U.S. patent application number 10/632716 was filed with the patent office on 2004-02-12 for water-repellent film-coated articles, water-repellent film-coating liquid composition and process for preparation of water-repellent film-coated articles.
This patent application is currently assigned to Nippon Sheet Glass Co., Ltd., Japan. Invention is credited to Kamitani, Kazutaka, Yamamoto, Hiroaki.
Application Number | 20040025747 10/632716 |
Document ID | / |
Family ID | 16726388 |
Filed Date | 2004-02-12 |
United States Patent
Application |
20040025747 |
Kind Code |
A1 |
Kamitani, Kazutaka ; et
al. |
February 12, 2004 |
Water-repellent film-coated articles, water-repellent film-coating
liquid composition and process for preparation of water-repellent
film-coated articles
Abstract
There are provided articles coated with high-performance
water-repellent films with high hardness that can withstand outdoor
use, which are water-repellent film-coated articles that comprise a
substrate and a water-repellent film composed mainly of silicon
oxide and having a water-repellent group coated on the surface of
the substrate, and are characterized by containing at least one
type of metal oxide selected from the group consisting of magnesium
oxide, calcium oxide, strontium oxide and boron oxide, as well as a
process for preparation of such water-repellent film-coated
articles at a high rate of productivity and a coating liquid
composition for preparation of such water-repellent film-coated
articles.
Inventors: |
Kamitani, Kazutaka;
(Osaka-fu, JP) ; Yamamoto, Hiroaki; (Osaka-fu,
JP) |
Correspondence
Address: |
EDWARDS & ANGELL, LLP
P.O. BOX 9169
BOSTON
MA
02209
US
|
Assignee: |
Nippon Sheet Glass Co., Ltd.,
Japan
|
Family ID: |
16726388 |
Appl. No.: |
10/632716 |
Filed: |
August 1, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10632716 |
Aug 1, 2003 |
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09822719 |
Mar 30, 2001 |
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6623863 |
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09822719 |
Mar 30, 2001 |
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PCT/JP00/05081 |
Aug 1, 2000 |
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Current U.S.
Class: |
106/287.1 ;
106/287.14; 428/447 |
Current CPC
Class: |
C09D 183/00 20130101;
C09D 1/00 20130101; C03C 17/009 20130101; Y10T 428/31612 20150401;
Y10T 428/31663 20150401 |
Class at
Publication: |
106/287.1 ;
106/287.14; 428/447 |
International
Class: |
C09K 003/00; B32B
009/04 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 2, 1999 |
JP |
H11(99)-218855 |
Claims
What is claimed is;
1. A water-repellent film-coated article comprising a substrate and
a water-repellent film, composed of silicon oxide and at least one
of metal oxide selected from the group consisting of magnesium
oxide, calcium oxide, strontium oxide and boron oxide and having a
water-repellent group, coated on the surface of the substrate.
2. A water-repellent film-coated article according to claim 1,
wherein said water-repellent film contains silicon oxide at 70-99
mole percent (based on SiO.sub.2), at least one of metal oxide
selected from the group consisting of magnesium oxide, calcium
oxide, strontium oxide and boron oxide at a total of 1-30 mole
percent (based on MgO, CaO, SrO and BO.sub.3/2), and a
water-repellent group at 0.01-20 wt %.
3. A water-repellent film-coated article according to claim 2,
wherein said water-repellent film further contains, in terms of
mole percent, at least one of metal oxide selected from the group
consisting of zirconium oxide, aluminum oxide, gallium oxide,
indium oxide, scandium oxide, yttrium oxide, lanthanumoxide,
ceriumoxide, cobalt oxide, iron oxide, nickel oxide, copper oxide
and zinc oxide at 0.5-5%, based on ZrO.sub.2, AlO.sub.3/2,
GaO.sub.3/2, InO.sub.3/2, ScO.sub.3/2, YO.sub.3/2, LaO.sub.3/2,
CeO.sub.3/2, CoO, FeO.sub.3/2, NiO.sub.2, CuO and ZnO.
4. A water-repellent film-coated article according to claim 1,
wherein said water-repellent film contains silicon oxide at 70-98
mole percent (based on SiO.sub.2), magnesium oxide and/or calcium
oxide at 1-29 mole percent (based on MgO and CaO), boron oxide
and/or zirconium oxide at 1-29 mole percent (based on BO.sub.3/2
and ZrO.sub.2) and a water-repellent group at 0.01-20 wt %.
5. A water-repellent film-coated article according to claim 4,
wherein said water-repellent film further contains, in terms of
mole percent, at least one of metal oxide selected from the group
consisting of aluminum oxide, gallium oxide, indium oxide, scandium
oxide, yttrium oxide, lanthanum oxide, cerium oxide, cobalt oxide,
iron oxide, nickel oxide, copper oxide and zinc oxide at 0.5-5%,
based on AlO.sub.3/2, GaO.sub.3/2, InO.sub.3/2, ScO.sub.3/2,
YO.sub.3/2, LaO.sub.3/2, CeO.sub.3/2, CoO, FeO.sub.3/2, NiO.sub.2,
CuO and ZnO.
6. A water-repellent film-coated article according to any one of
claims 1 to 5, wherein said water-repellent group is an alkyl group
or fluoroalkyl group.
7. A water-repellent film-coating composition containing (A) a
thoroughly hydrolyzable silane compound, (B) a silane compound with
a water-repellent group, (C) an acid and (D) a compound of at least
one of metal selected from the group consisting of magnesium,
calcium, strontium and boron.
8. A water-repellent film-coating composition according to claim 7
which contains said silane compound (A) at 0.01-2 wt % based on
Sio.sub.2, said silane compound (B) at 0.00001-0.15 wt % based on
SiO.sub.2, said acid at 0.001-3 N, water at 0-5 wt % and said
compound (D) at a molar ratio of 0.01-0.4, based on MgO, CaO, SrO
and BO.sub.3/2, with respect to said silane compound (A).
9. A water-repellent film-coating composition according to claim 7
or 8 which contains an alcohol as a solvent.
10. A water-repellent film-coating composition containing (A) a
thoroughly hydrolyzable silane compound or its hydrolysate at
0.01-2 wt % (based on SiO.sub.2), (B) a silane compound with a
water-repellent group at 0.00001-0.15 wt % (based on SiO.sub.2),
(C) an acid at 0.001-3 N, (D-1) amagnesium and/or calcium compound
at amolar ratio of 0.01-0.4, based on MgO and CaO, with respect to
said silane compound (A) (based on SiO.sub.2), (D-2) a boron and/or
zirconium compound at a molar ratio of 0.01-0.4, based on
BO.sub.3/2 and ZrO.sub.2, with respect to said silane compound (A)
(based on SiO.sub.2), (E) a compound of at least one of metal
selected from the group consisting of cobalt, iron, nickel, copper,
aluminum, gallium, indium, scandium, yttrium, lanthanum, cerium and
zinc at amolar ratio of 0-0.4, based on CoO, FeO.sub.3/2,
NiO.sub.2, CuO, AlO.sub.3/2, GaO.sub.3/2, InO.sub.3/2, ScO.sub.3/2,
YO.sub.3/2, LaO.sub.3/2, CeO.sub.3/2 and ZnO, with respect to said
silane compound (A) (based on SiO.sub.2), and (F) water at 0-20 wt
%.
11. A water-repellent film-coating composition according to claim
10 which contains an alcohol as the solvent.
12. A water-repellent film-coating composition according to any one
of claims 7 to 11, wherein said silane compound (A) is a
tetraalkoxysilane or tetrachlorosilane.
13. A water-repellent film-coating composition according to any one
of claims 7 to 12, wherein said acid is hydrochloric acid, nitric
acid, acetic acid, formic acid or trifluoroacetic acid.
14. A process for preparation of a water-repellent film-coated
article, characterized by applying a water-repellent film-coating
composition according to any one of claims 7 to 13 onto a substrate
surface and drying it.
15. A process for preparation of a water-repellent film-coated
article according to claim 14, wherein said drying is carried out
at room temperature.
16. A process for preparation of a water-repellent film-coated
article according to claim 14 or 15, wherein said drying is carried
out in an atmosphere at 40% relative humidity or lower.
17. A process for preparation of a water-repellent film-coated
article according to any one of claims 14 to 16, wherein said
drying is followed by heating at a temperature of from room
temperature up to 300.degree. C.
18. A process for preparation of a water-repellent film-coated
article according to any one of claims 14 to 16, wherein said
drying is followed by heating at a temperature of from room
temperature up to 150.degree. C.
Description
TECHNICAL FIELD
[0001] The present invention relates to articles provided with a
water-repellent film coating formed integrally with an primary
oxide film on the surface of a substrate made of glass, ceramic,
plastic, metal or the like, to a water-repellent film-coating
composition and to a process for preparation of water-repellent
film-coated articles.
BACKGROUND ART
[0002] The following techniques for formation of highly durable
water-repellent films on the surfaces of glass plates and other
substrates at a high rate of productivity are known, which involve
formation of a single film on a substrate using a mixed solution of
a primary layer component and a water-repellent component which
gives a primary layer and a water-repellent layer.
[0003] In Japanese Unexamined Patent Publication No. 4-338137 there
is disclosed a water-repellent glass characterized by applying of a
solution comprising a mixture of a silicon alkoxide or a
substituted silicon alkoxide wherein a portion of the alkoxyl
groups are substituted with fluoroalkyl groups, an alcohol, water
and an acid (or base) onto a glass substrate surface and
sintering.
[0004] In Japanese Unexamined Patent Publication No. 8-239653 there
are disclosed water-repellent articles treated with a composition
comprising a mixture of a perfluoroalkylalkylsilane and a
thoroughly hydrolyzable silane (for example, tetrachlorosilane)
dissolved in a solvent, preferably a non-aqueous solvent.
