KR20210149718A - Emulsion water repellent composition - Google Patents

Abstract

(A) 20-100 mass parts of specific amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group, (B) 0-80 mass parts of amino-modified silicone (however, the total amount of (A) component and (B) component) is 100 parts by mass), (C) 2 to 100 parts by mass of surfactant, (D) 1 to 25 parts by mass of a specific polyether-modified silicone, and (E) 10 to 2000 parts by mass of water. Accordingly, it is effectively used as a water repellent agent with excellent water repellency, and in particular, it gives good initial water repellency and water repellency durability to both the painted surface of a car and the glass surface, and also an emulsion that can give the glass surface the ability to eliminate glare due to oil film. A water repellent composition is provided.

Description

Emulsion water repellent composition

The present invention relates to an emulsion water repellent composition.

BACKGROUND ART Conventionally, in a coating imparting water repellency to a vehicle surface such as an automobile, an aqueous emulsion containing amino-modified polysiloxane as a main component has been applied. The amino-modified polysiloxane is a product in which a part of the methyl group of dimethylpolysiloxane is substituted with an aminoalkyl group or an aminoalkyl-substituted aminoalkyl group. When applied to a vehicle surface, the amino group is adsorbed to the vehicle surface, and durable water repellency compared to dimethylpolysiloxane performance can be given.

In the conventional method of use, it is used as an aqueous emulsion obtained by emulsifying amino-modified polysiloxane with a nonionic surfactant. In order to further increase the adsorption property of amino-modified polysiloxane, a coating agent by an aqueous emulsion using a specific cationic surfactant in combination is Patent Document 1 is disclosed in

In addition, Patent Document 2 discloses a gloss and water repellent composition obtained by emulsifying amino-modified polysiloxane and dimethylpolysiloxane with a nonionic surfactant each having a specific HLB, and mixing them.

The aqueous emulsion containing these amino-modified polysiloxanes as a main component is diluted tens to hundreds of times with water using a door-type automatic car wash, and spray applied, and is used to impart water repellency to vehicle surfaces such as automobiles.

In this case, not only the paint surface of the vehicle, but also performance provision to the glass surface, such as providing water repellency to the glass surface such as the windshield, and the absence of glare caused by the oil film, etc., is an important factor that is easily recognized by the driver.

However, in the prior art, although water repellency to the paint surface of a vehicle can be achieved, sufficient performance cannot be provided to a glass surface, and the improvement of the additional characteristic is calculated|required.

Japanese Patent Laid-Open No. H8-188745 Japanese Patent Laid-Open No. 2004-300387

The present invention has been made in view of the above circumstances, and is effectively used as a water repellent agent with excellent water repellency, in particular, it gives good initial water repellency and water repellency durability to both the painted surface of a car and the glass surface, and also prevents glare from the oil film on the glass surface. An object of the present invention is to provide an emulsion water repellent composition capable of imparting removal performance.

In order to achieve the above object, in the present invention,

The emulsion water repellent composition containing the following (A)-(E) component is provided. (A) amino-modified silicone, which is represented by the following general formula (1), has a viscosity of 30 to 2,000 mPa·s at 25° C., and has an amino group equivalent of 300 to 3,000 g/mol, end-blocked with a hydroxyl group or an alkoxy group: 20 to 100 parts by mass;

[Formula 1]

(Wherein, R ¹ is an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other, and R ² is each independently of the general formula (2): -R ⁴ -(NH-R ⁵ -) _p NH ₂ is a group represented by, in the formula (2), R ⁴ and R ⁵ are each independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1, R ³ is independently a hydroxyl group or, a group selected from a methoxy group and an ethoxy group, and a, b, c, d, and e are, respectively, 2≤a≤10, 10≤b≤1,000, 1≤c≤50, 0≤d≤5, 0≤ It is a real number that satisfies the range of e≤5),

(B) amino-modified silicone represented by the following general formula (3), having a viscosity of 50 to 5,000 mPa·s at 25° C., and having an amino group equivalent of 300 to 4,000 g/mol: 0 to 80 parts by mass (provided that (A) ) the total amount of the component and (B) component shall be 100 parts by mass),

[Formula 2]

(Wherein, R ¹ , R ² are the same as above, R ⁶ is a group independently selected from the options of R ¹ and R ² , and f, g, h, i, and j are each, 2≤f It is a real number satisfying the ranges of ≤10, 10≤g≤1,000, 0≤h≤50, 0≤i≤5, 0≤j≤5 However, when h=0 in the above formula (3), R ⁶ is a group selected from the options of R ^{2 ),}

(C) at least one surfactant selected from a nonionic surfactant, an anionic surfactant, a cationic surfactant, and a positive ionic surfactant: 2 to 100 parts by mass;

(D) polyether-modified silicone represented by the following average composition formula (4), having a viscosity of 10 to 10,000 mPa·s at 25°C, and having an HLB of 5 to 13: 1 to 25 parts by mass;

[Formula 3]

(Wherein, R ¹ is the same as above, and R ⁷ is each independently of the general formula (5): -R ⁹ -O-(C ₂ H ₄ O) _x -(C ₃ H ₆ O) _y -(C ₄ H ₈ O) _z -R ¹⁰ is a polyether group, in the formula (5), R ⁹ is a divalent organic group having 1 to 6 carbon atoms, R ¹⁰ is -H, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , and -(C=O)CH ₃ , wherein x, y and z are 5≤x≤30, 0≤y≤30 , is a real number satisfying the range of 0≤z≤30, R ⁸ is a group selected from the above R ¹ and R ⁷ or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , q and r are real numbers satisfying the ranges of 0≤q≤100 and 0≤r≤40, respectively, where R ⁸ is R ⁷ when r = 0);

(E) Water: 10 to 2,000 parts by mass.

This emulsion water repellent composition is effectively used as a water repellent agent with excellent water repellency, and in particular, it gives good initial water repellency and water repellency durability to both the painted surface of a car and the glass surface, and also gives the performance of eliminating glare due to oil film on the glass surface. it can be

It is preferable that this emulsion water repellent composition contains a nonionic surfactant.

When this emulsion water repellent composition contains a nonionic surfactant, it becomes a thing excellent in stability more.

The nonionic surfactant is preferably at least one selected from polyoxyalkylene alkyl ether and polyoxyethylene sorbitan fatty acid ester.

When the said nonionic surfactant is the said specific thing, this emulsion water repellent composition becomes a thing excellent in stability further.

