Emulsion hydrophobicizer composition

文档序号：261002 发布日期：2021-11-16 浏览：4次中文

阅读说明：本技术 乳液疏水剂组合物 (Emulsion hydrophobicizer composition ) 是由竹脇一幸于 2020-01-29 设计创作，主要内容包括：本发明涉及一种乳液疏水剂组合物,其含有：20～100质量份的(A)以羟基或烷氧基封端的特定的氨基改性有机硅；0～80质量份的(B)氨基改性有机硅,其中,将(A)成分与(B)成分的合计量设为100质量份；2～100质量份的(C)表面活性剂；1～25质量份的(D)特定的聚醚改性有机硅；及10～2000质量份的(E)水。由此提供一种乳液疏水剂组合物,其能够有效地用作疏水性优异的疏水剂,特别是能够对汽车的涂装面及玻璃面双方赋予良好的初始疏水性及疏水耐久性,并能够对玻璃面赋予去除因油膜导致的眩光的性能。(The invention relates to an emulsion hydrophobicizer composition comprising: 20 to 100 parts by mass of (A) a specific amino-modified silicone terminated with a hydroxyl group or an alkoxy group; 0 to 80 parts by mass of (B) an amino-modified silicone, wherein the total amount of the component (A) and the component (B) is 100 parts by mass; 2 to 100 parts by mass of (C) a surfactant; 1-25 parts by mass of (D) a specific polyether-modified silicone; and 10 to 2000 parts by mass of (E) water. Thus, an emulsion hydrophobizing agent composition is provided which can be effectively used as a hydrophobizing agent having excellent hydrophobicity, and which can impart good initial hydrophobicity and hydrophobic durability to both a coated surface and a glass surface of an automobile, and can impart a performance of removing glare due to an oil film to the glass surface.)

1. An emulsion hydrophobizing agent composition characterized by containing the following components (A) to (E):

20 to 100 parts by mass of (A) a hydroxyl-or alkoxy-terminated amino-modified silicone represented by the following general formula (1) having a viscosity of 30 to 2,000 mPas at 25 ℃ and an amino equivalent of 300 to 3,000g/mol,

[ chemical formula 1]

In the formula (1), R¹Independently of each other, an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R²Independently of one another, of the general formula (2): -R⁴-(NH-R⁵-)_pNH₂A group represented by the formula (2) wherein R is⁴And R⁵Independently of each other, a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1, R³Independently of one another, a, b, c, d and e are each a real number satisfying the range of 2. ltoreq. a.ltoreq.10, 10. ltoreq. b.ltoreq.1,000, 1. ltoreq. c.ltoreq.50, 0. ltoreq. d.ltoreq.5, 0. ltoreq. e.ltoreq.5;

0 to 80 parts by mass of (B) an amino-modified silicone represented by the following general formula (3) having a viscosity of 50 to 5,000 mPas at 25 ℃ and having an amino equivalent weight of 300 to 4,000g/mol, wherein the total amount of the component (A) and the component (B) is 100 parts by mass,

[ chemical formula 2]

In the formula (3), R¹、R²And the above-mentioned R¹、R²Same as R⁶Independently of one another are selected from R¹And R²F, g, h, i and j are real numbers satisfying the ranges of 2. ltoreq. f.ltoreq.10, 10. ltoreq. g.ltoreq.1,000, 0. ltoreq. h.ltoreq.50, 0. ltoreq. i.ltoreq.5, 0. ltoreq. j.ltoreq.5, respectively, wherein, when h is 0 in the above formula (3), R is⁶Is selected from R²A group in the option (1);

2 to 100 parts by mass of (C) at least 1 or more surfactant selected from the group consisting of nonionic surfactant, anionic surfactant, cationic surfactant and amphoteric surfactant;

1 to 25 parts by mass of (D) a polyether-modified silicone represented by the following average composition formula (4) having a viscosity of 10 to 10,000 mPas at 25 ℃ and an HLB of 5 to 13,

[ chemical formula 3]

In the formula (4), R¹And the above-mentioned R¹Same as R⁷Independently of one another, of the general formula (5): -R⁹-O-(C₂H₄O)_x-(C₃H₆O)_y-(C₄H₈O)_z-R¹⁰A polyether group represented by the formula (5) wherein R is⁹Is a divalent organic group having 1 to 6 carbon atoms, R¹⁰Is selected from-H, -CH₃、-C₂H₅、-C₃H₇、-C₄H₉And- (C ═ O) CH₃Wherein x, y and z are real numbers satisfying the ranges of 5. ltoreq. x.ltoreq.30, 0. ltoreq. y.ltoreq.30, 0. ltoreq. z.ltoreq.30, and R⁸Is selected from the group consisting of the R¹And R⁷A group selected from the group consisting of-OH, -OCH₃and-OC₂H₅Wherein q and R are real numbers satisfying the ranges of 0. ltoreq. q.ltoreq.100 and 0. ltoreq. r.ltoreq.40, respectively, and when R is 0, R is⁸Is R⁷；

10 to 2,000 parts by mass of (E) water.

2. Emulsion hydrophobe composition according to claim 1, characterized in that it comprises a non-ionic surfactant.

3. The emulsion hydrophobizing agent composition according to claim 2, wherein the nonionic surfactant is 1 or more selected from the group consisting of a polyoxyalkylene alkyl ether and a polyoxyethylene sorbitan fatty acid ester.

4. The emulsion hydrophobizing agent composition according to any one of claims 1 to 3, wherein the emulsified particles in the emulsion hydrophobizing agent composition have an average particle diameter of 300nm or less.

5. The emulsion hydrophobizing agent composition according to any one of claims 1 to 4, wherein the emulsion hydrophobizing agent composition is an emulsion hydrophobizing agent composition for use on a coating surface and a glass surface of an automobile.

Technical Field

The invention relates to an emulsion hydrophobing agent composition.

Background

Conventionally, in coating for imparting hydrophobicity to a surface of a vehicle such as an automobile, an aqueous emulsion containing an amino-modified polysiloxane as a main component is coated. The amino-modified polysiloxane is obtained by replacing a part of methyl groups of dimethylpolysiloxane with aminoalkyl groups or aminoalkyl groups substituted with aminoalkyl groups, and when it is applied to a vehicle surface, it is adsorbed on the vehicle surface via the amino groups, and can impart hydrophobic properties more durable than dimethylpolysiloxane to the vehicle surface.

In a conventional method of use, amino-modified polysiloxane is used as an aqueous emulsion emulsified with a nonionic surfactant, and patent document 1 discloses a coating agent obtained from an aqueous emulsion using a specific cationic surfactant in order to further improve the adsorbability of amino-modified polysiloxane.

