JPS58172243A - Treating agent for glass surface - Google Patents

Abstract

PURPOSE:To provide a treating agent that can provide water repellency, oil repellency, resistance to contamination, etc. to a glass surface for a long period of time by consisting the agent of a silane compd. contg. polyfluoroalkyl group, or a partially hydrolyzed condensate of said compd., a silane coupling agent and colloidal silica. CONSTITUTION:A silane compd. contg. polyfluoroalkyl group (Rf groups) expressed by the formula [e.g.; (RfCH2CH2)2SiCl2] or the partially hydrolyzed condensate of the compd. is prepared. The silane compd. contg. RF group, a silane coupling agent [e.g.; NH2(CH2)2NH(CH2)3(OCH3)3] and colloidal silica are mixed at 1:0.01-1:0.1-5 by weight at 0-60 deg.C by using an org. solvent such as acetone. The solvent is distilled away from the resulted mixture of reaction, whereby the intended treating agent is obtained. The treating agent is prepd. in optional forms 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, and more specifically, a polyfluoroalkyl group-containing silane compound or the compound. The present invention relates to a novel glass surface treatment agent comprising a partially hydrolyzed condensate, a silane coupling agent, and colloidal silica.

Moisture condenses on the surfaces of glass products such as glass plates, mirrors, glass containers, glass utensils, and eyeglass lenses due to the influence of atmospheric humidity and temperature, and when wet with water, glass components may dissolve into the moisture. It is well known that the surface becomes alkaline and 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, contaminating the glass surface, and water droplets such as rainwater may adhere to the windows of automobiles, aircraft, and railway cars, damaging the transparency of the glass. or obstructs visibility. 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 made of polysiloxane, surfactants, and the like are directly applied. However, many of these require pre-treatment for application, and are prone to uneven coating that occurs during application.
Alternatively, satisfactory results have not been obtained regarding long-term durability, oil repellency, and stain resistance due to the low adhesion of the treatment agent itself to glass.

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

That is, according to the research of the inventor, in a compound containing a polyfluoroalkyl group (hereinafter abbreviated as Rf group), Rf
The critical surface tension of the group is low at 20 dyn71 or less, which is lower than that of water as well as oils, so the glass surface can be
When coated with an f group-containing compound, water and oil repellency can be imparted, and in order to firmly adhere the Rf group-containing compound to the glass surface and impart water and oil repellency over a long period of time, it reacts with the 5iOH group on the glass surface. 81-〇-R, -3i-H
The presence of al (Hal is), rogen) is preferable, and -3
i-○-R hydrolyzes in the presence of water, causes a crosslinking reaction, reacts with 5iOH on the glass surface, and chemically adheres to it. Although silane compounds are superior and it is useful to mix colloidal silica to increase the hardness of the coating after applying the Rf group-containing silane compound to the glass surface, it is more effective than mixing colloidal silica alone. In order to increase the compatibility between the Rf group-containing silane compound and colloidal silica and to efficiently adhere the Rf group-containing silane compound to the glass surface, mixing it with a silane coupling agent will significantly improve the water and oil repellency and the hardness of the coating. We have discovered the fact that it significantly improves performance. In addition, if a thin film of such a specific surface treatment agent is formed on the glass surface, i
It is possible to reduce the reflectance of the surface of the unifer, and as a result, there is an advantage that it is possible to eliminate factors that inhibit the transparency of glass.

Thus, the present invention was completed based on the above findings, and provides a novel glass surface treatment agent comprising an Rf group-containing silane compound or a partially hydrolyzed condensate of the compound, a 7-run coupling agent, and colloidal silica. It is provided to

Therefore, the treatment agent of the present invention has excellent water and oil repellency stain resistance,
It exhibits low reflectivity and can maintain its performance for a long period of time.

The surface treatment agent in the present invention is composed of an Rf group-containing heptad compound or a partially hydrolyzed condensate of the compound, a silane coupling agent, and colloidal silica. Zl)bY'4-a
-b Rf group-containing silane compound is selected.

In the formula <1>, Rf is preferably a perfluoroalkyl group having 4 to 16 carbon atoms or ether-linked, and m is particularly preferably an integer of 2 to 10. Q
is a divalent organic group, and Zl is a lower alkyl group having 1 to 4 carbon atoms.

i) is -CI', -0CH3, -0C2H51CH3CO
O-, C2H6COO- is selected.

determined. a is an integer from 1 to 3, b is O or 1 to 2
is an integer.

Although the Rf group-containing silane compound of formula (1) can be obtained by various methods or routes, it is synthesized, for example, by a process including reaction of an RfQ compound and an R81Y3 compound. Such a synthetic reaction may use a solvent without active hydrogen, and is carried out at a reaction temperature of 0 to 150°C and a reaction time of 1 to 50 hours.

In the present invention, as the Rf group-containing silane compound of formula (1), for example, ■ RfCk CH25iCls-+ RfCk Ck S
I C12,y(Rf CTh C庚)zsic'b
,' R1-CHaC 5i (QC ratio) 3゜RfCO
NHCI(2CHaC&8i'(OCzT(a)s.

