U.S. patent application number 10/557243 was filed with the patent office on 2006-12-07 for nano-structured surface coating process, nano-structured coatings and articles comprising the coating.
Invention is credited to Edwin E. Currie, Guido Jozefina Wilhelmus Meijers, Atze Jan Nijenhuis, John Edmond Southwell, Jens Christoph J.C. Thies, Christopher Frederic Tronche.
Application Number | 20060275595 10/557243 |
Document ID | / |
Family ID | 39832562 |
Filed Date | 2006-12-07 |
United States Patent
Application |
20060275595 |
Kind Code |
A1 |
Thies; Jens Christoph J.C. ;
et al. |
December 7, 2006 |
Nano-structured surface coating process, nano-structured coatings
and articles comprising the coating
Abstract
The invention relates to a new process for the preparation of
nano-structured and/or nano-porous surfaces, coatings having a
nano-structured and/or nano-porous surface and articles comprising
said coatings. The invention also relates to the use of coatings
according to the invention, in particular as anti-reflective
coatings. The process for the preparation of the surface
nano-structured and/or nano-porous coatings is a process comprising
the steps of: a) applying a mixture to a substrate which mixture
comprises: i) reactive nano-particles; ii) at least one solvent;
iii) optionally a compound having at least one polymerisable group,
in an amount that results in an increase in the transmission of at
least 0.5%, for at least part of the electromagnetic spectrum
between 400 and 800 nm, after the mixture has been applied and
cured on a transparent substrate, in comparison with the same
substrate without a coating; b) inducing crosslinking and/or
polymerisation in the mixture applied to the substrate.
Inventors: |
Thies; Jens Christoph J.C.;
(Heugemer Molenstraat, NL) ; Meijers; Guido Jozefina
Wilhelmus; (Heisteeg, NL) ; Nijenhuis; Atze Jan;
(Gangellstraat, NL) ; Currie; Edwin E.; (Sittard,
NL) ; Tronche; Christopher Frederic; (Schaumburg,
CA) ; Southwell; John Edmond; (Elgin, CA) |
Correspondence
Address: |
NIXON & VANDERHYE, PC
901 NORTH GLEBE ROAD, 11TH FLOOR
ARLINGTON
VA
22203
US
|
Family ID: |
39832562 |
Appl. No.: |
10/557243 |
Filed: |
May 13, 2004 |
PCT Filed: |
May 13, 2004 |
PCT NO: |
PCT/NL04/00329 |
371 Date: |
November 16, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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60471746 |
May 20, 2003 |
|
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Current U.S.
Class: |
428/312.2 ;
427/180; 427/487 |
Current CPC
Class: |
Y10T 428/31504 20150401;
C04B 41/4584 20130101; Y10T 428/31935 20150401; C09D 4/00 20130101;
C03C 17/007 20130101; C08K 3/36 20130101; C04B 41/009 20130101;
C03C 2217/425 20130101; C08K 3/20 20130101; Y10T 428/249979
20150401; C08K 9/08 20130101; C04B 41/81 20130101; Y10T 428/31909
20150401; C09D 7/62 20180101; G02B 1/11 20130101; Y10T 428/249978
20150401; Y10T 428/249967 20150401; C04B 41/4584 20130101; C04B
41/483 20130101; C04B 41/4584 20130101; C04B 41/4842 20130101; C04B
41/4584 20130101; C04B 41/483 20130101; C04B 41/4584 20130101; C04B
41/4842 20130101; C04B 41/4584 20130101; C04B 41/483 20130101; C04B
41/4584 20130101; C04B 41/4842 20130101; C04B 41/4584 20130101;
C04B 41/483 20130101; C04B 41/4584 20130101; C04B 41/4842 20130101;
C04B 41/4584 20130101; C04B 41/483 20130101; C04B 41/4584 20130101;
C04B 41/4842 20130101; C04B 41/4584 20130101; C04B 41/483 20130101;
C04B 41/4584 20130101; C04B 41/4842 20130101; C04B 41/4584
20130101; C04B 41/483 20130101; C04B 41/4584 20130101; C04B 41/4842
20130101; C04B 41/4584 20130101; C04B 41/483 20130101; C04B 41/4584
20130101; C04B 41/4842 20130101; C04B 41/4584 20130101; C04B 41/483
20130101; C04B 41/4584 20130101; C04B 41/4842 20130101; C04B 41/009
20130101; C04B 35/14 20130101; C09D 4/00 20130101; C08F 220/10
20130101 |
Class at
Publication: |
428/312.2 ;
427/180; 427/487 |
International
Class: |
B05D 1/12 20060101
B05D001/12; C08F 2/46 20060101 C08F002/46; B32B 3/00 20060101
B32B003/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 20, 2003 |
EP |
03076510.1 |
Feb 20, 2004 |
EP |
04075534.0 |
Claims
1. A process for the preparation of a surface nano-structured
and/or nano-porous coating or film comprising the steps of a)
applying a mixture to a substrate which mixture comprises i)
reactive nano-particles, having reactive organic groups on their
surface, ii) at least one solvent iii) optionally a compound having
at least one polymerisable group in an amount small enough to allow
the formation of a nano-structures and/of nano-porous surface after
polymerisation of the mixture b) polymerising the mixture on the
substrate.
2. Process according to claim 1, wherein a mixture is used
comprising a compound having at least one polymerisable group, in
an amount that results in an increase in the transmission of at
least 0.5%, for at least one wave length in the spectrum between
400 and 800 nm, after the mixture has been applied as a coating, in
a thickness between 100 and 200nm, at one side of a transparent
substrate, in comparison with the same substrate without a
coating
3. A process according to claim 1, wherein the reactive
nano-particles are oxide particles.
4. A process according to claim 1 wherein the particles are silicon
oxide or zirconium oxide particles.
5. A process according to claim 1, wherein the reactive
nano-particles are elongated.
6. A process according to any one of claim 5, wherein the reactive
nano-particles have an aspect ratio greater than 5.
7. A process according to claim 1, wherein the reactive
nano-particles have a length of less than 350 nm.
8. A process according to claim 1, wherein the compound having at
least one polymerisable group is an acrylate.
9. A mixture according to claim 1, wherein the compound having at
least one polymerisable group has two or more polymerisable
groups.
10. A process according to claim 1, wherein the poymerisation is
achieved by applying UV-radiation.
11. A mixture as defined in claim 1.
12. A coating having a nano-structured and/or nano-porous surface
obtainable by the process according to claim 1.
13. A coating according to claim 12 containing an amount of
reactive nano-particles between 70-100 wt %, relative to the weight
of the coating.
14. A coating according to claim 12, having a thickness of between
50-200 nm.
15. A coating according to claim 12, which coating increases the
transmission by at least 0.5% for at least part of the
electromagnetic spectrum between 400 and 800 nm if the coating is
present on a transparent substrate in comparison with the same
substrate without a coating.
16. A coating according to claim 15, which coating increases the
transmission by at least 1%, preferably by at least 2%.
17. A coating according to claim 12, showing a static water contact
angle of less than 60.degree., more preferably, less than
40.degree..
18. A coating according to claim 12, showing a static water contact
angle of more than 90.degree., more preferably, more than
120.degree..
19. A coating according to claim 18, showing a contact angle of
more than 90.degree., more preferably, more than 120.degree. and
most preferably, more than 140.degree..
20. A coating prepared from a mixture comprising reactive
nano-particles, a solvent and a compound having at least one
polymerizable group, wherein the volume fraction of the compound
having at least one polymerizable group is less than 1-the random
close packing volume fraction of the reactive nano- particles.
21. Use of a coating according to claim 12 as an antireflective
coating.
22. Use of a coating obtainable by the process according to claim 1
as a membrane.
23. Use of the coating according to claim 12 in a process of
reverse sorption of at least one non-cross-linkable species.
24. An article comprising a coating obtainable by the process
according to claim 1.
25. An article according to claim 24, which article is a
display.
26. An article according to claim 25, which article is an organic
light emitting diode (OLED) display.
27. An article according to claim 24, which article is a polarizer
for a liquid crystal display (LCD).
28. An article according to claim 24, which article is a
polyethyleneterphtalate (PET) film or cellulosetriacetate (TAC)
film.
29. A display comprising the article according to claim 28.
Description
[0001] The invention relates to a new process for the preparation
of nano-structured and/or nano-porous surfaces, coatings having a
nano-structured and/or nano-porous surface and articles comprising
said coatings. The invention also relates to the use of said
coatings, in particular as anti-reflective coatings.
[0002] The drive for ever smaller features sizes in surfaces and
coatings has been brought about through a desire to achieve
attractive properties for applications in, for example
micro-electronics, anti-reflective coatings for displays and
super-hydrophobic or even self cleaning surfaces. The numerous
techniques for preparation of nano-structured surfaces or coatings
can be regarded as fitting into one of two classes.
