JP7063840B2 - Emulsion water repellent composition - Google Patents

Description

The present invention relates to an emulsion water repellent composition.

Conventionally, in a coating for imparting water repellency to the surface of a vehicle such as an automobile, an aqueous emulsion containing amino-modified polysiloxane as a main component has been applied. Amino-modified polysiloxane is a dimethylpolysiloxane in which a part of the methyl group is replaced with an aminoalkyl group or an aminoalkyl-substituted aminoalkyl group. When applied to the vehicle surface, the amino group adsorbs to the vehicle surface and dimethyl. It can impart more durable water-repellent performance than polysiloxane.

In the conventional method of use, it is used as an aqueous emulsion obtained by emulsifying an amino-modified polysiloxane with a nonionic surfactant, but in order to further increase the adsorptivity of the amino-modified polysiloxane, an aqueous emulsion using a specific cationic surfactant in combination is used. The coating agent is disclosed in Patent Document 1.
Further, Patent Document 2 discloses a glossy water-repellent-imparting composition obtained by emulsifying amino-modified polysiloxane and dimethylpolysiloxane with a nonionic surfactant having a specific HLB and mixing them.

These aqueous emulsions containing amino-modified polysiloxane as the main component are diluted tens to hundreds of times with water using a portal-type automatic car wash machine and spray-applied to make the surface of vehicles such as automobiles water-repellent. It is used to grant.
In this case, it is important to impart performance to the glass surface that is easily visible to the driver, such as imparting water repellency not only to the painted surface of the vehicle but also to the glass surface such as the windshield and no glare due to the oil film.
However, although it is possible to impart water repellency to the painted surface of the vehicle with the conventional technique, it is not possible to impart sufficient performance to the glass surface, and further improvement of the characteristics is required.

Japanese Unexamined Patent Publication No. 8-188745 Japanese Unexamined Patent Publication No. 2004-300387

The present invention has been made in view of the above circumstances, and is effectively used as a water repellent agent having excellent water repellency. In particular, it imparts good initial water repellency and water repellency durability to both the painted surface and the glass surface of an automobile. It is an object of the present invention to provide an emulsion water repellent composition capable of imparting a performance of eliminating glare due to an oil film on a glass surface.

（式中、Ｒ^１は互いに独立に炭素原子数１～２０の非置換一価炭化水素基であり、Ｒ^２は互いに独立に一般式（２）：－Ｒ^４－（ＮＨ－Ｒ^５－）_ｐＮＨ_２で表される基であり、前記式（２）においてＲ^４及びＲ^５は互いに独立に炭素原子数１～６の二価有機基であり、ｐは０または１であり、Ｒ^３は互いに独立に水酸基又は、メトキシ基及びエトキシ基から選ばれる基であり、ａ、ｂ、ｃ、ｄ、及びｅは夫々、２≦ａ≦１０、１０≦ｂ≦１，０００、１≦ｃ≦５０、０≦ｄ≦５、０≦ｅ≦５の範囲を満たす実数である）、
（Ｂ）下記一般式（３）で表され、２５℃で粘度５０～５，０００ｍＰａ・ｓを有し、アミノ基当量３００～４，０００ｇ／ｍｏｌを有するアミノ変性シリコーン：０～８０質量部（但し、（Ａ）成分と（Ｂ）成分の合計量を１００質量部とする）、

（式中、Ｒ^１、Ｒ^２は上記と同じであり、Ｒ^６は互いに独立にＲ^１及びＲ^２の選択肢から選ばれる基であり、ｆ、ｇ、ｈ、ｉ、及びｊは夫々、２≦ｆ≦１０、１０≦ｇ≦１，０００、０≦ｈ≦５０、０≦ｉ≦５、０≦ｊ≦５の範囲を満たす実数である。但し、上記式（３）においてｈ＝０の時、Ｒ^６はＲ^２の選択肢から選ばれる基である）、
（Ｃ）ノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、及び両イオン系界面活性剤から選ばれる少なくとも１の界面活性剤：２～１００質量部、
（Ｄ）下記平均組成式（４）で表され、２５℃で粘度１０～１０，０００ｍＰａ・ｓを有し、ＨＬＢ５～１３を有するポリエーテル変性シリコーン：１～２５質量部、

（式中、Ｒ^１は上記と同じであり、Ｒ^７は互いに独立に一般式（５）：－Ｒ^９－Ｏ－（Ｃ_２Ｈ_４Ｏ）_ｘ－（Ｃ_３Ｈ_６Ｏ）_ｙ－（Ｃ_４Ｈ_８Ｏ）_ｚ－Ｒ^１０で表されるポリエーテル基であり、前記式（５）において、Ｒ^９は炭素原子数１～６の二価有機基であり、Ｒ^１０は－Ｈ、－ＣＨ_３、－Ｃ_２Ｈ_５、－Ｃ_３Ｈ_７、－Ｃ_４Ｈ_９、及び－（Ｃ＝Ｏ）ＣＨ_３から選ばれる基であり、ｘ、ｙ及びｚは５≦ｘ≦３０、０≦ｙ≦３０、０≦ｚ≦３０の範囲を満たす実数であり、Ｒ^８は、前記Ｒ^１及びＲ^７の選択肢から選ばれる基又は、－ＯＨ、－ＯＣＨ_３及び－ＯＣ_２Ｈ_５から選ばれる基であり、ｑ及びｒは夫々、０≦ｑ≦１００、０≦ｒ≦４０の範囲を満たす実数である。但し、ｒ＝０のときＲ^８はＲ^７である）、
（Ｅ）水：１０～２，０００質量部。 In order to achieve the above problems, in the present invention,
Provided are an emulsion water repellent composition containing the following components (A) to (E).
(A) Represented by the following general formula (1), end-sealed with a hydroxyl group or an alkoxy group having a viscosity of 30 to 2,000 mPa · s at 25 ° C. and an amino group equivalent of 300 to 3,000 g / mol. Amino-modified silicone: 20-100 parts by mass,

