Title of Invention

A DISPERSION OF TITANIUM OXIDE PARTICLES, A TITANIUM OXIDE THIN FILM FORMED THEREFROM AND A SOLUTION FOR FORMING AN ORGANIC FUNCTIONAL FILM

Abstract A dispersion of titanium oxide particle which can form a fine organic thin film having impurities and can be a titanium oxide thin film forming material, a titanium oxide thin film formed from the dispersion, a solution for forming an organic functional film obtained by adding a metallic compound solution having a hydrolyzable group in the dispersion, a substrate having an organic functional film formed thereon which is obtained by using the Solution, and a production method thereof are provided. A dispersion of a titanium oxide particle obtained by adding water to an organic solvent solution of titanium chelate compound composed of a hydrolyzable group or a hydroxyl group and a chelate ligand bonding to a titanium atom, in which the amount of the water is five-fold or more by mole to the titanium chelate compound, a titanium oxide thin film formed by contacting this dispersion with the substrate surface composed of plastics or the like, a solution for forming organic functional film obtained by adding the dispersion in the organic solvent solution of metallic compound having hydrolyzable group, a method for producing a substrate having an organic functional film formed thereon which is obtained by using this solution for forming an organic functional film are provided.
Full Text DISPERSION OF TITANIUM OXIDE PARTICLES, TITANIUM OXIDE THIN FILM,
SOLUTION FOR FORMING ORGANIC FUNCTIONAL FILM, SUBSTRATE HAVING
ORGANIC FUNCTIONAL FILM FORMED THEREON, AND METHOD FOR
PRODUCING THE SAME
Technical Field
[0001]
The present invention relates a dispersion of titanium oxide particles obtained by
adding excess amount of water to an organic solvent solution containing a titanium chelate
compound and a method for producing the same. Also, the present invention relates to a
titanium oxide thin film formed from the dispersion, a solution for forming an organic
functional film obtained by adding a metallic compound solution having a hydrolyzable
group to the dispersion, and a substrate having the organic functional film formed thereon
obtained by using this solution and a method for producing the same.
Priority is claimed to Japanese application No. 2005-037616, filed February 15,
2005, and Japanese application No. 2005-273905, filed September 21, 2005, which are
incorporated herein by reference.
Background of the Invention
[0002]
The biodification of surfaces of substrates composed of glass, metal, plastic,
ceramics and so forth has been carried out for many purposes in various fields in the prior
art. For exajmple, a fluorine-containing silane coupling agent has been coated onto a
glass or plastib surface to impart water repellency and oil repellency thereto.
[0003]
Examples of methods for forming a coating film for modifying a substrate surface
are described in Patent document 1, which discloses a method for forming a chemically
adsorbed film covalently bonded by means of siloxane bonds by contacting a mixed
solution containing at least an alkoxysilane surfactant, a non-aqueous solvent free of

active hydrogen, and a silanol condensation catalyst with a substrate surface. Examples
of the silanol condensation catalyst disclosed therein include at least one substance
selected from the group consisting of a carboxylic acid metal salt, carboxylic acid ester
metal salt, carboxylic acid metal salt polymer, carboxylic acid metal salt chelate, titanic
acid ester, and titanic acid ester chelate.
[0004]
However, these methods had problems such as film formation requiring a long
period of time, and the silanol condensation catalyst inhibiting adsorption if film
formation is Carried out with the catalyst still present in the solution, thereby preventing
the formation of a fine monolayer.
Thus; there has been a desire for the development of a technology for rapidly
forming a fine monolayer having few impurities in fields such as fine patterning for the
design of electrical devices in particular.
[0005]
Relating to the present invention, Patent document 2 discloses a composition for
forming a transparent ceramics coating in which an acetyl acetonate compound is
uniformly dissolved or dispersed in a mixed solvent composed of water and an organic
solvent. The art in this document shows a composition for forming a transparent
ceramics coating which has high durability and is mar-proof to a substrate surface such as
glass, plastics, or the like, can control the refractive index or the dielectric constant freely,
and can be cured at a low temperature.
[0006]
Also, Patent document 3 discloses a composition for a coating obtained by
mixing (a) an organosilane represented by the general formula RxSi(ORy)3, in which Rx
represents an organic group having 1 to 8 carbon atoms and Ry represents an alkyl group
having 1 to 5 carbon atoms
(b) an organosilane represented by the general formula (Rx)2Si(ORy)2, in which Rx and Ry
represent the same as described above,
(c) at least one type selected from the group consisting of at least one type of metal

alcoholate selected from the group consisting of the general formula Zr(ORz)4, Ti(ORz)4,
and Al(ORz)3, in which Rz represents an alkyl group having 2 to 5 carbon atom, a chelate

compound obtained by reacting the metal alcoholate and β-diketones and/or β-ketoesters,
and a partial hydrolysate obtained by reacting the chelate compound with water,
(d) hydrophilic organic solvent, and (e) water and co-condensation the above component
(a) and the abbve component (b).
The art in this document shows a composition for a coating in order to form a
coating which has excellent water resistance, chemical resistance, crack resistance,
weather resistance, and adhesive properties on the surface of the metal or plastics.
[0007]
Non-Patent document 1 discloses a solution having a composition of
i
Ti(OPr)3(acac)/PriOH/EtOKH=1/1/3 obtained by treating Ti(OPri)4 with acetyl acetone
(acacH) followed by diluting with ethanol, this solution being a stabile photo-sensitive
colloid solution, having a particle size of the colloid included in the solution of 30 to 60A.
[0008]
Also; non-Patent document 2 discloses a method in which a solution including a
compound represented by Ti(OPr')4-x(L)x is obtained by adding a chelate agent such as
acetyl acetone to Ti(OPr')4 solution, and dispersion of fine particles of titanium oxide is
obtained by adding of a two-fold water equivalents to titanium atoms into the solution.
[0009]
However, the above Patent documents 2 and 3 and non-Patent documents 1 and 2
do not disclose that dispersion of titanium oxide particles suitable for forming a titanium
oxide thin film is obtained by adding excess amount of water (five-fold or more
equivalents to titanium atom).

[0010]
[Patent document 1] Japanese Laid-Open Patent Application No. H8-337654
[Patent document 2] Japanese Laid-Open Patent Application No. H2-048403
[Patent document 3] Japanese Patent publication Nos. 22924081
[Non-Patent document 1] Mat. Res. Symp. Proc., Vol. 121, P317-322, 1988

[Non-Patent document 2] Bull. Korean. Chem. Soc., Vol. 20, No. 12, 1999

Summary of the Invention
[0011]
In consideration of these circumstances, an object of the present invention is to
provide a dispersion of titanium oxide particles capable of rapidly forming a fine organic
thin film having few impurities and being a material for forming a titanium oxide thin film
and a method for producing the same, a titanium oxide thin film formed from this
dispersion, a solution for forming an organic functional film obtained by adding a solution
of a metallic compound having a hydrolyzable group into the dispersion, and a substrate
having an orginic functional film formed thereon which is obtained by using this solution
and a method for producing the same.
[0012]
In order to solve the aforementioned problems, the inventors of the present
invention extensively studied a method for forming a coating film on the surface of
substrate by using an organic solvent solution containing (partial) hydrolysis products of
titanium alkoxide. As a result, the inventors of the present invention found that excess
amount of water to the titanium chelate compound can be added to the organic solvent
solution including titanium chelate compound to obtain a dispersion in which fine
particles of titanium oxide having a particle size of 1-20 nm are uniformly dispersed and
this dispersion is applied on a substrate surface and dried to form a fine titanium oxide
thin film having few impurities with speed and ease.
[0013]
Also, the inventors found that the dispersion and a solution of a metallic
compound having a hydrolyzable group can be mixed in a prescribed ratio to obtain a
solution for forming an organic functional film which is capable of quickly forming an
organic functional film with suitable for a photo lithography method or the like and an
organic functional film can be formed on a substrate with ease and efficiency by using this
solution, and thus completed the present invention.
[0014]

According to a first aspect, dispersion of titanium oxide particles of the following
(1) to (12) are provided.
(1) dispersion of titanium oxide particle is obtained by mixing a titanium chelate
compound formed by bonding a hydrolyzable group or hydroxyl group and a chelate

ligand to a titanium atom and five-fold or more by mole of water to the titanium chelate
compound, wherein the content of the titanium oxide is within the range of 0.1 to 10 % by
weight as titanium oxide to the whole dispersion.
(2) the dispersion according to (1), wherein the titanium oxide particles are a fine
particles having the average particle size of 1 to 20 nm.
(3) the dispersion according to (1) or (2), wherein the content of the titanium
oxide is within the range of 0.1 to 5% by weight as titanium oxide to the whole dispersion.
[0015]
(4) the dispersion according to (1) to (3), wherein the titanium oxide particles
have amphipathicity.
(5) the dispersion according to (1) to (4), wherein the amount of mixed water is
ten-fold or more by mol to the titanium chelate compound.
(6) the dispersion according to (1) to (5), wherein the hydrolyzable group is an
optionally substituted alkoxyl group.
(7) the dispersion according to any one of (1) to (6), wherein the titanium chelate
compound is represented by the formula (I),
[0016]
[Chemical Formula 1]

[0017] |
wherein X represents chelate ligand, R1 represents an optionally substituted
alkoxyl group nl represents an integer of 1 to 3, when n 1 is 2 or more, R1 may be the
same or different, and when (4-nl) is 2 or more, X may be the same or different.
[0018]

(8) aj dispersion of titanium oxide particles is obtained by mixing a solution
obtained by adding a prescribed amount of a chelate compound to an organic solvent
solution of titanium alkoxide compound and five-fold or more by mole of water to the
titanium alkoxide compound.
(9) the dispersion according to (8) , wherein the amount of the mixed water is
ten-fold or moire by mole to the titanium alkoxide compound.

