JPS58172242A - Treating agent for glass surface - Google Patents

Abstract

PURPOSE:To provide a treating agent which provides water repellency, oil repellency, resistance to contamination, low reflectivity, etc. to a glass surface by composing an agent of a silane compd. contg. polyfluoroalkyl group or a partially hydrolyzed compd. thereof, and a reaction product of water glass with a proton dovating acid. CONSTITUTION:For example, RfCH2CH2SiCl3 is prepared as a silane compd. contg. polyalkyl group (Rf group) expressed by the formula. On the other hand, the product of reaction produced by reaction of the water glass selected from compsns. SiO2/NaO=0.5-4 as specified in JIS-K1408 in the presence of a proton dopating acid such as H2SO4 is prepared. The above-described silane compd. contg. RF groups and the above-described product of reaction are mixed and agitated at a room temp. in a water-soluble solvent of an aprotic acid (e.g.; THF). The mixing ratio of the silane compd. contg. RF groups and the product of reaction in this case is 1:0.1-5 by weight. The resulted treating agent is prepd. in an optional form such as emulsion, solvent soln., aerosol or the like according to conventional methods.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a treatment agent that imparts water repellency, oil repellency, stain resistance, low reflectivity, etc. to a glass surface. The present invention relates to a glass surface treatment agent comprising a partially hydrolyzed condensate of a compound and a reaction product obtained by reacting water glass in the presence of a protonic acid.

The surface of glass products such as glass plates, mirrors, glass containers, and eyeglass lenses has condensed moisture due to the influence of atmospheric humidity and temperature.When wet with water, glass components dissolve into this moisture and become alkaline. It is well known that the surface is easily eroded, resulting in so-called burns.

In addition, fine dust and oil droplets floating in the atmosphere may adhere to the glass surface and contaminate the glass surface, and water droplets such as rainwater may adhere to the windows of automobiles, aircraft, and railway vehicles, and the transparency or see-through of the glass may be affected. inhibit. For this reason, in order to make the glass surface water repellent, surface treatment agents have been proposed in which, for example, silicone waxes, silicone oils such as boria xane, surfactants, and the like are directly applied. As such, these require pretreatment prior to application.2. In addition, satisfactory results have not been obtained in terms of long-term durability, oil repellency, and stain resistance due to uneven coating that occurs during coating or the low adhesion of the treatment agent itself to glass.

Based on the recognition of the above-mentioned problems, the present inventor has conducted various studies in order to provide an excellent glass surface treatment agent that can impart water repellency, oil repellency, stain resistance, etc. to glass surfaces over a long period of time. As a result of repeated studies, the present invention was completed.

That is, according to the research carried out by the present inventor, in compounds containing polyfluoroalkyl groups (hereinafter abbreviated as Rf groups), the critical surface tension of Rf groups is as low as 20 dyn/cIn, and the critical surface tension of Rf groups is as low as 20 dyn/cIn. Since the resistance is even lower, coating the glass surface with an Rf group-containing compound can impart water and oil repellency, and furthermore, by firmly adhering the Rf group-containing compound to the glass surface, it is possible to maintain water and oil repellency over a long period of time. In order to give it, -3i-0-R, -5i-Hal which reacts with 5iOH on the glass surface.
(Hal is a halogen) is preferably present, -3i-0-
R hydrolyzes in the presence of water, causes a crosslinking reaction, and reacts with 5iOH on the glass surface to chemically adhere.
The Rf group-containing silane compound obtained by the reaction of the f group-containing compound and the silane compound is excellent, and the R
It has been discovered that durability can be significantly improved by mixing an f group-containing silane compound with a reaction product obtained by reacting water glass in the presence of a protonic acid. By forming a thin film of a specific surface treatment agent on the glass surface, it is possible to reduce the reflectance of the glass surface, and as a result, it has the advantage of being able to eliminate impeding factors such as the transparency of the glass. Ru.