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

(In the equation, R ¹ and R ² are the same as above, R ⁶ is a group independently selected from the options of R ¹ and R ² , and f, g, h, i, and j are 2 respectively. It is a real number that satisfies the range of ≦ f ≦ 10, 10 ≦ g ≦ 1,000, 0 ≦ h ≦ 50, 0 ≦ i ≦ 5, 0 ≦ j ≦ 5, where h = 0 in the above equation (3). At times, R ⁶ is the basis of choice for R ² ),
(C) At least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants: 2 to 100 parts by mass,
(D) A polyether-modified silicone represented by the following average composition formula (4), having a viscosity of 10 to 10,000 mPa · s at 25 ° C. and having HLBs 5 to 13, 1 to 25 parts by mass,

(In the formula, R ¹ is the same as above, and R ⁷ are independent of each other in the general formula (5): -R ⁹ -O- (C ₂ H ₄ O) _x- (C ₃ H ₆ O) _y- ( C ₄ H ₈ O) It is a polyether group represented by _z −R ¹⁰ , and in the above formula (5), R ⁹ is a divalent organic group having 1 to 6 carbon atoms, and R ¹⁰ is −H, A group selected from -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , and- (C = O) CH ₃ , where x, y and z are 5 ≤ x ≤ 30, It is a real number satisfying the range of 0 ≦ y ≦ 30, 0 ≦ z ≦ 30, and R ⁸ is a group selected from the options of R ¹ and R ⁷ or from -OH, -OCH ₃ and -OC ₂ H ₅ . It is a group to be selected, and q and r are real numbers satisfying the range of 0 ≦ q ≦ 100 and 0 ≦ r ≦ 40, respectively. However, when r = 0, R ⁸ is R ⁷ ).
(E) Water: 10 to 2,000 parts by mass.

This emulsion water repellent composition is effectively used as a water repellent agent having excellent water repellency, and in particular, imparts good initial water repellency and water repellency durability to both the painted surface and the glass surface of an automobile, and makes the glass surface. It is possible to give the performance of eliminating the glare caused by the oil film.

This emulsion water repellent composition preferably contains a nonionic surfactant.
When this emulsion water-repellent composition contains a nonionic surfactant, the stability becomes more excellent.

The nonionic surfactant is preferably one or more selected from polyoxyalkylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters.
When the nonionic surfactant is the specific one, the emulsion water repellent composition becomes more stable.

The average particle size of the emulsified particles in this emulsion water repellent composition is preferably 300 nm or less.
When 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 become a bluish white or transparent microemulsion in appearance.

This emulsion water repellent composition is preferably for a painted surface and a glass surface of an automobile.
When this emulsion water repellent composition is for a painted surface and a glass surface of an automobile, it gives good initial water repellency and water repellency durability to both the painted surface and the glass surface of the automobile, and an oil film on the glass surface. It will be possible to give the performance to eliminate the glare caused by.

The emulsion water repellent composition of the present invention is effectively used as a water repellent having excellent water repellency, and in particular, imparts good initial water repellency and water repellency durability to both the painted surface and the glass surface of an automobile, and glass. It is possible to give the surface the performance of eliminating the glare caused by the oil film.

As described above, it is effectively used as a water repellent agent having excellent water repellency, and in particular, it gives good initial water repellency and water repellency durability to both the painted surface and the glass surface of an automobile, and causes glare on the glass surface due to an oil film. There has been a need to develop a water repellent composition that can provide the ability to eliminate.

As a result of diligent studies on the above-mentioned problems, the present inventors have made a specific amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group, a surfactant, a specific polyether-modified silicone, and an amino-modified silicone containing water. The emulsion composition is effectively used as a water-repellent agent having excellent water repellency, and in particular, imparts good initial water repellency and water repellency durability to both the painted surface and the glass surface of an automobile, and causes glare on the glass surface due to an oil film. The present invention has been completed by finding that it can provide the ability to eliminate.