[0005] In Japanese Unexamined Patent Publication No. 11-71682 there
are disclosed water-repellent film-coated articles treated with a
composition comprising a chlorosilyl group-containing compound and
a fluoroalkyl group-containing silane compound dissolved in an
alcohol-based solvent.
[0006] In these conventional techniques, the final water-repellent
article has been obtained by applying the coating solution onto the
surface of the glass plate or the other substrate and then
sintering at a temperature of 100-250.degree. C. which is lower
than the decomposition temperature of the fluoroalkyl groups
(250-300.degree. C.), or simply drying at ordinary temperature. The
films obtained by these techniques are known as sol-gel
water-repellent films and are obtained through a process whereby a
hydrolyzable silane compound and a silane compound with a
water-repellent group are hydrolyzed in a solution, subjected to
dehydration/condensation reaction and then coated and dried on a
substrate; in the sol-gel film, however, the solvent progressively
evaporates as oxide bonds are formed, and therefore fine pores are
present in the film when it is dried at 400.degree. C. or below, so
that the film does not have high hardness. In order to avoid the
pores for increased film hardness, it has been essential to
accomplish sintering at 500-600.degree. C. However, heating at such
high temperatures results in decomposition of the fluoroalkyl
groups, making it impossible to achieve the desired water
repellency. Consequently, water-repellent films obtained by the
aforementioned technique of sintering at 250.degree. C. or below,
while being composed mainly of oxides, have not had the high
hardness as oxides and ceramics which is achieved by, for example,
melt methods.
[0007] When such water-repellent film-coated articles are used
outdoors, for example, their exposure to such conditions as blown
sand readily results in damage to the film surface, thus impairing
the water-repellent property. The water-repellent film can also be
damaged or peeled when the surface is wiped with a cloth or the
like to remove attached dust, dirt or sand. Even in the absence of
attached dust, etc., abrasion with a cloth or brush made of hard
fibers (such as surface wiping of automobile window glass with a
wiper, for example) forms small nicks and further promote
deterioration of the water-repellent film.
[0008] It is an object of the present invention, which has been
accomplished in light of these problems, to provide articles coated
with high-performance water-repellent films having high hardness
that can withstand outdoor use, a process for preparation of such
water-repellent film-coated articles at a high rate of
productivity, and a coating liquid composition for preparation of
such water-repellent film-coated articles.
DISCLOSURE OF THE INVENTION
[0009] As a result of much diligent research by the present
inventors aimed at overcoming the aforementioned problems, it has
been discovered that by providing a primary oxide film with two or
more components including SiO.sub.2 and at least one type selected
from among MgO, CaO, SrO and B.sub.2O.sub.3 in a water-repellent
film-coated article having a primary oxide layer and a
water-repellent layer integrally formed by a single coating
treatment, the hardness of the water-repellent film with the
integrally formed primary layer and water-repellent layer is
drastically improved.
[0010] In other words, the present invention relates to a
water-repellent film-coated article comprising a substrate and a
water-repellent film composed mainly of silicon oxide and having a
water-repellent group coated on the surface of the substrate, the
water-repellent film-coated article being characterized in that the
water-repellent film contains at least one type of metal oxide
selected from the group consisting of magnesium oxide, calcium
oxide, strontium oxide and boron oxide.
[0011] For formation of oxide films by a sol-gel method it is
common to use a silicon alkoxide as the starting material, and this
is because the reactivity of silicon alkoxides readily gives a
uniform, transparent film by a milder reaction than with alkoxides
of elements other than silicon. However since, as mentioned above,
the solvent progressively evaporates as bonds (siloxane bonds) are
formed between the Si (silicon) and O (oxygen) by
dehydration/condensation reaction in the sol-gel method, a porous
silica film is obtained wherein fine pores are present in the film.
Since the Si and O bonds are covalent bonds and Si and O bond with
a high bonding energy, when siloxane bonds form a somewhat
three-dimensional structure at the solvent volatilization stage,
contraction of the structure is suppressed even with subsequent
further dehydration/condensation reaction, such that a volatilized
portion of the solvent and the alcohol produced by the
dehydration/condensation reaction remains as fine pores, with
silanol or unreacted alkoxyl groups present in the fine pores. The
hardness of the porous silica film is not very high because of its
porosity. When the film is heated at a temperature of 500.degree.
C. or above, the fine pores in the film disappear producing a
non-porous silica film with high hardness, but it is difficult to
form an integral film with high hardness containing substances that
decompose at the heating temperature.
[0012] According to the invention, the strong ionic nature of
magnesium (Mg), calcium (Ca) and strontium (Sr) is utilized: they
are dissolved in the coating solution to be copresent with the
thoroughly hydrolyzable silane compound, such as a silicon
alkoxide, and exist in an ionic state in the solution even at the
solvent volatilization stage. Because Mg, Ca and Sr are divalent,
they react with silanol, eventually bonding with two oxygen atoms
in the film interior as shown in Equation (1), and forming an
"O.sup.-+M.sup.+-O " bond which has a freer bonding orientation
than an "Si--O--Si" bond, to thereby fill in the gaps of the
siloxane skeleton. 1
[0013] When simply dried at normal temperature, for example, this
film has about the same hardness as if a silica component alone was
used, but heating at a temperature of 50-300.degree. C. contracts
the siloxane bonds by action of the Mg (or Ca or Sr), and this
eliminates pores and results in a film with high hardness and high
durability comparable to inorganic glass prepared by a melt method.
That is, while heating at a temperature of 500.degree. C. or above
is necessary to eliminate the pores of a simple porous silica film,
the porous silica-based film of the invention which contains MgO,
CaO or SrO can be rendered pore-free at a temperature of
200.degree. C. or more below that temperature. Furthermore, since
the film is heated at a temperature lower than the decomposition
temperature of the water-repellent groups such as fluoroalkyl
groups or alkyl groups (300.degree. C. or higher), the fluoroalkyl
groups or alkyl groups contained in the coating solution reside on
the film surface without decomposition, thus providing excellent
water repellency and durability. When only a silica component with
water-repellent groups is present, the film has insufficient
hardness and low durability with heat hardening at 300.degree. C.
or below, and heating at a temperature of 500.degree. C. or above
is necessary to eliminate the film pores and increase the film
hardness, which in turn sacrifices the high water repellency.
[0014] Addition of an oxide of boron (B) to the silica also
provides a low temperature hardening property and gives a pore-free
film with high hardness by heating at a temperature of 300.degree.
C. or below, as with addition of Mg, Ca or Sr described above.
While it is not yet fully understood why B exhibits a similar
effect as Mg, Ca and Sr, it is thought to be attributable to a
change in the configuration of oxygen due to the heating
immediately after coating.
[0015] If the content of magnesium oxide, calcium oxide, strontium
oxide and boron oxide in the water-repellent film is too low the
low temperature hardening effect will not be obtained, while if it
is too high the oxides will segregate to a non-uniform condition,
thus lowering the film hardness; the water-repellent film therefore
preferably contains silicon oxide, magnesium oxide, calcium oxide,
strontium oxide and boron oxide in the following proportions, based
on SiO.sub.2, MgO, CaO, SrO and BO.sub.3/2, respectively:
[0016] silicon oxide at 70-99%, and
[0017] at least one type of metal oxide selected from the group
consisting of magnesium oxide, calcium oxide, strontium oxide and
boron oxide at a total of 1-30%,
[0018] in terms of mole percent; the water-repellent film also
preferably contains silicon oxide, magnesium oxide, calcium oxide,
boron oxide and zirconium oxide in the following proportions, based
on SiO.sub.2, MgO, CaO, BO.sub.3/2 and ZrO.sub.2, respectively:
[0019] silicon oxide at 70-98%,
[0020] magnesium oxide and/or calcium oxide at 1-29%,
[0021] and boron oxide and/or zirconium oxide at 1-29%,
[0022] in terms of mole percent.
[0023] Certain combinations among these give superior low
temperature hardening properties. Specifically, they are the four
combinations Si-Mg-B, Si-Ca-B, Si-Mg-Zr and Si-Ca-Zr. These sol-gel
oxide films harden by, for example, heating at 200-250.degree. C.
for films with a film thickness of about 150 nm and heating at
about 100.degree. C. for films with a film thickness of a few dozen
nm or less, giving water-repellent films with high hardness.
[0024] Thus, according to the present invention an oxide film of
two or more components including silicon oxide and at least one
type selected from among magnesium oxide, calcium oxide, strontium
oxide and boron oxide as essential components is used as the
primary oxide layer to allow elimination of pores from the primary
oxide film at below the decomposition temperature of the
water-repellent layer. Water-repellent film-coated articles
obtained thereby have high hardness or durability that has not been
possible in the past with water-repellent film-coated articles with
integrally formed primary oxide layers and water-repellent layers
by a single coating treatment.
[0025] The low temperature hardening property of the
water-repellent film of the invention is not impaired even when a
transition metal element or the like is further introduced into the
silica film for the purpose of adding another function in addition
to the water-repellent function, such as control of the refractive
index of the film or control of the visible light transmittance. In
other words, by including a metal element exhibiting a desired
function along with the Mg, Ca, Sr or B it is possible to obtain a
multifunctional film having very high hardness even with heating at
a temperature of 300.degree. C. or below, while also having both
water-repellent and other functions. For example, addition of
cobalt oxide, iron oxide, nickel oxide or copper oxide will impart
coloring to the water-repellent film.
[0026] When the water-repellent film of the invention contains
zirconium oxide, it may include as other components cobalt oxide,
iron oxide, nickel oxide, copper oxide, aluminum oxide, gallium
oxide, indium oxide, scandium oxide, yttrium oxide, lanthanum
oxide, cerium oxide and zinc oxide at a total of 0.5-5% in terms of
mole percent, based on CoO, FeO.sub.3/2, NiO.sub.2, CuO,
AlO.sub.3/2, GaO.sub.3/2, InO.sub.3/2, ScO.sub.3/2, YO.sub.3/2,
LaO.sub.3/2, CeO.sub.3/2 and ZnO.
