TW202104446A - Emulsion type water-repelling agent composition - Google Patents

Abstract

The present invention is an emulsion type water-repelling agent composition that contains: 20-100 parts by mass of (A) a specific amino-modified silicone that is terminally blocked with a hydroxyl group or an alkoxy group; 0-80 parts by mass of (B) an amino-modified silicone (here, the total amount of component (A) and component (B) is 100 parts by mass); 2-100 parts by mass of (C) a surfactant; 1-25 parts by mass of (D) a specific polyether-modified silicone; and 10-2000 parts by mass of (E) water. Provided by this configuration is an emulsion type water-repelling agent composition which is effective as a water-repelling agent having excellent water repellency, can impart good initial water repellency and long term water repellency to both a painted surface and a glass surface of a motor vehicle in particular, and can impart the property of eliminating glare due to an oil film on a glass surface.

Description

Emulsion water repellent composition

The invention relates to an emulsion water repellent composition.

So far, in coating agents for imparting water repellency to the surface of vehicles such as automobiles, the following aqueous emulsions have been applied: an aqueous emulsion containing modified amine-based polysiloxane as a main component. Amino-modified polysiloxane is made by substituting a part of the methyl group of dimethyl polysiloxane with amino alkyl or amino alkyl substituted by amino alkyl, and when applied to vehicles When it is on the surface, it can be adsorbed on the surface of the vehicle by the amine group, giving it more durable water-repellent performance than dimethyl polysiloxane.

In the previous method of use, it was used in the form of an aqueous emulsion: an aqueous emulsion obtained by emulsifying an amino-modified polysiloxane with a nonionic surfactant. Patent Document 1 discloses a coating agent, which It is obtained from the following aqueous emulsion: In order to further improve the adsorptivity of amine-modified polysiloxane, a specific cationic surfactant is used in combination. In addition, Patent Document 2 discloses a gloss and water-repellent imparting composition, which uses a nonionic surfactant having a specific hydrophilic-lipophilic balance (HLB) to modify amine-modified polysiloxane and dimethyl polysiloxane, respectively. After the alkane is emulsified, these are mixed together.

These aqueous emulsions with amine-modified polysiloxane as the main component have been used in the following: using a door-type automatic car washing machine, diluted with water to tens to hundreds of times and spray coating, and Gives water repellency to the surface of vehicles such as automobiles. At this time, not only the water repellency to the painted surface of the vehicle but also to the glass surface such as the front windshield of the vehicle, and the glare free from the oil film, the performance of the glass surface that is easy to be recognized by driving will become Important elements. However, although the prior art can achieve water repellency to the painted surface of a vehicle, it cannot provide sufficient performance to the glass surface, and further improvements in characteristics are being sought. [Prior Technical Literature] (Patent Document)

Patent Document 1: Japanese Patent Application Laid-Open No. 8-188745 Patent Document 2: Japanese Patent Application Publication No. 2004-300387

[The problem to be solved by the invention] The present invention was developed in view of the above-mentioned reasons, and its purpose is to provide an emulsion water-repellent composition that can be effectively used as a water-repellent with excellent water repellency, and can be particularly effective on both the painted surface and the glass surface of automobiles. Provides good initial water repellency and water repellency durability, and imparts the performance of removing glare caused by oil film to the glass surface. [Technical means to solve the problem]

式(1)中，R¹ 相互獨立地為碳原子數1～20的未被取代的一價烴基，R² 相互獨立地為由通式(2)也就是－Ｒ^４ －（ＮＨ－Ｒ^５ －）_ｐ ＮＨ_２ 表示的基，前述式(2)中，R⁴ 及R⁵ 相互獨立地為碳原子數1～6的二價有機基，p為0或1，R³ 相互獨立地為羥基或從甲氧基及乙氧基之中選出的基，a、b、c、d及e分別為滿足2≦a≦10、10≦b≦1,000、1≦c≦50、0≦d≦5、0≦e≦5的範圍的實數； (B)0～80質量份的胺基改質矽氧，其由下述通式(3)表示，在25℃時，具有黏度50～5,000 mPa・s且具有胺基當量300～4,000 g/mol，但是將(A)成分與(B)成分的合計量設為100質量份，

式(3)中，R¹ 、R² 與上述相同，R⁶ 相互獨立地為從R¹ 及R² 的選項中選出的基，f、g、h、i及j分別為滿足2≦f≦10、10≦g≦1,000、0≦h≦50、0≦i≦5、0≦j≦5的範圍的實數，但是上述式(3)中，h＝0時，R⁶ 為從R² 的選項中選出的基； (C)2～100質量份的界面活性劑，其為從非離子系界面活性劑、陰離子系界面活性劑、陽離子系界面活性劑及兩性離子系界面活性劑之中選出的至少1種； (D)1～25質量份的聚醚改質矽氧，其由下述平均組成式(4)表示，在25℃時，具有黏度10～10,000 mPa・s且具有親水親油平衡(HLB)值 5～13，

式(4)中，R¹ 與上述相同，R⁷ 相互獨立地為由通式(5)也就是－Ｒ^９ －Ｏ－（Ｃ_２ Ｈ_４ Ｏ）_ｘ －（Ｃ_３ Ｈ_６ Ｏ）_ｙ －（Ｃ_４ Ｈ_８ Ｏ）_ｚ －Ｒ^１０ 表示的聚醚基，前述式(5)中，R⁹ 為碳原子數1～6的二價有機基，R¹⁰ 為從－H、－CH₃ 、－C₂ H₅ 、－C₃ H₇ 、－C₄ H₉ 及－(C＝O)CH₃ 之中選出的基，x、y及z為滿足5≦x≦30、0≦y≦30、0≦z≦30的範圍的實數，R⁸ 為從前述R¹ 及R⁷ 的選項中選出的基、或從－OH、－OCH₃ 及－OC₂ H₅ 之中選出的基，q及r分別為滿足0≦q≦100、0≦r≦40的範圍的實數，但是r＝0時R⁸ 為R⁷ ； (E)10～2,000質量份的水。In order to solve the above-mentioned problem to be solved, the present invention provides an emulsion water repellent composition, which contains the following components (A) to (E): (A) 20-100 parts by mass of the terminal is hydroxy or alkoxy The blocked amine modified silica, which is represented by the following general formula (1), has a viscosity of 30 to 2,000 mPa·s and an amine equivalent of 300 to 3,000 g/mol at 25°C,

In the formula (1), R ^{1 is} independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ^{2 is} independently determined by the general formula (2), which is -R ^4- (NH-R ⁵ －) _{The group represented by p} NH ₂ , in the above formula (2), R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1, and R ^{3 is} independently a hydroxyl group Or a group selected from methoxy and ethoxy, a, b, c, d, and e satisfy 2≦a≦10, 10≦b≦1,000, 1≦c≦50, 0≦d≦5, respectively , A real number in the range of 0≦e≦5; (B) 0 to 80 parts by mass of amino modified silica, which is represented by the following general formula (3), and has a viscosity of 50 to 5,000 mPa at 25°C. s has an amine group equivalent of 300 to 4,000 g/mol, but the total amount of (A) component and (B) component is 100 parts by mass,