Thus, the present invention has been completed based on the above findings, and provides a reaction product obtained by reacting an Rf group-containing silane compound or a partially hydrolyzed condensate of the compound with water glass in the presence of a protonic acid. The present invention provides a novel glass surface treatment agent comprising:

Thus, the surface treatment agent of the present invention exhibits excellent water and oil repellency, stain resistance, and low reflectivity, and can maintain these properties for a long period of time.

The treatment agent in the present invention is composed of an Rf group-containing silane compound or a partially hydrolyzed composite of the compound, and a reaction product obtained by reacting water glass in the presence of a protonic acid in advance. (RfQ) as i
(Z) An Rf group-containing silane compound bY4-a-b is selected. In the above formula, Rt Iri has 4 to 4 carbon atoms.
It is particularly preferable that m is an integer of 2 to 10, including one or more of 16 perfluoroalkyl groups or ether bonds. Q is a divalent organic group, 2 is a lower alkyl group with 1 carbon number, and Y is preferably -C1°-Br
, -oc'Hs, -0C2H5,CH3COO-+
(4H5COO- is selected. a is an integer of 1 to 3, and b is 0 or an integer of 1 to 2.

Thus, the Rf group-containing silane compound of the above formula can be obtained by various methods or routes, but is synthesized, for example, by a process involving reaction of an RfQ compound and an R8i Y3 compound. Such a synthetic reaction may use a solvent that does not have active hydrogen, the reaction temperature is 0 to 150°C, and the reaction time is 1.
Performed in ~50 hours.

In the present invention, examples of the Rf group-containing silane compound of the above formula include RfCH2CH2SiC13, RfCH2C'! %5i
Br3+RfCH2CH2Si(OCzHs)3.
RfCHzCHz81Cb.

CH3 (RfCHzCHz)s 5iC1, Rf(CH2CH
g) + 5i(OCHs)z.

Rf C0NHCH1CH2NHCHg C island CH2S
iC13.

Rf CH2CH20CONHCH2CH2CH35i
C1s.

Rf CH2CH2NHCH2CH2Si C13H3 RfSO2NC穐CH2C0NHCH2CH2CH2S
i C13° is mentioned.

Water glass is JIS-1408. 8i02/Nag○=0.5~4
For example, sodium metasilicate (Nag
5ins) and hydrates in various proportions, sodium orthosilicate (Na4sto4), sodium disilicate (Na2Si205), sodium tetrasilicate (
40g of Na2Si), and each may be used alone or in combination.

The protonic acid to be reacted with water glass is, for example, H2SO4
,HCl, HNO3,HClO4,H3PO4,HB
r, HI.

Examples include HIO2 and CF2COOH.

To react water glass in the presence of protic acid, mix the water glass solution and protic acid solution with an aprotic water-soluble solvent,
Example 5. ．． For example, in addition to tetrahydrofuran, 1~
The mixture is mixed and stirred for 10 hours, preferably 2 to 5 hours. The mixing ratio of water glass and protonic acid is m
A volume ratio of 1:0.5 to 10 in ol/L is desirable. After the reaction is completed, the reaction product is obtained in an aprotic water-soluble solvent, preferably by adding NaCl and separating into two layers. In some cases, the reaction product may be extracted with an aqueous solvent.

The treatment agent of the present invention is produced by mixing and stirring an Rf group-containing silane compound and a reaction product obtained by reacting water glass with a protic acid in advance at room temperature for 10 minutes to 1 hour in an aprotic acid water-soluble solvent. can get. The mixing ratio of the Rf group-containing silane compound and the reaction product obtained by reacting water glass in the presence of a protonic acid in advance is selected from a weight ratio of 1:0.1 to 5.

The treatment agent of the present invention thus obtained is preferably prepared as a solution of one or two aprotic water-soluble solvents in a conventional manner. For an aerosol type, an aerosol propellant may be further added to the solvent solution, and the mixture may be placed in a suitable container as described in Section 9.