[0027] When the water-repellent film of the invention contains no
zirconium oxide, it may include as other components cobalt oxide,
iron oxide, nickel oxide, copper oxide, zirconiumoxide, aluminum
oxide, gallium oxide, indium oxide, scandium oxide, yttrium oxide,
lanthanum oxide, cerium oxide and zinc oxide at a total of 0.5-5%
in terms of mole percent, based on CoO, FeO.sub.3/2, NiO.sub.2,
CuO, ZrO.sub.2, AlO.sub.3/2, GaO.sub.3/2, InO.sub.3/2, SCO.sub.3/2,
YO.sub.3/2, LaO.sub.3/2, CeO.sub.3/2 and ZnO.
[0028] In either case, addition of these components at a total in
excess of 5 mole percent may produce an undesirable appearance,
such as film peeling or film whitening.
[0029] If the thickness of the water-repellent film is too great
the film hardness will tend to be lower, and if it is too small the
film durability will tend to be lower. The thickness of the
water-repellent film is therefore preferably 5-200 nm, more
preferably 5-100 nm and even more preferably 5-50 nm. The
water-repellent film preferably contains the water-repellent
groups, for example alkyl groups or fluoroalkyl groups, at 0.01-20
wt %. The water-repellent groups are present at a high density on
the outer surface of the water-repellent film.
[0030] The present invention also provides a water-repellent
film-coating composition containing
[0031] (A) a thoroughly hydrolyzable silane compound,
[0032] (B) a silane compound with a water-repellent group,
[0033] (C) an acid and
[0034] (D) at least one metal compound selected from the group
consisting of magnesium, calcium, strontium and boron.
[0035] The thoroughly hydrolyzable silane compound (A) according to
the invention is not particularly limited, and tetraalkoxysilanes
such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane
and tetrabutoxysilane, as well as tetrachlorosilane,
tetraacyloxysilane and tetraisocyanatesilane may be mentioned.
Tetraalkoxysilanes are preferred for use among these because of
their relative ease of handling. Among tetraalkoxysilanes, those of
relatively low molecular weight, for example tetraalkoxysilanes
comprising alkoxyl groups of 3 or fewer carbon atoms, are preferred
for use because they readily give dense films. Also, polymers of
these tetraalkoxysilanes, with average polymerization degrees of 5
or lower, are preferred for use.
[0036] The silane compound with a water-repellent group (B)
according to the invention is a silane compound with one, two or
more water-repellent groups (alkyl groups, fluoroalkyl groups,
etc.) in the molecule, and there may be mentioned silane compounds
which are the aforementioned silane compounds (A) a portion of
which is substituted with an alkyl group and/or fluoroalkyl
group.
[0037] Examples of alkyl group-containing silane compounds include
alkyl group-containing chlorosilanes such as
[0038] CH.sub.3(CH.sub.2).sub.30SiCl.sub.3,
CH.sub.3(CH.sub.2).sub.20SiCl.- sub.3,
[0039] CH.sub.3(CH.sub.2).sub.18 SiCl.sub.3,
CH.sub.3(CH.sub.2).sub.16SiCl- .sub.3,
[0040] CH.sub.3(CH.sub.2).sub.14SiCl.sub.3,
CH.sub.3(CH.sub.2).sub.12SiCl.- sub.3,
[0041] CH.sub.3(CH.sub.2).sub.10SiCl.sub.3,
CH.sub.3(CH.sub.2).sub.9SiCl.s- ub.3,
[0042] CH.sub.3(CH.sub.2) SiCl.sub.3,
CH.sub.3(CH.sub.2).sub.7SiCl.sub.3,
[0043] CH.sub.3(CH.sub.2).sub.6SiCl.sub.3,
CH.sub.3(CH.sub.2).sub.5SiCl.su- b.3,
[0044] CH.sub.3(CH.sub.2).sub.4SiCl.sub.3,
CH.sub.3(CH.sub.2).sub.3SiCl.su- b.3,
[0045] CH.sub.3(CH.sub.2).sub.2SiCl.sub.3,
CH.sub.3CH.sub.2SiCl.sub.3,
[0046] (CH.sub.3CH.sub.2).sub.2SiCl.sub.2,
(CH.sub.3CH.sub.2).sub.3SiCl,
[0047] CH.sub.3SiCl.sub.3, (CH.sub.3).sub.2SiCl.sub.2,
(CH.sub.3).sub.3SiCl;
[0048] alkyl group-containing alkoxysilanes such as
[0049] CH.sub.3(CH.sub.2).sub.30Si(OCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.20Si(OCH.sub.3).sub.3,
[0050] CH.sub.3(CH.sub.2),.sub.18Si(OCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.6Si(OCH.sub.3).sub.3,
[0051] CH.sub.3(CH.sub.2).sub.14Si(OCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.12Si(OCH.sub.3).sub.3,
[0052] CH.sub.3(CH.sub.2).sub.10Si(OCH.sub.3).sub.3 ,
CH.sub.3(CH.sub.2).sub.9Si(OCH.sub.3).sub.3,
[0053] CH.sub.3(CH.sub.2).sub.8Si(OCH.sub.3).sub.3 ,
CH.sub.3(CH.sub.2).sub.7Si(OCH.sub.3).sub.3,
[0054] CH.sub.3(CH.sub.2).sub.6Si(OCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.5Si(OCH.sub.3).sub.3,
[0055] CH.sub.3(CH.sub.2).sub.4Si(OCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.3Si(OCH.sub.3).sub.3,
[0056] CH.sub.3(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
CH.sub.3CH.sub.2Si(OCH.sub.3).sub.3,
[0057] (CH.sub.3CH.sub.2).sub.2Si(OCH.sub.3).sub.2,
(CH.sub.3CH.sub.2).sub.3SiOCH.sub.3,
[0058] CH.sub.3SI(OCH.sub.3).sub.3,
(CH.sub.3).sub.2Si(OCH.sub.3).sub.2,
(CH.sub.3).sub.3SiOCH.sub.3,
[0059] CH.sub.3(CH.sub.2).sub.30Si(OC.sub.2H.sub.5).sub.3,
CH.sub.3(CH.sub.2).sub.20Si(OC.sub.2H.sub.5).sub.3,
[0060] CH.sub.3(CH.sub.2).sub.18Si(OC.sub.2H.sub.5).sub.3,
CH.sub.3(CH.sub.2).sub.16Si(OC.sub.2H.sub.5).sub.3 ,
[0061] CH.sub.3(CH.sub.2).sub.14Si(OC.sub.2H.sub.5).sub.3,
CH.sub.3(CH.sub.2).sub.12Si(OC.sub.2H.sub.5).sub.3,
[0062] CH.sub.3(CH.sub.2).sub.10Si(OC.sub.2H.sub.5).sub.3,
CH.sub.3(CH.sub.2).sub.9Si(OC.sub.2H.sub.5).sub.3,
[0063] CH.sub.3(CH.sub.2).sub.8Si(OC.sub.2H.sub.5).sub.3,
CH.sub.3(CH.sub.2).sub.7Si(OC.sub.2H.sub.5).sub.3,
[0064] CH.sub.3(CH.sub.2).sub.6Si(OC.sub.2H.sub.5).sub.3,
CH.sub.3(CH.sub.2).sub.5Si(OC.sub.2H.sub.5).sub.3,
[0065] CH.sub.3(CH.sub.2).sub.4Si(OC.sub.2H.sub.5).sub.3,
CH.sub.3(CH.sub.2).sub.3Si(OC.sub.2H.sub.5).sub.3,
[0066] CH.sub.3(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
CH.sub.3CH.sub.2Si(OC.sub.2H.sub.5).sub.3,
[0067] (CH.sub.3CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.2,
(CH.sub.3CH.sub.2).sub.3SiOC.sub.2H.sub.5,
[0068] CH.sub.3Si(OC.sub.2H.sub.5).sub.3,
(CH.sub.3).sub.2Si(OC.sub.2H.sub- .5).sub.2,
(CH.sub.3).sub.3SiOC.sub.2H.sub.5;
[0069] alkyl group-containing acyloxysilanes such as
[0070] CH.sub.3(CH.sub.2).sub.30Si(OCOCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.20Si(OCOCH.sub.3).sub.3,
[0071] CH.sub.3(CH.sub.2).sub.18Si(OCOCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.16Si(OCOCH.sub.3).sub.3,
[0072] CH.sub.3(CH.sub.2).sub.14Si(OCOCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.12Si(OCOCH.sub.3).sub.3,
[0073] CH.sub.3(CH.sub.2).sub.10Si(OCOCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.9Si(OCOCH.sub.3).sub.3,
[0074] CH.sub.3(CH.sub.2).sub.8Si(OCOCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.7Si(OCOCH.sub.3).sub.3,
[0075] CH.sub.3(CH.sub.2).sub.6Si(OCOCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.5Si(OCOCH.sub.3).sub.3,
[0076] CH.sub.3(CH.sub.2).sub.4Si(OCOCH.sub.3).sub.3,
CH.sub.3(CH.sub.2).sub.3Si(OCOCH.sub.3).sub.3,
[0077] CH.sub.3(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
CH.sub.3CH.sub.2Si(OCOCH.sub.3).sub.3,
[0078] (CH.sub.3CH.sub.2).sub.2Si(OCOCH.sub.3).sub.2,
(CH.sub.3CH.sub.2 ) .sub.3SiOCOCH.sub.3,
[0079] CH.sub.3Si(OCOCH.sub.3).sub.3,
(CH.sub.3).sub.2Si(OCOCH.sub.3).sub.- 2,
[0080] (CH.sub.3).sub.3SiOCOCH.sub.3;
[0081] and alkyl group-containing isocyanatesilanes such as
[0082] CH.sub.3(CH.sub.2).sub.30Si(NCO).sub.3,
CH.sub.3(CH.sub.2).sub.20Si- (NCO).sub.3,
[0083] CH.sub.3(CH.sub.2).sub.18Si(NCO).sub.3,
CH.sub.3(CH.sub.2).sub.16Si- (NCO).sub.3,
[0084] CH.sub.3(CH.sub.2).sub.14Si(NCO).sub.3,
CH.sub.3(CH.sub.2).sub.12Si- (NCO).sub.3,
[0085] CH.sub.3(CH.sub.2).sub.10Si(NCO).sub.3,
CH.sub.3(CH.sub.2).sub.9Si(- NCO).sub.3,
[0086] CH.sub.3(CH.sub.2).sub.8Si(NCO).sub.3,
CH.sub.3(CH.sub.2).sub.7Si(N- CO).sub.3,
[0087] CH.sub.3(CH.sub.2).sub.6Si(NCO).sub.3,
CH.sub.3(CH.sub.2).sub.5Si(N- CO).sub.3,
[0088] CH.sub.3(CH.sub.2).sub.4Si(NCO).sub.3,
CH.sub.3(CH.sub.2).sub.3Si(N- CO).sub.3,
[0089] CH.sub.3(CH.sub.2).sub.2Si(NCO).sub.3,
CH.sub.3CH.sub.2Si(NCO).sub.- 3,
[0090] (CH.sub.3CH.sub.2).sub.2Si(NCO).sub.2,
(CH.sub.3CH.sub.2).sub.3SiNC- O,
[0091] CH.sub.3Si(NCO).sub.3, (CH.sub.3).sub.2Si(NCO).sub.2,
[0092] (CH.sub.3).sub.3SiNCO.