（式中、Ｒ^１は互いに独立に炭素原子数１～２０の非置換一価炭化水素基であり、Ｒ^２は互いに独立に一般式（２）：－Ｒ^４－（ＮＨ－Ｒ^５－）_ｐＮＨ_２で表される基であり、前記式（２）においてＲ^４及びＲ^５は互いに独立に炭素原子数１～６の二価有機基であり、ｐは０または１であり、Ｒ^３は互いに独立に水酸基又は、メトキシ基及びエトキシ基から選ばれる基であり、ａ、ｂ、ｃ、ｄ、及びｅは夫々、２≦ａ≦１０、１０≦ｂ≦１，０００、１≦ｃ≦５０、０≦ｄ≦５、０≦ｅ≦５の範囲を満たす実数である）、
（Ｂ）下記一般式（３）で表され、２５℃で粘度５０～５，０００ｍＰａ・ｓを有し、アミノ基当量３００～４，０００ｇ／ｍｏｌを有するアミノ変性シリコーン：０～８０質量部（但し、（Ａ）成分と（Ｂ）成分の合計量を１００質量部とする）、

（式中、Ｒ^１、Ｒ^２は上記と同じであり、Ｒ^６は互いに独立にＲ^１及びＲ^２の選択肢から選ばれる基であり、ｆ、ｇ、ｈ、ｉ、及びｊは夫々、２≦ｆ≦１０、１０≦ｇ≦１，０００、０≦ｈ≦５０、０≦ｉ≦５、０≦ｊ≦５の範囲を満たす実数である。但し、上記式（３）においてｈ＝０の時、Ｒ^６はＲ^２の選択肢から選ばれる基である）、
（Ｃ）ノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、及び両イオン系界面活性剤から選ばれる少なくとも１の界面活性剤：２～１００質量部、
（Ｄ）下記平均組成式（４）で表され、２５℃で粘度１０～１０，０００ｍＰａ・ｓを有し、ＨＬＢ５～１３を有するポリエーテル変性シリコーン：１～２５質量部、

（式中、Ｒ^１は上記と同じであり、Ｒ^７は互いに独立に一般式（５）：－Ｒ^９－Ｏ－（Ｃ_２Ｈ_４Ｏ）_ｘ－（Ｃ_３Ｈ_６Ｏ）_ｙ－（Ｃ_４Ｈ_８Ｏ）_ｚ－Ｒ^１０で表されるポリエーテル基であり、前記式（５）において、Ｒ^９は炭素原子数１～６の二価有機基であり、Ｒ^１０は－Ｈ、－ＣＨ_３、－Ｃ_２Ｈ_５、－Ｃ_３Ｈ_７、－Ｃ_４Ｈ_９、及び－（Ｃ＝Ｏ）ＣＨ_３から選ばれる基であり、ｘ、ｙ及びｚは５≦ｘ≦３０、０≦ｙ≦３０、０≦ｚ≦３０の範囲を満たす実数であり、Ｒ^８は、前記Ｒ^１及びＲ^７の選択肢から選ばれる基又は、－ＯＨ、－ＯＣＨ_３及び－ＯＣ_２Ｈ_５から選ばれる基であり、ｑ及びｒは夫々、０≦ｑ≦１００、０≦ｒ≦４０の範囲を満たす実数である。但し、ｒ＝０のときＲ^８はＲ^７である）、
（Ｅ）水：１０～２，０００質量部。 That is, the present invention is an emulsion water repellent composition containing the following components (A) to (E).
(A) Represented by the following general formula (1), end-sealed with a hydroxyl group or an alkoxy group having a viscosity of 30 to 2,000 mPa · s at 25 ° C. and an amino group equivalent of 300 to 3,000 g / mol. Amino-modified silicone: 20-100 parts by mass,

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

(In the equation, R ¹ and R ² are the same as above, R ⁶ is a group independently selected from the options of R ¹ and R ² , and f, g, h, i, and j are 2 respectively. It is a real number that satisfies the range of ≦ f ≦ 10, 10 ≦ g ≦ 1,000, 0 ≦ h ≦ 50, 0 ≦ i ≦ 5, 0 ≦ j ≦ 5, where h = 0 in the above equation (3). At times, R ⁶ is the basis of choice for R ² ),
(C) At least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants: 2 to 100 parts by mass,
(D) A polyether-modified silicone represented by the following average composition formula (4), having a viscosity of 10 to 10,000 mPa · s at 25 ° C. and having HLBs 5 to 13, 1 to 25 parts by mass,

(In the formula, R ¹ is the same as above, and R ⁷ are independent of each other in the general formula (5): -R ⁹ -O- (C ₂ H ₄ O) _x- (C ₃ H ₆ O) _y- ( C ₄ H ₈ O) It is a polyether group represented by _z −R ¹⁰ , and in the above formula (5), R ⁹ is a divalent organic group having 1 to 6 carbon atoms, and R ¹⁰ is −H, A group selected from -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , and- (C = O) CH ₃ , where x, y and z are 5 ≤ x ≤ 30, It is a real number satisfying the range of 0 ≦ y ≦ 30, 0 ≦ z ≦ 30, and R ⁸ is a group selected from the options of R ¹ and R ⁷ or from -OH, -OCH ₃ and -OC ₂ H ₅ . It is a group to be selected, and q and r are real numbers satisfying the range of 0 ≦ q ≦ 100 and 0 ≦ r ≦ 40, respectively. However, when r = 0, R ⁸ is R ⁷ ).
(E) Water: 10 to 2,000 parts by mass.

Hereinafter, the present invention will be described in more detail.
(A) Amino-modified silicone end-sealed with a hydroxyl group or an alkoxy group
The amino-modified silicone terminally sealed with (A) a hydroxyl group or an alkoxy group in the present invention is represented by the following average composition formula (1).

(A) The amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group has a viscosity of 30 to 2,000 mPa · s at 25 ° C. The viscosity is preferably 40 to 1,800 mPa · s, and more preferably 50 to 1,500 mPa · s. If the viscosity is less than the above lower limit, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate. On the other hand, if the upper limit is exceeded, the stability of the emulsion water repellent composition deteriorates, and glare occurs on the glass surface due to the oil film.

