JP2003206478A - Aqueous water-repellent coating agent for hard surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous water-repellent coating agent for hard surfaces having excellent adhesion to the hard surfaces, above all, vehicular surfaces, especially car body surface of automobiles, uniformly applicable without requiring a finish treatment such as wiping up, capable of forming a film having excellent water repellency, having excellent stability, suppressing the formation of gelled materials or solid materials and preventing clogging of pipes in a coating apparatus such as a car washer for a long period or further without leaving a coating mark. <P>SOLUTION: This water-repellent coating agent is obtained by including (A) an amino-modified silicone oil and (B) a stabilizer composed of at least one kind of modified silicone selected from an ammonium salt-modified silicone, a polyether-modified silicone, an esterified substance of the polyether-modified silicone, an aminopolyether-modified silicone and an amidopolyether-modified silicone. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is suitable for a coating agent for imparting water repellency to a hard surface such as a hard substrate surface, especially for vehicles, aircraft or ships, and particularly for vehicles such as automobiles. The present invention relates to a water-repellent coating agent for hard surfaces, which is suitable for car washing with a car wash machine such as a gate type car wash machine.

[0002]

2. Description of the Related Art Conventionally, as a water-repellent coating agent for imparting water repellency to the surface of a vehicle, especially the surface of a car body, an inert silicone oil represented by alkylpolysiloxane such as dimethylpolysiloxane and carnauba wax or A wax agent in combination with an inert ester wax represented by beeswax is often used. However, this product is excellent in initial water repellency and glossiness, but in order to fully bring out its effect, finishing treatment such as wiping by hand is required, and the work is unavoidably complicated. It was

Further, for car washing by a gate type car washing machine, it comprises an emulsion containing silicone, wax and a cationic surfactant (Japanese Patent Laid-Open No. 63-112249).
Also known is an emulsion containing a wax, a silicone and an anionic surfactant (JP-A-63-227680). These are also towels after passing through a car washing machine and a drying process. It was necessary to wipe it off with something like that.

On the other hand, a water-repellent coating agent containing an amino-modified silicone oil and a nonionic surfactant has been proposed as a material which attaches importance to the adhesion to the vehicle body surface, which improves water repellency. If you use a different formulation, the stability will decrease,
Amino-modified silicone oil polymerizes in the presence of water, silanol, carbon dioxide gas, etc. due to its reactivity due to its amino group to form a gel-like substance or a solid substance, and especially when used in a car wash machine such as a gate type car wash machine. In a short period of time, such a gel-like substance or a solid substance accumulates in the pipe and causes a problem of clogging the pipe, and when it is applied to the surface of the vehicle body, the application mark is left on a part of the vehicle body such as a door part. "Kata" remains in the form of streaks, and it is difficult to finish it evenly even if it is wiped off with a towel etc., which reduces workability, and the gloss is insufficient. And it wasn't quite satisfactory. Further, in order to prevent the trouble of the pipe clogging, it is possible to use a large amount of a nonionic surfactant to enhance the stability, but in that case, the adhesion of the water repellent coating agent to the vehicle body surface is lowered. It was inevitable that the water repellency would drop, such as dropping.

[0005]

The present invention overcomes the drawbacks of the conventional water repellent coating agents, and has excellent adhesion to hard surfaces, especially to vehicle surfaces, especially to car body surfaces.
It does not require finishing treatment such as wiping, can be applied uniformly, can form a coating film with excellent water repellency, and has excellent stability, and can be used as a gel or solid substance (hereinafter these are referred to as precipitates). To provide a water repellent coating agent for hard surfaces that can prevent the occurrence of such substances and can prevent clogging of pipes in coating devices such as car wash machines for a long period of time, as well as a water repellent coating agent for hard surfaces that does not leave application marks. It was made for the purpose.

[0006]

The inventors of the present invention have conducted various studies to develop a water-repellent coating agent for hard surfaces having the above-mentioned preferable properties, and as a result, contain a specific silicone oil and a specific stabilizer. It was found that an aqueous liquid, and further a water-repellent coating agent composed of a mixture of a surfactant and / or an aqueous solvent, is suitable for the purpose, and the present invention has been completed based on this finding. .