[0003] The first class is know as the top down approach and is
primarily concerned with the manufacture of progressively smaller
and smaller feature sizes in photolithographic processes. Top down
lithographic techniques are especially applied where regular and
straight features are required as is the case for photo-resists in
the microprocessor field. Manufacture of random, irregular
structures and structuring via these techniques over large surface
areas (dm.sup.2 to m.sup.2) is extremely difficult, time consuming
and therefore expensive.
[0004] The second class of nano-structuring techniques can be
regarded as so-called bottom up techniques and are usually based on
phase separation, which can be achieved in two ways. Firstly, by
phase separation of two incompatible polymers (e.g.
Polymethylmethacrylate and Polystyrene,Steiner et al., Science, Vol
283, pg 520-522, 1999), during the evaporation of a solvent. After
that the nano-structure is formed by removal of one of the polymers
by a selective solvent, that dissolves only one of the
polymers.
[0005] Secondly, phase separation can be induced by crosslinking a
mixture of components where at least one component is capable of
crosslinking and at least one other is not(Ibn-Elhaj and Schadt,
Nature, Vol 410, pg 796-799, 2001). The mixture is homogeneous
prior to crosslinking and the phase separation occurs during the
formation of the crosslinked network. The nano-structure is formed
by removal of the non-crosslinkable component. As phase separation
is a dynamic process, the size and distribution of the features
formed under both of the above techniques is strongly dependent on
the rate or kinetics of the phase separation. Parameters such as
temperature and in the case of photo-induced crosslinking the
photo-initiator concentration and/or radiation intensity all will
affect the feature size of the nano-structured coatings. Therefore
processing is complicated and reproducibility is poor. Also the
necessary washing to remove one of the components is a sizable
hurdle in the commercialisation of such technologies, especially
for large surface areas. Thus, there is a need for an simple
technique that allows the manufacture of nano-structured
coatings.
[0006] Surprisingly, a very elegant and simple process has now been
found for the preparation of surface nano-structured and/or
nano-porous coatings or films. The process according to the
invention, which is a process for the preparation of
nano-structured and/or nano-porous coatings, comprises the steps of
[0007] a) applying a mixture, which mixture comprises [0008] i)
reactive nano-particles, having reactive organic groups on their
surface [0009] ii) a solvent [0010] iii) optionally a compound
having at least one polymerisable group in an amount that is small
enough to allow the formation of a nano-structured surface after
cure of the formulation, [0011] to a substrate, [0012] b)
polymerising the mixture on the substrate.
[0013] Surprisingly by simply using no or only a little of the
compound having at least one polymerisable group, a coating or a
film is obtained with the propcess of the present invention having
a nano-structured surface. Furthermore the coating or film has
favourable mechanical properties and adheres well on several
substrates. The coating or film has a variety of applications,
amoung which are films or coatings having super hydrophobic
properties and especially coatings having anti-reflective
properties.
[0014] From U.S. Pat. No. 2,601,123 a coating for reducing surface
reflections is known for the coating of glass substrates. The
coating however must be sintered at very high temperatures, so that
it is not suitable for application on polymer substrates.
Furthermore it relates to very old and abandoned technology.
[0015] It is known from U.S. Pat. No. 5,582,859 that
anti-reflective properties may be obtained by preparing a
multilayer system of coatings in which each coating has a carefully
selected thickness and refractive index. However, multilayer
coatings suffer from two sets of problems. The first is that the
anti-reflective performance of multilayer coatings suffers from
angle-dependency (D. Chen, Solar Energy Materials & Solar
Cells, 86 (2001) 313-336). This means that transmission will vary
from the normal to oblique angles. Secondly, reproducible
processing of such multilayer coatings with precisely controlled
thickness and optical properties is difficult and therefore costly
and time-consuming.
[0016] Also in U.S. Pat. No. 6,455,103 a similar multi-layer
anti-reflective coating is applied, giving the same problems as
explained above.
[0017] In DE 19746885 A1 a process for coating a substrate with a
mixture comprising reactive nanoparticles is disclosed. However
there is no teaching given how to obtain the surface
nano-structured and/or nanoporous coating of the present invention
and the anti-reflective properties are poor.
[0018] Since the reactive nano-particles in step a) always have
more than one reactive group on their surface, the polymerisation
in step b results in the formation of a crosslinked phase,
comprising the nanoparticles interconnected. Therefore, in this
text, the terms polymerise or polymerisation is used
interchangeably with cross-linking or cross-linked and
polymerisable group is used interchangeably with cross-linking
group.
[0019] Within the context of the invention the term surface
nano-structured coatings refers to coatings having a surface
roughness, and in which surface the dimensions of the features on
the surface are larger than or equal to the smallest
cross-sectional dimension of an individual nano-particle.
Preferably the dimensions of the fatures are smaller than 1200 nm,
more preferably smaller than 800 nm, still more preferably smaller
than 400 nm, most preferably smaller than 300 nm. There also may be
nanosized voids in the coating.
[0020] In the framework of this invention the term "nano-particles"
is defined as particles of which the majority has a diameter of
less than a micrometer. Within the framework of the invention a
nano-particle is elongated when the aspect ratio, defined as the
length divided by the diameter is greater than unity. The
preparation of reactive nano-particles as such is known in the art,
and has been described in e.g. US06025455. In a preferred
embodiment of the process according to the invention, all
nano-particles are reactive.
[0021] The compound having at least one polymerisable group is in
this text also referred to as both diluent or reactive diluent. In
this text the term hard coat refers to a coating comprising
nano-particular species, optionally reactive nano-particular
species, in a crosslinked polymeric network, wherein the volume
fraction of reactive diluent is such that there are no or at least
hardly no void spaces and/or surface nano-structures present in the
coating.
[0022] For obtaining the nano-structured surface it is important
that no or a relatively small amount of the reactive diluent and
optional further components is present in the coating obtained with
the process according to the invention. If a too high amount of
reactive diluent and optional further components is used, the nano
particles will be embedded and a coating having a smooth surface
and not having any pores will be obtained. Normally the amount of
reactive diluent and eventually further components in the final
coating (after evaporation of the solvent) as expressed in volume
fraction may not exceed 1-(the random close packing volume fraction
of the reactive nanoparticles). The skilled person can easily
determine the amount of diluent and eventually further additives by
varying the amount and measuring the surface roughness or a
parameter as for instance the transmission or the reflection of the
coating as a function of this amount. Above a certain concentration
of reactive diluent (or optionally further additives) the surface
roughness of the coating has vanished and no special
anti-reflective properties are detected any more.
[0023] Furthermore the invention also relates to the mixture for
the preparation of nano-structured and/or nano-porous coatings, the
coatings or films obtained from the process according to the
invention, articles comprising said coatings and the use of said
coatings.
Reactive Nano-Particles
[0024] In a preferred embodiment, the majority of the
nano-particles in the mixture according to the invention have a
diameter of less than 400 nm, more preferably the majority of
particles have a diameter of less than 50 nm. Most preferably all
particles have a diameter of less than 50 nm. In a preferred
embodiment, the majority of the nano-particles have a length in the
range of 40 to 300 nm. Preferably, the particles used have such a
dimensions that they do not (or not significantly) influence the
transparency of the eventual coating. Most preferably the increase
in haze of a transparent substrate comprising the coating in a
thickness of 0.1 micrometer, compared to the substrate not yet
comprsising the coating is less than 2%, preferably less than 1%,
most preferably less than 0.5%.
[0025] As will be obvious to anyone skilled in the art, the random
packing density of the nano-particlar species is detemined by the
shape and the relative size and size distribution of the
nano-particles. Hence it may be advantageous to use nano-particles
of differing shapes and sizes to precisely control the size of the
surface nano-structures and/or nano-pores.
[0026] In a preferred embodiment, the reactive nano-particles have
an aspect ratio greater than 1, more preferably, they have an
aspect ratio (length/diameter) greater than 3, still more
preferably greater than 5, and most preferably, they have an aspect
ratio of greater than 10. If elongated reactive nano-particles are
used it is possible to obtain a coating having even further
improved anti-reflective properties or to use a higher
concentration of reactive diluent, which gives better mechanical
properties to the coating. More preferably the nanoparticles are
wormlike. Of a wormlike nano particle the primary axis is
curved.
[0027] Methods for determining the particle dimension include
optical or scanning electron microscopy, or atomic force microscopy
(AFM) imaging.