Further, (A) the amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group has an amino group equivalent of 300 to 3,000 g / mol at 25 ° C. The amino group equivalent is preferably 350 to 2,800 g / mol, more preferably 400 to 2,500 g / mol. If the amino group equivalent is less than the lower limit, the number of amino groups is too large, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate. Further, when the amino group equivalent exceeds the above upper limit value, the number of amino groups is too small, and the hydrophilicity to be given as the amino-modified silicone is insufficient. As a result, the stability of the emulsion water repellent composition deteriorates, and glare may occur on the glass surface due to the oil film.

In the above formula (1), R ¹ is an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other. For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a tetradecyl group and an octadecyl group. Examples thereof include an alkenyl group such as a vinyl group, an allyl group, a 5-hexenyl group and an oleyl group, and an aryl group such as a phenyl group, a trill group and a naphthyl group. Of these, a methyl group, a long-chain alkyl group and a phenyl group are preferable. In particular, a methyl group is preferable when weather resistance is required, and a methyl group and a long-chain alkyl group are preferable when water repellency is required. Further, when imparting compatibility with an organic compound such as wax, it is preferable to use a long-chain alkyl group and a phenyl group. Further, the compound of the formula (1) may have a plurality of types of organic substituents as R ¹ , but in the case of combined use, the content of the methyl group with respect to the total number of the substituents R ¹ , R ² and R ³ is contained. The rate is preferably 70% or more.

R ² is a group represented by the general formula (2): -R ^4- (NH-R ^5- ) _p -NH ₂ independently of each other. In the formula (2), R ⁴ and R ⁵ are divalent organic groups having 1 to 6 carbon atoms independently of each other, and particularly divalent hydrocarbon groups having 1 to 6 carbon atoms. For example, an alkylene group, an alkenylene group, an arylene group and the like can be mentioned. p is 0 or 1. Examples of the group represented by the formula (2) include a 2-aminoethyl group, a 3-aminopropyl group, a 6-aminohexyl group, an N- (2-aminoethyl) -3-aminopropyl group, and an N- ( Examples thereof include 3-aminopropyl) -3-aminopropyl group and N- (2-aminoethyl) -6-aminohexyl group. It is preferable to use a 3-aminopropyl group or an N- (2-aminoethyl) -3-aminopropyl group from the viewpoint of easy availability of raw materials and superior price.

R ³ is a group independently selected from a hydroxyl group or a methoxy group and an ethoxy group. Further, as the component (A), amino-modified silicone terminally sealed with these hydroxyl groups or alkoxy groups can be used alone or in combination of two or more. A hydroxyl group or a group selected from a methoxy group and an ethoxy group is adsorbed to a SiOH group on the glass surface via a hydrogen bond, and (A) an amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group is immobilized on the glass surface. It is possible to impart durable water repellency to the glass surface.

a is a real number that satisfies 2 ≦ a ≦ 10. When a is less than 2, the viscosity of the amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group becomes too high, and the stability of the emulsion water repellent composition deteriorates. If a exceeds 10, the viscosity of the amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group becomes too low, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate. .. Preferably a = 2.

b is a real number that satisfies 10 ≦ b ≦ 1,000. When b is less than 10, the viscosity of the amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group becomes too low, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate. If b exceeds 1,000, the viscosity of the amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group becomes too high, and the stability of the emulsion water repellent composition deteriorates. It is preferable to satisfy the range of 20 ≦ b ≦ 800.

c is a real number that satisfies 1 ≦ c ≦ 50. When c is less than 1, the amount of amino groups in the amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group is too small, and the water-repellent durability of the film formed from the emulsion water-repellent composition and the emulsion water-repellent composition Stability deteriorates, and glare may occur on the glass surface due to the oil film. When c exceeds 50, the amount of amino groups in the amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group is too large, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition are deteriorated. Deteriorate.

d is a real number that satisfies 0 ≦ d ≦ 5. When d exceeds 5, the viscosity of the amino-modified silicone whose end is sealed with a hydroxyl group or an alkoxy group becomes too high, the stability of the emulsion water repellent composition deteriorates, and glare due to an oil film occurs on the glass surface. There is. D = 0 is preferable.

e is a real number that satisfies 0 ≦ e ≦ 5. When e exceeds 5, the viscosity of the amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group becomes too high, the stability of the emulsion water repellent composition deteriorates, and glare due to an oil film may occur on the glass surface. be. Preferably e = 0.

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

(B) The amino-modified silicone has a viscosity of 50 to 5,000 mPa · s at 25 ° C. The viscosity is preferably 55 to 4,500 mPa · s, more preferably 60 to 4,000 mPa · s. If the viscosity is less than the above lower limit, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate. On the other hand, if the upper limit is exceeded, the stability of the emulsion water repellent composition deteriorates, and glare occurs on the glass surface due to the oil film.

Further, (B) amino-modified silicone has an amino group equivalent of 300 to 4,000 g / mol at 25 ° C. The amino group equivalent is preferably 320 to 3,800 g / mol, and more preferably 330 to 3,600 g / mol. If the amino group equivalent is less than the lower limit, the number of amino groups is too large, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate. Further, when the amino group equivalent exceeds the above upper limit value, the number of amino groups is too small, so that the hydrophilicity to be given as the amino-modified silicone is insufficient. As a result, the stability of the emulsion water repellent composition deteriorates, and glare may occur on the glass surface due to the oil film.

