U.S. patent application number 13/186510 was filed with the patent office on 2011-11-10 for coating composition for forming hydrophilic coating film.
This patent application is currently assigned to Asahi Glass Company, Limited. Invention is credited to Keisuke Abe, Akemi Kato, Takuya Nakao, Takashige Yoneda.
Application Number | 20110274914 13/186510 |
Document ID | / |
Family ID | 42561831 |
Filed Date | 2011-11-10 |
United States Patent
Application |
20110274914 |
Kind Code |
A1 |
Nakao; Takuya ; et
al. |
November 10, 2011 |
COATING COMPOSITION FOR FORMING HYDROPHILIC COATING FILM
Abstract
To provide a coating composition capable of forming a
hydrophilic coating film which has high transparency and which is
excellent in abrasion resistance (adhesion), hydrophilicity
(anti-fogging, wettability and anti-fouling properties) and
hydrophilic durability. A coating composition for forming a
hydrophilic coating film, which comprises boehmite particles,
silica particles, a binder and water, wherein the crystallite
diameter of the boehmite particles, as calculated from the
diffraction peak of the (120) plane, is from 20 to 50 nm, the
average particle diameter of the silica particles is from 5 to 50
nm, the proportion of the boehmite particles is from 20 to 80 mass
% based on the total amount of the boehmite particles and the
silica particles, and the proportion of the binder is from 0.5 to
15 parts by mass per 100 parts by mass in total of the boehmite
particles and the silica particles. The article having a
hydrophilic coating film on a surface of a base material, has a
hydrophilic coating film formed from the above coating
composition.
Inventors: |
Nakao; Takuya; (Tokyo,
JP) ; Kato; Akemi; (Tokyo, JP) ; Abe;
Keisuke; (Tokyo, JP) ; Yoneda; Takashige;
(Tokyo, JP) |
Assignee: |
Asahi Glass Company,
Limited
Chiyoda-ku
JP
|
Family ID: |
42561831 |
Appl. No.: |
13/186510 |
Filed: |
July 20, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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PCT/JP10/51986 |
Feb 10, 2010 |
|
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13186510 |
|
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Current U.S.
Class: |
428/325 ;
524/437; 977/773 |
Current CPC
Class: |
Y10T 428/249958
20150401; Y10T 428/249953 20150401; A01G 13/02 20130101; Y02A 40/25
20180101; Y10T 428/249986 20150401; Y10T 428/249987 20150401; Y10T
428/252 20150115; Y02A 40/252 20180101; A01G 9/1438 20130101; C09D
7/67 20180101; Y10T 428/249992 20150401; C09D 7/61 20180101 |
Class at
Publication: |
428/325 ;
524/437; 977/773 |
International
Class: |
B32B 5/16 20060101
B32B005/16; C08K 3/22 20060101 C08K003/22; B32B 27/06 20060101
B32B027/06 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 13, 2009 |
JP |
2009-030955 |
Feb 13, 2009 |
JP |
2009-030956 |
Claims
1. A coating composition for forming a hydrophilic coating film,
which comprises boehmite particles, silica particles, a binder and
water, wherein: the crystallite diameter of the boehmite particles,
as calculated from the diffraction peak of the (120) plane, is from
20 to 50 nm, the average particle diameter of the silica particles
is from 5 to 50 nm, the proportion of the boehmite particles is
from 20 to 80 mass % based on the total amount of the boehmite
particles and the silica particles, and the proportion of the
binder is from 0.5 to 15 parts by mass per 100 parts by mass in
total of the boehmite particles and the silica particles.
2. The coating composition according to claim 1, wherein the solid
content concentration is from 0.1 to 20 mass %.
3. The coating composition according to claim 1, wherein the binder
is a water-soluble organic binder.
4. The coating composition according to claim 1, wherein the binder
is a water-soluble polyvinyl alcohol.
5. The coating composition according to claim 1, which has a pH of
from 2.5 to 7.
6. The coating composition according to claim 1, which further
contains a water-soluble alcohol, wherein the proportion of the
water-soluble alcohol is from 10 to 70 mass %, based on the total
amount of the water and the water-soluble alcohol.
7. An article having, on a surface of a base material, a
hydrophilic coating film formed from the coating composition as
defined in claim 1.
8. The article according to claim 7, wherein the hydrophilic
coating film has a film thickness of from 100 to 700 nm.
9. The article according to claim 7, wherein the material for the
base material is a resin material.
10. The article according to claim 7, wherein the material for the
base material is a fluororesin.
Description
TECHNICAL FIELD
[0001] The present invention relates to a coating composition for
forming a hydrophilic coating film.
BACKGROUND ART
[0002] Transparent base materials made of glass, plastics, etc. are
used in various applications to e.g. various lamp covers, lenses
for eyeglasses, goggles, various instrument covers, transparent
roof materials or transparent side wall materials in plant
cultivation installations such as greenhouses. However, with these
base materials, the hydrophilicity is not high, and they have a
trouble such that dew condensation or fogging is likely to take
place. For example, in the case of an instrument cover which is
likely to be always exposed to outside air, dew condensation is
likely to take place on the inner surface of the cover to form
fogging, thus leading to a problem such that a sign or indication
becomes invisible. Further, in the case of a plastic film to be
used as a transparent roof material or a transparent side wall
material of a plant cultivation installation, the transmittance of
sunlight may be deteriorated by water drops or fogging, and the
growth of plants may be thereby adversely affected. Accordingly, it
has been attempted to form a hydrophilic coating film on the
surface for the purpose of improving the anti-fogging property,
wettability (property whereby water droplets are uniformly
wettingly spread to form a water film), anti-fouling property,
etc.
[0003] The following ones are known as coating compositions capable
of forming hydrophilic coating films.
[0004] (1) An anti-fogging composition comprising silica sol and
alumina sol having different average particle diameters, a
surfactant and a liquid dispersion medium (Examples 4 to 6 in
Patent Document 1).
[0005] (2) A coating fluid comprising colloidal alumina, colloidal
silica and an anionic surfactant in a specific ratio (Examples 1 to
7 in Patent Document 2).
[0006] (3) A coating anti-fogging agent comprising an aqueous
medium, colloidal alumina, colloidal silica and a water-soluble
resin in a specific ratio (Examples 1 to 14 in Patent Document
3).
[0007] (4) An inorganic coating composition comprising alumina
particles, of which an average of aspect ratios of agglomerated
particles in a dispersion medium is from 3 to 20, an average
particle diameter in a long axis direction is from 100 to 500 nm,
and an average particle diameter in a short axis direction is from
2 to 100 nm, silica/alumina composite particles, of which an
average particle diameter of agglomerated particles in a dispersion
medium is at most 150 nm, and water (Patent Document 4).
[0008] However, in the hydrophilic coating films formed by the
coating compositions (1) and (2), alumina particles and silica
particles are merely attached by a surfactant on the surface of a
base material film, and the adhesion between the coating film and
the base material film is inadequate. Accordingly, the abrasion
resistance of the hydrophilic coating film is inadequate. Further,
the water resistance of the hydrophilic coating film is low,
whereby the hydrophilicity cannot be maintained for a long period
of time.
[0009] The hydrophilic coating film formed by the coating
composition (3) contains a water-soluble resin (binder), whereby
the adhesion is improved as compared with the hydrophilic coating
films formed by the coating compositions (1) and (2), but the
adhesion to the base material is still inadequate. Accordingly, the
abrasion resistance of the hydrophilic coating film is inadequate.
Further, the water resistance of the hydrophilic coating film is
low, and the hydrophilicity cannot be maintained for a long period
of time.
[0010] As compared with the hydrophilic coating films formed by the
coating compositions (1) to (3), the hydrophilic coating film
formed by the coating composition (4) has high adhesion to the base
material, and the abrasion resistance is good. Further, in an
accelerated weather resistance test, the hydrophilicity can be
maintained for a long period of time. However, in a real outdoor
exposure test, the hydrophilicity abruptly drops at some time.
Therefore, it is desired to further improve the durability of
hydrophilicity (hereinafter referred to as hydrophilic
durability).
PRIOR ART DOCUMENTS
Patent Documents
[0011] Patent Document 1: JP-A-60-69181
[0012] Patent Document 2: JP-A-7-53747
[0013] Patent Document 3: JP-A-2003-49003
[0014] Patent Document 4: JP-A-2007-63477
DISCLOSURE OF INVENTION
Technical Problem
[0015] The present invention is to provide a coating composition
for forming a hydrophilic coating film capable of forming a
hydrophilic coating film which has a high transparency and which is
excellent in abrasion resistance (adhesion), hydrophilicity
(anti-fogging property, wettability and anti-fouling property) and
hydrophilic durability.
