U.S. patent application number 12/185378 was filed with the patent office on 2009-07-09 for antireflection film and method for manufacturing the same.
This patent application is currently assigned to Dai Nippon Printing Co., Ltd.. Invention is credited to Tomoyuki Horio, Toshio Yoshihara.
Application Number | 20090176084 12/185378 |
Document ID | / |
Family ID | 40504774 |
Filed Date | 2009-07-09 |
United States Patent
Application |
20090176084 |
Kind Code |
A1 |
Yoshihara; Toshio ; et
al. |
July 9, 2009 |
ANTIREFLECTION FILM AND METHOD FOR MANUFACTURING THE SAME
Abstract
There are provided an antireflection film for use primarily in
displays such as LCDs, which exhibits both antifouling properties
and mar-proofness, as well as a process for its production, the
antireflection film comprising at least one functional layer and a
low refractive index layer laminated in that order on a transparent
base material, wherein the at least one functional layer contains
leveling agent A in contact with the low refractive index layer,
the low refractive index layer containing in addition to leveling
agent B, the leveling agent A that has migrated from the at least
one functional layer, further wherein the migrated leveling agent A
and leveling agent B are uniformly distributed at the surface of
the low refractive index layer, and the process for its production
including: coating a functional layer-forming composition
containing leveling agent A onto a transparent base material or a
functional layer preformed thereover; half-curing it to form a
functional layer in contact with the low refractive index layer;
further coating the half-cured functional layer with a low
refractive index layer-forming composition containing leveling
agent B; and then completing the curing to form a low refractive
index layer, whereby the leveling agent A migrates into the surface
of the low refractive index layer, resulting in uniform
distribution of the leveling agent A and leveling agent B at the
surface of the low refractive index layer.
Inventors: |
Yoshihara; Toshio; (Okayama,
JP) ; Horio; Tomoyuki; (Chiba, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W., SUITE 800
WASHINGTON
DC
20037
US
|
Assignee: |
Dai Nippon Printing Co.,
Ltd.
Tokyo
JP
|
Family ID: |
40504774 |
Appl. No.: |
12/185378 |
Filed: |
August 4, 2008 |
Current U.S.
Class: |
428/313.3 ;
427/372.2; 428/332; 428/411.1; 428/447 |
Current CPC
Class: |
Y10T 428/31663 20150401;
Y10T 428/249971 20150401; G02B 1/111 20130101; Y10T 428/31504
20150401; Y10T 428/26 20150115 |
Class at
Publication: |
428/313.3 ;
428/411.1; 428/447; 428/332; 427/372.2 |
International
Class: |
B32B 3/26 20060101
B32B003/26; B32B 9/00 20060101 B32B009/00; B05D 3/02 20060101
B05D003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 2, 2007 |
JP |
2007-202415 |
Aug 1, 2008 |
JP |
2008-199372 |
Claims
1. An antireflection film comprising at least one functional layer
and a low refractive index layer laminated in that order on a
transparent base material, the at least one functional layer being
in contact with the low refractive index layer and comprising a
binder and a leveling agent A having neither functional groups that
react under ionizing radiation and nor polar groups that react
under heat, and the low refractive index layer comprising, in
addition to a binder and a leveling agent B that is crosslinked at
least with the binder, the leveling agent A that has migrated from
the at least one functional layer, wherein the migrated leveling
agent A and the leveling agent B are uniformly distributed on the
surface of the low refractive index layer.
2. An antireflection film according to claim 1, wherein the
functional layer in contact with the low refractive index layer is
a hard coat layer.
3. An antireflection film according to claim 1, wherein the
leveling agent A is a non-reactive fluorine-based leveling
agent.
4. An antireflection film according to claim 1, wherein the
leveling agent B is a reactive silicon-based leveling agent.
5. An antireflection film according to claim 3, wherein the
non-reactive fluorine-based leveling agent is a fluorinated
compound having a fluorinated alkyl group represented by the
general formula F(CF.sub.2).sub.2nCH.sub.2CH.sub.2-- where n is an
integer of 1-10.
6. An antireflection film according to claim 5, wherein the
fluorinated alkyl group is a perfluoro group.
7. An antireflection film according to claim 4, wherein the
reactive silicon-based leveling agent is a compound represented by
the following chemical formula (1): ##STR00009## wherein R.sup.a
represents a C.sub.1-20 alkyl group, R.sup.b represents a
C.sub.1-20 alkyl, C.sub.1-3 alkoxy or polyether-modified group
which is either unsubstituted or substituted with an amino, epoxy,
carboxyl, hydroxyl, acryloyl and/or methacryloyl group, and each
R.sup.a and R.sup.b may be the same or different; m represents an
integer of 0-200; and n represents an integer of 0-200.