[0028] For measuring the dimensions of the nano-particles the
particles are in a very dilute mixture applied on a surface in a
thin layer, so that at a SEM photographic image of the layer, the
single nano-particles are observable. Than from 100 nanoparticles,
ad random selected, the dimensions are determined and the average
value is taken. In case of particles having an aspect ratio above
1, like worm-shaped nano-particles, the total length is determined,
from one end to the other end, by following the primary axis as
projected in the plane of the photo. For the diameter the longest
straight line that can be drawn from one side of the particle to
the other side, perpendicular to the primary axis is taken.
[0029] In the process according to the invention the coating may
comprise either organic or inorganic nano-particles. Examples of
organic nano-particles are carbon nano-tubes or nano-spheres.
Preferably, the nano-particles are inorganic nano-particles.
Suitable inorganic particles are for example oxide particles.
Preferred oxide particles are particles of an oxide selected from
the group of aluminium oxide, silicium oxide, zirconium oxide,
titanium oxide, antimony oxide, zinc oxide, tin oxide, indium
oxide, and cerium oxide. It is also possible to use a mixture of
particles from different oxides or to use particles of mixed
oxides. Most preferably, the nano-particles are particles of
aluminium oxide, zirconium oxide or silicium oxide. The refractive
index of the coating and effective refractive index of the
coating/air interface can in part be tuned by the choice of oxide
used.
[0030] The nano-particles have reactive organic groups on their
surface. Such reactive nano-particles may or may not comprise
additional, non-reactive organic groups. Additional
non-polymerisable groups may be used to tune the overall polarity
and thus the hydrophobicity or hydrophilicity of the particle and
the resultant coating. In a preferred embodiment of the process
according to the invention, all nano-particles are reactive
nanoparticles. The reactive groups of the nano-partciles, and if
present, the polymerisable groups of the diluent may polymerise in
a homopolymerisation reaction or a copolymerisation reaction. In
such a case the reactive groups are polymerisable groups. A
copolymerisation reaction is possible when in the mixture different
groups are present that can polymerise, for example if the groups
of the particles and of the reactive diluent are different, or if
mixtures of reactive diluent and reactive/or particles are used
that comprise such different groups. It is also possible that the
reactive groups of the nanoparticles react with a polymer network
that is formed by the polymerisation of one or more reactive
diluents. Important however, is that the nanoparticles are
chemically interconnected in a cross-linked phase.
[0031] Preferably the reactive groups of the reactive
nano-particles are polymerisable groups.
[0032] The preparation of reactive nano-particles as such is known
in the art, and has been described in e.g. US06025455.
Substrates
[0033] A wide variety of substrates may be used as a substrate in
the process according to the invention. Suitable substrates are for
example flat or curved, rigid or flexible substrates including
films of for example polycarbonate, polyester, polyvinyl acetate,
polyvinyl pyrollidone, polyvinyl chloride, polyimide, polyethylene
naphthalate, polytetrafluoro ethylene, nylon, polynorbornene or
amorphous solids, for example glass or crystalline materials, such
as for example silicon or gallium arsenide. Metallic substrates may
also be used. Preferred substrates for use in display applications
are for example glass, polynorbornene, polyethersulfone,
polyethyleneterphtalate, polyimide, cellulose triacetate,
polycarbonate and polyethylenenaphtalate.
[0034] A free-standing single layer anti-reflective film obtainable
by a process according to the invention may be obtained by
preparing a film or coating on a substrate and subsequently
removing the film or coating from the substrate after crosslinking.
The removal of the film or coating from the substrate should always
take place after the crosslinking.
Application of the Mixture to a Substrate
[0035] The mixture may be applied onto the substrate by any process
known in the art of wet coating deposition. Examples of suitable
processes are spin coating, dip coating, spray coating, flow
coating, meniscus coating, capillary coating and roll coating.
[0036] Preferably he mixture according to the invention is applied
in a single layer. In this case it is possible that the mixture is
applied on a further coating, as long as this is not a coating
according to the invention.
[0037] Typically, the reactive nano-particles are mixed with at
least one solvent and, optionally crosslinking initiator and
optionally a reactive diluent, to prepare a mixture that is
suitable for application to the substrate using the chosen method
of application.
Solvent
[0038] In principle, a wide variety of solvents may be used. The
solvent preferably has the ability to form stable suspensions of
the reactive nano-particles in order to facilitate a random close
packing arrangement of the reactive nano-particles upon
application, i.e. after evaporation of the solvent.
[0039] Nano-particles typically are added to the mixture in the
form of a suspension. The same solvent as used in the suspension
may be used to adjust the mixture so that it has the desired
properties. However, other solvents may also be used.
[0040] Preferably the solvent used evaporates after applying the
mixture onto the substrate. In the process according to the
invention, optionally the mixture may after application to the
substrate be heated or treated in vacuum to aid evaporation of the
solvent.
[0041] Examples of solvent that may be suitable are 1,4-dioxane,
acetone, acetonitrile, chloroform, chlorophenol, cyclohexane,
cyclohexanone, cyclopentanone, dichloromethane, diethyl acetate,
diethyl ketone, dimethyl carbonate, dimethylformamide,
dimethylsulphoxide, ethanol, ethyl acetate, m-cresol, mono- and
di-alkyl substituted glycols, N,N-dimethylacetamide,
p-chlorophenol, 1,2-propanediol, 1-pentanol, 1-propanol,
2-hexanone, 2-methoxyethanol, 2-methyl-2-propanol, 2-octanone,
2-propanol, 3-pentanone, 4-methyl-2-pentanone,
hexafluoroisopropanol, methanol, methyl acetate, methyl
acetoacetate, methyl ethyl ketone, methyl propyl ketone,
n-methylpyrrolidone-2, n-pentyl acetate, phenol,
tetrafluoro-n-propanol, tetrafluoroisopropanol, tetrahydrofuran,
toluene, xylene and water. Alcohols, ketones and esters based
solvents may also be used, although the solubility of acrylates may
become an issue with high molecular weight alcohols. Halogenated
solvents (such as dichloromethane and chloroform) and hydrocarbons
(such as hexanes and cyclohexanes), may also be suitable.
Preferably methanol, methyl ethyl keton or isopropanol are
used.
Compound Having at Least One Polymerisable Group (Also Called
"Diluent" or "Reactive Diluent")
[0042] In principle, a wide variety of materials are suitable to be
used as the reactive diluent. The relative amount of reactive
diluent with respect to the relative amount of reactive
nano-particles must be so small that it allows formation of a
nano-structured surface. A way of determining of a coating has a
surface nano-structure and/or nano-pores, is to apply the coating
to a transparent substrate, crosslinking, and subsequently
measuring the transmission. Preferably the amount of reactive
diluent and optional further components in the mixture is that low,
that if applied as a coating at one side of a transparent
substrate, in a thickness between 100-200nm, there is an increase
in transmission of light at at least one wave length between 400
and 800 nm of at least 0.5% relative to the same substrate without
the coating. Preferably the increase in transmission is at least
0.75%, more preferably at least 1%, still more preferably at least
1.5%, still more preferably at least 2%, still more preferably at
least 2.5%, most preferaby at least 3%. The exact amount of
reactive diluent depends on the particle size, shape, and size
distribution, and can thus not be given exactly. In case of
elongated nano particles the amount of diluent may be less than 40
wt %, relative to the total weight of the mixture as applied in
step a) of the process according to the invention, however without
taking the solvent into account (total weight of solid).
Preferably, the amount of diluent is less than 20 wt %. Although it
is not necessary to use any diluent, the mechanical properties of
the coating will generally be better when at least some diluent is
present, e.g., at least 1 wt %, more preferably at least 2 wt. %,
still more preferably at least 5 wt. %, most preferably at least 10
wt. %. With respect to this aspect the advantage of the elongated
particles and of these especially the wormloke nano particles
becomes evident, as it is possible with these particles to apply a
relatively high amount of reactive diluent to obtain very
favourable mechanical properties and yet still having a well
developed nano-structured surface, resulting for example in good
antireflective properties.
[0043] As mentioned, in principle a wide variety of materials are
suitable to be used as the reactive diluent, for example monomers
or oligomers having crosslinking groups. Monomers or oligomers
having only one crosslinking group per molecule may be used, but
preferably in combination with other crosslinking components that
do have at least two crosslinking groups. Preferably monomers or
oligomers having at least two or more crosslinking groups per
molecule are used. It is also possible that the reactive diluent
comprises a mixture of compounds that after the induction of
crosslinking in step b, together form a crosslinked phase. The
mixture may comprise compounds that are by itself crosslinking,
such as for example different acrylates or it may comprise
compounds that will riot crosslink by itself but which form a
crosslinked phase in combination with another compound after
initiation of the crosslinking reaction, for example copolymerising
systems comprising electron rich and electron poor double bonds
such as for example maleate/vinyl ether copolymerising systems.