Further, patent document 2 discloses a gloss hydrophobicity-imparting composition obtained by emulsifying an amino-modified polysiloxane and a dimethylpolysiloxane with a nonionic surfactant having a specific hydrophilic-lipophilic balance (HLB) and mixing the emulsified amino-modified polysiloxane and dimethylpolysiloxane, respectively.

These aqueous emulsions containing amino-modified polysiloxane as a main component are diluted with water to several tens to several hundreds times and are applied by spraying using a gate-type automatic car washer to impart hydrophobicity to the surface of a vehicle such as an automobile.

In this case, it is important to impart water repellency to the coated surface of the vehicle and the glass surface of the windshield or the like, and to impart performance that is easy to recognize by the driver, such as no glare due to an oil film, to the glass surface.

However, in the conventional techniques, although the hydrophobic property can be imparted to the coated surface of the vehicle, sufficient performance cannot be imparted to the glass surface, and further improvement in the characteristics is required.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 8-188745

Patent document 2: japanese patent laid-open publication No. 2004-300387

Disclosure of Invention

Technical problem to be solved by the invention

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an emulsion hydrophobizing agent composition which can be effectively used as a hydrophobizing agent having excellent hydrophobicity, and in particular, can impart good initial hydrophobicity and hydrophobic durability to both a coated surface and a glass surface of an automobile, and can impart a performance of removing glare due to an oil film to the glass surface.

Means for solving the problems

In order to solve the above-mentioned problems, the present invention provides an emulsion hydrophobizing agent composition comprising the following components (a) to (E):

[ chemical formula 1]

[ chemical formula 2]

2 to 100 parts by mass of (C) at least 1 surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants;

1 to 25 parts by mass of (D) a polyether-modified silicone represented by the following average composition formula (4) having a viscosity of 10 to 10,000 mPas at 25 ℃ and an HLB of 5 to 13,

[ chemical formula 3]

10 to 2,000 parts by mass of (E) water.

The emulsion hydrophobizing agent composition can be effectively used as a hydrophobizing agent having excellent hydrophobicity, and can particularly impart good initial hydrophobicity and hydrophobic durability to both a coated surface and a glass surface of an automobile, and can impart a performance of removing glare due to an oil film to the glass surface.

The emulsion hydrophobe composition preferably comprises a nonionic surfactant.

If the emulsion hydrophobizing agent composition contains a nonionic surfactant, the stability is further excellent.

Preferably, the nonionic surfactant is 1 or more selected from the group consisting of polyoxyalkylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters.

If the nonionic surfactant is the specific nonionic surfactant, the emulsion hydrophobizing agent composition is more excellent in stability.

The average particle diameter of emulsified particles in the emulsion hydrophobizing agent composition is preferably 300nm or less.

When the average particle diameter of the emulsified particles in the emulsion hydrophobizing agent composition is 300nm or less, the emulsion hydrophobizing agent composition may form a microemulsion having a bluish white or transparent appearance.

The emulsion hydrophobicizer composition is preferably a composition for use on the coating side and the glass side of an automobile.

When the emulsion hydrophobizing agent composition is used for a coated surface and a glass surface of an automobile, both the coated surface and the glass surface of the automobile can be imparted with good initial hydrophobicity and hydrophobic durability, and the glass surface can be imparted with a performance of removing glare due to an oil film.

Effects of the invention

The emulsion hydrophobizing agent composition of the present invention can be effectively used as a hydrophobizing agent having excellent hydrophobicity, and can impart good initial hydrophobicity and hydrophobic durability to both a coated surface and a glass surface of an automobile, and can impart a performance of removing glare due to an oil film to the glass surface.

Detailed Description

As described above, development of a hydrophobizing agent composition which can be effectively used as a hydrophobizing agent having excellent hydrophobicity, and particularly can impart good initial hydrophobicity and hydrophobic durability to both a coated surface and a glass surface of an automobile, and can impart performance of removing glare due to an oil film to the glass surface has been demanded.

As a result of extensive and intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that an amino-modified silicone emulsion composition containing a specific amino-modified silicone terminated with a hydroxyl group or an alkoxy group, a surfactant, a specific polyether-modified silicone, and water can be effectively used as a water repellent having excellent hydrophobicity, and particularly that good initial hydrophobicity and hydrophobic durability can be imparted to both a coated surface and a glass surface of an automobile, and a performance of removing glare due to an oil film can be imparted to the glass surface, thereby completing the present invention.

That is, the present invention is an emulsion hydrophobizing agent composition containing the following components (a) to (E):

[ chemical formula 4]

[ chemical formula 5]

2 to 100 parts by mass of (C) at least 1 surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants;

1 to 25 parts by mass of (D) a polyether-modified silicone represented by the following average composition formula (4) having a viscosity of 10 to 10,000 mPas at 25 ℃ and an HLB of 5 to 13,

[ chemical formula 6]

In the formula (4), R¹And the above-mentioned R¹Same as R⁷Independently of one another, of the general formula (5): -R⁹-O-(C₂H₄O)_x-(C₃H₆O)_y-(C₄H₈O)_z-R¹⁰A polyether group represented by the formula (5) wherein R is⁹Is a divalent organic group having 1 to 6 carbon atoms, R¹⁰Is selected from-H, -CH₃、-C₂H₅、-C₃H₇、-C₄H₉And (a) and (b)C＝O)CH₃Wherein x, y and z are real numbers satisfying the ranges of 5. ltoreq. x.ltoreq.30, 0. ltoreq. y.ltoreq.30, 0. ltoreq. z.ltoreq.30, and R⁸Is selected from the group consisting of the R¹And R⁷A group selected from the group consisting of-OH, -OCH₃and-OC₂H₅Wherein q and R are real numbers satisfying the ranges of 0. ltoreq. q.ltoreq.100 and 0. ltoreq. r.ltoreq.40, respectively, and when R is 0, R is⁸Is R⁷；

10 to 2,000 parts by mass of (E) water.

The present invention will be described in further detail below.

(A) Amino-modified silicones terminated with hydroxy or alkoxy groups

The hydroxyl-or alkoxy-terminated amino-modified silicone (a) of the present invention is a silicone represented by the following average composition formula (1).

[ chemical formula 7]

(A) The hydroxyl-or alkoxy-terminated amino-modified silicone has a viscosity of 30 to 2,000 mPas at 25 ℃. The viscosity is preferably 40 to 1,800 mPas, and more preferably 50 to 1,500 mPas. If the viscosity is less than the above lower limit, the initial hydrophobicity and the durability of the hydrophobicity of the film formed from the emulsion hydrophobizing agent composition are deteriorated. If the viscosity exceeds the above upper limit, the stability of the emulsion hydrophobizing agent composition is deteriorated, and glare due to an oil film is generated on the glass surface.