8. An antireflection film according to claim 1, wherein the low
refractive index layer further comprises reactive hollow particles
crosslinked with at least the binder.
9. An antireflection film according to claim 8, wherein the low
refractive index layer further comprises reactive solid particles
crosslinked with at least the binder.
10. An antireflection film according to claim 2, wherein the hard
coat layer further comprises reactive inorganic fine particles
crosslinked with at least the binder.
11. An antireflection film according to claim 10, wherein the
reactive inorganic fine particles are solid particles.
12. An antireflection film according to claim 1, wherein the film
thickness of the functional layer is from 0.1 .mu.m to 30 .mu.m,
and the leveling agent A is present at from 0.01 wt % to 5 wt %
based on the total weight of the binder of the functional
layer.
13. An antireflection film according to claim 2, wherein the film
thickness of the low refractive index layer is from 0.05 .mu.m to
0.15 .mu.m, and the film thickness of the hard coat layer is from 5
.mu.m to 30 .mu.m.
14. A process for production of an antireflection film comprising
at least one functional layer and a low refractive index layer
laminated in that order on a transparent base material, the process
comprising: coating the transparent base material or a preformed
functional layer with a functional layer-forming composition
comprising a leveling agent A containing neither functional groups
that react under ionizing radiation and nor polar groups that react
under heat, and a binder; half-curing it to form a functional layer
in contact with the low refractive index layer; further coating the
half-cured functional layer with a low refractive index
layer-forming composition containing a binder and a leveling agent
B which is reactive at least with the binder; and then completing
the curing to form a low refractive index layer.
15. A process for production of an antireflection film according to
claim 14, wherein the leveling agent A migrates to the surface of
the low refractive index layer so that the leveling agent A and the
leveling agent B are uniformly distributed on the surface of the
low refractive index layer.
16. A process for production of an antireflection film according to
claim 15, wherein the leveling agent A is a non-reactive
fluorine-based leveling agent and the leveling agent B is a
reactive silicon-based leveling agent.
17. An antireflection film produced by a process for production of
an antireflection film according to claim 14.
18. An antireflection film according to claim 4, wherein the
non-reactive fluorine-based leveling agent is a fluorinated
compound having a fluorinated alkyl group represented by the
general formula F(CF.sub.2).sub.2nCH.sub.2CH.sub.2-- where n is an
integer of 1-10.
19. An antireflection film according to claim 18, wherein the
fluorinated alkyl group is a perfluoro group.
20. An antireflection film according to claim 18, wherein the
reactive silicon-based leveling agent is a compound represented by
the following chemical formula (1): ##STR00010## wherein R.sup.a
represents a C.sub.1-20 alkyl group, R.sup.b represents a
C.sub.1-20 alkyl, C.sub.1-3 alkoxy or polyether-modified group
which is either unsubstituted or substituted with an amino, epoxy,
carboxyl, hydroxyl, acryloyl and/or methacryloyl group, and each
R.sup.a and R.sup.b may be the same or different; m represents an
integer of 0-200; and n represents an integer of 0-200.
21. An antireflection film according to claim 3, wherein the
leveling agent B is a reactive silicon-based leveling agent.
22. An antireflection film according to claim 21, wherein the
reactive silicon-based leveling agent is a compound represented by
the following chemical formula (1): ##STR00011## wherein R.sup.a
represents a C.sub.1-20 alkyl group, R.sup.b represents a
C.sub.1-20 alkyl, C.sub.1-3 alkoxy or polyether-modified group
which is either unsubstituted or substituted with an amino, epoxy,
carboxyl, hydroxyl, acryloyl and/or methacryloyl group, and each
R.sup.a and R.sup.b may be the same or different; m represents an
integer of 0-200; and n represents an integer of 0-200.
23. An antireflection film according to claim 21, wherein the
non-reactive fluorine-based leveling agent is a fluorinated
compound having a fluorinated alkyl group represented by the
general formula F(CF.sub.2).sub.2nCH.sub.2CH.sub.2-- where n is an
integer of 1-10.
24. An antireflection film produced by a process for production of
an antireflection film according to claim 15.
25. An antireflection film produced by a process for production of
an antireflection film according to claim 16.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an antireflection film
mounted on the front sides of display devices (image display
devices) such as liquid crystal displays (LCD), organic and
inorganic electroluminescence displays (ELD), field emission
displays (FED), cathode ray tube display devices (CRT) and plasma
displays (PDP).
[0003] 2. Related Background Art
[0004] In the displays mentioned above, it is required to reduce
reflection of light rays irradiated from external light sources
such as fluorescent lamps in order to increase the visibility of
the display surfaces.
[0005] Antireflection films are already known that have a base
material/hard coat layer/low refractive index layer structure as
the basic layers.