(10) the dispersion according to (8) or (9), wherein the organic solvent is
water-miscible solvent.
(11) the dispersion according to (10), wherein the water-miscible solvent is a
solvent including alcohols.
[0019]
According to a second aspect, methods for producing dispersion of the following
(12) and (13) are provided.
(12) a method for producing the dispersion of any one of (1) to (11) includes
adding a prescribed amount of a chelate compound to an organic solvent solution of
titanum alkoxide compound and further adding five-fold or more by mole of water to the
titanum alkoxide compound.
(13) the method for producing dispersion according to (12), wherein the amount
of water added is ten-fold or more by mole to the titanum alkoxide compound.
[0020]
According to a third aspect, titanium oxide thin films of the following (14) to (26)
are provided.
(14) a titanium oxide thin film is formed by contacting the dispersion of any one
of (1) to (11) with a surface of a substrate.
(15) the titanium oxide thin film according to (14), wherein a film thickness is
500 nm or less.
(16) the titanium oxide thin film according to (14) or (15), wherein the substrate
is made of plastics.
[0021]

(17) the titanium oxide thin film according to any one of (14) to (16), wherein an
organic material contacting with the thin film can be decomposed/removed by photo
irradiation.
(18) the titanium oxide thin film according to (17), wherein the organic material
contacting with the thin film is a monolayer.
(19) the titanium oxide thin film according to (18), wherein the monolayer is
made of a silicon compound.
[0022]
(20) the titanium oxide thin film according to any one of (14) to (19), wherein the
titanium oxide thin film becomes a hydrophilic film having the water contact angle of 20°
or less by photo irradiation.
(21) the titanium oxide thin film according to any one of (17) to (20), wherein an
irradiation light using photo irradiation is ultraviolet rays.
(22) the titanium oxide thin film according to (21), wherein an irradiation light
using photo irradiation is ultraviolet rays having a wavelength of 250 to 350 nm.
[0023]
(23) the titanium oxide thin film according to any one of (17) to (22), wherein the
amount of irradiation light is 40J/cm2 or less.
(24) the titanium oxide thin film according to any one of (14) to (23), wherein the
titanium oxide thin film includes an organic material.
(25) me titanium oxide thin film according to any one of (14) to (24), wherein the
content of carbon element is within the range of 2 to 40%.
(26) the titanium oxide thin film according to any one of (14) to (25), wherein the
average surface roughness Ra is 1 nm or less.
[0024]
Accoirding to a fourth aspect, solutions for forming an organic functional film of
the following (24) to (40) are provided.
(27) a solution for forming an organic functional film includes a metallic
compound having a hydrolyzable group or hydroxyl group and a dispersion of any one of

(l)to(ll).
(28) the solution for forming an organic functional film according to (27),
wherein the metallic compound is used in two-fold or more by mole to 1 mole of the
titanium compound included in the dispersion.
i
(29) a solution for forming an organic functional film is obtained by mixing an
organic solvent solution of a metallic compound having a hydrolyzable group or hydroxyl
group, a solution of titanium chelate compound having a hydrolyzable group or hydroxyl
group and a chelate ligand, and five-fold or more by mole of water to the total number of
moles of the titanium chelate compound and metallic compound.
[0025]
(30) the solution for forming an organic functional film according to (29),
wherein the mixed water is ten-fold or more by mole to the total number of moles of the
titanium chelate compound and the metallic compound.
(31) the solution for forming an organic functional film according to (29) or (30),
wherein the hydrolyzable group of the titanium chelate compound is an optionally
substituted alkoxyl group.
(32) the solution for forming an organic functional film according to any one of
(29) to (31), wherein the metallic compound is used in two-fold or more by mole to 1
mole of the titanium chelate compound.
[0026]
(33) the solution for forming an organic functional film according to any one of
(29) to (32), wherein the total content of the titanium chelate compound and the metallic
compound is within the range of 0.1 to 10% by weight as metal oxide.
(34) a solution for forming organic functional film is obtained by mixing a
solution obtained by adding a chelate compound and metallic compound having a
hydrolyzable group to an organic solvent solution of titanium alkoxide compound in
respectively prescribed amount and five-fold or more by mole of water to the total number
of moles of the titanium alkoxide compound and metallic compound.
(35) the solution for forming an organic functional film according to (34),

wherein the amount of the mixed water is ten-fold or more by mole to the total number of
moles of the titanium alkoxide compound and metallic compound.
[0027]
(36) the solution for forming an organic functional film according to any one of
(27) to (35), wherein a metal of the metallic compound is at least one kind selected from
the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin,
tantalum, zinc, tungsten, and lead.
(37) the solution for forming an organic functional film according to any one of
(27) to (36), wherein the hydrolyzable group of the metallic compound is an optionally
substituted alkoxyl group.
(38) the solution for forming an organic functional film according to any one of
(27) to (37), wherein the metallic compound is represented by the formula (II),
[0028]
[Chemical Formula 2]

[0029]
in which R2 represents an optionally substituted hydrocarbon group, optionally
substituted halogenated hydrocarbon group, hydrocarbon group including a linking group,
or a halogenated hydrocarbon group including a linking group, M represents at least a
metal atom selected from the group consisting of a silicon atom, germanium atom, tin
atom, titanium atom, and zirconium atom, R3 represents an optionally substituted alkoxyl
group, m represents valence of M, n2 represents an integer of 0 to (m-1), when n2 is 2 or
more, R2 may be the same or different, and when (m-1) is 2 or more, R3 may be the same
or different.
(39) the solution for forming an organic functional film according to any one of
(27) to (38), Wherein the organic solvent is a water-miscible solvent.
(40) the solution for forming an organic functional film according (39), wherein
the organic solvent includes alcohols.

[0030]
According to the fifth aspect, substrates having the organic functional film
formed thereon of the following (41) and (52) are provided.
(41) a substrate having an organic functional film formed thereon has an organic
thin film formed by contacting a solution for forming an organic functional film of any
one of (27) to (40) with a substrate surface.
(42) the substrate having an organic functional film formed thereon according to
(41), wherein the substrate has a titanium oxide thin film formed from the dispersion of
any one of (1) to (11).
(43) the substrate having an organic functional film formed thereon according to
(41) or (42), wherein the substrate is made of at least one kind selected from the group
consisting of metal, ceramics, glass, and plastics.
[0031]
(44) the substrate having an organic functional film formed thereon according to
(41) to (43), wherein the substrate is made of plastics.
(45) the substrate having an organic functional film formed thereon according to
any one of (41) to (44), wherein an organic material contacting with the organic functional
film can be decomposed and/or removed by photo irradiation
(46) the substrate having an organic functional film formed thereon according to
any one of (41) to (45), wherein the organic functional film becomes a hydrophilic film
having a water contact angle of 20° or less by photo irradiation.
[0032]
(47) the substrate having an organic functional film formed thereon according to
(45) or (46), wherein an irradiation light using photo irradiation is ultraviolet rays.
(48) the substrate having an organic functional film formed thereon according to
(47), wherein an irradiation light using photo irradiation is ultraviolet rays having
wavelength of 250 to 350 nm.
(49) the substrate having an organic functional film formed thereon according to
(47) or (48), wherein the amount of the irradiation light is 40 J/cm2 or less.

[0033]
(50) the substrate having an organic functional film formed thereon according to
any one of (41;) to (49), wherein the organic functional film includes an organic material.
(51) the substrate having an organic functional film formed thereon according to
any one of (41) to (50), wherein the content of carbon element in the organic functional
film is within the range of 2 to 40%.
(52) the substrate having an organic functional film formed thereon according to
any one of (41) to (51), wherein a film thickness of the organic functional film is 500 nm
or less.
[0034]
According to a sixth aspect, a method for producing a substrate having an organic
functional film formed thereon of the following (53) is provided.
(53) a method for producing a substrate having an organic functional film formed
thereon of any one of (41) to (52), wherein the organic functional film is formed on the
titanium oxide thin film by contacting the substrate having the titanium oxide thin film
formed thereon in which the titanium oxide thin film of any one of (14) to (26) is formed
with the solution for forming an organic functional film of any one of (27) to (40).
[0035]
According to dispersion of titanium oxide particles of the present invention, a fine
particle of titalnium oxide having an average particle size of nanometer-order is dispersed
stably in the water solvent. The dispersion of the present invention is stable and is
almost not changed even if left at room temperature for 3 months. The dispersion of the

present invention can form a titanium oxide thin film which is a fine monolayer having
few impurities with speed and ease. Also, the dispersion of titanium oxide particles of
the present invention is useful as material for forming an organic functional film of the
present invention.
[0036]
According to the solution for forming an organic functional film of the present
invention, an organic functional film suitable for a photolithography method or the like

can be formed: on the substrate with ease and speed.
The substrate having an organic functional film formed thereon of the present
invention includes an organic functional film formed on a substrate and is suitable for use
for photolithography method.
Brief Description of the accompanying Drawings
[0037]
FIG. 1 is a graph showing the particle size distribution of a titanium oxide particle
included in A-3 solution.

FIG. 2 is a graph showing the TG-DTA analysis result of powder obtained by
drying the A-3 solution in a vacuum at room temperature.
FIG. 3 is a graph showing a measurement result of zeta potential of the A-3
solution.
FIG. 4 is observation graphs of a substrate by scanning probe microscopy before
and after coating A-3 solution, (a) is an observation graph showing a surface of a
polyester substrate before coating A-3 solution, (b) is an observation graph showing a
surface of a thin film formed from A-3 solution.
FIG. 5 is a graph showing an XPS analysis result of element distribution of thin
film (C-1) formed by using A-1 solution.
FIG. 6 is a graph showing an XPS analysis result of element distribution of thin
film (C-8) formed by using A-4 solution.
FIG.7 is a graph showing an XPS analysis result of element distribution of thin
film (CH-1) formed by using H-1 solution.
FIG. 8 is a graph showing an XPS analysis result of element distribution of thin
film (CH-2) f6rmed by using CH-2 solution.
Detailed Description of the Invention
[0038]
The following provides a detailed explanation of the present invention.
1) Dispersion of titanium oxide particles

The first aspect of the present invention provides dispersion of titanium oxide
particles obtained by mixing a titanium chelate compound, in which a hydrolyzable group
and chelate ligand are bonded to a titanium atom, and excess amount of water to the
titanium chelate compound.
[0039]
There is no particular limitation on the titanium chelate compound used in the
present invention, provided that the titanium compound is formed by bonding a
hydrolyzable group and chelate ligand to a titanium atom.
[0040]
A valence value of the titanium atom as a center metallic atom is normally 2 to 4
and preferably 4.
There is no particular limitation on the hydrolyzable group, provided the group is
decomposed by reacting with water. Specific hydrolyzable groups include an optionally
substituted alkoxyl group, optionally substituted acyloxy group, halogen group, isocyanate
group, cyano group, amino group, amide group, and the like.
[0041]
Examples of the optionally substituted alkoxyl group include a methoxy group,
ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group,
t-butoxy group, n-pentyloxy group, n-hexyloxy group, and the like.
[0042]
Examples of the optionally substituted acyloxy group include an acetoxy group,
propionyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group,
n-butylcarbonyloxy group, and the like.
Examples of the substituent of the alkoxyl group and acyloxy group include a
halogen group, carboxyl group, amide group, imide group, ester group, hydroxyl group,
and the like.
Examples of the halogen atom include a fluorine atom, chlorine atom, bromine
atom, and iodine atom.
[0043]

Among them, an optionally substituted alkoxyl group, optionally substituted
acyloxy group, halogen atom, or isocyanate group is preferable, an optionally substituted
alkoxyl group is more preferable, and an alkoxyl group having 1 to 4 carbon atom is
particularly preferable.
[0044]
There is no limitation on the chelate ligand, provided that the ligand can form a
chelate by bonding metal. A neutral ligand and anion may be included.
The chelate ligand may bond to a metallic atom on at least one part and may be a
unidentate ligand or polydentate ligand. For example, in the case of a bidentate ligand,
the bidentate ligand may not bond to one metallic atom.
[0045]
Specific examples of the chelate ligand include the following ligands. The
following examples are described as chelate compounds capable of being chelate ligands.
Specific examples of the chelate ligand include saturated aliphatic dicarboxylic
acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic
acid, suberic acid, azelaic acid, or sebacic acid; β-diketone such as acetylacetone, benzoyl
acetone, or hexafluoro acetyl acetone; p-ketoesters such as methyl acetoacetate or ethyl
acetoacetate; glycols such as ethylene glycol; glycol acids such as oxy acetic acid;
nitrogen-including compounds such as ethylenediaminetetraacetato (EDTA) and sodium
salt thereof, ethylenediamine, 1,3-propanediamine, diethylentriamine,
pentamethyldiethylenetriamine, hexamethyltriethylenetetramine,
tris[2-(dimethylamino)ethyl]amine, or tri(pyridinylmethyl)amine;
[0046]
other heterocyclic compounds such as furan carboxylic acid, thiophene
carboxylic acid, nicotinic acid, isonicotinic acid, phenanthroline, diphenanthroline,
substituted phenanthroline, 2,2':6',2"- terpyridine, pyridine imine, cross-1inking aliphatic
diamine, 4-4'-di(5-nonyl)-2,2'-bipyridine, bipyridine coordinated with O, S, Se, or Te,
alkyliminopyridine, alkylbipyridinylamine, alkyl substituted tripyridine,
di(alkyIamino)alkylpyridine, or ethylenediaminedipyridine; and

