Adsorbed monomolecular film and method of manufacturing the same

The invention seeks to provide a method of forming a monomolecular film of fluorine-containing molecules on a substrate surface such that the film has a uniform thickness with minimal surface irregularities and is substantially pin hole free. The invention also provides for a substrate obtained by using the same method which has excellent water- and oil-repelling, anti-fogging, and anti-contaminating properties. The monomolecular film is formed on the substrate surface either directly or via a given protective film. The monomolecular film coating is characterized by a plurality of different chlorosilane-based surface active materials which are different in molecular length and have a fluorine group. The surface irregularities of the film are generally confined to the molecular level.

FIELD OF THE INVENTION 
This invention relates to functional monomolecular films and, more 
particularly, to water-repellent, oil-repellent, anti-fogging and/or 
anti-contaminating films. More particularly, this invention relates to 
materials such as metals, ceramics, plastics, glass, etc. having a 
fluorine film coating. 
BACKGROUND OF THE INVENTION 
Heretofore, for improving the water- and oil-repelling properties of 
substrate surfaces, it has been a known practice to coat silicon-based 
surface active agents onto substrate surfaces or fluorocarbon-based 
polymer suspensions onto substrate surfaces. 
Generally, a material with a fluorine resin coating is obtained by making 
the surface coarse by means of electrolytic etching or surface roughening 
to increase adhesion with a fluorine-based polymer. The surface is coated 
with a fluorine-based polymer suspension, followed by baking. 
The prior art substrate is generally known to exhibit improved water- and 
oil-repelling properties and can be readily manufactured. However, if the 
film coating on the substrate surface is insufficiently thin, it results 
in generation of pin holes, so that sufficient water- and oil-repelling 
properties can not be obtained. In addition, even if the film coating is 
sufficiently thick, its water- and oil-repelling properties are sometimes 
inadequate. 
Furthermore, where a water-repelling oil-repelling film is provided on a 
transparent substrate such as a glass substrate, the transparency thereof 
is deteriorated due to the film thickness that is needed. 
In addition, the surface and fluorine-based polymer coating are weakly 
coupled together for there are no chemical bonds between the two. 
Therefore, when the material is used for a substantially long time, the 
adhesion deteriorates resulting in a separation of the fluorine-based 
coating from the surface of the material. 
Therefore, a material with a fluorine-based coating which is substantially 
free of pin holes, is uniform in thickness, and has excellent water- and 
oil-repelling properties is highly desirable. 
SUMMARY OF THE INVENTION 
The primary objective of this invention is to provide an adsorbed 
monomolecular film chemically bonded by a covalent bond each containing a 
--Si-- group to the surface of a substrate either directly or via an inner 
layer, the adsorbed monomolecular film being constituted by at least two 
different molecules having different molecular lengths. 
Another objective of this invention is to provide a process of 
manufacturing an adsorbed monomolecular film by a chemical adsorption 
process comprising the steps of: 
preparing a coating composition which comprises a blend surface active 
material in a non-aqueous solvent, the blend surface active material 
comprising two groups of molecules differing in molecular chain length and 
having at one end a halosilane or alkoxysilane group; and 
contacting the coating composition with a substrate having at the surface 
thereof an active hydrogen capable of reacting with the halosilane or 
alkoxysilane, thereby forming a monomolecular film on the substrate 
surface. 
Another objective of this invention is to provide a process of 
manufacturing an adsorbed monomolecular film by a chemical adsorption 
process comprising the steps of: 
preparing a coating composition constituted by a surface active material in 
a non-aqueous solvent, the surface active material having at one end a 
halosilane or alkoxysilane group, and contacting the coating composition 
with a substrate having at the surface thereof an active hydrogen capable 
of reacting with the halosilane or alkoxysilane, thereby forming an inner 
layer on the substrate surface; 
adding hydroxyl groups (--OH), amino groups (--NH.sub.2), or imino groups 
(--NH) on the inner layer surface; and 
preparing a coating composition which comprises a blend surface active 
material in a non-aqueous solvent, the blend surface active material 
comprising two groups of molecules differing in molecular chain length and 
having at one end a halosilane or alkoxysilane group, and contacting the 
coating composition with an inner layer having at the surface thereof an 
active hydrogen capable of reacting with the halosilane or alkoxysilane, 
thereby laminating a monomolecular film on the inner layer surface. 