The glass surface treatment agent of the present invention can be applied to a glass product to be treated by any method depending on the shape of the glass product and the preparation form. 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, under 100% relative humidity, 60
It is preferable to carry out the treatment at a temperature of 180° C. for 1 to 60 minutes, which can strengthen the adhesion of the treatment agent to the glass surface.

The processing agent of the present invention includes other Rf group-containing compounds, various compounds,
Other blenders may be mixed in, and additional additives such as antistatic agents and crosslinking agents may be added as appropriate.

Glass products that can be treated with the surface treatment agent of the present invention are not particularly limited, and include various examples, such as glass plates, mirrors, glass containers, glass appliances, and eyeglass lenses. .

The evaluation method for the treatment agent of the present invention is as follows.

That is, water repellency was determined by placing water on the glass surface and measuring the contact angle, and oil repellency was similarly determined by measuring the contact angle of hexadecane. Further, the reflectance was measured at an incident angle of 5° using a model 323 (automatic recording spectrophotometer manufactured by Hitachi, Ltd.) equipped with a specular reflection light measurement accessory.

In addition, the thickness of the coating film is "Talystep" (Rank T
aylor+1 (manufactured by Obson), and the needle pressure was measured.

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.

Synthesis example 1゜CnF2n+I CH= CH2 (n is 6.8.1.0
．． The average value for the mixture of 12 is 9.0') 9□""
9.2 f' (0,2 mol), (CHW2siHcl
1 s, 9 f (0,2 mol), H2PtCl4
- HzOO, 052 t was placed in a 200-volume four-tube flask equipped with a thermometer, cooling tube, and stirrer, and reacted at 80° C. for 200 hours while stirring slowly under a stream of dry nitrogen. After the reaction was completed, a reaction product was obtained by distillation. The reaction product was analyzed by gas chromatography, IR,N
When analyzed by MR, CnF2n+□CH2CH2S i
(CH3)2'CI and the conversion rate to it is 95
%Met.

Synthesis example 2°CnF2n+, C00CH(CRs)z (n is 6.
It is a mixture of 8.10.12 and the average value is 9.0)111
．． 2f (0.2 mol), H2N (CH2)a Si
(CH3)2 C130,3f (0.2 mol), dry tetrahydrofuran 1502 in an internal volume of 500 m7 equipped with a thermometer, cooling tube and stirrer! The mixture was placed in a four-piece flask, and reacted for 5 hours at reflux temperature (approximately 60° C.) with gentle stirring under a stream of dry nitrogen. Tetrahydrofuran was distilled off to obtain a reaction product. The reaction product was analyzed by gas chromatography and IRXNMR and was found to be CnF2n+1CO.
NH(CH2)3Si(CHa)zC1,
The conversion rate thereto was 100.

Synthesis example 3゜(0.1 mol), H1'N(CHj)3Si(O
C2H5)322.1? (0.1 mol) and dry tetrahydrofuran 1502 were reacted in the same manner as in Synthesis Example 2 to obtain a reaction product. The reaction product was analyzed by gas chromatography, IR, and NMR, and the conversion rate thereof was 100%.

Example 1゜Sodium disilicate (Na2Si205) 1 mol/l aqueous solution 25-1H2so, 0.7 mol/l aqueous solution 50ffi7! , tetrahydrofuran (40°C) was placed in a flask fully equipped with a stirrer, and the mixture was stirred at room temperature for 4 hours to react. After the reaction was completed, NaC'120f was added to separate the liquid into two layers. The tetrahydrofuran solution in which the reaction product was dissolved was separated and put into a 1 t Mitsuro flask equipped with a stirrer, and then the reaction product CnF' of Synthesis Example 1 was collected.
2n+I c) I2CH25i(CH3)2 C11,
09F was added, and the mixture was allowed to react for 30 minutes with stirring at room temperature. A solvent solution was prepared by adding 450 parts of acetone and 50 parts of water to the reaction solution.

