxyethylene behenyl ether, polyoxyethylene decyl tetradecyl ether, polyoxyethylene cholesteryl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene isodecyl ether, polyoxyethylene tridecyl ether, polyoxy Ethylene oxide added higher alcohols (AE) such as ethylene lanolin alcohol ether, polyoxyethylene poly Xylpropylene decyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl amine ether, polyoxyethylene allyl ether, polyoxyethylene alkyl allyl ether, alkyl glyceryl ether, etc. Ether based nonionic activator, polyoxyethylene glycol fatty acid ester, polyoxyethylene hydrogenated castor oil, ethylene oxide-added alkylphenol (APE), polyoxyethylene-added polyoxypropylene glycol, glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester , Polyoxyethylene sorbitan fatty acid ester, tetraoleic acid Polyoxyethylene sorbitol, alkanolamine - fatty acid condensates, alkanolamides, alkylpolyglycosides, etc., further can be suitably used a nonionic surfactant such as a fluorinated hydrocarbon group contained in these active agents. In particular, those that do not adversely affect the tire, such as cracks, are preferred, and 2-propanol, the above silicone dispersion medium, heptane, water containing the above ether nonionic activator, and the like are preferred.

  In the present invention, the first liquid and / or the second liquid include, for example, phenyl salicylate, in addition to the above-described components, in order to further improve performances such as protection of the coated surface and refreshment during use. You may add the 1 type (s) or 2 or more types of 3rd component chosen from ultraviolet inhibitors, rust preventives, fragrance | flavors, etc., such as 2, 4- dihydroxy benzophenone, to a dispersion medium previously.

  In the tire coating method of the present invention, the method of applying the first liquid and / or the second liquid may be any method as long as the finished surface has a uniform gloss, such as spray application, towel, sponge, nonwoven fabric, tissue, etc. The method of apply | coating by the means of this, brush coating etc. are mentioned.

  In addition, immediately after the first liquid is applied, the second liquid may be applied onto the black coating formed thereby. However, after the first liquid is applied, the dispersion medium of the first liquid is volatilized. More preferably, after the black film formed thereby is dried, the second liquid is applied onto the black film. Furthermore, after the second liquid is applied, the dispersion medium of the second liquid is volatilized, and the coating film formed thereby is dried, and then excess components on the coating film are removed from scratches such as towels, nonwoven fabrics, and fleeces. It may be finished by wiping with something difficult to attach.

  Hereinafter, embodiments of the present invention will be described with specific examples.

(Preparation of the first solution)
Each 1st liquid of the prescription examples 1-4 was prepared in each ratio shown in Table 1, respectively.

(Preparation of the second liquid)
Furthermore, each 2nd liquid of prescription examples 1-4 and comparative prescription examples 1-3 was prepared in each ratio shown in Table 2, respectively.

(Examples 1-7 and Comparative Examples 1-3)
The prescription example 1 of the first liquid prepared above is applied to about one third of the side surface of one tire of the four tires of a passenger car. Formulation Example 1 was applied (Example 1).

  Formula 1 of the first liquid prepared above was applied to another portion of about one third of the side surface of the same tire of the same passenger car, and further, Formula 1 of the second liquid was applied thereon. (Example 2).

  The first liquid formulation example 3 prepared above was applied to another third of the side of the same tire of the same passenger car, and the second liquid formulation example 1 was further applied thereon. (Example 3).

  The first liquid formulation example 4 prepared above was applied to about one third of the side surface of another tire of the same passenger car, and the second liquid formulation example 1 was further applied thereon (see FIG. Example 4).

  The first liquid formulation example 1 prepared above was applied to another third of the side of the same tire of the same passenger car, and the second liquid formulation example 2 was further applied thereon. (Example 5).

  The first liquid formulation example 1 prepared above was applied to another one third of the side of the same tire of the same passenger car, and the second liquid formulation example 3 was further applied thereon. (Example 6).

  Formulation Example 1 of the first liquid prepared above was applied to about one third of the side surface of another tire of the same passenger car, and then Formulation Example 4 of the second liquid was further applied thereon (see FIG. Example 7).

  The first liquid formulation example 1 prepared above is applied to another one third of the side surface of the same tire of the same passenger car, and the second liquid comparative formulation example 5 is further applied thereon. (Comparative Example 1).

  The first liquid formulation example 1 prepared above is applied to another one third of the side of the same tire of the same passenger car, and the second liquid comparative formulation example 6 is further applied thereon. (Comparative Example 2).

  The first liquid formulation example 1 prepared above was applied to about one third of the side surface of another tire of the same passenger car, and the second liquid comparative formulation example 7 was further applied thereon. (Comparative Example 3).

  After sufficiently drying (approx. 1 hour after application), or after traveling for about 500 km for 2 weeks after application, the gloss and gloss (after 2 weeks) The crack / peelability, stickiness, dust resistance, water resistance, and film removal performance were evaluated. The results are shown in Table 3.