It is preferable in this invention that at least two different molecules 
having different molecular lengths are alkyl fluoride groups. 
It is preferable in this invention that the adsorbed monomolecular film is 
formed as a lamination on the inner layer and the inner layer has a 
substantially uniform thickness. 
It is preferable in this invention that the inner layer is directly bonded 
by covalent bonds each having a --Si-- group to the substrate surface and 
is also bonded by covalent bonds each having a --Si-- group at the outer 
adsorbed monomolecular film. 
It is preferable in this invention that the adsorbed monomolecular film has 
molecular surface irregularities. 
It is preferable in this invention that the adsorbed monomolecular film is 
either water-repelling, oil-repelling, anti-fogging or anti-contaminating. 
It is preferable in this invention that the adsorbed monomolecular film 
comprises at least one monomolecular compound selected from the group 
consisting of formula [I] and [II]: 
EQU F(CF.sub.2).sub.m --(CH.sub.2).sub.n --Si(--R.sub.q)(--O--).sub.3-q (I) 
where m represents an integer ranging from 1 to 15, n represents an integer 
ranging from 0 to 15, the sum of m and n ranges from 10 to 30, q 
represents an integer ranging from 0 to 2, and R represents an alkyl group 
or an alkoxyl group. 
EQU F(CF.sub.2).sub.s --(CH.sub.2).sub.t --A--(CH.sub.2).sub.p 
--Si(--R.sub.q)(--O--).sub.3-q (II) 
where s represents an integer ranging from 1 to 8, t represents an integer 
ranging from 0 to 2, p represents an integer ranging from 5 to 25, q 
represents an integer ranging from 0 to 2, A represents a member of a 
group consisting of an oxy group (--O--), a carbonyl group (.dbd.CO), a 
carboxyl-ester group (--COO--) and dimethylsilylane group 
(--Si(CH.sub.3).sub.2 --), and R represents an alkyl group or an alkoxyl 
group. 
It is preferable in this invention that the molecules of the blend surface 
active material have an alkyl fluoride group. 
It is preferable in this invention that the molecules of the blend surface 
active material has at one end a trifluoromethyl group (--CF.sub.3) and at 
the other end a chlorosilane group (--SiCl). 
It is preferable in this invention that the blend surface active material 
contains a silane surface active material represented by the formula: 
EQU F(CF.sub.2).sub.m --(CH.sub.2).sub.n --Si(--R.sub.q)(--X.sub.3-q) 
where m represents an integer ranging from 1 to 15, n represents an integer 
ranging from 0 to 15, the sum of m and n ranges from 10 to 30, q 
represents an integer ranging from 0 to 2, and R represents an alkyl group 
or an alkoxyl group, X represents a halogen atom or an alkoxyl group, and 
by the formula: 
EQU F(CF.sub.2).sub.s --(CH.sub.2).sub.t --A--(CH.sub.2).sub.p 
--Si(--R.sub.q)(--X.sub.3-q) 
where s represents an integer ranging from 1 to 8, t represents an integer 
ranging from 0 to 2, p represents an integer ranging from 5 to 25, q 
represents an integer ranging from 0 to 2, X represents a halogen atom or 
an alkoxyl group, R represents an alkyl group or an alkoxyl group, A 
represents a member of a group consisting of an oxy group (--O--), a 
carbonyl group (.dbd.CO), a carboxyl-ester group (--COO--) and 
dimethylsilylane group (--Si(CH.sub.3).sub.2 --).

DETAILED DESCRIPTION OF THE INVENTION 
According to the invention, the above problems are solved by a 
water-repelling, oil-repelling, anti-fogging, and anti-contaminating film 
comprising a monomolecular film formed on a substrate surface and 
containing alkyl fluoride groups, the monomolecular film having minimal 
surface irregularities wherein the irregularities are generally confined 
to the molecular level. 