[0093] Among these alkyl group-containing silane compounds it is
preferred to use chlorosilanes, alkoxysilanes, acyloxysilanes and
isocyanatesilanes containing alkyl groups of 8 or more carbon
atoms, such as the following.
[0094] Octyltrimethyoxysilane
CH.sub.3(CH.sub.2).sub.7Si(OCH.sub.3).sub.3,
[0095] octyltrichlorosilane
CH.sub.3(CH.sub.2).sub.7Si(Cl).sub.3,
[0096] nonyltrimethoxysilane
CH.sub.3(CH.sub.2).sub.8Si(OCH.sub.3).sub.3,
[0097] nonyltrichlorosilane
CH.sub.3(CH.sub.2).sub.8Si(Cl).sub.3,
[0098] decyltrimethoxysilane
CH.sub.3(CH.sub.2).sub.9Si(OCH.sub.3).sub.3,
[0099] decyltrichlorosilane
CH.sub.3(CH.sub.2).sub.9Si(Cl).sub.3,
[0100] undecyltrimethoxysilane
CH.sub.3(CH.sub.2).sub.10Si(OCH.sub.3).sub.- 3,
[0101] undecyltrichlorosilane
CH.sub.3(CH.sub.2).sub.10Si(Cl).sub.3,
[0102] dodecyltrimethoxysilane
CH.sub.3(CH.sub.2).sub.11Si(OCH.sub.3).sub.- 3,
[0103] dodecyltrichlorosilane
CH.sub.3(CH.sub.2).sub.11Si(Cl).sub.3.
[0104] Examples of fluoroalkyl group-containing silane compounds
include fluoroalkyl group-containing trichlorosilanes such as
[0105] CF.sub.3(CF.sub.2 ).sub.11(CH.sub.2).sub.2SiCl.sub.3,
[0106] CF.sub.3(CF.sub.2).sub.10(CH.sub.2).sub.2Si(Cl).sub.3,
[0107] CF.sub.3(CF.sub.2).sub.9(CH.sub.2).sub.2SiCl.sub.3,
[0108] CF.sub.3(CF.sub.2).sub.8(CH.sub.2 ).sub.2SiCl.sub.3,
[0109] CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2SiCl.sub.3,
[0110] CF.sub.3(CF.sub.2).sub.6(CH.sub.2).sub.2SiCl.sub.3,
[0111] CF.sub.3(CF.sub.2 ).sub.5(CH.sub.2 ).sub.2SiCl.sub.3,
[0112] CF.sub.3(CF.sub.2).sub.4(CH.sub.2).sub.2SiCl.sub.3,
[0113] CF.sub.3(CF.sub.2).sub.3(CH.sub.2).sub.2SiCl.sub.3,
[0114] CF.sub.3(CF.sub.2 ).sub.2 l (CH.sub.2 ).sub.2SiCl.sub.3
,
[0115] CF.sub.3CF.sub.2 (CH.sub.2 ) .sub.2SiCl3,
[0116] CF.sub.3 (CH.sub.2 ).sub.2SiCl.sub.3;
[0117] fluoroalkyl group-containing trialkoxysilanes such as
[0118]
CF.sub.3(CF.sub.2).sub.11(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
[0119]
CF.sub.3(CF.sub.2).sub.10(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
[0120]
CF.sub.3(CF.sub.2).sub.9(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
[0121] CF.sub.3(CF.sub.2).sub.8(CH.sub.2).sub.2Si(OCH.sub.3) 3,
[0122]
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
[0123]
CF.sub.3(CF.sub.2).sub.6(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
[0124]
CF.sub.3(CF.sub.2).sub.5(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
[0125]
CF.sub.3(CF.sub.2).sub.4(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
[0126] CF.sub.3 (CF.sub.2 ).sub.3 (CH.sub.2 ).sub.2Si(OCH.sub.3)
.sub.3,
[0127]
CF.sub.3(CF.sub.2).sub.2(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
[0128] CF.sub.3CF.sub.2 (CH.sub.2).sub.2Si (OCH.sub.3) .sub.3,
[0129] CF.sub.3 (CH.sub.2).sub.2Si(OCH.sub.3) .sub.3,
[0130]
CF.sub.3(CF.sub.2).sub.11(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0131]
CF.sub.3(CF.sub.2).sub.10(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0132]
CF.sub.3(CF.sub.2).sub.9(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0133]
CF.sub.3(CF.sub.2).sub.8(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0134]
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0135]
CF.sub.3(CF.sub.2).sub.6(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0136]
CF.sub.3(CF.sub.2).sub.5(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0137]
CF.sub.3(CF.sub.2).sub.4(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0138]
CF.sub.3(CF.sub.2).sub.3(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0139]
CF.sub.3(CF.sub.2).sub.2(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0140]
CF.sub.3CF.sub.2(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3,
[0141] CF.sub.3(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3;
[0142] fluoroalkyl group-containing triacyloxysilanes such as
[0143]
CF.sub.3(CF.sub.2).sub.11(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0144]
CF.sub.3(CF.sub.2).sub.10(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0145]
CF.sub.3(CF.sub.2).sub.9(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0146]
CF.sub.3(CF.sub.2).sub.8(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0147]
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0148]
CF.sub.3(CF.sub.2).sub.6(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0149]
CF.sub.3(CF.sub.2).sub.5(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0150]
CF.sub.3(CF.sub.2).sub.4(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0151]
CF.sub.3(CF.sub.2).sub.3(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0152]
CF.sub.3(CF.sub.2).sub.2(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0153] CF.sub.3CF.sub.2(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3,
[0154] CF.sub.3(CH.sub.2).sub.2Si(OCOCH.sub.3).sub.3;
[0155] and fluoroalkyl group-containing triisocyanatesilanes such
as
[0156] CF.sub.3(CF.sub.2).sub.11(CH.sub.2).sub.2Si(NCO).sub.3,
[0157] CF.sub.3(CF.sub.2).sub.10(CH.sub.2).sub.2Si(NCO).sub.3,
[0158] CF.sub.3(CF.sub.2).sub.9(CH.sub.2).sub.2Si(NCO).sub.3,
[0159] CF.sub.3(CF.sub.2).sub.8(CH.sub.2).sub.2Si(NCO).sub.3,
[0160] CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2Si(NCO).sub.3,
[0161] CF.sub.3(CF.sub.2).sub.6(CH.sub.2).sub.2Si(NCO).sub.3,
[0162] CF.sub.3(CF.sub.2).sub.5 (CH.sub.2).sub.2Si(NCO).sub.3,
[0163] CF.sub.3(CF.sub.2).sub.4 (CH.sub.2).sub.2Si (NCO)
.sub.3,
[0164] CF.sub.3(CF.sub.2).sub.3(CH.sub.2).sub.2Si(NCO).sub.3,
[0165] CF.sub.3(CF.sub.2).sub.2(CH.sub.2).sub.2Si(NCO).sub.3,
[0166] CF.sub.3CF.sub.2(CH.sub.2).sub.2Si(NCO).sub.3,
[0167] CF.sub.3(CH.sub.2).sub.2Si(NCO).sub.3.
[0168] Among these fluoroalkyl group-containing silane compounds
there are preferred trichlorosilanes, trialkoxysilanes and
triisocyanatesilanes containing fluoroalkyl groups with 10 or more
fluorine atoms, of which
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2Si(OCH.sub.3).sub.3
(heptadecafluorodecyl trimethoxysilane) and
CF.sub.3(CF.sub.2).sub.7 (CH.sub.2).sub.2SiCl.sub.3
(heptadecafluorodecyl trichlorosilane) are particularly
preferred.
[0169] The acid (C) according to the invention is preferably a
volatile acid such as hydrochloric acid, hydrofluoric acid, nitric
acid, acetic acid, formic acid, trifluoroacetic acid or the like
from the standpoint of volatilization by drying at ordinary
temperature without remaining in the film, and hydrochloric acid is
particularly preferred among these because of its high degree of
electrolytic dissociation and volatilization and its relative
safety during handling.