[0044] Examples of monomers suitable for use as a reactive diluent
and having at least two crosslinking groups per molecule include
monomers containing (meth)acryloyl groups such as
trimethylolpropane tri(meth)acrylate, pentaerythritol
(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene
glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate,
1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,
neopentyl glycol di(meth)acrylate, polybutanediol di(meth)acrylate,
tripropyleneglycol di(meth)acrylate, glycerol tri(meth)acrylate,
phosphoric acid mono- and di(meth)acrylates, C7-C20 alkyl
di(meth)acrylates, trimethylolpropanetrioxyethyl (meth)acrylate,
tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate,
tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, pentaerythritol
tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,
dipentaerythritol monohydroxy pentacrylate, dipentaerythritol
hexacrylate, tricyclodecane diyl dimethyl di(meth)acrylate and
alkoxylated versions, preferably ethoxylated and/or propoxylated,
of any of the preceding monomers, and also di(meth)acrylate of a
diol which is an ethylene oxide or propylene oxide adduct to
bisphenol A, di(meth)acrylate of a diol which is an ethylene oxide
or propylene oxide adduct to hydrogenated bisphenol A, epoxy
(meth)acrylate which is a (meth)acrylate adduct to bisphenol A of
diglycidyl ether, diacrylate of polyoxyalkylated bisphenol A, and
triethylene glycol divinyl ether, adduct of hydroxyethyl acrylate,
isophorone diisocyanate and hydroxyethyl acrylate (HIH), adduct of
hydroxyethyl acrylate, toluene diisocyanate and hydroxyethyl
acrylate (HTH), and amide ester acrylate.
[0045] Examples of suitable monomers having only one crosslinking
group per molecule include monomers containing a vinyl group, such
as N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl
pyridine; isobornyl (meth)acrylate, bornyl (meth)acrylate,
tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate,
dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl
(meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloyl
morpholine, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate,
methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate,
isopropyl (meth)acrylate, butyl (meth)acrylate, amyl
(meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,
pentyl (meth)acrylate, caprolactone acrylate, isoamyl
(meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl
(meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate,
isodecyl (meth)acrylate, tridecyl (meth)acrylate, undecyl
(meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate,
isostearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate,
butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate,
benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, polyethylene
glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate,
methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate,
methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene
glycol (meth)acrylate, diacetone (meth)acrylamide,
beta-carboxyethyl (meth)acrylate, phthalic acid (meth)acrylate,
isobutoxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide,
t-octyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate,
*diethylaminoethyl (meth)acrylate, butylcarbamylethyl
(meth)acrylate, n-isopropyl (meth)acrylamide fluorinated
(meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate,.
N,N-diethyl (meth)acrylamide, N,N-dimethylaminopropyl
(meth)acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether,
cetyl vinyl ether, 2-ethylhexyl vinyl ether; and compounds
represented by the following formula (I)
CH.sub.2.dbd.C(R.sup.6)--COO(R.sup.7O).sub.m--R.sup.8 Formula I
wherein R.sup.6 is a hydrogen atom or a methyl group; R.sup.7 Is an
alkylene group containing 2 to 8, preferably 2 to 5 carbon atoms;
and m is an integer from 0 to 12, and preferably from 1 to 8;
R.sup.8 is a hydrogen atom or an alkyl group containing 1 to 12,
preferably 1 to 9, carbon atoms; or, R.sup.8 is a tetrahydrofuran
group- comprising alkyl group with 4-20 carbon atoms, optionally
substituted with alkyl groups with 1-2 carbon atoms; or R.sup.8 is
a dioxane group-comprising alkyl group with 4-20 carbon atoms,
optionally substituted with methyl groups; or R.sup.8 is an
aromatic group, optionally substituted with C.sub.1-C.sub.12 alkyl
group, preferably a C.sub.8-C.sub.9 alkyl group, and alkoxylated
aliphatic monofunctional monomers, such as ethoxylated isodecyl
(meth)acrylate, ethoxylated lauryl (meth)acrylate, and the
like.
[0046] Oligomers suitable for use as the reactive diluent are for
example aromatic or aliphatic urethane acrylates or oligomers based
on phenolic resins (ex. bisphenol epoxy diacrylates), and any of
the above oligomers chain extended with ethoxylates. Urethane
oligomers may for example be based on a polyol backbone, for
example polyether polyols, polyester polyols, polycarbonate
polyols, polycaprolactone polyols, acrylic polyols, and the like.
These polyols may be used either individually or in combinations of
two or more. There are no specific limitations to the manner of
polymerization of the structural units in these polyols. Any of
random polymerization, block polymerization, or graft
polymerization is acceptable. Examples of suitable polyols,
polyisocyanates and hydroxylgroup-containing (meth)acrylates for
the formation of urethane oligomers are disclosed in WO 00/18696,
which is incorporated herein by reference.
[0047] Combinations of compounds that together may result in the
formation of a crosslinked phase and thus that in combination are
suitable to be used as the reactive diluent are for example
carboxylic acids and/or carboxylic anhydrides combined with
epoxies, acids combined with hydroxy compounds, especially
2-hydroxyalkylamides, amines combined with isocyanates, for example
blocked isocyanate, uretdion or carbodiimide, epoxies combined with
amines or with dicyandiamides, hydrazinamides combined with
isocyanates, hydroxy compounds combined with isocyanates, for
example blocked isocyanate, uretdion or carbodiimide, hydroxy
compounds combined with anhydrides, hydroxy compounds combined with
(etherified) methylolamide ("amino-resins"), thiols combined with
isocyanates, thiols combined with acrylates or other vinylic
species (optionally radical initiated), acetoacetate combined with
acrylates, and when cationic crosslinking is used epoxy compounds
with epoxy or hydroxy compounds.
[0048] Further possible compounds that may be used as the reactive
diluent are moisture curable isocyanates, alkoxy titanates, alkoxy
zirconates, or urea-, urea/melamine-, melamine- formaldehyde or
phenol-formaldehyde (resol, novolac types), or radical curable
(peroxide- or photo-initiated) ethylenically unsaturated mono- and
polyfunctional monomers and polymers, e.g. acrylates,
methacrylates, maleate/vinyl ether), or radical curable (peroxide-
or photo-initiated) unsaturated e.g. maleic or fumaric, polyesters
in styrene and/or in methacrylates.
Method for Crosslinking or Polymerisation
[0049] Any cross-linking method that may cause the mixture to
crosslink so that a coating is formed is suitable to be used in the
process according to the invention. Suitable ways to initiate
crosslinking are for example electron beam radiation,
electromagnetic radiation (UV, Visible and Near IR), thermally and
by adding moisture, in case moisture curable compounds are used. In
a preferred embodiment crosslinking is achieved by UV-radiation.
The UV-crosslinking may take place through a free radical mechanism
or by a cationic mechanism, or a combination thereof. In another
preferred embodiment the crosslinking is achieved thermally.
Initiator
[0050] An initiator may be present in the mixture to initiate the
crosslinking reaction. The amount of initiator may vary between
wide ranges. A suitable amount of initiator is for example between
above 0 and 5 wt % with respect to total weight of the compounds
that take part in the crosslinking reaction.
[0051] When UV-crosslinking is used to initiate crosslinking, the
mixture preferably comprises a UV-photo-initiator. A
photo-initiator is capable of initiating a crosslinking reaction
upon absorption of light, thus, UV-photo-initiators absorb light in
the Ultra-Violet region of the spectrum. Any known
UV-photo-initiators may be used in the process according to the
invention.
[0052] The coating according to the invention can be prepared in
any desired thickness. The coatings according to the invention
typically have a thickness ranging between 50 nm to several
micrometer. In case of application as an anti-reflective coating
the thickness is preferably between 50 and 200 nm, more preferably
between 100 and 150 nm.
[0053] In a preferred embodiment, the nano-structured and/or
nano-porous films or coatings according to the invention increases
the optical transmission of a substrate on which they are present
for at least a range of visible wavelengths of the electromagnetic
spectrum. Therefore the coating shows a reflection of light, at at
least one wavelenth in the area between 400-800 nm, measured under
normal incidence of less than 3%, preferably less than 2%, more
preferably less than 1.5%, most preferably less than 1%, per coated
side of the substrate in a coating layer thickness between 100-200
nm.
[0054] The combination of good mechanical properties as well as
anti-reflective performance will allow for the use of these single
layer anti-reflective hard-coats in applications were mechanical
durability and anti-reflective performance on flat or on non-flat
substrates are advantageous. These applications include
anti-reflective coatings for automobile and airplane wind screens,
displays in general, television tubes, flexible displays and
lenses, for example in spectacles. It is possible that the
anti-reflective coating is applied to the substrate as a single
coating. It is also possible that before the application of the
anti-reflection coating, the substrate is coated with a further
coating, for example to improve the adhesion between the
anti-reflective coating and the substrate. At least an advantage of
the anti-reflective coating of the present invention is, that the
coating, bringing the anti-reflective properties only needs to be
applied in a single layer,
[0055] In yet a further embodiment the surface nano-structured
and/nano-porous coating according to the invention can be used to
affect the wetting properties of the coating.