[0047]
sulfur-including compounds such as mercapto alcohols such as 2-mercapto
ethanol; dithiols such as ethane dithiol; mercapto amines such as 2-mercapto ethyl amine;
or dithioketones such as 2,4-pentanedithione.
These compounds can be used alone or two or more types can be used in
combination.
[0048]
Preferable specific examples of the titanium chelate compound include one kind
or two or more kinds of a compound represented by the formula (I).
In the formula (I), R1 represents an optionally substituted alkoxyl group and X
represents a chelate ligand. Specific examples of R1 include the same examples as the
optionally substituted alkoxyl group of the hydrolyzable group previously described.
Specific examples of X include the same examples as the chelate ligand previously
described.
[0049]
n1 represents an integer of 1 to 3. n1 is preferably 1 for forming an organic thin
film having high density.
When nl is 2 or more, R1 may be the same or different. When (4-n1) is 2 or
more, X may be the same or different.
[0050]
There is no limitation on a method for producing a titanium chelate compound
and, for example, a method for adding a prescribed amount of chelate compound to an
organic solvent solution of titanium alkoxide compound, as described later, and the like
are included. The amount of chelate compound used is usually 1 to five-fold by mol and
preferably 1 to three-fold by mol to 1 mol of titanium alkoxide compound.
[0051]
There is no limitation on the water used for adjusting the dispersion of the present
invention, provided that the water is neutral. In view of obtaining a fine titanium oxide
thin film haying few impurities, it is preferable to use pure water, distilled water, or

ion-exchanged water.
[0052]
The amount of water used is excessive to the titanium chelate compound, and the
specifically amount of water used is five-fold or more by mole, preferably ten-fold or
more by mole, and more preferably twenty-fold or more by mole, to the titanium chelate
compound.
Also, the maximum amount of water used is determined according to the
concentration of titanium chelate compound in dispersion to be adjusted. For example,
in the case of adjusting dispersion having a concentration of 0.1% or more, the amount of
water used is iten thousand-fold or less by mole and preferably five thousand-fold or less
by mole to the titanium chelate compound. In the case of adjusting dispersion having a
concentration of 0.1% or less, the maximum amount of water used is more.
[0053]
The water used may be diluted by an organic solvent. Also, the water may be
added at once, may be added stepwise, and may be continuously added in a constant
amount.
[0054]
Examples of the organic solvent used include the same examples as an organic
solvent used as a solution of the titanium chelate compound described later.
[0055]
By mixing the titanium chelate compound and an excess amount of water, a
hydrolysis reaction of titanium chelate compound is begun.
Examples of the method for mixing the titanium chelate compound and an excess
amount of water include a method for adding water to an organic solvent solution of the
titanium chelate compound or a method for adding an organic solvent solution of the
titanium chelate compound to water.
[0056]
There is no limitation on the organic solvent used in the organic solvent solution
of the titaniurn chelate compound, for example, alcohols such as methanol, ethanol, or iso

propanol; halogenated hydrocarbons such as methylene chloride, chloroform, or
chlorobenzene; hydrocarbons such as hexane, cyclohexane, benzene, toluene, or xylene;
ethers such as tetrahydrofuran, diethylether, or dioxane; ketones such as acetone,
methylethylketone, or methylisobutylketone; amides such as dimethyl formamide or
N-methyl pyrrolidone; sulfoxides such as dimethyl sulfoxide; silicones such as
methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane,
methylphenylpolysiloxane, dimethylsilicone, phenylsilicone, alkyl-modified silicone, or
polyethersilicone (Japanese Laid-Open Patent Application No. H9-208438); frons; and
carbon fluorides such as CBr2ClCF3, CClF2CF2CCl3, CClF2CF2CHFCl, CF3CF2CHCl2,
CF3CBrFCBrF2, CClF2CClFCF2CCl3, Cl(CF2CFCl)2Cl, Cl(CF2CFCl)2CF2CCl3,
Cl(CF2CFCl)3Cl.
[0057]
Among them, because a hydrolysis reaction of titanium chelate compound or the
like progresses with ease, a fine titanium oxide thin film can be uniformly formed, and
dispersion which does not solidify at low temperature can be obtained, a water-miscible
solvent is preferable and a solvent including alcohols is more preferable.
[0058]
Examples of the solvent including alcohols include a solvent consisting of at least
one kind of alcohol or mixed solvent consisting of alcohols and another organic solvent,
and a mixed solvent consisting of alcohols and another organic solvent is preferable.
[0059]
As the mixed solvent consisting of alcohols and another organic solvent, a mixed
solvent which combines hydrocarbons such as toluene or xylene and lower alcohols such
as methanol, ethanol, isopropanol, or t-butanol is preferable.
Although there is no limitation on the mixing ratio of the mixed solvent, the
mixing ratio of hydrocarbons and lower alcohols is preferably whithin the range of 99/1 to
50/50 by volume.
[0060]
There is no particular limitation on the concentration of the titanium chelate

compound in the organic solvent, provided that the concentration is within the range in
which rapid exothermic heat is inhibited when adding water and the organic solvent has
flow properties capable of stirring. The concentration is preferably within the range of 1
to 50% by weight and more preferably the range of 5 to 30% by weight.
[0061]
Although a reaction temperature for the hydrolysis reaction of the titanium
chelate compound depends on the reactivity, stability, or the like of the used titanium
chelate compound, the reaction temperature is usually within the range of -100°C to the
reflux temperature of the organic solvent used and preferably within the range of -20°C to
room temperature. Also, the hydrolysis reaction and dehydration condensation reaction
may be further conducted by raising the temperature of the reacting solution from room
temperature to the reflux temperature of the solvent used following adding water to a
solution of titanium chelate compound at a lower temperature and aging for a certain time.
[0062]
The stirring time is usually from several minutes to several hours. In this case, it
is preferable to conduct ultrasonic wave treatment in order to obtain uniform dispersion.
[0063]
In addition, an acid, base, or dispersiontabilizer may be added during the
hydrolysis reaction of the titanium chelate compound with water. There are no particular
limitations on the acid or base, provided that it functions as a dispersing agent for
redispersing coagulated precipitate, a catalyst for producing a dispersoid such as colloidal
particles by hydrolyzing and dehydrating/condensing the titanium chelate, or a dispersant
for the formed dispersoid.
[0064]
Examples of acids used include inorganic acids such as hydrochloric acid, nitric
acid, boric acid or fluoroboric acid; organic acids such as acetic acid, formic acid, oxalic
acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid or methanesulfonic acid;
and, photoacid generators which generate acid by photoirradiation of diphenyliodinium
hexafluorophosphate, triphenylphosphonium hexafluorophosphate, or the like.

[0065]
Examples of used bases include triethanolamine, triethylamine,
l,8-diazabicyclo[5.4.0]-7-undecene, ammonia, dimethylformamide, phosphine, and the

like.
[0066]
Dispersion stabilizers indicates agents having the effect of stably dispersing a
dispersoid in a dispersion medium, examples of which include dispersing agents,
protective colloids, and anticoagulation agents such as surfactants. Specific examples
include multivalent carboxylic acids such as glycolic acid, gluconic acid, lactic acid,

tartaric acid, citric acid, malic acid or succinic acid; hydroxycarboxylic acids; phosphoric
acids such as pyrophosphoric acid or tripolyphosphoric acid; polydentate ligand
compounds having a strong chelating ability with respect to metal atoms such as acetyl
acetone, methyl acetoacetic acid, ethyl acetoacetic acid, n-propyl acetoacetic acid,
isopropyl acetoacetic acid, n-butyl acetoacetic acid, sec-butyl acetoacetic acid, t-butyl
acetoacetic acid, 2,4-hexanedione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione,
2,4-nonane-dione or 5-methyl-hexane-dione; fatty acid amines, hydrostearic acids or
polyester amines such as Solsperse 3000, 9000, 17000, 20000 or 24000 (all of the above
are products of Zeneca Corp.) or Disperbyk-161, -162, -163 or -164 (all of the above are
products of BYK-Chemie Corp.); and silicone compounds such as
dimethylpolysiloxane-methyl(polysiloxyalkylene)siloxane copolymer,
trimethylsiloxysilicic acid, carboxy-modified silicone oil or amine-modified silicone (see,
for example, Japanese Laid-Open Patent Application No. H9-208438 and 2000-53421).

[0067]
The content of titanium oxide in the dispersion of the present invention is within
the range of 0.1 to 10% by weight and preferably the range of 0.1 to 5% by weight as
titanium oxide to the total dispersion.
[0068]
The dispersion of the present invention is a dispersion of titanium oxide particles

in which the fine particles of titanium oxide being the hydrolysis product of the titanium


chelate compound have the property of stably dispersing without aggregating in water
solvent or organic solvent.
Here, the state of stably dispersing without aggregating refers to the state in
which a dispeirsoid of a hydrolysis product such as titanium chelate is not coagulated or
non-uniformly separated in an organic solvent and preferably refers to a transparent,
uniform state.
In addition, transparent refers to the state of having high transmittance in visible
light, and more specifically, refers to a state represented in terms of spectral transmittance
as measured under conditions of a dispersoid concentration of 0.5% by weight as oxide, a
quartz cell optical path length of 1 cm, the use of an organic solvent for the contrastive
sample, and a! light wavelength of 550 nm, and preferably refers to transmittance of 80 to
100%.
[0069]
The titanium oxide particles included in the dispersion of the present invention
preferably have amphipathic property. In other words, the particles of the titanium oxide
preferably have affinity for water solvent and organic solvent in order to obtain uniformly
stable dispersion.
A dispersion including such titanium oxide particles provides a titanium oxide
thin film in the form of a uniform film in which water is not repelled when coating on a
substrate, even if the water content exceeds 50% by weight to the total dispersion.
[0070]
There is no particular limitation on a particle size of a titanium oxide particles
included in the dispersion of the present invention, although the range is normally 1 to 100
nm, preferably 1 to 50 nm, and more preferably 1 to 20 nm. Also, a distribution of
titanium oxide particles is preferably monodispersed.
[0071]
Dispersion of the present invention has excellent keeping quality. In other words, an average particle size of the included titanium oxide particles is almost

unchanged and dispersion do not become clouded, even after the dispersion of the present

