Title of Invention

A PROCESS FOR FUNCTIONALIZING A TRANSPARENT OR TRANSLUCENT SUBSTRATE

Abstract The invention relates to a process for functionalizing a transparent or translucent substrate comprising forming a layer on the substrate, wherein: the layer is formed by; evaporating a composition comprising at least one organic or organometallic compound to obtain a vapor; dispensing the vapor over the substrate; and depositing an inorganic glass on the substrate by plasma- enhanced chemical vapor deposition; the inorganic glass is deposited on the glass substrate in the presence of the vapor; the layer comprises functional molecules derived from the composition comprising the at least one organic or organometallic compound dispersed in a matrix of the inorganic glass; and the functional molecules exhibit at least one function selected from the group consisting of coloring, reflection of visible light that varies with angle, electrical conductivity, infrared absorption or reflection, UV absorption or reflection, photochromism, thermochromism, electrochromism, electroluminescence, phosphorescence, fluorescence, antibacterial action, photocatalytic action, fungicidal action, odor absorbing or emitting, resisting tobacco smoke, hydrophilicity and hydrophobicity.
Full Text The present invention relates to a transparent or
translucent substrate, in particular of the type
requiring high optical quality: glazing for transport
vehicles, buildings, ophthalmic glass, display system
screen (television, computer, telephone), roadsign,
billboard, and the like. The case of the translucent
substrate is represented by surface-texturized and/or
printed and/or thick plastic or glass substrate
applications, in particular diffusing glazing panels,
illumination systems, functionalized glazing panels of
the electrochromic type, and the like.
The substrate of the invention is a glass, such as
soda-lime-silica glass or glass with another
composition, or a plastic which is transparent:
polycarbonate, polypropylene, poly(methyl meth-
acrylate) , ethylene/vinyl acetate copolymer,
poly(ethylene or butylene terephthalate), polyurethane,
polyvinylbutyral, cycloolefinic copolymer, that is to
say in particular copolymer of ethylene and of
norbornene or copolymer of ethylene and of
cyclopentadiene, ionomer resin (ethylene/(meth)acrylic
acid copolymer neutralized by polyamine, and the like),
unsaturated polyester, ethylene/vinyl acetate
copolymer, and the like.
The invention is targeted in particular at making
available a transparent substrate comprising a layer
which provides it, on a lasting basis, with varied
functions, in isolation or in combination, to a degree
adjustable, controllable, while retaining most of the
original transparency and optical quality.
As these functions are given, in the context of the
invention, by essentially organic or organometallic

molecules, the inventors have sought to transfer
these molecules onto the substrate in effective
amounts.
Various means are known: evaporating, spraying,
painting, and the like.
Protection of the layer is necessary against, for
example, heat, moisture, mechanical attacks (scratches,
and the like), chemical attacks, the presence of
oxygen, the presence of UV radiation, and the like.
Moreover, protective layers for the substrate itself,
in particular with regard to UV radiation or mechanical
attacks, often also prove to be necessary, in
particular when the substrate is a polymer, such as
polycarbonate.
Known protective layers are, for example, hard and
thermally stable inorganic glasses, for example
consisting of oxides and/or nitrides, among which may
be mentioned SiO2, TiO2, and the like.
These inorganic glass layers can be prepared by various
techniques: lacquers, sol-gel, plasma-enhanced chemical
vapour deposition (PECVD), the latter being
particularly favourable in that it makes possible the
preparation of hard and dense layers, on the one hand,
and of multilayers, on the other hand. The lacquer and
sol-gel techniques are not devoid of problems: poor
resistance to the diffusion of oxygen or of water, poor
mechanical strength, difficulty in preparing
multilayers and thus in combining different
corresponding functionalities.
Furthermore, organic molecules decompose at a
relatively low temperature and require particularly
mild transfer conditions.