Further, (A) the hydroxyl-or alkoxy-terminated amino-modified silicone has an amino equivalent weight of 300 to 3,000g/mol at 25 ℃. The amino equivalent is preferably 350 to 2,800g/mol, and more preferably 400 to 2,500 g/mol. If the amino group equivalent is less than the lower limit, the initial hydrophobicity and the durability of the hydrophobicity of the film formed from the emulsion hydrophobizing agent composition are deteriorated due to an excessive amount of amino groups. If the amino group equivalent exceeds the above upper limit, the hydrophilicity to be provided by the amino-modified silicone is insufficient because the amino group is too small. This may deteriorate the stability of the emulsion hydrophobizing agent composition, and may cause glare on the glass surface due to an oil film.

In the above formula (1), R¹Independently of each other, an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, and octadecyl; alkenyl groups such as vinyl, allyl, 5-hexenyl, oleyl, etc.; aryl groups such as phenyl, tolyl, and naphthyl. Among them, methyl, long-chain alkyl, and phenyl are preferable. In particular, when weather resistance is required, methyl is preferable, and when hydrophobicity is required, methyl and a long chain alkyl group are preferable. In addition, when compatibility with an organic compound such as wax is to be provided, a long-chain alkyl group and a phenyl group are preferably used. Furthermore, R as a compound of formula (1)¹May have a plurality of organic substituents, and when used simultaneously, the methyl group is opposite to the substituent R¹、R²And R³The content ratio of the total number of (2) is preferably 70% or more.

R²Independently of one another, of the general formula (2): -R⁴-(NH-R⁵-)_pNH₂The group shown. In the formula (2), R⁴And R⁵Independently of each other, a divalent organic group having 1 to 6 carbon atoms, particularly a divalent hydrocarbon group having 1 to 6 carbon atoms. For example, alkylene, alkenylene, arylene, and the like can be given. p is 0 or 1. Examples of the group represented by formula (2) include 2-aminoethyl group, 3-aminopropyl group, 6-aminohexyl group, N- (2-aminoethyl) -3-aminopropyl group, N- (3-aminopropyl) -3-aminopropyl group, and N- (2-aminoethyl) -6-aminohexyl group. From the viewpoint of easy availability of raw materials and advantages in price, it is preferable to use 3-aminopropyl or N- (2-aminoethyl) -3-aminopropyl.

R³Independently of one another, hydroxyl or a radical selected from the group consisting of methoxy and ethoxy. In addition, as the component (a), two or more of these hydroxyl-or alkoxy-terminated amino-modified silicones can be used alone or simultaneously. Hydroxyl or a group selected from methoxy and ethoxy is adsorbed to SiOH group on the glass surface via hydrogen bond, thereby (A) is adsorbed as hydroxyl orSince the alkoxy-terminated amino-modified silicone is fixed to the glass surface, the hydrophobic property having durability can be imparted to the glass surface.

a is a real number satisfying 2-10. If a is less than 2, the viscosity of the hydroxyl-or alkoxy-terminated amino-modified silicone becomes too high, and the stability of the emulsion hydrophobizing agent composition becomes poor. When a exceeds 10, the viscosity of the amino-modified silicone terminated with a hydroxyl group or an alkoxy group is too low, and the initial hydrophobicity and the durability of the hydrophobicity of the film formed from the emulsion hydrophobizing agent composition are deteriorated. Preferably a is 2.

b is a real number satisfying 10. ltoreq. b.ltoreq.1,000. If b is less than 10, the viscosity of the amino-modified silicone terminated with a hydroxyl group or an alkoxy group is too low, and the initial hydrophobicity and the hydrophobic durability of the film formed from the emulsion hydrophobizing agent composition become poor. If b exceeds 1,000, the viscosity of the hydroxyl-or alkoxy-terminated amino-modified silicone becomes too high, and the stability of the emulsion hydrophobizing agent composition becomes poor. Preferably, the range of 20. ltoreq. b.ltoreq.800 is satisfied.

c is a real number satisfying 1. ltoreq. c.ltoreq.50. If c is less than 1, the amount of amino groups in the hydroxyl-or alkoxy-terminated amino-modified silicone is too small, and the water repellency durability of the film formed from the emulsion hydrophobizing agent composition and the stability of the emulsion hydrophobizing agent composition are deteriorated, and glare due to an oil film may occur on the glass surface. When c exceeds 50, the amount of amino groups in the hydroxyl-or alkoxy-terminated amino-modified silicone becomes too large, and the initial hydrophobicity and the durability of hydrophobicity of the film formed from the emulsion hydrophobizing agent composition deteriorate.

d is a real number satisfying d being more than or equal to 0 and less than or equal to 5. If d exceeds 5, the viscosity of the hydroxyl-or alkoxy-terminated amino-modified silicone is too high, and the stability of the emulsion hydrophobizing agent composition is deteriorated, and glare may occur on the glass surface due to an oil film. Preferably, d is 0.

e is a real number satisfying 0-5. If e exceeds 5, the viscosity of the hydroxyl-or alkoxy-terminated amino-modified silicone is too high, and the stability of the emulsion hydrophobizing agent composition is deteriorated, and glare may occur on the glass surface due to an oil film. Preferably, e is 0.

(B) Amino-modified silicones

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

[ chemical formula 8]

(B) The amino-modified silicone has a viscosity of 50 to 5,000 mPas at 25 ℃. The viscosity is preferably 55 to 4,500 mPas, and more preferably 60 to 4,000 mPas. If the viscosity is less than the above lower limit, the initial hydrophobicity and the durability of the hydrophobicity of the film formed from the emulsion hydrophobizing agent composition are deteriorated. When the viscosity exceeds the above upper limit, the stability of the emulsion hydrophobizing agent composition is deteriorated, and glare due to an oil film is generated on the glass surface.

Further, the amino-modified silicone (B) has an amino equivalent of 300 to 4,000g/mol at 25 ℃. The amino equivalent is preferably 320 to 3,800g/mol, more preferably 330 to 3,600 g/mol. If the amino group equivalent is less than the lower limit, the number of amino groups is too large, and thus the initial hydrophobicity and the durability of the hydrophobicity of the film formed from the emulsion hydrophobizing agent composition are deteriorated. If the amino group equivalent exceeds the above upper limit, the amino group is too small, and thus the hydrophilicity to be provided by the amino group-modified silicone is insufficient. This may deteriorate the stability of the emulsion hydrophobizing agent composition, and may cause glare on the glass surface due to an oil film.