It is preferable that the average particle diameter of the emulsified particles in this emulsion water repellent composition is 300 nm or less.

When the average particle diameter of the emulsified particles in this emulsion water repellent composition is 300 nm or less, this emulsion water repellent composition may turn into a bluish-white or transparent microemulsion in appearance.

It is preferable that this emulsion water repellent composition is for the paint surface of an automobile and a glass surface.

If this emulsion water repellent composition is for a car painted surface and a glass surface, it gives good initial water repellency and water repellency durability to both the painted surface and the glass surface of the car, and can also impart the performance of eliminating glare caused by oil film on the glass surface. becomes a thing

The emulsion water repellent composition of the present invention is effectively used as a water repellent agent with excellent water repellency, and in particular, it gives good initial water repellency and water repellency durability to both the painted surface of a car and the glass surface, and also has the performance to eliminate glare due to oil film on the glass surface. that can be given

As described above, it is effectively used as a water repellent agent with excellent water repellency, and in particular, it gives good initial water repellency and water repellency durability to both the painted surface of a car and the glass surface, and can also impart the performance of eliminating glare caused by oil film on the glass surface. The development of a water repellent composition has been required.

The present inventors, as a result of repeated intensive studies on the above problems, have found an amino-modified silicone emulsion composition containing a specific amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group, a surfactant, a specific polyether-modified silicone, and water, It is effectively used as a water repellent agent with excellent water repellency, and in particular, it is possible to impart good initial water repellency and water repellency durability to both the painted surface of a car and the glass surface, and also the performance to eliminate glare caused by oil film on the glass surface. The present invention was completed.

That is, this invention is an emulsion water repellent composition containing the following (A)-(E) component.

(A) amino-modified silicone, which is represented by the following general formula (1), has a viscosity of 30 to 2,000 mPa·s at 25° C., and has an amino group equivalent of 300 to 3,000 g/mol, end-blocked with a hydroxyl group or an alkoxy group: 20 to 100 parts by mass;

[Formula 4]

(Wherein, R ¹ is an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other, and R ² is each independently of the general formula (2): -R ⁴ -(NH-R ⁵ -) _p NH ₂ is a group represented by, in the formula (2), R ⁴ and R ⁵ are each independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1, R ³ is independently a hydroxyl group or, a group selected from a methoxy group and an ethoxy group, and a, b, c, d, and e are, respectively, 2≤a≤10, 10≤b≤1,000, 1≤c≤50, 0≤d≤5, 0≤ It is a real number that satisfies the range of e≤5),

(B) amino-modified silicone represented by the following general formula (3), having a viscosity of 50 to 5,000 mPa·s at 25° C., and having an amino group equivalent of 300 to 4,000 g/mol: 0 to 80 parts by mass (provided that (A) ) the total amount of the component and (B) component shall be 100 parts by mass),

[Formula 5]

(Wherein, R ¹ , R ² are the same as above, R ⁶ is a group independently selected from the options of R ¹ and R ² , and f, g, h, i, and j are each, 2≤f It is a real number satisfying the ranges of ≤10, 10≤g≤1,000, 0≤h≤50, 0≤i≤5, 0≤j≤5 However, when h=0 in the above formula (3), R ⁶ is a group selected from the options of R ^{2 ),}

(C) at least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants, and cationic surfactants: 2 to 100 parts by mass;

(D) polyether-modified silicone represented by the following average composition formula (4), having a viscosity of 10 to 10,000 mPa·s at 25°C, and having an HLB of 5 to 13: 1 to 25 parts by mass;

[Formula 6]

(Wherein, R ¹ is the same as above, and R ⁷ is each independently of the general formula (5): -R ⁹ -O-(C ₂ H ₄ O) _x -(C ₃ H ₆ O) _y -(C ₄ H ₈ O) _z -R ¹⁰ is a polyether group, in the formula (5), R ⁹ is a divalent organic group having 1 to 6 carbon atoms, R ¹⁰ is -H, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , and -(C=O)CH ₃ , wherein x, y and z are 5≤x≤30, 0≤y≤30 , is a real number satisfying the range of 0≤z≤30, R ⁸ is a group selected from the above R ¹ and R ⁷ or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , q and r are real numbers satisfying the ranges of 0≤q≤100 and 0≤r≤40, respectively, where R ⁸ is R ⁷ when r = 0);

(E) Water: 10 to 2,000 parts by mass.

Hereinafter, the present invention will be described in more detail.

( A) Amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group

(A) The amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group in the present invention is represented by the following average composition formula (1).

[Formula 7]

(A) The amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group has a viscosity of 30 to 2,000 mPa·s at 25°C. The viscosity is preferably 40 to 1,800 mPa·s, more preferably 50 to 1,500 mPa·s. When the viscosity is less than the lower limit, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorates. Moreover, when the said upper limit is exceeded, the stability of an emulsion water repellent composition worsens, and glare by an oil film will generate|occur|produce on a glass surface.

Further, (A) the amino-modified silicone terminal-blocked by a hydroxyl group or an alkoxy group has an amino group equivalent of 300 to 3,000 g/mol at 25°C. The amino group equivalent is preferably 350 to 2,800 g/mol, more preferably 400 to 2,500 g/mol. If the amino group equivalent is less than the lower limit, since there are too many amino groups, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorates. In addition, when the amino group equivalent exceeds the above upper limit, since there are too few amino groups, the hydrophilicity to be imparted as an amino-modified silicone is insufficient. Thereby, the stability of the emulsion water repellent composition deteriorates, and the glare by an oil film may generate|occur|produce on a glass surface.

In the formula (1), R ¹ is each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a tetradecyl group, an octadecyl group, etc. alkenyl groups such as an alkyl group, vinyl group, allyl group, 5-hexenyl group, and oleyl group, and aryl groups such as phenyl group, tolyl group and naphthyl group. Among these, a methyl group, a long-chain alkyl group, and a phenyl group are preferable. In particular, when weather resistance is required, a methyl group is preferable, and when water repellency is required, a methyl group and a long-chain alkyl group are preferable. In addition, in the case of imparting compatibility with organic compounds such as wax, it is preferable to use a long-chain alkyl group and a phenyl group. In addition, the compound of formula (1) may have a plurality of types of organic substituents as ^{R 1} , but in the case of combined use, the content of methyl groups relative to the total number of ^{substituents R 1} , R ² , and R ^{3 is 70% or more} desirable.

