Title of Invention

PROCESS FOR PREPARING DISPERSIONS OF TIO2 NANOPARTICLES AND DISPERSIONS THEREOF

Abstract A description is given of a process for preparing nanoparticulate dispersions of Ti02 in the crystalline anatase form and the dispersions obtained with said process, useful for preparing photocatalytic coatings on surfaces and the photocatalytic decontamination of gas and liquids.
Full Text

PROCESS FOR PREPARING DISPERSIONS OF Ti02 IN THE FORM OF
NANOPARTICLES, AND DISPERSIONS OBTAINABLE WITH THIS PROCESS
AND FUCTIONAUZATION OF SURFACES BY APPLICATION OF T1O2
DISPERSIONS
Field of the invention
The present invention relates to the field of processes for preparing compounds in the
form of nanometric particles, and in particular regards a process for preparing
dispersions of T1O2 in the form of nanoparticles.
State of the art
Titanium dioxide is used as a white pigment of good covering power in particular in
paint and in the production of paper and synthetic rubber. More recent applications
of titanium dioxide are those that exploit its photocatalytic activity, i.e. its capacity to
generate, by the action of ultra-violet light, radical species able to catalyse the
oxidative degradation of noxious or toxic substances such as benzene, dioxane and
other organic pollutants, and also of unpleasant and infectious substances such as
moulds and bacteria. These applications extend from the fight against pollutants in
the environmental field, to the field of cleaning and sterilizing.
For said applications titanium dioxide is used as a coating on surfaces to be treated,
so as to maximize the photocatalytic effect. The crystalline form of titanium dioxide,
namely anatase, is preferred for this type of application because, in addition to being
chemically stable and easily available, it also has a greater photocatalytic activity than
the other two crystalline forms, rutile and brookite.
On the other hand, the overlap of the titanium dioxide absorption spectrum with the
solar spectrum is not very great even in its anatase form, indicating a low
photocatalytic efficiency. Various attempts have therefore been made to modify TiCfe,
for example by doping it with other metals or preparing the compound in question in
the form of nanoparticles; in this manner, the surface area and therefore
photocatalytic efficiency are vastly increased.
Various processes for preparing anatase Ti02 are known, even in nanoparticulate
form, but as far as the applicant is aware all these processes lead to powdered Ti02
being obtained.

A process for preparing a suspension of nanoparticies in high boiling point alcohol is
the polyol process described for example in C. Feldmann "Polyol mediated synthesis
of nanoscale functional materials" which allows the obtaining of suspensions very
stable for a long time but, contrary to the presently claimed process, it uses mineral
acid as inhibitor of polycondensation (see also in this connection WO 99/62822).
To be usable for preparing photocatalytic coatings this powdery material must be
dispersed in a suitable solvent and possibly formulated with additives to improve
coating adhesion. However, this causes the titanium dioxide particles to coagulate,
making it impossible to maintain the activity and photocatalytic efficiency of the
particulate material. Moreover, overtime the TiQ> particles in these dispersions tend
to sink to the bottom of the containers in which they are stored, giving rise to stability
problems during storage.
The need is therefore felt for providing a process which enables stable
nanoparticulate dispersions of titanium dioxide in the anatase form to be prepared.
Summary of the invention
The applicant has now devised a process by which nanoparticulate TiQ> in the
anatase form and already dispersed in suitable solvents is obtained, it being directly
usable for preparing photocatalytic coatings. The dispersions obtained with the
process of the invention have not led to particle coagulation phenomena even after
prolonged storage, allowing coatings to be prepared that maintain the photocatalytic
activity of the particulate material by virtue of dispersion homogeneity.
The present invention therefore provides a process for preparing nanoparticulate
dispersions of anatase TiO2in a mixture of water and a suitable complexing solvent,
comprising the following steps:
i) reacting a titanium alkoxide with a suitable complexing solvent;
ii) distilling the solution derived from stepi) until a small volume results;
iii) adding water to the solution derived from step ii) together with said complexing
solvent and one or more polycondensation inhibitors, then heating the reaction
mixture under reflux, to obtain the desired nanoparticulate dispersion.
Another process to obtain nanoparticle suspensions of titanium dioxide, Ti02, is the
aqueous hydrolysis of titanium alkoxides such as titanium methoxide, ethoxide,