[0170] At least one type of metal compounds selected from the group
consisting of magnesium, calcium, strontium and boron (D) according
to the invention may be any chlorides, oxychlorides, oxides,
hydroxides, nitrates, oxynitrates, etc. of the aforementioned
metals, so long as they undergo simple electrolytic dissociation to
dissolve in water or alcohol. Among these, it is particularly
preferred to use chlorides, oxychlorides, nitrates and
oxynitrates.
[0171] Specific examples for component (D) include MgCl.sub.2,
Mg(NO.sub.3).sub.2, CaCl.sub.2, Ca(NO.sub.3).sub.2, SrCl.sub.2,
Sr(NO.sub.3).sub.2 and H.sub.3BO.sub.3.
[0172] The zirconium oxide is not an essential component, but
including it with the magnesium oxide or calcium oxide increases
the low temperature hardening property, and therefore a zirconium
compound, for example a chloride, oxychloride, oxide, hydroxide,
nitrate or oxynitrate, which undergoes simple electrolytic
dissociation to dissolve in water or alcohol, may be included in
the water-repellent film-coating composition. Specific examples of
such compounds include ZrOCl.sub.2 and ZrO(NO.sub.3).sub.2.
[0173] As an additional component (component (E)) there may be
added to the water-repellent film-coating composition at least one
metal compound selected from the group consisting of cobalt, iron,
nickel, copper, aluminum, gallium, indium, scandium, yttrium,
lanthanum, cerium and zinc, such as a chloride, oxychloride, oxide,
hydroxide, nitrate or oxynitrate of one or more of these metals, as
the starting material for cobalt oxide, ironoxide, nickel oxide,
copperoxide, aluminumoxide, gallium oxide, indium oxide, scandium
oxide, yttrium oxide, lanthanum oxide, cerium oxide and zinc oxide,
for the purpose of imparting the aforementioned functions of
control of the refractive index of the film or control of the
visible light transmittance. Any of these compounds are suitable so
long as they dissociate in water or alcohol, and those that undergo
simple electrolytic dissociation are especially preferred. In other
words, it preferably decomposes without producing oxide
precipitation, etc., and is present in the coating solution in an
ion state.
[0174] Specific examples of the aforementioned component (E)
include AlCl.sub.3, GaCl.sub.3, InCl.sub.3, ScCl.sub.3, YCl.sub.3,
LaCl.sub.3, CeCl.sub.3, CoCl.sub.2, ZnCl.sub.2, Al (NO.sub.3
).sub.3, Ga(NO.sub.3).sub.3, In(NO.sub.3 ).sub.3,
Sc(NO.sub.3).sub.3, Y(NO.sub.3).sub.3, La(NO.sub.3).sub.3,
Ce(NO.sub.3).sub.3, Co(NO.sub.3).sub.2, Zn(NO.sub.3).sub.2.
[0175] The water-repellent film-coating composition preferably
contains the silane compound (A) at 0.01-2 wt % based on silica,
the silane compound (B) at 0.00001-0.15 wt % based on silica, the
acid at 0.001-3 N, water at 0-5 wt %, the compound (D) at a molar
ratio of 0.01-0.4 with respect to the silane compound (A), and the
component (E) at a molar ratio of 0-0.4 with respect to the silane
compound (A).
[0176] The solvent for the water-repellent film-coating composition
is not particularly limited, but hydrocarbons such as hexane,
toluene and cyclohexane, halogenated hydrocarbons such as methyl
chloride, carbon tetrachloride and trichloroethylene, ketones such
as acetone and methyl ethyl ketone, nitrogen-containing compounds
such as diethylamine, esters such as ethyl acetate, and alcohols
may be used. Preferred for use among these are alcohol-based
solvents, examples of which include methanol, ethanol, 1-propanol,
2-propanol, butyl alcohol, amyl alcohol and the like among which
straight-chain saturated monohydric alcohols of 3 or fewer carbon
atoms, such as methanol, ethanol, 1-propanol and 2-propanol are
even more preferred for use because of their high volatilization
rates at ordinary temperature.
[0177] These alcohols may also contain water at from 0 wt % to 50
wt %. Commercially available high-grade alcohols usually contain
water at 0.2 wt % or more, and according to the invention they are
preferably used to avoid cost-raising treatments such as dewatering
treatment. For addition of the metal starting materials, even when
the metal compounds are added after first being dissolved in water,
the amount of water in the final water-repellent film-coating
composition may be 50 wt % or less with respect to the amount of
solvent. The amount of water is preferably not greater than 50 wt %
because this will prevent a uniform, transparent film from being
formed.
[0178] A preferred water-repellent film-coating composition
according to the invention contains
[0179] (A) a thoroughly hydrolyzable silane compound or its
hydrolysate at 0.01-2 wt % (based on silica),
[0180] (B) a silane compound with a water-repellent group at
0.00001-0.15 wt % (based on silica),
[0181] (C) an acid at 0.001-3 N,
[0182] (D) at least one type of metal compound selected from the
group consisting of magnesium, calcium, strontium and boron at a
molar ratio of 0.01-0.4 based on MgO, CaO, SrO and BO.sub.3/2, with
respect to the silane compound (A),
[0183] (E) at least one type of metal compound selected from
thegroupconsistingofcobalt, iron, nickel, copper, zirconium,
aluminum, gallium, indium, scandium, yttrium, lanthanum, cerium and
zinc at a molar ratio of 0-0.4 based on CoO, FeO.sub.3/2,
NiO.sub.2, CuO, AlO.sub.3/2, GaO.sub.3/2, InO.sub.3/2, ScO.sub.3/2,
YO.sub.3/2, LaO.sub.3/2, CeO.sub.3/2 and ZnO, with respect to the
silane compound (A),
[0184] (F) water at 0-20 wt % and
[0185] (G) an alcohol constituting the remainder.
[0186] An even more preferred water-repellent film-coating
composition contains
[0187] (A) a thoroughly hydrolyzable silane compound or its
hydrolysate at 0.01-2 wt % (based on silica),
[0188] (B) a silane compound with a water-repellent group at
0.00001-0.15 wt % (based on silica),
[0189] (C) an acid at 0.001-3 N,
[0190] (D-1) amagnesiumand/orcalciumcompoundat amolar ratio of
0.01-0.4 based on MgO and CaO, with respect to the silane compound
(A) (based on SiO.sub.2),
[0191] (D-2) a boron and/or zirconium compound at a molar ratio of
0.01-0.4 based on BO.sub.3/2 and ZrO.sub.2, with respect to the
silane compound (A) (based on SiO.sub.2),
[0192] (E) at least one type of metal compound selected from
thegroupconsistingofcobalt, iron, nickel, copper, aluminum,
gallium, indium, scandium, yttrium, lanthanum, cerium and zinc at a
molar ratio of 0-0.4 based on CoO, FeO.sub.3/2, NiO.sub.2, CuO,
AlO.sub.3/2, GaO.sub.3/2, InO.sub.3/2, ScO.sub.3/2, YO.sub.3/2,
LaO.sub.3/2, CeO.sub.3/2 and ZnO, with respect to the silane
compound (A) (based on SiO.sub.2),
[0193] (F) water at 0-20 wt % and
[0194] (G) an alcohol constituting the remainder.
[0195] The method of coating the water-repellent film-coating
composition of the invention is not particularly limited, but
preferably the substrate is evenly wetted with the coating solution
composition and then stationed for drying to hardness. This allows
formation of a highly oriented water-repellent layer as the
fluoroalkyl groups and alkyl groups collect on the liquid surface
during volatilization of the solvent. Here, the stationing is
sufficient so long as the coating solution applied to the substrate
is not disturbed, and the substrate may even be gently moved in a
parallel direction during the application.
[0196] Specific examples of coating methods include dip coating,
flow coating, curtain coating, spin coating, spray coating, bar
coating, roll coating, brush coating and the like.
[0197] The drying according to the invention is carried out in an
atmosphere at room temperature or a temperature of 300.degree. C.
or below, and preferably at 40% or lower relative humidity. The
coated state of the highly oriented surface is therefore maintained
without decomposition of the integrally coated alkyl groups or
fluoroalkyl groups. As a result it is possible to obtain a
water-repellent film with a low temperature hardening property as
well as excellent water-repellent performance including droplet
roll-over properties and excellent durability due to its high
hardness. Because of the low heating temperature, even when an
alkali component is present in the substrate there is low diffusion
thereof in the water-repellent film, thus preventing reduction in
durability of the water-repellent property due the alkali.
[0198] As substrates for the invention there may be mentioned
transparent and non-transparent plates, bars and other various
forms of glass, ceramic, plastic or metal. When few hydrophilic
groups are present on the surface of the substrate, it is preferred
to pretreat the surface with an oxygen-containing plasma or corona
atmosphere for hydrophilic treatment, or to irradiate the substrate
surface with ultraviolet rays of a wavelength near 200-300 nm in an
oxygen-containing atmosphere for hydrophilic treatment, followed by
surface treatment.
BEST MODE FOR CARRYING OUT THE INVENTION
[0199] Embodiments of the present invention will now be explained
in detail by way of examples.
EXAMPLE 1
[0200] To 97.68 g of ethanol (moisture content: 0.35 wt %) there
were added 0.02 g of heptadecafluorodecyl trimethoxysilane
(CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2Si(OCH.sub.3).sub.3,
product of Shinetsu Silicone), 0.24 g of tetraethoxysilane
(Si(OCH.sub.2CH.sub.3).su- b.4, product of Shinetsu Silicone),
0.0586 g of magnesium chloride hexahydrate (product of Kanto
Kagaku) and 2 g of concentrated hydrochloric acid (35 wt %, product
of Kanto Kagaku) while stirring, to obtain a coating solution.
