JPH0953050A - Water-repellent lustering agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an emulsion-type water-repellent lustering agent which has excellent storage stability and compounding stability and provides good water-repellent and lustering effects excellent in persistence. SOLUTION: This agent mainly comprises a microemulsion which is obtd. by mixing an amino-functional polyorganosiloxane with a surfactant, adding a part of water to the resulting premixture under stirring, adding the rest of water to the resulting primary mixture, and adding an acid to the resulting secondary mixture to adjust the pH to 4-10 to thereby convert at least a part of the polyorganosiloxane into a salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsion-type water-repellent polish, and particularly to an amino-functional polyorganosiloxane that imparts an excellent water-repellent appearance and good gloss to various substrates. The present invention relates to a water repellent polish containing the microemulsion.

[0002]

2. Description of the Related Art Conventionally, in an aqueous polish containing mainly wax, in order to improve the polish effect and workability, an emulsion of polydiorganosiloxane such as polydimethylsiloxane or polymethylphenylsiloxane has been added. (Japanese Patent Laid-Open No. 52-141
493). Further, addition of a polyorganosiloxane microemulsion having an average particle diameter of 150 nm or less has also been carried out (see JP-A-63-301280).

However, JP-A-52-141493
The water-based polish shown in Japanese Patent Laid-Open Publication No. 2003-108242 is one in which a normal emulsion obtained by mechanically emulsifying a polyorganosiloxane oil with a surfactant and water is added, and the average particle diameter of the emulsion is very large (0.3 μm). Therefore, the stability as an aqueous polish is insufficient. That is, since the long-term storage stability and the compounding stability when used in combination with various additives such as abrasives are insufficient, the polyorganosiloxane oil is easily separated, and the emulsion separated as an oil is used as a polish. When it is used, there is a defect that unevenness of gloss, unevenness of unevenness, unevenness of wiping and / or stickiness occur on the substrate. Further, the oil-separated polish has a drawback in that the product value is remarkably reduced in appearance.

Further, the polyorganosiloxane microemulsion having an average particle size of 0.15 μm or less, which is disclosed in JP-A-63-301280, has alleviated the above-mentioned drawbacks, but has an amino group in the molecule of the polysiloxane. Since such a functional group does not exist, there is a drawback that the adhesion to the treated surface is poor and the water repellency and glossiness are not maintained well. Further, since the microemulsion is produced by an emulsion polymerization method, there is a restriction that it cannot be used in combination with various additives.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to eliminate the above-mentioned drawbacks of existing water-based polishes, has excellent storage stability and formulation stability, and has a substrate surface. It is an object of the present invention to provide an emulsion-type water-repellent polish which has excellent water-repellent property and has a good polishing effect, which is free from uneven coating, uneven wiping, uneven glossiness and stickiness, and has excellent durability.

[0006]

That is, according to the present invention, (A) an amino-functional polyorganosiloxane is mixed with a surfactant to form a premix; (B) a part of water is added to the premix. And stir to form a primary mixture; (C) add residual water to the primary mixture to form a secondary mixture; and (D) add acid to the secondary mixture. p
The present invention relates to a water-repellent polish which contains as a main component a microemulsion of an amino-functional polyorganosiloxane obtained by converting H to 4 to 10 and converting at least a part of the above-mentioned amino-functional polyorganosiloxane into a salt.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Step (A) is a step of incorporating a surfactant into an amino-functional polyorganosiloxane (hereinafter sometimes referred to as component (1)).

Component (1) provided for compounding in step (A) typically comprises the following siloxane units (a) and (b): (a) R _a Q _b SiO _{(4-ab) / 2} Unit: (b) R _c SiO _{(4-c) / 2} unit [wherein R may be the same or different from each other, 1
Represents a monovalent substituted or unsubstituted hydrocarbon having 6 to 6 carbon atoms (excluding Q described below), part of which may be a silicon functional group; Q is a general formula -R ¹ NZ ₂
(In the formula, R ¹ represents a divalent hydrocarbon group in which an ether bond, a thioether bond, an ester bond or a carbonylthioether bond may be present in the chain; Z may be the same or different; A hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a 2-aminoethyl group), and a is 0 to 2
B is a number from 1 to 3, where a + b is 1
Is a number of 3 to 3; c is a number of 1 to 3], and is an amino-functional polyorganosiloxane in which a silicon functional group may be present.