That is, the present invention is as follows. (1) (A) amino-modified silicone oil, and (B)
Ammonium salt modified silicone, polyether modified silicone, esterified product of polyether modified silicone,
A water-repellent coating agent having excellent stability, comprising at least one modified silicone selected from aminopolyether-modified silicone and amidepolyether-modified silicone. (2) The water-repellent coating agent for aqueous hard surfaces according to (1) above, which further contains (C) a surfactant. (3) The water-repellent coating agent for an aqueous hard surface according to (2), wherein the surfactant as the component (C) is at least one selected from a nonionic surfactant and an amphoteric surfactant. (4) The above (1) further containing (D) an aqueous solvent,
The water-repellent coating agent for water-based hard surfaces according to (2) or (3). (5) The water-repellent coating agent for an aqueous hard surface according to the above (4), wherein the aqueous solvent of the component (D) is isopropyl alcohol. (6) (A) Amino-modified silicone oil 0.1-10
%, (B) Ammonium salt-modified silicone, polyether-modified silicone, esterified product of polyether-modified silicone, aminopolyether-modified silicone, and at least one modified silicone selected from the group consisting of stable silicones Agent 0.1
10 mass%, 0.1-7 mass% of at least one kind of surfactant selected from (C ') nonionic surfactant and amphoteric surfactant, and 1-10 mass% of (D') isopropyl alcohol. A water-repellent coating agent for an aqueous hard surface, characterized by comprising an aqueous liquid containing the above, having excellent stability, and having no coating trace after being applied to the hard surface and washed with water. (7) The amino-modified silicone oil of component (A) has an amino equivalent of 800 to 10,000 and a kinematic viscosity of 50 to 3000.
The water-repellent coating agent for aqueous hard surfaces according to any one of (1) to (6) above, which has a cSt range. (8) In the above (1) to (7), the esterified product of the polyether-modified silicone in the stabilizer of the component (B) is at least one selected from fatty acid ester type and betaine ester type. The water-repellent coating agent for aqueous hard surfaces according to any one of claims. (9) The water-based hard surface repellent according to any one of (1) to (8) above, wherein the polyether-modified silicone contains an oxyalkylene group, a mixed oxyalkylene group, a polyoxyalkylene group, or a mixed polyoxyalkylene group. Water coating agent. (10) The water-repellent coating agent for an aqueous hard surface according to any one of the above (1) to (9), which further contains (D ″) glycerin in an amount not exceeding 20% by mass. The water-repellent coating agent for water-based hard surfaces according to any one of (1) to (10) above, which is for a ship (12) Any one of (1) to (11) above used in a car wash by a car wash machine. (13) The water-repellent coating agent for water-based hard surfaces according to (12), wherein the car wash is a gate-type car wash or a spray car wash.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The amino-modified silicone oil used as the component (A) in the water repellent coating agent of the present invention has an amino equivalent of 800 to 10,000,
Among them, 1,000 to 4,000, particularly 1,200 to 3,
000 is preferable, and the kinematic viscosity is 50.
To 3000 cSt, especially 250 to 2000 cSt, especially 400 to 1,500 cSt are preferred, and the amino equivalent is 1,300 to 2,500.
And a kinematic viscosity of 500 to 1,200c
Those in the range of St are preferable.

If the kinematic viscosity is less than 50 cSt, it is difficult to obtain sufficient water repellency, and if it exceeds 3000 cSt, the viscosity is too high and it is difficult to apply uniformly, and coating marks tend to remain as marks. Further, if the amino equivalent is less than 800, it is difficult to obtain sufficient stability as an aqueous system, and if it exceeds 10,000, the adhesion to the hard surface of the vehicle body is weakened and sufficient water repellency is obtained. It gets harder.

As the base silicone oil of the amino-modified silicone oil, alkylpolysiloxane is preferable, and as the alkylpolysiloxane, di-lower alkylpolysiloxane such as dimethylpolysiloxane, diethylpolysiloxane, dipropylpolysiloxane and dibutylpolysiloxane, Of these, dimethylpolysiloxane is preferable.