By incorporating onto the substrate surface a monomolecular film which 
contains a plurality of different fluorine groups having different 
molecular lengths, a coating in the form of a monomolecular film can be 
obtained which has minimal surface irregularities. Typically, such surface 
irregularities are confined to the molecular level. Because the surface 
has minimal irregularities and the molecules constituting the 
monomolecular film contain fluorine, the area of contact between water 
drops and the film surface can be reduced. Thus the film itself can have a 
very high water-repelling property. The film similarly repels oil drops, 
and therefore provides an improved oil-repelling property. With both of 
these effects, the anti-fogging and anti-contaminating properties can also 
be improved. 
The substrate to be used according to the invention is of such materials as 
pure metals, e.g., aluminum, copper and iron, alloys or like composite 
materials, semiconductors, fiber, cloth, fabric, fur, leather, wood e.g., 
silicon and germanium, glass and plastics. According to the invention, a 
hydrophilic substrate is used. Where the substrate is made of a common 
base metal or a semiconductor, it is made hydrophilic by a natural oxide 
film formed on its surface. In case of a relatively non-hydrophilic 
substrate such as a plastic substrate, a hydrophilic property is imparted 
by, for instance, corona treatment, plasma treatment or an ion beam 
irradiation. Furthermore, with a relatively non-hydrophilic substrate, it 
is recommended to from a monomolecular film in advance of a surface active 
material having unsaturated carbon-carbon bond groups by using such means 
as a Langmuir-Blodgett's technique (hereinafter referred to a LB process) 
or a chemical adsorption process and then forcibly rendering the film 
hydrophilic by such means as causing breakage of the unsaturated bonds in 
an atmosphere containing oxygen, nitrogen, etc. This is preferred because 
many hydrophilic groups are formed on the surface of the substrate, and a 
high concentration of monomolecular film can be obtained at the surface of 
the substrate. As a reagent for rendering the substrate surface 
hydrophilic the following compounds may be used 
EQU CH.sub.2 .dbd.CH--(CH.sub.2).sub.n --SiCl.sub.3 
and 
EQU CH.sub.2 .dbd.CH--(CH.sub.2).sub.n --COOH 
(where n represents an integer desirably about 10 to 20). The monomolecular 
film may be formed by ordinary means such as the LB process or the 
chemical adsorption process. Unsaturated bonds may be broken by ordinary 
means such as treatment with an electron beam, X-rays, gamma-rays, 
ultraviolet rays or an ion beam, plasma or corona treatment 
However, plastics having --NH groups such as polyamide or polyurethane 
substrates are not necessary in a surface oxygen treatment. Because --NH 
groups have active hydrogen, it is relatively easy to reduce the groups by 
initiating the dehydrochloric acid reaction using the chlorosilyl groups 
of the surface active agent. 
The film coating according to the invention is formed by utilizing a very 
thin monomolecular film, and therefore the initial surface state of the 
substrate may be maintained as such. 
The monomolecular film according to the invention may be formed on the 
substrate either directly or via a protective film or the like. 
Particularly, the monomolecular film according to the invention is 
suitably formed via such a functional film as a protective film, an 
anti-reflection film or an infrared-absorbing film. By doing so, it is 
possible to maintain high anti-reflecting or infrared-absorbing properties 
for a relatively long time and as well as to obtain a protective or like 
functional effect in addition to the water-repelling, oil-repelling, 
anti-fogging and anti-contaminating effects owing to the monomolecular 
film. 
According to the invention, on a substrate surface is formed either 
directly or via a given film such as a protective film a water-repelling, 
oil-repelling, anti-fogging, and anti-contaminating film in the form of a 
monomolecular film, which contains a plurality of different kinds of 
fluorine (F) containing groups having different molecular lengths, the 
surface of which is predominantly confined to molecular irregularities. 
The monomolecular film may be formed by the LB process, the chemical 
adsorption process or any other usual process. In the chemical adsorption 
process, the reagent is adsorbed via chemical bonds to the substrate, and 
therefore this process is preferred to maintain highly close contact with 
the substrate. Moreover, high mechanical strength of the monomolecular 
film can be obtained. 
