JPS58122979A - Water/oil repellent for glass surface - Google Patents

Abstract

PURPOSE:To provide a water/oil repellent which consists of a polyfluoloalkyl group-contg. silane compd. (or partially condensed hydrolyzate thereof) and a silane compd. and imparting durable water and oil repellency and stain resistance to the surface of glass. CONSTITUTION:90-10wt% polyfluoroalkyl group-contg. silane compd. of formulaI(A) (or partially condensed hydrolyzate thereof)[where Rf is a 1-20C polyfluoroalkyl group which may contain one or more other bonds; R<1> is H or lower alkyl; X is -CON(R<2>)-Q- or -SO2N(R<2>)-Q-, where R<2> is identical with R<1> and Q is a divalent organic group; A is alkylene; Z is alower alkyl; Y<1> is halogen, alkoxyl or R<3>COO-, where R<3> is identical with R<1>; n is 0 or 1; a is 1-3; b is 0-2]is made to react with 10-90wt% silane compd. of formula II (B) (where Y<2> is identical with Y<1>; c is 0-3) in the presence of water which is used in 10-1,000mol% of (A).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water repellent/oil agent that imparts water (f-1), oil repellency and stain resistance to a glass surface, more specifically, polyfluoroalkyl A well-known glass surface repellent compound consisting of a group-containing silane compound or a partially hydrolyzed condensate of the compound and an alkoxy or °It concerns oil agents.

The surface of glass products such as glass roots, halberds, glass containers, crow utensils, and mechanical lenses may condense moisture due to atmospheric humidity and temperature, or may be wetted by water. It is well known that the ingredients are eluted and become alkaline, so that the surface of the field is easily eroded, resulting in so-called scorching. In addition, fine dust and oil droplets floating in the atmosphere may arrive and contaminate the glass surface, and water droplets such as rainwater may be added to the tar on the windows of self-driving cars, airlines, and JI vehicles and cause damage to the glass. Transparency or
Interferes with pentavision. For this reason, in order to make the surface of the crow water-resistant, a page 1 of surface treatment was published in which, for example, silicone thread wax, silicone oil made of polyroxane, a surfactant, etc. were applied. However, many of these require pretreatment for application, especially 4
No fabric uniformity, long-term durability, oil-folding properties, and stain resistance could be improved.

The present invention provides water repellency on the surface of the crow, which can impart water repellency, oil repellency, and stain resistance to the surface of the crow for a long period of time, based on the above-mentioned weave of the interstices. After much research and study in order to provide an oil repellent, we have now completed the present invention.

(81 That is, according to the research of the present inventor, polyfluoroalkyl group (hereinafter abbreviated as Rf group)-containing Rf
The critical different surface tension of the group is as low as 2 (l cl, yn/m or less, which is lower than that of not only water but also oil), so when the Rf group covers the glass surface, it can impart water and oil repellency. Effectively orient the group to the carousel surface: ←
It has been discovered that the r-amide group is useful and has the ability to improve water and oil repellency. In addition, in order to firmly attach the Rff-containing compound to the glass surface and impart water and oil repellency over a long period of time, -8i -0-R, -8i-Hal (Ha), which reacts with the 5iOH group on the glass surface, is・
-8i-0-R is preferably hydrolyzed in the presence of water and causes a crosslinking reaction, and can chemically adhere to the glass surface by reacting with B and OH on the glass surface. becomes possible.

According to the research of Akira Honhi, k17Rf group-containing compound %
When a silane compound such as alkoxy or rhalokeno is used in combination with the Rf group-containing silane compound synthesized by the reaction of + and silane compound 1, glass (4) However, it has been discovered that a high-performance adhesive agent with improved adhesiveness, adhesiveness, and oiliness can be obtained.