[0056] Generally, a hydrophobic material or coating is
characterised by a static contact angle of water of 90.degree. or
above.
[0057] Hydrophobic polymeric materials such as
poly(tetrafluorethene) (PTFE) or polypropylene (PP) have been
available for decades. These materials suffer from a limited
hydrophobicity, as well as inferior mechanical properties as
compared to engineering materials or highly crosslinked coatings.
For instance, PP has a static contact angle of water of roughly
100.degree. whereas PTFE, which is amongst the most hydrophobic
polymeric material known, has a static contact angle of water of
roughly 112.degree..
[0058] Some hydrophobic coatings are being referred to in the art
as superhydrophobic coatings. Superhydrophobic coatings are
generally defined by a static water contact angle above 140.degree.
(Nun, Oles & Schleich, Macromol. Symp. 187 (2002) 677-682).
[0059] Within the framework of the invention, a combination of
surface roughness, due to surface nano-structures and/or
nano-pores, together with polar surface chemistry achieves static
water contact angles below 60.degree., preferably below 40.degree..
Conversely, the coating may also be affected so that the static
water contact angle is above 90.degree. and preferably 120.degree.
if the surface chemistry of the nano-structured and/nano-porous
coating is apolar, for example via the presence of apolar surface
modifying groups on the nano-particles.
[0060] Combining the wetting properties with the anti-reflection
properties, the surface nano-structured and/or nano-porous films or
coatings according to the invention increases the optical
transmission of a substrate on which they are present to visible
wavelengths of the electromagnetic spectrum while simultaneously
exhibiting a static water contact angle of above 90.degree.,
preferably 120.degree. and most preferably 140.degree..
[0061] Furthermore due to the surface nano-structures and/or nano
pores other properties such as low refractive index, low optical
dissipation (low optical loss), low dielectric constant, high
relative surface area, low contact area, low adhesion and coating
porosity are envisaged. Applications derived from the above
properties include the following: anti-reflective coatings for all
kinds of display applications, for biological devices and coatings
with improved wetting characteristics; easy to clean and
self-cleaning coatings; easy to clean and self-cleaning
anti-reflective coatings; non-stick coatings, low dielectric
coatings for semi-conductors, low dissipation (low optical loss)
coatings for optical wave guides; controlled release coatings, hard
membranes, biologically active surfaces, anti-fouling and
anti-bacterial coatings.
[0062] When it is desireable to have patterned coatings, for
example, alternating hydrophobic and hydrophilic regions, this can
also be achieved by the process according to the invention, by
using photolithographic processes. Hence, applications where
patterning of nano-structured and/or nano-porous coatings is
desired may also result. This could lead to coatings and articles
where the optical or wetting properties are patterned as
desired.
[0063] In a preferred embodiment the mixture according to the
invention comprises an adhesion promoter. An adhesion promoter
enhances the adhesion between the coating of the present invention
and its substrate. In this way the scratch resistance of the
coating is also improved.
[0064] The skilled artisan knows how to select a suitable adhesion
promoter for given groups at the surface of the reactive
nano-particles, reactive diluent and substrate.
[0065] Examples of suitable adhesion promoters are compounds having
at least one reactive group capable of reacting with the groups at
the surface of the reactive nano particles and/or with the reactive
diluent and further have at least one reactive group capable of
reacting or physically interacting, e.g. H bonding with the
substrate.
[0066] For glass substrates adhesion promoters can include but are
not limited to acrylate, methacrylate or thiol functional trialkoxy
silanes, where the trialkoxy groups of the silane can be propoxy or
butoxy but is preferably ethoxy or methoxy. Examples of silane
adhesion promoters include:
.gamma.-mercaptopropylmethylmonomethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane,
.gamma.-mercaptopropylmonoethoxysilane,
.gamma.-mercaptopropyldiethoxysilane,
.gamma.-mercaptopropyltriethoxysilane,
.beta.-mercaptoethylmonoethoxysilane,
.beta.-mercaptoethyltriethoxysilane,
.beta.-mercaptoethyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyidimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
.gamma.-glycidoxylpropyltrimethoxysilane,
.gamma.-glycidoxylpropylmethyldimethoxysilane,
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
.gamma.-chloropropylmethyidimethoxysilane,
.gamma.-chloropropyltrimethoxysilane, and
.gamma.-methacryloyloxypropyltrimethoxysilane. Examples of
commercially available products of these compounds include SILAACE
S310, S311, S320, S321, S330, S510, S520, S530, S610, S620, S710,
S810 (manufactured by Chisso Corp.), Silquest A-174NT (manufactured
by OSI Specialties--Crompton Corp.). SH6062, AY43-062, SH6020,
SZ6023, SZ6030, SH6040, SH6076, SZ6083 (manufactured by Toray-Dow
Corning Silicone Co., Ltd.), KBM403, KBM503, KBM602, KBM603,
KBM803, KBE903 (manufactured by Shin-Etsu Silicone Co., Ltd.), and
the like. Also acidic adhesion promoters such as acrylic acid may
be used. Phosphate esters such as Eb168 or Eb170 from UCB are
feasible adhesion promoters.
[0067] For adhesion to polymeric substrates such as, for example
polyethylene terephthalate (PET) and or cellulose triacetate(TAC)
the above adhesion promoters may be feasible but also good results
are obtained with epoxy functional acrylate or methacrylate
compounds.
[0068] Surprisingly, it has been found that for substrates
containing vinyllic unsaturation, for example acrylate or
methacrylate based substrates, like a crosslinked coating, for
example a hard coat, compounds comprising at least one thiol group
are very suitable as adhesion promoters. Such thiol compounds may
be mono-functional, di-functional, preferably tri-functional and
most preferably tetra-functional with respect to the number of
thiol groups per molecular species. The thiol compounds may
comprise next to the thiol group a further reactive group. In case
the thiol compound comprises only one thiol group, it must comprise
at least one further reactive group. Examples of thiol compounds
may be any of those known in the art. A description of the most
common thiol compounds may be found at column 9, lines 1-41 of U.S.
Pat. No. 3,661,744, which is incorporated herein by reference.
Certain polythiols such as the aliphatic monomeric polythiols
e.g.ethane dithiol, hexamethylene dithiol, decamethylene dithiol,
tolylene-2,4-dithiol, and the like, and some polymeric polythiols
such as a thiol-terminated ethylcyclohexyl dimercaptan polymer, and
the like, and similar polythiols which are conveniently and
ordinarily synthesized on a commercial basis are suitable. Examples
of the polythiol compounds preferred because of relatively low odor
level include but are not limited to esters of thioglycolic acid
(HS--CH.sub.2COOH), .alpha.-mercaptopropionic acid
(HS--CH(CH.sub.3)--COOH and .beta.-mercaptopropionic acid
(HS--CH.sub.2CH.sub.2COOH) with polyhydroxy compounds such as
glycols, triols, tetraols, pentaols, hexaols, and the like.
Specific examples of the preferred polythiols include but are not
limited to ethylene glycol bis(thioglycolate), ethylene glycol bis
(.beta.-mercaptopropionate), trimethylolpropane
tris(thioglycolate), trimethylolpropane tris
(.beta.-mercaptopropionate), pentaerythritol tetrakis
(.beta.-mercaptopropionate), all of which are commercially
available. A specific example of a preferred polymeric polythiol is
polypropylene ether glycol bis(.beta.-mercaptopropionate) which is
prepared from polypropylene-ether glycol (e.g. Pluracol P201,
Wyandotte Chemical Corp.) and .beta.-mercaptopropionic acid by
esterfication. Poly-.alpha.-mercaptoacetate or
poly-.beta.-mercaptopropionate esters, particularly the
trimethylopropane triesters or pentaerythritol tetra esters are
preferred. Other polythiols which can be suitably employed include
alkyl thiol functional compounds such as 1,2-dimercapthoethane,
1,6-dimercaptohexane and the like. Thiol terminated polysulfide
resins may also be employed.
[0069] Suitable examples of aliphatic dithiols include
1,2-ethanedithiol, butanedithiol, 1,3-propanedithiol,
1,5-pentanedithiol, 2,3-dimercapto-1-propanol, dithioerythritol,
3,6-dioxa-1,8-octanedithiol, 1,8-octanedithiol hexanedithiol,
dithiodiglycol, pentanedithiol,decanedithiol, 2-methyl 1,4
butanedithiol, bis-mercaptoethylphenyl methane,
1,9-nonanedithiol(1,9-dimercaptononane), glycol
dimercaptoacetate.