R ² is each independently a group represented by the general formula (2): -R ⁴ -(NH-R ⁵ -) _p -NH ₂ . In the formula (2), R ⁴ and R ⁵ each independently represent a divalent organic group having 1 to 6 carbon atoms, and particularly a divalent hydrocarbon group having 1 to 6 carbon atoms. For example, an alkylene group, an alkenylene group, an arylene group, etc. are mentioned. p is 0 or 1. As group represented by Formula (2), 2-aminoethyl group, 3-aminopropyl group, 6-aminohexyl group, N-(2-aminoethyl)-3-aminopropyl group, N-(3) -aminopropyl)-3-aminopropyl group, N-(2-aminoethyl)-6-aminohexyl group, etc. are mentioned. It is preferable to use a 3-aminopropyl group or an N-(2-aminoethyl)-3-aminopropyl group from the viewpoint of easiness of raw material availability and superiority in price.

R ³ is each independently a hydroxyl group or a group selected from a methoxy group and an ethoxy group. Moreover, as (A) component, the amino-modified silicone terminal-blocked by these hydroxyl groups or alkoxy groups can be used individually or in combination of 2 or more types. A hydroxyl group or a group selected from a methoxy group and an ethoxy group is adsorbed through a hydrogen bond with a SiOH group on the glass surface, (A) By immobilizing an amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group on the glass surface, durable water repellency on the glass surface can be given

a is a real number satisfying 2≤a≤10. When a is less than 2, the viscosity of the amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group becomes too high, and the stability of the emulsion water repellent composition deteriorates. In addition, when a exceeds 10, the viscosity of the amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group is too low to deteriorate the initial water repellency and water repellency durability of a film formed from the emulsion water repellent composition. Preferably, a=2.

b is a real number satisfying 10≤b≤1,000. If b is less than 10, the viscosity of the amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group becomes too low, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorates. In addition, when b exceeds 1,000, the viscosity of the amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group becomes too high, and the stability of the emulsion water repellent composition deteriorates. Preferably, it is good to satisfy the range of 20≤b≤800.

c is a real number satisfying 1≤c≤50. When c is less than 1, the amount of amino groups in the amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group is too small, and the water repellency durability of the film formed from the emulsion water repellent composition and the stability of the emulsion water repellent composition deteriorate, and glare due to the oil film occurs on the glass surface there is In addition, when c exceeds 50, the amount of amino groups in the amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group is too large, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorates.

d is a real number satisfying 0≤d≤5. When d exceeds 5, the viscosity of the amino-modified silicone whose terminal is blocked with a hydroxyl group or an alkoxy group becomes too high, the stability of the emulsion water repellent composition deteriorates, and glare by an oil film may occur on the glass surface. Preferably, d=0 is good.

e is a real number satisfying 0≤e≤5. When e exceeds 5, the viscosity of the amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group becomes too high, the stability of the emulsion water repellent composition deteriorates, and glare by an oil film may occur on the glass surface. Preferably, e=0 is good.

(B) amino-modified silicone

The amino-modified silicone (B) in the present invention is represented by the following average composition formula (3).

[Formula 8]

(B) The amino-modified silicone has a viscosity of 50 to 5,000 mPa·s at 25°C. The viscosity is preferably 55 to 4,500 mPa·s, more preferably 60 to 4,000 mPa·s. When the viscosity is less than the lower limit, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorates. Moreover, when the said upper limit is exceeded, the stability of an emulsion water repellent composition worsens, and glare by an oil film will generate|occur|produce on a glass surface.

Moreover, (B) amino-modified silicone has an amino group equivalent in 25 degreeC of 300-4,000 g/mol. The amino group equivalent is preferably 320 to 3,800 g/mol, and more preferably 330 to 3,600 g/mol. If the amino group equivalent is less than the lower limit, since there are too many amino groups, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorates. In addition, when the amino group equivalent exceeds the above upper limit, since there are too few amino groups, the hydrophilicity to be imparted as an amino-modified silicone is insufficient. Thereby, the stability of the emulsion water repellent composition deteriorates, and the glare by an oil film may generate|occur|produce on a glass surface.

(B) When the addition amount of amino-modified silicone makes the total amount of (A) component and (B) component 100 mass parts, it is 0-80 mass parts. When the said addition amount exceeds 80 mass parts, the water repellency durability in the glass surface of the film|membrane formed from the emulsion water repellent composition will worsen.

In the formula (3), R ¹ is the same as R ¹ in the formula (1). Among them, a methyl group, a long-chain alkyl group and a phenyl group are preferable. Further, R ² is the same as R ² in the above (1). Among them, it is preferable to use a 3-aminopropyl group or an N-(2-aminoethyl)-3-aminopropyl group.

R ⁶ is each independently a group selected from the ^{above-mentioned options of R 1} and R ^{2 .} However, when h=0 in the formula (3), R ⁶ is a group selected from the options of R ^{2 .} Moreover, as (B) component, these amino-modified silicone can be used individually or in combination of 2 or more types.

f is a real number satisfying 2≤f≤10. When f is less than 2, the viscosity of the amino-modified silicone becomes too high, and the stability of the emulsion water repellent composition deteriorates. In addition, when f exceeds 10, the viscosity of the amino-modified silicone becomes too low, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate. Preferably f=2.

g is a real number satisfying 10≤g≤1,000. If g is less than 10, the viscosity of the amino-modified silicone becomes too low, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate. In addition, when g exceeds 1,000, the viscosity of the amino-modified silicone becomes too high, and the stability of the emulsion water repellent composition deteriorates. Preferably, it is good to satisfy the range of 20≤g≤800.

h is a real number satisfying 0≤h≤50. In particular, when h is 1 or more, (B) the amount of amino groups in the amino-modified silicone is large, the water repellency durability of the film formed from the emulsion water repellent composition and the stability of the emulsion water repellent composition are improved, and the glass surface does not glare due to the oil film. However, when h=0, R ⁶ is a group selected from the options of R ^{2 .} In addition, when h exceeds 50, the amount of amino groups in the amino-modified silicone is too large, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorates.

i is a real number satisfying 0≤i≤5. When i exceeds 5, the viscosity of the amino-modified silicone becomes too high, the stability of the emulsion water repellent composition deteriorates, and glare by an oil film may occur on the glass surface. Preferably, i=0 is good.

j is a real number satisfying 0≤j≤5. When j exceeds 5, the viscosity of the amino-modified silicone becomes too high, the stability of the emulsion water repellent composition deteriorates, and glare by an oil film may occur on the glass surface. Preferably, j=0 is good.