Where the LB process is used to form the monomolecular film according to 
the invention, a carboxylic acid (--COOH) having an alkyl fluoride group 
in molecule, a carboxylic acid salt, an ester, a trialcoxysilane, a 
trihydrosilane, etc. may be used. 
Where the chemical adsorption process is used to form the monomolecular 
film according to the invention, fluorochlorosilane-based surface active 
materials containing an alkyl fluoride group and a chlorosilyl group, 
fluorotitanium-based surface active materials containing an alkyl fluoride 
group and a titanate group, fluorothiol surface active materials having an 
alkyl fluoride group and a thiol group may be used. 
As for the fluorochlorosilane-based surface active agents to be used 
according to the invention, they are suitably those represented such as in 
the formulas [A] and [B]. These fluorochlorosilane-based surface active 
materials are suitable because they are readily available and have 
pronounced water-repelling, oil-repelling, anti-fogging and 
anti-contaminating effects. They are suitably those represented by the 
formulas: 
EQU CF.sub.3 (CH.sub.2).sub.2 Si(CH.sub.3).sub.2 (CH.sub.2).sub.15 SiCl.sub.3, 
EQU F(CF.sub.2).sub.4 (CH.sub.2).sub.2 Si(CH.sub.3).sub.2 (CH.sub.2).sub.9 
SiCl.sub.3, 
EQU CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 SiCl.sub.3, 
EQU CF.sub.3 COO(CH.sub.2).sub.15 SiCl.sub.3, 
EQU CF.sub.3 (CF.sub.2).sub.9 (CH.sub.2).sub.2 SiCl.sub.3, 
EQU CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3, 
EQU CF.sub.3 (CF.sub.2).sub.5 (CH.sub.2).sub.2 SiCl.sub.3 
As the fluorotitanium-based or fluorothiol-based surface active agents for 
producing the monomolecular film according to the invention by the 
chemical adsorption process, those compounds obtained by substituting 
titanate or thiol for the chlorosilyl group of the above 
chlorosilane-based surface active material may be used. 
Where an alkoxysilane-based surface active material is used, adsorption is 
effected with an alcohol removal reaction when forming a chemically 
adsorbed monomolecular film. When a fluorothiol-based surface active 
material is used, adsorption is effected with a hydrous reaction. These 
surface active materials are therefore preferred to surface active 
materials having chlorosilyl groups, because they do not cause damage to 
metal substrates. 
The invention can widely be applied in the following uses. Materials made 
of metal, ceramic or plastic, glass, wood, stone, fiber, cloth, fabric, 
fur, leather, etc. are applicable to the substrate. The surface of the 
substrate can also be coated with paint or the like. 
Examples of cutlery: a kitchen knife, scissors, a knife, a cutter, a 
graver, a razor, hair clippers, a saw, a plane, a chisel, a gimlet, a 
bodkin, bite (cutting tools), an edge of a drill, an edge of a mixer, a 
juicer, a blade of a mill, a blade of a lawn mower, a punch, a straw 
cutter, a staple of a stapler, a can opener or a surgical knife and the 
like. 
Examples of needles: an acupuncture, a needle, a sewing needle, a matting 
needle, an injection needle, a surgical needle, a safety pin and the like. 
Examples of products in pottery (ceramics) industry: products made of 
pottery, glass, ceramics or an enameled products. For example, sanitary 
potteries (a chamber pot, a wash-bowl, a bathtub, etc.), tableware (a 
rice-bowl teacup, a dish (plate) a bowl, a teacup, a glass, a bottle, a 
coffee-pot (siphon), a pan, an earthenware mortar (a cup and the like), 
vases (a flower bowl, a flowerpot, a bud vase and the like), water tanks 
(a breeding cistern, an aquarium water tank and the like), chemical 
experiment appliances (a beaker, a reactor vessel, a test tube, a flask, a 
laboratory dish, condenser, a mixing rod, a stirrer, a mortar, a bat, a 
syringe etc.) a roof tile, enameled ware, an enameled washbowl, an 
enameled pan and the like. 
Examples of molding parts: dies for press molding, dies for case molding, 
dies for injection molding, dies for transfer molding, dies for 
compression molding, dies for transfer molding, dies for inflation 
molding, dies for vacuum molding, dies for blow forming, dies for 
extrusion molding, dies for fiber spinning, a calendar processing roll and 
the like. 