R in the above (a) unit and (b) unit is methyl, ethyl, propyl, butyl, amyl,
Alkyl groups such as hexyl; alkenyl groups such as vinyl and allyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; phenyl groups; 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl , Halogenated hydrocarbon groups such as chlorophenyl and bromophenyl; and mercaptohydrocarbon groups such as 3-mercaptopropyl, 6-mercaptohexyl and mercaptophenyl. Further, a part of R is a hydroxyl group; or methoxy,
It may be an alkoxy group such as ethoxy and propoxy. As R, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is most preferable. In addition, since a fine microemulsion can be obtained, R
It is preferred that some of the above are silicon functional groups.

In the amino functional group Q of the unit (a), R ¹ bonded to the silicon atom is methylene, trimethylene, 2-methyltrimethylene, tetramethylene,
Alkylene groups such as hexamethylene and decamethylene;
Arylene groups such as phenylene, biphenylene, bis (phenylene-4-yl) methylene, naphthylene;
_{(CH 2) 3 OCH 2 -} , - (CH 2) 3 O (CH 2) 2 -,
_{- (CH 2) 3 S (} CH 2) 2 - 2 divalent hydrocarbon group having a chain ether bond or a thioether bond in the like;
_{- (CH 2) 3 C (} O) OCH 2 -, - (CH 2) 3 C
_{(O) O (CH 2)} 2 -, - (CH 2) 3 C (O) S (CH
₂ ) _2- divalent hydrocarbon groups having an ester bond or a carbonylthioether bond in the chain are exemplified.
A trimethylene group is most preferred because it is easy to synthesize and stable.

As mentioned above, Z is a hydrogen atom or an alkyl group such as methyl, ethyl, propyl or butyl;
Most preferably, it is a 2-aminoethyl group, and at least one of the two Z is a 2-aminoethyl group.

That is, the amino functional group Q is most preferably an N- (2-aminoethyl) -3-aminopropyl group having two amino groups.

The amino group content of the amino-functional polyorganosiloxane is preferably 0.1 to 3.0 meq / g, more preferably 0.3 to 1.5 meq / g, and even more preferably 0.1.
Most preferred is 6 to 1.0 meq / g. 0.1 meq
If it is less than / g, even if a salt is formed in the step (D), the average particle size of the oil phase of the emulsion becomes 0.07 μm or more, and a stable microemulsion suitable for the purpose of the present invention cannot be obtained. Further, when it exceeds 3.0 meq / g, uneven coating on the substrate occurs.

To obtain such an amino group content,
The molar ratio of the (a) unit to the (b) unit is 1: 2 to 1:39.
The range of 0 is preferable, 1: 5 to 1:65 is more preferable, and 1:15 to 1:20 is the most preferable.

Component (1) includes, for example, when R ¹ is a trimethylene group, an amino group represented by the general formula: CH ₂ ═CHCH ₂ NZ ₂ (wherein Z is as described above) in the polyorganohydrogensiloxane. The unsaturated compound can be synthesized by reacting the unsaturated compound in the presence of a hydrosilylation catalyst.

Component (1) is, for example, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-.
Obtained by ring-opening polymerization of a low-molecular weight cyclic polydiorganosiloxane such as octamethylcyclotetrasiloxane in the presence of an amino group-containing alkoxysilane such as (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. You can

In this case, an amino-functional polyorganosiloxane having an alkoxy group such as methoxy, ethoxy or propoxy or a silicon functional group such as a hydroxyl group formed by hydrolysis of the alkoxy group at the molecular end and in some cases in the molecule. Is obtained. In order to form a microemulsion having a fine oily phase, those having such a silicon functional group are preferable. Depending on the purpose, this may be treated with a silylating agent such as hexamethyldisilazane and substituted with a trimethylsilyl group before use.

Preferred amino-functional polyorganosiloxanes have the general formula (I):

Embedded image (Wherein, Z is in as described above, preferably - (CH _{2) 2}
NH ₂ ; R ² is a methyl group, R ³ or the following formula

Embedded image And R ³ is a methyl group, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group; x is a number of 1 to 20, y and z are each 0;
˜800, where y and z are chosen such that the number of dimethylsiloxy groups in the molecule is 20-800). x is preferably 5-10, most preferably 8. The above formula (I) represents the number of siloxane units, and does not mean a block copolymer.