The stabilizer used as the component (B) in the water repellent coating agent of the present invention is a specific modified silicone, that is, an ammonium salt modified silicone, a polyether modified silicone, an esterified product of a polyether modified silicone, an aminopolyether modified silicone. And amide polyether modified silicone. These may be used alone or in combination of two or more. Here, the polyether-modified silicone preferably contains an oxyalkylene group, a mixed oxyalkylene group, a polyoxyalkylene group or a mixed polyoxyalkylene group, and further, these groups have 2 to 4 carbon atoms in the alkylene moiety. It is preferable that, among them, an oxyethylene group as an oxyalkylene group, an oxypropylene group, an oxyethylene-oxypropylene group as a mixed oxyalkylene group, an oxyethylene-oxypropylene-oxyethylene group, and a polyoxyalkylene group. A polyoxyethylene group and a polyoxypropylene group are preferable, and a mixed polyoxyalkylene group is preferably a polyoxyethylene-polyoxypropylene group and a polyoxyethylene-polyoxypropylene-polyoxyethylene group. As the esterified product of the polyether-modified silicone, a fatty acid ester-type or betaine ester-type compound, that is, a compound in which the hydroxyl group of the polyether portion of the polyether-modified silicone is esterified with a fatty acid or betaine (in a broad sense) is preferable. Examples of this fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, coconut oil fatty acid, palm oil fatty acid, tallow fatty acid and the like, and examples of betaine include glycine betaine, alanine betaine and the like. Can be mentioned. The stabilizer as the component (B) suppresses the generation of precipitates for a long period of time. It is speculated that this is because the reactivity of the amino-modified silicone oil of the component (A) is suppressed by the stabilizer of the component (B).

The component (C) surfactant, which is optionally used in the water-repellent coating agent of the present invention, disperses or solubilizes the amino-modified silicone oil of component (A) in an aqueous medium, and at the same time provides a water-repellent coating. When the agent is applied, it exhibits an action of spreading it evenly on the coated surface, and as such a surfactant, a nonionic surfactant or an amphoteric surfactant is preferable.

The nonionic surfactant is not particularly limited, but is preferably an alkylolamide such as fatty acid diethanolamide; an alkylamine oxide such as lauryldimethylamine oxide or dihydroxyethyllaurylamine oxide; a polyoxyethylene alkyl ether, Examples thereof include polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine.

The amphoteric surfactant is not particularly limited, but preferably alkylbetaine such as lauryldimethylaminoacetic acid betaine and amidopropylbetaine such as fatty acid amidepropylbetaine are mentioned.

These surfactants may be used alone or in combination of two or more. Among these surfactants, alkylolamide, alkylamine oxide, polyoxyethylene alkyl ether,
Alkyl betaines, amidopropyl betaines, especially alkylolamides are preferred. Examples of commercially available products of the predetermined surfactant used as the component (C) include Amizole CDE and Amizole LDE manufactured by Kawaken Fine Chemicals, and Aromox DMC-W manufactured by Lion.
Aromox DM12D-W, Aromox DM14D
-N, Enagicor C30-B and Enagicor L-3
0B, Kaohsha's Amchtol 20BS, Amchtol 24B and the like.

The aqueous solvent of the component (D), which is optionally used in the water repellent coating agent of the present invention, assists the action of the above-mentioned surfactant, suppresses the foaming by the surfactant, and immediately exhibits water repellency. As such an aqueous solvent, hydrophilic ones such as alcohol, especially isopropyl alcohol and glycerin are preferable.

In the water-repellent coating agent of the present invention, if necessary, glycerin as the component (D) is further promoted to prevent the situation that coating marks remain after application and washing with water and the finishing work is impaired. It is used to

The water repellent coating agent of the present invention mainly contains water in addition to the above composition components. When the aqueous solvent of the component (D) is also contained, the aqueous solvent is contained in a small amount with respect to water, for example, 3
The amount is preferably in the range of not exceeding 0% by mass.