Examples of forming molds for food: cake, cookies, bread-baking, chocolate, 
jelly, ice cream, an oven ware, an ice tray and the like. 
Examples of cookware kitchen utensils (a pan and a pot), a kettle, a pot, a 
frying-pan, a hot plate, a gridiron net, a takoyaki plate and the like. 
Examples of resin(s): a polyolefin such as a polypropylene and 
polyethylene, a polyvinylchloride plastic, a polyamide, a polyimide, a 
polyamideimide, a polyester, an aromatic polyester, a polycarbonate, a 
polystyrene, a polysulfide, a polysulfone, a polyethersulfone, a 
polyphenylenesulfide, a phenolic resin, a furan resin, a urea resin, an 
epoxy resin, a polyurethane, a silicon resin, an ABS resin, a methacrylic 
resin, an acrylate resin, a polyacetal, a polyphenylene oxide, a 
polymethylpentene, a melamine resin, an alkyd resin, an unsaturated 
polyester cured resin and the like. 
Examples of rubber(s): a styrene-butadiene rubber, a butyl rubber, a nitril 
rubber, a chloroprene rubber, a polyurethane rubber, a silicon rubber and 
the like. 
Examples of household electric appliances: a refrigerator, a freezer, an 
air conditioner, a juicer, a mixer, a blade of an electric fan, a lighting 
apparatus, a dial plate, a dryer for a perm and the like. 
Examples of sporting goods: skis, a fishing rod, a pole for the pole vault, 
a boat, a yacht, a surfboard, a fishing line, a float and the like. 
Examples applying to vehicle parts: 
(1) ABS resin: a lamp cover, an installment pannel, trimming parts, a 
protector for a motorcycle. 
(2) Cellulose plastic: a car mark, a steering wheel 
(3) FRP (fiber reinforced plastics): a bumper, an engine cover (jacket) 
(4) Phenolic resin: a brake 
(5) Polyacetal: wiper gear, a gas valve 
(6) Polyamide: a radiator fan 
(7) Polyacrylate (polycondensation polymerization by bisphenol A and pseudo 
phthalic acid): a direction indicator lamp (or lens) a cowl board lens, a 
relay case 
(8) Polybutylene terephthalate (PBT): a rear end, a front fender 
(9) Poly amino-bismaleimide: engine parts, a gear box, a wheel, a 
suspension drive system 
(10) Methacrylate resin: a lamp cover lens, a meter pannel and its cover, a 
center mark 
(11) Polypropylene: a bumper 
(12) Polyphenylene oxide a radiator grill, a wheel cap 
(13) Polyurethane: a bumper, a fender, an installment pannel, a fan 
(14) Unsaturated polyester resin: a body, a fuel tank, a heater housing, a 
meter pannel. 
Examples of office supplies: a desk, a chair, a bookshelf, a rack, a 
telephone stand table, a rule (measure), a drawing instrument and the 
like. 
Examples of building materials: materials for a roof, and outer wall and 
interiors. Roof materials such as brick, slate and tin (a galvanized iron 
sheet) and the like. Outer wall materials such as wood (including 
processed manufactured wood), mortar, concrete, ceramic sizing, metallic 
sizing, brick, stone, plastic and metal like an aluminum. Interior 
materials such as wood (including processed wood), metal like an aluminum, 
plastic, a paper, fiber and the like. 
Examples of building stones: granite, marble and others for use as a 
building, a building material, an architecture, an ornament, a bath, a 
grave stone, a monument, a gatepost, a stone wall, a paving stone and the 
like. 
Examples of the others: a high resisting voltage insulator such as a 
thermos bottle, a power supplying insulator for a vacuum system machinery 
or a spark plug, which has high water-repelling, oil-repelling, 
anti-fogging and anti-contaminating effects. 
Specific examples of the process of chemical adsorption of a 
water-repelling, oil-repelling, anti-fogging, anti-contaminating film 
coating according to the invention will now be described with references 
to FIGS. 1 to 5. 