In formula (3), R ¹ and R ² are the same as above, R ^{6 is} independently ^{a group selected from the options of R 1} and R ² , and f, g, h, i, and j are each satisfying 2≦f≦ 10. 10≦g≦1,000, 0≦h≦50, 0≦i≦5, 0≦j≦5, but in the above formula (3), when h=0, R ⁶ is the range from R ² The base selected from the options; (C) 2-100 parts by mass of surfactant, which is selected from nonionic surfactants, anionic surfactants, cationic surfactants and zwitterionic surfactants (D) 1-25 parts by mass of polyether modified silica, which is represented by the following average composition formula (4), at 25°C, has a viscosity of 10-10,000 mPa·s and has a hydrophilic affinity Oil balance (HLB) value 5～13,

In the formula (4), R ¹ is the same as above, and R ^{7 is} independent of each other by the general formula (5), which is -R ⁹ -O-(C ₂ H ₄ O) _x- (C ₃ H ₆ O) _y- (C ₄ H ₈ O) _Z -R ¹⁰ represents a polyether group. In the aforementioned formula (5), R ⁹ is a divalent organic group with 1 to 6 carbon atoms, and R ¹⁰ is from -H, -CH ₃ , －C ₂ H ₅ , －C ₃ H ₇ , －C ₄ H ₉ and －(C＝O)CH ₃ are selected bases, x, y and z satisfy 5≦x≦30, 0≦y≦30 , A real number in the range of 0≦z≦30, R ⁸ is a group selected from the aforementioned ^{options of R 1} and R ⁷ or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , q and r is a real number satisfying the ranges of 0≦q≦100 and 0≦r≦40, respectively, but when r=0, R ⁸ is R ⁷ ; (E) 10 to 2,000 parts by mass of water.

This emulsion water-repellent composition can be effectively used as a water-repellent with excellent water-repellency, and can particularly impart good initial water-repellent and water-repellent durability to both the painted surface and glass surface of automobiles, and The glass surface provides the ability to remove the glare caused by the oil film.

Preferably, the emulsion water repellent composition contains a nonionic surfactant. If this emulsion water repellent composition contains a nonionic surfactant, the stability will be more excellent.

Preferably, the aforementioned nonionic surfactant is one or more selected from polyoxyalkylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters. If the aforementioned nonionic surfactant is the aforementioned specific substance, the stability of the emulsion water-repellent composition will be more excellent.

Preferably, in the emulsion water repellent composition, the average particle diameter of the emulsified particles is 300 nm or less. If the average particle size of the emulsified particles in this emulsion water repellent composition is 300 nm or less, the emulsion water repellent composition may sometimes become a blue-white or transparent microemulsion.

Preferably, the emulsion water repellent composition is used for coating surfaces and glass surfaces of automobiles. If this emulsion water repellent composition is used for the painted surface and glass surface of an automobile, it can impart good initial water repellency and water repellency durability to both the painted surface and glass surface of the automobile, and the application to the glass surface will be improved by The performance of removing glare caused by oil film. [effect]

The emulsion water-repellent composition of the present invention can be effectively used as a water-repellent excellent in water-repellency, and can particularly impart good initial water-repellent and water-repellent durability to both the painted surface and glass surface of automobiles. And to give the glass surface the performance of removing the glare caused by the oil film.

As mentioned above, it has been sought to develop a water repellent composition that can be effectively used as a water repellent with excellent water repellency, and can particularly impart good initial water repellency to both the painted surface and glass surface of automobiles. And water-repellent durability, and impart the performance of removing the glare caused by the oil film to the glass surface.

The inventor of the present invention has repeatedly studied the above-mentioned problem to be solved, and found the following facts and completed the present invention: an amino-modified silica emulsion composition can be effectively used as a water repellent with excellent water repellency It can be used to impart good initial water repellency and water repellency to both the painted surface and glass surface of the automobile, and to provide the glass surface with the performance of removing the glare caused by the oil film. This amino-modified silicon The oxygen emulsion composition contains: a specific amine modified siloxane whose ends are blocked by a hydroxyl group or an alkoxy group, a surfactant, a specific polyether modified siloxane, and water.

式(1)中，R¹ 相互獨立地為碳原子數1～20的未被取代的一價烴基，R² 相互獨立地為由通式(2)也就是－Ｒ^４ －（ＮＨ－Ｒ^５ －）_ｐ ＮＨ_２ 表示的基，前述式(2)中，R⁴ 及R⁵ 相互獨立地為碳原子數1～6的二價有機基，p為0或1，R³ 相互獨立地為羥基或從甲氧基及乙氧基之中選出的基，a、b、c、d、及e分別為滿足2≦a≦10、10≦b≦1,000、1≦c≦50、0≦d≦5、0≦e≦5的範圍的實數； (B)0～80質量份的胺基改質矽氧，其由下述通式(3)表示，在25℃時，具有黏度50～5,000 mPa・s且具有胺基當量300～4,000 g/mol，但是將(A)成分與(B)成分的合計量設為100質量份，

式(3)中，R¹ 、R² 與上述相同，R⁶ 相互獨立地為從R¹ 及R² 的選項中選出的基，f、g、h、i及j分別為滿足2≦f≦10、10≦g≦1,000、0≦h≦50、0≦i≦5、0≦j≦5的範圍的實數，但是上述式(3)中，h＝0時，R⁶ 為從R² 的選項中選出的基； (C)2～100質量份的界面活性劑，其為從非離子系界面活性劑、陰離子系界面活性劑、陽離子系界面活性劑及兩性離子系界面活性劑之中選出的至少1種； (D)1～25質量份的聚醚改質矽氧，其由下述平均組成式(4)表示，在25℃時，具有黏度10～10,000 mPa・s且具有親水親油平衡(HLB)值 5～13，

式(4)中，R¹ 與上述相同，R⁷ 相互獨立地為由通式(5)也就是－Ｒ^９ －Ｏ－（Ｃ_２ Ｈ_４ Ｏ）_ｘ －（Ｃ_３ Ｈ_６ Ｏ）_ｙ －（Ｃ_４ Ｈ_８ Ｏ）_ｚ －Ｒ^１０ 表示的聚醚基，前述式(5)中，R⁹ 為碳原子數1～6的二價有機基，R¹⁰ 為從－H、－CH₃ 、－C₂ H₅ 、－C₃ H₇ 、－C₄ H₉ 及－(C＝O)CH₃ 之中選出的基，x、y及z為滿足5≦x≦30、0≦y≦30、0≦z≦30的範圍的實數，R⁸ 為從前述R¹ 及R⁷ 的選項中選出的基、或從－OH、－OCH₃ 及－OC₂ H₅ 之中選出的基，q及r分別為滿足0≦q≦100、0≦r≦40的範圍的實數，但是r＝0時R⁸ 為R⁷ ； (E)10～2,000質量份的水。In other words, the present invention is an emulsion water repellent composition containing the following components (A) to (E): (A) 20-100 parts by mass of amino modified silicon whose ends are blocked by hydroxyl or alkoxy Oxygen, which is represented by the following general formula (1), has a viscosity of 30 to 2,000 mPa·s and an amino group equivalent of 300 to 3,000 g/mol at 25°C,