normal-propoxide, isopropoxide, normal-butoxide, and isobutoxide. The titanium
isopropoxide is preferred for the same reasons previously described.
Titanium isopropoxide is added to a hot water solution containing mineral acid (such
as hydrochloridric or nitric acid) and a non-ionic surfactant (such as Triton X-100).
The hydrolysis process is maintaining to reflux for 24 hours.
The invention also provides nanoparticulate dispersions of anatase TiQz in a mixture
of water and a suitable complexing solvent, obtainable with the aforesaid process,
and their use for preparing photocatalytic surface coatings for antibacterial action,
photocatalytic decontamination of gas and liquids, and. for preparing cosmetic
formulations which protect the skin against sunlight.
The characteristics and advantages of the invention will be illustrated in detail in the
following description.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 shows the diffractogram attained from XRD analysis of the product obtained
in example 1, after drying it at 200°C for 12 hours.
Figure 2 shows a TEM photo of "TIO2 nanoparticles (90000x).
Figure 3 shows the diffractogram attained from XRD analysis of the product obtained
in example 8.
Detailed description of the invention
With the process of the invention, the formation of TiQ> in anatase form takes place
directly in the water/complexing solvent mixture used in stepi), obtaining at the end of
the process a dispersion of TiQ> particles between 3 and 20 nm in size. Particle size
measurement was undertaken with different techniques well known to the expert of
the art, such as XRD (X-ray diffraction), FEG-SEM (Field Emission Gun - Scanning
Electron Microscopy), TEM (Transmission Electron Microscopy) and DLS (Dynamic
Light Scattering). These dispersions, in contrast to those prepared by dispersing
nanometric powers in solvent mixtures, exhibit neither agglomerate formation nor
coagulation and precipitation phenomena, even after prolonged storage of the
dispersion.
The advantages of dispersions of this type are evident, and related to the uniformity
and photocatalytic effectiveness of the coatings which can be prepared therewith.

The polydispersion index of the dispersions obtainable with the process of the invention, measured by the DLS (Dynamic Light Scattering) technique, is less than 0.3, hence differentiating the dispersions of the invention from those obtainable with the traditional method of preparing the nanoparticulate powder and then dispersing it in solvent. A typical TEM image of our nanoparticles dispersion is shown in Fig.2. The titanium alkoxide used as the starting product in the present process can be chosen for example from the group consisting of titanium methoxide, ethoxide, normal-propoxide, isopropoxide, normal-butoxide, and isobutoxide. Among these products, titanium isopropoxide is the preferred starting compound in the present process for various reasons. Among the titanium compounds that can be used it is the least expensive and the one which has the best reactivity under the conditions of the present process; moreover, its use leads to isopropyl alcohol being obtained as by-product of step ii), a product easily recoverable from the process of the invention and valued for its wide usage in the detergent industry. The compiexing solvents typically used in the present process are ethylenglycol, diethylenglycol and polyethylene glycols, having molecular weights for example of between 200 and 600. Longer chain polyethylene glycols of molecular weight up to 10,000 can also be used. In this case, at the end of the process and after cooling, instead of a TiO2 dispersion in a liquid, nanoparticles of Ti02 are obtained dispersed in a solid matrix. The final product preserves the nanometric dimensions of TiQ? and the low polydispersion index observed for liquid dispersions. The preferred compiexing solvent is diethylene glycol.
Excellent results have been obtained by conducting reaction step i) using titanium isopropoxide and diethylene glycol in a 1:3 molar ratio.
Within the scope of the present invention, the term "polycondensation inhibitor" means typically a mixture comprising at least one mineral acid and one organic acid, where the mineral acid can be chosen for example from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, hydrobromic acid, and hydroiodic acid, and the organic acid is preferably acetic acid. In accordance with a particularly preferred embodiment of the present process, the polycondensation inhibitor is a mixture of hydrochloric acid and acetic acid.