RfCONHCH2CH2NH (Jh'C
○C2 ratio) 3゜C'Hs Shadow RfS 02 N C quick C Mi C'0NHC'-C ratio C Mi 5i (0 (4 ratio) 3゜RfCH2CH20COCH2C
)12SCH2CH2CH2S1(oCH3)3゜Rf
CH2CH20CONHCH2CH2C5,8i (QC
! 2H6)3.

RfCO0CFh CHC＆OCFb CHs CH
25x (0C2H& )3 +CH Tool' convex RfCH2CFb NHCHa C island 5i (QC ratio) 3
゜RfC'H2C)bNHcHzcHzsi(OC-C
H2oC ratio) 3°.

The silane coupling agent is selected from the formula (n) (X(A)()aSl(Z2)bY2a-ab). -4 lower alkyl groups are selected.ψ hahalogen, alkoxy group, atd1-3
b is an integer of 0 or 1 to 2, and C is an integer of 0 or 1.
is an integer.

In the present invention, the silane coupling agent of formula (I[) is, for example, NHII (CH2)2NH(CH2)3 S i (
0CHs)s.

NHa(CH2)asi(OCHs)a, CH2-
CH8i(OCHa)3°CH2-CH! 3iC13,
CH2=C700(CHgCH2=C700(CH.

H8(CH2)3Si(OCHa)s, NC0(C
&) asi(OCzHs)3゜C1(CI(z)ssi
(OCHs) 3° may be mentioned.

Colloidal silica can be a common one, Al2O
3 may be contained. Solid concentration (dispersion concentration) is 5
~4096, the particle size is preferably 1 to 100 mμ, the acidic type has a pH of 2 to 4, and the alkaline type has a pH of p
Any of H8 to H11.5 may be selected.

The treatment agent of the present invention can be obtained by mixing and reacting the Rf group-containing silane compound of formula (1), a silane coupling agent, and colloidal silica. The mixing ratio of the Rf group-containing silane compound, silane coupling agent, and colloidal silica is selected from a heavy acid ratio of 1:0.01 to 1:0.1 to 5, particularly 1:0.1 to o, s:
0.5-2.5 is preferable.

The mixed reaction uses a suitable organic solvent, such as acetone,
The reaction is completed in 1 to 24 hours at a temperature of 0 to 60°C, and a reaction mixture is obtained by distilling off the solvent.

The processing agent of the present invention thus obtained can be prepared in any form such as an emulsion, a solvent solution, or an aerosol according to a conventional method. For example, a solvent solution type is prepared by dissolving the reaction mixture in one or a mixed solvent of two or more suitable organic solvents such as chlorine-based or fluorine-based solvents. For an aerosol type, an aerosol propellant may be further added to the solvent solution and the mixture may be filled into a suitable container. Usually, the reaction mixture is prepared as a solution of 10 to 30% by weight in a solvent, but 15 to 25% by weight is preferred from the viewpoint of workability of coating.

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 winding with 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
Preferably, the treatment is carried out at a temperature of 180 DEG C. for 1 to 60 minutes to ensure strong adhesion of the treatment agent to the glass surface.

The surface treatment agent of the present invention may be mixed with other Rf group-containing compounds, various compounds, other blenders, etc., and may also be used with the addition of appropriate additives such as antistatic agents and crosslinking agents. .

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

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, oil repellency was determined by similarly measuring the contact angle of hexadecane, and hardness was determined using a pencil scratch tester (JIS-K5401). ) was used to measure pencil hardness. Furthermore, 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. The thickness of the coating film is determined by 'Talystep' (Rank Tail).
The stylus pressure was determined using a stylus (manufactured by OrHobson).

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+lCH=CH2 (n is 6, 8, 10.12
The average value is 9.0 ) 99.29 (0
,2 mol), Hstcx3s 2.5 y (0,24
0.052 f of P tC16.H2O was placed in a 200-volume four-bottle flask equipped with a thermometer, a cooling tube, and a stirrer, and reacted at 80° C. for 200 hours with slow stirring under a stream of dry nitrogen. After the reaction was completed, a reaction product was obtained by distillation. When analyzed by gas chromatography, the reaction products were found to be CnF2n+, CH2CH25
The conversion rate to IC13 was 95%.

Synthesis Example 2 Product of Synthesis Example 1Cn'F2n+1C&C)TzSiC
1365.2t (a, 1 mol) and 20f of methanol were mixed and reacted while bubbling dry nitrogen to remove generated HCl. The end point of the reaction was confirmed by quantifying the amount of HCI produced. After the reaction was completed, excess methanol was distilled off to obtain a reaction product. When the reaction product was analyzed by gas chromatography, it was found to be CnF2n-zcHzcHzsi(
OCi13)3, and the conversion rate is 100Y.
;Met.

Synthesis Example 3, mol), H2N(CHz)3Si(Oc4&)s2
2.1? (0.1 mol) and dry tetrahydrofuran 1502 were placed in a 300-cm Yotsuro flask equipped with a thermometer, a cooling tube, and a stirrer, and while stirring slowly under a stream of dry nitrogen, the mixture was heated to reflux temperature (approximately 60°C). ) for 5 hours. Tetrahydrofuran was distilled off to obtain a reaction product. The reaction product was analyzed by gas chromatography, and the conversion rate thereto was 100%.