EXAMPLE 1 
A solution containing 80% wt n-hexadecane, 12% wt carbon tetrachloride and 
8% wt chloroform was prepared by using CH.sub.2 .dbd.CH--(CH.sub.2).sub.16 
--SiCl.sub.3 as a silane surface active material and dissolving the same 
to a concentration of 3.times.10.sup.-3 to 5.times.10.sup.-2 mol, and a 
tempered glass substrate 1, as shown in FIG. 1, was held dipped in this 
solution at a room temperature for one hour. Since the surface of the 
substrate 1 contained hydroxyl groups, a reaction between the chlorosilyl 
groups of the chlorosilane-based surface active material and the hydroxyl 
groups, thus forming on the surface bonds represented such as the formula 
[1]. 
##STR1## 
The tempered glass substrate 1 was then washed by freon 113 to remove the 
material remaining on the surface without reaction, followed by washing 
with water or exposing to air to react with moisture in the air. The 
--SiCl group was changed to a --SiOH groups as in formula [2]. 
##STR2## 
Each silanol group (--SiOH) was then dehydrated and crosslinked to form a 
siloxane bond (--SiO--) as in formula [3]. 
##STR3## 
By the consecutive reaction, a single adsorbed monomolecular film 3 having 
vinyl (CH.sub.2 .dbd.CH--) groups 2 was formed to a thickness of about 2.5 
nm such that it was chemically bonded (covalent bond) to a protective film 
via oxygen atoms. 
This glass substrate 1 was irradiated with about 3 Mrad. of X-rays in an 
atmosphere containing oxygen and also in an atmosphere containing 
nitrogen. Where the substrate 1 was irradiated in the oxygen-containing 
atmosphere, a monomolecular film 3' (inner layer), as shown in FIG. 2, was 
obtained, which contained hydroxyl (--OH) groups 4 added to the vinyl 
groups 2. Where the irradiation was done in the nitrogen-containing 
atmosphere, a monomolecular film 3" (inner layer) was obtained, as shown 
in FIG. 3, which contained amino groups (--NH.sub.2) 5 added to the vinyl 
groups 2. The addition of the functional groups, i.e., the --OH, 
--NH.sub.2 and --NH groups, to the vinyl groups, was confirmed as a result 
of a FTIR analysis. 
Subsequent to the addition of --OH groups, a solution containing 80% wt 
n-hexadecane, 12% wt carbon tetrachloride and 8% wt chloroform was 
prepared by using 
EQU CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 SiCl.sub.3 
and 
EQU CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 SiCl.sub.3 
as respective chemical adsorption reagents and dissolving these reagents to 
respective concentrations of about 2.times.10.sup.-3 to 5.times.10.sup.-2 
Mol and at a mixing ratio of 3:1 to 1:3, and the glass substrate 1 forming 
the monomolecular film 3', as shown in FIG. 2, was dipped into the 
solution and held for one hour. Since --OH groups 4 were exposed at the 
surface of the substrate 1, the chlorosilic groups of the chlorosilane- 
based surface active material having fluorine and --OH groups 4 were 
reacted. Thus, bonds represented by formulas [4] and [5] were produced on 
the surface substantially at the above mixing ratio. This reaction 
proceeded substantially the same as above in formulas [1] to [3]. 
##STR4## 
Thus, a high concentration monomolecular lamination film 7 can be obtained 
on the surface of the glass substrate 1, as shown in FIG. 4. The film 7 
includes an adsorbed monomolecular film 6 which has a fluorine group and 
surface irregularities. The adsorbed monomolecular film is chemically 
bonded (i.e., covalently bonded) to the inner layer 3'. 
The wetting angle to water, measured at the surface of the adsorbed 
monomolecular film 6, was from 140 to 150 degrees. The measured value 
showed an improvement by about 20 to 30 degrees from 120 degrees, which 
was obtained by using only a single kind of fluorosilane-based surface 
active material. The resultant glass therefore can be used to obtained a 
wiper-free vehicle window glass and to prevent fogging on, for instance, 
glass lens surfaces. 