invention is kept stoppered tightly for 3 months at room temperature. Also, a titanium
oxide thin film in the form of a uniform film can be obtained if dispersion which has been
kept for 3 months is used.
[0072]
The dispersion and thin film of the present invention are fine and sensitive, has
few impurities, and therefore can be used for an inorganic film for pattern formation, a
surface treatment film for printing plates, groundwork inorganic film for forming a SAM
film, LCD, PDP, SED (Surface Conduction Electron Emission Display);
functional film used for various displays such as electronic paper, such as an insulating
film, oriented film, reflection film, or anti-reflection film;
optical film such as a high refraction film for an anti-reflection film, or a low refraction
film, a film for a semiconductor element, a photocatalyst film and precursor film thereof;
an ink adhesion improvement film, formations such as modified films of plastics
surfaces, groundwork materials which improve wettability and adhesion for forming these
films, adhesion agents, hardening agents or crosslinking agents for paint or coating agents,
a reaction catalyst such as an ester or the like, a production in an obscure glass, in which
the glass substrate is coated, binders such as antimicrobial or mildewproofing agents, a
carrier, or the like.
The dispersion of the present invention is useful as production materials of the
titanium oxide thin film and organic functional film of the present invention as described
later.
[0073]
2 ) Method for producing dispersion of the present invention
The second aspect of the present invention provides a method for producing
dispersion of the present invention including mixing a solution obtained by adding
prescribed chelate compound to an organic solvent solution of titanium alkoxide
compound and an excess amount of water to the titanium alkoxide compound.
According to this method, a titanium alkoxide compound which is easily
available can be used to produce the dispersion of the present invention with ease and

effect.
[0074]
Examples of the titanium alkoxide compound of the present invention include a
titanium alkoxide, hydrolysis product of titanium alkoxide, or composite alkoxide
including a titanium atom, and the like.
[0075]
Specific examples of titanium alkoxide include Ti(OCH3)4, Ti(OC2H5)4,
Ti(OC3H7-i)4, Ti(OC4H9)4, Ti[OSi(CH3)3]4, Ti[OSi(C2H5)3]4, and the like.
These titanium alkoxides can be used alone or two or more types can be used in
combination.
[0076]
A hydrolysis product of titanium alkoxide is a compound obtained by hydrolyzing
all or part of titanium alkoxide with water. The amount of water used in order to obtain a
partially hydrolysis product of titanium alkoxide is two-fold or more equivalents to the
titanium alkoxide.
[0077]
Examples of the composite alkoxide include (i) a composite alkoxide obtained by
reacting titanium alkoxide with metal alkoxide and (ii) a composite alkoxide obtained by
reacting one kind or two or more kinds of titanium alkoxide with one kind or two or more
kinds of metallic salt.
[0078]
Examples of (i) a composite alkoxide obtained by reacting titanium alkoxide with
a metal alkoxide include a composite alkoxide and the like obtained by reacting an
alkoxide of alkali metal or alkali earth metal with titanium alkoxide. Specific examples
of a composite alkoxide of (i) include BaTi(OR)6, SrTi(OR)6, and the like, in which R
represents an alkyl group or the like.
[0079]
Examples of a metallic salt used for synthesis of a composite alkoxide of (ii)
include metallic chloride, nitrate, sulfate, acetate, formate, oxalic acid salt, and the like.

Examples of the metal of metallic salt include metals of group 1 to 14 in the periodic law
(long period type).
[0080]
There is no particular limitation on the chelate compound used in the present
invention, provided that a compound is capable of coordination with a titanium atom.
Particular examples include the same examples of a chelate compound capable of being a
chelate ligand of the titanium chelate compound.
The amount of chelate compound added is normally one- to five- fold by mole
and preferably one- to three- fold by mole to 1 mole of the titanium atom.
[0081]
There is no particular limitation on an organic solvent used in the present
invention, although specific examples of the organic solvents include alcohols such as
methanol, ethanol or isopropanol; halogenated hydrocarbons such as methylene chloride,
chloroform or chlorobenzene; hydrocarbons such as hexane, cyclohexane, benzene,
toluene or xylene; ethers such as tetrahydrofuran, diethylether or dioxane; ketones such as
acetone, methyl ethylketone or methylisobutylketone; amides such as dimethylformamide
or N-methylpyrrolidone; sulfoxides such as dimethylsulfoxide; silicones such as
methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentane siloxane or
methylphenylpolysiloxane (see, for example, Japanese Laid-Open Patent Application No.
H9-208438); frons; and fluorinated carbons such as CBr2ClCF3, CClF2CF2CCl3,
CClF2CF2CHFCl, CF3CF2CHCl2, CF3CBrFCBrF2, CClF2CClFCF2CCl3) Cl(CF2CFCl)2Cl,
Cl(CF2CFCl)2CF2CCl3, or Cl(CF2CFCl)3Cl.
[0082]
Of these, the organic solvent used is preferably a water-miscible solvent and more
preferably a solvent including alcohol because the hydrolysis reaction of the titanium
chelate compound or the like easily progresses, a fine uniform titanium oxide thin film can
be formed, and dispersion which does not solidify at low temperature can be obtained.
[0083]
Examples of the solvent including the alcohols include solvents consisting of one

or more kinds of alcohols or a mixed solvent consisting of alcohols and other organic
solvent and a mixed solvent consisting of alcohols and other organic solvent is preferable.
[0084]
The solvent consisting of alcohols and other organic solvent is preferably a mixed
solvent combining hydrocarbons such as toluene or xylene and a lower alcohol such as
methanol, ethanol, isopropanol, or t-butanol. There is no particular limitation on the
mixing ratio of the mixed solvent, although the mixing ratio of a hydrocarbon solvent and
lower alcohol solvent is preferably within the range of 99/1 to 50/50 by volume.
[0085]
There is no particular limitation on the water used, provided that water is neutral,
although it is preferable that pure water, distilled water, or ion-exchanged water be used in
view of obtaining a fine titanium oxide thin film having few impurities.
[0086]
The water may be diluted by an organic solvent. Also, the water may be added
at once, may tie added stepwise, and may be continuously added in a constant amount.
Examples of organic solvents used herein include the same examples as the
organic solvent dissolving the titanium alkoxide compound.
[0087]
The amount of water used is excessive to the titanium alkoxide compound, and
the specific amount of water used is five-fold or more by mole, preferably ten-fold or
more by mole, and more preferably twenty-fold or more by mole, to the titanium chelate
compound or titanium alkoxide compound.
Also, the maximum amount of water used is determined according to the
concentration of titanium chelate compound in dispersion to be adjusted. For example,
in the case of adjusting dispersion having a concentration of 0.1% or more, the amount of
water used is ten thousand-fold or less by mole and preferably five thousand-fold or less
by mole to the titanium chelate compound. In the case of adjusting dispersion having a
concentration of 0.1% or less, the maximum amount of water used is greater.
[0088]

Examples of the method for mixing the solution obtained by adding a chelate
compound to an organic solvent solution of titanium alkoxide compound and water
include a method for adding water or water diluted with an organic solvent to the solution
obtained by adding a chelate compound to an organic solvent solution of a titanium
alkoxide compound and a method for adding a solution obtained by adding a chelate
compound to an organic solvent solution of titanium alkoxide compound to water or
organic solvent in which water is suspended or dissolved, although the former is
preferable because of obtaining a hydrolysis product of the target product with high yield.
[0089]
It is conceivable that a chelate compound be added to an organic solvent solution
of titanium alkoxide compound to obtain an organic solvent solution of a titanium chelate
compound and an excess amount of water be added to this solution to start the hydrolysis
reaction of titanium chelate compound or the like.
[0090]
Although a reaction temperature of this hydrolysis reaction depends on reactivity,
stability, or the like of the titanium alkoxide compound or chelate compound used, the
reaction temperature is generally within the range of-100°C to the reflux temperature of
the organic solvent used and preferably in the range of-20°C to room temperature. Also,
the hydrolysis reaction and dehydration condensation reaction may be further conducted
by raising the temperature of the reacting solution from room temperature to the reflux
temperature of the solvent used following adding water to the solution obtained by adding
the chelate compound to the organic solvent solution of titanium alkoxide at a lower
temperature and aging for a certain time.
[0091]
The stirring time is usually from several minutes to several hours. In this case, it
is preferable to conduct ultrasonic wave treatment in order to obtain a uniform solution for
forming an organic thin film.
Also, when conducting the hydrolysis reaction with water in which water is added
to a solution obtained by adding a chelate compound to an organic solvent solution of

titanium alkoxide compound, acid, base, or dispersion stabilizer may be added. Specific
examples of acid, base, or dispersion stabilizer include the same examples as acid, base, or
dispersion stabilizer which can be added when conducting the hydrolysis reaction of
titanium chelate compound with water.
[0092]
As described above, a dispersion of titanium oxide particles of the present
invention can be obtained.
Also, in the present invention, the dispersion of the present invention can be
produced by the method in which the titanium chelate compound is isolated from the
solution obtained by adding the chelate compound to the organic solvent solution of
titanium alkoxide compound, the isolated titanium chelate compound is re-dissolved in the
organic solvent, and water is added.
[0093]
Although insoluble materials may be separated in the prepared dispersion, these
separation materials can be removed by conducting filtration, decantation, or the like to
obtain uniform dispersion.
[0094]
3) Titanium oxide thin film
The third aspect of the present invention provides a titanium oxide thin film
which is formed by contacting the surface of the substrate including at least one kind
selected from the group consisting of metals, ceramics, glass, and plastics with the
dispersion of the present invention.
[0095]
The substrate used in the present invention is preferably a substrate consisting of
at least one kind selected from the group consisting of metal, ceramics, glass, and plastics
and a substrate consisting of plastics is preferable.
[0096]
Although there is no limitation on plastics, examples of the plastics include
polyimide, polyamide, polyamideimide, polyphenyleneether, polyetherketone,

polyetheretherketone, polyolefin, polyester, polycarbonate, polysulphone, polyether
sulphone, polyphenylenesulfide, polyallylate, acrylic-series resin, cyclolefin-series
polymer, aromatic-series polymer, and the like.
[0097]
Although there is no limitation on the substrate used of the present invention, a
substrate having an active hydrogen such as a hydroxyl group or the like on the surface
may be used for the purpose of improving adhesion properties with a thin film.
[0098]
Although there is no limitation on the method for contacting dispersion of the
present invention with the substrate surface, generally known methods may be adopted.
Specific examples of the method include a dipping method, spin coating method, spray
method, roller coating method, mayer bar coater method, screen printing method, brush
coating method, and the like.
[0099]
The titanium oxide thin film of the present invention can decompose and/or
remove an organic compound contacting with the thin film by photoirradiation.
Although there is no limitation on the organic compound contacting with this thin film, a
monolayer is effective because high-speed decomposition can proceed. Especially,
silicon compound such as a silane-series surfactant or the like is effective, because a
self-assembled monolayer is formed on the titanium oxide thin film.
[0100]
Although examples of the method for forming a monolayer of the organic
compound include various methods such as a vapor phase evaporation method, method of
chemical adsorption from a solution in which an organic compound is dissolved, or LB
method, any method may be used.
[0101]
When using the method of chemical adsorption from a solution, there is no
limitation on a temperature used to contact the solution with the substrate surface,
provided that the temperature is within the range that maintains the stability of the solution.