Thus, the present invention has been completed based on the previous t' findings, good,
R1 is a hydrogen atom or a lower alkyl group, X is -coN(R
”) -o, - or -3O2N (R2) -Q- (wherein, R2 is a water atom or a lower alkyl group, Q is a divalent organic group), A is an alkylene group, 2 is a lower alkyl group , Yl and Y2 are each a halogen, an alkoxy group or R'COO- (provided that R3 is hydrogen or an alkyl group), an integer of n (60 degrees), an integer of 1 to 3, b −0 or an integer from 1 to 2.]
A silane compound containing 6 mome or a caustic hydrolyzate of the compound, condensation, and the general formula 8iR2oY24-c (
II) (However, R2, Y2f'f - same as above, c
l', O or an integer from 1 to 3); 4. The present invention provides a novel glass surface phase/water punch oil agent consisting of a silane compound 'f/+.

The water- and oil-repellent agent of the present invention is expected to exhibit high water- and oil-repellency since the Rf groups are highly dense. In addition, it contains an amide group, which makes it easy to arrange Rf groups on the glass surface.Furthermore, by hydrolyzing in the presence of silane water, crosslinking reaction and reaction with 5iOH groups of glass are promoted. Chemically adheres to surfaces. Silane compounds are also useful for increasing crosslinking density, and can further improve adhesion and water and oil repellency.

The pestle water oil agent in the present invention is composed of the Rf group-containing silane compound of the general formula (I) as described above or a partially hydrolyzed condensate of the compound, and the silane compound compound of the general formula (n). , Rff of Rff-containing silane compound: % 1~
0〒°0Y containing 20 perfluoroalkyl groups or one or more ether bonds.

cFacr2cF2o (cFcp2o) mcF-dezo)
It is particularly preferable to use a perfluoroalkyl group having 4 to 12 carbon atoms, where m is an integer of 2 to 10. R1 may be either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X is 10ON (R2)-Q,-
or -8O2N(R2)-Q- is selected, where R2 is a water ice atom or a lower alkyl group having 1 to 4 carbon atoms, and Q
is a divalent specific group, preferably -(OH2)2-+(C
H2) 3 + (CI(2)s- is selected. Human is an alkyl group and -(cnz)3- is preferable. 2 is a (13-class alkyl group having 1 to 4 carbon atoms) is selected. Yl and Y2 are each halogen, alkoxy group or R'00
0- is R3 radical or lower alkyl group, and Yl and Y2 are preferably CI, -00Ha, -0C2
H5, 0H3000-.

C2H6Coo- is selected. It is an integer of n x 0, where a is an integer from 1-1 to 3, and b is an integer from 1 to 3.
It is an integer of 2.

Therefore, the Rf group-containing silane compound of the general formula (1) can be obtained by various methods or by Lie-+&, but it is usually obtained as an Rf(x) n-00OR' compound. H2N
It is synthesized by a process involving reaction with an ASiYs compound. Such a synthetic reaction may use a solvent without active hydrogen, and the reaction temperature is 0 to 150°C, preferably 40 to 150°C.
80°C, reaction time 1 to 50 hours, preferably 2 to 10 hours
done in time.

In the present invention, as an Rf group-containing silane compound of the general formula (D), for example, CgF19CONH(CH2)3si(OC2H5)3
゜CIgF1gcONH(0')T2)3SiO13゜CI-fs CgF,gCONH(OH2)3SiC12゜09Fl
! 100NH(CH2)NH(CH2) 3Si (
OC2H6) 3゜CsF+ 5cONH(OH2)
5CONH(CH2) 3Si (002Hs) a
.

CI6F+ 7SO2NH(CH2) 50ONH(O
H2)3Si(002H5)3.

# is given.

After silane compounding of general formula (n) 5iR2cY24-c, R2Jti is selected from 1 water atom or a lower alkyl group with a carbon number of ~4, Y2 is selected from norogen, an alkoxy group having 1 to 4 carbon atoms, or R3COO-. , preferably illusion C! 1. -0CR3, -002H5, CH3COO-
.

It is C2H6COO-.