In the formula (1), R ^{1 is} independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ^{2 is} independently determined by the general formula (2), which is -R ^4- (NH-R ⁵ －) _{The group represented by p} NH ₂ , in the above formula (2), R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1, and R ^{3 is} independently a hydroxyl group Or a group selected from methoxy group and ethoxy group, a, b, c, d, and e respectively satisfy 2≦a≦10, 10≦b≦1,000, 1≦c≦50, 0≦d≦ 5. A real number in the range of 0≦e≦5; (B) 0 to 80 parts by mass of amino modified silica, which is represented by the following general formula (3), and has a viscosity of 50 to 5,000 mPa at 25°C・S and has an amine group equivalent of 300 to 4,000 g/mol, but the total amount of (A) component and (B) component is 100 parts by mass,

In formula (3), R ¹ and R ² are the same as above, R ^{6 is} independently ^{a group selected from the options of R 1} and R ² , and f, g, h, i, and j are each satisfying 2≦f≦ 10. 10≦g≦1,000, 0≦h≦50, 0≦i≦5, 0≦j≦5, but in the above formula (3), when h=0, R ⁶ is the range from R ² The base selected from the options; (C) 2-100 parts by mass of surfactant, which is selected from nonionic surfactants, anionic surfactants, cationic surfactants and zwitterionic surfactants (D) 1-25 parts by mass of polyether modified silica, which is represented by the following average composition formula (4), has a viscosity of 10 to 10,000 mPa·s and has a hydrophilic affinity at 25°C Oil balance (HLB) value 5～13,

In the formula (4), R ¹ is the same as above, and R ^{7 is} independent of each other by the general formula (5), which is -R ⁹ -O-(C ₂ H ₄ O) _x- (C ₃ H ₆ O) _y- (C ₄ H ₈ O) _Z -R ¹⁰ represents a polyether group. In the aforementioned formula (5), R ⁹ is a divalent organic group with 1 to 6 carbon atoms, and R ¹⁰ is from -H, -CH ₃ , －C ₂ H ₅ , －C ₃ H ₇ , －C ₄ H ₉ and －(C＝O)CH ₃ are selected from the group, x, y and z satisfy 5≦x≦30, 0≦y≦30 , A real number in the range of 0≦z≦30, R ⁸ is a group selected from the aforementioned ^{options of R 1} and R ⁷ or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , q and r is a real number satisfying the ranges of 0≦q≦100 and 0≦r≦40, respectively, but when r=0, R ⁸ is R ⁷ ; (E) 10 to 2,000 parts by mass of water.

Hereinafter, the present invention will be explained in more detail. [(A) Modified silica with amine group blocked by hydroxyl or alkoxy at its end] In the present invention, (A) modified silica with amine at its end blocked by hydroxy or alkoxy is composed of the following average composition formula (1) Representation.

(A) The amine modified silica with the end blocked by hydroxyl or alkoxy has a viscosity of 30 to 2,000 mPa·s at 25°C. The aforementioned viscosity is preferably 40 to 1,800 mPa·s, more preferably 50 to 1,500 mPa·s. If the viscosity does not reach the above lower limit, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition will deteriorate. In addition, if the viscosity exceeds the above upper limit, the stability of the emulsion water-repellent composition will deteriorate, and glare caused by the oil film will occur on the glass surface.

In addition, (A) modified silica with an amino group whose end is 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 amine group equivalent is preferably 350 to 2,800 g/mol, more preferably 400 to 2,500 g/mol. If the amine group equivalent is less than the aforementioned lower limit, there will be too many amine groups, and therefore the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition will deteriorate. In addition, if the amine group equivalent exceeds the above upper limit, the amine group will be too few, so the hydrophilicity imparted to the modified silica as the amine group will be insufficient. Therefore, the stability of the emulsion water-repellent composition may deteriorate, and glare caused by the oil film may occur on the glass surface.

In the above formula (1), R ^{1 is} independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. For example: methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, octadecyl, etc. Alkyl; vinyl, allyl, 5-hexenyl, oleyl and other alkenyl groups; phenyl, tolyl, naphthyl and other aryl groups. Among these, methyl, long-chain alkyl, and phenyl are preferred. When weather resistance is particularly required, methyl is preferred, and when water repellency is sought, methyl and long-chain alkyl are preferred. In addition, when 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 plural kinds of organic substituents as R ¹ , and when used in combination, it is preferable that the content ratio of the ^{methyl group to the total number of the substituents R 1} , R ² and R ^{3 is} More than 70%.

式(2)中，R⁴ 及R⁵ 相互獨立地為碳原子數1～6的二價有機基，特別是碳原子數1～6的二價烴基。可舉例如：伸烷基、伸烯基、及伸芳基等。p為0或1。式(2)表示的基可舉例如：2-胺基乙基、3-胺基丙基、6-胺基己基、N-(2-胺基乙基)-3-胺基丙基、N-(3-胺基丙基)-3-胺基丙基、N-(2-胺基乙基)-6-胺基己基等。從容易取得原料及價格面的優越度的觀點來看，較佳是使用3-胺基丙基或N-(2-胺基乙基)-3-胺基丙基。R ² is a group represented by the general formula (2) independently of each other.

In the formula (2), R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, particularly a divalent hydrocarbon group having 1 to 6 carbon atoms. For example, an alkylene group, an alkenylene group, and an arylene group can be mentioned. p is 0 or 1. The group represented by the formula (2) includes, for example, 2-aminoethyl, 3-aminopropyl, 6-aminohexyl, N-(2-aminoethyl)-3-aminopropyl, N -(3-aminopropyl)-3-aminopropyl, N-(2-aminoethyl)-6-aminohexyl, etc. From the viewpoints of easy availability of raw materials and superiority in price, it is preferable to use 3-aminopropyl or N-(2-aminoethyl)-3-aminopropyl.

R ^{3 is} independently a hydroxyl group or a group selected from a methoxy group and an ethoxy group. In addition, the component (A) can be used alone or in combination of two or more of these amino-modified silicas whose ends are blocked by a hydroxyl group or an alkoxy group. The hydroxyl group or the group selected from the methoxy group and the ethoxy group can impart durable water repellency to the glass surface in the following manner: the SiOH group on the glass surface is adsorbed via hydrogen bonding, and the (A) terminal is hydroxy Or alkoxy-blocked amine modified silica is fixed on the glass surface.

a is a real number that satisfies 2≦a≦10. If a is less than 2, the viscosity of the amine modified silica whose terminal is blocked by a hydroxyl group or an alkoxy group will be too high, and the stability of the emulsion water repellent composition will deteriorate. In addition, if a exceeds 10, the viscosity of amine modified silica whose ends are blocked by hydroxyl or alkoxy will be too low, and the initial water repellency and water repellency of the film formed by the emulsion water repellent composition will be too low. Sex will deteriorate. Preferably a=2.

b is a real number that satisfies 10≦b≦1,000. If b is less than 10, the viscosity of amine modified silica whose terminal is blocked by hydroxyl or alkoxy will be too low, and the initial water repellency and water repellency of the film formed by the emulsion water repellent composition Will get worse. In addition, if b exceeds 1,000, the viscosity of the amine modified silica whose terminal is blocked by a hydroxyl group or an alkoxy group will be too high, and the stability of the emulsion water repellent composition will deteriorate. It is more preferable to satisfy the range of 20≦b≦800.

c is a real number satisfying 1≦c≦50. If c is less than 1, sometimes the amine group equivalent in modified silica with the terminal blocked by hydroxyl or alkoxy may be too small, and the stability of the film formed by the emulsion water repellent composition may deteriorate. , And glare caused by the oil film will occur on the glass surface. In addition, if c exceeds 50, the amine group equivalent in the modified silica with the terminal blocked by the hydroxyl or alkoxy group will be too much, and the initial water repellency and repellency of the film formed by the emulsion water repellent composition Water durability will deteriorate.

d is a real number satisfying 0≦d≦5. If d exceeds 5, the viscosity of amine modified silica whose ends are blocked by hydroxyl or alkoxy may be too high, and the stability of the emulsion water repellent composition may deteriorate, and the glass surface may cause damage. Glare caused by oil film. Preferably, d=0.

e is a real number satisfying 0≦e≦5. If e exceeds 5, the viscosity of amine modified silica whose ends are blocked by hydroxyl or alkoxy may be too high, and the stability of the emulsion water repellent composition may deteriorate, and the glass surface may cause damage. Glare caused by oil film. Preferably, e=0.

