JP3228085B2 - Water repellent agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conventional organic material which provides an inorganic surface such as glass, metal or ceramics with excellent water repellency and antifouling property, and has excellent durability and can maintain these effects for a long period of time. It relates to a water-repellent agent soluble in a solvent.

[0002]

2. Description of the Related Art
Various studies have been made to improve the properties of the surface of inorganic materials such as glass, ceramics, and metals by treating them with various surface treatment agents, thereby improving the performance and expanding the range of application. As one of the methods, a method has been proposed in which a hydrophilic surface is treated with a silicone composition to modify the surface to a water-repellent surface, and in particular, JP-A-58-147484 and JP-A-58-147484.
No. 0-221470 and JP-A-4-96935 describe that polysiloxane or polysilazane containing a perfluoroalkyl group is excellent in water repellency.

[0003] However, the above-mentioned water-repellent agent is excellent in water-repellent effect but is inferior in the dropping property of water droplets. Therefore, when the agent is applied as an antifouling agent for window glass of buildings such as houses and buildings, Water droplets did not fall and remained in a polka dot shape on the glass surface, which sometimes caused dust and oil in the air to adhere and contaminate them.

Japanese Unexamined Patent Publication (Kokai) No. 3-29037 proposes a fluorine-containing silazane compound. This compound has the above-mentioned disadvantages, but has a poor solubility in general organic solvents, and is subject to CFC regulations. However, there is a problem that it is stably soluble only in fluorocarbons such as 1,1,3-trichlorotrifluoroethane and expensive fluorohydrocarbons, which limits the range of application. .

Further, Japanese Patent Publication No. 50-15473 proposes a mixture of dimethylpolysiloxane and a strong acid. However, although this mixture is excellent in both water repellency and water dropping property, it has poor durability and has a drawback that these effects cannot be maintained for a long time. Tokiko Sho 52
JP-A-38950 discloses an antifouling agent comprising a perfluoroalkoxysilane, an alkoxysilane and a diol compound, and JP-A-2-233535 discloses
A surface treatment agent for glass comprising a silane having a perfluoroalkyl group, an organopolysiloxane, an acid, and a volatile organic solvent is disclosed. JP-A-4-144940 discloses an organopolysiloxane, a perfluoroalkyl group-containing silane or Although a water / oil repellent composition comprising siloxane and acid has been proposed, the water repellency has been improved to some extent, but the durability and water repellency have been insufficient. Therefore, development of a higher performance water repellent agent is desired.

The present invention has been made in view of the above circumstances,
Provide a water-repellent agent which is excellent in water-repellent effect and water droplet dropping effect, can provide excellent water-repellent and antifouling properties to the surface of the object to be treated for a long time, and is soluble in general organic solvents. The purpose is to:

[0007]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, have found that a perfluoroalkyl group-containing organosilicon compound represented by the following general formula (I) is obtained. A co-hydrolyzate of a hydrolyzable group-containing methylpolysiloxane compound represented by the following general formula (II) in a hydrophilic solvent;
It has been found that when an organopolysiloxane represented by the formula (1) and a strong acid are blended, a water-repellent agent having excellent properties without the above-mentioned problems can be obtained.

[0008]

Embedded image (Wherein, R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ² is an alkoxy group or an acyloxy group having 1 to 4 carbon atoms, and Q is a divalent organic group having 2 to 10 carbon atoms. A is 0 or 1, and p is an integer of 4 to 12.)

[0009]

Embedded image(Where R^ThreeIs a monovalent hydrocarbon having 1 to 4 carbon atoms
Group, R^FourIs an alkoxy group having 1 to 4 carbon atoms or acylo
A xy group, A is a methyl group or -Z-Si (R^Three _b) R
^Four _3-b(B is 0, 1 or 2), and Z is
An oxygen atom or a divalent organic group having 2 to 10 carbon atoms
You. M is an integer of 3 to 100; n is an integer of 0 to 50
And 5 ≦ m + n ≦ 100, and when n = 0, both
At least one of the terminal A is -Z-Si
(R^Three _b) R^Four _3-bIs a group represented by Note that -Z-Si
(R^Three _b) R^Four _3-bWhen there are two or more
They may be one or different. )

[0010]

Embedded image (Wherein, R ⁵ is the same or different and has 1 carbon atom)
-20 are monovalent hydrocarbon groups, and B is the same or different and is a hydroxy group or a monovalent hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group or an acyloxy group. r is an integer of 1 to 100. )