The quantity of polycondensation inhibitor added is such that the quantity of the
mineral acid is between 0.1 and 10% by volume on the total volume of the reaction
mixture, while the quantity of the organic acid is between 1 and 20% by volume on the
total volume of the reaction mixture.
The water/complexing solvent mixture used in accordance with the invention also
enables the dispersion to be used directly for preparing photocatalytic coatings
practically for any type of application, even for applications in the cosmetic or textile
fields for coating products destined for contact with the skin.
Where they are used for preparing coatings, the present dispersions can possibly be
formulated with additives and diluents commonly used in the field of surface coatings
such as adhesion improving agents or solvents like water or ethanol to obtain the
desired dilution.
Where they are instead used to decontaminate liquid or gaseous products, the
present dispersions are respectively adsorbed on a silica gel support, or on another
suitable inorganic support with good adhesion characteristics such as glass,
ceramic, porous ceramics, fibres, textiles and so on, which is then immersed in the
liquid or placed, as such or diluted, into containers through which the gas to be
purified is bubbled.
The supports onto which a surface coating prepared with the present dispersions can
be applied are very varied, ranging from fibre fabrics, either on the roll or made-up, to
ceramic products, to glass, metal or mirror supports and the like.
Photocatalytic activity of the surface coating in accordance with the invention is
exhibited after exposing the coating itself to light at a suitable wavelength, typically
less than 388 nm, to produce a surface with antibacterial, bacteriostatic and super-
hydrophilic properties following exposure to UV light The TiO2 coated supports
demonstrate a complete absence of water repellance, known as super-hydrophilicity,
thus rendering the TiO2treated surfaces self-cleaning.
Moreover, given the very small TiO2particle size, the present dispersions are almost
transparent, thus leaving unchanged the appearance of the surface to which they are
applied. Their transparency also makes them suitable for use in the cosmetic field for
preparing high protection UV sun filters.

A further advantage of the present dispersions is their behaviour at high
temperatures. In this respect, applying the surface coating onto ceramic supports
requires high temperature treatment of the support onto which the dispersion has
been applied, the present dispersions maintaining unchanged the appearance, the
crystalline form of anatase and the nanoparticulate nature of the coating prior to
heating.
In accordance with a particular embodiment of the present process, doping of the Ti
can be achieved with a metal chosen from the transition metal group and in particular
Ag, Cu or Ce by the addition of one of their salts to step i) or alternatively to step iii) of
the present process. In this manner, the process will result in the formation of an Ag,
Cu orCe doped TiO2 dispersion, able to exhibit its catalytic activity even without UV
light irradiation.
Some illustrative and non-limiting examples of the invention are given hereinafter.
EXAMPLE 1
Preparation of nanoparticulate dispersion of anatase TiO2 in water/diethylene glycol
starting from Ti isopropoxide
5.53 litres of diethylene glycol are fed into a 20 litre flask to which are added 5.54
litres of titanium isopropoxide. The reaction mixture is maintained under agitation for
5 minutes, then heated to 120°C distilling off the isopropyl alcohol which forms, until a
small volume results. 11.1 litres of diethylene glycol, 125 ml of 32-33% w/w
hydrochloric acid, 2.07 litres of glacial acetic acid and 125 ml of deionised water are
added. The temperature is brought to 180°C and the mixture maintained under reflux
for 2 hours.
The product thus obtained was characterised as follows.
Firstly, the concentration of TiCfe in the final product was measured using the
technique of inductively coupled plasma atomic emission (ICP) in accordance with
standard methodology. From this analysis the quantity of TiQ> in the dispersion was
found to be equal to 5.7% by weight on the total weight of the dispersion.
A sample of the dispersion obtained as aforedescribed was oven dried at 200°C for
12 hours until the solvent was completely evaporated. The powder thus obtained was
then analysed by XRD using a Philips X'Pert PRO diffractometer, in order to