As the surfactant to be blended in the step (A), polyoxyethylene lauryl ether, polyoxyethylene trimethylnonyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, Polyoxyethylene alkyl ether-based surfactants such as oxyethylene oleyl ether; polyoxyethylene alkylaryl ether-based surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether ; Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene Nonionic surfactants such as ester-based surfactants such as modified castor oil, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester; and cations such as alkylammonium salt and alkylbenzylammonium salt Examples of the surface active agent include one type, which may be used alone, or two or more types may be used in combination.
Among these, at least a part is preferably a nonionic type because a stable microemulsion is obtained, and polyoxyethylene lauryl ether,
It is further preferable to use a polyoxyethylene alkyl ether such as polyoxyethylene trimethyl nonyl ether and a polyoxyethylene alkyl phenyl ether such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether in combination.

In order to obtain a good and stable microemulsion, when a nonionic surfactant is used, its HLB is
The composition ratio of the surfactant is preferably selected so that the weighted average of the values is 10 to 16.

The ratio of the surfactant used in the step (A) is preferably 10 to 60 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of the component (1).
Particularly preferred is 5 to 35 parts by weight. If it is less than 10 parts by weight, a good microemulsion cannot be obtained, and if it is used in excess of 60 parts by weight, an excessive amount of the surfactant inhibits the adhesion of the amino-functional polyorganosiloxane to the substrate, resulting in water repellency and gloss. Is not durable enough.

The step (A) is a step of mixing a surfactant with the component (1). Mixing may be performed at room temperature, but 1
The surfactant may be heated to a temperature lower than 00 ° C., and particularly when a solid surface active agent is used at room temperature, the surface active agent may be mixed in a liquid state by appropriately heating the surface active agent according to their melting points. preferable.

In the step (B), a portion of water contained in the finally obtained microemulsion is gradually added to the premix obtained in the step (A) to form a W / O type emulsion, and then the emulsion is added. It is a step of forming a primary mixture which is an O / W type emulsion. The amount of water added in step (B) is preferably 15 to 50 parts by weight, and most preferably 15 to 25 parts by weight, per 100 parts by weight of the premix.
Parts by weight. Water may be added dropwise over 5 to 50 minutes, or may be slowly added in several times.

The primary mixture formed in step (B) is of sufficient time to form a homogeneous mixture, typically 5 to.
Stir for 50 minutes. In step (B), the mixture of oil and surfactant, and the water added thereto, is typically mixed such that during the addition of water, the surfactant forms a homogeneous emulsion of the water phase and the oil phase. 5 to 60
Stir for minutes. The time required to form a homogeneous mixture in step (B) depends on the parameters of the mixing equipment, which can be easily determined by the person skilled in the art.

The step (C) is the one formed in the step (B).
It is a step of adding the remainder of water contained in the microemulsion to the next mixture to dilute it. In step (C), the water is such that the total amount of water added in steps (B) and (C) is typically at least 50 parts by weight, preferably 100 to 2,000, per 100 parts by weight of the premix.
Parts by weight, most preferably in the range of 300 to 500 parts by weight. The addition of water in two separate steps, namely steps (B) and (C), requires that water be added in this way in order to obtain a clear microemulsion, It is important to the present invention.

Next, in step (D), an acid is added to convert at least a part of the (1) amino-functional polyorganosiloxane in the system into a salt to form a transparent and stable microemulsion. Let The acid may be a carboxylic acid or an inorganic acid, but the carboxylic acid is preferably one having 1 to 4 carbon atoms such as formic acid, acetic acid, propionic acid and butyric acid. Further, as the inorganic acid, hydrochloric acid, hydrobromic acid,
Examples include hydroiodic acid, sulfuric acid, nitric acid and the like. These acids are usually added after diluting with water.

The amount of acid added is such that the pH of the mixture is between 4 and
The amount is 10. Preferably, the pH on the alkaline side is more than 7 and 10 or less, and more preferably 7.1 to 8.
An amount of acid giving a pH of 5 is added to partially convert the amino groups of the amino-functional polyorganosiloxane into salts. As a result, a good microemulsion having good transparency is formed.