That is, in the above co-hydrolyzate, the perfluoroalkyl group-containing organosilicon compound of the formula (I) has a water repellency-imparting effect, and the hydrolyzable group-containing methylpolysiloxane compound of the formula (II) has a water droplet. And the silanol groups generated by co-hydrolysis of these components are highly reactive with the inorganic surface. Further, the organopolysiloxane of the formula (III) further improves the effect of improving the dropping property of water droplets, and the strong acid reacts the above perfluoroalkyl group-containing organosilicon compound and hydrolyzable group-containing methylpolysiloxane compound with the inorganic surface. It has the effect of further improving the properties, imparting excellent durability and maintaining the effect for a long period of time. Furthermore, since all of these components are soluble in a hydrophilic solvent, it is not necessary to use a special fluorinated solvent.

Therefore, by blending each of the above-mentioned components, it is possible to provide an excellent water repellent effect and an effect of improving the dropping property of water droplets, and to provide an excellent water repellent and antifouling property to the surface of the object to be treated over a long period of time. In addition, they have found that a water-repellent treatment agent that can be widely used without limitation of use can be obtained, and the present invention has been accomplished.

Accordingly, the present invention relates to (1) a method of preparing a perfluoroalkyl group-containing organosilicon compound represented by the general formula (I) and a hydrolyzable group-containing methylpolysiloxane compound represented by the general formula (II) Provided is a water-repellent agent comprising (2) an organopolysiloxane represented by the above general formula (III) and (3) a strong acid in a hydrophilic solvent.

Hereinafter, the present invention will be described in more detail. The first component of the water-repellent treating agent of the present invention comprises a perfluoroalkyl group-containing organosilicon compound represented by the following general formula (I) and the following general formula (I) It is a co-hydrolyzate in a hydrophilic solvent with a hydrolyzable group-containing methylpolysiloxane compound represented by II).

Here, the perfluoroalkyl group-containing organosilicon compound is represented by the following general formula (I).

[0016]

Embedded image (Wherein, R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ² is an alkoxy group or an acyloxy group having 1 to 4 carbon atoms, and Q is a divalent organic group having 2 to 10 carbon atoms. A is 0 or 1, and p is an integer of 4 to 12.)

[0017] In the above formula (I), for example a methyl group as R ^1, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, s- butyl group and the like, as R ² is For example, a methoxy group, an ethoxy group,
Examples thereof include an n-propoxy group, an isopropoxy group, an isopropenoxy group, an n-butoxy group, and an acetoxy group.
Q is a group connecting a perfluoroalkyl group and a silicon atom, and a divalent hydrocarbon group such as an alkylene group or an oxygen atom, -NH group, CONH group, OCONH group, S
Examples include an oxygen atom such as an O ₂ group, a nitrogen atom, and a divalent hydrocarbon group such as an alkylene group containing a sulfur atom.
CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ —, —CON
_{HCH 2 CH 2 CH 2 -,} - CONHCH 2 CH 2 NHCH 2
CH ₂ CH ₂ —, —SO ₂ NHCH ₂ CH ₂ CH ₂ —, —CH
_{2 CH 2 OCONHCH 2 CH 2 CH} 2 - group and the like. Further, p represents the number of carbon atoms of the perfluoroalkyl group and is 4 to 12, and if p exceeds 12, the solubility in an organic solvent becomes poor. a is 0 or 1.

Specific examples of the perfluoroalkyl group-containing organosilicon compound of the above formula (I) include the following compounds, and one of these compounds may be used alone or as a mixture of two or more. be able to.

[0019]

Embedded image Among them, C ₄ F ₉ CH ₂ CH ₂ Si (CH ₃ ) (O
CH ₃ ) ₂ and C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ are preferred.

Next, the hydrolyzable group-containing methylpolysiloxane compound is a compound represented by the following general formula (II).

[0021]

Embedded image(Where R^ThreeIs a monovalent hydrocarbon having 1 to 4 carbon atoms
Group, R^FourIs an alkoxy group having 1 to 4 carbon atoms or acylo
A xy group, A is a methyl group or -Z-Si (R^Three _b) R
^Four _3-b(B is 0, 1 or 2), and Z is
Oxygen atom or divalent as in Q having 2 to 10 carbon atoms
Is an organic group. Also, m is an integer of 3 to 100, and n is 0
An integer of from 50 to 50 and 5 ≦ m + n ≦ 100, and n =
When 0, one or both of A at both ends is -Z-
Si (R^Three _b) R^Four _3-bIs a group represented by Note that -Z-
Si (R^Three _b) R^Four _3-bIf there are two or more
May be the same or different. )

Here, R ³ is the same group as R ^1, and R ⁴ is the same group as R ² . As Z, an oxygen atom or an alkylene group is preferable, and the following alkylene groups are exemplified.