The amount of the amino-modified silicone (B) is 0 to 80 parts by mass, based on 100 parts by mass of the total amount of the component (A) and the component (B). If the amount exceeds 80 parts by mass, the durability of the film formed from the emulsion hydrophobizing agent composition to be hydrophobic on the glass surface is deteriorated.

In the above formula (3), R¹And R in the above formula (1)¹The same is true. Among them, methyl, long-chain alkyl and phenyl are preferable. Furthermore, R²And R in the above formula (1)²The same is true. Among them, 3-aminopropyl group or N- (2-aminoethyl) -3-aminopropyl group is preferably used.

R⁶Independently of one another, are selected from the abovementioned radicals R¹And R²A group in the option (1). Wherein, when h is 0 in the above formula (3), R⁶Is selected from R²A group in the option (1). The amino-modified silicone may be used alone or two or more of these amino-modified silicones may be used together as component (B).

f is a real number satisfying 2 ≤ f ≤ 10. If f is less than 2, the viscosity of the amino-modified silicone becomes too high, and the stability of the emulsion hydrophobizing agent composition becomes poor. If f exceeds 10, the viscosity of the amino-modified silicone is too low, and the initial hydrophobicity and the durability of the hydrophobicity of the film formed from the emulsion hydrophobizing agent composition deteriorate. Preferably, f is 2.

g is a real number satisfying 10. ltoreq. g.ltoreq.1,000. If g is less than 10, the viscosity of the amino-modified silicone is too low, and the initial hydrophobicity and the hydrophobic durability of the film formed from the emulsion hydrophobizing agent composition deteriorate. When g exceeds 1,000, the viscosity of the amino-modified silicone becomes too high, and the stability of the emulsion hydrophobizing agent composition becomes poor. Preferably, the range of 20. ltoreq. g.ltoreq.800 is satisfied.

h is a real number satisfying h is more than or equal to 0 and less than or equal to 50. In particular, when h is 1 or more, the amount of amino groups in the (B) amino-modified silicone is large, so that the water repellency durability of the film formed from the emulsion hydrophobizing agent composition and the stability of the emulsion hydrophobizing agent composition are high, and glare due to an oil film does not occur on the glass surface. Wherein, when h is 0, R⁶Is selected from R²A group in the option (1). When h exceeds 50, the amount of amino groups in the amino-modified silicone becomes too large, and the initial hydrophobicity and the durability of hydrophobicity of the film formed from the emulsion hydrophobizing agent composition deteriorate.

i is a real number satisfying 0. ltoreq. i.ltoreq.5. If i exceeds 5, the viscosity of the amino-modified silicone is too high, and the stability of the emulsion hydrophobizing agent composition is deteriorated, and glare may occur on the glass surface due to an oil film. Preferably, i is 0.

j is a real number satisfying j being 0 or more and 5 or less. If j exceeds 5, the viscosity of the amino-modified silicone is too high, and the stability of the emulsion hydrophobizing agent composition is deteriorated, and glare may occur on the glass surface due to an oil film. Preferably, j is 0.

The surfactant (C) contained in the emulsion hydrophobizing agent composition of the present invention is not particularly limited as long as it can emulsify and disperse the component (a) and the component (B) in water, and examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene fatty acid esters.

Specific examples of these surfactants include Polyoxyethylene octyl ether, Polyoxyethylene nonyl ether, Polyoxyethylene decyl ether, Polyoxyethylene oxypropylene decyl ether, Polyoxyethylene lauryl ether, Polyoxyethylene polyoxypropylene ether, Polyoxyethylene tridecyl ether, Polyoxyethylene oxypropylene tridecyl ether, cetyl Polyoxyethylene ether, Polyoxyethylene stearyl ether (polyoxyyethylene stearyl ether), Polyoxyethylene oleyl ether, Polyoxyethylene sorbitan monolaurate, Polyoxyethylene sorbitan monopalmitate, Polyoxyethylene sorbitan monostearate, Polyoxyethylene sorbitan tristearate, Polyoxyethylene sorbitan monooleate, and Polyoxyethylene sorbitan trioleate. These nonionic surfactants may be used alone or 2 or more of these nonionic surfactants may be used in combination as component (C).

In addition, anionic surfactants such as alkyl sulfate, alkylbenzene sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and amphoteric surfactants such as alkylbetaines and alkylimidazolines.

The amount of component (C) added is 2 to 100 parts by mass per 100 parts by mass of the total amount of components (A) and (B). If the addition amount is less than 2 parts by mass, the stability of the emulsion hydrophobizing agent composition deteriorates, and if the addition amount exceeds 100 parts by mass, the initial hydrophobicity and the hydrophobicity durability of the film formed from the emulsion hydrophobizing agent composition deteriorate. The addition amount is preferably 2 to 50 parts by mass. When the amount is 2 parts by mass or more, the stability of the emulsion hydrophobizing agent composition is good, and when the amount is 50 parts by mass or less, the initial hydrophobicity and the hydrophobicity durability of the film formed from the emulsion hydrophobizing agent composition are further good. The amount of the additive is more preferably 3 to 40 parts by mass, and still more preferably 4 to 30 parts by mass.

The surfactant preferably has an HLB value of 3.0 to 19.0. When 2 or more species are used simultaneously, the total HLB value may be 7.0 to 16.0.

(D) Polyether modified organic silicon

The polyether-modified silicone (D) of the present invention is represented by the following average composition formula (4).

[ chemical formula 9]

(D) The polyether modified organic silicon has HLB of 5-13 at 25 ℃. The HLB is preferably 5.5 to 12.5, and more preferably 6.0 to 12.0. If the HLB is less than 5, it is difficult to sufficiently emulsify and disperse the components (a) and (B). Further, the polyether-modified silicone having an HLB of more than 13 has poor compatibility with the component (a) and the component (B), and the stability, particularly dilution stability of the obtained emulsion hydrophobizing agent composition is poor.

(D) The polyether modified organic silicon has viscosity of 10-10,000 mPa & s at 25 ℃. The viscosity is preferably 40 to 5,000 mPas, and more preferably 50 to 4,000 mPas. If the amount is less than the above lower limit, it is difficult to sufficiently emulsify and disperse the component (a) and the component (B). If the amount exceeds the above upper limit, the emulsion hydrophobizing agent composition is difficult to handle.

In the above formula (4), R¹And R in the above formula (1)¹The same is true. Among them, methyl, long-chain alkyl and phenyl are preferable. (D) Since the component (C) is used together with the component (A) for emulsifying and dispersing the components (A) and (B), a strongly hydrophobic group is not preferable. However, when the dispersibility with an organic compound such as wax is to be improved, it is preferable to use a long-chain alkyl group and a phenyl group. Further, R as a compound represented by the formula (4)¹Plural organic substituents may be used simultaneously, and when plural are used simultaneously, methyl is preferable to the substituent R¹、R⁷And R⁸The content of (b) is 90% or more.