[(B) Amino-modified silica] In the present invention, (B) Amino-modified silica is represented by the following average composition formula (3).

(B) Amino modified silica, with a viscosity of 50 to 5,000 mPa·s at 25°C. The aforementioned viscosity is preferably 55 to 4,500 mPa·s, more preferably 60 to 4,000 mPa·s. If the viscosity does not reach the above lower limit, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition will deteriorate. In addition, if the viscosity exceeds the above upper limit, the stability of the emulsion water-repellent composition will deteriorate, and glare caused by the oil film will occur on the glass surface.

In addition, (B) amine modified silica has an amine equivalent of 300 to 4,000 g/mol at 25°C. The aforementioned amine group equivalent is preferably 320 to 3,800 g/mol, more preferably 330 to 3,600 g/mol. If the amine group equivalent is less than the aforementioned lower limit, there will be too many amine groups, and therefore the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition will deteriorate. In addition, if the amine group equivalent exceeds the above upper limit, the amine group will be too few, so the hydrophilicity that should be imparted as the amine group-modified silica will be insufficient. Therefore, the stability of the emulsion water-repellent composition may deteriorate, and glare caused by the oil film may occur on the glass surface.

When the total amount of (A) component and (B) component is 100 parts by mass, the addition amount of (B) amino-modified silica is 0 to 80 parts by mass. If the aforementioned addition amount exceeds 80 parts by mass, the water-repellent durability of the film formed from the emulsion water-repellent composition on the glass surface will deteriorate.

In the formula (3), R ¹ is as described in (1) R in the above formula ¹ so. Among them, preferred are methyl, long-chain alkyl, and phenyl. The image R ² is (1) R in the above formula ² so. Among them, 3-aminopropyl or N-(2-aminoethyl)-3-aminopropyl is preferably used.

R ^{6 is} independently a group selected from the above-mentioned ^{options of R 1} and R ^2. However, in the above formula (3), when h=0, R ⁶ is a base selected ^{from the options of R 2.} In addition, the component (B) can be used alone or in combination of two or more of these amino-modified silicas.

f is a real number satisfying 2≦f≦10. If f is less than 2, the viscosity of the amino-modified silica will be too high, and the stability of the emulsion water-repellent composition will deteriorate. In addition, if f exceeds 10, the viscosity of the amino-modified silica will be too low, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition will deteriorate. Preferably, f=2.

g is a real number that satisfies 10≦g≦1,000. If g is less than 10, the viscosity of the amino-modified silica will be too low, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition will deteriorate. In addition, if g exceeds 1,000, the viscosity of the amino-modified silica will be too high, and the stability of the emulsion water-repellent composition will deteriorate. Preferably, it satisfies the range of 20≦g≦800.

h is a real number satisfying 0≦h≦50. In particular, if h is 1 or more, the (B) amino-modified silica has a large amine equivalent, and the water-repellent durability of the film formed from the emulsion water-repellent composition is improved, and the The glare caused by the oil film does not occur on the glass surface. However, when h=0, R ⁶ is a base selected ^{from the options of R 2.} In addition, if h exceeds 50, the amine group equivalent in the amine-modified silica will be too much, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition will deteriorate.

i is a real number satisfying 0≦i≦5. If i exceeds 5, the viscosity of the amino-modified silica may be too high, the stability of the emulsion water repellent composition may deteriorate, and glare caused by the oil film may occur on the glass surface. Preferably, i=0.

j is a real number satisfying 0≦j≦5. If j exceeds 5, the viscosity of the amino-modified silica may be too high, the stability of the emulsion water repellent composition may deteriorate, and glare caused by the oil film may occur on the glass surface. Preferably, j=0.

[(C) Surfactant] The (C) surfactant contained in the emulsion water-repellent composition of the present invention is not particularly limited as long as it can emulsify and disperse the (A) component and (B) component in water. Examples include polyoxyethylene Alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc., from From the viewpoint of the stability of the emulsion water repellent composition, polyoxyethylene alkyl ether, polyoxyethylene oxypropylene alkyl ether, and polyoxyethylene sorbitan are particularly preferred. Fatty acid esters.

Specific examples of these include: polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene oxypropylene decyl ether, polyoxyethylene Oxyethylene lauryl ether, polyoxyethylene oxypropylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene oxypropylene tridecyl ether, polyoxyethylene oxypropylene Ethyl 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 monooleate Ethyl sorbitan trioleate and so on. (C) Component can use these nonionic surfactants individually or in combination of 2 or more types.

In addition, it is also possible to use: alkyl sulfate, alkyl benzene sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, etc. Cationic surfactants such as anionic surfactants, quaternary ammonium salts and alkyl amine acetates; and amphoteric surfactants such as alkyl betaines and alkyl imidazolines.

The addition amount of (C) component is 2-100 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. If the aforementioned addition amount is less than 2 parts by mass, the stability of the emulsion water repellent composition will deteriorate. If the aforementioned addition amount exceeds 100 parts by mass, the initial water repellency of the film formed by the emulsion water repellent composition And the durability of water repellency will deteriorate. The aforementioned addition amount is preferably 2-50 parts by mass. If the aforementioned addition amount is 2 parts by mass or more, the stability of the emulsion water repellent composition will be good, and if the aforementioned addition amount is 50 parts by mass or less, the initial repellency of the film formed by the emulsion water repellent composition will be Water and water repellency durability will be better. The aforementioned addition amount is more preferably 3 to 40 parts by mass, and still more preferably 4 to 30 parts by mass. The above-mentioned surfactant preferably has an HLB value of 3.0 to 19.0. When two or more types are used in combination, the total HLB value should be 7.0 to 16.0.

[(D) Polyether-modified silica] In the present invention, (D) polyether-modified silica is represented by the following average composition formula (4).

(D) Polyether modified silica has a hydrophilic-lipophilic balance (HLB) value of 5-13 at 25°C. The aforementioned HLB is preferably 5.5 to 12.5, more preferably 6.0 to 12.0. If it is a polyether modified silica less than HLB 5, it is difficult to sufficiently emulsify and disperse the (A) component and (B) component. In addition, the compatibility of the polyether-modified silica with HLB over 13 with (A) and (B) components deteriorates, and the obtained emulsion water repellent composition has stability, especially dilution stability. Sex will deteriorate.

