JPS58147483A - Water and oil repellent for glass surface - Google Patents

Abstract

PURPOSE:The titled water and oil repellent that is composed of a silane compound containing polyfluoroalkyl groups, a silane coupling agent and colloidal silica, thus giving glass surfaces high water and oil repellency for a long period of time. CONSTITUTION:(A) A silane compound bearing polyfluoroalkyl groups of formulaI Rf is 4-16C polyfluoroalkyl, preferably 4-16C perfluoroalkyl of formula II (m is 1 or more) and may contain one or more ehter linkages; Q is divalent organic group; Z<1> is lower alkyl; Y<1> is halogen, alkoxy, RCOO- (R is H, lower alkyl); a is 1, 2, 3; b is 0, 1, 2 or its partial hydrolyzate, (B) a silane coupling agent of formula III (X is formula IV, NH2, NH2CH2CH2NH-; A is alkylene, Z<2> is lower alkyl; Y<2> is halogen; a is 1, 2, 3; b is 0, 1, 2; c is 0, 1) and (C) colloidal silica are mixed at a weight ratio of 1:(0.01-1):(0.1-5) to give the objective water and oil repellent.

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 a glass surface, and more specifically, the present invention relates to a water and oil repellent that imparts water repellency, oil repellency, and stain resistance to a glass surface. This invention relates to a novel water and oil repellent for glass surfaces, which is composed of a hydrolyzed condensate, a silane coupling agent, and colloidal silica.

The surfaces of glass products, such as glass plates, bells, glass containers, glass utensils, and eyeglass lenses, may condense due to the effects of atmospheric humidity and temperature, or if they become wet with water.
It is well known that glass components are present in this moisture and the surface becomes alkaline, easily corroding the surface and causing so-called burns. In addition, fine dust and oil droplets floating in the atmosphere may adhere and contaminate the glass surface, especially in automobiles.
O 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, 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 products require pre-treatment before application, and problems such as long-term durability, oil repellency, and resistance arise due to uneven coating that occurs during application or the low adhesion of the treatment agent itself to the glass. No satisfactory results have been obtained regarding contamination.

Based on the recognition of the above-mentioned problems, the present inventor conducted various studies in order to provide an excellent water damage oil agent 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 studies, the present invention has been completed.

That is, according to the research of the present inventors, compounds containing polyfluoroalkyl groups (hereinafter abbreviated as Rf groups) have a low Rf group end critical surface tension of 20 dyn/am or less, and are resistant to water and oils. Since the rue is lower than that of the glass surface fRf
Water and oil repellency can be imparted when covered with a group-containing compound;
Furthermore, an Rff-containing compound [Glass@1] is required to firmly adhere to the glass surface and provide long-term water and oil repellency.
-81-0-R, -8 reacts with i1oston group
The presence of 1-Hal (Hal is halogen) is preferable,
-81-0-Rij An Rff-containing silane compound obtained by the reaction of an Rff-containing compound and a silane compound because it hydrolyzes in the presence of water, causes a crosslinking reaction, and reacts with 810H on the glass surface to chemically bond. In addition, mixing colloidal silica is useful in order to increase the hardness of the coating after applying the Rf group-containing 7-ranium compound to the glass surface. F-, which increases the compatibility of the contained silane compound with colloidal silica and O, and efficiently adheres the Rff-containing silane compound to the glass surface, is used in combination with a silane coupling agent to improve water and oil repellency and the coating's wearability. I found out one fact.

Thus, the present invention was completed based on the above findings, and provides a novel water-repellent glass surface comprising a partially hydrolyzed condensate of an Rff-containing silane compound or a nuclear compound, a silane coupling agent, and colloidal silica. It provides oil solutions.

Thus, the water and oil repellent of the present invention exhibits excellent water and oil repellency and can maintain this performance for a long period of time.

The water and oil repellent in the present invention comprises a partially hydrolyzed condensate of an Rff-containing silane compound or a core compound, a silane coupling agent, and colloidal silica. (zsb''4-a-b Rf group-containing sine compound is selected.

In the formula (1) rC, Rf is preferably a perfluoroalkyl group having 4 to 16 carbon atoms or an ether group, and m is particularly preferably an integer of 2 to 1o.

Q is a divalent organic group, and zl is a lower alkyl group having carbons #11 to #4. yl Fi halogen, alkoxy group or i! I'EOOO-TER is preferably hydrogen or a lower alkyl group. 11-01. -0CH
1,-00@H@, OH龜000-.

0, H, Coo- are selected. a is an integer of 1 to 5, and b is 0 or an integer of F'i1 to 2.

Although the Rf group-containing silane compound of formula 1 (summer) can be obtained by various methods or routes, it is synthesized, for example, by a process including reaction of an RfQ compound and a 181Ys compound. The synthesis reaction may be carried out using a solvent having no active hydrogen, at a reaction temperature of 0 to 150°C, and for a reaction time of 1 to 50 hours.