Solution to Problem
[0016] The coating composition for forming a hydrophilic coating
film of the present invention comprises boehmite particles, silica
particles, a binder and water, wherein:
[0017] the crystallite diameter of the boehmite particles, as
calculated from the diffraction peak of the (120) plane, is from 20
to 50 nm,
[0018] the average particle diameter of the silica particles is
from 5 to 50 nm,
[0019] the proportion of the boehmite particles is from 20 to 80
mass % based on the total amount of the boehmite particles and the
silica particles, and
[0020] the proportion of the binder is from 0.5 to 15 parts by mass
per 100 parts by mass in total of the boehmite particles and the
silica particles.
[0021] The solid content concentration in the coating composition
for forming a hydrophilic coating film of the present invention, is
preferably from 0.1 to 20 mass %.
[0022] The above binder is preferably a water-soluble organic
binder.
[0023] Such a water-soluble organic binder is preferably a
water-soluble polyvinyl alcohol.
[0024] The coating composition for forming a hydrophilic coating
film preferably has a pH of from 2.5 to 7.
[0025] The coating composition for forming a hydrophilic coating
film preferably further contains a water-soluble alcohol, wherein
the proportion of the water-soluble alcohol is from 10 to 70 mass
%, based on the total amount of the water and the water-soluble
alcohol.
[0026] Further, the present invention provides an article having,
on a surface of a base material, a hydrophilic coating film formed
from the above coating composition for forming a hydrophilic
coating film.
[0027] The hydrophilic coating film preferably has a film thickness
of from 100 to 700 nm.
[0028] The material for the base material is preferably a resin
material, more preferably a fluororesin.
ADVANTAGEOUS EFFECTS OF INVENTION
[0029] According to the coating composition for forming a
hydrophilic coating film of the present invention, it is possible
to form a hydrophilic coating film which has high transparency and
which is excellent in abrasion resistance (adhesion),
hydrophilicity (anti-fogging property, wettability and anti-fouling
property) and hydrophilic durability.
DESCRIPTION OF EMBODIMENT
Coating Composition for Forming Hydrophilic Coating Film
[0030] The coating composition for forming a hydrophilic coating
film of the present invention comprises the boehmite particles, the
silica particles, the binder and water and may further contain, as
the case requires, an organic solvent, a surfactant, metal oxide
particles other than the boehmite particles and the silica
particles, an additive, etc.
[0031] The solid content concentration of the coating composition
for forming a hydrophilic coating film is preferably from 0.1 to 20
mass %, more preferably from 0.1 to 10 mass %. When the solid
content concentration is at least 0.1 mass %, non-uniformity is
less likely to occur when the coating composition for forming a
hydrophilic coating film is applied to the surface of the base
material, and the performance of hydrophilicity, etc. becomes
easily obtainable. When the solid content concentration is at most
20 mass %, the operation efficiency at the time of coating will be
good, deterioration of the transparency of the hydrophilic coating
film is suppressed, and further, the storage stability of the
coating composition for forming a hydrophilic coating film of the
present invention will be good. Such a solid content concentration
is preferably from 1 to 15 mass %, more preferably from 3 to 10
mass %.
[0032] The pH of the coating composition for forming a hydrophilic
coating film of the present invention is preferably from 2.5 to 7,
more preferably from 3.5 to 7, further preferably from 4 to 6. When
the pH is at least 2.5, dissolution of the boehmite particles can
be prevented. When the pH is at most 7, the dispersion stability of
the silica particles and the boehmite particles will be good.
Boehmite Particles
[0033] As the coating composition for forming a hydrophilic coating
film of the present invention contains boehmite particles, it is
possible to form a hydrophilic coating film which has high
hydrophilicity and which is excellent in adhesion to the base
material and abrasion resistance.
[0034] The crystallite diameter of the boehmite particles, as
calculated from the diffraction peak of the (120) plane, is from 20
to 50 nm. When such a crystallite diameter is at least 20 nm, a
dense hydrophilic coating film can be obtained, the abrasion
resistance will be good, and the hydrophilic durability of the
hydrophilic coating film will be improved. When such a crystallite
diameter is at most 50 nm, the transparency and hydrophilicity of
the hydrophilic coating film will be good. The crystallite diameter
is more preferably from 30 to 40 nm.
[0035] The crystallite diameter of the boehmite particles, as
calculated from the diffraction peak of the (120) plane, can be
calculated by the X-ray diffraction (XRD) analysis.
[0036] The shape of the boehmite particles may, for example, be a
plate-shape, a needle-shape, a fiber-shape or a feather-shape,
preferably a plate-shape. When the hydrophilic coating film
contains plate-shaped boehmite particles, crystal alignment will be
obtained, whereby adhesion of the hydrophilic coating film to the
base material is further improved, the abrasion resistance will be
maintained for a long period of time, and the hydrophilic coating
film can sufficiently follow a flexible base material (such as a
film).
[0037] The boehmite particles may be commercially available ones or
may be ones obtainable by a known production method. A method for
producing boehmite particles may, for example, be a method wherein
an alkali metal aluminate and an acidic aluminum salt (such as
aluminum chloride, aluminum nitrate or aluminum sulfate), and, if
required, an acidic solution, are mixed to obtain a hydrated gel,
which is aged and then deflocculated by adding an acid; a method
wherein an acidic aluminum salt is ion-exchanged to obtain a
hydrated gel, which is aged and then deflocculated; or a method
wherein an aluminum alkoxide is hydrolyzed and then
deflocculated.
[0038] The proportion of the boehmite particles is from 20 to 80
mass %, preferably from 40 to 60 mass %, based on the total amount
of the boehmite particles and the silica particles. When the
boehmite particles are at least 20 mass %, the adhesion to the base
material or the hydrophilicity of the hydrophilic coating film will
be good. When the boehmite particles are at most 80 mass %,
deterioration of the film strength of the hydrophilic coating film
can be suppressed, and deterioration of the transparency can also
be suppressed.
Silica Particles
[0039] As the coating composition for forming a hydrophilic coating
film of the present invention contains silica particles, a porous
hydrophilic coating film is formed by agglomeration with the
boehmite particles, whereby the hydrophilicity of the hydrophilic
coating film will be improved. Further, the storage stability of
the coating composition for forming a hydrophilic coating film will
be good. Further, it is possible to form a hydrophilic coating film
having high transparency and high abrasion resistance.
[0040] The average particle diameter of the silica particles is
from 5 to 50 nm. The average particle diameter of the silica
particles is more preferably from 5 to 30 nm, most preferably from
8 to 15 nm. When the average particle diameter is from 5 to 50 nm,
agglomeration of the silica particles and the boehmite particles
can be properly controlled, and as a result, it is possible to form
a porous coating film having a large pore volume to exhibit
hydrophilicity and to form a transparent coating film. The average
particle diameter of agglomerated particles of the silica particles
in a dispersion medium is preferably at most 700 nm.
[0041] The average particle diameter of the silica particles is one
obtained by measuring the lengths of the long axes and short axes
of 20 silica particles randomly selected among ones in a
transmission electron microscopic (TEM) image and averaging them.
As mentioned above, the boehmite particles are particles having a
shape of e.g. a plate, and as mentioned hereinafter, the silica
particles are particles having a shape of e.g. a spherical shape.
Therefore, in the TEM image, the boehmite particles and the silica
particles which are different in the shape and size, can clearly be
distinguished.
[0042] The shape of the silica particles may, for example, be a
chain-shape, a linked-shape or a spherical shape, and is preferably
a spherical shape.
[0043] The silica particles may be commercially available ones or
may be ones obtainable by a known production method.
[0044] The proportion of the silica particles is from 20 to 80 mass
%, preferably from 40 to 60 mass %, based on the total amount of
the boehmite particles and the silica particles. When the silica
particles are at least 20 mass %, deterioration of the film
strength of the hydrophilic coating film can be suppressed, and the
transparency of the hydrophilic coating film will also be improved.
When the silica particles are at most 80 mass %, the adhesion to
the base material or the hydrophilicity of the hydrophilic coating
film will be good.
Binder
[0045] The coating composition for forming a hydrophilic coating
film contains a binder, whereby the abrasion resistance of the
hydrophilic coating film will be improved.
[0046] As such a binder, an organic binder or an inorganic binder
may be mentioned, and an organic binder is preferred. Further, the
binder is preferably a hydrophilic binder. If a hydrophobic binder
is used, the contact angle of the hydrophilic coating film to water
may increase, whereby the hydrophilicity may decrease. The binder
is particularly preferably a water-soluble hydrophilic binder.
Further, in a case where the coating composition contains an
organic solvent, it is possible to use a binder which is soluble in
the organic solvent.
[0047] As the organic binder, a water-soluble organic binder is
preferred. The water-soluble organic binder may, for example, be
polyvinyl alcohol, a modified polyvinyl alcohol, polyethylene
glycol, a polyacrylic acid or its salt, a water-soluble
polyurethane, or a water-soluble cellulose derivative such as
hydroxyethyl cellulose. Further, among water-soluble organic
binders, a nonionic water-soluble organic binder is more preferred.
