JPH0239555B2 - GARASUHYOMENNOHATSUSUIHATSUYUZAI - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water and oil repellent that imparts water repellency, oil repellency and stain resistance to glass surfaces, and more specifically, to a water and oil repellent for glass surfaces made of a silicone block oligomer containing a polyfluoroalkyl group. It is. Moisture may condense on the surface of glass products such as glass plates, mirrors, glass containers, glass appliances, and eyeglass lenses due to the influence of atmospheric humidity and temperature, and when wet with water, glass components may be present in the moisture. It is well known that the surface is easily eroded because it dissolves and becomes alkaline, resulting in so-called burns. In addition, fine dust and oil droplets floating in the atmosphere may adhere and contaminate the glass surface, especially in automobiles.
Water droplets such as rainwater adhere to the windows of aircraft and railway vehicles, impeding the transparency or see-through of the glass. For this reason, in order to make the glass surface water repellent, for example, silicone waxes, silicone oils made of polysiloxane, and surfactants have been proposed. However, many of these require pretreatment for application, and particularly satisfactory results have not been obtained with respect to uneven application, long-term durability, oil repellency, and stain resistance. Based on the recognition of the above-mentioned problems, the present invention provides various water and oil repellents for glass surfaces that can impart water repellency, oil repellency, and stain resistance to glass surfaces for a long period of time. As a result of repeated research and consideration, the present invention was completed. That is, according to research by the present inventors, in water and oil repellents containing polyfluoroalkyl groups (hereinafter abbreviated as R _f groups), the critical surface tension of the R _f groups is as low as 20 dyn/cm or less, and is suitable for water as well as oils. Since the R _f group is lower than that of the glass surface, water and oil repellency can be imparted when the R f group covers the glass surface.Furthermore, when the R _f group is densified so as to be blocked, the R _f group can efficiently cover the glass surface. It has been found that it can be coated with a base and therefore impart high water and oil repellency even with low concentration treatment. In addition, in order for R _f to firmly adhere the group-containing compound to the glass surface and impart water and oil repellency over a long period of time, -SiO-R, -Si-Hal (Hal is halogen) is preferable, and -SiO-R is hydrolyzed in the presence of water,
A compound in which the R _f group and the -SiO- moiety are blocked has a high performance repellency because it can cause a cross-linking reaction and react with SiOH on the glass surface to chemically adhere to the glass surface. It was discovered that a water and oil repellent can be obtained. Thus, the present invention has been completed based on the above findings, and the formula (However, R in the formula is a hydrogen atom or a methyl group, R _f
is a polyfluoroalkyl group having 1 to 20 carbon atoms and may contain one or more ether bonds, Q ₁
and Q ₂ is a divalent organic group, Y is a halogen or alkoxy group, Z is a lower alkyl group, a is an integer of 1 to 3, b is an integer of 0 or 1 to 2, and n is an integer of 1 or more. ) The present invention provides a water and oil repellent for glass surfaces, which is made of a silicone block oligomer containing an R _f group represented by the following formula. The water and oil repellent of the present invention has a high density of R _f groups, so it can exhibit high water and oil repellency, and the alkoxysilane is hydrolyzed in the presence of water, resulting in a crosslinking reaction and glass The reaction with the SiOH group is promoted, and by chemically adhering to the glass surface, it is possible to improve the adhesion to the glass surface and the water and oil repellency. The water and oil repellent in the present invention is composed of a silicone block oligomer containing an R _f group, where R _f contains one or more perfluoroalkyl groups having 1 to 20 carbon atoms or ether bonds. It is particularly preferable that the group is a perfluoroalkyl group having 4 to 12 carbon atoms, and m is an integer of 2 to 10. R may be a hydrogen atom or a methyl group. Q ₁ and Q ₂ are divalent organic groups,
Q ₁ is -O-Q ₃ ,