(D) Polyether modified silica has a viscosity of 10～10,000 mPa·s at 25°C. The aforementioned viscosity is preferably 40 to 5,000 mPa·s, more preferably 50 to 4,000 mPa·s. If it does not reach the above lower limit, it is difficult to sufficiently emulsify and disperse the (A) component and (B) component. Moreover, if it exceeds the said upper limit, it will become difficult to handle when using an emulsion water-repellent composition.

In the formula (4), R ¹ is as described in (1) R in the above formula ¹ so. Among them, preferred are methyl, long-chain alkyl, and phenyl. Since the component (D) is used for emulsifying and dispersing the component (C) together with the component (A) and the component (B), a strong hydrophobic group is not preferable. However, when it is desired to improve the dispersibility with organic compounds such as waxes, it is preferable to use long-chain alkyl groups and phenyl groups. In addition, the compound represented by the formula (4) may use a plurality of organic substituents as R ^{1 in combination} , and when used in combination, it is preferable that the content of the methyl group with respect to the total number of the ^{substituents R 1} , R ⁷ and R ⁸ It is more than 90%.

式(5)中，R⁹ 為碳原子數1～6的二價有機基，可舉例如：伸烷基、伸烯基、伸芳基等。R¹⁰ 為從－H、－CH₃ 、－C₂ H₅ 、－C₃ H₇ 、－C₄ H₉ 及－(C＝O)CH₃ 之中選出的基。R ^{7 is} independently a polyether group represented by the general formula (5).

In the formula (5), R ⁹ is a divalent organic group having 1 to 6 carbon atoms, and examples thereof include an alkylene group, an alkenylene group, and an arylene group. 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, the HLB of the (D) component will be too low, and it will be difficult to sufficiently emulsify and disperse the (A) component and (B) component. In addition, when x exceeds 30, since the viscosity of the component (D) increases or it becomes a solid at room temperature, it is difficult to handle during use. Preferably, it satisfies the range of 5≦x≦25.

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

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

R ⁸ is a group selected from the aforementioned ^{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 above formula (4), R ⁸ is a base selected ^{from the options of R 7.}

q is a real number satisfying the range of 0≦q≦100. When q exceeds 100, since the HLB of the (D) component is too low, it is difficult to sufficiently emulsify and disperse the (A) component and (B) component. It is more preferable to satisfy the range of 5≦q≦80.

r is a real number satisfying the range of 0≦r≦40. In particular, if r is 1 or more, the HLB of the (D) component is appropriate, and the (A) component and (B) component can be sufficiently emulsified and dispersed. However, when R ⁸ =R ⁷ , r may not reach 1, especially r=0. In addition, when r exceeds 40, the viscosity of the (D) component will be too high, so it is difficult to handle when used.

The addition amount of (D) component is 1-25 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. The aforementioned addition amount is preferably 3 to 23 parts by mass, more preferably 5 to 20 parts by mass. If the addition amount of the component (D) is outside this range, a stable emulsion water-repellent composition cannot be obtained.

[(E)Water] The emulsion water-repellent composition of the present invention can be prepared by mixing (E) water with the above-mentioned (A) component, (B) component, (C) component and (D) component and following the usual method To make it emulsified and dispersed. (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 relative to 100 parts by mass of the total amount of (A) component and (B) component. The above-mentioned components (A) to (E) are mixed and emulsified and dispersed to obtain the emulsion water-repellent composition of the present invention. Especially the oil-in-water (O/W type) emulsion water repellent composition usually becomes a white emulsion, but when the average particle size of the emulsified particles is 300 m or less, the appearance may be blue. White or transparent microemulsion. In addition, it is possible to further add water to the obtained emulsion water-repellent composition to dilute and then use it for the application described later. The amount of water used for dilution is not particularly limited, as long as it is appropriately adjusted due to the application. The emulsion water repellent composition of the present invention still has excellent stability after being diluted.

[Other additives] In the emulsion water-repellent composition of the present invention, in addition to the above-mentioned (A) to (E) components, various additives can be blended as needed. For example, in order to improve the stability of the emulsion, it can be formulated with acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, stearic acid, lactic acid, and citric acid. The addition amount of the additive can be set arbitrarily, but it is preferable to adjust the pH of the emulsion water-repellent composition of the present invention to an amount of 3-7. In addition, thickeners, antifreeze agents, preservatives, rust inhibitors, antioxidants, and ultraviolet absorbers may also be included as other additives.

[Emulsion water repellent composition] In the emulsion water repellent composition of the present invention, the average particle size of the emulsified particles is preferably 300 nm or less, more preferably 200 nm or less. In addition, in the present invention, the average particle size is a volume-based average particle size, which can be measured using a submicron particle size distribution measuring device (COULTER N4 Plus) manufactured by Beckman Coulter Co., Ltd.

The emulsion water repellent composition of the present invention can be easily used in the coating process of automobiles and other vehicles using an automatic car washer. The automatic car washer is, for example, a door-type car washer, a continuous door-type car washer, and a spray -Type car washing machine, etc. In other words, the emulsion water-repellent composition of the present invention is useful as a coating agent for vehicles. When spraying or coating on the surface of a vehicle, the concentration of the coating agent is not particularly limited, and it is usually set so that the concentration of the amine-modified silica of the (A) component and (B) component becomes about 0.01 to 0.5% by mass. The concentration of the inventive emulsion water repellent composition and the automatic dilution ratio of the automobile-type car washing machine are sufficient. The emulsion water-repellent composition of the present invention can have long-term sustainable water repellency, gloss, lubricity, etc. on the painted surface and glass surface of a vehicle. In addition, the emulsion water repellent composition of the present invention can of course also be applied to other applications requiring water repellency. [Example]

Hereinafter, examples and comparative examples are given to illustrate the present invention in more detail, but the present invention is not limited by the following examples. In addition, in the following examples, parts represent parts by mass, and% represents mass%. The average particle size is a volume-based average particle size, and is a value measured using a submicron particle size distribution measuring device COULTER N4 Plus manufactured by Beckman Coulter Co., Ltd. The particle size is an absolute viscosity measured at 25°C using a B-type rotary viscometer, and is a value measured using a TVB-10 viscometer manufactured by Toki Sangyo Co., Ltd.