[0023]

Embedded image

M is an integer of 3 to 100, and n is 0 to 5
An integer of 0 and 5 ≦ m + n ≦ 100, preferably 10
≦ m + n ≦ 50, and when m + n is less than 5, the dropping property of the above-mentioned droplets is insufficient and the antifouling property is deteriorated, and when it exceeds 100, the stability of the co-hydrolyzate is deteriorated.

The following are examples of the compound of the formula (II).

[0026]

Embedded image (M and n have the same meaning as above.)

Among them, -Z-Si (R^Three _b) R^Four _3-b
Is preferably at the end of the molecular chain. B is 0 or
1 is preferred, and 0 is particularly preferred. Like this
From the above, as the compound of the formula (II), the above formulas (a) and
The compound of (b) is preferred.

The compounding ratio of the perfluoroalkyl group-containing organosilicon compound of the above formula (I) and the hydrolyzable group-containing methylpolysiloxane compound of the above formula (II) is (I) / (II) in weight ratio. 10/90 to 90/10, especially 20
/ 80 to 80/20. If the compounding ratio of the compound of the formula (I) is less than 10% by weight, sufficient water repellency may not be obtained, and if it exceeds 90% by weight, dropping property of water drops is insufficient and sufficient antifouling property cannot be obtained. .

The hydrophilic solvent used for the cohydrolysis of the two compounds is not particularly limited as long as it dissolves the compounds of the above formulas (I) and (II) and water. Alcohols such as isopropanol, n-propanol, n-butanol, i-butanol, s-butanol and t-butanol; cellosolves such as methylcellosolve, ethylcellosolve, butylcellosolve, cellosolve acetate; Ethers such as dioxane and tetrahydrofuran; The amount of the hydrophilic solvent to be used is not particularly limited, but is preferably in the range where the concentration of the compounds of the formulas (I) and (II) is 1 to 30% by weight, particularly 3 to 15% by weight.

Further, a hydrophobic solvent may be added and mixed during or after co-hydrolysis using the above-mentioned hydrophilic solvent. Examples of the hydrophobic solvent include n-hexane, cyclohexane, and isoparaffin-based hydrocarbon. The amount of the hydrophobic solvent to be added is not particularly limited, but is preferably 70% by weight or less based on the total amount of the solvent and the hydrophilic solvent.

In addition, water is used in the co-hydrolysis, and the amount of water to be added is suitably 0.5 to 2 equivalents to the alkoxy group contained in the compounds of the formulas (I) and (II). 0.
If the amount is less than 5 equivalents, the hydrolysis rate is insufficient, so that the reactivity with the inorganic surface may be weakened.

In the present invention, a small amount of an acid may be added for the purpose of accelerating the reaction during co-hydrolysis. As the acid, hydrochloric acid,
Sulfuric acid, nitric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, trichloroacetic acid, phosphoric acid, and the like.

The cohydrolysis reaction is not particularly limited, but is preferably performed at 50 to 100 ° C. for 2 to 10 hours.

Next, in the present invention, an organopolysiloxane represented by the following general formula (III) is blended as the second component.

[0035]

Embedded image (Wherein R ⁵ is the same or different and has 1 to 20 carbon atoms)
B is a hydroxy group or a group having 1 carbon atom
And a monovalent hydrocarbon group, an alkoxy group or an acyloxy group, and r is an integer of 1 to 100. )

In the above formula (III), examples of R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-hexyl group, a cyclohexyl group and a phenyl group. As B,
Hydroxy group, methyl group, ethyl group, n-propyl group,
Examples include an isopropyl group, an n-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an acetoxy group. r is an integer of 1 to 100, preferably an integer of 3 to 100. If r is less than 3, the dropping properties of the above-mentioned water droplets may be insufficient and the mixing thereof may not be worthwhile. If it is more than 100, the solubility in the co-hydrolysis solution may be poor, and the stability as a water-repellent agent may be reduced. Worse.

The following are examples of the organopolysiloxane of the above formula (III).

[0038]

Embedded image (R has the same meaning as above. Also, s + t = r.)