The preferred content ratios of the above composition components in the water repellent coating agent of the present invention will be described below. The amino-modified silicone oil as the component (A) is preferably selected in the range of 0.1 to 10% by mass, especially 0.5 to 5% by mass.
If this proportion is less than 0.1% by mass, the water-repellent effect will not be sufficiently exhibited, and if it exceeds 10% by mass, the stability as an aqueous system will not be good and coating unevenness will occur, making uniform finishing after coating difficult. As a result, white marks are likely to remain on the hard surface, especially on the vehicle body, especially on the vehicle body of the automobile after the water-repellent coating treatment, which often requires wiping work.

Regarding the stabilizer of the component (B),
It is preferable to select in the range of 0.1 to 10% by mass, and particularly 0.5 to 5% by mass. If this ratio is less than 0.1% by mass, the effect of addition, that is, the effect of suppressing the generation of precipitates, is not sufficient, and if it exceeds 10% by mass, the water repellency tends to decrease.

Further, when the surfactant as the component (C) is contained, it is preferable to select the surfactant in the range of 0.1 to 7% by mass, especially 0.5 to 5% by mass. If this ratio is less than 0.1% by mass, the effect of dissolution / dispersion in an aqueous system will not be sufficiently exerted, and if it exceeds 7% by mass, the wettability will increase and the water-repellent effect tends to be impaired.

Furthermore, when the aqueous solvent of the component (D) is contained, the content ratio is preferably selected in the range of 1 to 30% by mass, preferably 2 to 25% by mass. Among them, alcohol as the aqueous solvent, In particular, when isopropyl alcohol is used, its content is particularly preferably selected in the range of 1 to 10% by mass, preferably 2 to 5% by mass. If the content ratio is too low, the effect of improving the solubility / dispersibility is not sufficiently exerted, and if it is too high, the stability is impaired, and separation or layer separation occurs.

When glycerin is contained as the aqueous solvent, the content ratio should be selected not to exceed 20% by mass, preferably 5 to 15% by mass.
If this ratio is less than 5% by mass, the effect of preventing coating defects and coating unevenness will not be sufficiently exhibited, and if it exceeds 20% by mass, the wettability will increase and the water repellent effect will tend to be impeded.

The water-repellent coating agent of the present invention is preferably, for example, 20 parts by weight of component (B) per 100 parts by weight of component (A).
500 parts by mass, especially 30 to 300 parts by mass, (C) component 20 to 500 parts by mass, especially 30 to 300 parts by mass, in particular, further (D) component to (A) component 100 parts by mass. 30 to 1000 parts by mass, 5 in particular
Examples thereof include those added in the range of 0 to 800 parts by mass.

The water-repellent coating agent of the present invention which does not leave a coating trace is (A) 0.1 to 10% by mass of amino-modified silicone oil, (B) ammonium salt-modified silicone, polyether-modified silicone, polyether. Stabilizer consisting of at least one modified silicone selected from esterified products of modified silicone, aminopolyether-modified silicone and amidepolyether-modified silicone, 0.1-10% by mass, (C ') nonionic surfactant And an aqueous liquid containing 0.1 to 7% by mass of at least one surfactant selected from the group of amphoteric surfactants and 1 to 10% by mass of (D ′) isopropyl alcohol. In particular, in this product, the product further containing (D ″) glycerin in an amount not exceeding 20% by mass has a further coating mark. This is preferable because it does not remain.
(A) Amino-modified silicone oil 0.5 to 5% by mass,
(B) Stabilizer comprising at least one modified silicone selected from ammonium salt modified silicone, polyether modified silicone, esterified product of polyether modified silicone, aminopolyether modified silicone and amide polyether modified silicone. 5 to 5% by mass, at least one surfactant selected from the group consisting of (C ′) nonionic surfactant and amphoteric surfactant 0.5 to 5
Mass%, (D ') isopropyl alcohol 2-5 mass%
The water-soluble liquid may be a water-soluble liquid, and in particular, a water-based liquid containing 5 to 15% by mass of (D ″) glycerin is preferable because it leaves no trace of coating. A particularly preferable coating agent is (B) component 2 per 100 parts by weight of (A) component.
0-500 parts by mass, especially 30-300 parts by mass, (C
′) Component 20 to 500 parts by mass, especially 30 to 300 parts by mass, (D ′) component or a combination of (D ′) component and (D ″) component 30 to 1000 parts by mass, especially 50 to 800 parts by mass. There are some.