The components used in the examples and comparative examples are described below. [(A) Modified silica with amine group blocked by hydroxyl or alkoxy] Modified silica with amine group blocked by hydroxy or alkoxy 1: A compound composed of the following average composition formula (1) Means, and 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, with viscosity: 65 mPa·s, amine equivalent: 780 g/mol

Modified Siloxane 2: A compound whose terminal is blocked by a hydroxyl group or an alkoxy group is modified by the above average composition formula (1), and 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, and viscosity: 700 mPa·s, amine equivalent: 1,860 g/mol

Amino modified silica with the end blocked by a hydroxyl or alkoxy group 3: a compound represented by the above average composition formula (1), and R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -OC ₂ H ₅ , a=2, b=120, c=2.5, d=0, e=0, and viscosity: 350 mPa·s, amine equivalent: 1,900 g/mol

Modified Siloxane 4 (comparative use) with amino groups whose ends are blocked by hydroxyl or alkoxy groups: a compound represented by the above average composition formula (1), and R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NH ₂ , R ³ : -OH, a=2, b=1078, c=2.2, d=0, e=0, and viscosity: 30,000 mPa·s, amine equivalent: 20,000 g/mol

[(B) Amino modified silica] Amino modified silica 5: A compound represented by the following average composition formula (3), and 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, and viscosity: 70 mPa·s, amine equivalent: 350 g/ mol

Amine modified silica 6: a compound represented by the above average composition formula (3), and 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, and viscosity: 1,200 mPa·s, amine equivalent: 1,800 g/mol

Amine modified silica 7: a compound represented by the above average composition formula (3), and 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, and viscosity: 3,600 mPa·s, amine equivalent: 1,800 g/mol

Amine modified silica 8: a compound represented by the above average composition formula (3), and 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, and viscosity: 1,500 mPa·s, amine equivalent: 3,500 g/mol

Amine modified silica 9 (for comparison): a compound represented by the above average composition formula (3), and 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, and has a viscosity: 1,200 mPa·s, amine equivalent: 11,000 g/mol

Table 1 summarizes the composition list of (A) component and (B) component. [Table 1]

[(C) Surfactant] NOIGEN XL-40 (trade name): Polyoxyalkylene decyl ether manufactured by Daiichi Industrial Pharmaceutical Company, HLB=10.5 NOIGEN XL-400D (trade name): A 65 mass% aqueous solution of polyoxyalkylene decyl ether manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., HLB=18.4 Newcol 1004 (trade name): Polyoxyethylene octyl ether manufactured by Japan Emulsifier Company, HLB=11.5 Newcol 1008 (trade name): Polyoxyethylene octyl ether manufactured by Japan Emulsifier Company, 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=11.0

[(D) Polyether modified silica] Polyether modified silica 1: A compound represented by the following average composition formula (4), and 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, and viscosity: 1,600 mPa·s, HLB: 7

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

Polyether modified silica 3: a compound represented by the above average composition formula (4), and 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, and viscosity: 70 mPa·s, HLB: 12

Polyether modified silica 4 (for comparison): a compound represented by the above average composition formula (4), and 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, and viscosity: 20 mPa·s, HLB: 14

Table 2 summarizes the composition list of component (D). [Table 2]

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

[Example 1] Use a homogenizer to modify the amine group whose end (A) is blocked by methoxy group into silica 1 (viscosity: 65 mPa·s, amine group equivalent: 780 g/mol) 20 parts by mass, (A) end with methoxy group Amine modified silica 2 (viscosity: 700 mPa·s, amine equivalent: 1,860 g/mol) 80 parts by mass, (C) NOIGEN XL-40 (HLB=10.5) 20 parts by mass, (C) NOIGEN XL-400D (HLB=18.4, 65 mass% aqueous solution) 30 mass parts, (D) polyether modified silica 1 (viscosity: 1,600 mPa·s, HLB: 7) 10 mass parts, (E) ion exchange water 462.5 parts by mass, 3.0 parts by mass of acetic acid, and 0.2 parts by mass of preservative were mixed and emulsified and dispersed to obtain a colorless and transparent amino-modified silicon-oxygen emulsion water repellent composition (I-1). The amino-modified silicon The oxygen-emulsion water-repellent composition (I-1) had a non-volatile content at 105° C./3 hours of 23.8%, and the average particle diameter of the emulsified particles in the emulsion water-repellent composition was 30 nm.

[Example 2] Use a homogenizer to modify (A) the amino group whose end is blocked by a methoxy group to modify silica 1 (viscosity: 65 mPa·s, amine group equivalent: 780 g/mol) 30 parts by mass, (B) to modify the amine group Siloxane 6 (viscosity: 1,200 mPa·s, amine equivalent: 1,800 g/mol) 70 parts by mass, (C)NOIGEN XL-40 (HLB=10.5) 20 parts by mass, (C)NOIGEN XL-400D (HLB= 18.4, 65 mass% aqueous solution) 30 mass parts, (D) polyether modified silica 1 (viscosity: 1,600 mPa·s, HLB: 7) 10 mass parts, (E) ion exchange water 462.5 mass parts, acetic acid 3.2 mass Parts, and 0.2 parts by mass of the preservative, mixed and emulsified and dispersed to obtain a colorless and transparent amino-modified silicone emulsion water-repellent composition (I-2), the amino-modified silicone emulsion water-repellent composition The non-volatile content of the compound (I-2) at 105°C/3 hours was 24.4%, and the average particle diameter of the emulsified particles in the emulsion water-repellent composition was 45 nm.

[Example 3] Use a homogenizer to modify (A) the amine group whose end is blocked by a methoxy group to modify silica 2 (viscosity: 700 mPa·s, amine group equivalent: 1,860 g/mol) 80 parts by mass, (B) to modify the amine group Siloxane 5 (viscosity: 70 mPa·s, amine equivalent: 350 g/mol) 20 parts by mass, (C) NOIGEN XL-40 (HLB=10.5) 20 parts by mass, (C) NOIGEN XL-400D (HLB= 18.4, 65 mass% aqueous solution) 30 mass parts, (D) polyether modified silica 2 (viscosity: 430 mPa·s, HLB: 10) 10 mass parts, (E) ion exchange water 462.5 mass parts, acetic acid 4.0 mass Parts, and 0.2 parts by mass of the preservative, mixed and emulsified and dispersed to obtain a colorless and transparent amino-modified silicone emulsion water-repellent composition (I-3), the amino-modified silicone emulsion water-repellent composition The non-volatile content of the compound (I-3) at 105°C/3 hours was 24.6%, and the average particle size of the emulsified particles in the emulsion water repellent composition was 120 nm.

[Example 4] Use a homogenizer to modify (A) the amine group whose end is blocked by a methoxy group to modify silica 1 (viscosity: 65 mPa·s, amine group equivalent: 780 g/mol) 20 parts by mass, (B) to modify the amine group Siloxane 7 (viscosity: 3,600 mPa·s, amine equivalent: 1,800 g/mol) 80 parts by mass, (C) Newcol 1004 (HLB=11.5) 20 parts by mass, Newcol 1008 (HLB=14.6) 20 parts by mass, ( D) Polyether modified silica 3 (viscosity: 70 mPa·s, HLB: 12) 10 parts by mass, (E) 462.5 parts by mass of ion exchange water, 3.1 parts by mass of acetic acid, and 0.2 parts by mass of preservative are mixed and emulsified and dispersed , And obtain a colorless and transparent amino-modified silicone emulsion water-repellent composition (I-4). The amino-modified silicone emulsion water-repellent composition (I-4) is at 105℃/3 The non-volatile content within an hour was 24.6%, and the average particle diameter of the emulsified particles in the emulsion water-repellent composition was 30 nm.

[Example 5] Use a homogenizer to modify (A) the amino group whose end is blocked by a methoxy group to modify silica 1 (viscosity: 65 mPa·s, amine group equivalent: 780 g/mol) 30 parts by mass, (B) to modify the amine group Siloxane 8 (viscosity: 1,500 mPa·s, amine equivalent: 3,500 g/mol) 70 parts by mass, (C) Newcol 1004 (HLB=11.5) 20 parts by mass, (C) Newcol 1008 (HLB=14.6) 20 parts by mass Parts, (D) polyether modified silica 1 (viscosity: 1,600 mPa·s, HLB: 7) 10 parts by mass, (E) 462.5 parts by mass of ion exchange water, 2.4 parts by mass of acetic acid, and 0.2 parts by mass of preservative And emulsify and disperse to obtain a colorless and transparent amino-modified silica emulsion water-repellent composition (I-5). The amino-modified silica emulsion water-repellent composition (I-5) is at 105 The non-volatile content in °C/3 hours was 24.9%, and the average particle diameter of the emulsified particles in the emulsion water-repellent composition was 60 nm.