Moreover, it is obviously advisable to transfer them
in such a way that their transfer product provides the
product obtained with the desired function.
Finally,it is necessary to establish the conditions of
durability of the new function.
To this end, a subject-matter of the invention is a
process for the functionalization of a transparent or
translucent substrate by formation of a layer which is
distinguished in that it comprises the stages
consisting in:
evaporating over the substrate at least one type of
organic or organometallic functionalization
molecule,
simultaneously with the formation, by plasma-
enhanced chemical vapour deposition, of an inorganic
glass matrix forming part of the layer.
An organic molecule comprises here C, H, 0, N, S, P,
halogen atoms; an organometallic molecule additionally
comprises metal atoms, such as Al, Ti, Mg, Si, and the
like. It is capable of exhibiting all types of bonds
usual in organic molecules, in particular sp3 carbon-
carbon single bonds, carbon-carbon double bonds,
benzene rings, and the like.
It is important for the vapour pressure of the
functionalization molecule or molecules at the
evaporation temperature to be sufficiently high for a
sufficient flow to be obtained over the substrate at
the pressure at which the deposition is carried out.
Typically, these vapour pressures vary between 1 and
1000 Pa depending on the molecule. An increase in this
vapour pressure can result from the substitution of
certain atoms or groups (H or CH3) of the organic
molecule by F atoms, for example.

In addition, the molecule can be modified or
transformed for the purpose of incorporating therein
bonds or groups which make it possible to promote the
grafting thereof in the matrix.
The matrix consists of an inorganic glass according to
the above definition. An example thereof is an "SiOx
matrix", which is understood to mean a network of
crosslinked chains composed essentially of Si and 0
atoms but also of smaller proportions of C, H or N
atoms, for example.
This matrix is formed by a plasma-enhanced chemical
vapour deposition (PECVD): gaseous silicon-comprising
precursors, such as hexamethyldisiloxane (HMDSO),
tetramethyldisiloxane (TMDSO), tetraethoxysilane (TEOS)
or tetramethoxysilane (TMOS), are projected over the
substrate under an argon-oxygen plasma, for example.
The precursors are thus polymerized/crosslinked.
The inventors realized that the condensation of vapour
of varied organic and/or organometallic molecules on
the substrate, during plasma polymerization of the
inorganic glass matrix, made it possible to
incorporate, in the latter, derivatives of these
organic and/or organometallic molecules capable of
providing various functions, under excellent conditions
of protection by the matrix and thus of durability.
The process of the invention makes possible the ready
incorporation of various functionalities due to the
ease of control of the flows which is inherent to it.
It makes possible in particular the mixing of different
functional molecules (for example, different colours)
in the same layer, in optional combination with
stabilizers for one or more functional molecules or for
the matrix.

The process of the invention also facilitates the
preparation of stacks of different layers, in
particular:
one or more "pure" matrix layers having the function
of barrier to oxygen, of barrier to water or of
protecting against the diffusion of various chemical
compounds,
adhesion layer,
finishing layer: hydrophobic, hydrophilic, slipping
(low coefficient of friction),
gradual transition layer (gradient layer),
mechanical protection layer, and the like.
Furthermore, the compatibility of these molecules with
the matrix makes it possible to obtain perfect
transparency and optical quality.
As regards the nature of these molecules once
incorporated in the matrix, it is probable that simple
grafting products of the starting molecules in the more
or less separate state are concerned; the properties of
the starting molecules are retained and are transferred
into the matrix.
The operating conditions of flow rate, pressure,
temperatures, characteristics of the plasma and nature
of the organic/organometallic molecules could be chosen
in order for sufficient amounts of the molecules to be
incorporated in the matrix in order to functionalize it
to the desired degree.
For a given molecule, the vapour pressure can be
modified by varying the evaporation temperature, it
being known that some molecules decompose from a given
temperature, which should therefore not be exceeded.
Likewise, the flow at a given temperature depends on
the geometry of the injection system and on the surface
area of the evaporator.