The amount of the amino-modified silicone (B) added is 0 to 80 parts by mass, where 100 parts by mass is the total amount of the component (A) and the component (B). If the amount added exceeds 80 parts by mass, the water-repellent durability of the film formed from the emulsion water-repellent composition on the glass surface deteriorates.

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

R ⁶ is a group independently selected from the above-mentioned options of R ¹ and R ² . However, when h = 0 in the above equation (3), R ⁶ is a group selected from the options of R ² . Further, as the component (B), these amino-modified silicones can be used alone or in combination of two or more.

f is a real number that satisfies 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 water repellent composition deteriorates. If f exceeds 10, the viscosity of the amino-modified silicone becomes too low, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate. Preferably f = 2.

g is a real number that satisfies 10 ≦ g ≦ 1,000. When g is less than 10, the viscosity of the amino-modified silicone becomes too low, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate. If g exceeds 1,000, the viscosity of the amino-modified silicone becomes too high, and the stability of the emulsion water repellent composition deteriorates. It is preferable to satisfy the range of 20 ≦ g ≦ 800.

h is a real number that satisfies 0 ≦ h ≦ 50. In particular, when h is 1 or more, the amount of amino groups in (B) amino-modified silicone is large, and the water-repellent durability of the film formed from the emulsion water-repellent composition and the stability of the emulsion water-repellent composition are high. No glare due to the oil film on the glass surface. However, when h = 0, R ⁶ is a base selected from the options of R ² . On the other hand, when h exceeds 50, the amount of amino groups in the amino-modified silicone is too large, and the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition deteriorate.

i is a real number that satisfies 0 ≦ i ≦ 5. If i exceeds 5, the viscosity of the amino-modified silicone becomes too high, the stability of the emulsion water-repellent composition deteriorates, and glare may occur on the glass surface due to the oil film. Preferably i = 0.

j is a real number that satisfies 0 ≦ j ≦ 5. If j exceeds 5, the viscosity of the amino-modified silicone becomes too high, the stability of the emulsion water-repellent composition deteriorates, and glare may occur on the glass surface due to the oil film. Preferably j = 0 is preferable.

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

Specific examples of these include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene oxypropylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene oxypropylene lauryl ether, and polyoxyethylene. Tridecyl ether, polyoxyethylene oxypropylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene Examples thereof include sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan trioleate. As the component (C), these nonionic surfactants can be used alone or in combination of two or more.

Further, anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, alkylsulfosuccinates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, quaternary ammonium salts, alkylamine acetates and the like. Cationic surfactants, and amphoteric surfactants such as alkylbetaine and alkylimidazolin can also be used.

The amount of the component (C) added is 2 to 100 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). When the added amount is less than 2 parts by mass, the stability of the emulsion water repellent composition deteriorates, and when the added amount exceeds 100 parts by mass, the initial repellent of the film formed from the emulsion water repellent composition is deteriorated. Water-based and water-repellent durability deteriorates. The addition amount is preferably 2 to 50 parts by mass. When the addition amount is 2 parts by mass or more, the stability of the emulsion water repellent composition is improved, and when the addition amount is 50 parts by mass or less, the initial water repellency and water repellency durability of the film formed from the emulsion water repellent composition are improved. The sex becomes better. The addition amount is more preferably 3 to 40 parts by mass, still more preferably 4 to 30 parts by mass.
The 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 Silicone The (D) polyether-modified silicone in the present invention is represented by the following average composition formula (4).

(D) The polyether-modified silicone has HLBs 5 to 13 at 25 ° C. The HLB is preferably 5.5 to 12.5, more preferably 6.0 to 12.0. With a polyether-modified silicone having a HLB of less than 5, it becomes difficult to sufficiently emulsify and disperse the component (A) and the component (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 of the obtained emulsion water repellent composition, particularly the dilution stability, is deteriorated.

(D) The polyether-modified silicone has a viscosity of 10 to 10,000 mPa · s at 25 ° C. The viscosity is preferably 40 to 5,000 mPa · s, more preferably 50 to 4,000 mPa · s. If it is less than the above lower limit, it becomes difficult to sufficiently emulsify and disperse the component (A) and the component (B). Further, if the above upper limit value is exceeded, it becomes difficult to handle the emulsion water repellent composition at the time of use.

In the above formula (4), R ¹ is the same as R ¹ in the above formula (1). Of these, a methyl group, a long-chain alkyl group and a phenyl group are preferable. Since the component (D) is used to emulsify and disperse the components (A) and (B) together with the component (C), a strong hydrophobic group is not preferable. However, when it is desired to improve the dispersibility with an organic compound such as wax, it is preferable to use a long-chain alkyl group and a phenyl group. Further, the compound represented by the formula (4) may be used in combination with a plurality of types of organic substituents as R ¹ , but in the case of the combined use, the methyl group with respect to the total number of substituents R ¹ , R ⁷ and R ⁸ is used. The content is preferably 90% or more.