(C) Surfactant

The surfactant (C) contained in the emulsion water repellent composition of the present invention is not particularly limited as long as the component (A) and the component (B) can be emulsified and dispersed in water. For example, polyoxyethylene alkyl ether, poly oxyethyleneoxypropylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, etc. are mentioned. From the viewpoint of stability of the emulsion water repellent composition, in particular, polyoxyethylene alkyl ether, polyoxyethylene Oxypropylene alkyl ether and polyoxyethylene sorbitan fatty acid ester are preferable.

Specific examples thereof include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene oxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethyleneoxypropylene lauryl ether, poly Oxyethylene tridecyl ether, polyoxyethylene oxypropylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan mono Palmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, etc. are mentioned. (C) As a component, these nonionic surfactant can be used individually or in combination of 2 or more types.

In addition, anionic surfactants such as alkyl sulfates, alkylbenzenesulfonates, alkylsulfosuccinates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkylphenyl ether sulfates, and cationic surfactants such as quaternary ammonium salts and alkylamine acetates , and amphoteric surfactants such as alkylbetaine and alkylimidazoline can also be used.

(C) As addition amount of a component, it is 2-100 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. When the added amount is less than 2 parts by mass, the stability of the emulsion water repellent composition deteriorates, and when the added amount exceeds 100 parts by mass, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorates. It is preferable that the said addition amount is 2-50 mass parts. When the amount added is 2 parts by mass or more, the stability of the emulsion water repellent composition is improved, and when it is 50 parts by mass or less, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition are better. The said addition amount becomes like this. More preferably, it is 3-40 mass parts, More preferably, it is 4-30 mass parts.

The surfactant preferably has an HLB value of 3.0 to 19.0. When using 2 or more types together, it is good for the sum total of HLB values to be set to 7.0-16.0.

(D) Polyether-modified silicone

(D) Polyether-modified silicone in the present invention is represented by the following average composition formula (4).

[Formula 9]

(D) Polyether-modified silicone has HLB 5-13 in 25 degreeC. The HLB is preferably 5.5 to 12.5, more preferably 6.0 to 12.0. In the polyether-modified silicone having an HLB of less than 5, it becomes difficult to sufficiently emulsify and disperse the component (A) and the component (B). In addition, the polyether-modified silicone having an HLB of more than 13 deteriorates the compatibility with the component (A) and the component (B), and the stability of the emulsion water repellent composition obtained, particularly the dilution stability, deteriorates.

(D) Polyether-modified silicone has a viscosity of 10 to 10,000 mPa·s at 25°C. The viscosity is preferably 40 to 5,000 mPa·s, more preferably 50 to 4,000 mPa·s. It becomes difficult to fully emulsify and disperse (A) component and (B) component as it is less than the said lower limit. Moreover, when the said upper limit is exceeded, handling at the time of use of an emulsion water repellent composition will become difficult.

R ¹ in the formula (4) is the same as R ¹ in the formula (1). Among them, a methyl group, a long-chain alkyl group and a phenyl group are preferable. (D) Since component is used in order to emulsify-disperse (A) component and (B) component with (C)component, a strong hydrophobic group is not preferable. However, in order to improve dispersibility with organic compounds such as wax, it is preferable to use a long-chain alkyl group and a phenyl group. In addition, the expression a compound represented by the formula (4) may be used in combination with a plurality of types of organic substituents as R ¹ and, in the case of a combination, the substituents R ^1, R ^7, and the content of a methyl group to 90% of the total number of R ⁸ more preferably.

R ⁷ is each independently represented by the general formula (5): -R ⁹ -O-(C ₂ H ₄ O) _x -(C ₃ H ₆ O) _y -(C ₄ H ₈ O) _z -R ¹⁰ It is a polyether group. In Formula (5), R<^9> is a C1-C6 divalent organic group, For example, they are an alkylene group, an alkenylene group, an arylene group, etc. R ¹⁰ is a group selected from -H, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , and (C=O)CH ₃ .

x is a real number satisfying the range of 5≤x≤30. If x is less than 5, HLB of (D)component becomes low too much, and it becomes difficult to emulsify-disperse (A)component and (B)component fully. Moreover, since the viscosity of (D)component becomes high or it becomes normal temperature solid when x exceeds 30, the handling at the time of use becomes difficult. Preferably, it is good to satisfy the range of 5≤x≤25.

y is a real number satisfying the range 0≤y≤30. When y exceeds 30, HLB of (D)component becomes low too much, and it becomes difficult to fully emulsify and disperse (A)component and (B)component. Preferably, it is good to satisfy the range of 0≤y≤25.

z is a real number satisfying the range 0≤z≤30. When z exceeds 30, HLB of (D)component becomes low too much, and it becomes difficult to fully emulsify and disperse (A)component and (B)component. Preferably, it is good to satisfy the range of 0≤z≤15.

R ⁸ is ^{a group selected from the options of R 1} and R ⁷ or a group selected from a hydroxyl group, a methoxy group, and an ethoxy group. However, when r=0 in the formula (4), R ⁸ is a group selected from the options of R ^{7 .}

q is a real number satisfying the range 0≤q≤100. When q exceeds 100, since HLB of (D)component becomes low too much, it becomes difficult to emulsify-disperse (A)component and (B)component sufficiently. Preferably, it is good to satisfy the range of 5≤q≤80.

r is a real number satisfying the range 0≤r≤40. In particular, HLB of (D)component is suitable as r is 1 or more, and (A)component and (B)component can fully be emulsified and dispersed. However, in ^{the case of R 8} =R ⁷ , r may be less than 1, particularly r=0. Moreover, since the viscosity of (D)component becomes high too much when r exceeds 40, the handling at the time of use becomes difficult.

(D) The addition amount of component is 1-25 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. The said addition amount becomes like this. Preferably it is 3-23 mass parts, More preferably, it is 5-20 mass parts. (D) A stable emulsion water repellent composition cannot be obtained as the addition amount of a component is outside the said range.