understand its crystalline structure: as can be seen in figure 1, the position and the
intensity of the peak shown by the diffractogram are typical of anatase.
From the diffractogram of figure 1, and in particular from the width of the principal
peak, the average dimensions of the TIO2 particles were calculated by applying
Sherrer's formula, to find an average diameter value equal to 4.5 nm.
This value was also confirmed from transmission electron microscope observation on
a sample of the dispersion obtained as aforedescribed, after being diluted 1:100 with
ethanol.
EXAMPLE 2
Preparation of nanoparticulate dispersion of anatase TiO2 in water/diethylene glycol
starting from Ti ethoxide
5.53 litres of diethylene glycol were loaded into a 20 litre flask to which were added
3.76 litres of titanium ethoxide. The reaction mixture is maintained under agitation for
5 minutes, then heated to 130°C distilling away the ethanol that forms. 11.1 litres of
diethylene glycol, 125 ml of 32-33% w/w hydrochloric acid, 2.07 litres of glacial acetic
acid and 125 ml of deionised water are added. The temperature is brought to 180°C
and the mixture maintained under reflux for 2 hours.
This product was characterised in the same manner as that given in example 1 to
obtain the same crystalline phase and particles of similar dimensions. In addition the
product obtained was used to carry out the same tests described above in examples
2, 3 and 4 with similar results to those obtained for the product prepared as in
example 1.
EXAMPLE 3
Preparation of nanoparticulate dispersion of anatase T\Og in water starting from Ti
isopropoxide
18.720 Kg of water solution obtained mixing water with 100gr of hydrochloridric acid
and 80gr of a 1% w/w solution of Triton X-100 in water are fed into 20 litre flask. The
reaction mixture is heated to 50°C. 1.280 Kg of titanium isopropoxide are added.
The reaction mixture is manteined under reflux to SO'C for 24 hours. The product thus
obtained was characterised as follows.
Firstly, the concentration of TiC>2 in the final product was measured using the

technique of inductively coupled plasma atomic emission (ICP) in accordance with standard methodology. From this analysis the quantity of TiQ? in the dispersion was found to be equal to 1.8% by weight on the total weight of the dispersion. A sample of the dispersion obtained as aforedescribed was oven dried at 100°C for 12 hours until the solvent was completely evaporated. The powder thus obtained was then analysed by XRD using a Philips X'Pert PRO diffractometer, in order to understand its crystalline structure. EXAMPLE 4
Application of nanoparticulate dispersion of TiO2 in water/diethylene glycol onto fabric 25 ml of deionised water were added to 75 ml of the dispersion prepared as aforedescribed in example 1 and the dispersion thus diluted was placed in a bowl. A 20 cm x 60 cm strip of cotton fabric was immersed in the bowl for 10 seconds, then removed and passed between two rollers of silicone material to remove excess solvents. The fabric was then oven dried, washed in a washing machine, dried again and the UV ray protection factor (UPF) offered by the coated fabric was measured with the standard spectrophotometric methods for this type of measurement, a UPF of 35.40 being found. EXAMPLE 5
Application of nanoparticulate dispersion of T\Ch in water/diethylene glycol onto wool 25 ml of deionised water were added to 75 ml of the dispersion prepared as aforedescribed in example 1 and the dispersion thus diluted was placed in a bowl. A 20 cm x 60 cm strip of wool fabric was immersed in the bowl for 10 seconds, then removed and passed between two rollers of silicone material to remove excess solvents. The fabric was then oven dried, washed in a washing machine and dried again. Onto this wood fabric was tested antibacterial properties in observance of rule AATCC TM 100:99. In the following table are reported the results of tests.