In the present invention, the compounding amount of the organopolysiloxane of the above formula (III) is determined by mixing the perfluoroalkyl group-containing organosilicon compound of the above formula (I) with the above formula (II)
The amount of the active ingredient (the amount obtained by removing the hydrophilic solvent from the co-hydrolysate) of the co-hydrolyzate with the hydrolyzable group-containing methyl polysiloxane compound of the formula (I) is mixed with the organopolysiloxane of the above formula (III). 10 / 90-99 / 1 by weight ratio,
Particularly, a range of 40/60 to 90/10 is preferable. If the amount of the active ingredient of the co-hydrolysate is less than 10% by weight, sufficient durability may not be obtained. If it exceeds 99% by weight, the water droplets fall short and sufficient antifouling property is obtained. May disappear.

Further, examples of the strong acid as the third component include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, trifluoroacetic acid, and phosphoric acid. Not something.

The compounding amount of the strong acid is 0.01 to 100 parts by weight, especially 0.1 to 50 parts by weight, based on 100 parts by weight of the total amount of the above-mentioned co-hydrolysate and the above-mentioned organopolysiloxane. Parts by weight are preferred. If the amount is less than 0.01 part by weight, sufficient durability may not be obtained, and if it exceeds 100 parts by weight, the stability of the water-repellent treatment agent itself may be deteriorated.

The water-repellent treating agent of the present invention may be used as it is by mixing the above-mentioned components. However, if necessary, the above-mentioned hydrophilic solvent or aromatic hydrocarbons such as benzene, toluene and xylene may be used. May be diluted with an organic solvent such as an ester such as ethyl acetate or isobutyl acetate to a concentration of about 0.1 to 5% before use. As a method of use on the object to be treated, a durable water-repellent / soil-resistant surface can be obtained by dipping, spraying, brushing, spinner or the like on the surface of the object to be treated and dried. Drying at room temperature is sufficient, but heating at 40 to 200 ° C. for 5 to 60 minutes is more preferable in terms of durability.

[0043]

The water-repellent treating agent of the present invention has excellent water-repellent effects, an effect of improving the dropping property of water drops, and excellent durability, and has excellent water-repellent and antifouling properties on the surface of the object to be treated. Can be applied over a long period of time, and is soluble in organic solvents, and can be used for surface treatment of various materials having inorganic surfaces. It is suitable for window glass of buildings, railways, vehicles, aircraft, etc., as well as optical components such as mirrors and glass lenses, various glassware, ceramics, tiles,
It can be widely used for surface treatment of plastic materials treated with inorganic antireflection coat or silicone hard coat.

[0044]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. All parts in each example are parts by weight.

Example 1 A 1 liter glass reactor equipped with a thermometer, a stirrer and a cooler was charged with the formula C ₈ F ₁₇ CH ₂ CH ₂ S.
10.0 g of a perfluoro group-containing organosilicon compound represented by i (OCH ₃ ) ₃ , 10.0 g of a hydrolyzable group-containing methylpolysiloxane compound represented by the following formula, 480.0 g of isopropanol as a hydrophilic solvent and 0.1 N hydrochloric acid 1.94 g of water was charged and co-hydrolyzed at 80 ° C. for 5 hours to obtain a solution of the co-hydrolyzate in isopropanol.

[0046]

Embedded image

Next, 10.0 g of an organopolysiloxane represented by the following formula and 5.0 of methanesulfonic acid were added thereto.
g was added and stirred for 10 minutes to obtain a water-repellent treating agent solution.

[0048]

Embedded image

[Examples 2 to 9, Comparative Examples 1 to 3]
Except that the perfluoro group-containing silicon compound, hydrolyzable group-containing methylpolysiloxane compound, hydrochloric acid water, hydrophilic solvent, organopolysiloxane and the type and amount of strong acid, and the cohydrolysis conditions were changed as shown in Table 1. In the same manner as in Example 1, a water repellent treatment solution was obtained.

Next, 0.1 ml of the water-repellent treatment solution obtained in each of the above-mentioned Examples and Comparative Examples was previously degreased and washed with acetone, and was spread 30 times with a cotton cloth on a dried 70 mm × 150 mm glass plate. After wiping off the excess coating solution with a dry cloth, a heat treatment was performed at 100 ° C. for 10 minutes.

In order to investigate the durability, the water-repellent treated glass plate was immersed in hot water at 100 ° C. for 6 hours.

For these surfaces, the contact angle of water and the drop angle of water droplets were measured by the following methods, and the initial water repellency and the durability water repellency were examined. Table 1 shows the results. Contact angle of water 5 μl of water is dropped on a glass plate kept horizontal, and a contact angle measuring device [Contact Angle Meter] is used.
CA-A (manufactured by Kyowa Science Co., Ltd.)]. Water Drop Fall Angle Static Friction Coefficient Measuring Machine (Shinto Kagaku Co., Ltd., HEIDON
(−10 type), the glass plate was set horizontally, and 100 μl of water was dropped on the glass plate. Then, the glass plate was gradually tilted, and the angle at which the water started to fall was measured.