[0070] Suitable examples of aromatic dithiols include
1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol,
2,4,6-trimethyl-1,3-benzenedimethanethiol,
durene-.alpha.1,.alpha.2-dithiol, 3,4-dimercaptotoluene,
4-methyl-1,2-benzenedithiol, 2,5-dimercapto-1,3,4-thiadiazole,
4,4'-thiobisbezenedithiol,
bis(4-mercaptophenyl)-2,2'-propane(bisphenoldithiol) (made
according to the method of Meng Y. Z., Hay. A. S., J. of App.
Polym. Sci., V74, 3069-3077(1999).
[0071] Suitable examples of oligomeric dithiols include
difunctional mercapto functional urethane oligomers derived from
end capping moieties of hydroxyethyl mercaptan, hydroxypropyl
mercaptan, dimercaptopropane, dimercapto ethane as described in
patent by Shustack U.S. Pat. No. 5,744,514.
[0072] Examples of suitable trithiol functional compounds include,
trimethylolethane tris-mercaptopropionate, trimethylolpropane
tris-mercaptopropionate (TMPTSH), trimethylolethane
tris-mercaptoacetate, and trimethylolpropane tris-mercaptoaacetate
glycerol tri(11-mercaptoundecanoate), trimethylol propane
tri(11-mercaptoundecate). A preferred trithiol is
trimethylolpropane tris(2-mercapto-propionate) TMPTSH.
[0073] Examples of suitable tetrafunctional thiols include
pentaerythritol tetramercapto propionate, pentaerythritol
tetramercapto acetate, and
pentathritoltetra(11-mercaptoundecate)
[0074] Examples of multifunctional thiols having functionality
greater than 4, include polythiols as described on page 7 of WO
88/02902.
[0075] Multi functional thiols can be obtained by reacting
thioalkyl carboxylic acids e.g. thioglycolic acid, mercapto
propionic acid with high functional alcohols, amines and thiols.
Furthermore, multifunctional thiols can be obtained by reacting
mercapto alkyl trialkoxy silanes with silanols that may be
polymeric or silica based silanols.
[0076] Other preferred multifunctional thiols are obtained using
thiol carboxylic acids (HS--R--COOH) where R=alkyl, or aryl groups
eg thioundecanoic acid of which the COOH groups are reacted with
reactive enes, alcohols, thiols or amines that are
multifunctional.
[0077] The adhesion promoters may be used in an amount of 0.1-10
wt-% of the total solids in the mixture, after evaporation of the
solvent. Preferably the adhesion promoter is used in an amount of
5-10 wt-%.
[0078] A further improvement of the scratch resistance is obtained
if the mixture according to the invention comprises a compound
having a surface energy of less than 25 milli Joules per square
meter (mJ/m.sup.2). The surface energy is preferably measured of
the pure compound according to ASTM D2578, preferably using a ACCU
DYNE TEST.TM. marker pen. An example of such compounds are reactive
polydimetylsiloxane compounds. Preferred are reactive fluoro
compounds. Reactive fluoro compounds are for example described in
U.S. Pat. No. 6,391,459. The fluoro compounds further have the
advantage that they don't disturb the anti-reflective properties
very much.
[0079] In a further improved embodiment the substrate is in a first
step coated with a first coating, preferably a highly crosslinked
coating or a hard coat, and in a second step the mixture according
to the present invention is applied on top of the first coating. In
this way the first coating acts as the substrate for the mixture of
the present invention. In this case the first coating preferably
comprises vinyllic unsaturations and thiol compounds are preferably
used as adhesion promotors. In this way a still better scratch
resistance of the coating of the present invention is obtained.
[0080] Suitable examples for the first coating are the coatings
described in EP-A-1276810.
[0081] Preferably in the first step of application of the first
coating, the first coating is partly cured at least at the surface.
In case that in the hard coat, a radical curing resin system is
used, like for example an acrylate based resin system, partly
surface curing is preferably obtained by curing in the presence of
oxygen, for example curing in an air atmosphere. In this way a
still further improved adhesion between the hard coating and the
antireflective coating is obtained, resulting in a still further
improvement of the scratch resistance of the coating according to
the present invention.
[0082] The scratch resistance can be still further improved by
thermally treating the first coating and the coating according to
the invention, by for example Infra red lamps or thermal ovens.
Good results are obtained if the coating according to the invention
and preferably also the first coating comprise a thermal initiator
for subsequent cross-linking during thermal post-treatment,
especially if the cure of hard coat and nano-structured coatings
has been induced photo-chemically. The skilled artisan knows how to
select such a thermal initiator.
[0083] It is also possible to produce a film out of the composition
according to the invention, and to use the film as a membrane.
[0084] It is also possible to use the coating according to the
invention in a process of reverse sorption of at least one
non-cross-linkable species.
EXAMPLES
Nano-Silicate Particles.
[0085] Nano-silicate particles MT-ST (spherical particles) and
IPA-ST-UP (elongated particles) were obtained from Nissan Chemical
American Corporation. These particles were used in illustration of
the invention. Their properties and properties of their supensions
are listed in table 1 below. TABLE-US-00001 TABLE 1 Types and
properties of nano-silica particles. Nano- Particle SiO.sub.2
H.sub.2O Viscosity Specific Particle particle Size (nm) (wt %) (%)
(mPa s.) Gravity pH Shape Solvent MT-ST 10-15 30-31 <2.0 <5
0.98-1.02 2-4 Spherical Methanol IPA-ST- 9-15 15-16 <1.0 <20
0.85-0.90 2-4 Elongated* Isopropanol UP Elongated* *Elongated
particles have a diameter of 9-15 nm with a length of 40-300 nm.
(Information source www.snowtex.com).
A. Grafting of Spherical or Elongated Silica Nano-Particles:
[0086] Reactive organic groups were grafted onto the silica
nano-oxide particles by adding a trimethoxy-silane compound
comprising an acrylate group (e.g., a compound according to formula
II) together with p-methoxy-phenol, a compound that inhibits
polymerization of the acrylate groups, to a suspension of the oxide
particles in methyl ethyl ketone. Table 2 shows the exact amounts
of chemicals used. After stirring, a catalytic amount of water was
added to the mixture and the mixture was refluxed at 80.degree. C.
for at least 3 hours. Subsequently as a dehydrating agent trimethyl
orthoformate was added to remove any traces of water, and the
resultant mixture stirred at 60.degree. C. for at least one hour.
Another method for preparing the grafted particles was to add a
methoxy-silane compound comprising an acrylate group together with
p-methoxy-phenol, to a suspension of the oxide particles in
methanol. After stirring, the mixture was refluxed at 60.degree. C.
for at least 1.5 hours for MT-ST nano-silicates particles or at
least 3 hours for IPA-ST-UP nano-silicate particles, and
subsequently a trialkoxy silane compound, was added. As subsequent
trialkoxy silane methyl trimethoxy silane, or in case hydrophobic
apolar surface characteristics are required a perfluoroalkyl
trialkoxy silane was used. After refluxing for at least one more
hour at 60.degree. C., a dehydrating agent was added and the
resultant mixture was stirred at 60.degree. C. for at least one
hour.
B: Preparation of a Coating or Film on a Substrate
[0087] Thin films of various mixtures were prepared on microscope
glass slides or polyethyleneteraphthalate (PET) films (for
transmission measurements) and/or silicon wafers (for measurements
of wetting properties and thickness determination) by the following
procedure.
[0088] A drop of a mixture (see table 3 and 4 for the mixtures) was
applied to the substrate by spin-coating at a rate of 4800 r.p.m.
Thin films (100-200 nm) were spin coated from mixtures containing
less than 10 wt-% solids while thicker (1-5 .mu.m) coatings were
spin coated from formulations with ca 35-50 wt-% solids, see table
3, 4 and 5. The resultant wet film was crosslinked with UV
radiation using a D-bulb under nitrogen at a dose of 1.7 J/cm2. The
thickness of the crosslinked transparent coating was measured with
a multi-spectral reflectometer (F20, AG Electro Optics). Samples
for contact angle determination were post baked (i.e heated) for 1
hour at 70.degree. C., prior to contact angle determination.
C: Optical Properties of Surface Nano-Structured and/or Nano-Porous
Coatings
[0089] Nano-structured and/or nano-porous films or coatings were
prepared as described under "B. Preparation of a coating on a
substrate", on one side or both sides of either glass microscope
slides or polyethyleneteraphthalate (PET) films from various
formulations as listed in Table 3, 4 and 5. Spectral transmission
in the visible region of the spectrum was measured with a
Perkin-Elmer Lambda-20 UV-Vis spectrometer.