The temperature is normally within the range of room temperature to reflux temperature of
the organic solvent used. It is acceptable to heat the dispersion or the substrate itself in
order to set the preferable temperature for contact.
[0102]
Also, after contacting the dispersion of the present invention with the substrate
i
surface, an ultrasonic wave may be used in order to facilitate film formation.
The step of contacting the substrate surface may be conducted for a long time at
once or may be divided into several short-time applications.
[0103]
After forming the monolayer, a cleaning step may be performed in order to
remove excess agent, impurities, or the like adhered on the film surface. By providing
the cleaning step, the film thickness can be further controlled.
[0104]
There is no limitation on the cleaning step, provided that the step can remove an
I
adhered material. Examples of the method include a method for immersing a substrate in
a solvent able to dissolve the titanium chelate compound; a method for leaving the
substrate under a vacuum or normal pressure to vaporize the adhered material; a method
for spraying With inactive gas such as dried nitrogen gas and blowing out the adhered
material; and the like.
[0105]
After contacting the dispersion of the present invention with the substrate or
cleaning the substrate, it is preferable to heat the substrate in order to stabilize the film

formed on the substrate surface. The heating temperature can be determined according to
the kind of substrate, the stability of the formed monolayer, or the like.
[0106]
Although a mechanism for forming the monolayer of silicon compound is not
obvious in detail, it is assumed that the surface is coated by forming the rigid band of
Ti-O-Si after silicon compound physically adsorbs or chemically adsorbs to a titanium
oxide thin film having active hydrogen on the surface.

[0107]
Although there is no limitation on film thickness of the titanium oxide thin film
of the present invention obtained as above, the film thickness is normally 500 nm or less,
preferably 1 to 100 nm, and more preferably 5 to 50 nm.
[0108]
The titanium oxide thin film of the present invention is preferably a thin film
including an Organic compound and more preferably a thin film having a carbon element
content of 2 to 40%.
[0109]
Also, a titanium oxide thin film of the present invention has excellent flatness.
The average roughness Ra of the titanium oxide thin film is 2 nm or less and preferably 1
nm or less. Therefore, a flat organic functional film can be formed on this titanium oxide
thin film as described later.
[0110]
A titanium oxide thin film generally has thin film properties which are changed
by photoirradiation. It is preferable that the titanium oxide thin film of the present
invention be a photocatalytically active film which can decompose and/or remove an
organic compound contacting with the titanium oxide thin film by photoirradiation.
[0111]
The irradiation light using the photoirradiation is preferably ultraviolet rays and
more preferably ultraviolet rays having a wavelength of 250 to 350nm.
The amount of the irradiation light is 40 J/cm2 or less and preferably 5 J/cm2 or
less.
[0112]
The titanium oxide thin film of the present invention is preferably a hydrophilic
film having a Water contact angle of 20 ° or less by photoirradiation.
When the titanium oxide thin film of the present invention has these properties, a
resist film with a prescribed pattern can be formed and a specific part of the titanium oxide
thin film can be changed to be a hydrophilic thin film by photoirradiation with a

prescribed pattern.
[0113]
The titanium oxide thin film of the present invention is quickly formed on the
substrate surface by using the dispersion of the present invention and is a fine film having
few impurities regardless of a kind of substrate used.
[0114]
These titanium oxide thin films can be applied to design patterns for forming
electric devices or the like, electronic products, and especially ultra thin film coating such
as for electric appliances, automobiles, industrial equipment, mirrors, eyeglass lenses, or
the like which require heat resistance, resistance to weather, and abrasion resistance, as
well as a photocatalyst film.
Also, as described later, this titanium oxide thin film is coated with an organic
functional film by using a solution for forming an organic functional film or the like to act
as a photo catalyst layer and conduct photo lithography with ease.
[0115]
4) Solution f6r forming organic functional film
The fourth aspect of the present invention provides a solution for forming an
organic functional film obtained by adding the dispersion of the present invention to the
organic solvent solution of a metallic compound having a hydrolyzable group.
[0116]
There is no limitation on a metallic compound used in the present invention,
provided that the metallic compound has at least one hydrolyzable group. There is no
limitation on the hydrolyzable group, provided that the hydrolyzable group can be
decomposed by reacting with water. Specific examples include an optionally substituted
alkoxyl group optionally substituted acyloxy group; a halogen atom such as a fluorine
atom, chlorine atom, bromine atom, iodine atom, or the like; isocyanate group; cyano
group; amino group; amide group; and the like.
[0117]
These specific examples include the same specific examples as the hydrolyzable

group of the titanium chelate compound. Among them, an optionally substituted alkoxyl
i
group is preferable. Specific examples of an optionally substituted alkoxyl group include
the same specific examples as the optionally substituted alkoxyl group of the titanium
chelate compound.
[0118]
Although there is no limitation on the metal of the metallic compound used in the
present invention, examples include at least one kind selected from the group consisting of
titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten,
and lead.
[0119]
Among them, the metallic compound used in the present invention is preferably
the compound represented by formula (II).
In the formula (II), R2 represents an optionally substituted hydrocarbon group,
optionally substituted halogenated hydrocarbon group, hydrocarbon group including a
linking group, or halogenated hydrocarbon group including a linking group.
[0120]
Examples of the base hydrocarbon group in the optionally substituted
hydrocarbon group include an alkyl group having 1 to 30 carbon atoms such as a methyl
group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group,
sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl
group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-decyl group,
n-octadecyl group, or the like; alkenyl group having 2 to 30 carbon atoms such as vinyl
group, propenyl group, butenyl group, pentenyl group, n-decynyl group, n-octadecynyl
group, or the like; and aryl group such as phenyl group, or naphthyl group.
[0121]
Examples of the base halogenated hydrocarbon group of the optionally
substituted halogenated hydrocarbon group include a halogenated alkyl group having 1 to
30 carbon atoms, halogenated alkenyl group having 2 to 30 carbon atoms, halogenated
aryl group, and the like. Specific examples include a group in which at least one

hydrogen atom in the exemplified hydrocarbon group is substituted with a halogen atom
such as a fluorine atom, chlorine atom, bromine atom, or the like.
[0122]
Among them, the group in which two hydrogen atoms or more in the alkyl group
having 1 to 30 carbon atoms are substituted with a halogen atom is preferable and a
fluorinated alkyl group in which two hydrogen atoms or more in the alkyl group having 1
to 30 carbon atoms are substituted with a fluorine atom is more preferable. Also, when
the fluorinated alkyl group has a branched structure, the branched portion has preferably 1
to 4 carbon atoms and more preferably a short chain having 1 to 2 carbon atoms.
[0123]
A fluorinated alkyl group is preferably the group in which one fluorine atom or
more bonds to the terminal carbon atom and more preferably the group in which three
fluorine atoms bond to the terminal carbon atoms i.e., the group having a CF3 group,
especially preferably is the group having perfluoro alkyl portion at a terminal portion in
which all hydrogen atoms of the alkyl group are substituted with fluorine atoms and
having an alkylene group represented by -(CH2)h- (wherein, h represents an integer of 1
to 6 and preferably 2 to 4) between the metal atom M described later and the terminal
portion.
When the number of fluorine atoms in the fluorinated alkyl group is expressed as
[(the number of fluorine atoms in the fluorinated alkyl group)/(the number of hydrogen
atom existing in alkyl group having the same number of carbon atoms as the fluorinated
alkyl group) 100]%, the number is preferably 60% or more and more preferably 80% or
more.
[0124]
Examples of the substituent of the optionally substituted hydrocarbon group or
optionally substituted halogenated hydrocarbon group include a carboxyl group; amide

group; imide group; ester group; alkoxyl group such as methoxy group, ethoxy group, or
the like; and hydroxyl group. The number of these substituent is preferably 0 to 3.
[0125]


Specific examples of the base hydrocarbon group in the hydrocarbon group
including a linking group include the same examples as the base hydrocarbon group of the
optionally substituted hydrocarbon group.
Specific examples of the base halogenated hydrocarbon group in the halogenated
hydrocarbon group including a linking group include the same examples as the base
halogenated hydrocarbon group of the optionally substituted halogenated hydrocarbon
group.
[0126]
The linking group exists preferably between a carbon-carbon bond of the
hydrocarbon group or the halogenated hydrocarbon group or between the carbon atom of
the hydrocarbon group and the metal atom M described later.
Specific examples of the linking group include -0-, -S-, -S02-,-CO-,-C(=0)0-,
or -C(=0)NR -, wherein R represents an alkyl group such as a hydrogen atom; methyl
group, ethyl group, n-propyl group, isopropyl group, or the like.
[0127]
Among them, R is preferably an alkyl group having 1 to 30 carbon atoms,
fluorinated alkyl group having 1 to 30 carbon atoms, or fluorinated alkyl group having a
linking group in view of water repellency and durability.
[0128]



to these.
[0131]
M represents at least one kind of metal atom selected from the group consisting
of a silicon atom, germanium atom, tin atom, titanium atom, and zirconium atom, and a
silicon atom is especially preferable.
[0132]
R3 represents an optionally substituted alkoxyl group. Specific examples of the
optionally substituted alkoxyl group include the same as listed in the above paragraph of
the optionally substituted alkoxyl group of the titanium chelate compound.
[0133]
m represents the valence of M.
n2 represents an integer of 0 to (m-1) and when n2 is 2 or more, R2 may be the
same or different and when (m-1) is 2 or more, R3 may be the same or different.
[0134]
A compound represented by the formula (II) is more preferably a compound

represented by the formula (III).
[0135]


[0136]
In formula, M, R , m, and n2 represent the same as described above.
R4 and R5 represent independently a hydrogen atom or fluorine atom.
[0137]
R6 represents an alkylene group, vinylene group, ethynylene group, arylene group,
or dihydric linking group including a silicon atom and/or oxygen atom. Specific
examples of R6 are described as follows.
[0138] ;
[Chemical Formula 4]


[0139]
Wherein, a and b represent arbitrary natural numbers.
W represents a hydrogen atom; alkyl group such as a methyl group, ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl
group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group,
isohexyl group, or the like; alkoxyl group such as a methoxy group, ethoxy group,
n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group,

n-pentyloxy group, n-hexyloxy group, or the like; a fluorine-including alkyl group in
which all or part of the hydrogen atoms of the alkyl group are substituted with a fluorine
atom; or fluorine-including alkoxyl group in which all or part of the hydrogen atoms of the
alkoxyl group are substituted with a fluorine atom; and the like.
[0140]
n2 is preferably 0 in order to form an organic thin film with a high density.
When n2 is 2 or more, W may be the same or different and when (m-n2-1) is 2 or more, R
may be the same or different. Also, p represents 0 or an integer and q represents 0 or 1.
[0141]
Preferable specific examples of the metallic compound are shown as follows.
Although the; compounds in which the metallic atom is a silicon atom are shown as
representative examples, the metallic compounds are not limited to those compounds.
[0142]