[Formula] (where Q ₃ is an alkylene group having 1 to 10 carbon atoms, R is hydrogen or a lower alkyl group), for example -
OCH ₂ CH ₂ −, −OCH ₂ CH ₂ N(CH ₃ )SO ₂ −, −
OCH ₂ CH ₂ N(C ₃ H ₇ )SO ₂ − is selected. _Q2 is preferably an alkylene group having 1 to 10 carbon atoms, and for example, -( _CH2 ) _2- , -( _CH2 ) _3- , and -( _CH2 ) _5- are selected. Y is a halogen or _an alkoxy group, and preferably Cl, _-OCH3 , _-OC2H5 is selected. Z
A lower alkyl group having 1 to 4 carbon atoms is selected. a is an integer from 1 to 3, and b is 0 or 1 to 2
is an integer of 1 or more, and n is an integer of 1 or more. Although the R _f group-containing silicone block oligomer can be obtained by various methods or routes, it is usually synthesized by a process including the following telomerization reaction. That is, A telomerization reaction can be employed. Such telomerization reaction is carried out in a solvent in the presence of an initiator for radical polymerization of a vinyl compound,
For example, benzotrifluoride as a solvent, and
Azobisisobutyronitrile is used as a polymerization initiator. In the present invention, examples of the R _f group-containing silicone block oligomer include: can be mentioned. The thus obtained water and oil repellent of the present invention can be prepared in any form such as an emulsion, a solvent solution, or an aerosol according to a conventional method. For example, in the case of a solvent solution type, the R _f group-containing silicone block oligomer is dissolved in a suitable organic solvent such as a chlorine-based or fluorine-based solvent.
It is prepared by dissolving it in a seed or a mixed solvent of two or more kinds. For the aerosol type, a solvent solution as described above may be prepared, an aerosol propellant may be added thereto, and the mixture may be filled into a suitable container. Usually, the R _f group-containing silicone block oligomer is prepared as a 10 to 30% by weight solution in a solvent, but from the viewpoint of coating workability, it is preferably 15 to 25% by weight. The glass surface water and oil repellent of the present invention can be applied to the glass product to be treated by any method depending on the shape of the glass product to be treated and the adjustment mode. For example, in the case of a solvent solution type, a method of adhering to the surface of the glass product by a known coating method such as dip coating or spraying may be employed. After adhering to the glass surface, it is preferable to perform a treatment at a temperature of 60 to 180° C. for 1 to 60 minutes under 100% relative humidity, which can strengthen the adhesion of the water and oil repellent to the glass surface. The water and oil repellent of the present invention includes other R _f group-containing polymers,
Various polymers, other blenders, etc. may be mixed, and further additives such as antistatic agents and crosslinking agents may be added as appropriate. Glass products that can be treated with the water and oil repellent of the present invention are not particularly limited, and include various examples,
For example, it can be applied to glass plates, mirrors, glass containers, glass appliances, eyeglass lenses, etc. In the evaluation method of the water and oil repellent of the present invention, water repellency was determined by placing water on a glass surface and measuring the contact angle, and oil repellency was similarly determined by measuring the contact angle of hexadecane. Next, examples of the present invention will be described in more detail, but it goes without saying that this description does not limit the present invention. Example 1 C _o F _2o+1 CH ₂ OCOCH=CH ₂ (n is 6, 8,
It is a mixture of 10 and 12, and the average value is 9.0) 113.6g (0.2
HS( _CH2 ) _3Si ( _OCH3 ) ₃ 39.2g (0.2mol),
Put 4.6 g of azobisisobutyronitrile and 150 g of dry benzotrifluoride into a 300 ml four-necked flask equipped with a thermometer, condenser, and stirrer, and stir gently under a stream of dry nitrogen to approx.
The reaction was carried out at a temperature of 60°C for 20 hours. The benzotrifluoride was distilled off to obtain a reaction product. The reaction products are analyzed using gas chromatography.

The conversion rate to [Formula] was 100%. A solvent solution was prepared by diluting 20 g of the product to 100 g with trichlorotrifluoroethane. Separately,
Prepare a glass plate (soda-lime glass) that has been cleaned with detergent and acetone, immersed in a 1% hydrochloric acid solution, and then dried. Apply the adjusted solvent solution to the surface with an applicator (about 5 μ thick) to give a 100% in relative humidity
After curing at 160°C for 20 minutes, the contact angles of water and hexadecane were measured. The measurement results are shown in Table 1. Example 2 C _o F _2o+1 CH ₂ CH ₂ OCOCH=CH ₂ (n is the average value
9.0) 113.6g (0.2mol), HS( _CH2 ) _3Si
(OCH ₂ ) ₃ 13.1g (0.067 mol), azobisisobutyronitrile 3.8g, dry benzotrifluoride 150
g was reacted in the same manner as in Example 1 to obtain a reaction product. The reaction products are analyzed by osmotic chromatography.

The conversion rate to [Formula] (n is 3) was 100%. The product was applied to a glass plate in the same manner as in Example 1, and after curing, the contact angles of water and hexadecane were measured. The measurement results are shown in Table 1. Example 3 C _o F _2o+1 CH ₂ OCOCH=CH ₂ (n is average value 9.0)
113.6g (0.2mol), HS( _CH2 ) _3Si ( _OCH2 ) _33.9
(0.02 mol), 3.5 g of azobisisobutyronitrile,
150 g of dry benzotrifluoride was reacted in the same manner as in Example 1 to obtain a reaction product. The reaction products are analyzed using gas chromatography.

The conversion rate to [Formula] (n is 10) was 100%. The product was applied to a glass plate in the same manner as in Example 1, and after curing, the contact angles of water and hexadecane were measured. The measurement results are shown in Table 1.

[Table] Examples 4 to 11 C _o F _2o+1 CH ₂ CH ₂ OCOCH=CH ₂ and/or HS
A reaction product was obtained in the same manner as in Example 1 except that (CH ₂ ) ₃ Si(OCH ₃ ) ₃ was different, and the product was applied to a glass plate in the same manner as in Example 1. After curing, the contact angles of water and hexadecane were measured.
The measurement results are shown in Table 2.

【table】

【table】

Claims (1)

[Claims] 1 formula (However, R in the formula is a hydrogen atom or a methyl group, R _f
is a polyfluoroalkyl group having 1 to 20 carbon atoms and may contain one or more ether bonds, Q ₁
and Q ₂ is a divalent organic group, Y is a halogen or alkoxy group, Z is a lower alkyl group, a is an integer of 1 to 3, b is an integer of 0 or 1 to 2, and n is an integer of 1 or more. ) A water and oil repellent for glass surfaces comprising a polyfluoroalkyl group-containing silicone block oligomer. 2. The water and oil repellent according to claim 1, wherein R _f is a perfluoroalkyl group having 1 to 20 carbon atoms. 3 R _f (However, m is an integer of 1 or more.) The water and oil repellent according to claim 1.