These effects can be obtained by forming a monomolecular film containing 
alkyl fluoride groups on the outermost substrate surface wherein the alkyl 
fluoride groups have different molecular lengths such as formulas 4 and 5, 
with the surface being substantially pin hole free. 
Where no intermediate monomolecular film is necessary between the surface 
water-repelling, oil-repelling film and the glass substrate, a singularly 
adsorbed monomolecular film 8 containing fluorine may be formed on a glass 
surface, as shown in FIG. 5, by using a chlorosilane-based surface active 
material having fluorine and a mixing ratio of, for example, 1:1. Such a 
glass was shown to have sufficient water- and oil-repelling properties. 
Where a plurality of intermediate monomolecular films are necessary, the 
steps of chemical adsorption and subsequent radiation irradiation are 
repeated a number of times corresponding to the necessary laminated film 
number. For example, CH.sub.2 .dbd.CH(CH.sub.2).sub.16 --SiCl.sub.3 and a 
plurality of different chlorosilane-based surface active materials having 
a fluorine group and different molecular lengths can be adsorbed as 
adsorption reagents. By doing so, a water-repelling, oil-repelling film 
having a single fluorine-containing adsorbed monomolecular film can be 
formed on a glass surface via a number of intermediate laminated 
monomolecular films. 
In the above example, as the reagent for forming the outermost surface 
adsorbed monomolecular film containing fluorine and dimethylsilane or an 
oxygen atom or a carboxy ester the following can be used: 
EQU CF.sub.3 (CH.sub.2).sub.2 Si(CH.sub.3).sub.2 (CH.sub.2).sub.15 SiCl.sub.3, 
EQU F(CF.sub.2).sub.4 (CH.sub.2).sub.2 Si(CH.sub.3).sub.2 (CH.sub.2).sub.9 
SiCl.sub.3, 
EQU CF.sub.3 COO(CH.sub.2).sub.15 SiCl.sub.3, 
EQU CF.sub.3 (CF.sub.2).sub.9 (CH.sub.2).sub.2 SiCl.sub.3, 
EQU CF.sub.3 (CF.sub.2).sub.5 (CH.sub.2).sub.2 SiCl.sub.3 
EXAMPLE 2 
A solution containing 80% wt n-hexadecane, 12% wt carbon tetrachloride and 
8% wt chloroform was prepared by using CF.sub.3 (CF.sub.2).sub.7 
(CF.sub.2).sub.2 SiCl.sub.3 and CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 
SiCl.sub.3 as silane surface active materials. The surface active 
materials were each dissolved to a concentration of 1% wt. A Nylon-6,6 
substrate was dipped into this solution and held at room temperature for 
one hour. Since the surface of the Nylon-6,6 substrate contained imino 
groups (--NH), a reaction between the chlorosilyl groups of the 
chlorosilane-based surface active material and the imino groups formed 
surface bonds as represented in the formulas [6] and [7]. This reaction 
proceeded substantially as in formulas [1] to [3]. 
##STR5## 
Thus, a high concentration monomolecular film 8 can be obtained on the 
surface of the Nylon-6,6 substrate 9 as shown in FIG. 5. The adsorbed 
monomolecular film 8 has a fluorine group and surface irregularities which 
are generally molecular surface irregularities. The adsorbed monomolecular 
film is chemically bonded (i.e., covalently bonded) to the substrate 9. 
The wetting angle to water, measured at the surface of the monomolecular 
adsorbed film 8, was from 140 to 150 degrees. A water-repelling, 
oil-repelling film having a single fluorine-containing monomolecular 
adsorbed film was formed on the substrate 9. 
EXAMPLE 3 
This example, like Example 1, concerns the formation of the 
water-repelling, oil-repelling, antifogging, anti-contaminating film 
coating by the LB process using a tempered glass substrate. 
A blend surface active agent was obtained by mixing two different surface 
active materials, i.e., 
EQU CF.sub.3 (CF.sub.2).sub.7 (CH.sub.2).sub.2 COOH 
and 
EQU CF.sub.3 CH.sub.2 O(CH.sub.2).sub.15 COOH, 
at a mixing ratio of 1:1, and 10 mg was dissolved in 100 g of chloroform. 
The solution was then quietly developed on the water surface. 