The water-repellent coating agent of the present invention contains, if necessary, a diluting solvent, a stabilizing solvent, an antifreezing agent, an anticorrosive agent, an antiseptic agent, an abrasive agent, and an ultraviolet absorbing agent as long as the object of the present invention is not impaired. A coloring agent such as an agent or a dye can be blended. Examples of rust preventives include benzotriazole and dicyclohexyl ammonium nitrate. Examples of preservatives include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3
-On and so on.

To prepare the water repellent coating agent of the present invention, the required components may be mixed in water. Further, first, an amino-modified silicone oil, a stabilizer and water are emulsified with a surfactant, preferably a nonionic surfactant and / or an amphoteric surfactant in the presence of an aqueous solvent, preferably isopropanol or glycerin with it. Alternatively, after being made into a microemulsion, water may be further added to obtain an appropriate concentration.

The water repellent coating agent of the present invention is preferably applied to a hard surface, for example, a hard substrate surface. Examples of the hard surface include glass, metal such as stainless steel and steel, plastic, a surface of a coated or plated product of metal, plastic, wood, and the like. Specifically, walls inside and outside the house,
Floors, ceilings, roofs, kitchen stoves, ventilation fans, furniture, various industrial products, and all other dirty hard surfaces, especially automobiles,
Examples thereof include vehicles such as railway vehicles, aircraft, ships, and particularly car bodies.

The water-repellent coating agent of the present invention is preferably applied to an automatic application method for a vehicle surface, particularly an automatic application method using a car wash machine such as a gate type car wash machine, a continuous gate type car wash machine or a spray car wash machine. Used. In such a vehicle water repellent coating method using a car wash machine, in order to advantageously use the water repellent coating agent of the present invention, an aqueous wax containing a cationic surfactant is previously applied to the vehicle before the application. Is good.

As the aqueous wax containing a cationic surfactant, those conventionally used are used. Examples of such an aqueous wax include paraffin wax, montan wax, carnauba wax, bees wax, rice wax and liquid wax. Paraffin, petroleum solvent,
Examples thereof include those containing a combination of compounding ingredients such as a cationic surfactant and a water-soluble solvent, and preferably containing paraffin wax, dialkyldimethylammonium chloride, α-olefin, ethylene glycol, and aliphatic amine acetate. Water-based waxes, especially paraffin wax and dialkyldimethylammonium chloride (where the alkyl group has 16 carbon atoms)
~ 18), α-olefin (C16-
18), ethylene glycol, aliphatic amine acetate (wherein the aliphatic group has 16 to 18 carbon atoms)
The content of these compounding components is preferably 0.5 to 8% by mass of paraffin wax, and dialkyldimethylammonium chloride preferably has an alkyl group of 16 to 18 carbon atoms.
3 to 15% by mass, α-olefin, preferably 16 to 18 carbon atoms, 2 to 10% by mass, ethylene glycol 5 to 15% by mass, aliphatic amine acetate, preferably the aliphatic group has carbon atoms. 1 to 10 which is 16 to 18
It is in the range of mass%, and water is usually used in addition to these compounding ingredients.

When the water-repellent coating agent of the present invention is used in a gate type car wash machine, an aqueous wax containing such a cationic surfactant is applied in advance and the water-repellent coating agent is applied at the final application step of the car wash step. Treatment with a water repellent coating agent is preferable because it provides a good appearance and an excellent water repellent effect.

The water-repellent coating agent of the present invention is diluted 20 to 200 times by the ejector suction or pump in this step and spray-coated on the coated surface. The water-repellent coating agent of the present invention sufficiently adheres to and is water-repellent on the coated surface only by spray coating.