Separately, prepare a glass plate (Nuda lime glass) that has been washed with detergent and acetone, immersed in 1T hydrochloric acid solution, and then dried.
Apply the prepared solvent solution to the surface with an applicator,
10011b Cured at 160° C. for 20 minutes in relative humidity. The contact angle of water was measured by dropping water on this surface, and the contact angle of hexadecane was measured by dropping hexadecane. The measurement results are shown in Table 11.

Examples 2-3 Reaction products of Synthesis Example 2 CnF2n+, C0NH(CH2
)s 5l(CH3)2C1141? Alternatively, a solvent solution was prepared in the same manner as in Example 1, except that the product 90f of Synthesis Example 3 was used, and after coating and treating the glass surface in the same manner as in Example 1, the contact angles of water and hexadecane were determined. It was measured. The measurement results are shown in Table 1.

Comparative Examples 1 to 3 Solvent solutions of the reaction products of Synthesis Examples 1 to 6 alone (20% by weight)
Acetone solution) was prepared and applied to the glass surface in the same manner as in Example 1, and after treatment, the contact angles of water and hexadecane were measured. The measurement results are shown in Table 1.

Table 1 Example 4゜Composition 5f described in Table 1 in Example 1 was mixed with a mixed solvent of trichlorotrifluoroethane/acetone (3/1).
The solution was diluted to 500 t to prepare a solvent solution. Separately, a glass plate (Nuda lime glass) was prepared which was washed with a detergent and acetone, immersed in a 1T hydrochloric acid solution, and then dried. This glass plate was immersed in the solvent solution, and the pulling rate was 50 ctn/
It was pulled up for 1 minute and dried at 160°C for 1 hour.

The film thickness was 0.1μ, and the reflectance was 1.0% (light wavelength 540mμ). The reflectance of the untreated glass plate is 4.
．． It was 2%.

Example 5 In Example 4, the composition of Example 1 was replaced with -2
Processing was performed in the same manner except that the composition of
A thin film of was formed on the surface of a glass plate. The reflectance was 1.1.

Example 6 In Example 4, Example 6 was substituted for the composition of Example 1.
The reflectance of a glass plate treated in the same manner except that the composition was used was 1.0.

Examples 7 to 8 Solvent solutions were prepared in the same manner as in Example 1, except that Water Glass No. 1 or Water Glass No. 3 was used, and contact angles were measured in the same manner as in Example 1. The measurement results are shown in Table 2.

Table 2 Examples 9-11 Protonic acid HCl + H3PO4', CF3C
A solvent solution was prepared in the same manner as in Example 1, except that ○○H was used, and the contact angle was measured in the same manner as in Example 1. The measurement results are shown in Table 3.

Table 3 A solvent solution was prepared in the same manner as in Example 1, except that the Rf group-containing silane compound was different, and contact 1: angle, .: Zheng measurement was performed in the same manner as in Example 1. The measurement results are shown in Table 4.

Claims (5)

[Claims] (1) A glass surface treatment agent comprising a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed condensate of the compound and a reaction product obtained by reacting water glass in the presence of a protonic acid. (2) The polyfluoroalkyl group-containing silane compound has the formula % formula % [However, in the above formula, Rf is a polyfluoroalkyl group having 4 to 16 carbon atoms, and is an etegen, alkoxy group, or RCO〇-(R is a hydrogen atom or a lower alkyl group), a is an integer of 1 to 3, and b is an integer of 0 or 1 to 2. ] The processing agent according to claim 1. (3) The processing agent according to claim 1 or 2, wherein the polyfluoroalkyl group is a fluoroalkyl group having 4 to 16 carbon atoms. (4) The processing agent according to claim 1 or 2, wherein the polyfluoroalkyl group is an integer of 1 or more. (5) The polyfluoroalkyl group-containing silane compound and the reaction product obtained by reacting water glass in the presence of a protonic acid in advance at a weight ratio of 1:0.1 to 5. Processing agent.