(E) water

The emulsion water repellent composition of this invention can be prepared by mixing (E) water with the above-mentioned (A) component, (B) component, (C) component, and (D) component, and emulsifying and dispersing according to a conventional method. (E) The water is preferably ion-exchanged water. (E) Content of water is 10-2,000 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and it is preferable that it is 50-1,000 mass parts. The emulsion water repellent composition is obtained by mixing and emulsifying and dispersing the said (A)-(E) component. In particular, it is an oil-in-water (O/W type) emulsion water repellent composition, and it is usually a white emulsion. When the average particle diameter of the emulsified particles is 300 nm or less, the appearance may be a bluish-white or transparent microemulsion. In addition, water can be further added to the obtained emulsion water repellent composition to dilute it, and it can be used for the use mentioned later. The amount of water for dilution is not particularly limited, and may be appropriately adjusted according to the use. The emulsion water repellent composition of the present invention has excellent stability even after dilution.

other additives

Various additives can be mix|blended with the emulsion water repellent composition of this invention as needed other than the said (A)-(E) component. For example, acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, stearic acid, lactic acid, and citric acid may be blended to improve the stability of the emulsion. The amount of the additive may be arbitrarily set, but it is preferable that the pH of the emulsion water repellent composition of the present invention is adjusted to 3-7.

In addition, as other additives, a thickener, an anti-freezing agent, a preservative, a rust preventive agent, an antioxidant, and a UV absorber may be included.

Emulsion water repellent composition

The average particle diameter of the emulsified particles in the emulsion water repellent composition of the present invention is preferably 300 nm or less, and more preferably 200 nm or less. On the other hand, in the present invention, the average particle diameter is a volume-based average particle diameter, and can be measured by a submicron particle size distribution measuring device (Coulter N4Plus) manufactured by Beckman Coulter Co., Ltd.

The emulsion water repellent composition of the present invention can be easily used for coating treatment of vehicles such as automobiles using automatic car washes, for example, door-type car washes, continuous door-type car washes, spray-type car washes, and the like. That is, the emulsion water repellent composition of the present invention is useful as a coating agent for vehicles. The concentration of the coating agent when sprayed or applied to the vehicle surface is not particularly limited, but usually, the emulsion water repellent of the present invention is such that the concentration of the amino-modified silicone of component (A) and component (B) is about 0.01 to 0.5 mass%. It is good to set the concentration of the composition and the automatic dilution ratio of the automatic car wash. The emulsion water repellent composition of the present invention can impart water repellency, glossiness, lubricity, etc. with long lasting durability to the painted surface or glass surface of a vehicle.

It goes without saying that the emulsion water repellent composition of the present invention can also be applied to other uses requiring water repellency.

Example

Hereinafter, the present invention will be described in more detail by showing examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following example, a part represents a mass part, and % represents mass %. The average particle diameter is a volume-based average particle diameter, and is a value measured using a submicron particle size distribution measuring device Coulter N4Plus manufactured by Beckman Coulter Co., Ltd. Viscosity is an absolute viscosity measured at 25°C with a B-type rotational viscometer, and is a value measured with a TVB-10-type viscometer manufactured by Toki Industrial Co., Ltd.

Each component used in the Example and the comparative example is described below.

( A) Amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group

Amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group 1: represented by the following average composition formula (1), R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -OCH ₃ , a=2, b=38, c=2, d=0, e=0, viscosity: 65 mPa·s, amino group equivalent: 780 g/mol

[Formula 10]

Amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group 2: represented by the above average formula (1), R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -OCH ₃ , a=2, b=198, c=4, d=0, e=0, a compound having a viscosity: 700 mPa·s, an amino equivalent: 1,860 g/mol

Amino-modified silicone terminal-blocked with a hydroxyl group or an alkoxy group 3: represented by the above average composition formula (1), R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -OC ₂ A compound having H ₅ , a=2, b=120, c=2.5, d=0, e=0, viscosity: 350 mPa s, amino equivalent: 1900 g/mol

Amino-modified silicone 4 terminal-blocked with a hydroxyl group or an alkoxy group (for comparison): represented by the above average formula (1), R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NH ₂ , R ³ :-OH, A compound having a=2, b=1078, c=2.2, d=0, e=0, viscosity: 30,000 mPa·s, amino group equivalent: 20,000 g/mol

(B) amino-modified silicone

Amino-modified silicone 5: represented by the following average composition formula (3), R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ⁶ : -CH ₃ , f=2, g= 28, h=4, i=0, j=0, viscosity: 70 mPa s, amino group equivalent: 350 g/mol

[Formula 11]

Amino-modified silicone 6: represented by the above average composition formula (3), R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ⁶ : -CH ₃ , f=2, g= 294, h=6.3, i=0, j=0, viscosity: 1,200 mPa·s, amino group equivalent: 1,800 g/mol

Amino-modified silicone 7: represented by the above average composition formula (3), R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ⁶ : -CH ₃ , f=2, g= 634, h=14.5, i=0, j=0, viscosity: 3,600 mPa s, amino group equivalent: 1,800 g/mol

Amino-modified silicone 8: represented by the above average composition formula (3), R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ⁶ : -CH ₃ , f=2, g= 350, h=3.5, i=0, j=0, viscosity: 1,500 mPa·s, amino group equivalent: 3,500 g/mol

Amino-modified silicone 9 (for comparison): represented by the above average composition formula (3), R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ⁶ : -CH ₃ , f= 2, g = 300, h = 1.0, i = 0, j = 0, viscosity: 1,200 mPa s, amino group equivalent: a compound having 11,000 g / mol

(A) The list of compositions of component and (B) component is put together in Table 1.

[Table 1]

(C) Surfactant

Neugen XL-40 (brand name): Jeil Industrial Pharmaceutical Co., Ltd. polyoxyalkylenedecyl ether, HLB=10.5

Neugen XL-400D (trade name): 65% by mass aqueous solution of polyoxyalkylenedecyl ether manufactured by Jeil Industrial Co., Ltd., HLB=18.4

Nucol 1004 (trade name): polyoxyethylene octyl ether manufactured by Nippon Oil Co., Ltd., HLB = 11.5

Nucol 1008 (trade name): polyoxyethylene octyl ether manufactured by Nippon Oil Co., Ltd., HLB = 14.6

RHEODOL TW-L106 (trade name): Polyoxyethylene sorbitan monolaurate manufactured by Kaos, HLB=13.3

Leodol TW-O320V (trade name): Kaos Corporation polyoxyethylene sorbitan monooleate, HLB = 11.0

(D) Polyether-modified silicone

Polyether-modified silicone 1: represented by the following average composition formula (4), R ¹ : -CH ₃ , R ⁷ : -C ₃ H ₆ O-(C ₂ H ₄ O) ₂₃ (C ₃ H ₆ O) ₂₃ C ₄ H ₉ , R ⁸ : -CH ₃ , q=27, r=3, viscosity: 1,600 mPa·s, HLB: 7 compound

[Formula 12]

Polyether-modified silicone 2: represented by the above average composition formula (4), R ¹ : -CH ₃ , R ⁷ : -C ₃ H ₆ O-(C ₂ H ₄ O) _9.4 H, R ⁸ : -CH ₃ , A compound having q=24, r=4, viscosity: 430 mPa·s, HLB: 10

Polyether-modified silicone 3: represented by the above average formula (4), R ¹ : -CH ₃ , R ⁷ : -C ₃ H ₆ O-(C ₂ H ₄ O) ₁₀ CH ₃ , R ⁸ : -CH ₃ , q=10, r=5, a compound having a viscosity: 70 mPa·s, HLB: 12

Polyether-modified silicone 4 (for comparison): represented by the above average formula (4), R ¹ : -CH ₃ , R ⁷ : -C ₃ H ₆ O-(C ₂ H ₄ O) ₈ CH ₃ , R ⁸ : -CH ₃ , q=0, r=1, viscosity: 20 mPa s, HLB: 14 compound

(D) The list of compositions of the component is put together in Table 2.