[Example 6] Use a homogenizer to modify (A) the amine group whose end is blocked by a methoxy group to modify silica 3 (viscosity: 350 mPa·s, amine group equivalent: 1,900 g/mol) 100 parts by mass, (C) Newcol 1004 (HLB) =11.5) 20 parts by mass, Newcol 1008 (HLB=14.6) 20 parts by mass, (D) polyether modified silica 2 (viscosity: 430 mPa·s, HLB: 10) 10 parts by mass, (E) ion exchange water 462.5 parts by mass, 2.2 parts by mass of acetic acid, and 0.2 parts by mass of preservative were mixed and emulsified and dispersed to obtain a colorless and transparent amino-modified silicon oxide emulsion water repellent composition (I-6). The amino-modified silicon The oxygen-emulsion water-repellent composition (I-6) had a non-volatile content at 105° C./3 hours of 23.4%, and the average particle size of the emulsified particles in the emulsion water-repellent composition was 40 nm.

[Example 7] Use a homogenizer to modify the amine group whose end (A) is blocked by methoxy group into silica 1 (viscosity: 65 mPa·s, amine group equivalent: 780 g/mol) 20 parts by mass, (A) end with methoxy group Amine modified silica 2 (viscosity: 700 mPa·s, amine equivalent: 1,860 g/mol) 80 parts by mass, (C) RHEODOL TW-L106 (HLB=13.3) 20 parts by mass, (C) RHEODOL TW-O320V (HLB=11.0) 20 parts by mass, (D) polyether modified silica 1 (viscosity: 1,600 mPa·s, HLB: 7) 10 parts by mass, (E) ion exchange water 462.5 parts by mass, acetic acid 3.0 parts by mass and 0.2 parts by mass of the preservative are mixed and emulsified and dispersed to obtain a colorless and transparent amino-modified silicone emulsion water repellent composition (I-7), which is water-repellent The non-volatile content of the agent composition (I-7) at 105°C/3 hours was 23.7%, and the average particle diameter of the emulsified particles in the emulsion water-repellent composition was 50 nm.

[Comparative Example 1] Use a homogenizer to modify the amine group whose end (A) is blocked by a methoxy group into silica 1 (viscosity: 65 mPa·s, amine group equivalent: 780 g/mol) 70 parts by mass, (A) end with methoxy group Amine modified silica 4 (viscosity: 30,000 mPa·s, amine equivalent: 20,000 g/mol) 30 parts by mass, (C) NOIGEN XL-40 (HLB=10.5) 20 parts by mass, NOIGEN XL- 400D (HLB=18.4, 65 mass% aqueous solution) 30 mass parts, (D) polyether modified silica 1 (viscosity: 1,600 mPa·s, HLB: 7) 10 mass parts, (E) ion exchange water 462.5 mass parts , 3.8 parts by mass of acetic acid, and 0.2 parts by mass of preservative were mixed and emulsified and dispersed to obtain a white milky amino-modified silicone emulsion water repellent composition (II-1). The amino-modified silicone emulsified The liquid water-repellent composition (II-1) had a non-volatile content at 105°C/3 hours of 24.9%, and the average particle diameter of the emulsified particles in the emulsion water-repellent composition was 250 nm.

[Comparative Example 2] Use a homogenizer to modify (A) the amine group whose end is blocked by a methoxy group to modify silica 1 (viscosity: 65 mPa·s, amine group equivalent: 780 g/mol) 70 parts by mass, (B) to modify the amine group Siloxane 9 (viscosity: 1,200 mPa·s, amine equivalent: 11,000 g/mol) 30 parts by mass, (C)NOIGEN XL-40 (HLB=10.5) 20 parts by mass, (C)NOIGEN XL-400D (HLB= 18.4, 65 mass% aqueous solution) 30 mass parts, (D) polyether modified silica 1 (viscosity: 1,600 mPa·s, HLB: 7) 10 mass parts, (E) ion exchange water 462.5 mass parts, acetic acid 3.8 mass parts Parts and 0.2 parts by mass of the preservative are mixed and emulsified and dispersed to obtain a blue-white slightly turbid amino-modified silica emulsion water repellent composition (II-2), which is water-repellent The non-volatile content of the agent composition (II-2) at 105° C./3 hours was 24.2%, and the average particle diameter of the emulsified particles in the emulsion water-repellent composition was 120 nm.

[Comparative Example 3] Use a homogenizer to modify (B) amino group modified silica 7 (viscosity: 3,600 mPa·s, amine group equivalent: 1,800 g/mol) 100 parts by mass, (C) Newcol 1004 (HLB=11.5) 20 parts by mass, Newcol 1008 (HLB=14.6) 20 parts by mass, (D) Polyether modified silica 2 (viscosity: 430 mPa·s, HLB: 10) 10 parts by mass, (E) 462.5 parts by mass of ion exchange water, 2.5 parts by mass of acetic acid Parts, and 0.2 parts by mass of the preservative, mixed and emulsified and dispersed to obtain a colorless and transparent amino-modified silicone emulsion water-repellent composition (II-3), the amino-modified silicone emulsion water-repellent composition The non-volatile content of the compound (II-3) at 105°C/3 hours was 23.8%, and the average particle diameter of the emulsified particles in the emulsion water-repellent composition was 40 nm.

[Comparative Example 4] Use a homogenizer to modify the amine group whose end (A) is blocked by methoxy group into silica 1 (viscosity: 65 mPa·s, amine group equivalent: 780 g/mol) 20 parts by mass, (A) end with methoxy group Amine modified silica 2 (viscosity: 700 mPa·s, amine equivalent: 1,860 g/mol) 80 parts by mass, (C) NOIGEN XL-40 (HLB=10.5) 20 parts by mass, (C) NOIGEN XL-400D (HLB=18.4, 65 mass% aqueous solution) 30 mass parts, (D) polyether modified silica 4 (viscosity: 20 mPa·s, HLB: 14) 10 mass parts, (E) ion exchange water 462.5 parts by mass, 3.0 parts by mass of acetic acid, and 0.2 parts by mass of preservative were mixed and emulsified and dispersed to obtain a colorless and transparent amino-modified silicon-oxygen emulsion water repellent composition (II-4). The amino-modified silicon The oxygen-emulsion water-repellent composition (II-4) had a non-volatile content at 105° C./3 hours of 24.8%, and the average particle size of the emulsified particles in the emulsion water-repellent composition was 70 nm.