R ⁷ is independently represented by the general formula (5): -R ⁹ -O- (C ₂ H ₄ O) _x- (C ₃ H ₆ O) _y- (C ₄ H ₈ O) _z -R ¹⁰ . It is a polyether group. In the formula (5), R ⁹ is a divalent organic group having 1 to 6 carbon atoms, for example, an alkylene group, an alkenylene group, an arylene group and the like. 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 that satisfies the range of 5 ≦ x ≦ 30. When x is less than 5, the HLB of the component (D) becomes too low, and it becomes difficult to sufficiently emulsify and disperse the components (A) and (B). If x exceeds 30, the viscosity of the component (D) becomes high or the solid becomes a solid at room temperature, which makes it difficult to handle during use. It is preferable to satisfy the range of 5 ≦ x ≦ 25.

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

z is a real number that satisfies the range of 0 ≦ z ≦ 30. When z exceeds 30, the HLB of the component (D) becomes too low, and it becomes difficult to sufficiently emulsify and disperse the components (A) and (B). It is preferable to satisfy the range of 0 ≦ z ≦ 15.

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

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

r is a real number that satisfies the range of 0 ≦ r ≦ 40. In particular, when r is 1 or more, the HLB of the component (D) is appropriate, and the components (A) and (B) can be sufficiently emulsified and dispersed. However, when R ⁸ = R ⁷ , r may be less than 1, especially r = 0. If r exceeds 40, the viscosity of the component (D) becomes too high, which makes it difficult to handle during use.

The amount of the component (D) added is 1 to 25 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (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 the component (D) added is out of the range, a stable emulsion water repellent composition cannot be obtained.

(E) Water In the emulsion water repellent composition of the present invention, (E) water is mixed with the above-mentioned components (A), (B), (C) and (D), and according to a conventional method. It can be prepared by emulsifying and dispersing. (E) The water is preferably ion-exchanged water. The content of (E) water is 10 to 2,000 parts by mass and preferably 50 to 1,000 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). An emulsion water repellent composition can be obtained by mixing the above components (A) to (E) and emulsifying and dispersing them. In particular, it is an oil droplet (O / W type) emulsion water repellent composition in water, and is usually a white emulsion, but when the average particle size of the emulsified particles is 300 nm or less, the appearance is bluish white or transparent. It may be a microemulsion. Further, water can be further added to the obtained emulsion water repellent composition to dilute it, and the composition can be used for the purposes described later. The amount of water for dilution is not particularly limited and may be appropriately adjusted according to the intended use. The emulsion water repellent composition of the present invention has excellent stability even after dilution.

Other Additives In addition to the above components (A) to (E), various additives can be added to the emulsion water repellent composition of the present invention, if necessary. For example, acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, stearic acid, lactic acid, and citric acid can be blended to improve the stability of the emulsion. The amount of the additive added can be arbitrarily set, but it is preferably an amount that adjusts the pH of the emulsion water repellent composition of the present invention to 3 to 7.
Further, as other additives, a thickener, an antifreeze agent, a preservative, a rust inhibitor, an antioxidant, an ultraviolet absorber and the like may be contained.

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

The emulsion water repellent composition of the present invention can be easily used for coating a vehicle such as an automobile by using an automatic car wash machine, for example, a gate type car wash machine, a continuous gate type car wash machine, a spray type car wash machine, or the like. be able to. That is, the emulsion water repellent composition of the present invention is useful as a coating agent for vehicles. The concentration of the coating agent when sprayed or applied to the vehicle surface is not particularly limited, but usually, the concentration of the amino-modified silicone of the component (A) and the component (B) is about 0.01 to 0.5% by mass. It is advisable to set the concentration of the emulsion water repellent composition of the present invention and the automatic dilution ratio of the automatic car wash machine. The emulsion water repellent composition of the present invention can impart long-lasting water repellency, glossiness, slipperiness and the like to a painted surface, a glass surface and the like of a vehicle.
Needless to say, the emulsion water repellent composition of the present invention can also be applied to other uses requiring water repellency.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following example, "parts" means "parts by mass" and "%" means "% by 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 N4Plus manufactured by Beckman Coulter Co., Ltd. The viscosity is an absolute viscosity measured at 25 ° C. by a B-type rotational viscometer, and is a value measured by a TVB-10 type viscometer manufactured by Toki Sangyo.

Each component used in Examples and Comparative Examples is described below.
(A) Amino-modified silicone end-sealed with a hydroxyl group or an alkoxy group
Amino-modified silicone terminally sealed with a hydroxyl group or an alkoxy group 1: Represented by the following average composition formula (1), R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -OCH ₃ , a = 2, b = 38, c = 2, d = 0, e = 0, viscosity: 65 mPa · s, amino group equivalent: 780 g / mol.

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

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

Amino-modified silicone 4 terminally sealed with a hydroxyl group or an alkoxy group (for comparison): represented by the above average composition formula (1), 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, viscosity: 30,000 mPa · s, amino group equivalent: 20,000 g / mol.

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

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

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

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

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

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

(C) Surfactant Neugen XL-40 (trade name): Polyoxyalkylene decyl ether manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., HLB = 10.5
Neugen XL-400D (trade name): 65% by mass aqueous solution of polyoxyalkylene decyl ether manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., HLB = 18.4
Newcol 1004 (trade name): Polyoxyethylene octyl ether manufactured by Nippon Embroidery Co., Ltd., HLB = 11.5
Newcol 1008 (trade name): Polyoxyethylene octyl ether manufactured by Nippon Embroidery Co., Ltd., HLB = 14.6
Leodor TW-L106 (trade name): Kao Polyoxyethylene sorbitan monolaurate, HLB = 13.3
Leodor TW-O320V (trade name): Kao Polyoxyethylene sorbitan monooleate, HLB = 11.0

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

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

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

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

(D) The composition list of the components is summarized in Table 2.