In the process of the invention, it is often the case
that a proportion, generally a low proportion, of the
organic or organometallic molecules introduced at the
start is not finally incorporated in the final
substrate provided with its layer. If the transfer of
the molecules into the layer is not 100%, it is
important simply that it be sufficient. Likewise, if a
portion of the molecules are modified during the
transfer, it is important that a sufficient number of
molecules carrying the functionality be incorporated.
The temperature of the substrate is a parameter of the
process of the invention which makes it possible to
vary the haze of the product obtained. This temperature
is just as easily greater than as less than the melting
point of the organic or organometallic molecule or
molecules incorporated. When a weak haze is desired,
which is generally the case with glazings, the
temperature of the substrate during the deposition has
to be sufficiently high.
On the other hand, it is advisable to prevent the
temperature of the substrate from reaching, during the
deposition, excessively high values capable of limiting
the amount of molecules grafted up to eliminating them
altogether.
In a preferred implementation of the invention, the
vapour of each organic/organometallic molecule is
heated, between the creation thereof and the coming
into contact thereof with the substrate, so that its
temperature increases when it is moving, in metal pipes
in particular. This measure facilitates the desired
circulation of the vapour.
Another subject-matter of the invention is a
transparent substrate comprising a functional layer
prepared according to the process described above, in

which the function provided by an organic or
organometallic molecule is a function of colouring,
reflection of visible light which can vary with the
angle, electrical conductivity, infrared absorption or
reflection, UV absorption or reflection, photochromism,
thermochromism, electrochromism, electroluminescence,
phosphorescence, fluorescence, antibacterial action,
photocatalytic action, fungicidal action, odour
absorbing or emitting, resisting tobacco smoke,
hydrophilicity or hydrophobicity.
Advantageously, the functional layer comprises at least
one agent for protecting the organic or organometallic
molecule or molecules, such as an ultraviolet absorber
or an antioxidant.
Examples of organic or organometallic molecules are
naphthalene, anthracene, pyrene, anthraquinone and
their derivatives. Mention may be made, as
representatives of the latter, of:
1, 4-di(butylamino)anthraquinone,
1,2-dihydroxyanthraquinone,
1,5-dihydroxyanthraquinone,
1,8-dihydroxyanthraquinone.
Mention may additionally be made of:
the family of the azo dyes, that of the perylenes
and that of the phthalocyanine dyes;
the dyes used for coloured lasers, such as, for
example, the family of the polyphenyls or the family
of the phenyloxazoles (for example, the dyes
produced by Lambdachrome - LC 3300, 3400, 3500, 359,
3600, 3640, 3650, 3690, 3700, 4230, 3690, 3930,
3590, 3720, and the like);
the molecules used as dyes for medical, biological
or industrial applications, such as for dyeing the
hair, tissues (indanthrene) , polymers, and the like,
and more generally any molecule having colouring

properties and a vapour pressure compatible with
the process of the invention;
molecules known to act as precursors for conducting
polymers, for example N-allyl-N-methylaniline
(CAS 6628-0-7-5), poly(3-hexylthiophene-2,5-diyl)
(CAS 104 934-50-1), phenyl vinyl sulphoxide
(CAS 20451-53-0) or p-xylylenebis(tetrahydro-
thiophenium) chloride (CAS 52547-07-6);
as photochromic molecules, the family of the
spirobenzopyrans, of the furylfulgides and of the
diarylethenes,-
as thermochromic molecules, variously substituted
derivatives of the rylenes (Stefan Becker, Monomere
und polymere Rylenfarbstoffe als funktionelle
Materialien [Monomeric and polymeric rylene
colorants as functional materials] , Thesis, Mainz,
2000), in particular the compounds with the
following expanded formula, with the various R
substituents below.

molecules known for the manufacture of organic LEDs
(light emitting devices);

transition metal complexes, such as
ruthenium tris(bipyridine).
Mention may be made, as additives and stabilizers, of
the stabilizers and antioxidants commonly used for
polymers, in particular benzophenones, benzotriazoles,
cyanoacrylates, oxanilides, triazines or phenyl
salicylates. These molecules exist under various
registered trademarks according to the manufacturers:
Ciba-Geigy: Tinuvin-123, -144, -213, -234, -312,
-326, -327, -328, -360, -571, -622, -765, -770,
-1577, -P; Chimassorb-81, Irganox-245, -1010, -1076,
-1098, -1135, -1141, -5057, Uvitex OB;
Cytec: Cyasorb UV-9, -24, -81, -90, -531, -1164,
-2908, -3638, -3853, -3853S, -5411; Cyanox 425;
- BASF: Uvinul-3000, -3030, -3040, -3049, -3050,
-3035, -MBC 95; -D 50, -BMBM, -A Plus, -N 539 T,
-MC 80.
Moreover, mention may be made of molecules comprising
aluminium, such as aluminium alkoxide, aluminium
isopropoxide, aluminium p-diketonate, (p-diketonato)-
alkoxyaluminate, aluminium acetylacetate or aluminium
2,4-pentanedionate.
According to an advantageous characteristic made
possible by the process of the invention, the substrate
obtained is transparent and has a haze at most equal to
2%.
Moreover, a subject-matter of the invention is a device
for the implementation of the process described above,
comprising
for each organic or organometallic molecule, means
for evaporating and for dispensing the vapour
produced comprising an injection grid composed of
nozzles uniformly distributed over the surface of
the substrate,