Example 1 Reaction product CnF2n+ of Synthesis Example 1, CH2CH25I
C13t, colloidal silica (acidic type, 20% aqueous dispersion: zoaor, acetone 3302) were placed in a 500-liter Yotsuro flask equipped with a thermometer, cooling tube, and stirrer, and reacted for 24 hours with stirring at 20°C. and acetone was distilled off to obtain a reaction mixture.

The above reaction mixture 20f was diluted with acetone to make 100f to prepare a solvent solution. Separately, prepare a glass plate (soda-lime glass) that has been washed with detergent and acetone, immersed in 1% hydrochloric acid solution, and then dried. Apply the prepared solvent solution to the surface with an applicator, and place it in 100% relative humidity for 1. 60
Cure for 20 minutes. Determine the contact angle of water by dropping water on this surface, and determine the contact angle of water by dropping hexadecane.

The contact angle of hexadecane was measured respectively. The pencil hardness of the coated surface was also measured using a pencil scratch tester. The measurement results are shown in Table 1.

Example 2 Reaction product CnF2n+, CH2CH251 of Synthesis Example 2
(○CHa)s Colloidal silica (acidic type, 20%
Example 1: aqueous dispersion) 10&Of, acetone 3002
A reaction mixture was obtained in the same manner as above.

Applying the above mixture to a glass plate in the same manner as in Example 1,
After treatment, water and hexadecane contact angles and pencil hardness were measured. The measurement results are shown in Table 1.

Example 3 Reaction product 6 1,8 f of Synthesis Example 3, CH2-CHC%0 (CI(a)
ssi (OC2Hs) a 2 α6\ 1 2, colloidal silica (acidic type, 20% aqueous dispersion)
10&0'f and acetone 350f were reacted in the same manner as in Example 1 to obtain a reaction mixture.

The above reaction mixture was applied to a glass plate in the same manner as in Example 1, and after treatment, the contact angles of water and hexadecane and pencil hardness were measured. The measurement results are shown in Table 1. .

Example 4 A reaction mixture was obtained in the same manner as in Example 1 except that colloidal silica (alkaline type, 2% aqueous dispersion) was used, and then the contact angle and pencil hardness were measured in the same manner as in Example 1. It was measured. The measurement results are shown in Table 1.

Comparative Examples 1 to 3 Reaction mixtures were obtained in the same manner as in Examples 1 to 3, except that the glass was not used, and then the contact angle and pencil hardness were measured in the same manner as in Example 1. It is shown in Table 1.

Example 5 The reaction mixture 52 in Example 1 (listed in Table 1) was diluted to 5002 with a trichlorotrifluoroethane/acetone mixed solvent (3/1) to prepare a solvent solution. Glass plate (soda-lime glass) washed separately with detergent and acetone, immersed in 1% hydrochloric acid solution and dried
prepared. Immersing this glass plate in the solvent solution,
It was pulled up at a pulling speed of 50 tan/min and dried at 160°C for 1 hour. The film thickness was 0.1μ, and the reflectance was 2.8% (light wavelength 540mμ). The reflectance of the untreated glass plate was 4.2%.

Example 6 In Example 5, except that the reaction mixture of Example 3 was used instead of the reaction mixture of Example 1, the same treatment was carried out to form a thin film with a thickness of 0.1 μm on the surface of a glass plate. Reflectance is 2
．． It was 6%.

Examples 7 to 13 A reaction mixture was obtained in the same manner as in Example 11 except that the Rf group-containing silane compound was different, and then the contact angle and pencil hardness were measured in the same manner as in Example 1. The measurement results are shown in Table 2.

Examples 14 to 20 A reaction mixture was obtained in the same manner as in Example 1 except that the silane coupling agent was different, and then the contact angle and pencil hardness were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

209-

Claims (1)

[Claims] 1. A glass surface treatment agent comprising a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed condensate of the compound, a silane coupling agent, and colloidal silica. 2. The polyfluoroalkyl group-containing silane compound has the formula (1) %Formula% (1) [However, in the above formula, Rf is a polyfluoroalkyl group having 4 to 16 carbon atoms and having one or more ether bonds. may contain, Q' is a divalent organic group, zl is a lower alkyl group, halogen, alkoxy group or RCOO
-(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 the above integer. The 5,7-run coupling agent has the formula (It) (X(A)
C) aS i (Z”)1) Y24-a-bNH2-
, NH2cH2cH2NH-, H8-, C1-, c island =
C"H-. Luxy 4, -r is halogen, alkoxy group, a is 1-3
b is an integer of 0 or 1 to 2, and C is an integer of 0 or 1). 6. Polyfluoroalkyl group-containing silane compound, silane coupling agent, and colloidal silica in a ratio of 1:0.0
The processing agent according to claim 1, which has a weight ratio of 1 to 1:α1 to 5.