As compared with an ionic water-soluble organic binder, the
nonionic water-soluble organic binder brings about no substantial
agglomeration of inorganic particles whereby the storage stability
of the liquid is high. As such a nonionic water-soluble organic
binder, polyvinyl alcohol, a modified polyvinyl alcohol or
polyethylene glycol is, for example, preferred.
[0048] Here, in the present invention, the modified polyvinyl
alcohol means one having some of hydroxy groups in a polyvinyl
alcohol changed to another group. For example, it may be one having
the hydroxy groups esterified by e.g. a carboxylic acid (excluding
acetic acid), one having the hydroxy groups formal-modified by an
aldehyde, one having the hydroxy groups alkyl-etherified, or the
like. As the modified polyvinyl alcohol, a modified product having
a reactive group introduced to some of hydroxy groups, is
preferred. For example, a modified polyvinyl alcohol (tradename:
Gohsefimer Z100) used in Examples is a modified polyvinyl alcohol
having an acetoacetyl group introduced to some of hydroxy
groups.
[0049] Further, as the nonionic water-soluble organic binder, for
the following reasons, polyvinyl alcohol and a modified polyvinyl
alcohol (hereinafter these may generally be referred to as a
water-soluble polyvinyl alcohol) are more preferred. It is possible
to use, as the binder, a combination of a plurality of
water-soluble polyvinyl alcohols of different types in e.g. the
saponification degree, molecular weight, modification, etc.
[0050] When the coating composition for forming a hydrophilic
coating film contains a water-soluble polyvinyl alcohol, the pore
characteristics of the hydrophilic coating film will be good, it
becomes possible to simultaneously attain high hydrophilicity and
transparency and to impart abrasion resistance, and further, the
uniform forming property of the hydrophilic coating film will be
excellent. Further, as compared with a case where polyethylene
glycol is used as the water-soluble binder, the adhesion to the
base material is improved, and the abrasion resistance tends to be
good, and accordingly, by using such a water-soluble polyvinyl
alcohol, the abrasion resistance can be improved by its addition in
a small amount.
[0051] Whether or not the hydrophilic coating film contains a
water-soluble polyvinyl alcohol can be ascertained by a .sup.1H-NMR
analysis. A sample liquid for measurement may be prepared in such a
manner that from the base material, the hydrophilic coating film is
scraped to recover a powder sample, which is diluted with water to
5 mass %, followed by dispersion treatment by an ultrasonic
dispersing apparatus for 30 minutes to obtain a dispersion, which
is subjected to centrifugal separation to a supernatant and a
precipitate, whereupon the supernatant is concentrated.
[0052] As the inorganic binder, a precursor for a metal oxide may
be mentioned, and a precursor for silica or alumina is preferred.
The precursor for silica or alumina is obtainable by a known
production method.
[0053] The silica precursor may be one obtained by a method of
hydrolyzing a silicic acid alkoxide (such as ethyl silicate); one
obtained by a method of decomposing an alkali metal silicate with
an acid, followed by electrolytic dialysis; one obtained by a
method of deflocculating an alkali metal silicate; or one obtained
by a method of dialyzing an alkali metal silicate by an ion
exchange resin.
[0054] The alumina precursor may, for example, be one obtained by a
method of hydrolyzing an aluminum alkoxide; or a water-soluble
aluminum salt or an aluminum chelate compound.
[0055] The proportion of the binder is from 0.5 to 15 parts by
mass, preferably from 1 to 5 parts by mass, per 100 parts by mass
in total of the boehmite particles and the silica particles. When
the binder is at most 15 parts by mass, pores of the hydrophilic
coating film are less likely to be embedded by the binder, whereby
a large pore volume can be obtained. When the binder is at least
0.5 part by mass, the effect to improve the abrasion resistance can
readily be obtainable.
Water
[0056] In the coating composition for forming a hydrophilic coating
film, water plays a role as a dispersion medium to disperse the
boehmite particles and the silica particles.
[0057] The proportion of water is preferably from 500 to 100,000
parts by mass, more preferably from 600 to 10,000 parts by mass,
further preferably from 1,000 to 3,000 parts by mass, per 100 parts
by mass of the total solid content in the coating composition for
forming a hydrophilic coating film. When the water is at least 500
parts by mass, the concentration of the coating composition for
forming a hydrophilic coating film is not too high, and the storage
stability will be good. When the water is at most 100,000 parts by
mass, the concentration of the coating composition for forming a
hydrophilic coating film is not too low, and it is possible to form
a hydrophilic coating film having an adequate thickness.
Organic Solvent
[0058] The coating composition for forming a hydrophilic coating
film of the present invention may contain an organic solvent within
a range not to impair the dispersion stability of the boehmite
particles and the silica particles. As such an organic solvent, a
water-soluble organic solvent is preferred, and as its amount, it
is preferred to use an amount of at most its solubility in water.
Further, the boiling point of the organic solvent is preferably at
most 120.degree. C., particularly preferably at most 100.degree.
C.
[0059] As such an organic solvent, a water-soluble alcohol may be
mentioned such as methanol, ethanol, n-propanol, isopropanol,
n-butanol, isobutanol, sec-butanol, t-butanol or ethylene
glycol.
[0060] In order to obtain a defoaming property at the time of
coating a base material with the coating composition for forming a
hydrophilic coating film, it is preferred to incorporate a
water-soluble organic solvent. As such a water-soluble organic
solvent, a water-soluble alcohol is preferred which may be mixed at
an optional proportion with water. In such a case, the amount of
the alcohol is preferably adjusted so that the proportion of the
alcohol will be from 10 to 70 mass % based on the total amount of
water and the alcohol. When the alcohol is at least 10 mass %, a
defoaming effect can be obtained, and when the alcohol is at most
70 mass %, the stability of the coating composition for forming a
hydrophilic coating film is good. As such a water-soluble alcohol,
methanol, ethanol or isopropanol is preferred from the viewpoint of
the stability. Such alcohols may be used alone, or two or more of
them may be used in combination. The proportion of the alcohol
based on the total amount of water and the alcohol is more
preferably from 30 to 60 mass %.
Other Components
[0061] The coating composition for forming a hydrophilic coating
film of the present invention may contain, in addition to the
boehmite particles and the silica particles, other additives such
as metal oxide particles, a surfactant, a defoaming agent, a
crosslinking agent, a water resistant curing agent, a coloring dye,
a pigment, an ultraviolet absorber, an antioxidant, etc., as the
case requires. The total amount of other components to constitute a
solid content is preferably at most 50 parts by mass, more
preferably at most 30 parts by mass, per 100 parts by mass in total
of the boehmite particles and the silica particles. If the total
amount of other components to constitute a solid content becomes
too large, the properties obtainable by the essential components
may be deteriorated.
[0062] The coating composition for forming a hydrophilic coating
film of the present invention may contain metal oxide particles
other than the boehmite particles and the silica particles, as the
case requires. For example, in a case where cerium oxide particles
are contained, an ultraviolet shielding function may be imparted.
In a case where titanium oxide particles are contained, an
ultraviolet shielding performance or a photocatalytic performance
may be imparted. In a case where indium-doped tin oxide (ITO)
particles, antimony-doped tin oxide (ATO) particles or tin oxide
particles are contained, electroconductivity or an ultraviolet
shielding performance may be imparted. In a case where alumina
particles other than boehmite particles are contained, the
hydrophilicity (such as wettability) or the film strength of the
hydrophilic coating film may be further improved.
[0063] The average particle diameter of the metal oxide particles
is preferably from 1 to 500 nm, more preferably from 1 to 200 nm.
When the average particle diameter of the metal oxide particles is
at least 1 nm, the properties of the metal oxide particles can
readily be obtainable. When the average particle diameter of the
metal oxide particles is at most 500 nm, deterioration of the
transparency of the hydrophilic coating film can be suppressed.
[0064] The proportion of the metal oxide particles is preferably at
most 30 parts by mass, per 100 parts by mass in total of the
boehmite particles and the silica particles. In order to obtain the
above-mentioned properties by using the metal oxide particles,
their amount is preferably at least 1 part by mass per 100 parts by
mass in total of the boehmite particles and the silica
particles.
[0065] In a case where the coating composition contains a
surfactant, the coating property of the coating composition will be
improved, whereby a uniform hydrophilic coating film having a good
appearance can be formed, and the hydrophilicity is also
improved.
[0066] The surfactant may be an anionic surfactant, a cationic
surfactant, an amphoteric surfactant or a nonionic surfactant. Such
a surfactant may be a surfactant having hydrogen atoms of an alkyl
group moiety substituted by fluorine atom (i.e. a fluorinated
surfactant). As the surfactant, a nonionic surfactant is preferred
in that the dispersion stability of the boehmite particles and the
silica particles in the coating composition for forming a
hydrophilic coating film will thereby be good.