The amount of such an acid required to provide, for example, pH 8 per aminofunctional polyorganosiloxane used in step (A) is determined by the amino group content of the aminofunctional polyorganosiloxane. , Depends on the type of acid. For example, when acetic acid is used as the acid, when the component (1) has an amino content of 0.6 meq / g,
The amount of acid sufficient to provide a pH in the desired range is 1.5 parts by weight per 100 parts by weight of component (1). With an amino content of 3 meq / g, the amount of acid is 7.5 parts by weight per 100 parts by weight of component (1). 0.3
When using component (1) having an amino content in the preferred range of ~ 1.5 meq / g, the amount of acid is from 0.75 to 3.75 parts by weight per 100 parts by weight of component (1). When using component (1) with a range and a most preferred range of amino content of 0.6-1.0 meq / g, the amount of acid is based on 100 parts by weight of component (1). It is in the range of 1.5 to 2.5 parts by weight.

The addition of such an acid is carried out in steps (A) to
It should be done after (C). This is because if an acid is added before this, an opaque microemulsion or gel is produced.

The method of the present invention preferably further comprises, as step (E), a step of adding a water-soluble polyhydric alcohol to the microemulsion formed in step (D). Examples of the water-soluble polyhydric alcohol include glycerin; water-soluble alkylene glycols such as ethylene glycol and propylene glycol; and water-soluble polyalkylene glycols such as polyethylene glycol, low molecular weight polypropylene glycol, and oxyethylene / oxypropylene copolymer. And glycerin is most preferred. The water-soluble polyhydric alcohol has an effect of improving the transparency of the emulsion, and is added in a ratio effective for achieving this purpose. Specifically, the water-soluble polyhydric alcohol is typically 2 to 20 parts by weight, preferably 2 to 12 parts by weight, and most preferably 4 to 8 parts by weight per 100 parts by weight of the microemulsion formed in step (D). The range is parts by weight.

The method of the present invention further comprises, as step (F), for protecting the microemulsion formed in step (D) or further through step (E) from potentially harmful microorganisms. It is preferred to include the step of adding an effective amount of a biocide or preservative.

Examples of the biocides or preservatives include carboxylic acids such as sorbic acid, benzoic acid and vanillic acid; methyl parahydroxybenzoate, ethyl parahydroxybenzoate, propyl parahydroxybenzoate and butyl parahydroxybenzoate. Para-hydroxybenzoates such as; condensed esters such as dehydroacetic acid; quaternary ammonium salts such as cetyltrimethylammonium chloride, didodecenyldimethylammonium chloride, benzalkonium chloride, benzethorium chloride, cetylpyridinium chloride Imidazole compounds such as 2- (4-thiazolyl) benzimidazole, sulfur compounds such as tetramethylthiuram disulfide, 1,2-benzisothiazolone; and 1- (3-chloroallyl) -3 chloride;
Adamantane compounds such as 5,7-triaza-1-azonia adamantane may be mentioned.

The ratio of the biocide or preservative added in the step (F) varies depending on the kind of the biocide or preservative used, but it is 1- (3-chloroallyl chloride) chloride.
Taking -3,5,7-triaza-1-azonia adamantane as an example, it is typically added at a rate of 2 to 5 parts by weight per 100 parts by weight of the premix formed in step (A). .

The microemulsion thus obtained may be used as it is as a water-repellent polish.
Alternatively, two or more kinds may be mixed and used. Alternatively, it may be further diluted with water before use, or may be used in combination with a conventional silicone oil emulsion and / or wax emulsion.

The silicone oil emulsion used in combination with the microemulsion of the present invention includes dimethyl silicone emulsion, methylphenyl silicone emulsion, alkyl modified silicone emulsion, fatty acid modified silicone emulsion, carboxyl modified silicone emulsion, alcohol modified silicone emulsion and polyether modified. Examples thereof include silicone emulsion and trifluoropropyl modified silicone emulsion.

Similarly, examples of the wax emulsion used in combination with the microemulsion of the present invention include emulsions of natural or synthetic waxes such as carnauba wax, beeswax, montan wax, paraffin wax, microcrystalline wax and polyethylene wax. .