R⁷Independently of one another, of the general formula (5): -R⁹-O-(C₂H₄O)_x-(C₃H₆O)_y-(C₄H₈O)_z-R¹⁰Polyether radical. In the formula (5), R⁹Examples of the divalent organic group having 1 to 6 carbon atoms include alkylene, alkenylene, and arylene groups. R¹⁰Is selected from-H, -CH₃、-C₂H₅、-C₃H₇、-C₄H₉And- (C ═ O) CH₃The group of (1).

x is a real number satisfying a range of 5. ltoreq. x.ltoreq.30. When x is less than 5, the HLB of component (D) is too low, and it is difficult to sufficiently emulsify and disperse components (A) and (B). Further, when x exceeds 30, handling at the time of use is difficult because the viscosity of the (D) component increases or a solid is formed at normal temperature. Preferably, it satisfies the range of 5. ltoreq. x.ltoreq.25.

y is a real number satisfying the range of 0. ltoreq. y.ltoreq.30. When y exceeds 30, HLB of the component (D) is too low, and it is difficult to sufficiently emulsify and disperse the components (A) and (B). Preferably, the range of 0. ltoreq. y.ltoreq.25 is satisfied.

z is a real number satisfying a range of 0. ltoreq. z.ltoreq.30. When z exceeds 30, the HLB of the component (D) is too low, and it is difficult to sufficiently emulsify and disperse the components (A) and (B). Preferably, it satisfies the range of 0. ltoreq. z.ltoreq.15.

R⁸Is selected from the group consisting of the R¹And R⁷Or a group selected from the group consisting of hydroxyl, methoxy and ethoxy. Wherein, when R is 0 in the above formula (4), R⁸Is selected from R⁷A group in the option (1).

q is a real number satisfying a range of 0. ltoreq. q.ltoreq.100. When q exceeds 100, it is difficult to sufficiently emulsify and disperse the component (a) and the component (B) because the HLB of the component (D) is too low. Preferably, it satisfies the range of 5. ltoreq. q.ltoreq.80.

r is a real number satisfying a range of 0. ltoreq. r.ltoreq.40. In particular, when r is 1 or more, the HLB of the component (D) is suitable, and the components (a) and (B) can be sufficiently emulsified and dispersed. Wherein when R is⁸＝R⁷When r is less than 1, r may be 0. When r exceeds 40, the viscosity of the component (D) is too high, and therefore handling is difficult in use.

The amount of component (D) added is 1 to 25 parts by mass per 100 parts by mass of the total amount of components (A) and (B). The addition amount is preferably 3 to 23 parts by mass, and more preferably 5 to 20 parts by mass. If the amount of component (D) is outside this range, a stable emulsion hydrophobizing agent composition cannot be obtained.

[ (E) Water ]

The emulsion hydrophobizing agent composition of the present invention can be prepared by mixing (E) water with the above-mentioned component (a), (B), (C) and (D) and emulsifying and dispersing them according to a conventional method. (E) The water is preferably ion-exchanged water. The content of (E) water is 10 to 2,000 parts by mass, preferably 50 to 1,000 parts by mass, based on 100 parts by mass of the total amount of the component (A) and the component (B). An emulsion hydrophobizing agent composition can be obtained by mixing the above components (a) to (E) and emulsifying and dispersing the mixture. In particular, an oil-in-water (O/W type) emulsion hydrophobizing agent composition usually forms a white emulsion, but when the average particle diameter of emulsified particles is 300nm or less, a blue-white or transparent microemulsion may be formed in appearance. The obtained emulsion hydrophobizing agent composition can be diluted with water and used for the application described later. The amount of water used for dilution is not particularly limited as long as it is appropriately adjusted according to the use. The emulsion hydrophobe compositions of the present invention have excellent stability after dilution.

Other additives

In addition to the components (a) to (E), various additives may be blended in the emulsion hydrophobizing agent composition of the present invention as needed. 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 additive may be added in any amount, but it is preferable to adjust the pH of the emulsion hydrophobizing agent composition of the present invention to 3 to 7.

Further, as other additives, a thickener, an antifreeze, an antiseptic, a rust inhibitor, an antioxidant, an ultraviolet absorber, and the like may be included.

Emulsion hydrophobicizer composition

The average particle diameter of the emulsified particles in the emulsion hydrophobizing agent composition of the present invention is preferably 300nm or less, and more preferably 200nm or less. In the present invention, the average particle size is a volume-based average particle size, and can be measured using a submicron particle size distribution measuring apparatus (Coulter N4 Plus) manufactured by Beckman Coulter co.

The emulsion hydrophobizing agent composition of the present invention can be easily used for coating treatment of vehicles such as automobiles using automatic car washers such as door type car washers, continuous door type car washers, and spray type car washers. That is, the emulsion hydrophobizing agent composition of the present invention can be used as a coating agent for vehicles. The concentration of the coating agent when spraying or coating the surface of the vehicle is not particularly limited, and the concentration of the emulsion hydrophobizing agent composition of the present invention and the automatic dilution ratio of the automatic car washer may be set so that the concentrations of the amino-modified silicone of the component (a) and the component (B) are about 0.01 to 0.5 mass%. The emulsion hydrophobizing agent composition of the present invention can impart hydrophobicity, glossiness, smoothness, and the like having long-term persistence to a coated surface, a glass surface, and the like of a vehicle.

Furthermore, the emulsion hydrophobicizer compositions of the invention can of course also be suitable for other applications where hydrophobicity is required.

Examples

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, parts represent parts by mass and% represents% by 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 N4 Plus manufactured by Beckman Coulter co. The viscosity is an absolute viscosity measured at 25 ℃ using a type B rotary viscometer, and is a value measured using a TVB-10 type viscometer manufactured by Toki Sangyo co.

The components used in the examples and comparative examples are described below.