[0147]
In order to prepare the solution for forming an organic functional film of the
present invention, an organic solvent, water, and titanium chelate compound can be the
same as the organic solvent, water, and titanium chelate as described in the above
paragraph "dispersion", respectively.
[0148]

In the solution for forming an organic functional film of the present invention, the
amount of the metallic compound used is two-fold or more by mole to 1 mole of titanium

compound included in the dispersion. Also, the amount of metallic compound used
which is two-fold or more by mole is thousand-fold or less by mole at maximum,
preferably hundred-fold or less by mole, and more preferably twenty-fold or less by mole.
[0149]
In the solution for forming an organic functional film, the total content of
titanium oxide and metallic compound preferably is 0.1 to 10% by weight as metallic
oxide.
[0150]
The solution for forming an organic functional film of the present invention is, as
described above, obtained by (a) adding the prescribed amount of dispersion of the present
invention to an organic solvent solution of metallic compound having a hydrolyzable
group.
[0151]
Also, the solution for forming an organic functional film of the present invention
may be obtained by a method (b) of adding the prescribed amount of titanium chelate
compound to the organic solvent solution of the metallic compound having a hydrolyzable
group and excess amount of water to the metallic compound and the titanium chelate
compound or a method (c) of adding the prescribed amount of the chelate compound and
metallic compound to the organic solvent solution of the titanium alkoxide compound and
excess amount of water to the metallic compound and titanium alkoxide compound.
[0152]

In the method (b), the dispersion of the present invention is prepared within the
system in the presence of the metallic compound having a hydrolyzable group. Also, in

the method (c), the titanium chelate compound is prepared within the system in the
presence of the metallic compound having a hydrolyzable group and the dispersion of the
present invention is prepared within the system by adding excess amount of water.
[0153]
In the method (b), the amount of water added is excessive, preferably five-fold or
more by mole, more preferably ten-fold or more by mole, and particular preferably
twenty-fold of more by mole to the total moles of the titanium chelate compound and the
metallic compound.
Also, the amount of water used is determined according to the density of the
titanium chelate compound in the dispersion to be prepared, for example, when the
dispersion has the density of 0.1% or more, the amount of water used is ten thousand-fold
or less by mole and preferably five thousand-fold or less by mole to the titanium chelate
compound. When the dispersion has the density of 0.1% or less, the maximum amount
of the water is more.
[0154]
In the method (c), the amount of water added is excessive, preferably five-fold or
more by mole, more preferably ten-fold or more by mole, and particular preferably
twenty-fold or more by mole to the total moles of the titanium alkoxide compound and the
metallic compound.
Also, the amount of water used is determined according to the density of the

titanium chelate compound in the dispersion to be prepared, for example, when the
dispersion has the density of 0.1% or more, the amount of water used is ten thousand-fold
or less by mole and preferably five thousand-fold or less by mole to the titanium chelate
compound. When the dispersion has the density of 0.1% or less, the maximum amount
of water is more.
[0155]
By adding water, the hydrolysis reaction and hydrolysis condensation

polymerization can be started. Usually this reaction proceeds smoothly by adding water
or water diluted with an organic solvent to an organic solvent solution of a metallic
compound and titanium chelate compound. Also, the reaction may proceed by adding an
organic solvent solution of a metallic compound and titanium chelate compound or a
metallic compound and titanium chelate compound to an organic solvent in which water is
suspended or dissolved.
[0156]
The reaction conditions such as reaction temperature, reaction time, or the like,
can be the same as when preparing the dispersion of the present invention.
Also in the reaction solution, the same acid, base, or dispersion stabilizer as
described above may be added to conduct the reaction.
[0157]
5) Substrate having organic functional film formed thereon and production method thereof
The fifth aspect of the present invention provides a substrate having an organic
functional film formed thereon which has an organic thin film formed from the solution
for forming the organic functional thin film of the present invention on the substrate
surface.
[0158]
The substrate having an organic functional film formed thereon of the present
invention can be produced by contacting the solution for forming an organic functional
film with the Substrate surface or the side of the titanium oxide thin film forming substrate
where the titanium oxide thin film is formed.
[0159]
A method for forming an organic functional film by contacting the solution for
forming an organic functional film can use the same method as for forming the titanium

oxide thin film on the substrate surface.

[0160]
Although there is no limitation on the substrate used, examples of the substrate

include the same examples as the substrate for forming the titanium oxide thin film and

the substrate having a titanium oxide thin film thereon which has a titanium oxide thin
film formed from the dispersion of the present invention on the substrate and the latter is
preferable.
[0161]
When using the substrate having a titanium oxide thin film thereon, the substrate

having the organic functional film formed thereon in which the organic functional film is
formed on the titanium oxide thin film of the substrate can be applied to photo lithography
or the like because of the photocatalyst activity function of the titanium oxide thin film.
[0162]
Although there is no limitation on the film thickness of the obtained organic
functional film, the film thickness normally is 500 nm or less. Also the obtained organic functional film is preferably a thin film including the
organic compound and more preferably a thin film including an organic compound in
which the content of carbon element is within the range of 2 to 40%.
[0163]
It is preferable for the organic functional film to be able to decompose and/or
remove an organic compound contacting with the organic functional film by
photoirradiation.
[0164]
Also, it is preferable for the organic functional film to be a hydrophilic film
having a contact angle of water of 20° or less by photoirradiation.
By using these organic functional films, a resist film with a prescribed pattern can
be formed and a specific part of the organic functional film can be changed to be a
hydrophilic thin film by photoirradiation with a prescribed pattern.
[0165]
The irradiation light used in photoirradiation is preferably ultraviolet rays and
more preferably ultraviolet rays having a wavelength of 250 to 350nm.
The amount of irradiation light is 40 J/cm2 or less and preferably 5 J/cm2 or less.

Examples
[0166]
The present invention will be explained below in more detail by reference to the
following Examples, but the invention should not be construed as being limited thereto.
(1) Solution for forming thin film
(Example 1) preparation of solution for forming thin film (1)
181.8 g of diisopropoxy bisacetylacetonatetitanium (Trade name: "T-50"
manufactured by Nippon Soda Co., Ltd., solid content of 16.5% by weight as titanium
oxide) was dissolved in 2518.2 g of mixed solvent of ethanol/ethyl acetate=50/50 (volume
ratio). 300 g (44.4-fold by mol to diisopropoxy bisacetylacetonatetitanium) of
ion-exchanged water was slowly added dropwise into this solution at room teperature
while stirring. Following completion of addition, the solution was hydrolyzed by stirring
for 2 hours and left standing for 1 day to obtain a yellow, transparent solution for forming
a thin film (hereinafter referred to as "Solution A-1") which included titanium oxide
particles (average particle size of 4.3 nm) having a concentration of 2% by weight as
titanium oxide. The above operations were conducted at room temperature.
[0167]
(Example 2) Preparation of solution for forming thin film (2)
363.6 g of diisopropoxybisacetylacetonatetitanium (Trade name: "T-50"
manufactured by Nippon Soda Co., Ltd., solid content of 16.5% by weight as titanium
oxide) was dissolved in 2336.4 g of 2-butanol. 300 g (22.2-fold by mol to diisopropoxy

bisacetylacetonatetitanium) of ion-exchanged water was slowly added dropwise into this
solution at room temperature while stirring. Following completion of addition, the
solution was hydrolyzed by stirring for 2 hours and left standing for 2 days to obtain a
yellow, transparent solution for forming a thin film (hereinafter referred to as "Solution
A-2") which included titanium oxide particles (average particle size of 5.0 nm) having the
concentration of 1% by weight as titanium oxide. The above operations were conducted

at room temperature.

[0168]
(Example 3) Preparation of solution for forming thin film (3)
181.8 g of diisopropoxybisacetylacetonatetitanium (Trade name: "T-50"
manufactured! by Nippon Soda Co., Ltd., solid content of 16.5% by weight as titanium
oxide) was slowly added dropwise into 2818.2 g (417-fold by mol to diisopropoxy
bisacetylacetonatetitanium) of ion-exchanged water at room temperature while stirring.
Following completion of addition, the solution was hydrolyzed by stirring for 2 hours and
left standing for 1 day to obtain a yellow, transparent solution for forming thin film
(hereinafter referred to as "Solution A-3") which included titanium oxide particles
(average particle size of 4.0 nm) having a concentration of 1% by weight as titanium oxide.
The above operations were conducted at room temperature.
[0169]
(Example 4) Preparation of solution for forming thin film (4)
After dissolving 47.12g of methyl silicate (Trade name "MS-56" manufactured by
Mitsubishi Chemical Corporation, solid content of 57.3% by weight as silicon oxide) in
2634.7 g of mixed solvent of ethanol/ethyl acetate=50/50 (volume ratio), 18.2 g of
diisopropoxy bisacetylacetonatetitanium (Trade name: "T-50" manufactured by Nippon
Soda Co., Ltd, solid content of 16.5% by weight as titanium oxide) was added to obtain a
solution. 300g (34.2-fold by mol to the total number of moles of methyl silicate and
diisopropoxy bisacetylacetonatetitanium) of ion-exchanged water was slowly added
dropwise into; the obtained solution at room temperature while stirring. Following
completion of addition, the solution was hydrolyzed by stirring for 2 hours and left

standing for 1 day to obtain a yellow, transparent solution for forming thin film

(hereinafter referred to as "Solution A-4") which included titanium oxide particles
(average particle size of 8.3 nm) having a concentration of 1% by weight as titanium oxide.
The above operations were conducted at room temperature.
[0170]

(Example 5) Preparation of solution for forming thin film (5)
4 g of octadecyltrimethoxysilane (ODS) was dissolved in 396 g of toluene.