Further, as the additives to be added to the microemulsion of the present invention, there may be mentioned solvents, thickeners, rust preventives, abrasives, colorants, ultraviolet absorbers, fragrances and the like.
These may be contained in a silicone oil emulsion or a wax emulsion to be emulsified, or those emulsified with various emulsifiers may be added. Further, a water-soluble substance may be added as it is to the microemulsion of the present invention. As the solvent, toluene, xylene, kerosene,
Examples include thickeners such as naphtha and mineral spirits; examples of thickeners include silica, diatomaceous earth, bentonite, aluminum silicate, hydrated calcium silicate, magnesium oxide, iron oxide and tin oxide.

[0038]

EFFECT OF THE INVENTION The water-repellent polish of the present invention has excellent storage stability and compounding stability, is excellent in stability by simple work, and has uneven stretch, uneven wiping, and uneven gloss on the surface of a substrate. Also, it is possible to impart a long-lasting excellent gloss effect and water repellency without stickiness.

The silicone emulsion water-repellent polish of the present invention is useful for polishing various base materials such as automobiles, furniture, glass, leather, rubber and plastics, and is particularly useful when used outdoors or in water. , Excellent in water repellency and long lasting gloss effect.

[0040]

The present invention will be described in more detail with reference to Preparation Examples, Examples and Comparative Examples. In these examples, parts represent parts by weight and% represent% by weight, unless stated otherwise. The invention is not limited by these examples.

In the following examples, the amino-functional polyorganosiloxane has the formula (I):

Embedded image In, a silicone oil having an average molecular structure as shown in Table 1 was used.

[0042]

[Table 1]

Preparation Example 1 An interface containing 200 parts of amino-functional polyorganosiloxane S-1 and 5 parts of a 70% aqueous solution of polyoxyethylene (9) lauryl ether and polyoxyethylene (40) octylphenyl ether. Blended with the activator mixture to obtain a premix. Then the first 5.0 parts of water was slowly added to the mixture. The resulting mixture was stirred for 15 minutes to give a homogeneous, good emulsion. Then the remaining 500 parts of water were added more quickly than the first part of the water. The obtained emulsion had an average particle size of the oil phase of 0.06 μm and had a bluish white opaque appearance.

The pH of the system was adjusted to 7.5 by adding 3.5 parts of 0.5% acetic acid aqueous solution to this emulsion. The resulting emulsion is translucent and is 0.018μ
It had an average particle size of m and a solids content of 28%. Addition of glycerin (0.5%) to this emulsion increased transparency. Then, as a biocide, Dawicil 200 (trade name, Dow Chemical Company, chloride-1
-(3-chloroallyl) -3,5,7-triaza-1-
0.5 parts of azonia adamantane) was added and stirred to obtain a translucent microemulsion E-1 according to the present invention. The average particle size of the oil phase of the finally obtained microemulsion was 0.018 μm. Japan Precision Optics Co., Ltd.
When the light transmittance of the microemulsion was measured using a micro turbidimeter manufactured by Japan, it was 97%.

Preparation Example 2 The procedure of Preparation Example 1 was repeated except that S-2 was used as the amino-functional polyorganosiloxane and 2.1 parts of acetic acid was added, and the average particle size of the oil phase was 0.019 μm. Translucent microemulsion E- according to the invention with a transmission of 97%
2 was obtained.

Preparation Example 3 The same procedure as in Preparation Example 1 except that S-3 was used as the amino-functional polyorganosiloxane and 8.4 parts of acetic acid was added, and the average particle size of the oil phase was 0.011 μm. Translucent microemulsion E-according to the invention with a transmittance of 99%
3 was obtained.

Preparation Example 4 The procedure of Preparation Example 1 was repeated except that S-4 was used as the amino-functional polyorganosiloxane and 1.3 parts of acetic acid was added, and the average particle size of the oil phase was 0.025 μm. Translucent microemulsion E- according to the invention with a transmission of 96%
4 was obtained.

Preparation Example 5 The procedure of Preparation Example 1 was repeated except that S-5 was used as the amino-functional polyorganosiloxane and 0.9 part of acetic acid was added, and the average particle size of the oil phase was 0.030 μm. Semi-transparent microemulsion E- according to the invention with a transmission of 95%
5 was obtained.

Preparation Example 6 The procedure of Preparation Example 1 was repeated except that S-6 was used as the amino-functional polyorganosiloxane and 2.0 parts of acetic acid was added, and the average particle size of the oil phase was 0.015 μm. A translucent microemulsion E-6 according to the invention with a transmission of 98% was obtained.