means for dispensing at least one precursor of the
inorganic glass matrix comprising a specific
injection grid, and
a plasma source.
The latter is advantageously offset, that is to say-
that the plasma is emitted at a certain distance from
the substrate, towards which it is projected while
passing through the flows of precursor of the matrix
and of organic/organometallic molecules, for their part
confined close to the substrate.
Another subject-matter of the invention is the
application of the substrate defined above to a glazing
for land, sea or air transport vehicles, for buildings,
to interior decoration, to an aquarium, domestic
electrical appliances, to street furniture, bus
shelters, billboards, notice boards, to an illumination
system, in-particular covers for the lights, including
headlights, of transport vehicles, a greenhouse, a
mirror, a rear-view mirror, a display system screen of
the computer, television or telephone type, an
electrically controllable glazing, such as an
electrochromic glazing, a liquid crystal glazing or an
electroluminescent glazing, or a photovoltaic glazing.
The invention is illustrated by the examples which
follow.
Example 1
Use is made of a deposition chamber equipped with a
large-size (350 x 900 mm) microwave plasma source
composed of several individual microwave antennae
operating in post-discharge mode with a total maximum
power of 16 kW at a frequency of 2.4 5 GHz. The gases
necessary for the deposition process (oxygen, argon and
hexamethyldisiloxane) are introduced into the chamber
through bulk flow control devices and metal pipes
heated to 45°C.

The organic/organometallic molecule or molecules is/are
stored in (an) evaporator(s) (metal canisters) and
introduced into the chamber via metal pipes arranged in
(a) tree structure(s) through electropneumatic valves
heated according to the molecule. Thus, it is
guaranteed that the vapour of these molecules has a
temperature which is constantly increasing as it moves
through the pipes, which movement is found to be
facilitated thereby.
The injection grid for the organic molecule and that
for the hexamethyldisiloxane (HMDSO) are in the
immediate proximity of the substrate (polycarbonate
glazing) and are cited by order of distance from the
latter. It would also be possible to envisage fitting
them into one another at an equal distance from the
substrate.
The pressure in the chamber during the deposition is
2 Pa, usually between 1 and 10 Pa.
The organic molecule is 1,4-di(butylamino)anthraquinone
(CAS 17354-14-2).
The duration of deposition of the various constituents,
the argon, oxygen and HMDSO flow rates in sccm
(standard cubic centimetre per minute) and the
microwave power (kW) are specified in the table below.


The substrate is heated to and maintained at 95°C
during the deposition, the melting point of 1,4-
di(butylamino)anthraquinone being 120-122°C.
Several tests are carrie0d out by varying the
temperature of the 1,4-di(butylamino)anthraquinone in
the evaporator from 184°C to 219°C. Within this
temperature range, the vapour pressure of this molecule
varies between 1 and 15 Pa, which corresponds, with the
given injection and evaporation system, to a flow
varying approximately between 0.1 and 5 sccm.
Between these two temperatures, the light transmission
with a wavelength of 595 nm decreases from 87 to 66%.
In other words, the deposited layer gives a blue
colouring to the glazing which becomes more pronounced
as the temperature of the evaporator increases.
The haze of this glazing is at most 0.25%.
Example 2
The 1,4-di(butylamino)anthraquinone molecule is
replaced by pyrene (CAS 12 9-00-0). This molecule has an
absorption peak at approximately 325 nm in solution in
cyclohexane and a fluorescence peak (excitation
wavelength 317 nm) at approximately 400 nm.
Pyrene has a vapour pressure of approximarely 100 Pa at
175°C (deposited material L5), of 200 Pa at 190°C
(deposited material L4) and of approximately 300 Pa at
200°C (deposited material L3) , which corresponds, with
the given injection and evaporation system, to a flow
of approximately 150, 500 and 1250 sccm respectively.
The optical density of the three substrates provided
with their layer is measured with respect to that of a
substrate provided with a layer devoid of organic
molecule. A peak in the vicinity of 330 nm is observed,
the intensity of which increases with the flow of the