D: Measurement of Water Contact Angle
[0090] Static contact angles were measured using a FTA (First Ten
Angstroms) 200 apparatus. This piece of equipment consisted of a
motorised syringe pump, a sample stage and a video camera. The
software used with the system was FTA Video drop shape analysis
version 1.98 Build B.
[0091] Before the measurements were carried out the surface tension
of the water in the syringe was measured. This was done by
dispensing a droplet from the syringe, and then recording an image
whilst the droplet was still attached to the syringe. The droplet
was lit from behind, so it appeared black on a white background.
The software measured the dimensions of the droplet and used them
to calculate the surface tension.
[0092] The static contact angle of a coating was measured by
dispensing a 12 .mu.l droplet of distilled water onto the surface
of a coated substrate. 65 images of the droplet were taken over a
130 second period. From the images the software determined the
baseline (the surface) and the edges of the droplet, the contact
angle was calculated where these lines intercept. The contact
angles were determined for at least two droplets on different areas
of the surface, the average of these measurements was quoted as the
contact angle. Results of static contact angles for various
coatings are given in table 6. Contact angle measurements were
carried out either directly or after post-baking (t=0) or 2.5 days
after post-baking (t=2.5 days). The values in table 6 are the
contact angles 100 seconds after the drop had been deposited onto
the surface of the samples of various ages.
E. Measurement of Hardness and Reduced Modulus of Coatinas
[0093] To determine the hardness and reduced modulus of the
spincoated coatings, three coatings were prepared as described
above in B. The hardness measurements were performed with a
Hysitron TriboScope, using a calibrated Berkovich diamond tip as
indenter. The tip was inserted into the coatings with a known load,
and the penetration depth in the coating was recorded. A typical
load function used is shown in FIG. 8, this results in a graph of
force versus displacement. The hardness was calculated via the
relationship H (in GPa)=Fmax/24.5d.sup.2, where Fmax is the highest
load applied and d is the penetration depth. The reduced modulus
was calculated from the force - displacement curve using Er=0.5
(.pi./24.5d.sup.2).sup.1/2 (.delta.F/.delta.d). More details
concerning nano-indentation experiments may be found in F. J. Balta
Calleja & S. Fakirov, Microhardness of Polymer, Cambridge Un.
Press, 2000.
[0094] It should be noted the results from nano-identation with
respect to hardness and reduced modulus are dependant on the
geometry of the tip of the indenter used. Therefore, direct
comparison can only be made by using an experimental set up with a
tip of similar geometry. TABLE-US-00002 TABLE 2 Compounds in weight
percentage used for acrylation and surface modification of silica
nano particles Modified Modified Modified nano- nano- nano-
particle B particle C particle A (Acry-IPA-ST- (Acry-F-MT- Material
(Acry-MT-ST) UP) ST) MT-ST nano-silica 24.75 wt-% 23.81 wt-%
Particle size 10-15 nm IPA-ST-UP elongate nano-silica 13.85 wt-%
Particle diameter 9-15 nm Particle length 40-300 nm Int-12A
(coupling agent) 7.84 wt-% 4.55 wt-% 7.71 wt-% (See formula II)
Hydroquinnone mono-methylether 0.14 wt-% 0.87 wt-% 0.14 wt-% (HQMME
polymerization inhibitor) Methyltrimethoxysilane 1.23% wt-% 0.72
wt-% (MTMS surface derivatisation agent)
1H,1H,2H,2H-(Perfluorooctyl) triethoxysilane 4.63 wt-% (apolar
surface derivatisation agent) Methanol (solvent) 57.75 wt-% 55.54
Isopropanol (solvent) 75.31 wt-% Trimethyl orthoformate 8.29 wt-%
4.70 wt-% 8.17 wt-% OFM (dehydrating agent) Total 100 wt-% 100 wt-%
100 wt-%
[0095] TABLE-US-00003 TABLE 3 Formulations for examples and
comparative experiments. Comparative experiment 1 Example 2 Example
3 Example 4 Example 5 Example 6 Material mg mg mg mg mg mg Modified
nano- 41.5 30.5 -- -- -- -- particle A (Acry-MT-ST) (without
solvent) Modified nano- -- -- 84.0 1556.2 -- 236.1 particle C
(Acry-F-MT-ST) (without solvent) Modified nano- -- -- -- -- 23.52
-- particle B (Acry-IPA-ST-UP) (without solvent) Dipentaerythritol
22.1 -- -- -- -- pentaacrylate (reactive diluent) Ethoxylated (9)
14.6 -- -- -- -- trimethylolpropane triacrylate (reactive diluent)
Methanol (solvent) 1379.4 1016 1588.9 2621.7 460.75 498.9
Isopropanol -- -- -- -- 99.57 -- (solvent) Photoinitiator 0.39 0.31
0.21 3.9 0.15 10 (Irgacure 184 trademark by Ciba) 1H,1H,6H,6H- --
-- -- -- -- 248 Perfluoro-1,6-hexyl diacrylate. (reactive
diluent)
[0096] TABLE-US-00004 TABLE 4 Formulations for examples and and
values for transmission, effect of increasing amount of reactive
diluent on anti-reflective properties. wt-% Dipentaerythritol
pentaacrylate w.r.t. total weight of modified particle B Example 7
Example 8 Example 9 Example 10 Example 11 and diluent (0%) (2.7%)
(5.8%) (11.2%) (15.6%) Material Mg mg mg mg mg Modified nano 21.7
22.1 28.0 26.5 23.3 particle B (Acry-IPA-ST-UP) Dipentaerythritol 0
0.62 1.72 3.36 4.29 pentaacrylate (reactive diluent) Methanol
(solvent) 531.0 530.9 680.2 639.8 561.8 Isopropanol 92.0 94.7 118.6
112.2 98.4 (solvent) Photo initiator 0.13 0.14 0.19 0.18 0.16
(Irgacure 184 trademark by Ciba) Maximum 97.40 97.40 97.25 97.20
96.80 Transmission (%)
[0097] The data from table 4, examples 7-11 show the effect of
increasing amount (wt-%) of reactive diluent (Dipentaerythritol
pentaacrylate) on the anti-reflective properties of surface
nano-structured and nano-porous coating comprising elongated
acrylated nano-particles (modified particle B (Acry-IPA-ST-UP)). It
can be seen that increasing the relative weight percentage of
reactive diluent with respect to nano-particles reduces the
anti-reflective performance of the coatings as the maximum
percentage of transmission decreases.
[0098] Transmission spectra from this series of examples can be
found in FIG. 7. If the relative amount of reactive diluent is
increased to the point that all nanoparticles are embedded, a non
surface nano-structured and/or nano-porous coating will result.
Such coatings will display no or extremely little anti-reflective
performance. This can be seen illustrated by the comparative
experiment, a conventional hard coat sample (thickness 100-200 nm)
the transmission spectra of which can be seen as spectrum 4 in FIG.
3. Here there is almost no improvement in the maximum transmission
(95%) and in hence anti-reflective performance with respect to the
transmission of the glass microscope slide substrate, spectrum 5 in
FIG. 7 (94.8%). TABLE-US-00005 TABLE 5 Influence photo initiator
concentration on Anti-reflective properties % Irgacure184 Example
Example w.r.t. modified Example 12 Example 13 14 155 particle B
(0.10%) (0.51%) (0.93%) (2.09%) Material mg Mg mg mg Modified nano
27.4 28.7 35.2 23.5 particle B (Acry-IPA-ST-UP) Methanol (solvent)
664.1 672.5 855.8 570.6 Isopropanol 119.5 139.8 150.0 100.0
(solvent) Photo initiator 0.026 0.148 0.327 0.490 (Irgacure 184
trademark by Ciba) Transmission 97.2 97.2 97.3 97.2 Maximum
[0099] As is shown in the results of table 5, there is no influence
on the anti-reflective properties by the coatings according to the
invention of the concentration of the photo initiator system. This
is very favourable, and it shows the robustness of the process and
the coatings according to our invention, while known systems suffer
with respect to this aspect. TABLE-US-00006 TABLE 6 Contact angles
of various hydrophobic and hydrophilic nano-structured and/or
nano-porous coatings. Contact angle Contact angle Formulation Rmax
t = 0 days t = 2.5 days comp. exp.(Hard coat) 6 nm 62.1.degree.
Example 2 119 nm 50.3.degree. (Acry-MT-ST) Example 3 133.5 nm
97.3.degree. 120.7.degree. (Acry-F-MT-ST) (thickness 100-200 nm)
Example 4 65.5 nm 95.9.degree. 114.1.degree. (Acry-F-MT-ST)
(thickness 1-5 .mu.m) Example 5 108 nm 28.2.degree.
(Acry-IPA-ST-UP) Example 6 (Example 3 + 27 nm 108.5.degree.