Preparation Example 7 350 parts of amino-functional polyorganosiloxane S-1 was taken, to which 40 parts of polyoxyethylene (9) lauryl ether and 20 parts of 70% aqueous solution of polyoxyethylene (40) octylphenyl ether were added. And heated to 40 ° C. with stirring. With continued stirring, 60 parts of water was slowly added to this mixture. Then, this was passed through a colloid mill and put into 400 parts of water for emulsification.
After stirring this for 10 minutes, water was further added to adjust the solid content to 35%, and the emulsion M- for comparison was used.
1 was prepared. The obtained emulsion has a light transmittance of 0.
It was 1% white and opaque, and the average particle size of the oil phase was 0.5 μm.

Preparation Example 8 50 parts of polydimethylsiloxane having a viscosity of 500 cSt at 25 ° C. was mixed with 18 parts of carnauba wax, 3 parts of montan wax and 125 parts of paraffin wax 125P, and further 10 parts of sorbitan monolaurate and polyoxyethylene. (32) After adding 10 parts of monostearate and heating to 120 ° C. to completely dissolve it, 90 ° C.
Cooled down. To this, add 200 parts of water at 90 ° C,
The mixture was emulsified using a homogenizer and allowed to cool to room temperature to prepare an emulsion M-2 for compounding.

Preparation Example 9 40 parts of beeswax, 25 parts of paraffin wax 145P,
Oleic acid (10 parts), glycerin (10 parts) and polyoxyethylene (6) nonylphenyl ether (15 parts) at 90 ° C.
Heated to melt. To this, 200 parts of water at 90 ° C. was added, emulsified using a homogenizer, and allowed to cool to room temperature to prepare a wax emulsion M-3 for compounding.

Preparation Example 10 20 parts of polyoxyethylene (9) nonylphenyl ether was added to 80 parts of polydimethylsiloxane having a viscosity of 500 cSt at 25 ° C., and the mixture was heated to 50 ° C. and uniformly mixed. To this, 200 parts of water at 50 ° C. was added, emulsified using a homogenizer, and allowed to cool to room temperature to prepare a silicone oil emulsion M-4 for compounding.

Examples 1 to 10 and Comparative Examples 1 to 3 Using the emulsions obtained in Preparation Examples 1 to 10, one or two emulsions and water were uniformly mixed with the composition shown in Table 2. , A water repellent polish was prepared.

The obtained water-repellent polish was evaluated as follows. That is, using a tissue paper on each surface of a test piece having a size of 75 mm × 100 mm × 1.5 mm obtained by cutting from a body coating plate of an automobile (manufactured by Toyota Motor Corporation, Mark II new car) A water-repellent polish was evenly applied, left at 25 ° C. for 5 minutes, immersed in water for 30 minutes, and wiped off with water with a tissue paper. Using this surface-treated test piece, the contact angle was measured using a surface tensiometer (Kyowa Scientific Co., Ltd., CA-A type). Further, immersion in water was carried out for 24 hours, and the contact angle was similarly measured. The appearance and gloss of the coated surface after immersion for 24 hours were visually evaluated. The results are shown in Table 2.

[0056]

[Table 2]

Claims (5)

[Claims] 1. (A) Amino-functional polyorganosiloxane is blended with a surfactant to form a premix; (B) A portion of water is added to the premix and stirred to form a primary mixture. (C) adding residual water to the primary mixture to form a secondary mixture; and (D) adding acid to the secondary mixture to form p.
A water-repellent polish containing, as a main agent, a microemulsion of an amino-functional polyorganosiloxane obtained by converting H to 4 to 10 and converting at least a part of the above-mentioned amino-functional polyorganosiloxane into a salt. 2. The amino-functional polyorganosiloxane has an amino group content of 0.1 to 3 meq / g.
Water-repellent polish as described. 3. The water-repellent polish according to claim 1, wherein the oil phase of the microemulsion has an average particle size of 0.005 to 0.05 μm. 4. The water repellent polish according to claim 1, wherein the amino-functional polyorganosiloxane has a silicon functional group. 5. The water-repellent polish according to claim 1, wherein the pH in (D) is more than 7 and 10 or less, and the amino-functional polyorganosiloxane partially forms a salt.