The folded book oil repellent of the present invention can be provided by mixing the Rf group-containing silane compound of general formula (1) and the silane compound of general formula (n), but by mixing both compounds in the presence of water. It can be obtained by reaction. The mixing ratio of both compounds is 1 part of the silane compound to 7 parts of the Rf group-containing compound.
It is 0 to 90 weight, preferably 30 to 70 weight.

The amount of water added is 10 to 1 per silane compound containing Rf group.
000 molti, preferably 100 to 500 molti.

The thus obtained oil and oil repellent of the present invention can be converted into any form such as an emulsion, a solvent solution, or an aerosol according to a conventional method.
i-me-san, ru. For example, a liquid type with pre-flooding agent (d) is prepared by dissolving the mixed product in a suitable solvent such as dichlorine-based or fluorine-based, or a mixed solvent of 2 or more hydroxides. 4. For aerosol type products, simply adjust the solvent flow rate of the solvent type as described above, add an aerosol propellant, and fill it into a suitable container.Normally, the reaction product 1 is dissolved in a solvent. It is prepared as a 10-30% solution by weight,
From the viewpoint of workability of coating, 15 to 25 needles are preferred.

Glass surface folding of the present invention) The frame oil 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 above-mentioned adjustment form. For example, for a station building of Solvent Melting Method 1, a method of adhering it to the surface of the glass product by known methods such as dipping and coating, spraying, etc. may be adopted. After adhering to the glass surface, it is preferable to carry out the treatment under 100 degrees relative humidity and at a muddy level of 100 degrees Celsius or more for at least 20 minutes, to strengthen the contact of the snoring water repellent to the crow's blush. obtain.

The extract oil repellent of the present invention contains other Rf, i￥-containing polymers, each f
It is also possible to mix the 1h polymer and other blenders, and it is also possible to add greenhouse additives such as anti-seizure agents and cross-linking agents for one-time use.

Glass products treated with the uninvented 桦Xf oil agent are not particularly limited, and include various examples, such as glass plates, glasses, glass containers, glass utensils, eyeglass lenses, etc.

Evaluation method of water-absorbing oil agent of the present invention←j1 Water resistance was determined by placing water on a glass coating surface and measuring the contact angle using a contact angle button, and oil repellency was similarly determined by measuring the contact angle of hexadephnone.

Next, the embodiments of the present invention will be explained in more detail. , brightness do not limit the present invention, of course.

Synthesis Example I C! nH21+IC0OCH(OH3)2 (n is 6.
It is a mixture of 8.10.12 and the average value is 9.0)]
]], 2y (0.2 mol), H2N(CH2)35i(
OC2)(s)s 44.2? (0.2 mol) and 150 ii' of dry tetrahydrofuran were placed in a four-eye glass flask with an internal volume of 300 ml equipped with candy, a thermometer, a cooling tube, and a cedar stirrer, and the mixture was slowly stirred under a stream of dry nitrogen. Shinakakara η1. The reaction was carried out at a temperature of about 60° C. for 5 hours. Tetrahydrofuran was distilled off to obtain reaction product hy1. Reaction production% + ij When analyzed by gas chromatography, CnF2n + IC0NH (OH2)3s1 (OC
The conversion rate IJ to 2H5)3 was 100%.

Synthesis example 2 073 C? '3 CFsCF20F20 (CFCF20) 20FC (JO
O2H569,OS' (0.1 mol), H2N (cH
z)3Si(OC2Hs)322. ] ? (0,1 mol), -rg dried tetrahydro7ran) 509 synthesized f
The reaction was carried out in the same manner as lJ1.

The reaction product is Kaschroma!・Analysis using graphics (OC2
The conversion rate to H1i)3 was 100%.

Example] CnF2y synthesized in Synthesis Example 1, +10ONH (CH2
)3Sj(002H5)3 (n is 6I8.10.12
The average value is 9.0)7], 7fF (
0, ] mol), 5i(OC2H5)435.8y(0
, 2 mol), water 6.60f (037 mol) k l&
Pour the contents into a 250ml three-bottle flask equipped with a temperature meter and a stirrer, and incubate at 25°C for 1 minute (while stirring).
The reaction was carried out for 20 minutes with stirring at °C, and CnF2n+,
C0NH(OHJ35i(OC2H6)3/5i(
A reaction product of 002H6)4 was obtained.