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

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

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

[Example 3]
(A) methoxy group-terminated closed amino-modified silicone 2 (viscosity: 700 mPa · s, amino group equivalent: 1,860 g / mol) 80 parts by mass, (B) amino-modified silicone 5 (viscosity: 70 mPa · s, amino group equivalent:: 350 g / mol) 20 parts by mass, (C) Neugen XL-40 (HLB = 10.5): 20 parts by mass, and (C) Neugen XL-400D (HLB = 18.4, 65% by mass aqueous solution) 30 parts by mass. , (D) Polyether-modified silicone 2 (viscosity: 430 mPa · s, HLB: 10) 10 parts by mass, (E) ion-exchanged water 462.5 parts by mass, 4.0 parts by mass of acetic acid, and 0.2 parts by mass of preservative. The parts were mixed and emulsified and dispersed using a homomixer, and the non-volatile content 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, blue. A white, slightly turbid amino-modified silicone emulsion water-repellent composition (I-3) was obtained.

[Example 4]
(A) methoxy group-terminated closed amino-modified silicone 1 (viscosity: 65 mPa · s, amino group equivalent: 780 g / mol) 20 parts by mass, (B) amino-modified silicone 7 (viscosity: 3,600 mPa · s, amino group equivalent:) 1,800 g / mol) 80 parts by mass, (C) Newcol 1004 (HLB = 11.5): 20 parts by mass, Newcol 1008 (HLB = 14.6) 20 parts by mass, (D) polyether-modified silicone 3 (viscosity: 70 mPa · s, HLB: 12) 10 parts by mass, (E) ion exchanged water 462.5 parts by mass, acetic acid 3.1 parts by mass, and preservative 0.2 parts by mass using a homomixer. Mix and emulsify and disperse, the non-volatile content at 105 ° C / 3 hours is 24.6%, and the average particle size of the emulsified particles in the emulsion water repellent composition is 30 nm. A colorless and transparent amino-modified silicone emulsion water repellent. The agent composition (I-4) was obtained.

[Example 5]
(A) methoxy group-terminated closed amino-modified silicone 1 (viscosity: 65 mPa · s, amino group equivalent: 780 g / mol) 30 parts by mass, (B) amino-modified silicone 8 (viscosity: 1,500 mPa · s, amino group 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, (D) Poly Ether-modified silicone 1 (viscosity: 1,600 mPa · s, HLB: 7) 10 parts by mass, (E) ion-exchanged water 462.5 parts by mass, acetic acid 2.4 parts by mass, and preservative 0.2 parts by mass. A colorless and transparent amino which is mixed and emulsified and dispersed using a homomixer, has a non-volatile content of 24.9% at 105 ° C./3 hours, and has an average particle size of emulsified particles of 60 nm in the emulsion water repellent composition. A modified silicone emulsion water repellent composition (I-5) was obtained.

[Example 6]
(A) ethoxy group terminal blocking amino-modified silicone 3 (viscosity: 350 mPa · s, amino group equivalent: 1,900 g / mol) 100 parts by mass, (C) Neucol 1004 (HLB = 11.5): 20 parts by mass , 20 parts by mass of Newcol 1008 (HLB = 14.6), (D) 10 parts by mass of polyether-modified silicone 2 (viscosity: 430 mPa · s, HLB: 10), (E) 462.5 parts by mass of ion-exchanged water, 2.2 parts by mass of acetic acid and 0.2 parts by mass of preservative were mixed using a homomixer to emulsify and disperse. A colorless and transparent amino-modified silicone emulsion water-repellent composition (I-6) having an average particle size of emulsified particles of 40 nm was obtained.

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

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

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

[Comparative Example 3]
(B) Amino-modified silicone 7 (viscosity: 3,600 mPa · s, amino group equivalent: 1,800 g / mol) 100 parts by mass, (C) Neucol 1004 (HLB = 11.5): 20 parts by mass. Cole 1008 (HLB = 14.6) 20 parts by mass, (D) polyether-modified silicone 2 (viscosity: 430 mPa · s, HLB: 10) 10 parts by mass, (E) ion-exchanged water 462.5 parts by mass, acetate 2 .5 parts by mass and 0.2 parts by mass of the preservative were mixed using a homomixer to emulsify and disperse, and the non-volatile content at 105 ° C./3 hours was 23.8% in the emulsion water repellent composition. A colorless and transparent amino-modified silicone emulsion water-repellent composition (II-3) having an average particle size of 40 nm of emulsified particles was obtained.

[Comparative Example 4]
(A) methoxy group-terminated closed amino-modified silicone 1 (viscosity: 65 mPa · s, amino group equivalent: 780 g / mol) 20 parts by mass, (A) methoxy group-terminated closed amino-modified silicone 2 (viscosity: 700 mPa · s, amino group) Equivalent amount: 1,860 g / mol) 80 parts by mass, (C) Neugen XL-40 (HLB = 10.5): 20 parts by mass, and (C) Neugen XL-400D (HLB = 18.4, 65% by mass) aqueous solution. ) 30 parts by mass, (D) polyether-modified silicone 4 (viscosity: 20 mPa · s, HLB: 14) 10 parts by mass, (E) ion-exchanged water 462.5 parts by mass, acetic acid 3.0 parts by mass, and preservative. 0.2 parts by mass was mixed using a homomixer to emulsify and disperse, the non-volatile content at 105 ° C / 3 hours was 24.8%, and the average particle size of the emulsified particles in the emulsion water repellent composition was 70 nm. A colorless and transparent amino-modified silicone emulsion water-repellent composition (II-4) was obtained.