molecule, indicating an increasing amount of
organic molecule incorporated in the layer.
Figure 1 shows a fluorescence spectrum of the layer of
the deposited material L4 at an excitation wavelength
of 317 nm. The fluorescence emission is expressed on a
decimal logarithmic scale as a function of the
wavelength (nm). A peak centred around 400 nm is
observed, showing that the substrate with the molecule
has fluorescent properties.
Example 3
Example 1 is repeated while inserting, between the
deposition of the organic layer and that of the
protective layer (see table), a stage of incorporation
of pyrene according to the preceding example.
The resulting layer has a green colouring.
Example 4
Example 1 is repeated while replacing, in the
evaporator, 1,4-di(butylamino)anthraquinone by 2-(2H-
benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)phenol,
sold by Ciba-Geigy under the registered trademark
Tinuvin 32 8.
The evaporator is at a temperature of 213°C. Figure 2
shows '"the true transmission (that is to say, with
subtraction of that of the layer devoid of organic
molecule), expressed as %, as a function of the
wavelength in nm. It is found that a functionality of
absorption of UV radiation is indeed bestowed on the
layer by the molecule.
Example 5
Example 1 is repeated while varying the temperature of
the substrate. The haze is measured in each test.


The haze can thus be controlled as a function of the
temperature of the substrate during the deposition.

WE CLAIM
1. A process for functionalizing a transparent or translucent substrate
comprising forming a layer on the substrate, wherein:
the layer is formed by;
evaporating a composition comprising at least one organic or
organometallic compound to obtain a vapor;
dispensing the vapor over the substrate; and
depositing an inorganic glass on the substrate by plasma-enhanced
chemical vapor deposition;
the inorganic glass is deposited on the glass substrate in the presence of
the vapor;
the layer comprises functional molecules derived from the composition
comprising the at least one organic or organometallic compound dispersed
in a matrix of the inorganic glass; and
the functional molecules exhibit at least one function selected from the
group consisting of coloring, reflection of visible light that varies with
angle, electrical conductivity, infrared absorption or reflection, UV

absorption or reflection, photochromism, thermochromism,
electrochromism, electroluminescence, phosphorescence, fluorescence,
antibacterial action, photocatalytic action, fungicidal action, odor
absorbing or emitting, resisting tobacco smoke, hydrophilicity and
hydrophobicity.
2. The process as claimed in claim 1, further comprising heating the vapor
before dispensing the vapor over the substrate.
3. The process as claimed in claim 1, wherein depositing an inorganic glass
comprises employing a gaseous silicon-comprising precursor selected from
the group consisting of hexamethyldisiloxane (HMDSO),
tetramethyldisiloxane (TMDSO), tetraethoxysilane (TEOS) and
tetramethoxysilane (TMOS).
4. The process as claimed in claim 1, wherein depositing an inorganic glass
comprises employing oxygen, argon and hexadimethyldisiloxane gases.
5. The process as claimed in claim 1, wherein the matrix of the inorganic
glass is an SiOx matrix.
6. The process as claimed in claim 1, wherein the at least one organic or
organometallic compound comprises a compound selected from the group
consisting of naphthalene, anthracene, pyrene, anthraquinone and
derivatives thereof.

7. The process as claimed in claim 1, wherein the at least one organic or
organometallic compound comprises a compound selected from the group
consisting of 1,4-di(butylamino)anthraquinone, pyrene and 2-(2H-
benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)phenol.