[0067] The nonionic surfactant is preferably a compound having at
least one type of structural unit selected from the group
consisting of --CH.sub.2CH.sub.2CH.sub.2O--, --CH.sub.2CH.sub.2O--,
--SO.sub.2--, --NR-- (wherein R is a hydrogen atom or an organic
group), --NH.sub.2, --SO.sub.3Y and --COOY (wherein Y is a hydrogen
atom, a sodium atom, a potassium atom or an ammonium group). Such a
compound may, for example, be an alkylpolyoxyethylene ether, an
alkylpolyoxyethylene-polyoxypropylene ether, a fatty acid
polyoxyethylene ester, a fatty acid polyoxyethylene sorbitane
ester, a fatty acid polyoxyethylene sorbitol ester, an
alkylpolyoxyethyleneamine, an alkylpolyoxyethyleneamide or a
polyether-modified silicone surfactant.
[0068] The proportion of the surfactant in the coating composition
for forming a hydrophilic coating film is preferably at most 15
parts by mass, more preferably at most 10 parts by mass, per 100
parts by mass in total of the boehmite particles and the silica
particles. When the surfactant is at most 15 parts by mass,
deterioration of the abrasion resistance of the hydrophilic coating
film can be suppressed. In order to obtain the above-described
properties by using the surfactant, its amount is preferably at
least 1 part by mass per 100 parts by mass in total of the boehmite
particles and the silica particles.
[0069] The crosslinking agent for the binder may, for example, be
an inorganic compound such as an inorganic aluminum compound, an
inorganic boron compound, an inorganic zirconium compound or an
inorganic titanium compound, or an organic compound such as
glyoxal, a hydrazide compound or an isocyanate compound. By
crosslinking the binder by using such a crosslinking agent, it is
possible to suppress deterioration of the abrasion resistance of
the hydrophilic coating film and to improve the durability of
wettability. The proportion of the crosslinking agent in the
coating composition for forming a hydrophilic coating film is
preferably at most 10 parts by mass, more preferably at most 5
parts by mass, per 100 parts by mass in total of the boehmite
particles and the silica particles. When the crosslinking agent is
at most 10 parts by mass, the stability of the coating liquid can
be obtained, and it is possible to suppress an increase of the haze
of the hydrophilic coating film. In order to obtain the
above-described properties by using the crosslinking agent, its
amount is preferably at least 0.1 part by mass per 100 parts by
mass in total of the boehmite particles and the silica
particles.
[0070] The water resistant curing agent may, for example, be an
aqueous emulsion, aqueous dispersion or the like, of an acrylic
resin, a polyester resin, a polyolefin resin, an urethane resin or
a vinyl acetate resin.
Preparation Method
[0071] The coating composition for forming a hydrophilic coating
film of the present invention can be prepared by mixing a boehmite
sol containing boehmite particles, a silica sol containing silica
particles and a binder. At the time of preparing the coating
composition for forming a hydrophilic coating film, water or an
organic solvent (such as ethanol or methanol) may be added, as the
case requires.
[0072] The boehmite sol is one having boehmite particles dispersed
in water, a mixed solvent of water and a water-soluble organic
solvent, or another aqueous medium. The water-soluble organic
solvent is preferably a water-soluble alcohol such as ethanol,
methanol or isopropanol. The solid content concentration of the
boehmite sol is preferably from 0.1 to 30 mass %, more preferably
from 3 to 20 mass %.
[0073] In order to stabilize the boehmite particles in the
dispersion medium, the boehmite sol preferably contains anions
derived from an inorganic acid or organic acid (such as chlorine
ions, sulfate ions or acetate ions). The concentration of anions is
preferably at most 35 parts by mass per 100 parts by mass of Al.
When the concentration of anions is at most 35 parts b mass, it is
possible to suppress deterioration of the water resistance or
hydrophilicity of the hydrophilic coating film. In a case where the
concentration of anions in the boehmite sol is high, it is
preferred to reduce the anion concentration by means of an ion
exchange resin, electrical dialysis, ultrafiltration or the
like.
[0074] The pH of the boehmite sol is preferably from 4 to 6.8,
since it is thereby possible to obtain a coating film excellent in
the water resistance and transparency. When the pH is at least 4,
the anions may not be too much, and the water resistance of the
hydrophilic coating film will be good. When the pH is at most 6.8,
the boehmite particles are less likely to be agglomerated, and it
is possible to secure the transparency of the hydrophilic coating
film and the adhesion to the base material and to suppress
deterioration of the abrasion resistance.
[0075] The solid content concentration of the silica sol is
preferably from 5 to 40 mass %, more preferably from 10 to 35 mass
%. The pH of the silica sol is preferably from 9 to 10.5 from the
viewpoint of the stability. It is also possible to use a silica sol
having a pH of at most 7, or it is also possible to adjust the pH
to be at most 7 before mixing a silica sol having a pH of from 9 to
10.5 with the boehmite sol.
[0076] As mentioned above, the pH of the coating composition for
forming a hydrophilic coating film of the present invention is
preferably from 2.5 to 7. Even if a silica sol having a pH of from
9 to 10.5 is used, the pH of the coating composition for forming a
hydrophilic coating film can be made to be from 2.5 to 7 by mixing
it with a boehmite sol having a low pH. Otherwise, as the case
requires, after mixing with the boehmite sol, etc., the pH of the
composition may be adjusted to a level of from 2.5 to 7. The
adjustment of the pH of the composition is preferably carried out
by adding an inorganic acid such as nitric acid.
Hydrophilic Coating Film
[0077] The hydrophilic coating film is a coating film formed by
applying the coating composition for forming a hydrophilic coating
film of the present invention to a base material.
[0078] The base material may be an inorganic base material (base
material made of an inorganic material such as glass) or an organic
base material (base material made of a resin material such as a
polyethylene terephthalate resin, an acrylic resin, a polycarbonate
resin, a polyolefin resin, a polyvinylchloride resin or a
fluororesin). The base material is preferably made of a transparent
material. From the viewpoint of the durability, weather resistance,
chemical resistance, adhesion to the hydrophilic coating film,
etc., a base material made of a fluororesin is preferred. The
fluororesin is negatively chargeable at its surface, and thus, its
adhesion to boehmite particles which are positively charged,
becomes high.
[0079] The shape of the base material is not particularly limited,
and it may be one formed into various shapes. Preferred is a base
material of a film form or sheet form, and by using such a base
material, a hydrophilic coating film having a uniform thickness can
efficiently be formed. The hydrophilic coating film may be formed
on one side or each side of the base material of e.g. film form,
depending upon the purpose.
[0080] Hereinafter, a film-form base material and a sheet-form base
material will be generally referred to as a film. Further, in the
present invention, an article means a product having a base
material having a hydrophilic coating film formed thereon.
[0081] The fluororesin may be a homopolymer of a fluoroolefin, a
copolymer of two or more fluoroolefins, or a copolymer of at least
one fluoroolefin with one or more other monomers.
[0082] A fluoroolefin is a monomer having a polymerizable
unsaturated bond and fluorine atoms and may further have hydrogen
atoms, chlorine atoms, oxygen atoms, etc. As such a fluoroolefin,
for example, tetrafluoroethylene, vinyl fluoride, vinylidene
fluoride, a perfluoro(alkyl vinyl ether), chlorotrifluoroethylene
or hexafluoropropylene is preferred. As the perfluoro(alkyl vinyl
ether), perfluoro(propyl vinyl ether) is particularly
preferred.
[0083] Other monomers are preferably non-fluorinated monomers. For
example, olefins such as ethylene, propylene, butene, norbornene,
etc.; alkenyl ethers such as cyclohexylmethyl vinyl ether, isobutyl
vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether,
2-ethylhexyl vinyl ether, ethylallyl ether, etc.; and alkenyl
esters such as vinyl acetate, vinyl pivalate, vinyl versatate,
allyl pivalate, allyl versatate, etc., are preferred.
[0084] As fluororesins obtained by polymerizing such monomers, a
tetrafluoroethylene/ethylene copolymer, a
tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer,
polyvinyl fluoride, polyvinylidene fluoride,
polychlorotrifluoroethylene, a chlorotrifluoroethylene/ethylene
copolymer, a vinylidene fluoride/tetrafluoroethylene copolymer, a
vinylidene fluoride/hexafluoropropylene copolymer, a
tetrafluoroethylene/hexafluoropropylene copolymer, a
vinylidene-fluoride/tetrafluoroethylene/hexafluoropropylene
copolymer, a tetrafluoroethylene/propylene copolymer and a
tetrafluoroethylene/hexafluoropropylene/ethylene copolymer are
preferred. Among tetrafluoroethylene/perfluoro(alkyl vinyl ether)
copolymers, a tetrafluoroethylene/perfluoro(propyl vinyl ether)
copolymer is preferred. Among them, a tetrafluoroethylene/ethylene
copolymer is particularly preferred from the viewpoint of the
processability and the physical properties of the film to be
used.