In the present invention, examples of the Rf group-containing silane compound of formula (1) include OH.

RfCHHOHgBiOlg, RfCHHOHgB
iOlg.

(RfCH10113) TomiB101s-RfOH101
1181(00H1)8゜RfCo)IHcH,c)I
, CHtB i (00,El)s.

Rfaonacn, cam MHOHI Cl1l
OHM 81 (002H@)1.

CHt RfBO, M cH*OH, C0NHOH, OHI O
H,81(OG,H,)s.

RfOH OH10OOOHHOH1B OH1OBM
OHH81(0('H3)3.

Rf(A1. OB, 0CONHO1I!cam O
HM 81 (00,H,)S.

RfooooH,0H011t00111101110
H@81 (00@Hs%.

OH RfCHl OHM HHOBz OHM 81 (0
OH3)3゜RfOH* 011g HHOBz OH
HS i (003110H100Ha)s - is mentioned.

The silane coupling agent is selected from the formula (II) (X(mu)c)a"(')bY24-ab. In the formula [), X Id OHI-0H
(:!H!--MHI--ゝ./ MC0- is desirable, M is an alkylene group, zRF
i A lower alkyl group having 1 to 4 carbon atoms is selected. Y3
hahalogen, alkoxy group, a 11i an integer of 1 to 3, boo or an integer of Fi 1 to 2; C is an integer of 0 or 10;

Therefore, in the present invention, as the silane coupling agent 2〇), for example, OHI-CHOHlo(CHl)m81(004)1-
\1 NH3(CM))1NH(OH1)18i(OCH3:
)IsNl(,(OH,),81(OOHs)s,
CHt-OH81 (OOHs).

CHt) an,-casicl,, an,=aaoo(cu
), 5t(ooas),.

H8(OJ)m81(OCH1%lMC0(OHz)s
B1cOo@H@)@.

al(ca,)sai(ocHm)s.

an, mQpeDOHlNH(CH2)IIJH(04)
181(OOHI)1°°0-on, aH,5Boaa=).

I get rL.

Colloidal silica can be used as a waste material.
It may contain i k. The solid content concentration (dispersion concentration) is preferably 5 to 40 cm, the particle size is preferably 1 to 100 mp, and the acidic type has a pH of 2 to 4, and the alkaline type has a pH of 2 to 4 mp.
Any t from H8 to 1t5 may be selected.

The water and oil repellent of the present invention can be obtained by mixing the ORf group-containing silane compound of formula (I), a silane coupling agent, and colloidal silica to react with each other. The mixing ratio of the Rf group-containing silane compound, the silane coupling agent, and the colloidal silica 0 is selected from a weight ratio of 1:α01 to 1:α1 to 50, particularly preferably 1:α1 to I15:α5 to z5. The mixing reaction is completed in 1 to 24 hours at a temperature of ~60°C using a suitable organic solvent, such as acetone, and the reaction mixture is obtained by distilling off the solvent.

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, 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 in an amount of 10 to 30 weight by weight relative to the solvent, but preferably 15 to 25 weight by weight from the viewpoint of workability of coating.

Glass surface iii of the present invention] The water and oil repellent 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 preparation form. For example, in the case of a solvent solution type, a method of adhering to the surface of the glass product by known coating methods such as dip coating, spraying, etc. may be employed. After adhering to the glass surface, it is preferable to perform a treatment for 1 to 60 minutes at a temperature of 60 to 180°C under 100 - relative humidity, which can strengthen the adhesion of the water and oil repellent Q to the glass surface. .

The water and oil repellent of the present invention may be mixed with other Rf group-containing compounds, various juvenile compounds, and other blenders, and may also be used by adding appropriate additives such as antistatic agents and crosslinking agents. It is.

Glass products that can be treated with the water and oil repellent of the present invention are not particularly limited, and include a variety of examples, such as glass plates, mirrors, glass containers, glass appliances, and eyeglass lenses.

The liver value method for the water and oil repellent 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 similarly to oil repellency kFi, by measuring the contact angle of hexadecane. Further, the hardness was determined by measuring pencil hardness using a pencil scratch tester (JIB-K5401).

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 CnF2n410H-OJ (n, a, 10.
120 mixture, the average value of υ is t O) 99.2 t
((L 2 mol), H8101m 32.5 F (
124 mol)% H, Pt01...H,O[LO52ft
"Thermometer, cooling tube and stirrer (equipped internal volume 200-
The mixture was placed in a four-hole flask and reacted at 80° C. for 200 hours with gentle stirring 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 and was found to be CnF2n+10HI.
CH 8101m, conversion rate Fi95
%Met.

Synthesis Example 2 Product of Synthesis Example 1 0n72n+1040H181011
6121 (0.1 mol) and methanol 20F were mixed,
The reaction was carried out while bubbling with dry nitrogen to remove generated HOi. The end point of the reaction was confirmed by quantifying the produced HOI. 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 ○nF2n410HsOHt81 (OCR
s) i, and the conversion rate to it is 100-, which is good.