As an example of a method of washing a vehicle by using the water repellent coating agent of the present invention in a gate type car wash machine, a gate type traveling frame is provided which travels back and forth in the front-rear direction across a stopped or moving vehicle. In a two-way car wash using a gate-type car washer, the water is sprayed onto the car body surface from the rinse device provided on the gate-shaped traveling frame to clean the car body surface at the time of one trip, and the foam agent is applied at one return. The water repellent coating agent of the present invention is used to polish the vehicle body surface with a rotating brush provided on the frame while appropriately diluting it with a coating device provided on the frame to apply it to the vehicle body surface in a foaming state. Is applied to the vehicle body surface by the coating device provided on the frame, and subsequently, fresh water is sprayed from the rinse device to the vehicle body surface, and the excess water repellent coating agent on the vehicle body surface is washed off and rinsed. Dried by blower That way, and the like.

[0034]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 Amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 500 cSt, amino equivalent 18)
00) 5 parts by mass of TSF4452 (trade name, manufactured by GE Toshiba Silicone, polyether modified silicone (PO /
EO = 50/50), 900 cSt) 5 parts by mass, amizole CDE (trade name, manufactured by Kawaken Fine Chemical Co., coconut oil fatty acid diethanolamide) 5 parts by mass, isopropanol 5 parts by mass, glycerin 10 parts by mass, benzotriazole 0. A water repellent coating agent was prepared by adding 1 part by mass, 5-chloro-2-methyl-4-isothiazolin-3-one (0.1 part by mass) and water (75 parts by mass).

Example 2 Amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 1100 cSt, amino equivalent 1
700) 2.5 parts by mass of KF615A (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., poly (oxyethylene-oxypropylene) methylpolysiloxane, 125 cSt, HLB1
4, cloud point 65 ° C) 5 parts by mass, Aromox DMC-W
(Trade name, manufactured by Lion Corporation, coconut oil alkyldimethylamine oxide) 7 parts by mass, isopropanol 3 parts by mass, glycerin 5 parts by mass, benzotriazole 0.1 part by mass,
A water repellent coating agent was prepared by adding 0.1 parts by mass of 5-chloro-2-methyl-4-isothiazolin-3-one and 82.5 parts by mass of water.

Example 3 Amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 800 cSt, amino equivalent 15)
00) 3 parts by mass of BY16-837 (trade name, Toray.
Aminopolyether-modified silicone, 300 cSt, amino equivalent 4000) 5 parts by mass, polyoxyethylene alkyl (C16-C18) ether 9 parts by mass, isopropanol 8 parts by mass, glycerin 15
Parts by mass, benzotriazole 0.1 parts by mass, 2-methyl-4-isothiazolin-3-one 0.1 parts by mass, water 65
A water repellent coating agent was prepared by adding parts by mass.

Example 4 Amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 1000 cSt, amino equivalent 1
600) 3 parts by mass, BY16-891 (trade name, manufactured by Toray Dow Corning, amide polyether modified silicone, 750 cSt, amino equivalent 4000) 5 parts by mass,
Amizole LDE (trade name, manufactured by Kawaken Fine Chemical Co., Ltd., lauric acid diethanolamide) 3 parts by mass, isopropanol 5 parts by mass, benzotriazole 0.1 parts by mass, 2-methyl-4-isothiazolin-3-one 0.1
A water repellent coating agent was prepared by adding 9 parts by weight of water and 91 parts by weight of water.

Example 5 Amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 800 cSt, amino equivalent 15)
00) 3 parts by mass, 5 parts by mass of Tegoprene 6922 (trade name, modified silicone manufactured by Gold Schmidt), 10 parts by mass of Enadicol C-30B (trade name, manufactured by Lion, palm oil fatty acid amide propyl betaine), 10 parts of isopropanol A water repellent coating agent was prepared by adding 10 parts by mass of glycerin, 0.1 part by mass of benzotriazole, 0.1 part by mass of 2-methyl-4-isothiazolin-3-one, and 67 parts by mass of water.