This solution was added dropwise into 600 g of Solution A-1 at room temperature while
stirring. Following completion of addition, the solution was hydrolyzed by stirring for
24 hours to obtain a yellow, transparent solution for forming a thin film (the solution was
referred to as "Solution A-5" and the water content is 38.9-fold by moles to the total
number of mole of titanium oxide and ODS) which included fine particles of reaction
product obtained by reacting ODS with titanium oxide. The above operations ware
conducted at room temperature.
[0171]
(Comparative {Example 1) Preparation of solution for forming thin film (6)
181.8 g of diisopropoxy diacetylacetonatetitanium (Trade name: "T-50"
manufactured by Nippon Soda Co., Ltd., the solid content of 16.5% by weight as titanium
oxide) was dissolved in 2818.2 g of mixed solvent of ethanol/ethyl acetate=50/50 (volume
ratio) to obtain a yellow, transparent solution for forming a thin film (hereinafter referred
to as "Solution H-1") having a concentration of 1% by weight as titanium oxide. The
above operations were conducted at room temperature.
[0172]
(Comparative Example 2) Preparation of solution for forming thin film (7)
181.8 g of diisopropoxydisacetylacetonatetitanium (Trade name: "T-50"
manufactured by Nippon Soda Co., Ltd., solid content of 16.5% by weight as titanium
oxide) was dissolved in 2794.6 g of mixed solvent of ethanol/ethyl acetate=50/50(volume
ratio). 24.31 g (3.6-fold by mol to diisopropoxy bisacetylacetonatetitanium) of
ion-exchanged water was slowly added dropwise into this solution at room temperature
while stirring io obtain a yellow, transparent solution for forming a thin film (hereinafter
referred to as "Solution H-2") having a concentration of 1% by weight as titanium oxide.
The above operations were conducted at room temperature.
[0173] (2) Evaluation method of solution
Physical properties of the solution for forming a thin film (Solution A-1 to
Solution A-5) prepared in Examples 1 to 5 and the solution for forming a thin film

(Solution H-1 and Solution H-2) prepared in Comparative Examples 1 and 2 were
evaluated by the following evaluation methods.
[0174]
(i) Measurement of particle size of metallic compound in solution
The particle size of the metallic compound in the solution was measured by using
a particle diameter measurement apparatus (HPPS, manufactured by Malvern Instruments
Ltd.).
Also, the particle size of the metallic compound in the solution for forming a thin
film (Solution A-1 to A-5, H-1, and H-2) which had kept at room temperature for 3
months was measured.
The measurement results are shown in Table 1. In Table 1, "particle size"
indicates an average particle size.
[0175]
[Table 1]


[0176]
As shown in Table 1, the titanium chelate compounds in Solution A-1 to A-5
proceeded with the hydrolysis-condensation by adding a large amount of water and were
polymerized to particles of titanium oxide having a particle size of 4 to 10 nm and were
extremely similar structure to titanium oxide.
[0177]
A particle size distribution of titanium oxide particles included in Solution A-3 is
shown in Fig. 1. In Fig. 1, the horizontal axis shows average particle size (nm) and the
vertical axis shows peak strength (Intensity). The titanium oxide particles included in
Solution A-3 show a monodispersed distribution with extremely sharp peak.
[0178]
Also, as shown in Table 1, the keep stability was excellent. Even the solution
which had been kept for 3 months had particles having the particle size of 13 nm or less
and was transparent. This showed that the examples of the present invention have
excellent keeping stability.
[0179]

On the other hand, in case of Comparative Example 1 in which water was not
added at all, particles of titanium compound were not formed and the particle size could
not be measured, because the hydrolysis reaction did not occur.
In the case of Comparative Example 2 in which the amount of the water added
was 3.6-fold by mole to the titanium, the isopropoxy group proceeded with
hydrolysis-condensation to produce particles having a particle size of about 1 nm.
However, the! chelate portion did not sufficiently proceed with hydrolysis-condensation
and, as a result, an aggregation occurred to form a large agglomerate having a size of 86
nm and the stability was poor.
[0180]
(ii) TG/DTA measurement of titanium oxide particles in Solution A-3
Solution A-3 was concentrated at 50°C under reduced pressure and dried at 50°C
in a vacuum, to be a powder. TG/DTA (diffential thermogravimetric analysis) was
measured under the condition in which the rate of temperature increase was 20°C/min
under nitrogen gas. A result of measurement analysis is shown in Fig. 2. In Fig. 2, a
sharp endothermic peak according to decomposition of the propoxy group and
acetylacetonate group, which was observed in the case of diisopropoxy
diacetylacetoriatetitanium (T-50) as raw material, was not observed in the case of Solution
A-3. For this reason, it was suggested that almost all of the isopropoxy group and
acetylacetonate group in Solution A-3 were hydrolyzed. It was assumed that the weight
was reduced by elimination of moisture adsorbing to particles, isopropanol, acetyl acetone
alcohol, and hydroxyl group surface.
Also, in FT-IR analysis and H-NMR analysis, isopropoxy group and
acetylacetonate group bonding to titanium atom were not observed.
[0181]
(iii) Measurement of zeta potential of solution in pH titration
The zeta potential was measured by changing pH of Solution A-3 in Example 3
from 2 to 12 by using hydrochloric acid of 0.2 mol/L and aqueous sodium hydroxide of
0.2 mol/L. The measurement results are shown in Fig. 3. The measurement results of

zeta potential of Solution A-3 shown in Fig.3 showed pH of the isoelectric point of 6.29
and almost the same results as anatase-type titanium oxide. It was suggested that the
particles were charged positively to be stable, because pH of Solution A-3 was about 5.
[0182]
(iv) Amphipathic property evaluation of titanium oxide particles
Each of Solutions A-1 to A-3 was added to a solution in either of 0.1 g or 1 g in
which 1 g of toluene was added to 9 g of water and dispersed with supersonic waves, and
whether or not the stably dispersed emulsification products were obtained was evaluated.
In all cases of Solutions A-1 to A-3, stably, dispersed emulsification products were
obtained. It seems that the outer surface of toluene drops was encircled with amphiphilic
nanoparticles.
[0183]
In analysis results of 'H-NMR, the total of alkoxyl group and chelate group
bonding to Ti was four-fold by mole in the case of the Comparative Example 1 and 0.8
-fold by mole in case of the Comparative Example 2. In Solution H-1 of the
Comparative Example 1 and Solution H-2 of the Comparative Example 2, the hydrolysis
of titanium chelate compound was insufficient. Also, no obvious zeta potential was
observed in Solutions H-1 and H-2.
[0184]
(3) Forming thin film
(Examples 6 to 17, Comparative Examples 3 and 4)
The following substrates for forming a thin film were prepared and the surfaces
thereof were cleaned by ethanol and dried. Next, each substrate surface was coated with
each solution (Solution A-1 to Solution A-5) prepared in the above Examples 1 to 5 and
solution (Solution H-1 and Solution H-2) prepared in the above Comparative Examples 1
and 2 by mayer bar coater (using bar No. 3) and dried at 60°C for 10 minutes to form a
thin film. The obtained thin films were referred as to C-1 to C-12, CH-1, and CH-2.

Because the film is obtained by drying at 60°C, the solution could be applied to the

substrate such as plastics having no heat resistance.

[0185]
The following substrate was used as the substrate for forming a thin film.
B-1: polyester sheet (Trade name "Lumirror" manufactured by Toray Industries, INC.)
B-2: polyimide sheet (Trade name "Kapton" manufactured by DU PONT-TORAY
CO.,LTD)
B-3: Soda lime glass substrate plate (SLG)
B-4: aluminum plate
A kind of substrate and solution for forming a thin film are shown together in Table 1.
[0186]
(4) Evaluation method of thin film
Next, the physical properties of the thin film (C-1 to C-12, CH-1, CH-2) formed
in the above (3) were measured by the following test methods and evaluated.
[0187]
(i) Crystallizability of thin film
The crystallizability of the thin film was evaluated by measuring with an X-ray
diffraction instrument.
All of thin films (C-1 to C-12) were amorphous films having a film thickness of
10 to 40 ran.
[0188]
(ii) Film appearance
The shifts of haze degree by coating the thin film were measured, the appearances
of the thin films were observed by viewing, and the thin films were evaluated as follows.
Evaluation O: transparent, shift of haze degree of 0.5% or less, film spot absence
Evaluation X: shift of haze degree of 0.5% or more, film spot presence
[0189] (iii) Adhesion properties (tape peeling test)
After cellophane-tape was applied to each sample and rubbed a few times with a
finger cushion, when the tape was peeled, whether or not the thin films on the substrate
were separated was evaluated by elemental analysis with XPS and evaluated as follows.

Evaluation O: no separation

Evaluation X: separation
[0190]
The above evaluation results are shown in Table 2.
In Table 2, the film appearances of the thin films (C-1 to C-12) were excellent
and the adhesion properties were also excellent. The thin film (CH-1) of theComparative
example 3 and the thin film (CH-2) of the Comparative Example 4 had fogging and the
adhesion properties thereof were not excellent.
[0191]
(iv) Surface smoothness of thin film
The average surface roughness (Ra) by scanning probe microscopy before and
after coating bf Solution A-3 is shown in Fig. 4. Fig. 4 shows that while the average
surface roughness of polyester substrate was 1.37 ran, the average surface roughness Ra
was 0.70 ran after coating of the film, and thus the surface roughness was improved to
provide surface smoothness.
[0192]
(v) Element distribution in thin film
The element distribution along the depth direction of the films was measured by
using an XPS analyzer (Quantum 2000 manufactured by Ulvac-Phi, Inc).
The film was removed by argon sputtering at 1 kV at 0.25 minute intervals and
measured by X ray photoelectron spectroscopy to obtain the content rates by percentage of
carbon atom, oxygen atom, titanium atom, or the like in the film by using the following
formula.
[0193] [Formula 1]
Content ratio of carbon element by percentage (%)
=(Concentration of carbon atom)/{(Concentration of oxygen atom) +
(Concentration of carbon atom) + (Concentration of the total metal atom)}* 100
[0194]

The element distribution in the thin film (C-1) formed from Solution A-1 was
evaluated by XPS and the results thereof are shown in Fig. 5. In the analysis result, the
samples obtained by coating the substrate of polyester with Solution A-1 and drying at
60°C were measured along the depth direction. In the thin film, the content rate of the
carbon by percentage depending on the organic compound was extremely low, 10% or less
by weight, showing that the thin film was almost an titanium oxide.
[0195]
The element distribution in the thin film (C-8) formed from Solution A-4 was
evaluated by XPS and the results thereof are shown in Fig. 6. Even in this case, the
content rate of residual carbon in the thin film was extremely low, 10% or less by weight,
despite drying at 60°C.
[0196]
On the other hand, the thin film (CH-1) similarly formed by using Solution H-1
of the Comparative Example 1, in which, as shown in Fig. 7, the hydrolysis proceeded by
moisture in the air at the film surface (the depth of 0 to 100 nm) to be a comparatively low
carbon content with a large amount of carbon remaining at the inside of the film (the depth
of 10 to 40 nm) was non-uniform weak film having low hardness.
[0197]
Also, the thin film similarly formed by using Solution H-2 of the Comparative
Example 2 in which, as shown in Fig. 8, the carbon content by percentage depending on
the organic compound was high and titanium oxide was not formed, was a weak film.
[0198]
(vi) Measurement of Water Contact Angle
After adding 5 ul of water and toluene onto the surface of each sample from a
microsyringe, the contact angle was measured 30 seconds later using a contact angle
measuring instrument (Model 360S manufactured by Erma Inc.).
The measurement results are shown in Table 2.
[0199]
(vii) Evaluation of ultraviolet (UV) sensitivity

I
As a lamp for UV irradiation, the following two kinds of lamp were used.
UV1: Bactericidal lamp (Trade name "GL-15" manufactured by Toshiba Corporation: UV
of 254 nm), Intensity of 4 mW/cm2
UV2: Black light (Trade name "FL15BLB" manufactured by Toshiba Corporation: UV of
365 nm), Intensity of 2 mW/cm2
[0200]
The film was irradiated with the above ultraviolet and the water contact angle was
measured to evaluate the change of the surface wettability. The UV irradiation energy

was calculated until the water contact angle became 20° or less (the thin film became
hydrophilic).
The calculated results are shown in Table 2.
An example in which Solution A-1 of Example 1 and UV2 as a light source was
used, was defined as the Reference Example 1.
[0201]
The thin film obtained in examples immediately showed hydrophilicity by
irradiation of UV of 254 nm to show the contact angle of 20° or less.
The contact angle of the thin film of Example 13 was about 20° showing
hydrophilicty, even before irradiation of UV. By the irradiation of UV of 254 nm, the
hydrophilicity; of the thin film increased.
[0202]
The thin films (C-10 to C-12) formed by using Solution A-5 showed extremely
high water repellency and showed hydrophilicity by irradiation of UV of 254 nm having
low energy. Because of this, it is possible that a hydrophilic-hydrophobic pattern is

produced by irradiation with a photomask, and the use in which a functional film is

individuated by coating ink or plating can be expected.
[0203]
When the thin film was treated with UV ozone for 3 minutes by using a UV
ozone device (Eyeozon cleaning device, manufactured by Eyegraphics CO., LTD.,
low-pressure marcury lamp) instead of irradiation of UV of 254 nm by UV 1, the thin film

had hydrophilicity and the water contact angle of 10° or less. The thin film provided the
same effects as the film when using UV1.
[0204]
However, the thin film formed from Solution H-1 could not active hydrophilicity
by irradiation, because of the residual organic compound in the thin film.
The thin film formed from Solution H-2 of the Comparative Example 2 showed
hydrophilicity, although it needed a long time until the thin film showed hydrophilicity (i.e.