[Table 2]

Additive: The preservative used in the following examples and comparative examples is "Proxel-BDN" (trade name: manufactured by Arch Chemicals).

[Example 1]

(A) Methoxy group-terminated amino-modified silicone 1 (viscosity: 65 mPa·s, amino group equivalent: 780 g/mol) 20 parts by mass, (A) methoxy group-terminated amino-modified silicone 2 (viscosity: 700 mPa·s, amino group equivalent: 1,860 g/mol) 80 parts by mass, (C) Neugen XL-40 (HLB=10.5): 20 parts by mass, and (C) Neugen XL-400D (HLB=18.4, 65 mass% aqueous solution) 30 parts by mass; (D) 10 parts by mass of polyether-modified silicone 1 (viscosity: 1,600 mPa·s, HLB: 7), (E) 462.5 parts by mass of ion-exchanged water, 3.0 parts by mass of acetic acid, and 0.2 parts by mass of a preservative were mixed using a homomixer was emulsified and dispersed, and the non-volatile content at 105° C./3 hours was 23.8%, and the average particle diameter of the emulsified particles in the emulsion water repellent composition was 30 nm, to obtain a colorless and transparent amino-modified silicone emulsion water repellent composition (I-1). .

[Example 2]

(A) 30 parts by mass of methoxy group terminal blocking amino-modified silicone 1 (viscosity: 65 mPa·s, amino equivalent: 780 g/mol), (B) amino-modified silicone 6 (viscosity: 1,200 mPa·s, amino equivalent: 1,800 g/ mol) 70 parts by mass, (C) Neugen XL-40 (HLB = 10.5): 20 parts by mass, (C) Neugen XL-400D (HLB = 18.4, 65 mass % aqueous solution) 30 parts by mass, (D) 10 parts by mass of polyether-modified silicone 1 (viscosity: 1,600 mPa·s, HLB: 7), (E) 462.5 parts by mass of ion-exchanged water, 3.2 parts by mass of acetic acid, and 0.2 parts by mass of a preservative were mixed using a homomixer to emulsify and disperse. and a colorless and transparent amino-modified silicone emulsion water repellent composition (I-2) having a nonvolatile content of 24.4% at 105°C/3 hours and an average particle diameter of the emulsified particles in the emulsion water repellent composition of 45 nm.

[Example 3]

(A) methoxy group terminal blocking amino-modified silicone 2 (viscosity: 700 mPa·s, amino group equivalent: 1,860 g/mol) 80 parts by mass, (B) amino-modified silicone 5 (viscosity: 70 mPa·s, amino group equivalent: 350 g/mol) ) 20 parts by mass, (C) Neugen XL-40 (HLB = 10.5): 20 parts by mass, (C) Neugen XL-400D (HLB = 18.4, 65 mass % aqueous solution) 30 parts by mass, (D) Poly 10 parts by mass of ether-modified silicone 2 (viscosity: 430 mPa·s, HLB: 10), (E) 462.5 parts by mass of ion-exchanged water, 4.0 parts by mass of acetic acid, and 0.2 parts by mass of a preservative are mixed and emulsified and dispersed using a homomixer, An amino-modified silicone emulsion water repellent composition (I-3) having a non-volatile content of 24.6% at 105° C./3 hours and an average particle diameter of the emulsified particles in the emulsion water repellent composition of 120 nm was obtained.

[Example 4]

(A) Methoxy group terminal block chain amino-modified silicone 1 (viscosity: 65 mPa·s, amino group equivalent: 780 g/mol) 20 parts by mass, (B) amino-modified silicone 7 (viscosity: 3,600 mPa·s, amino group equivalent: 1,800 g/ mol) 80 parts by mass, (C) Nucol 1004 (HLB=11.5): 20 parts by mass, Nucol 1008 (HLB=14.6) 20 parts by mass, (D) Polyether-modified silicone 3 (viscosity: 70 mPa·s, HLB: 12) 10 parts by mass, (E) 462.5 parts by mass of ion-exchanged water, 3.1 parts by mass of acetic acid, and 0.2 parts by mass of a preservative were mixed and emulsified and dispersed using a homomixer, and the nonvolatile content at 105°C/3 hours was 24.6% , A colorless and transparent amino-modified silicone emulsion water repellent composition (I-4) was obtained, in which the average particle diameter of the emulsified particles in the emulsion water repellent composition was 30 nm.

[Example 5]

(A) 30 parts by mass of (A) methoxy group terminal blocking amino-modified silicone 1 (viscosity: 65 mPa·s, amino group equivalent: 780 g/mol), (B) amino-modified silicone 8 (viscosity: 1,500 mPa·s, amino group equivalent: 3,500 g/ mol) 70 parts by mass, (C) Nucol 1004 (HLB=11.5): 20 parts by mass, (C) Nucol 1008 (HLB=14.6) 20 parts by mass, (D) Polyether-modified silicone 1 (viscosity: 1,600 mPa· s, HLB: 7) 10 parts by mass, (E) 462.5 parts by mass of ion-exchanged water, 2.4 parts by mass of acetic acid, and 0.2 parts by mass of a preservative were mixed and emulsified and dispersed using a homomixer, and nonvolatile matter at 105°C/3 hours A colorless and transparent amino-modified silicone emulsion water repellent composition (I-5) having an average particle diameter of 60 nm of the emulsified particles in the emulsion water repellent composition was obtained.