The reaction product 202 is converted into Freon (R-113: Asahi 4!-
00ii' and the solvent solution was adjusted to 100%. Separately, wash and wash with acetone, 1%
Prepare a glass plate (soda-lime glass) that has been immersed in salt solution and dried, apply the adjusted bath agent solution to the surface with an applicator, and heat at 120°C at 20°C in a relative humidity of 100%.
After performing hemorrhoid ringing for a minute, the contact angles of water and hexadecane were measured. The measurement results are shown in Table 1.

Example 2 73 CF30 synthesized in Synthesis Example 2]? '2 cF2o (C
Fcr+'20)20Y'3 0FCONH(OH2) 3 Si (002H5)
3 and Si(OC2)(s) in the same manner as in Example 1 to obtain C! F30F20F20A
°I゛.

(OFOF20) 2C! FCONH (CH2) 3
Si (OC2H5) 3 / Si (OC2H5)
.

The reaction product is obtained. This reaction product was coated on a glass plate in the same manner as in Example 1, and the contact angles of the treated film, water, and hexadecane were measured. The measured results are shown in Table 1.

Comparative Examples 1-2 Combined hs:, ? /11] C! nF2n+4
C0NH(OH2)3S](OC2H5)a and r in Synthesis Example 2, f3V, 0F3cF2 CF2
O°〒°°r.

(CFC!F20)20FcONH(CH2) 3S
i (OC2H5) 3 was applied to a glass plate in the same manner as in Example 1, treated, and the contact angles of water and hexadecane were measured. The results for each are shown in Table 1.

Table 1 Examples 3 to 8 The Rf group-containing silane compound was different. After the reaction product was recovered in the same manner as in Synthesis Example 1, it was reacted with a silane compound in the same manner as in Example 1. Reacting rl '+'tt
It was coated and treated on the surface of a glass plate containing r-containing water and hexadecane glue.

Measurement results 4 are shown in Table 2.

Table 2 Examples 9 to 11 CnF2H+I C0NH(C
H2) Using 3Si (Oo2es)3, the reaction product glass surface obtained by the same reaction method as in Example 1 was coated and treated with the exception of changing the silane compound, and the contact angle of water and hexadecane was determined. It was measured. The measured results are shown in Table 3.

Table 3 0'7) -63:

Claims (1)

[Claims] General formula (Rf (x) nC0NA) aSj
, (z) bY' 4-B, a polyfluoroalkyl group-containing silane compound represented by 1 or a condensate of the compound 7, Raki 1 (fractionated moisture 1), and
A silane compound 1 represented by the general formula Si, R2o'Y24-C on the surface of the crow surface, Usui SE/Aburoki I0 [However, in the above general formula, Rf is a polyfluoroalkyl group having 1 to 20 carbon atoms. R1 and R2 are hydrogen atoms or JI alkyl groups, X i < j, -C! ON (R2)-Q- or -8O2N(R2) Q- (However, R2!71: Same as above, Q represents a divalent group), A is an alkylene group, 2 is lower alkyl The groups, Y' and Y2 are respectively Sowano-rogen, alkoxy, or R, "000- (However, I (a represents a hydrant atom or lower alkyl group), ni
;jOO12 integer, a is the number of walls from 1 to 3, b is 0 or (7
an integer of tl to 2, c (represents d O or an integer of 1 to 2)] (2'i Rf is a perfluoroalkyl group having 1 to 20 carbon atoms, Claim 171 → First sequence) Water and oil repellent. Prison?1゛(8j' Rf or CFaCF2C!F20(CFC!
F20) CF- (however, m is an integer of 1 or more), a water and oil repellent that is suitable for use in the first month of November.