the thin film needed a large energy for hydrophilicity).
Also; the thin film of Example 1 did not show hydrophilicity by irradiation of UV
of 365 nm and therefore it is different from the film having a normal anatase-type titanium
oxide photo icatalyst which showed hydrophilicity by irradiation of UV of 365 nm
(Reference Example 1).
[0205]
[Table 2]





[0206]
(Example 18)
The thin film C-13 was formed on the substrate B-1 by using Solution A-3. This
substrate was set on the belt conveyer at the top of which a high pressure mercury vapor
lamp (manufactured by Eyegraphics CO., LTD., 160 W/cm of lamp intensity, lamp height
of 10 cm, wavelength distribution referring the following table 3) was provided so as to
take the surface of the thin film C-13 at the upper side and passed at a rate of 16.67 cm/sec
under the high pressure mercury vapor lamp by the belt conveyer. At this time, the
irradiation time was 0.6 seconds by the high pressure mercury vapor lamp. This
operation was repeated 10 times and the water contact angle of the thin film C-13 was
measured each time. The measurement results are shown in Table 4.
[0208]
[0207]



[0209]
From Table 4, when the pass time was 7 times (4.2 seconds of the total irradiation
time), the water contact angle of the thin film C-13 was 7.0°. The result shows that
according the substrate of Example 18, the irradiated surface of the thin film C-13 can
show hydrophilicity (the water contact angle of 20° or less) by irradiation of ultraviolet
light for an extremely short time (about 3.0 seconds).
[0210]
The dispersion of titanium oxide particles of the present invention is composed of
fine particles of titanium oxide having an average particle size of nanometer-order
dispersed in water solvent.
The dispersion of the present invention is stable and is almost not changed even
after the dispersion is kept at room temperature for 3 months.
By using the dispersion of the present invention, a titanium oxide film of a fine
monolayer having few impurities can be formed with ease and speed. Also, the
dispersion of titanium oxide particles of the present invention is useful as material for
forming an organic functional film.
[0211]
By using the solution for forming an organic functional film of the present

invention, an organic functional film which can be applied to a photolithography method
or the like can be formed on a substrate with speed and ease.
The substrate having an organic functional film formed thereon of the present
invention includes an organic functional film formed on a substrate and is suitable for
photolithography method.

WE CLAIM ; 60
1. A dispersion of titanium oxide particles obtained by mixing a titanium chelate
compound formed by bonding a hydrolyzable group or a hydroxyl group and chelate ligand
to a titanium atom and five-fold or more by mole of water to the titanium, chelate
compound, wherein the content of the titanium oxide is within the range of 0.1 to 10% by
weight as titanium oxide to the whole dispersion, and the titanium chelate compound
proceeds with hydrolysis-condensation polvmerization.
2. The dispersion as claimed in claim 1, wherein the titanium oxide particles are fine
particles having an average particle size of 1 to 20 nm.

3. The dispersion as claimed in claim 1, wherein the content of the titanium oxide is
within the range of 0.1 to 5% by weight as titanium oxide to the whole dispersion.
4. The dispersion as claimed in claim 1, wherein the hydrolyzable group is an
optionally substituted alkoxyl group.

5. A titanium oxide thin film which is formed by contacting the dispersion as claimed
in claim 1 with a substrate surface.
6. A solution for forming an organic functional film comprising: a metallic compound
having a hydrolyzable group or a hydroxyl group and the dispersion as claimed in claim 1.
7. The solution for forming an organic functional film as claimed in claim 6, wherein
the metallic compound is used in two-fold or more by mole to 1 mole of the titanium
compound included in the dispersion.
8. A solution for forming an organic functional film obtained by mixing an organic
solvent solution of a metallic compound having a hydrolyzable group or a hydroxyl group, a
solution of a titanium chelate compound having a hydrolyzable group or a hydroxyl group
and a chelate ligand, and water of five-fold or more by mole to the total number of moles of
the titanium chelate compound and metallic compound, wherein the titanium chelate

compound proceeds with hydrolysis-condensation polymerization.
9. The solution for forming an organic functional film as claimed in claim 8, wherein
the hydrolyzable group of the titanium chelate compound is an optionally substituted
alkoxyl group.
10. The solution for forming an organic functional film as claimed in claim 8 or 9,
wherein the metallic compound is used in two-fold or more by mole to 1 mole of the
titanium chelate compound.
11. The solution for forming an organic functional film as claimed in claim 8 or 9,
wherein the total content of the titanium chelate compound and the metallic compound is
within the range of 0.1 to 10% by weight as metal oxide.
12. The solution for forming an organic functional film as claimed in claim 6 or 8,
wherein a metal of the metallic compound is at least one selected from the group consisting
of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten,
and lead.
13. The solution for forming an organic functional film as claimed in claim 6 or 8,
wherein the hydrolyzable group of the metallic compound is an optionally substituted
alkoxyl group.
14. A substrate having an organic functional film formed thereon comprising: an organic
thin film formed by contacting the solution for forming an organic functional film as
claimed in claim 6 or 8 with a substrate surface.


Abstract

A dispersion of titanium oxide particle which can form a fine organic thin film
having impurities and can be a titanium oxide thin film forming material, a titanium oxide
thin film formed from the dispersion, a solution for forming an organic functional film
obtained by adding a metallic compound solution having a hydrolyzable group in the
dispersion, a substrate having an organic functional film formed thereon which is obtained
by using the Solution, and a production method thereof are provided. A dispersion of a
titanium oxide particle obtained by adding water to an organic solvent solution of titanium

chelate compound composed of a hydrolyzable group or a hydroxyl group and a chelate
ligand bonding to a titanium atom, in which the amount of the water is five-fold or more
by mole to the titanium chelate compound, a titanium oxide thin film formed by
contacting this dispersion with the substrate surface composed of plastics or the like, a
solution for forming organic functional film obtained by adding the dispersion in the
organic solvent solution of metallic compound having hydrolyzable group, a method for
producing a substrate having an organic functional film formed thereon which is obtained
by using this solution for forming an organic functional film are provided.

Documents:

02944-kolnp-2007-abstract.pdf

02944-kolnp-2007-claims.pdf

02944-kolnp-2007-correspondence others 1.1.pdf

02944-kolnp-2007-correspondence others.pdf

02944-kolnp-2007-description complete.pdf

02944-kolnp-2007-drawings.pdf

02944-kolnp-2007-form 1.pdf

02944-kolnp-2007-form 18.pdf

02944-kolnp-2007-form 3.pdf

02944-kolnp-2007-form 5.pdf

02944-kolnp-2007-gpa.pdf

02944-kolnp-2007-international publication.pdf

02944-kolnp-2007-international search report.pdf

02944-kolnp-2007-others.pdf

02944-kolnp-2007-priority document.pdf

2944-KOLNP-2007-(02-03-2012)-CORRESPONDENCE.pdf

2944-KOLNP-2007-(11-04-2012)-CORRESPONDENCE.pdf

2944-KOLNP-2007-(14-06-2012)-CORRESPONDENCE.pdf

2944-KOLNP-2007-ASSIGNMENT 1.3.pdf

2944-KOLNP-2007-ASSIGNMENT.1.2.pdf

2944-kolnp-2007-correspondence 1.1.pdf

2944-KOLNP-2007-CORRESPONDENCE 1.3.pdf

2944-KOLNP-2007-CORRESPONDENCE.1.2.pdf

2944-KOLNP-2007-CORRESPONDENCE.pdf

2944-KOLNP-2007-EXAMINATION REPORT 1.3.pdf

2944-KOLNP-2007-EXAMINATION REPORT.1.2.pdf

2944-KOLNP-2007-FORM 13 1.3.pdf

2944-KOLNP-2007-FORM 13.1.2.pdf

2944-KOLNP-2007-FORM 18 1.3.pdf

2944-KOLNP-2007-FORM 18.1.2.pdf

2944-KOLNP-2007-FORM 3 1.3.pdf

2944-KOLNP-2007-FORM 3.1.2.pdf

2944-KOLNP-2007-FORM 5 1.3.pdf

2944-KOLNP-2007-FORM 5.1.2.pdf

2944-KOLNP-2007-GPA 1.3.pdf

2944-KOLNP-2007-GPA.1.2.pdf

2944-KOLNP-2007-GRANTED-ABSTRACT.pdf

2944-KOLNP-2007-GRANTED-CLAIMS.pdf

2944-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

2944-KOLNP-2007-GRANTED-DRAWINGS.pdf

2944-KOLNP-2007-GRANTED-FORM 1.pdf

2944-KOLNP-2007-GRANTED-FORM 2.pdf

2944-KOLNP-2007-GRANTED-SPECIFICATION.pdf

2944-KOLNP-2007-OTHERS 1.3.pdf

2944-KOLNP-2007-OTHERS.1.2.pdf

2944-KOLNP-2007-PA.pdf

2944-KOLNP-2007-REPLY TO EXAMINATION REPORT 1.3.pdf

2944-KOLNP-2007-REPLY TO EXAMINATION REPORT.1.2.pdf

abstract-02944-kolnp-2007.jpg


Patent Number 253515
Indian Patent Application Number 2944/KOLNP/2007
PG Journal Number 30/2012
Publication Date 27-Jul-2012
Grant Date 26-Jul-2012
Date of Filing 10-Aug-2007
Name of Patentee NIPPON SODA CO., LTD.
Applicant Address 2-1, OHTEMACHI 2-CHOME CHIYODA-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 KIMURA NOBUO C/O NIPPON SODA CO., LTD., R&D LABORATORY FOR HIGH-PERFORMANCE MATERIALS, 12-54, GOIMINAMIKAIGAN, ICHIHARA-SHI, CHIBA-KEN
2 SHIBATA HIROMOTO C/O NIPPON SODA CO., LTD., R&D LABORATORY FOR HIGH-PERFORMANCE MATERIALS, 12-54, GOIMINAMIKAIGAN, ICHIHARA-SHI, CHIBA-KEN
PCT International Classification Number C01G 23/053
PCT International Application Number PCT/JP2006/302454
PCT International Filing date 2006-02-13
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2005-037616 2005-02-15 Japan
2 2005-273905 2005-09-21 Japan