[Example 6]

(A) 100 parts by mass of ethoxy group terminal blocking amino-modified silicone 3 (viscosity: 350 mPa s, amino group equivalent: 1,900 g/mol), (C) Nucol 1004 (HLB = 11.5): 20 parts by mass, Nucol 1008 (HLB) = 14.6) 20 parts by mass, (D) 10 parts by mass of polyether-modified silicone 2 (viscosity: 430 mPa·s, HLB: 10), (E) 462.5 parts by mass of ion-exchanged water, 2.2 parts by mass of acetic acid, and 0.2 parts by mass of a preservative , mixed using a homomixer to emulsify and disperse, the nonvolatile matter at 105° C./3 hours is 23.4%, and the average particle diameter of the emulsified particles in the emulsion water repellent composition is 40 nm, a colorless and transparent amino-modified silicone emulsion water repellent composition ( I-6) was obtained.

[Example 7]

(A) Methoxy group-terminated amino-modified silicone 1 (viscosity: 65 mPa·s, amino group equivalent: 780 g/mol) 20 parts by mass, (A) methoxy group-terminated amino-modified silicone 2 (viscosity: 700 mPa·s, amino group equivalent: 1,860 g/mol) 80 parts by mass, (C) Reodol TW-L106 (HLB = 13.3): 20 parts by mass, (C) Reodol TW-O320V (HLB = 11.0) 20 parts by mass, (D) polyether 10 parts by mass of modified silicone 1 (viscosity: 1,600 mPa s, HLB: 7), (E) 462.5 parts by mass of ion-exchanged water, 3.0 parts by mass of acetic acid, and 0.2 parts by mass of a preservative are mixed and emulsified and dispersed using a homomixer, A colorless and transparent amino-modified silicone emulsion water repellent composition (I-7) having a nonvolatile content of 23.7% at 105°C/3 hours and an average particle diameter of the emulsified particles in the emulsion water repellent composition was 50 nm was obtained.

[Comparative Example 1]

(A) 70 parts by mass of (A) methoxyl group-terminated amino-modified silicone 1 (viscosity: 65 mPa s, amino group equivalent: 780 g/mol), (A) hydroxyl-terminated amino-modified silicone 4 (viscosity: 30,000 mPa s, amino group equivalent: 20,000 g/mol) 30 parts by mass, (C) Neugen XL-40 (HLB=10.5): 20 parts by mass, and Neugen XL-400D (HLB=18.4, 65 mass % aqueous solution) 30 parts by mass, (D) 10 parts by mass of polyether-modified silicone 1 (viscosity: 1,600 mPa·s, HLB: 7), (E) 462.5 parts by mass of ion-exchanged water, 3.8 parts by mass of acetic acid, and 0.2 parts by mass of a preservative were mixed using a homomixer to emulsify and disperse. and a white emulsion amino-modified silicone emulsion water repellent composition (II-1) having a nonvolatile content of 24.9% at 105°C/3 hours and an average particle diameter of the emulsified particles in the emulsion water repellent composition of 250 nm was obtained.

[Comparative Example 2]

(A) methoxy group terminal blockade amino-modified silicone 1 (viscosity: 65 mPa s, amino group equivalent: 780 g/mol) 70 parts by mass, (B) amino-modified silicone 9 (viscosity: 1,200 mPa s, amino group equivalent: 11,000 g/ mol) 30 parts by mass, (C) Neugen XL-40 (HLB = 10.5): 20 parts by mass, (C) Neugen XL-400D (HLB = 18.4, 65 mass % aqueous solution) 30 parts by mass, (D) 10 parts by mass of polyether-modified silicone 1 (viscosity: 1,600 mPa·s, HLB: 7), (E) 462.5 parts by mass of ion-exchanged water, 3.8 parts by mass of acetic acid, and 0.2 parts by mass of a preservative were mixed using a homomixer to emulsify and disperse. and amino-modified silicone emulsion water repellent composition (II-2) having a non-volatile content of 24.2% at 105° C./3 hours and an average particle diameter of the emulsified particles in the emulsion water repellent composition of 120 nm was obtained.

[Comparative Example 3]

(B) 100 parts by mass of amino-modified silicone 7 (viscosity: 3,600 mPa·s, amino equivalent: 1,800 g/mol), (C) Nucol 1004 (HLB=11.5): 20 parts by mass, and Nucol 1008 (HLB=14.6) 20 parts by mass, (D) 10 parts by mass of polyether-modified silicone 2 (viscosity: 430 mPa·s, HLB: 10), (E) 462.5 parts by mass of ion-exchanged water, 2.5 parts by mass of acetic acid, and 0.2 parts by mass of a preservative by a homomixer A colorless and transparent amino-modified silicone emulsion water repellent composition (II-3) which is mixed and emulsified and dispersed, the nonvolatile matter is 23.8% at 105°C/3 hours, and the average particle diameter of the emulsified particles in the emulsion water repellent composition is 40 nm (II-3) ) was obtained.

[Comparative Example 4]

(A) Methoxy group terminal blocking amino-modified silicone 1 (viscosity: 65 mPa·s, amino group equivalent: 780 g/mol) 20 parts by mass, (A) methoxy group terminal blocking amino-modified silicone 2 (viscosity: 700 mPa·s, amino group equivalent: 1,860 g/mol) 80 parts by mass, (C) Neugen XL-40 (HLB=10.5): 20 parts by mass, and (C) Neugen XL-400D (HLB=18.4, 65 mass% aqueous solution) 30 parts by mass; (D) 10 parts by mass of polyether-modified silicone 4 (viscosity: 20 mPa·s, HLB: 14), (E) 462.5 parts by mass of ion-exchanged water, 3.0 parts by mass of acetic acid, and 0.2 parts by mass of a preservative were mixed using a homomixer. It was emulsified and dispersed, and the non-volatile matter at 105° C./3 hours was 24.8%, and the average particle diameter of the emulsified particles in the emulsion water repellent composition was 70 nm, to obtain a colorless and transparent amino-modified silicone emulsion water repellent composition (II-4).

[Comparative Example 5]

(A) Methoxy group-terminated amino-modified silicone 1 (viscosity: 65 mPas, amino group equivalent: 780 g/mol) 20 parts by mass, (A) methoxy group-terminated amino-modified silicone 2 (viscosity: 700 mPa·s, amino group equivalent: 1,860 g) /mol) 80 parts by mass, (C) Neugen XL-40 (HLB = 10.5): 20 parts by mass, (C) Neugen XL-400D (HLB = 18.4, 65 mass % aqueous solution) 30 parts by mass, (E ) 462.5 parts by mass of ion-exchanged water, 3.0 parts by mass of acetic acid, and 0.2 parts by mass of a preservative were mixed and emulsified and dispersed using a homomixer, and the non-volatile content at 105° C./3 hours was 22.3%, emulsification in the emulsion water repellent composition A colorless and transparent amino-modified silicone emulsion water repellent composition (II-5) having an average particle diameter of 80 nm was obtained.