Synthesis Example 3 ([11 mol), El, N((!H,), 81(00,
H,)s22.1F (α1 mole) and 150 V of dry tetrahydro 7 run were placed in a 300-volume four-loaf flask equipped with a thermometer, cooling tube, and stirrer, and slowly stirred under a stream of dry nitrogen. 5 at reflux temperature (approximately 60°C) while
Allowed time to react. Tetrahydro7rane was distilled off to obtain a reaction product. The reaction product was analyzed by gas chromatography and showed a conversion rate of 100%.

Example 1 Reaction product of Synthesis Example 1 cn'2n+10HM cHg
8101 Hataket, colloidal silica (# type, 20-water dispersion)
105 OF and 5 sat of acetone were placed in a 500-〇 four-bottle flask equipped with a thermometer, a cooling tube, and a stirrer, and the reaction was carried out for 24 hours with stirring at 20°C.
was distilled off to obtain a reaction mixture.

The above reaction mixture 20f was diluted with acetone to make 100t to prepare a solvent solution. Separately, prepare a glass plate (soda-lime glass) that has been washed with detergent and acetone, immersed in a chronic hydrochloric acid solution and dried, and apply the prepared solvent solution to the surface with an applicator at 160°C in 100 - relative humidity. ,
It was cured for 20 minutes. The contact angle of water was measured by dropping water on this surface, and the contact angle of hexadecane was measured by dropping hexadecane. or.

The pencil hardness of the coated surface was measured using a lead chain scratch tester.

The fixed results are shown in Table 1.

Example 2 Reaction product Cnll2n+10H of Synthesis Example 2! OH intention 8
1 (00Ha) sf1 Coroita” Rusilica (fill type, 20% aqueous dispersion) 1050f, acetone 300
F and 2 were reacted in the same manner as in Example 1 to obtain a reaction mixture.

Apply the above mixture to a glass plate using method O 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 of Synthesis Example 3\1f, colloidal silica (acidic type, 20-aqueous dispersion)
1010F and acetone 350F were reacted in the same manner as in Example 1 using method O to obtain a reaction mixture.

After coating and treating the upper reaction mixture on a glass plate in the same manner as in Example 1, the contact angles of water and hexadecane and pencil hardness were measured. The measurement results are shown in Table 181.

Example 4 A reaction mixture was obtained in the same manner as in Example 9Ij 1 except that colloidal silica (alkaline type, 20-water dispersion) was used, and then the contact angle and pencil hardness were measured in the same manner as in Example 1. It was measured. Measurement results #1! Shown below.

Comparative Examples 1 to 3 Reaction mixtures were obtained in the same manner as in Examples 1 to 5 except that KLL was not used, 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 1.

Examples 5 to 11 A reaction mixture was obtained in the same manner as in Example 1 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 12-18 Sila/coupling agent [Same as Example 1 except for differences II
After obtaining a reaction mixture using the method described above, the contact angle and pencil hardness were measured using the same method as in Example 1. The results are shown in Table 5.

F Continuing amendment (method) July 1980 ∆ Director-General of the Patent Office Mr. Kazuo Wakasugi 1 Extra indication F Sowa 57 Rod Patent Application No. 28949 3 Person making the amendment 5j Relationship with F case Patent applicant 11 “1”+i 2-1 Marunouchi, Chiyoda-ku, Tokyo
Number 2 No. 4, Agent 1i1i1i Toranomon, Minato-ku, Tokyo - Dingji 24-11 No. 5, ? dtd', tU Order's Roy 1jZ Amendment Subject Full Text Specification of Contents of Amendment 8 is revised in the attached document.

(Change in content 7zL)

Claims (1)

[Scope of Claims] t. A water and oil repellent for glass surfaces, comprising a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed metal condensate of the compound O, 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 14 carbon atoms and may contain 1 or more ether bonds, and q is a divalent organic group. , zl is a lower alkyl group, then...rogen, alkoxy group or RQOO-(
Rij is a hydrogen atom or a lower alkyl group), aij is an integer of 1 to 5, and b is an integer of 0 or 1 to 20. ] Is the patent claim expressed by v! A. The water and oil repellent according to item 1. 5. The water and oil repellent according to claim 1 or 2, wherein the polyfluoroalkyl group is a perfluoroalkyl group having 4 to 16 carbon atoms. 4. The water and oil repellent agent according to claim 1 or 2, wherein the polyfluoroalkyl group is an integer above. S the silane coupling agent has the formula 1) % formula % lower alkyl group % de is a halogen, a is an alkoxy group, a is 1
-3 integer, b is 0 or an integer from 1 to 2, C is 0 or 10
(integer) A water and oil repellent according to claim 1. Direct polyfluoroalkyl group-containing sifun compound, silane coupling agent, and colloidal silica are 1:α01~1
:(The water and oil repellent according to claim 1, which has a weight ratio of 11 to 50.