Example 6 Amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 500 cSt, amino equivalent 18)
00) 3 parts by mass, tegoprene 6922 5 parts by mass, isopropanol 10 parts by mass, glycerin 10 parts by mass, benzotriazole 0.1 part by mass, 2-methyl-4-isothiazolin-3-one 0.1 part by mass, water 67 A water repellent coating agent was prepared by adding parts by mass.

Example 7 Amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 500 cSt, amino equivalent 18)
00) 3 parts by mass, tegoprene 6922 5 parts by mass, isopropanol 10 parts by mass, benzotriazole 0.1
A water repellent coating agent was prepared by adding 0.1 part by mass of 2-methyl-4-isothiazolin-3-one and 67 parts by mass of water.

Example 8 Amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 500 cSt, amino equivalent 18)
00) 3 parts by mass, SH3746 (trade name, manufactured by Toray Dow Corning, polyether modified silicone, 120
cSt) 5 parts by mass, glycerin 10 parts by mass, benzotriazole 0.1 part by mass, 2-methyl-4-isothiazolin-3-one 0.1 part by mass, and water 67 parts by mass to prepare a water repellent coating agent. .

Comparative Example 1 15 parts by weight of amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 20,000 cSt, amino equivalent 1800), 5 parts by weight of amizole CDE, 5 parts by weight of isopropanol, 5 parts by weight of glycerin,
A water repellent coating agent was prepared by adding 0.1 part by mass of benzotriazole, 0.1 part by mass of 5-chloro-2-methyl-4-isothiazolin-3-one and 83 parts by mass of water.

Comparative Example 2 Amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 1100 cSt, amino equivalent 1
700) 2.5 parts by mass, polyoxyethylene alkyl (C16-C18) ether 15 parts by mass, isopropanol 5 parts by mass, glycerin 10 parts by mass, benzotriazole 0.1 parts by mass, 5-chloro-2-methyl-4 -Isothiazolin-3-one (0.1 parts by mass) and water (67.5 parts by mass) were added to prepare a water repellent coating agent.

Comparative Example 3 Amino-modified silicone oil (amino-modified dimethylpolysiloxane, kinematic viscosity 800 cSt, amino equivalent 15
00) 3 parts by mass, Enajicol C-30B 1 part by mass,
25 parts by mass of isopropanol, 10 parts by mass of glycerin,
A water repellent coating agent was prepared by adding 0.1 part by mass of benzotriazole, 0.1 part by mass of 2-methyl-4-isothiazolin-3-one and 62 parts by mass of water.

(A) Stability Each water repellent coating agent sample of each Example and Comparative Example was diluted with water so that the concentration of itself was 5% by mass, and this diluted sample solution was subjected to the following test. did. In other words, set a sample solution circulation line with piping installed in a storage tank containing this sample solution, an ejector and a circulation pump similar to those used in gate-type car wash machines, and place the sample solution in this circulation line at room temperature at room temperature. After conducting a test in which the medium is circulated for 10 hours for a total of 50 hours for 5 days, the circulation line is disassembled, the deposits in the pipes and the ejector are visually observed, and the stability of each water repellent coating agent sample is evaluated according to the following criteria. did. ⊚: No change from before test ○: Very few precipitates △: Significant precipitates ×: Almost plugged with precipitates

(B) Uniform coating property Each water-repellent coating agent sample of each Example and Comparative Example was treated with water for 20 times.
Diluted twice, and using this diluted solution as a coating solution, 5 ml of it was uniformly applied onto a black coated plate by hand spraying in accordance with JIS K2236, washed with water, and naturally dried to prepare a water repellent coated plate. The presence or absence of coating marks of the coating agent on this water-repellent coated plate was visually observed and evaluated according to the following criteria. ◎: No coating marks are observed ○: Almost no coating marks are observed △: Some coating marks are recognized ×: The coating marks are clearly visible as white

(C) Water repellency Water was applied to the water repellent coated plate prepared in the same manner as above, and the contact angle of the attached water droplet was measured with a contact angle meter (CA-Z type, manufactured by Kyowa Interface Science Co., Ltd.). The evaluation criteria were as follows. The contact angle was the average of 5 measurements. ○: Greater than 105 ° △: 95 to 105 ° ×: Less than 95 °

[0049]

[Table 1]

From Table 1, the coating agent samples of each comparative example have drawbacks such as difficulty in uniform coating property, poor water repellency, poor stability, etc. It can be seen that the water coating agent sample is excellent in uniform coating property and stability, has good water repellency, and has a good overall balance of these properties.