[Water-repellent durability]

The amino-modified silicone emulsion water repellent composition obtained in Examples 1 to 7 and Comparative Examples 1 to 5 was diluted 150 times with tap water, and then sprayed onto the painted surfaces and glass surfaces of automobiles using a spray gun. After completion of spraying, one round trip washing was performed with tap water, and the time until the water film was broken after washing was stopped was measured. The results are shown in Tables 3 and 4 below as initial values. After that, it was further washed 15 rounds with tap water, and the time until the water film broke after stopping the washing was measured. The results are shown in Tables 3 and 4 below.

[Glare of glass surface]

After the water-repellent durability test was completed, the glass surface was wiped 3 times with a rubber wiper. The presence or absence of oil film residue and glare on the glass surface at that time was visually observed. The results are shown in Tables 3 and 4 below.

<Evaluation criteria>

○: no oil film, △: slightly oil film, ×: oil film and glare.

[stability]

The amino-modified silicone emulsion water repellent composition (stock solution) prepared in Examples 1 to 7 and Comparative Examples 1 to 5 was placed in a glass bottle, and the presence or absence of separation when stored at 40° C. for 2 weeks was visually observed. It was evaluated as "stock solution stability" based on the following criteria. The results are shown in Tables 3 and 4.

<Evaluation criteria>

○: no separation, △: light and shade separation, ×: two-layer separation

In addition, the presence or absence of separation when the amino-modified silicone emulsion water repellent composition (undiluted solution) prepared in Examples 1 to 7 and Comparative Examples 1 to 5 was diluted 150 times with tap water in a glass bottle and stored at 40° C. for 2 weeks was visually observed. It evaluated as "dilution stability" based on the following index|index. The results are shown in Tables 3 and 4.

<Evaluation criteria>

○: no precipitate, △: slightly precipitated, ×: precipitated

[Table 3]

[Table 4]

As shown in Table 3 above, the emulsion water repellent composition of the present invention is effectively used as a water repellent agent with excellent water repellency, and in particular, it gives good initial water repellency and water repellency durability to both the painted surface of a car and the glass surface, and also provides an oil film to the glass surface. It eliminates the glare from

Industrial Applicability

The emulsion water repellent composition of the present invention provides excellent water repellency to both a painted surface and a glass surface, and also eliminates glare of the glass surface. Furthermore, it is excellent in stock solution stability and dilution stability. The emulsion water repellent composition of the present invention is useful as a cleaning agent and coating agent for coating a vehicle using an automatic car wash.

In addition, this invention is not limited to the said embodiment. The above-mentioned embodiment is an illustration, and any thing which has substantially the same structure as the technical idea described in the claim of this invention, and shows the same effect is included in the technical scope of this invention.

Claims (5)

The following (A)-(E) component is contained, The emulsion water repellent composition characterized by the above-mentioned.
(A) amino-modified silicone, which is represented by the following general formula (1), has a viscosity of 30 to 2,000 mPa·s at 25° C., and has an amino group equivalent of 300 to 3,000 g/mol, end-blocked with a hydroxyl group or an alkoxy group: 20 to 100 parts by mass;
[Formula 1]

(Wherein, R ¹ is an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other, and R ² is each independently of the general formula (2): -R ⁴ -(NH-R ⁵ -) _p NH ₂ is a group represented by, in the formula (2), R ⁴ and R ⁵ are each independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1, R ³ is independently a hydroxyl group or, a group selected from a methoxy group and an ethoxy group, and a, b, c, d, and e are, respectively, 2≤a≤10, 10≤b≤1,000, 1≤c≤50, 0≤d≤5, 0≤ It is a real number that satisfies the range of e≤5),
(B) amino-modified silicone represented by the following general formula (3), having a viscosity of 50 to 5,000 mPa·s at 25° C., and having an amino group equivalent of 300 to 4,000 g/mol: 0 to 80 parts by mass (provided that (A) ) the total amount of the component and (B) component shall be 100 parts by mass),
[Formula 2]

(Wherein, R ¹ , R ² are the same as above, R ⁶ is a group independently selected from the options of R ¹ and R ² , and f, g, h, i, and j are each, 2≤f It is a real number satisfying the ranges of ≤10, 10≤g≤1,000, 0≤h≤50, 0≤i≤5, 0≤j≤5 However, when h=0 in the above formula (3), R ⁶ is a group selected from the options of R ^{2 ),}
(C) at least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants, and cationic surfactants: 2 to 100 parts by mass;
(D) polyether-modified silicone represented by the following average composition formula (4), having a viscosity of 10 to 10,000 mPa·s at 25°C, and having an HLB of 5 to 13: 1 to 25 parts by mass;
[Formula 3]

(Wherein, R ¹ is the same as above, and R ⁷ is each independently of the general formula (5): -R ⁹ -O-(C ₂ H ₄ O) _x -(C ₃ H ₆ O) _y -(C ₄ H ₈ O) _z -R ¹⁰ is a polyether group, in the formula (5), R ⁹ is a divalent organic group having 1 to 6 carbon atoms, R ¹⁰ is -H, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , and -(C=O)CH ₃ , wherein x, y and z are 5≤x≤30, 0≤y≤30 , is a real number satisfying the range of 0≤z≤30, R ⁸ is a group selected from the above R ¹ and R ⁷ or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , q and r are real numbers satisfying the ranges of 0≤q≤100 and 0≤r≤40, respectively, where R ⁸ is R ⁷ when r = 0);
(E) Water: 10 to 2,000 parts by mass. According to claim 1,
An emulsion water repellent composition comprising a nonionic surfactant. 3. The method of claim 2,
Emulsion water repellent composition, characterized in that the nonionic surfactant is at least one selected from polyoxyalkylene alkyl ether and polyoxyethylene sorbitan fatty acid ester. 4. The method according to any one of claims 1 to 3,
The emulsion water repellent composition, characterized in that the average particle diameter of the emulsified particles in the emulsion water repellent composition is 300 nm or less. 5. The method according to any one of claims 1 to 4,
The emulsion water repellent composition is an emulsion water repellent composition, characterized in that it is for the painted surface and glass surface of an automobile.