Table 1 shows the types and amounts (molar ratios) of the
tetraethoxysilane (TEOS), heptadecafluorodecyl trimethoxysilane
(FAS), and magnesium or calcium starting materials in the coating
solution. The total weight of the TEOS and magnesium starting
material (or calcium starting material) in the coating solution (wt
% based on SiO.sub.2, MgO and CaO) was 0.08 wt %. This
water-repellent coating solution was applied to the surface of a
washed soda lime silicate glass-composed glass substrate (3.4
mm.times.150.times.150 mm) at 30% humidity and room temperature
(20.degree. C.) using a flow coating method, and then dried at room
temperature for about one minute to obtain a water-repellent glass
plate. The composition of the water-repellent film was as shown in
Table 1. The value for the water-repellent groups is given with
respect to 100 mole percent as the total for all of the oxides, and
it was 2.4 mole percent based on FAS (likewise for the following
examples and comparative examples). The proportion of
water-repellent groups (the
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2- portion) was 16 wt % with
respect to the total weight of the film.
[0201] The water contact angle for the resulting water-repellent
glass plate was measured using a contact angle instrument (CA-DT,
product of Kyowa Surfactant Chemistry, KK.), as the static contact
angle for a water droplet of 2 mg weight. A larger value for the
contact angle indicates better static water repellency.
[0202] As an index for the roll-over performance of water droplets
on the surface of the water-repellent glass plate, a 5-mm diameter
water droplet was placed on the horizontally positioned
water-repellent glass plate surface, and then the water-repellent
glass plate was slowly tilted until the water droplet placed on the
surface first began to roll, at which point the tilt angle
(critical tilt angle) of the glass plate was measured. A smaller
critical tilt angle indicates better dynamic water repellency, and
for example, better dispersion of rain droplets adhering to the
front glass window of a moving automobile, thus causing less
blockage of the field of vision of the driver.
[0203] Evaluation of the hardness of the water-repellent film was
carried out according to the abrasion test specified by JIS R 3212.
Specifically, a commercially available Taber abrasion test was
conducted with 1000 abrasion passes at a weight of 500 g, with
measurement of the haze value before and after the abrasion test
and optical microscope observation of any film peeling before and
after the abrasion test. The film was checked for peeling after the
abrasion test, and any film that exhibited no peeling was also
measured for haze value.
[0204] Table 2 shows the film thickness, contact angle, critical
tilt angle, haze value before and after the Taber abrasion test and
film peeling before and after the abrasion test for the
water-repellent film. The resulting film had an especially low
critical tilt angle of 4.degree., and this was believed to indicate
that the Mg ions had filled the gaps in the silica porous body,
thus improving the smoothness of the film.
EXAMPLES 2-10
[0205] Water-repellent glass was obtained in the same manner as
Example 1, except that the metal atom starting materials and
addition amounts in the coating solution of Example 1 were changed
to those shown in Table 1. The compositions of the water-repellent
films were as shown in Table 1. The results of measurement in the
same manner as Example 1 are shown in Table 2. The total weight of
the TEOS and magnesium starting material (or calcium or strontium
starting material) in the coating solutions (wt % based on
SiO.sub.2, MgO, CaO or SrO) was 0.08 wt %.
[0206] The films obtained in the same manner as Example 1 had very
low critical tilt angles of 40, and this was believed to indicate
that the Mg, Ca and Sr ions had filled the gaps in the silica
porous bodies, thus improving the smoothness of the films.
COMPARATIVE EXAMPLE 1
[0207] To 85.3 g of ethanol there were added 40 g of
tetraethoxysilane and 1.92 g of heptadecafluorodecyl
trimethoxysilane, and after 20 minutes of stirring, 16.6 g of water
and 20.8 g of 0.1 N hydrochloric acid were added and the mixture
was stirred for 2 hours, placed in a sealed container and allowed
to stand at 25.degree. C. for 24 hours to obtain a water-repellent
coating solution. The composition of the water-repellent coating
solution is shown in Table 1. A washed glass plate was immersed in
the water-repellent coating solution and lowered for coating, and
after drying it was fired at 250.degree. C. for one hour to obtain
a water-repellent glass plate. The composition of the
water-repellent film was as shown in Table 1. The TEOS weight in
the coating solution (based on SiO.sub.2) was 6.5 wt %.
[0208] As shown in Table 2, the resulting water-repellent glass
plate had an initial critical tilt angle of 18.degree., which was
large compared to Examples 1-7, and poor water droplet roll-over.
When Comparative Example 1 was dried at room temperature instead of
at 250.degree. C. for one hour, the water droplet roll-over was
unchanged but the film underwent considerable scratching by mere
light rubbing with a cloth.
COMPARATIVE EXAMPLE 2
[0209] To 97.68 g of ethanol (moisture content: 0.35 wt %) there
were added 0.02 g of heptadecafluorodecyl trimethoxysilane
(CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2Si(OCH.sub.3) .sub.3,
product of Shinetsu Silicone), 0.3 g of tetraethoxysilane
(Si(OCH.sub.2CH.sub.3).sub- .4, product of Shinetsu Silicone) and 2
g of concentrated hydrochloric acid (35 wt %, product of Kanto
Kagaku) while stirring, to obtain a coating solution. A
water-repellent glass plate was otherwise obtained in the same
manner as Example 1. The composition of the water-repellent film
was as shown in Table 1. The weight of the TEOS in the coating
solution (based on SiO.sub.2) was 0.08 wt %.
[0210] As shown in Table 2, the resulting water-repellent glass
plate had an initial critical tilt angle of 8.degree., which was
large compared to Examples 1-7, and inferior droplet roll-over.
Even when Comparative Example 2 was heated at 200.degree. C. for 30
minutes instead of drying at room temperature, peeling of the film
occurred after the abrasion test.
1TABLE 1 Com- ponent Water- ratio Film composition repellent
Starting (molar (mole %) groups material ratio) SiO.sub.2 MgO CaO
SrO (based on FAS) Examples 1 TEOS/MgCl.sub.2.6H.sub.2O 80/20 80 20
0 0 2.4 2 TEOS/Mg(NO.sub.3).sub.2.6H.sub.2O 80/20 80 20 0 0 2.4 3
TEOS/Mg(OH).sub.2.6H.sub.2O 80/20 80 20 0 0 2.4 4 TEOS/MgO 80/20 80
20 0 0 2.4 5 TEOS/CaCl.sub.2 80/20 80 0 20 0 2.4 6
TEOS/Ca(NO.sub.3).sub.2.4H.sub.2O 80/20 80 0 20 0 2.4 7
TEOS/Ca(OH).sub.2.4H.sub.2O 80/20 80 0 20 0 2.4 8 TEOS/SrCl.sub.2
80/20 80 0 0 20 2.4 9 TEOS/Sr(NO.sub.3).sub.2 80/20 80 0 0 20 2.4
10 TEOS/Sr(OH).sub.2.8H.sub.2O 80/20 80 0 0 20 2.4 Comparative
Examples 1 TEOS 100 0 0 0 1.8 2 TEOS 100 0 0 0 2.4
[0211]
2TABLE 2 Haze value Critical Haze value (%) after Film Contact tilt
(%) before abrasion thickness angle angle abrasion test/film (nm)
(degree) (degree) test peeling Example 1 30 108 4 0.0 peeling
Example 2 30 108 4 0.0 peeling Example 3 30 108 4 0.0 peeling
Example 4 30 108 4 0.0 peeling Example 5 30 108 4 0.0 peeling
Example 6 30 108 4 0.0 peeling Example 7 30 108 4 0.0 peeling
Example 8 30 108 4 0.0 peeling Example 9 30 108 4 0.0 peeling
Example 10 30 108 4 0.0 peeling Comparative 40 100 15 0.0 peeling
Example 1 Comparative 40 108 7 0.0 peeling Example 2
EXAMPLES 11-32
[0212] Water-repellent glass was obtained in the same manner as
Example 1, except that the metal atom starting materials and
addition amounts in the coating solution of Example 1 and the
drying temperature and time after coating were changed to those
shown in Table 3. The compositions of the water-repellent films
were as shown in Tables 4 and 5. The results of measurement in the
same manner as Example 1 are shown in Table 6. The total content of
the TEOS and different metal oxide starting materials in the
coating solutions (wt % based on SiO.sub.2, MgO, CaO,
B.sub.2O.sub.3, Al.sub.2O.sub.3, Ga.sub.2O.sub.3, In.sub.2O.sub.3,
Sc.sub.2O.sub.3, Y.sub.2O.sub.3, La.sub.2O.sub.3, Ce.sub.2O.sub.3,
CoO, ZnO, ZrO.sub.2) was 0.08 wt %.
[0213] The resulting films had small initial critical tilt angles
of 5-8.degree., and were very hard water-repellent films with no
film peeling even after Taber abrasion.
Examples 33-36
[0214] Water-repellent glass was obtained in the same manner as
Example 1, except that the metal atom starting materials and
addition amounts in the coating solution of Example 1 and the
drying temperature and time after coating were changed to those
shown in Table 7. The compositions of the water-repellent films
were as shown in Table 8. The results of measurement in the same
manner as Example 1 are shown in Table 9. The total content of the
TEOS and different metal oxide starting materials in the coating
solutions (wt % based on SiO.sub.2, MgO, CaO and B.sub.2O.sub.3)
was 0.08 wt %.
[0215] The resulting films had small initial critical tilt angles
of 5-7.degree., and were very hard water-repellent films with no
film peeling even after Taber abrasion.
EXAMPLES 37-40
[0216] Water-repellent glass was obtained in the same manner as
Example 1, except that heptadecafluorodecyl trimethoxysilane was
changed to dodecyltrimethoxysilane
(CH.sub.3(CH.sub.2).sub.9Si(OCH.sub.3).sub.3, product of Tokyo
Kasei, hereunder also referred to as "AS"), and the metal atom
starting materials and addition amounts in the coating solution of
Example 1 and the drying temperature and time after coating were
changed to those shown in Table 7. The compositions of the
water-repellent films were as shown in Table 8. The results of
measurement in the same manner as Example 1 are shown in Table 9.