[0085] To the base material, surface treatment may preliminarily be
applied to the surface on which the hydrophilic coating film is to
be formed. By applying such surface treatment, wettability of the
base material will be improved, whereby it is possible to improve
the adhesion of the hydrophilic coating film to the base material
or the uniformity of the hydrophilic coating film. Especially when
a fluororesin base material is used, it is preferred to
preliminarily apply surface treatment to the surface on which the
hydrophilic coating film is formed, in order to improve
wettability. The surface treatment may, for example, be discharge
treatment (plasma treatment, corona discharge treatment, etc.), UV
treatment, ozone treatment, chemical treatment using an acid,
alkali, etc., or physical treatment using an abrasive material.
[0086] The coating method may, for example, be brush coating,
roller coating, manual coating, spin coating, dip coating, coating
by various printing systems, bar coating, curtain flow coating, die
coating, flow coating or spray coating. In a case where the base
material is a film, coating by means of a gravure coater is
preferred, since it is thereby possible to carry out uniform
coating over a large area.
[0087] For the purpose of improving the film strength of the
hydrophilic coating film, heating or irradiation with ultraviolet
rays, electron rays, etc. may be carried out. The heating
temperature may be decided taking into consideration the heat
resistance of the base material. For example, in the case of a
fluororesin film, the heating temperature is preferably from 40 to
100.degree. C.
[0088] The thickness of the hydrophilic coating film is preferably
from 100 to 700 nm, more preferably from 250 to 450 nm. When the
thickness of the hydrophilic coating film is at least 100 nm, it is
possible to suppress deterioration of the hydrophilicity and
hydrophilic durability. When the thickness of the hydrophilic
coating film is at most 700 nm, the hydrophilic coating film is
less susceptible to cracking, interference fringe is less likely to
occur, and even if scratched, such a scratch mark is
unnoticeable.
[0089] The hydrophilic coating film is required to have
transparency. The transparency of the hydrophilic coating film can
be evaluated by its haze value. The haze value of the hydrophilic
coating film is preferably at most 5.0%, more preferably at most
3.0%. When the haze value is at most 5.0%, the hydrophilic coating
film can be regarded as having sufficient transparency.
[0090] The haze value of the hydrophilic coating film can be
calculated by subtracting the haze value of the base material from
the haze value of the article having the hydrophilic coating film
formed on the surface of the base material.
[0091] The hydrophilicity of the hydrophilic coating film can be
evaluated by its contact angle to water. The contact angle of the
hydrophilic coating film to water is preferably at most 40.degree.,
more preferably at most 20.degree., further preferably at most
10.degree.. When the contact angle is at most 40.degree., the
hydrophilicity of the hydrophilic coating film becomes sufficient,
and the wettability can easily be obtainable. If soil is deposited
on the surface of the hydrophilic coating film, the contact angle
to water may increase, and the wettability may be lost in many
cases. In the case of the hydrophilic coating film in the present
invention, the surface is gradually washed out and renewed, whereby
the wettability can be maintained for a long period of time.
[0092] The hydrophilic coating film may be used as a hydrophilic
primer layer, and another coating film may further be formed on the
hydrophilic primer layer. For example, in a case where on the
hydrophilic coating film, a photocatalytic film containing fine
particles of e.g. anatase type titanium oxide, rutile type titanium
oxide, tin oxide, zinc oxide, tungsten trioxide, ferric oxide or
strontium titanate, is formed, it is possible to suppress
deterioration by decomposition of an organic base material, by the
photocatalytic film.
Agricultural Film
[0093] The coating composition for forming a hydrophilic coating
film of the present invention is useful particularly as a coating
composition to form a hydrophilic coating film on a base material
to be used as an agricultural film (a plastic film to be used as a
transparent roof material or transparent side wall material of a
plant cultivation installation). The hydrophilic coating film is
formed on at least one side of the agricultural film. Further, in a
case where the hydrophilic coating film is formed on one side only,
an anti-fouling film, an antistatic film, a heat-shielding film or
an ultraviolet-shielding film may, for example, be formed on the
other side.
[0094] The material for such an agricultural film may, for example,
be a polyethylene terephthalate resin, an acrylic resin, a
polycarbonate resin, a polyolefin resin, a polyvinylchloride resin
or a fluororesin, and a fluororesin is preferred. In a case where
the agricultural film is a fluororesin film, the surface is
negatively chargeable, whereby the adhesion to the hydrophilic
coating film containing boehmite particles which are positively
charged, will be high. As the material for the agricultural film, a
tetrafluoroethylene/ethylene copolymer is particularly
preferred.
[0095] In the coating composition for forming a hydrophilic coating
film of the present invention as described in the foregoing, the
crystallite diameter of boehmite particles, as calculated from the
diffraction peak of the (120) plane, is from 20 to 50 nm, and the
average particle diameter of the silica particles is from 5 to 50
nm, whereby it is possible to form a hydrophilic coating film which
has high transparency and which is excellent in abrasion resistance
(adhesion), hydrophilicity (anti-fogging property, wettability,
anti-fouling property) and hydrophilic durability.
EXAMPLES
[0096] Now, Examples will be described.
[0097] Examples 1 to 3, 8 to 10, 12, 13 and 15 to 17 are Working
Examples of the present invention, and Examples 4 to 7, 11,14 and
18 to 20 are Comparative Examples. As the base material, a
tetrafluoroethylene/ethylene copolymer film having corona discharge
treatment applied to one side on which a hydrophilic coating film
is to be formed (tradename: Aflex manufactured by Asahi Glass
Company, Limited, surface wetting index after the corona discharge
treatment: 42, thickness: 100 .mu.m) was used (hereinafter referred
to as an ETFE film). In the following Examples, an ETFE film
provided with a hydrophilic coating film was evaluated as an
agricultural film.
Crystallite Diameter of Boehmite Particles as Calculated from the
Diffraction Peak of the (120) Plane
[0098] With respect to a powder sample recovered by drying the
coating composition for forming a hydrophilic coating film, the XRD
analysis was carried out twice, and the crystallite diameter of the
boehmite particles was calculated from the diffraction peak of the
(120) plane of the boehmite particles.
[0099] (XRD apparatus) Model: TTR-III manufactured by Rigaku
Corporation
[0100] (Measuring conditions) X-ray output: 50 kV-300 mA, optical
system: parallel beam, scan speed: 2.degree./min, rotation: yes
(100 RPM), sampling interval: 0.02.degree./step
[0101] (Analytical conditions) Software: JADE7, correction
standard: Si powder (NIST SRM640c), analytical peak: boehmite (120)
plane, fitting function: Pearson-VII, exponent: 1.5, baseline:
fourth ordered polynominal
Average Particle Diameter of Silica Particles
[0102] The coating composition for forming a hydrophilic coating
film was diluted with water to obtain a diluted liquid having a
solid content concentration of about 0.1 mass %, and then, such a
diluted liquid was dropped on a collodion film and dried to form an
observation film. Such an observation film was observed by TEM, and
the lengths of the long axes and short axes of 20 silica particles
randomly selected among ones in the TEM image were measured, and
they were averaged to obtain an average particle diameter of the
silica particles.
[0103] (TEM) Model: JEM-1230, manufactured by JEOL Ltd.
Thickness of Hydrophilic Coating Film
[0104] An ETFE film having a hydrophilic coating film formed on one
side was cut by a razor, and the cut surface was observed by a
scanning electron microscope (SEM), whereby the thicknesses at
three portions of the hydrophilic coating film were measured, and
they were averaged.
[0105] (SEM) Model: S-4300 manufactured by Hitachi, Ltd.
[0106] (Measuring conditions) Accelerating voltage: 5 kV,
conductive coating: Pt
Appearance
[0107] The appearance of the hydrophilic coating film in the ETFE
film having a hydrophilic coating film formed on one side was
visually evaluated, whereby one free from foreign matter defects,
warpage, cracking and non-uniformity was designated by
.largecircle. (good), and one having any one of such defects was
designated by .times. (no good).
Haze Value
[0108] In accordance with JIS K7105, the haze values of the ETFE
film before forming a hydrophilic coating film and the ETFE film
having a hydrophilic coating film formed on one side were measured
by means of a haze computer (model: HGM-3DP manufactured by Suga
Test Instruments Co., Ltd.), and the haze value of the hydrophilic
coating film was calculated by subtracting the haze value of the
ETFE film before forming a hydrophilic coating film from the haze
value of the ETFE film having a hydrophilic coating film formed on
one side.
[0109] One having a haze value of at most 5% was regarded as
acceptable, and one having a haze value exceeding 5% was regarded
as unacceptable.
Transmittance
[0110] In accordance with JIS K7105 (1981), the total light
transmittance of the ETFE film having a hydrophilic coating film
formed on one side was measured by means of a haze meter (model:
HGM-2K, SM color computer model SM-5, manufactured by Suga Test
Instruments Co., Ltd.).
Contact Angle
[0111] The contact angles of the hydrophilic coating film of the
ETFE film having a hydrophilic coating film formed on one side to
water were measured at optional five different portions by means of
a contact angle meter (model: CA-X150 manufactured by Kyowa
Interface Science Co., LTD.), and they were averaged. The contact
angle serves as an index for the hydrophilicity.