(A) Amino-modified silicones terminated with hydroxy or alkoxy groups

Amino-modified silicone terminated with hydroxyl or alkoxy groups 1: a compound represented by the following average composition formula (1) having a viscosity of 65 mPas and an amino equivalent weight of 780g/mol, wherein R¹：-CH₃，R²：-C₃H₆NHC₂H₄NH₂，R³：-OCH₃，a＝2，b＝38，c＝2，d＝0，e＝0

[ chemical formula 10]

Amino-modified silicone 2 terminated with hydroxyl or alkoxy groups: a compound represented by the average composition formula (1) having a viscosity of 700 mPas and an amino equivalent weight of 1,860g/mol, wherein R¹：-CH₃，R²：-C₃H₆NHC₂H₄NH₂，R³：-OCH₃Amino-modified silicone 3 terminated with hydroxyl or alkoxy groups, a ═ 2, b ═ 198, c ═ 4, d ═ 0, e ═ 0: a compound represented by the average composition formula (1) having a viscosity of 350 mPas and an amino equivalent weight of 1,900g/mol, wherein R¹：-CH₃，R²：-C₃H₆NHC₂H₄NH₂，R³：-OC₂H₅，a＝2，b＝120，c＝2.5，d＝0，e＝0

Amino-modified silicone 4 terminated with hydroxyl or alkoxy groups (comparative): a compound represented by the average composition formula (1) above, having a viscosity of 30,000 mPas and an amino equivalent weight of 20,000g/mol, wherein R¹：-CH₃，R²：-C₃H₆NH₂，R³：-OH，a＝2，b＝1078，c＝2.2，d＝0，e＝0

(B) Amino-modified silicones

Amino-modified silicone 5: a compound represented by the following average composition formula (3) having a viscosity of 70 mPas and an amino equivalent weight of 350g/mol, wherein R¹：-CH₃，R²：-C₃H₆NHC₂H₄NH₂，R⁶：-CH₃，f＝2，g＝28，h＝4，i＝0，j＝0

[ chemical formula 11]

Amino-modified silicone 6: a compound represented by the average composition formula (3) having a viscosity of 1,200 mPas and an amino equivalent weight of 1,800g/mol, wherein R¹：-CH₃，R²：-C₃H₆NHC₂H₄NH₂，R⁶：-CH₃，f＝2，g＝294，h＝6.3，i＝0，j＝0

Amino-modified silicone 7: a compound represented by the average composition formula (3) having a viscosity of 3,600 mPas and an amino equivalent weight of 1,800g/mol, wherein R¹：-CH₃，R²：-C₃H₆NHC₂H₄NH₂，R⁶：-CH₃，f＝2，g＝634，h＝14.5，i＝0，j＝0

Amino-modified silicone 8: a compound represented by the average composition formula (3) having a viscosity of 1,500 mPas and an amino equivalent weight of 3,500g/mol, wherein R¹：-CH₃，R²：-C₃H₆NHC₂H₄NH₂，R⁶：-CH₃，f＝2，g＝350，h＝3.5，i＝0，j＝0

Amino-modified silicone 9 (comparative): average of the aboveA compound represented by the compositional formula (3) having a viscosity of 1,200 mPas and an amino equivalent of 11,000g/mol, wherein R¹：-CH₃，R²：-C₃H₆NHC₂H₄NH₂，R⁶：-CH₃，f＝2，g＝300，h＝1.0，i＝0，j＝0

Table 1 shows a composition list of the components (A) and (B).

[ Table 1]

[ (C) surfactant ]

NOIGEN XL-40 (trade name): DKS co.ltd. polyoxyalkylenedecyl ether with HLB of 10.5 is produced

NOIGEN XL-400D (trade name): DKS co.ltd. production of a 65 mass% aqueous solution of polyoxyalkylene decyl ether with HLB of 18.4

Newcol 1004 (trade name): nippon Nyukazai co., ltd. manufacture polyoxyethylene octyl ether, HLB 11.5

Newcol1008 (trade name): nippon Nyukazai co., ltd. manufacture polyoxyethylene octyl ether, HLB 14.6

RHEODOL TW-L106 (trade name): polyoxyethylene sorbitan monolaurate manufactured by Kao Corporation, HLB 13.3

RHEODOL TW-O320V (trade name): polyoxyethylene sorbitan monooleate manufactured by Kao Corporation, HLB being 11.0

(D) Polyether modified organic silicon

Polyether modified silicone 1: a compound represented by the following average composition formula (4) and having a viscosity of 1,600 mPas and an HLB of 7, wherein R¹：-CH₃，R⁷：-C₃H₆O-(C₂H₄O)₂₃(C₃H₆O)₂₃C₄H₉，R⁸：-CH₃，q＝27，r＝3

[ chemical formula 12]

Polyether modified silicone 2: a compound represented by the average composition formula (4) and having a viscosity of 430 mPas and an HLB of 10, wherein R is¹：-CH₃，R⁷：-C₃H₆O-(C₂H₄O)_9.4H，R⁸：-CH₃，q＝24，r＝4

Polyether modified silicone 3: a compound represented by the average composition formula (4) and having a viscosity of 70 mPas and an HLB of 12, wherein R¹：-CH₃，R⁷：-C₃H₆O-(C₂H₄O)₁₀CH₃，R⁸：-CH₃，q＝10，r＝5

Polyether modified silicone 4 (comparative): a compound represented by the average composition formula (4) and having a viscosity of 20 mPas and an HLB of 14, wherein R is¹：-CH₃，R⁷：-C₃H₆O-(C₂H₄O)₈CH₃，R⁸：-CH₃，q＝0，r＝1

The composition of component (D) is shown in Table 2.

[ Table 2]

	Viscosity (mPa. s)	HLB
			Polyether modified organosilicon 1	1,600	7
Polyether modified organosilicon 2	430	10
			Polyether modified organosilicon 3	70	12
Polyether modified Silicone 4 (for comparison)	20	14

Additive: the preservative used in the following examples and comparative examples was "Proxel-BDN" (trade name: Arch Chemicals, Inc.)

[ example 1]

Using a homogenizer to mix (A) 20 parts by mass of methoxy-terminated amino-modified silicone 1 (viscosity: 65 mPas, amino equivalent: 780g/mol), (A) 80 parts by mass of methoxy-terminated amino-modified silicone 2 (viscosity: 700 mPas, amino equivalent: 1,860g/mol), (C) 20 parts by mass of NOIGEN XL-40 (HLB: 10.5), (C) 30 parts by mass of NOIGEN XL-400D (HLB: 18.4, 65% by mass aqueous solution), (D) 10 parts by mass of polyether-modified silicone 1 (viscosity: 1,600 mPas, HLB: 7), (E) 462.5 parts by mass of ion-exchanged water, 3.0 parts by mass of acetic acid, and 0.2 part by mass of a preservative, and emulsify and disperse to obtain a colorless and transparent amino-modified silicone emulsion water repellent composition (I-1) having a non-volatile component of 23.8% at 105 ℃/3 hours, the emulsified particles in the emulsion hydrophobizing agent composition had an average particle diameter of 30 nm.