EXAMPLE 6
Application of nanoparticulate dispersion of TIO2 in water/diethylene glycol onto a
Cotton wire
25 ml of deionised water were added to 75 ml of the dispersion prepared as
aforedescribed in example 1 and the dispersion thus diluted was placed in a bowl.
A cotton wire was immersed in the bowl, dried in a oven and rolled onto a spool.
With this wire was obtained a knitted fabric and was tested the UV ray protection
factor (UPF) offered by the coated fabric. This properties was measured with the
standard spectrophotometric methods and a UPF of 30.20 being found.
EXAMPLE 7
Application of nanoparticulate dispersion of TiQ^ in water/diethylene glycol onto
ceramic surfaces - studies of adherence and resistance to high temperatures
The nanoparticulate dispersion prepared as aforedescribed in example 1 was used
to create a photocatalytic coating on an unglazed gres support, adding 5% by weight
of a low melting frit, to facilitate adherence of the titanium dioxide to the support. The
frit used had a relatively low hemisphere temperature, equal to 700°C, and the
following chemical composition:
Si02 48.32% CaO 6.95%
Al203 2.22% MgO 1.94%
K20 0.049% Li20 13.9%
Na20 0.06% ZnO 4.05%
B203 22.55%
The dispersion of example 1 was applied by dip-coating to the support, which was
subjected to thermic cycles at both 700°C and 600°C. After the firing treatment the
support maintained its original appearance and demonstrated good adhesion

between coating and substrate.
The behaviour of the present coating at high temperatures was studied by high
temperature powder diffractometry (XRD-HT). It was thus observed that the phase
transition from anatase to rutile begins at only about 800°C, arriving at completion at
about 900°C. By applying Sherrer's formula, the nanocrystal dimensions at the
various temperatures was also calculated.
Table 1 below gives the 20 angle at which the measurement was taken, the width of
the peak at half height which when inserted in Sherrer's formula serves to calculate
the crystallite dimensions, the crystallite dimensions and the temperature relative to
the preceding dimensions.

The same method was used to evaluate increase in crystallite size at a constantly maintained frit firing temperature but at differing times, and in this case good coating adherence was found even for prolonged firing times, the crystallite size increasing over time but to an acceptable extent such as not to reduce the photocatalytic effectiveness of the coating.
To verify the adherence of the coating to the substrate the entire sample was subjected to ultrasound cycles in ethanol and in acetone for different times (5 and 60 minutes) and to repeated washings with cloths of different abrasiveness (sponging).

After every ultrasound cycle an XRD analysis was carried out to verify any reduction in
the amount of anatase present in the coating, finding however that the treatments
carried out have not influenced either the crystalline form of TiO2 or adherence of the
coating to the support.
EXAMPLE 8
Application of nanoparticulate dispersion of TIO2 in water/diethylene glycol onto
ceramic surfaces - Photocatalytic effect
Two samples of the same gres, glazed in white, were "stained" with the same quantity
of a solution containing 10 ppm of methylene blue. Only one of the two samples had
previously been coated with the dispersion of the invention as described in example
4.
The two samples were then exposed to light from a UV lamp for various periods of
time: 10, 30, 60, 90 and 120 minutes. While on the untreated sample no change in
the methylene blue stain was observed, a progressive disappearance of the blue
stain was observed for the sample covered with the dispersions of the invention. The
same experiment was repeated with a indelible marker stain, only observing
disappearance of the stain on the coated sample after 45 minutes' exposure to UV
light.
The two above experiments were repeated in sunlight instead of with a UV lamp, and
the same results were obtained.
EXAMPLE 9
Application of nanoparticulate dispersion of TiO? in water/diethylene glycol onto
glass.
The dispersion of example 1 was applied by dip-coating or spray to the support,
which was subjected to thermic cycles for 30 minutes at 200°C and for 30 minutes at
500°C. After the firing treatment the support maintained its original appearance and
demonstrated good adhesion between coating and substrate.
This sample was "stained" with a solution containing 10 ppm of methylene blue. The
sample was then exposed to light from a UV lamp and a progressive disappearance
of the blue stain was observed. This experiments was repeated in sunlight instead of
with a UV lamp, and the same result was obtained.