[Comparative Example 5] Use a homogenizer to modify the amine group whose end (A) is blocked by methoxy group into silica 1 (viscosity: 65 mPa·s, amine group equivalent: 780 g/mol) 20 parts by mass, (A) end with methoxy group Amine modified silica 2 (viscosity: 700 mPa·s, amine equivalent: 1,860 g/mol) 80 parts by mass, (C) NOIGEN XL-40 (HLB=10.5) 20 parts by mass, (C) 30 parts by mass of NOIGEN XL-400D (HLB=18.4, 65% by mass aqueous solution), 462.5 parts by mass of (E) ion exchange water, 3.0 parts by mass of acetic acid, and 0.2 parts by mass of preservative are mixed and emulsified to obtain a colorless and transparent amine Based modified silica emulsion water-repellent composition (II-5), the non-volatile components of the amino-modified silica emulsion water-repellent composition (II-5) at 105°C/3 hours are 22.3%, and the average particle diameter of the emulsified particles in the emulsion water repellent composition was 80 nm.

[Water repellency durability] The amino-modified silica emulsion water-repellent composition obtained in the above Examples 1-7 and Comparative Examples 1-5 was diluted with tap water to 150 times, and then sprayed on the painted surface of the automobile with a spray gun. Glass surface. After spraying, it was washed back and forth with tap water once, and the time until the water film was interrupted after the washing was stopped was measured. The results are shown in Tables 3 and 4 below. Then, it was further washed back and forth 15 times with tap water, and the time until the water film was interrupted after the washing was stopped was measured. The results are shown in Tables 3 and 4 below.

[Glare on the glass surface] After the above-mentioned water repellency durability test was completed, the glass surface was wiped 3 times with a rubber wiper. At this time, observe with the naked eye whether there is any remaining oil film/glare on the glass surface. The results are shown in Tables 3 and 4 below. ＜Evaluation criteria＞ ○: No oil film, △: Slight oil film, ×: Oil film/glare

[Stability] The amino-modified silica emulsion water-repellent composition (stock solution) prepared in the above-mentioned Examples 1-7 and Comparative Examples 1-5 was put into a glass bottle and stored at 40°C for 2 weeks, and then exposed to the naked eye. Observe for separation. According to the following criteria, it is evaluated as "the stability of the original solution". The results are shown in Tables 3 and 4. ＜Evaluation criteria＞ ○: no separation, △: concentration separation, ×: separation into two layers In addition, the amino-modified silica emulsion water-repellent composition (stock solution) obtained in the foregoing Examples 1 to 7 and Comparative Examples 1 to 5 was diluted to 150 times with tap water to obtain a diluted solution, and then diluted After adding the solution to a glass bottle and storing it at 40°C for 2 weeks, the presence or absence of separation was observed with the naked eye. It is evaluated as "dilution stability" according to the following indicators. The results are shown in Tables 3 and 4. ＜Evaluation criteria＞ ○: No precipitate, △: Some precipitate, ×: There is precipitate

[table 3]

[Table 4]

As shown in Table 3 above, the emulsion water-repellent composition of the present invention can be effectively used as a water-repellent with excellent water repellency, and can particularly impart good initial repellency to both the painted surface and glass surface of automobiles. Water-based and water-repellent durability, and the ability to remove glare caused by the oil film is imparted to the glass surface, and the liquid stability and dilution stability are also excellent. [Industrial availability]

The emulsion water repellent composition of the present invention can impart excellent water repellency to both the painted surface and the glass surface, and can remove glare on the glass surface. In addition, the stability of the stock solution and the stability of dilution are also excellent. The emulsion water-repellent composition of the present invention is useful as a detergent and coating agent, which is used for coating a vehicle using an automatic car washing machine.

In addition, the present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiments are only examples, and as long as they have substantially the same configuration and produce the same effects as the technical ideas described in the scope of the patent application of the present invention, whatever they are, they are included in the technical scope of the present invention.

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Claims (7)

An emulsion water-repellent composition, characterized by containing the following components (A) to (E): (A) 20-100 parts by mass of amine modified silica whose end is blocked by a hydroxyl group or an alkoxy group, It is represented by the following general formula (1). At 25°C, it has a viscosity of 30 to 2,000 mPa·s and an amino group equivalent of 300 to 3,000 g/mol,

In the formula (1), R ^{1 is} independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ^{2 is} independently determined by the general formula (2), which is -R ^4- (NH-R ⁵ －) _{The group represented by p} NH ₂ , in the above formula (2), R ⁴ and R ⁵ are independently a divalent organic group having 1 to 6 carbon atoms, p is 0 or 1, and R ^{3 is} independently a hydroxyl group Or a group selected from methoxy and ethoxy, a, b, c, d, and e satisfy 2≦a≦10, 10≦b≦1,000, 1≦c≦50, 0≦d≦5, respectively , A real number in the range of 0≦e≦5; (B) 0 to 80 parts by mass of amino modified silica, which is represented by the following general formula (3), and has a viscosity of 50 to 5,000 mPa at 25°C. s has an amine group equivalent of 300 to 4,000 g/mol, but the total amount of (A) component and (B) component is 100 parts by mass,

In formula (3), R ¹ and R ² are the same as above, R ^{6 is} independently ^{a group selected from the options of R 1} and R ² , and f, g, h, i, and j are each satisfying 2≦f≦ 10. 10≦g≦1,000, 0≦h≦50, 0≦i≦5, 0≦j≦5, but in the above formula (3), when h=0, R ⁶ is the range from R ² The base selected from the options; (C) 2-100 parts by mass of surfactant, which is selected from nonionic surfactants, anionic surfactants, cationic surfactants and zwitterionic surfactants (D) 1-25 parts by mass of polyether modified silica, which is represented by the following average composition formula (4), has a viscosity of 10 to 10,000 mPa·s and has a hydrophilic affinity at 25°C Oil balance HLB value 5～13,

In the formula (4), R ¹ is the same as above, and R ^{7 is} independent of each other by the general formula (5), which is -R ⁹ -O-(C ₂ H ₄ O) _x- (C ₃ H ₆ O) _y- (C ₄ H ₈ O) _Z -R ¹⁰ represents a polyether group. In the aforementioned formula (5), R ⁹ is a divalent organic group with 1 to 6 carbon atoms, and R ¹⁰ is from -H, -CH ₃ , －C ₂ H ₅ , －C ₃ H ₇ , －C ₄ H ₉ and －(C＝O)CH ₃ are selected from the group, x, y and z satisfy 5≦x≦30, 0≦y≦30 , A real number in the range of 0≦z≦30, R ⁸ is a group selected from the aforementioned ^{options of R 1} and R ⁷ or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , q and r is a real number satisfying the ranges of 0≦q≦100 and 0≦r≦40, respectively, but when r=0, R ⁸ is R ⁷ ; (E) 10 to 2,000 parts by mass of water. The emulsion water-repellent composition according to claim 1, which contains a nonionic surfactant. The emulsion water repellent composition according to claim 2, wherein the nonionic surfactant is selected from polyoxyalkylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters More than one kind of. The emulsion water-repellent composition according to claim 1, wherein in the emulsion water-repellent composition, the average particle diameter of the emulsified particles is 300 nm or less. The emulsion water-repellent composition according to claim 2, wherein, in the emulsion water-repellent composition, the average particle diameter of the emulsified particles is 300 nm or less. The emulsion water-repellent composition according to claim 3, wherein, in the emulsion water-repellent composition, the average particle diameter of the emulsified particles is 300 nm or less. The emulsion water-repellent composition according to any one of claims 1 to 6, wherein the emulsion water-repellent composition is for coating surfaces and glass surfaces of automobiles.