[ example 2]

A colorless and transparent amino-modified silicone emulsion water repellent composition (I-2) having a non-volatile content of 24.4% at 105 ℃ C./3 hr, which was obtained by mixing (A) 30 parts by mass of methoxy-terminated amino-modified silicone 1 (viscosity: 65 mPas, amino equivalent: 780g/mol), (B) 70 parts by mass of amino-modified silicone 6 (viscosity: 1,200 mPas, amino equivalent: 1,800g/mol), (C) 20 parts by mass of NOIGEN XL-40 (HLB: 10.5), (C) 30 parts by mass of NOIGEN XL-400D (HLB: 18.4, 65% by mass aqueous solution), (D) 10 parts by mass of polyether-modified silicone 1 (viscosity: 1,600 mPas, HLB: 7), (E) 462.5 parts by mass of ion-exchanged water, 3.2 parts by mass of acetic acid, and 0.2 part by mass of a preservative, using a homogenizer and emulsifying and dispersing the mixture, the emulsified particles in the emulsion hydrophobizing agent composition had an average particle diameter of 45 nm.

[ example 3]

80 parts by mass of (A) methoxy-terminated amino-modified silicone 2 (viscosity: 700 mPas, amino equivalent: 1,860g/mol), 20 parts by mass of (B) amino-modified silicone 5 (viscosity: 70 mPas, amino equivalent: 350g/mol), 20 parts by mass of (C) NOIGEN XL-40 (HLB: 10.5), 20 parts by mass of (C) NOIGEN XL-400D (HLB: 18.4, 65% by mass aqueous solution), 30 parts by mass of (D) polyether-modified silicone 2 (viscosity: 430 mPas, HLB: 10), 10 parts by mass of (E) ion-exchanged water 462.5 parts by mass of (E), acetic acid 4.0 parts by mass of (acetic acid), and preservative 0.2 parts by mass were mixed and emulsified and dispersed using a homogenizer to obtain a bluish-white slightly turbid amino-modified silicone emulsion water repellent composition (I-3) having a non-volatile component of 24.6% at 105 ℃/3 hours, the emulsified particles in the emulsion hydrophobizing agent composition had an average particle size of 120 nm.

[ example 4]

Using a homogenizer to mix (a) 20 parts by mass of methoxy-terminated amino-modified silicone 1 (viscosity: 65mPa · s, amino equivalent: 780g/mol), (B) 80 parts by mass of amino-modified silicone 7 (viscosity: 3,600mPa · s, amino equivalent: 1,800g/mol), (C) 20 parts by mass of Newcol 1004(HLB ═ 11.5), 20 parts by mass of Newcol1008(HLB ═ 14.6), (D) 10 parts by mass of polyether-modified silicone 3 (viscosity: 70mPa · s, HLB: 12), (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, and emulsify and disperse to obtain a colorless and transparent amino-modified silicone emulsion hydrophobizing agent composition (I-4), the non-volatile component of the amino-modified silicone emulsion hydrophobizing agent composition (I-4) at 105 ℃/3 hours was 24.6%, and the average particle diameter of the emulsified particles in the emulsion hydrophobizing agent composition was 30 nm.

[ example 5]

A colorless and transparent amino-modified silicone emulsion water repellent composition (I-5) having 24.9% of non-volatile components at 105 ℃/3 hours was obtained by mixing (A) 30 parts by mass of methoxy-terminated amino-modified silicone 1 (viscosity: 65 mPas, amino equivalent: 780g/mol), (B) 70 parts by mass of amino-modified silicone 8 (viscosity: 1,500 mPas, amino equivalent: 3,500g/mol), (C) 20 parts by mass of Newcol 1004 (HLB: 11.5), (C) 20 parts by mass of Newcol1008 (HLB: 14.6), (D) 10 parts by mass of polyether-modified silicone 1 (viscosity: 1,600 mPas, HLB: 7), (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 with a homogenizer and emulsifying and dispersing the mixture, the emulsified particles in the emulsion hydrophobizing agent composition had an average particle size of 60 nm.

[ example 6]

100 parts by mass of (a) methoxy group-terminated amino-modified silicone 3 (viscosity: 350mPa · s, amino equivalent: 1,900g/mol), (C) 20 parts by mass of Newcol 1004 (HLB: 11.5), 20 parts by mass of Newcol1008 (HLB: 14.6), (D) 10 parts by mass of polyether-modified silicone 2 (viscosity: 430mPa · s, HLB: 10), (E) 462.5 parts by mass of ion-exchanged water, 2.2 parts by mass of acetic acid, and 0.2 part by mass of a preservative were mixed by a homogenizer and emulsified and dispersed to obtain a colorless and transparent amino-modified silicone emulsion water repellent composition (I-6), in which the nonvolatile content at 105 ℃/3 hours of the amino-modified silicone emulsion water repellent composition (I-6) was 23.4%, and the average particle size of emulsified particles in the emulsion water repellent composition was 40 nm.

[ example 7]

A colorless and transparent amino-modified silicone emulsion water repellent composition (I-7) having a nonvolatile component of 23.7% at 105 ℃/3 hours was obtained by mixing (A) 20 parts by mass of methoxy-terminated amino-modified silicone 1 (viscosity: 65 mPas, amino equivalent: 780g/mol), (A) 80 parts by mass of methoxy-terminated amino-modified silicone 2 (viscosity: 700 mPas, amino equivalent: 1,860g/mol), (C) 20 parts by mass of RHEODOL TW-L106 (HLB: 13.3), (C) 20 parts by mass of RHEODOL TW-O320V (HLB: 11.0), (D) 10 parts by mass of polyether-modified silicone 1 (viscosity: 1,600 mPas, 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 with a homogenizer and emulsifying and dispersing, the emulsified particles in the emulsion hydrophobizing agent composition had an average particle size of 50 nm.

Comparative example 1

70 parts by mass of (A) methoxy-terminated amino-modified silicone 1 (viscosity: 65 mPas, amino equivalent: 780g/mol), (A) hydroxy-terminated amino-modified silicone 4 (viscosity: 30,000 mPas, amino equivalent: 20,000g/mol)30 parts by mass, (C) NOIGEN XL-40 (HLB: 10.5)20 parts by mass, NOIGEN XL-400D (HLB: 18.4, 65% by mass aqueous solution) 30 parts by mass, (D) polyether-modified silicone 1 (viscosity: 1,600 mPas, HLB: 7)10 parts by mass, (E) 462.5 parts by mass of ion-exchanged water, 3.8 parts by mass of acetic acid, and 0.2 part by mass of a preservative were mixed and emulsified and dispersed using a homogenizer to obtain a white emulsified amino-modified silicone emulsion water repellent composition (II-1) which had a non-volatile component of 24.9% at 105 ℃/3 hours, the emulsified particles in the emulsion hydrophobizing agent composition had an average particle size of 250 nm.