Fluorodiacrylate)
[0100] The static water contact angle of Example 1 as shown in
Table 6 is typical that of a polar acrylate hard coating. If the
surface is surface nano-structured and/or nano-porous, the static
water contact angle drops significantly. This is the case for
Example 2 (Acry-MT-ST) where the value of the contact angle was
50.3.degree. and for Example 5 (Acry-lPA-ST-UP) where the value is
28.2.degree.. Similary, the static water contact angle of Example
6, a coating of a formulation comprising hydrophobically modified
reactive nano-particles (Acry-F-MT-ST) with hydrophobic reactive
diluents (Fluorodiacrylate), was 108.5.degree. and its roughness
was relatively low, 27 nm. In the case of Example 4 (Acry-F-MT-ST)
(thickness 1-5 .mu.m) and 3 (Acry-F-MT-ST) (thickness 100-200 nm)
the value of the roughness increased and therefore the static
contact angle increased respectively as well. This demonstrates
that by controlling both the surface chemistry in terms of polarity
of the nanoparticles and the roughness of the resultant coating
through the process according to the invention, the wettting
properties can be varied greatly as well. TABLE-US-00007 TABLE 7
Hardness, Reduced Modulus and Scratch results of example 2, 3 and 7
Formulation Hardness (Gpa) Reduced Modulus (Gpa) Example 2 Acr
MT-ST 1.2 +/- 0.1 22 +/- 2 Example 3 Acr FI MT-ST 0.5 +/- 0.05 14
+/- 1 Example 7 Acry-IPA-ST-UP 2.5 +/- 0.2 45 +/- 5
[0101]
[0102] FIG. 1 depicts the three dimensional (3D) topography of the
coatings obtained in various examples and the comparative
experimentas acquired by atomic force microscopy (AFM). The maximum
height of the features (Rmax) in these images is given as the
maximum height difference over the whole area of the image. FIG. 1a
shows the surface roughness ofthe coating according to the
comparative experiment, the conventional hard coat sample, the
components of which can be found in table 3, example 1. As can be
deduced form this AFM image the surface roughness of the coating is
very small and only in the range of ca 6 nm, which is well below
the smallest dimension of the nanoparticles used in the coating.
Therefore this is a not a nano-structured and/or nano-porous
coating as described within the framework of the invention. For
this hard coat the relative volume of reactive diluent is so large
that all nanoparticles are embedded and do not contribute to the
formation of a nano-structured and/or nano-porous coating. This
roughness however is typical for acrylate coatings, irrespective of
the presence of nanoparticles. FIG. 1b and FIG. 1c show the surface
topography of coatings of fluorinated acrylated spherical
nano-silicates (modified nano-particle C) (Table 3, Example 3) and
a coating of acrylated spherical nano-silicates (modified
nano-particle A) (Table 3, Example 2), respectively. For both of
these coating the lack of any reactive diluent leads to the
formation of nano-structured and nano-porous coatings as described
within the framework of the invention. Similarly FIG. 1d shows a
coating with a surface roughness of ca 140 nm, which is formed by
the crosslinking of elongated acrylated nano-silicate particle
(modified nano-particle B) (table 4, example7) without any reactive
diluent. Here again the absence of any reactive diluent leads to
the formation of nano-structured and nano-porous coatings. FIG. 1e
(table 4, example 8) shows the effect of small amount of reactive
diluents (2.7wt-% of total solids) on the surface topography of
coatings comprising elongated acrylated nano-silicates (modified
nano-particle B). It can be seen that the addition of small volumes
of reactive diluents lead to a decrease of the maximum feature
height (Rmax). However again the relative volumes of reactive
diluent are so low that the content is below 1-the random close
volume packing of the nanoparticles and thus form nano-structured
and nano-porous coatings.
[0103] FIG. 2 shows the cross-sectional topography as acquired by
Atomic force microscopy. For these cross-sections, the Rmax given
in FIG. 2 is the maximum height difference across the
cross-section. FIG. 2a shows the cross-sectional topography of a
coating of acrylated spherical nano-silicates (modified
nano-particle A) (Table 3, Example 2). Here a surface
nano-structure (roughness on the surface) as well as nano-pores
(deeper features) can be seen. Similarly FIG. 2b shows the
cross-sectional topography of a coating of elongated acrylated
nano-silicates (modified nano-particle B) (Table 4, Example 7).
Again here the roughness on the surface is the surface
nano-structure while the deepest features can be regarded as
nano-pores. It is also expected that small voids of air Will exist
in the bulk of the coating between individual nano-particles or
clusters thereof however, these nano-pores cannot be visualised by
AFM.
[0104] FIG. 3 shows the visible transmission spectra of a number of
example and comparative coatings on one side of a glass microscope
slide substrate. Spectrum 5 is of an uncoated glass microscope
slide. Spectrum 1 is of unmodified MT-ST nano-particles, which were
spin-coated at 4800 rpm from a suspension of 3wt-% solids, giving a
coating thickness in the range of 100-200 nm. This spectrum shows
that unmodified MT-ST nano-silicates display anti-reflective
properties as the maximum transmission increases to ca 96.8% with
respect to the maximum that of the uncoated glass microscope slides
(94.8%). Obviously such a coating would have no mechanical
durability as the unmodified MT-ST nano-particles are not surface
modified with reactive groups and therefore are incapable of
crosslinking. In this coating there is a maximum space between
nano-particles, as the surface of the MT-ST nano-particles is not
modified. Once the surface of these particles is grafted, the space
between the nano-particles is partially filled by the polymerisable
organic groups and spectrum 2 results.
[0105] This effect can be seen again when the surface modifying
agent methyltrimethoxysilane groups are replaced with even bulkier
groups such as 1H,1H,2H,2H-(Perfluorooctyl) triethoxysilane (apolar
surface derivatisation agent), see spectrum 3. In the case of
spectrum 4 the space between the nano-particle is completely filled
with reactive diluent and thus this conventional hard coat has a
maximum transmission (95.0%), which differs very slightly from that
of the uncoated glass microscope slide (94.8%).
[0106] FIG. 4 shows the visible transmission spectra of of the
coatings of example 7 (spherical particles, spectrum 2) and example
7(elongated particles, spectrum 1) Spectrum 3 is the uncoated glass
microscope slide. It is clearly shown that the coating compriseng
elongated particles shows even furher improved anti-reflctive
properties compared to the coating comprising the spherical
particles.
[0107] FIGS. 5 and 6 show the effect of coating both sides of
reflective substrate, glass microscope slides in the case of FIG. 5
and PET films in case of FIG. 6, with a coating of crosslinked
acrylated elongated nano-particles (Acry-IPA-ST-UP, modified
particle B). As both the top and bottom surface of the untreated
substrates cause reflection transmission greater than 98% are
usually only possible if both sides of the substrate have been
coated. In the case of both of these examples the coating on both
sides of the substrates results in objects, which are almost
invisible to the naked eye and where surface reflections are only
observable, by direct reflection of bright light sources.
FIG. 7 shows that in case of elongated particles there is only a
small decrease in anti-reflective properties if a reactive diluent
is used.
EXAMPLE 16
Preparation of Durable Anti-Reflective Coating System on Tog of
Hard Coat
[0108] In the first step a hard coat according to comparative
experiment 1 is applied to the substrate to a thickness of ca 3-5
.mu.l and cured in Air at a total UV dose of 0.75 Jcm.sup.2. The
surface of the resulting hard coat was parially cured. In the
second step a coating according to the invention is applied on top
of the Hard coat to a thickness of 100-200 nm by spin coating as
described previously.
[0109] The said coating according to the invention consists of the
following components; 0.376 g (dry weight) reactive nano-partilce
(modified Particle B. Table 2), 0.061 g of Dipentaerythritol
penta-acrylate (reactive diluent), 0.013 g tri-methylolpropane
tri-(3-mercaptopropionate) (reactive diluent and adhesion
promoter), 0.8 mg of propyl gallate (polymerisation inhibitor), 5.1
mg of Irgacure 907 (photo-initiator), 12.902 g of methyl ethyl
ketone (solvent) and 1.642 g of isopropanol (solvent).
[0110] The said coating according to the invention is then fully
cured with a total of 2.times.1Jcm.sup.-2 and subsequently heated
to 120.degree. for ca 1 minute using an infra red lamp. The
resultant nano-structured coating has a pencil hardness of 2-3H
according to ASTM D3363-00, while retaining anti-reflective
properties.
[0111] The use of hard coat which is partially cured at the
surface, addition of multi-functional thiols and subsequent thermal
post-backing, after fully UV curing the combined system, as
described above, improves the mechanical durability of all coatings
with respect to the coatings where these steps are not taken.
##STR1##
* * * * *
References