EXAMPLE 10
Application of nanoparticulate dispersion of TiO2, in water/diethylene alycol onto
glass-ceramic surface.
The dispersion of example 1 was applied by dip-coating or spray to the support,
which was subjected to thermic cycles for 30 minutes at 200°C and for 30 minutes at
700oC. After the firing treatment the support maintained its original appearance and
demonstrated good adhesion between coating and substrate.
This sample was "stained" with a solution containing 10 ppm of methylene blue. The
sample was then exposed to light from a UV lamp and a progressive disappearance
of the blue stain was observed. This experiments was repeated in sunlight instead of
with a UV lamp, and the same result was obtained.
EXAMPLE 11
Application of nanoparticulate dispersion of TiO2 in water/diethylene glycol onto
various surface (glass, glass-ceramic, glaze, body gres).
At the dispersion of example 1 was added 0.01 to 10% of surfactant as for example a
non ionic surfactant (such as Triton X-100) to improve the spreading onto the surface.
This solution was applied by dip-coating or spray to the support, which was subjected
to thermic cycles for 30 minutes at 200°C and for 30 minutes at 500°C for glass or
700*0 for glass-ceramics, glaze and body gres. After the firing treatment the support
maintained its original appearance and demonstrated good adhesion between
coating and substrate.
This sample was "stained" with a solution containing 10 ppm of methylene blue. The
sample was then exposed to light from a UV lamp and a progressive disappearance
of the blue stain was observed. This experiments was repeated in sunlight instead of
with a UV lamp, and the same result was obtained.
EXAMPLE 12
Application of nanoparticulate dispersion of T\Ch in water onto ceramic composite
obtained with inorganic material and a polyester resin.
50 ml of deionised water were added to 50 ml of the dispersion prepared as
aforedescribed in example 1 bis and the dispersion thus diluted was placed in a
spray gun. This sample was sprayed onto surface of composite material and after

was kept at 100)C for 1 hour.
This sample was "stained" with a solution containing 10 ppm of methylene blue. The sample was then exposed to light from a UV lamp and a progressive disappearance of the blue stain was observed. This experiments was repeated in sunlight instead of with a UV lamp, and the same result was obtained.




CLAIMS
1. Process for preparing nanoparticulate dispersions of anatase TIO2 in a mixture of
water and a suitable complexing solvent comprising the following steps:
i) reacting a titanium alkoxide with a suitable complexing solvent;
ii) distilling the solution derived from step i) until a small volume results;
iii) adding, under acidic conditions, water to the solution derived from step ii) together
with said complexing solvent and one or more polycondensation inhibitors, then
heating the reaction mixture under reflux to obtain the desired nanoparticulate
dispersion.
2. Process as claimed in claim 1, wherein said complexing solvent is a polyethylene glycol.
3. Process as claimed in claim 2, wherein said complexing solvent is diethylene glycol.
4. Process as claimed in claim 1, wherein said titanium alkoxide is chosen from the group consisting of titanium methoxide, ethoxide, normal-propoxide, isopropoxide, normal-butoxide, and isobutoxide.

5. Process as claimed in claim 4, wherein said titanium alkoxide is titanium isopropoxide.
6. Process as claimed in claim 1, wherein said polycondensation inhibitor is a mixture comprising at least one mineral acid and one organic acid.
7. Process as claimed in claims 1 and 6, wherein the quantity of polycondensation inhibitor added in step iii) is such that the quantity of the mineral acid is between 0.1 and 10% by volume on the total volume of the reaction mixture, while the quantity of the organic acid is between 1 and 20% by volume on the total volume of the reaction mixture.
8. Process as claimed in claim 6, wherein said mineral acid is chosen from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, hydrobromic acid, and hydriodic acid, said organic acid being acetic acid.
9. Process as claimed in claim 6, wherein said polycondensation inhibitor is a mixture of hydrochloric acid and acetic acid.
10. Process as claimed in claim 1, wherein the molar ratio of said titanium alkoxide