Comparative example 2

70 parts by mass of (A) methoxy-terminated amino-modified silicone 1 (viscosity: 65 mPas, amino equivalent: 780g/mol), (B) amino-modified silicone 9 (viscosity: 1,200 mPas, amino equivalent: 11,000g/mol)30 parts by mass, (C) NOIGEN XL-40 (HLB: 10.5)20 parts by mass, (C) NOIGEN XL-400D (HLB: 18.4, 65% by mass aqueous solution) 30 parts by mass, (D) polyether-modified silicone 1 (viscosity: 1,600 mPas, HLB: 7)10 parts by mass, (E) 462.5 parts by mass of ion-exchanged water, 3.8 parts by mass of acetic acid, and 0.2 part by mass of a preservative were mixed and emulsified and dispersed using a homogenizer to obtain a blue-white slightly turbid amino-modified silicone emulsion water repellent composition (II-2) having a non-volatile component of 24.2% at 105 ℃/3 hours, the emulsified particles in the emulsion hydrophobizing agent composition had an average particle size of 120 nm.

Comparative example 3

100 parts by mass of (B) amino-modified silicone 7 (viscosity: 3,600mPa · s, amino equivalent: 1,800g/mol), (C) 20 parts by mass of Newcol 1004 (HLB: 11.5), 20 parts by mass of Newcol1008 (HLB: 14.6), (D) 10 parts by mass of polyether-modified silicone 2 (viscosity: 430mPa · s, HLB: 10), (E) 462.5 parts by mass of ion-exchanged water, 2.5 parts by mass of acetic acid, and 0.2 part by mass of a preservative were mixed by a homogenizer and emulsified and dispersed to obtain a colorless and transparent amino-modified silicone emulsion water repellent composition (II-3), in which the nonvolatile content at 105 ℃/3 hours of the amino-modified silicone emulsion water repellent composition (II-3) was 23.8%, and the average particle size of emulsified particles in the emulsion water repellent composition was 40 nm.

Comparative example 4

Using a homogenizer to mix (a) 20 parts by mass of methoxy-terminated amino-modified silicone 1 (viscosity: 65mPa · s, amino equivalent: 780g/mol), (a) 80 parts by mass of methoxy-terminated amino-modified silicone 2 (viscosity: 700mPa · s, amino equivalent: 1,860g/mol), (C) 20 parts by mass of NOIGEN XL-40(HLB ═ 10.5), (C) 30 parts by mass of NOIGEN XL-400D (HLB ═ 18.4, 65% by mass aqueous solution), (D) 10 parts by mass of polyether-modified silicone 4 (viscosity: 20mPa · 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, and emulsify and disperse to obtain a colorless and transparent amino-modified silicone emulsion water repellent composition (II-4) having a non-volatile component of 24.8% at 105 ℃/3 hours, the emulsified particles in the emulsion hydrophobizing agent composition had an average particle size of 70 nm.

Comparative example 5

20 parts by mass of (A) methoxy-terminated amino-modified silicone 1 (viscosity: 65 mPas, amino equivalent: 780g/mol), 80 parts by mass of (A) methoxy-terminated amino-modified silicone 2 (viscosity: 700 mPas, amino equivalent: 1,860g/mol), 20 parts by mass of (C) NOIGEN XL-40 (HLB: 10.5), 30 parts by mass of (C) NOIGEN XL-400D (HLB: 18.4, 65% by mass aqueous solution), 462.5 parts by mass of ion-exchanged water, 3.0 parts by mass of acetic acid, and 0.2 part by mass of a preservative were mixed by a homogenizer and emulsified and dispersed to obtain a colorless and transparent amino-modified silicone emulsion hydrophobizing agent composition (II-5), the non-volatile component of the amino-modified silicone emulsion hydrophobizing agent composition (II-5) at 105 ℃/3 hours was 22.3%, and the average particle diameter of the emulsified particles in the emulsion hydrophobizing agent composition was 80 nm.

[ hydrophobic durability ]

The amino-modified silicone emulsion hydrophobizing agent compositions obtained in examples 1 to 7 and comparative examples 1 to 5 were diluted 150-fold with tap water, and then sprayed onto the coating surface and glass surface of an automobile using a spray gun. After completion of spraying, washing was repeated 1 time with tap water, and the time from the stop of washing to the break of the water film was measured. The results are shown in tables 3 and 4 below as initial values. Then, the cleaning was repeated 15 times with tap water, and the time from the stop of the cleaning to the break of the water film was measured. The results are shown in tables 3 and 4 below.

[ Glare of glass surface ]

After the above-mentioned test of the hydrophobic durability was completed, the glass surface was wiped 3 times with a rubber wiper (wiper). The glass surface at this time was visually observed to have oil-free film residue/glare. The results are shown in tables 3 and 4 below.

< evaluation criteria >

O: no oil film; and (delta): a trace oil film exists; x: with oil film/glare

[ stability ]

The amino-modified silicone emulsion hydrophobizing agent compositions (stock solutions) prepared in examples 1 to 7 and comparative examples 1 to 5 were put into a glass bottle, stored at 40 ℃ for 2 weeks, and then visually observed for the presence or absence of separation. "stock solution stability" was evaluated according to the following criteria. The results are shown in tables 3 and 4.

< evaluation criteria >

O: no separation is carried out; and (delta): carrying out concentration separation; x: separated into two layers

Furthermore, the amino-modified silicone emulsion hydrophobizing agent compositions (stock solutions) prepared in examples 1 to 7 and comparative examples 1 to 5 were diluted 150-fold with tap water, and the resulting dilutions were placed in glass bottles, and after storage at 40 ℃ for 2 weeks, the presence or absence of separation was visually observed. The "dilution stability" was evaluated according to the following criteria. The results are shown in tables 3 and 4.

< evaluation criteria >

O: no precipitate is generated; and (delta): there is a trace of precipitate; x: with precipitates

[ Table 3]

[ Table 4]

As shown in table 3, the emulsion hydrophobizing agent composition of the present invention can be effectively used as a hydrophobizing agent having excellent hydrophobicity, and particularly, can impart good initial hydrophobicity and hydrophobic durability to both a coated surface and a glass surface of an automobile, and can remove glare caused by an oil film on the glass surface, and is also excellent in stock solution stability and dilution stability.

Industrial applicability

The emulsion hydrophobizing agent composition of the present invention imparts excellent hydrophobicity to both a coated surface and a glass surface, and removes glare on the glass surface. Further, the stock solution stability and dilution stability are also excellent. The emulsion hydrophobizing agent composition of the present invention is useful as a cleaning agent or a coating agent for coating a vehicle using an automatic car washer.

The present invention is not limited to the above embodiments. The above embodiments are merely exemplary, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operational effects are included in the technical scope of the present invention.

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