The invention relates to a process for functionalizing a transparent or translucent
substrate comprising forming a layer on the substrate, wherein: the layer is
formed by; evaporating a composition comprising at least one organic or
organometallic compound to obtain a vapor; dispensing the vapor over the
substrate; and depositing an inorganic glass on the substrate by plasma-
enhanced chemical vapor deposition; the inorganic glass is deposited on the
glass substrate in the presence of the vapor; the layer comprises functional
molecules derived from the composition comprising the at least one organic or
organometallic compound dispersed in a matrix of the inorganic glass; and the
functional molecules exhibit at least one function selected from the group
consisting of coloring, reflection of visible light that varies with angle, electrical
conductivity, infrared absorption or reflection, UV absorption or reflection,
photochromism, thermochromism, electrochromism, electroluminescence,
phosphorescence, fluorescence, antibacterial action, photocatalytic action,
fungicidal action, odor absorbing or emitting, resisting tobacco smoke,
hydrophilicity and hydrophobicity.

Documents:

00718-kolnp-2007-correspondence-1.1.pdf

00718-kolnp-2007-others-1.1.pdf

0718-kolnp-2007 abstract.pdf

0718-kolnp-2007 assignment.pdf

0718-kolnp-2007 claims.pdf

0718-kolnp-2007 correspondence others.pdf

0718-kolnp-2007 description(complete).pdf

0718-kolnp-2007 drawings.pdf

0718-kolnp-2007 form-1.pdf

0718-kolnp-2007 form-2.pdf

0718-kolnp-2007 form-3.pdf

0718-kolnp-2007 form-5.pdf

0718-kolnp-2007 international publication.pdf

0718-kolnp-2007 international search authority report.pdf

0718-kolnp-2007 others.pdf

718-KOLNP-2007-ABSTRACT 1.1.pdf

718-KOLNP-2007-AMANDED CLAIMS.pdf

718-KOLNP-2007-CANCELLED PAGES 1.1.pdf

718-kolnp-2007-correspondence.pdf

718-KOLNP-2007-DESCRIPTION (COMPLETE) 1.1.pdf

718-KOLNP-2007-DRAWINGS 1.1.pdf

718-kolnp-2007-examination report.pdf

718-KOLNP-2007-FORM 1 1.1.pdf

718-kolnp-2007-form 18.1.pdf

718-kolnp-2007-form 18.pdf

718-KOLNP-2007-FORM 2 1.1.pdf

718-KOLNP-2007-FORM 3 1.1.pdf

718-kolnp-2007-form 3.pdf

718-KOLNP-2007-FORM 5 1.1.pdf

718-kolnp-2007-form 5.pdf

718-KOLNP-2007-FORM-27.pdf

718-kolnp-2007-gpa.pdf

718-kolnp-2007-granted-abstract.pdf

718-kolnp-2007-granted-claims.pdf

718-kolnp-2007-granted-description (complete).pdf

718-kolnp-2007-granted-drawings.pdf

718-kolnp-2007-granted-form 1.pdf

718-kolnp-2007-granted-form 2.pdf

718-kolnp-2007-granted-specification.pdf

718-kolnp-2007-others.pdf

718-KOLNP-2007-PETITION UNDER RULE 137.pdf

718-kolnp-2007-priority document.pdf

718-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

718-kolnp-2007-reply to examination report1.1.pdf

718-kolnp-2007-translated copy of priority document.pdf

abstract-00718-kolnp-2007.jpg


Patent Number 248217
Indian Patent Application Number 718/KOLNP/2007
PG Journal Number 26/2011
Publication Date 01-Jul-2011
Grant Date 28-Jun-2011
Date of Filing 27-Feb-2007
Name of Patentee SAINT-GOBAIN GLASS FRANCE
Applicant Address 18 AVENUE D'ALSACE F-92400 COURBEVOIE
Inventors:
# Inventor's Name Inventor's Address
1 HOFRICHTER, ALFRED RETHELSTRASSE 1 52062 AACHEN
2 HANS, ALFRED GRUNEPLEISTRASSE 35A 52159 ROTGEN
PCT International Classification Number C03C 17/00, C03C 17/34, C08J 7/06
PCT International Application Number PCT/FR2005/050682
PCT International Filing date 2005-08-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0451907 2004-08-26 France