[Glossiness]
About glossiness, about 1 hour after coating the first and second liquids on the side surface of the tire, the appearance of the film formed on the side surface of the tire was visually observed, and ◎: very good gloss, ○ The evaluation was made in four grades: good gloss, Δ: slight gloss, x: almost no gloss.

[Glossiness (after 2 weeks)]
For glossiness (after 2 weeks), the first and second liquids were applied to the side surface of the tire, and after running for 2 weeks, the appearance of the coating formed on the side surface of the tire was visually observed. Evaluation was made in four grades: good gloss, ○: good gloss, Δ: slight gloss, x: almost no gloss.

[Crack resistance / peeling resistance]
As for crack resistance and peel resistance, the first and second liquids were applied to the side surface of the tire, and after running for 2 weeks, the appearance of the film was visually observed. ◎: No cracking, ○: Mostly Evaluation was made in four stages: no cracking, Δ: slight cracking, and x: cracking.

[Becky]
About stickiness, about 1 hour after coating the first and second liquids on the side surface of the tire, the film formed on the side surface of the tire was directly touched and observed, ◎: no stickiness, ○: almost Evaluation was made in four stages: no stickiness, Δ: slightly sticky, ×: sticky.

[With dust resistance]
For dust resistance, the first and second liquids are applied to the side of the tire and run for 2 weeks, and then the film formed on the side of the tire is directly touched and observed. A: No dust , ○: Almost no dust was attached, Δ: Some dust was attached, and X: Dust was attached.

〔water resistant〕
As for water resistance, about 1 hour after applying the first and second liquids to the side surface of the tire, the state of the film after visually applying water for 10 minutes was visually observed. No, ○: Almost no change, Δ: Thin gloss, x: No coating, evaluation was made in four stages.

[Coating removal performance]
Regarding the film removal performance, about 1 hour after applying the first and second liquids on the side surface of the tire, rubbing 10 times with a sponge containing water and car shampoo, and then visually checking the state of the film Observed, the evaluation was made in four stages: ◯: completely removed, ◯: part of the film remained, Δ: hardly removed, ×: not removed at all.

Claims (6)

  A tire coating agent set comprising: a first liquid obtained by dispersing a black product in a dispersion medium; and a second liquid obtained by dissolving a silicone graft acrylic resin in a solvent. Silicone graft acrylic resin is represented by the following general formula (1)

(R ¹ is hydrogen or a methyl group, R ² is a C 1-12 divalent hydrocarbon group which may be interrupted by an oxygen atom, R ³ is a C 1-6 monovalent hydrocarbon group, m is 1 2 or 3, n represents an integer of 3 to 200)
The tire coating agent set according to claim 1, which has the following structure. Silicone graft acrylic resin is represented by the following general formula (2)

(R ¹ is hydrogen or a methyl group, R ² is a C 1-12 divalent hydrocarbon group which may be interrupted by an oxygen atom, R ³ is a C 1-6 monovalent hydrocarbon group, R ⁴ is Hydrogen or methyl group, m is 1, 2 or 3, n represents an integer of 3 to 200)
The tire coating agent set according to claim 2, wherein the tire coating agent set has the following structure. Silicone graft acrylic resin is represented by the following general formula (3)

(R ¹ is hydrogen or a methyl group, R ² is a C 1-12 divalent hydrocarbon group which may be interrupted by an oxygen atom, R ³ is a C 1-6 monovalent hydrocarbon group, R ⁴ is Hydrogen or methyl group, R ⁵ is hydrogen or methyl group, R ⁶ is other alkyl group or functional group-containing alkyl group, m is 1, 2 or 3, and n is an integer of 3 to 200)
The tire coating agent set according to claim 3, wherein the tire coating agent set has the following structure. The second liquid is represented by the following general formula (1)

(R ¹ is hydrogen or a methyl group, R ² is a C 1-12 divalent hydrocarbon group which may be interrupted by an oxygen atom, R ³ is a C 1-6 monovalent hydrocarbon group, m is 1 2 or 3, n represents an integer of 3 to 200)
Or the following general formula (2)

(R ¹ is hydrogen or a methyl group, R ² is a C 1-12 divalent hydrocarbon group which may be interrupted by an oxygen atom, R ³ is a C 1-6 monovalent hydrocarbon group, R ⁴ is Hydrogen or methyl group, m is 1, 2 or 3, n represents an integer of 3 to 200)
A silicone-grafted acrylic resin having the following structure:

(R ⁴ represents hydrogen or a methyl group, R ⁵ represents hydrogen or a methyl group, and R ⁶ represents another alkyl group or a functional group-containing alkyl group.)
The tire coating agent set according to claim 2, wherein the tire coating agent set is obtained by mixing and dispersing a resin having the structure:   A first liquid obtained by dispersing a black material in a dispersion medium is applied, and a second liquid obtained by dissolving a silicone graft acrylic resin in a solvent is applied on the black film formed thereby. Tire coating method to do.