The total content of the TEOS and different metal oxide starting
materials in the coating solutions (wt % based on SiO.sub.2, MgO,
CaO, B.sub.2O.sub.3 and ZrO.sub.2) was 0.08 wt %.
[0217] The resulting films had small critical tilt angles, though
slightly larger than Example 1, and were hard water-repellent films
with no film peeling even after Taber abrasion.
EXAMPLES 41-60
[0218] Water-repellent glass was obtained in the same manner as
Example 1, except that the metal atom starting materials and
addition amounts in the coating solution of Example 1 and the
drying temperature and time after coating were changed to those
shown in Table 10. The compositions of the water-repellent films
were as shown in Table 11. The results of measurement in the same
manner as Example 1 are shown in Table 12. The total content of the
TEOS and different metal oxide starting materials in the coating
solutions (wt % based on SiO.sub.2, MgO, CaO, B.sub.2O.sub.3,
Al.sub.2O.sub.3, CoO, Fe.sub.2O.sub.3, NiO and CuO) was 0.08 wt
%.
[0219] The resulting films had small critical tilt angles, though
slightly larger than Example 1, and were hard water-repellent films
with no film peeling even after Taber abrasion.
[0220] Also, coloration due to the added transition metals was
found in Examples 43-50 and 53-60, so that the resulting
water-repellent films were very hard and colored.
COMPARATIVE EXAMPLES 3 and 4
[0221] Water-repellent glass was obtained in the same manner as
Example 1, except that the metal atom starting materials and
addition amounts in the coating solution of Example 1 and the
drying temperature and time after coating were changed to those
shown in Table 13. The results of measurement in the same manner as
Example 1 are shown in Table 14. The total content of the TEOS and
different metal oxide starting materials in the coating solutions
(wt % based on SiO.sub.2, La.sub.2O.sub.3 and CoO) was 0.08 wt
%.
[0222] Comparative Examples 3 and 4 both had inferior outer
apperances of the films, and their hardnesses were such that the
films completely peeled off after the Taber test.
3TABLE 3 Compo- nent ratio Heating Exam- (molar temperature/ ple
Starting material ratio) time 11
TEOS/MgCl.sub.2.6H.sub.2O/H.sub.3BO.sub.3 98/1/1 100.degree. C.-30
min. 12 TEOS/CaCl.sub.2/H.sub.3BO.sub.3 98/1/1 100.degree. C.-30
min. 13 TEOS/MgCl.sub.2.6H.sub.2O/AlCl.su- b.3.6H.sub.2O 97/2/1
200.degree. C.-30 min. 14 TEOS/CaCl.sub.2/AlCl.sub.3.6H.sub.2O
97/2/1 200.degree. C.-30 min. 15
TEOS/MgCl.sub.26H.sub.2O/GaCl.sub.3 97/2/1 200.degree. C.-30 min.
16 TEOS/CaCl.sub.2/GaCl.sub.3 97/2/1 200.degree. C.-30 min. 17
TEOS/MgCl.sub.26H.sub.2O/InCl.sub.3.4H.sub.2O 97/2/1 200.degree.
C.-30 min. 18 TEOS/CaCl.sub.2/InCl.sub.3.4H.sub.2O 97/2/1
200.degree. C.-30 min. 19
TEOS/MgCl.sub.26H.sub.2O/ScCl.sub.3.6H.sub.2O 97/2/1 200.degree.
C.-30 min. 20 TEOS/CaCl.sub.2/ScCl.sub.3.6H.sub.2O 97/2/1
200.degree. C.-30 min. 21 TEOS/MgCl.sub.26H.sub.2O/YCl.sub.-
3.6H.sub.2O 97/2/1 200.degree. C.-30 min. 22
TEOS/CaCl.sub.2/YCl.sub.3.6H.sub.2O 97/2/1 200.degree. C.-30 min.
23 TEOS/MgCl.sub.26H.sub.2O/LaCl.sub.3.7H.sub.2O 97/2/1 200.degree.
C.-30 min. 24 TEOS/CaCl.sub.2/LaCl.sub.3.7H.sub.2O 97/2/1
200.degree. C.-30 min. 25
TEOS/MgCl.sub.26H.sub.2O/CeCl.sub.3.7H.sub.2O 97/2/1 200.degree.
C.-30 min. 26 TEOS/CaCl.sub.2/CeCl.sub.3.7H.sub.2O 97/2/1
200.degree. C.-30 min. 27 TEOS/MgCl.sub.2.6H.sub.2O/CoCl.su-
b.2.6H.sub.2O 97/2/1 200.degree. C.-30 min. 28
TEOS/CaCl.sub.2/CoCl.sub.2.6H.sub.2O 97/2/1 200.degree. C.-30 min.
29 TEOS/MgCl.sub.2.6H.sub.2O/ZnCl.sub.2 97/2/1 200.degree. C.-30
min. 30 TEOS/CaCl.sub.2/ZnCl.sub.2 97/2/1 200.degree. C.-30 min. 31
TEOS/MgCl.sub.2.6H.sub.2O/ZrOCl.sub.2.8H.sub.2O 98/1/1 100.degree.
C.-30 min. 32 TEOS/CaCl.sub.2/ZrOCl.sub.2.8H.sub.2O 98/1/1
100.degree. C.-30 min.
[0223]
4TABLE 4 Water-repellent Film composition (mole %) groups Example
SiO.sub.2 MgO CaO B.sub.2O.sub.3 Al.sub.2O.sub.3 Ga.sub.2O.sub.3
In.sub.2O.sub.3 Sc.sub.2O.sub.3 (based on FAS) 11 98.5 1.0 0 0.5 0
0 0 0 2.4 12 98.5 0 1.0 0.5 0 0 0 0 2.4 13 97.5 2.0 0 0 0.5 0 0 0
2.4 14 97.5 0 2.0 0 0.5 0 0 0 2.4 15 97.5 2.0 0 0 0 0.5 0 0 2.4 16
97.5 0 2.0 0 0 0.5 0 0 2.4 17 97.5 2.0 0 0 0 0 0.5 0 2.4 18 97.5 0
2.0 0 0 0 0.5 0 2.4 19 97.5 2.0 0 0 0 0 0 0.5 2.4 20 97.5 0 0 0 0 0
0 0.5 2.4
[0224]
5TABLE 5 Water-repellent Film composition (mole %) groups Example
SiO.sub.2 MgO CaO ZrO.sub.2 Y.sub.2O.sub.3 La.sub.2O.sub.3
Ce.sub.2O.sub.3 CoO ZnO (based on FAS) 21 97.5 2.0 0 0 0.5 0 0 0 0
2.4 22 97.5 0 2.0 0 0.5 0 0 0 0 2.4 23 97.5 2.0 0 0 0 0.5 0 0 0 2.4
24 97.5 0 2.0 0 0 0.5 0 0 0 2.4 25 97.0 2.0 0 0 0 0 1.0 0 0 2.4 26
97.0 0 2.0 0 0 0 1.0 0 0 2.4 27 97.0 2.0 0 0 0 0 0 1.0 0 2.4 28
97.0 0 2.0 0 0 0 0 1.0 0 2.4 29 97.0 2.0 0 0 0 0 0 0 1.0 2.4 30
97.0 0 2.0 0 0 0 0 0 1.0 2.4 31 98.0 1.0 0 1.0 0 0 0 0 0 2.4 32
98.0 0 2.0 1.0 0 0 0 0 0 2.4
[0225]
6TABLE 6 Critical Haze Haze value (%) Film Contact tilt value (%)
after abrasion thickness angle angle before test/film Example (nm)
(degree) (degree) abrasion test peeling 11 30 109 6 0.0 1.2 12 30
110 6 0.1 0.9 13 30 108 7 0.2 1.1 14 30 107 8 0.1 1.3 15 30 107 7
0.1 1.1 16 30 108 7 0.1 1.2 17 30 109 7 0.2 1.2 18 30 108 8 0.1 1.4
19 30 107 8 0.1 1.1 20 30 108 7 0.0 1.1 21 30 107 7 0.1 1.3 22 30
107 8 0.0 1.1 23 30 107 8 0.0 1.2 24 30 107 8 0.1 1.4 25 30 108 8
0.0 1.2 26 30 107 7 0.2 1.3 27 30 107 8 0.1 1.2 28 30 108 7 0.1 1.4
29 30 108 8 0.1 1.2 30 30 107 8 0.0 1.3 31 30 109 5 0.0 0.9 32 30
109 6 0.0 1.0
[0226]
7TABLE 7 Compo- nent ratio Heating Exam- (molar temperature/ ple
Starting material ratio) time 33 TEOS/MgCl.sub.2.6H.sub.2O 80/20
200.degree. C.-30 min. 34 TEOS/CaCl.sub.2 80/20 200.degree. C.-30
min. 35 TEOS/H.sub.3BO.sub.3 95/5 200.degree. C.-30 min. 36
TEOS/H.sub.3BO.sub.3 99/1 200.degree. C.-30 min. 37
TEOS/MgCl.sub.2.6H.sub.2O/H.sub.3BO.sub.3 98/1/1 200.degree. C.-30
min. 38 TEOS/CaCl.sub.2/H.sub.3BO.sub.3 98/1/1 200.degree. C.-30
min. 39 TEOS/MgCl.sub.2.6H.sub.2O/ZrOCl.sub.2.8H.sub.2O 98/1/1
200.degree. C.-30 min. 40 TEOS/CaCl.sub.2/ZrOCl.sub.2.8H.sub.2O
98/1/1 200.degree. C.-30 min.