Low Temperature Wettability
[0112] From the ETFE film having a hydrophilic coating film formed
on one side, a sample of 14 cm.times.8 cm was cutout. A roof-form
frame made of an acrylic resin was set at an angle of 15.degree. to
a horizontal plane, on a constant temperature water tank set in a
constant temperature environment test room, and the sample was set
on the frame so that the hydrophilic coating film faced down. The
environment test room was adjusted to be 10.degree. C., and the
constant temperature water tank was adjusted to be 20.degree. C.
The state of water droplets on the surface of the hydrophilic
coating film was observed and evaluated by the following standards.
.circleincircle., .largecircle. and .DELTA. are regarded as
acceptable, and .times. and .times..times. are regarded as
unacceptable.
[0113] .circleincircle. (excellent): After one hour from initiation
of evaluation, the film surface is uniformly wet.
[0114] .largecircle. (good): After two hours from initiation of
evaluation, the film surface is uniformly wet.
[0115] .DELTA. (permissible): After 3 hours from initiation of
evaluation, the film surface is uniformly wet.
[0116] .times. (not permissible): After 3 hours from initiation of
evaluation, water droplet-deposited portions are partially observed
on the film surface.
[0117] .times..times. (bad): After 3 hours from initiation of
evaluation, water droplets are deposited and white fogging is
observed over the entire film surface.
Durability of Wettability
[0118] A sample was set in the same environment test room as for
the evaluation of the low temperature wettability, and left to
stand for three months while maintaining the environment test room
at 20.degree. C. and the constant temperature water tank at
80.degree. C. Upon expiration of the three months, the sample was
taken out. Then, with respect to such a sample, evaluation of the
low temperature wettability was carried out, whereby the state of
water droplets on the surface of the hydrophilic coating film was
observed, and the durability of wettability was evaluated by the
same standards as for the evaluation of the low temperature
wettability.
[0119] In an agricultural house, in a winter time, early in the
morning or evening when outside air temperature is low, an
agricultural film is likely to have fogging, and suppression of
fogging is required for the agricultural film. For such suppression
of fogging, "low temperature wettability" will be an index.
Further, an agricultural film is required to show wettability even
after exposure for a long period of time, and for this purpose,
"durability of wettability" will be an index.
Abrasion Resistance
[0120] A sample of the ETFE film having a hydrophilic coating film
formed on one side was set in a flat surface abrasion tester
(model: TESTER SANGYO AB-301 COLOR FASTNESS RUBBING TESTER,
manufactured by Coating Tester Kougyo, Inc.), and BEMCOT
(tradename: BEMCOT M-1, manufactured by Asahi Chemical Industry
Co., Ltd.) was attached as an abrading material, whereupon an
abrasion test of the hydrophilic coating film was carried out under
such conditions that the load was 200 g, the contact area was 15
mm.times.20 mm and the number of abrasion was one reciprocation,
whereby the Al-deposited amounts (.mu.g/cm.sup.2) before and after
the test were measured by a fluorescent X-ray apparatus (model:
RIX3000 manufactured by Rigaku Corporation), and the abrasion
resistance was evaluated by Al-deposited amount after the
test/initial Al-deposited amount.times.100 (%). One wherein the
Al-deposited amount was at least 70% to the initial Al-deposited
amount, was regarded as acceptable.
Example 1
[0121] To 792 g of ion-exchanged water, 8 g of 1N nitric acid was
added, then 200 g of boehmite (tradename: DISPAL 11N7-80
manufactured by SASOL Ltd.) was added with stirring, and after
continuing the stirring for 30 minutes, the system was left to
stand at room temperature for one day, to obtain a boehmite
dispersion having a solid content concentration of 20 mass % and a
pH of 5.0.
[0122] To 100 g of the boehmite dispersion, 81.8 g of silica sol
(tradename: SNOWTEX OS manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 20 mass %, pH: 3.0), 315.4 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 29.1 g of an aqueous solution
containing 5 mass % of polyvinyl alcohol (tradename: PVA105
manufactured by Kuraray Co., Ltd., saponification degree: 98 to 99
mol %, polymerization degree: 500) and 104.5 g of ion-exchanged
water were added with stirring, followed by stirring for 5 minutes,
to obtain a coating composition for forming a hydrophilic coating
film comprising, by a solid content ratio, 55 parts by mass of
boehmite, 45 parts by mass of silica and 4 parts by mass polyvinyl
alcohol and having a solid content concentration of 6 mass % and a
pH of 4.1.
[0123] 2 mL of the above coating composition for forming a
hydrophilic coating film was applied to the corona
discharge-treated surface of an ETFE film having A4 size by a bar
coater and then dried at 80.degree. C. for 5 minutes to form a
hydrophilic coating film having a thickness of 0.35 .mu.m thereby
to obtain an ETFE film having a hydrophilic coating film formed on
one side.
[0124] The composition of the solid content, the solid content
concentration and the sizes of the respective particles in the
coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 2
[0125] A coating composition for forming a hydrophilic coating film
having pH 4.5 was obtained in the same manner as in Example 1
except that as the boehmite, tradename: DISPAL 10F4 manufactured by
SASOL Ltd. was used instead of tradename: DISPAL 11N7-80
manufactured by SASOL Ltd., and instead of the polyvinyl alcohol
(tradename: PVA105 manufactured by Kuraray Co., Ltd.), a modified
polyvinyl alcohol (tradename: Gohsefimer Z100 manufactured by
Nippon Synthetic Chemical Industry Co., Ltd.) was used. Further, an
ETFE film having a hydrophilic coating film formed on one side was
obtained in the same manner as in Example 1 except that such a
coating composition for forming a hydrophilic coating film was
used.
[0126] The composition of the solid content, the solid content
concentration and the sizes of the respective particles in the
coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 3
[0127] A boehmite dispersion was obtained in the same manner as in
Example 1.
[0128] To 100 g of the boehmite dispersion, 66.7 g of silica sol
(tradename: Organosilica sol IPA-ST manufactured by Nissan Chemical
Industries, Ltd., solid content concentration: 30 mass %), 56 g of
an aqueous solution containing 10 mass % of polyethylene glycol
(PEG2000, molecular weight: 2000), 0.8 g of a surfactant
(tradename: SN Wet L manufactured by San Nopco Limited), 280 g of
ion-exchanged water and 270 g of industrial ethanol (tradename:
SOLMIX AP-1 manufactured by Japan Alcohol Trading Company Limited)
were added with stirring, followed by stirring for 5 minutes, to
obtain a coating composition for forming a hydrophilic coating film
comprising, by a solid content ratio, 50 parts by mass of boehmite,
50 parts by mass of silica, 14 parts by mass of PEG2000 and 2 parts
by mass of the surfactant and having a solid content concentration
of 6 mass % and a pH of 5.5. Further, an ETFE film having a
hydrophilic coating film formed on one side was obtained in the
same manner as in Example 1 except that such a coating composition
for forming a hydrophilic coating film was used.
[0129] The composition of the solid content, the solid content
concentration and the sizes of the respective particles in the
coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 4
Comparative Example
[0130] An ETFE film provided with a hydrophilic coating film was
produced in the same manner as in Example 1 except that as the
boehmite, tradename: DISPAL 18N4-80 manufactured by SASOL Ltd. was
used instead of tradename: DISPAL 11N7-80 manufactured by SASOL
Ltd.
[0131] The composition of the solid content, the solid content
concentration and the sizes of the respective particles in the
coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 5
Comparative Example
[0132] An ETFE film provided with a hydrophilic coating film was
obtained in the same manner as in Example 1 except that the amount
of the boehmite dispersion was changed to 163.6 g, and the amount
of the silica sol was changed to 18.2 g.
[0133] The composition of the solid content, the solid content
concentration and the sizes of the respective particles in the
coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 6
Comparative Example
[0134] An ETFE film provided with a hydrophilic coating film was
obtained in the same manner as in Example 1 except that the amount
of the boehmite dispersion was changed to 18.2 g, and the amount of
the silica sol was changed to 163.6 g.
[0135] The composition of the solid content, the solid content
concentration and the sizes of the respective particles in the
coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 7
Comparative Example
[0136] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 18N4-80 manufactured by SASOL Ltd.) was added
with stirring, and after continuing the stirring for 30 minutes,
the system was left to stand at room temperature for one day, to
obtain a boehmite dispersion having a solid content concentration
of 20 mass % and a pH of 3.6.
[0137] To 19.0 g of the boehmite dispersion, 10.3 g of silica sol
(tradename: SNOWTEX S manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 30 mass %, pH: 10), 50.0 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 1.5 g of 1N nitric acid, 6.0 g of
an aqueous solution containing 7 mass % of polyvinyl alcohol
(tradename: PVA105 manufactured by Kuraray Co., Ltd.,
saponification degree: 98 to 99 mol %, polymerization degree: 500),
and 18.9 g of ion-exchanged water were added with stirring,
followed by stirring for 5 minutes, to obtain a coating composition
for forming a hydrophilic coating film comprising, by a solid
content ratio, 55 parts by mass of boehmite, 45 parts by mass of
silica and 6 parts by mass of polyvinyl alcohol and having a solid
content concentration of 7 mass % and pH 5.0.