[0051]

The water-repellent coating agent of the present invention has excellent adhesion to hard surfaces, especially to the surface of vehicles, especially to the body surface of automobiles,
It can be applied uniformly without requiring finishing treatment such as wiping, can form a coating film with excellent water repellency, and also has excellent stability and suppresses the generation of precipitates, and can be used in coating equipment such as car wash machines. It is possible to prevent clogging of the pipes for a long period of time, and in addition, in the case of the formulation described in the above (6) to (10), in particular, the formulation described in the above (10), in addition to this, a remarkable effect such as no coating trace remains. In particular, it is preferably used for an automatic coating method, especially for a water repellent coating treatment using an automatic car washing machine such as a gate type car washing machine.

Claims (13)

[Claims] 1. Selected from (A) amino-modified silicone oil and (B) ammonium salt-modified silicone, polyether-modified silicone, esterified product of polyether-modified silicone, aminopolyether-modified silicone and amide-polyether-modified silicone. A water-repellent coating agent for an aqueous hard surface having excellent stability, which comprises a stabilizer composed of at least one modified silicone. 2. The water-repellent coating agent for aqueous hard surfaces according to claim 1, which further comprises (C) a surfactant. 3. The water-repellent coating agent for an aqueous hard surface according to claim 2, wherein the surfactant as the component (C) is at least one selected from nonionic surfactants and amphoteric surfactants. 4. The water-repellent coating agent for aqueous hard surfaces according to claim 1, 2 or 3, which further comprises (D) an aqueous solvent. 5. The water-repellent coating agent for an aqueous hard surface according to claim 4, wherein the aqueous solvent of the component (D) is isopropyl alcohol. 6. (A) Amino-modified silicone oil
1-10% by mass, (B) at least one modified silicone selected from ammonium salt-modified silicone, polyether-modified silicone, esterification product of polyether-modified silicone, aminopolyether-modified silicone and amide-polyether-modified silicone 0.1-10% by mass of a stabilizer consisting of (C ′) 0.1-7% by mass of at least one surfactant selected from (C ′) nonionic surfactants and amphoteric surfactants, (D ′ ) It is composed of an aqueous liquid containing 1 to 10% by mass of isopropyl alcohol, has excellent stability, and is applied to a hard surface and washed with water,
A water-repellent coating agent for water-based hard surfaces, which is characterized by leaving no traces of application. 7. The amino-modified silicone oil of component (A) has an amino equivalent of 800-10,000 and a kinematic viscosity of 50-.
The water-repellent coating agent for water-based hard surfaces according to any one of claims 1 to 6, which has a range of 3000 cSt. 8. The esterified product of the polyether-modified silicone in the stabilizer of the component (B) is at least one selected from fatty acid ester type and betaine ester type. The water-repellent coating agent for water-based hard surfaces according to Crab. 9. The water repellent for an aqueous hard surface according to claim 1, wherein the polyether-modified silicone contains an oxyalkylene group, a mixed oxyalkylene group, a polyoxyalkylene group or a mixed polyoxyalkylene group. Coating agent. 10. The water-repellent coating agent for an aqueous hard surface according to claim 1, which further contains (D ″) glycerin in an amount not exceeding 20% by mass. 11. The water-repellent coating agent for a water-based hard surface according to claim 1, which is for a vehicle, an aircraft or a ship. 12. The water-repellent coating agent for water-based hard surfaces according to claim 1, which is used in car washing with a car washing machine. 13. The water-repellent coating agent for an aqueous hard surface according to claim 12, wherein the car wash is a gate type car wash or a spray car wash.