A tempered glass substrate as in Example 1 was then dipped at a speed of 1 
cm/min. under a pressure of 50 mN/m and then raised. 
As a result, a film coating having molecular surface irregularities and 
containing alkyl fluoride groups was formed on the tempered glass 
substrate. This film coating had the same water-repelling property as the 
film obtained in Example 1. 
The water-repelling effect obtained in this example is attributable to the 
fact that like Example 1 the monomolecular film containing alkyl fluoride 
groups is formed as the outermost surface layer on the substrate. The 
alkyl fluoride groups are characterized by having different constituent 
molecules different molecular lengths and are substantially pin hole free. 
Any of the above examples can also use two different surface active 
materials in combination. By using three or more different reagents, a 
monomolecular film having three or more different reagents can be 
obtained. Such a monomolecular film has similar water- and oil-repelling 
effects. 
Where a glass surface has a protective film or anti-reflecting film such as 
metal or a metal oxide film, or an infrared-absorbing film such as color 
formed infrared film, a chemically adsorbed film can be formed by 
appropriately controlling the adsorption time so long as the surface has 
hydrophilic groups such as hydroxyl groups. 
Adsorbed films can also be obtained under similar conditions by using, in 
lieu of the above chlorosilane-based surface active materials, 
fluorotitanate-based surface active materials such as a combination of 
F(CF.sub.2).sub.8 Si(CH.sub.3).sub.2 (CH.sub.2).sub.9 
TiOCH(CH.sub.3).sub.2 and CF.sub.3 (CF.sub.2).sub.9 (CH.sub.2).sub.2 
TiOCH(CH.sub.3).sub.2, or F(CF.sub.2).sub.4 (CH.sub.2).sub.2 
Si(CH.sub.3).sub.2 (CH.sub.2).sub.9 TiCl.sub.3, CF.sub.3 (CF.sub.2).sub.5 
(CH.sub.2).sub.2 SiTi.sub.3, or a fluorothiol-based surface active 
material such as a combination of F(CF.sub.2).sub.4 (CH.sub.2).sub.20 
(CH.sub.2).sub.15 SH and CF.sub.3 (CF.sub.2).sub.9 (CH.sub.2).sub.2 SH or 
adsorption liquids which can be obtained by adding, for instance, CH.sub.3 
(CH.sub.2).sub.19 SH to chlorosilane-based or fluorotitanate-based or 
fluorothiol-based surface active agents. 
While the above examples, are primarily concerned with tempered glass 
substrates, the invention is applicable to all kinds of glass, which 
require improved water- and oil-repelling properties such as window glass 
or mirrors used for buildings or vehicles, trains and airplanes or glass 
vessels or lenses. 
With a glass substrate having surface irregularities on the order of 
microns, the anti-contaminating property is slightly inferior. However, 
the water wetting angle is from 145 to 155 degrees, and the water- and 
oil-repelling properties and anti-fogging property are improved. 
The water-repelling, oil-repelling, anti-fogging, anti-contaminating film 
coating according to the invention can be formed not only on glass 
substrates, but the invention is applicable to substrates made of metals 
semiconductors, plastics, etc. as well. 
As has been described in the foregoing, the water-repelling, oil-repelling, 
anti-fogging, anti-contaminating film coating according to the invention 
comprises a monomolecular film formed on a substrate surface and having 
minimal surface irregularities which are generally confined to 
irregularities at the molecular level. Thus, it is possible to form a high 
density organic thin film coating, which is substantially free of pin 
holes, has a uniform thickness, is very thin and has excellent water- and 
oil-repelling properties. That is, with the treatment according to the 
invention, it is possible to obtain a highly durable surface treatment and 
prevent contamination, fogging and wetting of substrate surfaces. 
As has been shown, the invention is greatly beneficial to industry. 
The invention may be embodied in other specific forms without departing 
from the spirit or essential characteristics thereof. The present 
embodiment is to be considered in all respects as illustrative and not 
restrictive, the scope of the invention being indicated by the appended 
claims rather than by the foregoing description and all changes which come 
within the meaning and range of equivalency of the claims are intended to 
be embraced therein.