[0138] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 8
[0139] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 14N4-80 manufactured by SASOL Ltd.) was added
with stirring, and after continuing the stirring for 30 minutes,
the system was left to stand at room temperature for one day, to
obtain a boehmite dispersion having a solid content concentration
of 20 mass % and a pH of 4.0.
[0140] To 19.0 g of the boehmite dispersion, 10.3 g of silica sol
(tradename: SNOWTEX S manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 30 mass %, pH: 10), 50.0 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 1.5 g of 1N nitric acid, 6.0 g of
an aqueous solution containing 7 mass % of polyvinyl alcohol
(tradename: PVA105 manufactured by Kuraray Co., Ltd.,
saponification degree: 98 to 99 mol %, polymerization degree: 500),
and 19.0 g of ion-exchanged water were added with stirring,
followed by stirring for 5 minutes, to obtain a coating composition
for forming a hydrophilic coating film comprising, by a solid
content ratio, 55 parts by mass of boehmite, 45 parts by mass of
silica and 6 parts by mass of polyvinyl alcohol and having a solid
content concentration of 7 mass % and pH 5.1.
[0141] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 9
[0142] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 11 N7-80 manufactured by SASOL Ltd.) was added
with stirring, and after continuing the stirring for 30 minutes,
the system was left to stand at room temperature for one day, to
obtain a boehmite dispersion having a solid content concentration
of 20 mass % and a pH of 5.3.
[0143] To 19.0 g of the boehmite dispersion, 10.3 g of silica sol
(tradename: SNOWTEX S manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 30 mass %, pH: 10), 50.0 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 1.5 g of 1N nitric acid, 4.0 g of
an aqueous solution containing 7 mass % of modified polyvinyl
alcohol (tradename: Gohsefimer Z100 manufactured by Nippon
Synthetic Chemical Industry Co., Ltd.), 1.0 g of an aqueous
solution containing 10% of zirconium oxychloride octahydrate, 19.0
g of ion-exchanged water and 1.0 g of an aqueous solution
containing 10 mass % of a surfactant (tradename: SN Wet L
manufactured by San Nopco Limited) were added with stirring,
followed by stirring for 5 minutes, to obtain a coating composition
for forming a hydrophilic coating film comprising, by a solid
content ratio, 55 parts by mass of boehmite, 45 parts by mass of
silica and 4 parts by mass of polyvinyl alcohol and having a solid
content concentration of 7 mass % and pH 5.8.
[0144] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 10
[0145] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 10F4 manufactured by SASOL Ltd.) was added with
stirring, and after continuing the stirring for 30 minutes, the
system was left to stand at room temperature for one day, to obtain
a boehmite dispersion having a solid content concentration of 20
mass % and a pH of 4.0.
[0146] To 19.0 g of the boehmite dispersion, 10.3 g of silica sol
(tradename: SNOWTEX S manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 30 mass %, pH: 10), 50.0 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 1.5 g of 1N nitric acid, 6.0 g of
an aqueous solution containing 7 mass % of modified polyvinyl
alcohol (tradename: Gohsefimer Z100 manufactured by Nippon
Synthetic Chemical Industry Co., Ltd.) and 19.0 g of ion-exchanged
water were added with stirring, followed by stirring for 5 minutes,
to obtain a coating composition for forming a hydrophilic coating
film comprising, by a solid content ratio, 55 parts by mass of
boehmite, 45 parts by mass of silica and 6 parts by mass of
polyvinyl alcohol and having a solid content concentration of 7
mass % and pH 5.2.
[0147] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 11
Comparative Example
[0148] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 60 manufactured by SASOL Ltd.) was added with
stirring, and after continuing the stirring for 30 minutes, the
system was left to stand at room temperature for one day, to obtain
a boehmite dispersion having a solid content concentration of 20
mass % and a pH of 7.0.
[0149] To 19.0 g of the boehmite dispersion, 10.3 g of silica sol
(tradename: SNOWTEX S manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 30 mass %, pH: 10), 50.0 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 1.5 g of 1N nitric acid, 6.0 g of
an aqueous solution containing 7 mass % of modified polyvinyl
alcohol (tradename: Gohsefimer Z100 manufactured by Nippon
Synthetic Chemical Industry Co., Ltd.) and 19.0 g of ion-exchanged
water were added with stirring, followed by stirring for 5 minutes,
to obtain a coating composition for forming a hydrophilic coating
film comprising, by a solid content ratio, 55 parts by mass of
boehmite, 45 parts by mass of silica and 6 parts by mass of
polyvinyl alcohol and having a solid content concentration of 7
mass % and pH 6.8.
[0150] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 12
[0151] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 11 N7-80 manufactured by SASOL Ltd.) was added
with stirring, and after continuing the stirring for 30 minutes,
the system was left to stand at room temperature for one day, to
obtain a boehmite dispersion having a solid content concentration
of 20 mass % and a pH of 5.3.
[0152] To 19.0 g of the boehmite dispersion, 15.5 g of silica sol
(tradename: SNOWTEX XS manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 20 mass %, pH: 10), 50.0 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 1.2 g of 1N nitric acid, 6.0 g of
an aqueous solution containing 7 mass % of modified polyvinyl
alcohol (tradename: Gohsefimer Z100 manufactured by Nippon
Synthetic Chemical Industry Co., Ltd.) and 13.8 g of ion-exchanged
water were added with stirring, followed by stirring for 5 minutes,
to obtain a coating composition for forming a hydrophilic coating
film comprising, by a solid content ratio, 55 parts by mass of
boehmite, 45 parts by mass of silica and 6 parts by mass of
polyvinyl alcohol and having a solid content concentration of 7
mass % and pH 5.5.
[0153] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 13
[0154] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 11 N7-80 manufactured by SASOL Ltd.) was added
with stirring, and after continuing the stirring for 30 minutes,
the system was left to stand at room temperature for one day, to
obtain a boehmite dispersion having a solid content concentration
of 20 mass % and a pH of 5.3.
[0155] To 19.0 g of the boehmite dispersion, 15.5 g of silica sol
(tradename: SNOWTEX 20L manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 20 mass %, pH: 10), 50 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 1.2 g of 1N nitric acid, 6.0 g of
an aqueous solution containing 7 mass % of modified polyvinyl
alcohol (tradename: Gohsefimer Z100 manufactured by Nippon
Synthetic Chemical Industry Co., Ltd.) and 13.8 g of ion-exchanged
water were added with stirring, followed by stirring for 5 minutes,
to obtain a coating composition for forming a hydrophilic coating
film comprising, by a solid content ratio, 55 parts by mass of
boehmite, 45 parts by mass of silica and 6 parts by mass of
polyvinyl alcohol and having a solid content concentration of 7
mass % and pH 4.9.
[0156] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 14
Comparative Example
[0157] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 11 N7-80 manufactured by SASOL Ltd.) was added
with stirring, and after continuing the stirring for 30 minutes,
the system was left to stand at room temperature for one day, to
obtain a boehmite dispersion having a solid content concentration
of 20 mass % and a pH of 5.3.
[0158] To 19.0 g of the boehmite dispersion, 7.7 g of silica sol
(tradename: Cataloid SI80P manufactured by Catalysts &
Chemicals Industries Co., Ltd., solid content concentration: 40
mass %, pH: 10), 50.0 g of industrial ethanol (tradename: SOLMIX
AP-1 manufactured by Japan Alcohol Trading Company Limited), 1.5 g
of 1N nitric acid, 6.0 g of an aqueous solution containing 7 mass %
of modified polyvinyl alcohol (tradename: Gohsefimer Z100
manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and
21.6 g of ion-exchanged water were added with stirring, followed by
stirring for 5 minutes, to obtain a coating composition for forming
a hydrophilic coating film comprising, by a solid content ratio, 55
parts by mass of boehmite, 45 parts by mass of silica and 6 parts
by mass of polyvinyl alcohol and having a solid content
concentration of 7 mass % and pH 4.7.
[0159] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 15
[0160] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 11 N7-80 manufactured by SASOL Ltd.) was added
with stirring, and after continuing the stirring for 30 minutes,
the system was left to stand at room temperature for one day, to
obtain a boehmite dispersion having a solid content concentration
of 20 mass % and a pH of 5.3.
[0161] To 15.5 g of the boehmite dispersion, 12.6 g of silica sol
(tradename: SNOWTEX S manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 30 mass %, pH: 10), 50.0 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 1.8 g of 1N nitric acid, 6.0 g of
an aqueous solution containing 7 mass % of modified polyvinyl
alcohol (tradename: Gohsefimer Z100 manufactured by Nippon
Synthetic Chemical Industry Co., Ltd.) and 12.6 g of ion-exchanged
water were added with stirring, followed by stirring for 5 minutes,
to obtain a coating composition for forming a hydrophilic coating
film comprising, by a solid content ratio, 45 parts by mass of
boehmite, 55 parts by mass of silica and 6 parts by mass of
polyvinyl alcohol and having a solid content concentration of 7
mass % and pH 4.9.