to said complexing solvent is 1:3.
11. Process as claimed in claim 1, also comprising the addition of a salt of metals of
the first or second transition group to step i) or alternatively to step iii).
12. Process as claimed in claim 11, wherein said first or second transition group
metals are chosen from Ag, Cu and Ce.
13. Nanoparticulate dispersions of anatase TiO2 in a mixture of water and a suitable
complexing solvent, obtainable with the process as defined in claims 1-12.
14. Dispersions as claimed in claim 13, wherein said complexing solvent is a
polyethylene glycol.
15. Dispersions as claimed in claim 14, wherein said complexing solvent is
diethylene glycol.
16. Use of nanoparticulate dispersions of TiO2 as defined in claims 13-15 for
preparing photocatalytic coatings on surfaces which require said treatment.
17 Use as claimed in claim 16 wherein said photocatalytic coatings comprise a surfactant.
18. Use according to Claim 18 wherein said surfactant is a non ionic surfactant.
19. Use according to claim 18 wherein such non ionic surfactant is Triton x 100.
20. Use as claimed in claims 16 - 19 , wherein said surfaces are chosen from the
surfaces of textile, metallic, ceramic products, and glazes.
21. Use of nanoparticulate dispersions of Ti02 as defined in claims 13-15 for
photocatalytic decontamination of gas and liquids.
22. Use of nanoparticulate dispersions of TIO2 as defined in claims 13-15 for
preparing cosmetic formulations with high protection of the skin against the sun.


Documents:

2987-CHENP-2007 AFFIDATIVE 07-10-2013.pdf

2987-CHENP-2007 AMENDED CLAIMS 07-10-2013.pdf

2987-CHENP-2007 AMENDED PAGES OF SPECIFICATION 07-10-2013.pdf

2987-CHENP-2007 CORRESPONDENCE OTHERS. 08-04-2013.pdf

2987-CHENP-2007 EXAMINATION REPORT REPLY RECEIVED 07-10-2013.pdf

2987-CHENP-2007 FORM-3 07-10-2013.pdf

2987-CHENP-2007 OTHER PATENT DOCUMENT 07-10-2013.pdf

2987-CHENP-2007 POWER OF ATTORNEY 07-10-2013.pdf

2987-chenp-2007-abstract.pdf

2987-chenp-2007-claims.pdf

2987-chenp-2007-correspondnece-others.pdf

2987-chenp-2007-description(complete).pdf

2987-chenp-2007-drawings.pdf

2987-chenp-2007-form 1.pdf

2987-chenp-2007-form 3.pdf

2987-chenp-2007-form 5.pdf

2987-chenp-2007-pct.pdf


Patent Number 257793
Indian Patent Application Number 2987/CHENP/2007
PG Journal Number 45/2013
Publication Date 08-Nov-2013
Grant Date 05-Nov-2013
Date of Filing 04-Jul-2007
Name of Patentee COLOROBBIA ITALIA S.p.A.
Applicant Address VIA PIETRAMARINA, 19,I-50053 SOVIGLIANA, VINCI,
Inventors:
# Inventor's Name Inventor's Address
1 BALDI, GIOVANNI VIA TIZZAVOLI, 4, I-50025 MONTESOERTOLI,
2 BITOSSI, MARCO VIA BOTTINACCIO, 14, I-50056 MONTELUPO FIORENTINO, ITALY
3 BARZANTI, ANDREA VIA SAN GIUSEPPE 8, I-50056 MONTELUPO FIORENTINO, ITALY
PCT International Classification Number C01G 23/053
PCT International Application Number PCT/EP05/56478
PCT International Filing date 2005-12-05
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 FI2004A000252 2004-12-06 Italy