From the results shown in Table 1, the water-repellent treating agent of the present invention was
It has been confirmed that it has excellent water repellency and improvement effect of drop of water droplets, has high durability, and gives excellent water repellency and antifouling property to the surface of the object to be treated over a long period of time.

[0054]

[Table 1] * Hydrophobic solvent

[0055]

Embedded image

COMPARATIVE EXAMPLE 4 10 g of the compound of the above formula (2) 10 g of dimethylpolysiloxane having OH groups at both ends (viscosity 60 cs, 25 ° C.) 10 g An agent solution was obtained.

Comparative Example 5 30 g of the compound of the above formula (2) 23 g of methyltrimethoxysilane 23 g of dimethylpolysiloxane having OH groups at both ends (viscosity 60 cs, 25 ° C.) were mixed with 0.1 N hydrochloric acid while stirring. 0.5 g of water was added dropwise to carry out co-hydrolysis, aging was performed at 70 ° C. for 1 hour, followed by cooling and pouring into 1500 g of isopropyl alcohol to obtain a water-repellent treating agent solution.

Comparative Example 6 23 g of the compound of the above formula (2)
0.5 g of 0.1N hydrochloric acid aqueous solution was added dropwise to perform hydrolysis,
After aging at 70 ° C. for 1 hour, the mixture was cooled, and dimethylpolysiloxane having OH groups at both ends (viscosity 60 cs, 25
C.) 12 g and methanesulfonic acid 15 g were added, and the mixture was poured into isopropyl alcohol 1500 g to obtain a water-repellent treating agent solution.

Table 2 shows the results obtained by examining the initial water repellency and the durable water repellency of the water repellent treatment solutions of Comparative Examples 4 to 6 in the same manner as described above.
Shown in

[0060]

[Table 2]

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Jin Uehara 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inotoro Ono, Inshiro-gun, Gunma Prefecture 1-10 Hitomi, Matsuidamachi Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Hiroaki Kobayashi 3-5-11 Doshomachi, Chuo-ku, Osaka-shi, Osaka Nippon Sheet Glass Co., Ltd. (72) Invention Person Atsushi Kawaguchi 3-5-11 Doshomachi, Chuo-ku, Osaka-shi, Japan Inside Nippon Sheet Glass Co., Ltd. (72) Inventor Satoshi Shiiki 3-5-11 Doshomachi, Chuo-ku, Osaka-shi, Osaka Nippon Sheet Glass Co., Ltd. (72 ) Inventor Kazushi Mitani 3-5-11 Doshomachi, Chuo-ku, Osaka City, Osaka Prefecture Inside Nippon Sheet Glass Co., Ltd. 4-144940 (JP, A) JP-A-3-275726 (JP, A) JP-A-2-233535 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09K 3/18 104 C08L 83/00-83/16 C09D 183/06-183/16 C08G 77/00-77/62

Claims (1)

(57) [Claims] (1) A hydrophilic solvent comprising a perfluoroalkyl group-containing organosilicon compound represented by the following general formula (I) and a hydrolyzable group-containing methylpolysiloxane compound represented by the following general formula (II) Co-hydrolysate in water (Wherein, R ¹ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ² is an alkoxy group or an acyloxy group having 1 to 4 carbon atoms, and Q is a divalent organic group having 2 to 10 carbon atoms. A is 0 or 1, and p is an integer of 4 to 12.) (Where R ³ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ⁴ is an alkoxy group or an acyloxy group having 1 to 4 carbon atoms, A is a methyl group or -Z-Si (R ³ _b ) R
⁴ _{3-b (b} is 0, 1 or 2.) A group represented by, Z is a divalent organic radical oxygen atom or 2 to 10 carbon atoms. Further, m is an integer of 3 to 100, n is an integer of 0 to 50, and 5 ≦ m + n ≦ 100. When n = 0, at least one of A at both ends is -Z-Si
A group represented by _{^{(R 3 b) R 4 3}} -b. Note that -Z-Si
(R ³ _b) if R ⁴ _3-b there are two or more, they may being the same or different. (2) Organopolysiloxane represented by the following general formula (III): (Wherein, R ⁵ is the same or different and has 1 carbon atom)
-20 are monovalent hydrocarbon groups, and B is the same or different and is a hydroxy group or a monovalent hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group or an acyloxy group. r is an integer of 1 to 100. (3) A water-repellent agent characterized by comprising a strong acid.