[0162] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 16
[0163] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 11 N7-80 manufactured by SASOL Ltd.) was added
with stirring, and after continuing the stirring for 30 minutes,
the system was left to stand at room temperature for one day, to
obtain a boehmite dispersion having a solid content concentration
of 20 mass % and a pH of 5.3.
[0164] To 27.6 g of the boehmite dispersion, 4.6 g of silica sol
(tradename: SNOWTEX S manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 30 mass %, pH: 10), 50.0 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 0.6 g of 1N nitric acid, 6.0 g of
an aqueous solution containing 7 mass % of modified polyvinyl
alcohol (tradename: Gohsefimer Z100 manufactured by Nippon
Synthetic Chemical Industry Co., Ltd.) and 17.0 g of ion-exchanged
water were added with stirring, followed by stirring for 5 minutes,
to obtain a coating composition for forming a hydrophilic coating
film comprising, by a solid content ratio, 80 parts by mass of
boehmite, 20 parts by mass of silica and 6 parts by mass of
polyvinyl alcohol and having a solid content concentration of 7
mass % and pH 5.0.
[0165] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 17
[0166] To 800 g of ion-exchanged water, 200 g of boehmite
(tradename: DISPAL 11 N7-80 manufactured by SASOL Ltd.) was added
with stirring, and after continuing the stirring for 30 minutes,
the system was left to stand at room temperature for one day, to
obtain a boehmite dispersion having a solid content concentration
of 20 mass % and a pH of 5.3.
[0167] To 6.9 g of the boehmite dispersion, 18.4 g of silica sol
(tradename: SNOWTEX S manufactured by Nissan Chemical Industries,
Ltd., solid content concentration: 30 mass %, pH: 10), 50.0 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 2.6 g of 1N nitric acid, 6.0 g of
an aqueous solution containing 7 mass % of modified polyvinyl
alcohol (tradename: Gohsefimer Z100 manufactured by Nippon
Synthetic Chemical Industry Co., Ltd.) and 21.6 g of ion-exchanged
water were added with stirring, followed by stirring for 5 minutes,
to obtain a coating composition for forming a hydrophilic coating
film comprising, by a solid content ratio, 20 parts by mass of
boehmite, 80 parts by mass of silica and 6 parts by mass of
polyvinyl alcohol and having a solid content concentration of 7
mass % and pH 4.7.
[0168] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 18
Comparative Example
[0169] By using a coating composition having the modified polyvinyl
alcohol omitted from the hydrophilic coating material in Example
11, coating and evaluations were carried out in the same manner as
in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 19
Comparative Example
[0170] 35.0 g of silica sol (tradename: SNOWTEX OS manufactured by
Nissan Chemical Industries, Ltd., solid content concentration: 20
mass %, pH: 3), 50.0 g of industrial ethanol (tradename: SOLMIX
AP-1 manufactured by Japan Alcohol Trading Company Limited), 6.0 g
of an aqueous solution containing 7 mass % of modified polyvinyl
alcohol (tradename: Gohsefimer Z100 manufactured by Nippon
Synthetic Chemical Industry Co., Ltd.) and 15.0 g of ion-exchanged
water were added with stirring, followed by stirring for 5 minutes,
to obtain a coating composition for forming a hydrophilic coating
film comprising 100 parts by mass of silica and 6 parts by mass of
polyvinyl alcohol and having a solid content concentration of 7
mass % and pH 3.3.
[0171] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
Example 20
Comparative Example
[0172] 35.0 g of boehmite dispersion in Example 3, 50.0 g of
industrial ethanol (tradename: SOLMIX AP-1 manufactured by Japan
Alcohol Trading Company Limited), 6.0 g of an aqueous solution
containing 7 mass % of modified polyvinyl alcohol (tradename:
Gohsefimer Z100 manufactured by Nippon Synthetic Chemical Industry
Co., Ltd.) and 15.0 g of ion-exchanged water were added with
stirring, followed by stirring for 5 minutes, to obtain a coating
composition for forming a hydrophilic coating film comprising 100
parts by mass of boehmite and 6 parts by mass of polyvinyl alcohol
and having a solid content concentration of 7 mass % and pH
5.0.
[0173] Coating and evaluations were carried out in the same manner
as in Example 1. The composition of the solid content, the solid
content concentration and the sizes of the respective particles in
the coating composition for forming a hydrophilic coating film, are
shown in Table 1, and the evaluation results are shown in Table
2.
TABLE-US-00001 TABLE 1 Coating composition for forming hydrophilic
coating film Composition of solid content (parts by mass)
Crystallite Average Solid content diameter of particle Boehmite
Silica Crosslinking concentration boehmite diameter of particles
particles Binder Surfactant agent (mass %) (nm) silica (nm) Ex. 1
55 45 4 6 32 12 Ex. 2 55 45 4 6 40 12 Ex. 3 50 50 14 2 6 32 12 Ex.
4 (Comp. Ex.) 55 45 4 6 15 12 Ex. 5 (Comp. Ex.) 90 10 4 6 32 12 Ex.
6 (Comp. Ex.) 10 90 4 6 32 12 Ex. 7 (Comp. Ex.) 55 45 6 7 15 12 Ex.
8 55 45 6 7 23 12 Ex. 9 55 45 4 1 1 7 32 12 Ex. 10 55 45 6 7 40 12
Ex. 11 (Comp. Ex.) 55 45 6 7 61 12 Ex. 12 55 45 6 7 32 5 Ex. 13 55
45 6 7 32 45 Ex. 14 (Comp. Ex.) 55 45 6 7 32 80 Ex. 15 45 55 6 7 32
12 Ex. 16 80 20 6 7 32 12 Ex. 17 20 80 6 7 32 12 Ex. 18 (Comp. Ex.)
20 80 7 32 12 Ex. 19 (Comp. Ex.) 100 6 7 15 Ex. 20 (Comp. Ex.) 100
6 7 32
TABLE-US-00002 TABLE 2 Low Thickness Haze Transmittance Contact
temperature Durability of Abrasion (nm) Appearance value (%) (%)
angle (.degree.) wettability wettability resistance Ex. 1 350
.largecircle. 1.5 95 15 .circleincircle. .largecircle. 92 Ex. 2 350
.largecircle. 3 94 15 .largecircle. .largecircle. 95 Ex. 3 280
.largecircle. 2.5 94 15 .circleincircle. .largecircle. 75 Ex. 4
(Comp. Ex.) 350 .largecircle. 3 93 20 X -- 50 Ex. 5 (Comp. Ex.) 350
.largecircle. 8 95 15 .largecircle. .DELTA. 30 Ex. 6 (Comp. Ex.)
350 .largecircle. 1 95 15 .largecircle. X 90 Ex. 7 (Comp. Ex.) 350
.largecircle. 1 94 27 .DELTA. .DELTA. 61 Ex. 8 350 .largecircle.
1.1 94 26 .largecircle. .largecircle. 93 Ex. 9 350 .largecircle.
1.5 94 7 .circleincircle. .circleincircle. 94 Ex. 10 350
.largecircle. 3 94 9 .circleincircle. .largecircle. 92 Ex. 11
(Comp. Ex.) 350 .largecircle. 60 93 10 .largecircle. .DELTA. 90 Ex.
12 350 .largecircle. 1.3 94 7 .circleincircle. .DELTA. 95 Ex. 13
350 .largecircle. 4.7 94 8 .largecircle. .largecircle. 80 Ex. 14
(Comp. Ex.) 350 .largecircle. 8 94 15 .largecircle. .DELTA. 75 Ex.
15 600 .largecircle. 2.5 94 12 .circleincircle. .circleincircle. 82
Ex. 16 350 .largecircle. 5 93 15 .largecircle. .largecircle. 70 Ex.
17 350 .largecircle. 1 94 12 .largecircle. .DELTA. 90 Ex. 18 (Comp.
Ex.) 100 .largecircle. 0.8 94 8 .circleincircle. X 74 Ex. 19 (Comp.
Ex.) 350 .largecircle. 0.9 94 20 .largecircle. XX 90 Ex. 20 (Comp.
Ex.) 350 .largecircle. 1 93 25 .largecircle. X 55
INDUSTRIAL APPLICABILITY
[0174] By the coating composition for forming a hydrophilic coating
film of the present invention, it is possible to form a hydrophilic
coating film on various articles such as various lamp covers,
lenses for eyeglasses, goggles, various instrument covers, sign
boards, protective films, laminated films, agricultural films or
solar cell sheets.
[0175] The entire disclosures of Japanese Patent Application No.
2009-030955 filed on Feb. 13, 2009 and Japanese Patent Application
No. 2009-030956 filed on Feb. 13, 2009 including specifications,
claims, drawings and summaries are incorporated herein by reference
in their entireties.
* * * * *