[0227]
8TABLE 8 Film composition (mole %) Water-repellent groups Example
SiO.sub.2 MgO CaO B.sub.2O.sub.3 ZrO.sub.2 (based on FAS or AS) 33
80 20 0 0 0 0.036 34 80 0 20 0 0 0.036 35 95 0 0 5 0 0.036 36 99 0
0 1 0 0.036 37 98.5 1 0 0.5 0 0.036 38 98.5 0 1 0.5 0 0.036 39 98.0
1 0 0 1 0.036 40 98.0 0 1 0 1 0.036
[0228]
9TABLE 9 Haze value (%) Haze value (%) Film Contact Critical before
after abrasion thickness angle tilt angle abrasion test/film
Example (nm) (degree) (degree) test peeling 33 30 109 6 0.0 1.1 34
30 109 7 0.0 1.2 35 30 109 6 0.0 1.1 36 30 109 5 0.0 1.0 37 30 109
6 0.0 1.0 38 30 109 6 0.0 1.0 39 30 109 5 0.0 0.9 40 30 109 6 0.0
1.0
[0229]
10TABLE 10 Starting material Example (component ratio (molar
ratio)) Heating temperature/time 41
TEOS/MgCl.sub.2.multidot.6H.sub.2O/H.sub.3BO.sub.3/AlCl.sub.3.multidot-
.6H.sub.2O(96/2/1/1) 200.degree. C.-30 min. 42
TEOS/CaCl.sub.2/H.sub.3BO.sub.3/AlCl.sub.3.multidot.6H.sub.2O(96/2/1/1)
200.degree. C.-30 min. 43 TEOS/MgCl.sub.2.multidot.6H.sub.2O/H.sub-
.3BO.sub.3/CoCl.sub.2.multidot.6H.sub.2O(93/2/1/4) 200.degree.
C.-30 min. 44
TEOS/CaCl.sub.2/H.sub.3BO.sub.3/CoCl.sub.2.multidot.6H.sub.2O(9-
3/2/1/4) 200.degree. C.-30 min. 45
TEOS/MgCl.sub.2.multidot.6H.sub.-
2O/H.sub.3BO.sub.3/FeCl.sub.2(93/2/1/4) 200.degree. C.-30 min. 46
TEOS/CaCl.sub.2/H.sub.3BO.sub.3/FeCl.sub.2(93/2/1/4) 200.degree.
C.-30 min. 47
TEOS/MgCl.sub.2.multidot.6H.sub.2O/H.sub.3BO.sub.3/NiCl.su-
b.2.multidot.6H.sub.2O(93/2/1/4) 200.degree. C.-30 min. 48
TEOS/CaCl.sub.2/H.sub.3BO.sub.3/NiCl.sub.2.multidot.6H.sub.2O(93/2/1/4)
200.degree. C.-30 min. 49 TEOS/MgCl.sub.2.multidot.6H.sub.2O/H.sub-
.3BO.sub.3/CuCl.sub.2.multidot.4H.sub.2O(93/2/1/4) 200.degree.
C.-30 min. 50
TEOS/CaCl.sub.2/H.sub.3BO.sub.3/CuCl.sub.2.multidot.4H.sub.2O(9-
3/2/1/4) 200.degree. C.-30 min. 51
TEOS/MgCl.sub.2.multidot.6H.sub.-
2O/ZrO(NO.sub.3).sub.2.multidot.8H.sub.2O/AlCl.sub.3.multidot.6H.sub.2O
200.degree. C.-30 min. (96/2/1/1) 52
TEOS/CaCl.sub.2/ZrO(NO.sub.3).sub.2.multidot.8H.sub.2O/AlCl.sub.3.multido-
t.6H.sub.2O 200.degree. C.-30 min. (96/2/1/1) 53
TEOS/MgCl.sub.2.multidot.6H.sub.2O/ZrOCl.sub.2.multidot.8H.sub.2O/CoCl.su-
b.2.multidot.6H.sub.2O 200.degree. C.-30 min. (96/2/1/4) 54
TEOS/CaCl.sub.2/ZrOCl.sub.2.multidot.8H.sub.2O/CoCl.sub.2.multidot.6H.sub-
.2O(93/2/1/4) 200.degree. C.-30 min. 55
TEOS/MgCl.sub.2.multidot.6H-
.sub.2O/ZrOCl.sub.2.multidot.8H.sub.2O/FeCl.sub.2(93/2/1/4)
200.degree. C.-30 min. 56
TEOS/CaCl.sub.2/ZrOCl.sub.2.multidot.8H.sub.2O/FeCl.-
sub.2(93/2/1/4) 200.degree. C.-30 min. 57
TEOS/MgCl.sub.2.multidot.-
6H.sub.2O/ZrOCl.sub.2.multidot.8H.sub.2O/NiCl.sub.2.multidot.6H.sub.2O
200.degree. C.-30 min. (93/2/1/4) 58
TEOS/CaCl.sub.2/ZrOCl.sub.2.multidot.8H.sub.2O/NiCl.sub.2.multidot.6H.sub-
.2O(93/2/1/4) 200.degree. C.-30 min. 59
TEOS/MgCl.sub.2.multidot.6H-
.sub.2O/ZrOCl.sub.2.multidot.8H.sub.2O/CuCl.sub.2.multidot.4H.sub.2O
200.degree. C.-30 min. (93/2/1/4) 60
TEOS/CaCl.sub.2/ZrOCl.sub.2.multidot.8H.sub.2O/CuCl.sub.2.multidot.4H.sub-
.2O(93/2/1/4) 200.degree. C.-30 min.
[0230]
11 TABLE 11 Film composition (mole %) Example SiO.sub.2 MgO CaO
B.sub.2O.sub.3 ZrO.sub.2 Al.sub.2O.sub.3 CoO Fe.sub.2O.sub.3 NiO
CuO 41 97.0 2.0 0 0.5 0 0.5 0 0 0 0 42 97.0 0 2.0 0.5 0 0.5 0 0 0 0
43 93.5 2.0 0 0.5 0 0 4.0 0 0 0 44 93.5 0 2.0 0.5 0 0 4.0 0 0 0 45
95.4 2.1 0 0.5 0 0 0 2.1 0 0 46 95.4 0 2.1 0.5 0 0 0 2.1 0 0 47
93.5 2.0 0 0.5 0 0 0 0 4.0 0 48 93.5 0 2.0 0.5 0 0 0 0 4.0 0 49
93.5 2.0 0 0.5 0 0 0 0 0 4.0 50 93.5 0 2.0 0.5 0 0 0 0 0 4.0 51
96.5 2.0 0 0 1.0 0.5 0 0 0 0 52 96.5 0 2.0 0 1.0 0.5 0 0 0 0 53
96.0 2.0 0 0 1.0 0 4.0 0 0 0 54 96.0 0 2.0 0 1.0 0 4.0 0 0 0 55
94.9 2.0 0 0 1.0 0 0 2.0 0 0 56 94.9 0 2.0 0 1.0 0 0 2.0 0 0 57
93.0 2.0 0 0 1.0 0 0 0 4.0 0 58 93.0 0 2.0 0 1.0 0 0 0 4.0 0 59
93.0 2.0 0 0 1.0 0 0 0 0 4.0 60 93.0 0 2.0 0 1.0 0 0 0 0 4.0
[0231]
12TABLE 12 Haze value (%) Haze value (%) Film Contact Critical
before after abrasion thickness angle tilt angle abrasion test/film
Example (nm) (degree) (degree) test peeling 41 30 109 6 0.0 1.2 42
30 110 6 0.1 0.9 43 30 108 7 0.2 1.1 44 30 107 8 0.1 1.3 45 30 107
7 0.1 1.1 46 30 108 7 0.1 1.2 47 30 109 7 0.2 1.2 48 30 108 8 0.1
1.4 49 30 107 8 0.1 1.1 50 30 108 7 0.0 1.1 51 30 107 7 0.1 1.3 52
30 107 8 0.0 1.1 53 30 107 8 0.0 1.2 54 30 107 8 0.1 1.4 55 30 108
8 0.0 1.2 56 30 107 7 0.2 1.3 57 30 107 8 0.1 1.2 58 30 108 7 0.1
1.4 59 30 108 8 0.1 1.2 60 30 107 8 0.0 1.3
[0232]
13TABLE 13 Comparative Starting material Heating Example (molar
ratio) temperature/time 3 TEOS/CoCl.sub.2.6H.sub.2O(98/2)
250.degree. C.-30 min. 4 TEOS/LaCl.sub.3.7H.sub.2O(98/2)
250.degree. C.-30 min.
[0233]
14TABLE 14 Film Critical Haze value (%) thick- Contact tilt Haze
value after abrasion Comparative ness angle angle (%) before
test/film Example (nm) (degree) (degree) abrasion test peeling 3 30
107 8 11.1 peeling 4 30 107 7 8.1 peeling
[0234] Industrial Applicability
[0235] As explained above, by providing a primary oxide film as a
composite oxide film with two or more components including
Sio.sub.2 and at least one selected from among MgO, CaO, SrO and
B.sub.2O.sub.3 in a water-repellent film-coated article having an
integrally formed primary oxide layer and a water-repellent layer
by a single coating treatment according to the present invention,
it is possible to drastically improve the hardness of the
water-repellent film with the integrally formed primary layer and
water-repellent layer. According to the invention there is no need
for high-temperature sintering after formation of the
water-repellent film, and therefore large-sized equipment is not
required so that preparation costs may be reduced.
[0236] Moreover, since a silane compound including water-repellent
groups such as alkyl groups or fluoroalkyl groups is added to the
water-repellent coating solution, it is possible to form the
primary oxide layer and water-repellent layer by application of one
type of solution, thus allowing better productivity.
[0237] In addition, since the water-repellent groups are naturally
oriented during film formation according to the invention, it is
possible to form a water-repellent layer with satisfactory
orientation. The water-repellent articles of the invention
therefore have very excellent water droplet roll-over properties
and high abrasion resistance.
* * * * *