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

[Water repellent durability]
The amino-modified silicone emulsion water-repellent composition obtained in Examples 1 to 7 and Comparative Examples 1 to 5 was diluted 150-fold with tap water and then sprayed onto the painted surface and the glass surface of an automobile using a spray gun. bottom. After the spraying was completed, it was washed once with tap water, and the time until the water film was cut after the washing was stopped was measured. The results are shown in Tables 3 and 4 below as initial values. After that, it was further washed with tap water for 15 reciprocations, and the time until the water film was cut after the washing was stopped was measured. The results are shown in Tables 3 and 4 below.

[Glitter on the glass surface]
After the water repellency durability test was completed, the glass surface was wiped three times with a rubber wiper. At that time, the presence or absence of oil film residue and glare on the glass surface was visually observed. 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 silicone emulsion water-repellent composition (undiluted solution) prepared in Examples 1 to 7 and Comparative Examples 1 to 5 was placed in a glass bottle and stored at 40 ° C. for 2 weeks, and the presence or absence of separation was visually observed. It was evaluated as "stock solution stability" based on the following criteria. The results are shown in Tables 3 and 4.
<Evaluation criteria>
◯: No separation, Δ: Dilution, ×: Two-layer separation In addition, the amino-modified silicone emulsion water-repellent composition (stock solution) prepared in Examples 1 to 7 and Comparative Examples 1 to 5 was 150 times as much as tap water. The diluted solution was placed in a glass bottle and stored at 40 ° C. for 2 weeks, and the presence or absence of separation was visually observed. It was evaluated as "dilution stability" based on the following indicators. The results are shown in Tables 3 and 4.
<Evaluation criteria>
◯: No precipitate, Δ: Slightly precipitate, ×: With precipitate

As shown in Table 3 above, the emulsion water repellent composition of the present invention is effectively used as a water repellent having excellent water repellency, and particularly good initial water repellency and water repellency on both the painted surface and the glass surface of an automobile. It imparts durability and eliminates glare due to an oil film on the glass surface, and is also excellent in undiluted solution stability and dilution stability.

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

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.

Claims (5)

An emulsion water repellent composition comprising the following components (A) to (E).
(A) Represented by the following general formula (1), end-sealed with a hydroxyl group or an alkoxy group having a viscosity of 30 to 2,000 mPa · s at 25 ° C. and an amino group equivalent of 300 to 3,000 g / mol. Amino-modified silicone: 20-100 parts by mass,

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

(In the equation, R ¹ and R ² are the same as above, R ⁶ is a group independently selected from the options of R ¹ and R ² , and f, g, h, i, and j are 2 respectively. It is a real number that satisfies the range of ≦ f ≦ 10, 10 ≦ g ≦ 1,000, 0 ≦ h ≦ 50, 0 ≦ i ≦ 5, 0 ≦ j ≦ 5, where h = 0 in the above equation (3). At times, R ⁶ is the basis of choice for R ² ),
(C) At least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants: 2 to 100 parts by mass,
(D) A polyether-modified silicone represented by the following average composition formula (4), having a viscosity of 10 to 10,000 mPa · s at 25 ° C. and having HLBs 5 to 13, 1 to 25 parts by mass,

(In the formula, R ¹ is the same as above, and R ⁷ are independent of each other in the general formula (5): -R ⁹ -O- (C ₂ H ₄ O) _x- (C ₃ H ₆ O) _y- ( C ₄ H ₈ O) It is a polyether group represented by _z −R ¹⁰ , and in the above formula (5), R ⁹ is a divalent organic group having 1 to 6 carbon atoms, and R ¹⁰ is −H, A group selected from -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , and- (C = O) CH ₃ , where x, y and z are 5 ≤ x ≤ 30, It is a real number satisfying the range of 0 ≦ y ≦ 30, 0 ≦ z ≦ 30, and R ⁸ is a group selected from the options of R ¹ and R ⁷ , or from -OH, -OCH ₃ and -OC ₂ H ₅ . It is a group to be selected, and q and r are real numbers satisfying the range of 0 ≦ q ≦ 100 and 0 ≦ r ≦ 40, respectively. However, when r = 0, R ⁸ is R ⁷ ).
(E) Water: 10 to 2,000 parts by mass. The emulsion water-repellent composition according to claim 1, wherein the emulsion contains a nonionic surfactant. The emulsion water repellent composition according to claim 2, wherein the nonionic surfactant is one or more selected from polyoxyalkylene alkyl ether and polyoxyethylene sorbitan fatty acid ester. The emulsion water-repellent composition according to any one of claims 1 to 3, wherein the average particle size of the emulsified particles in the emulsion water-repellent composition is 300 nm or less. The emulsion water repellent composition according to any one of claims 1 to 4, wherein the emulsion water repellent composition is for a painted surface and a glass surface of an automobile.