[0006] When such an antireflection film is applied for a display
surface to prevent damage to the display surface, the low
refractive index layer surface of the antireflection film must also
have antifouling properties, including fingerprint wiping. It is
extremely important for such an antireflection film to have surface
flatness on the hard coat layer, in order to avoid formation of
film thickness variation in the anti-reflection layer that can
cause color streaks and defects.
[0007] In an antireflection film having such a hard coat layer,
often the surface of the hard coat layer is flattened (by leveling
to create a smooth surface), and a silicon compound (silicon-based
leveling agent) or fluorinated compound (fluorine-based leveling
agent) is added to the hard coat layer-forming resin composition to
impart an antifouling property, thus forming a hard coat layer. The
silicon compound (silicon-based leveling agent) has the function of
imparting to the layer surface slidability and antifouling
properties against markers in addition to fingerprints, for
improved mar-proofness. The fluorinated compound (fluorine-based
leveling agent), on the other hand, has the function of providing
the layer surface with improved antifouling properties including
fingerprint wiping.
SUMMARY OF THE INVENTION
[0008] However, silicon compounds (silicon-based leveling agents)
and fluorinated compounds (fluorine-based leveling agents) have
very poor compatibility, and phase separation readily occurs.
[0009] Phase separation generates areas where the silicon compound
(silicon-based leveling agent) is aggregated on the surface of the
low refractive index layer and areas where the fluorinated compound
(fluorine-based leveling agent) is aggregated (opaque areas) to
render the surface opaque, which increase the haze of the
antireflection film, thus leading to a problem of lowering the
visibility of the display surface. It has, therefore, been
impossible to combine sufficient amounts of fluorinated compounds
with silicon compounds to impart antifouling properties.
[0010] Although the slidability of the surface is improved by
addition of silicone oil to the low refractive index layer in
Patent document 1, silicone has high affinity for fingerprints and
thus has a drawback that fingerprints sticking to the surface
cannot be wiped off. Patent document 2 proposes adding to the low
refractive index layer, a fluorinated compound that forms a
covalent bond with part of the binder component; but although
fluorinated compounds are effective for improving fingerprint
wiping, they have affinity for other types of fouling such as
markers and thus has a drawback that marker ink attaching to the
surface cannot be wiped off. Also, Patent document 3 teaches that
adding silicone oil to a low refractive index layer comprising a
monomer copolymer including vinylidene fluoride and
hexafluoropropylene can impart mar-proofness and fingerprint
wiping, but the soft nature of fluorine-containing binders prevents
adequate mar-proofness from being obtained, while the compatibility
with silicone is lower with higher molecular weights; therefore,
haze increases and it is difficult to obtain a uniform film.
[0011] [Patent document 1] Japanese Unexamined Patent Publication
No. 2003-147268
[0012] [Patent document 2] Japanese Unexamined Patent Publication
No. 2005-99778
[0013] [Patent document 3] Japanese Unexamined Patent Publication
No. 2000-178469
[0014] The present invention has been accomplished with the aim of
solving the problems described above, and the main object of the
invention is to provide an antireflection film obtained by
combining two or more leveling agents (particularly, silicon-based
leveling agent and fluorine-based leveling agent) to be included in
the low refractive index layer, to maintain the haze of the low
refractive index layer to a low level while providing the low
refractive index layer on the antireflection film surface with
excellent antifouling properties, fingerprint wiping and
mar-proofness, as well as a process for its production.
[0015] As a result of much diligent research aimed at solving the
aforementioned problems, the present inventors have completed this
invention upon finding that if, instead of mixing two or more
leveling agents, a leveling agent A having neither functional
groups that react under ionizing radiation nor polar groups that
react under heat is included in a functional layer-forming
composition, a binder and a leveling agent B that is reactive with
at least the binder are included in a low refractive index
layer-forming composition, and the functional layer-forming
composition is coated onto a transparent base material or a
preformed functional layer, it is then half-cured to form a
functional layer in contact with the low refractive index layer
(different from the preformed functional layer), and further the
low refractive index layer-forming composition is coated onto the
half-cured functional layer and fully cured to form a low
refractive index layer, the leveling agent A migrates into the
surface of the low refractive index layer resulting in uniform
distribution of the leveling agent A and the leveling agent B on
the surface of the low refractive index layer, so that the leveling
agents are uniformly distributed without aggregation or opacity,
thus allowing the combined properties of leveling agents A and B to
be adequately exhibited while maintaining low haze for the low
refractive index layer.
[0016] Specifically, the features of the invention that solve the
problems described above are the following two points.
[0017] The antireflection film of the invention is an
antireflection film comprising at least one functional layer and a
low refractive index layer laminated in that order on a transparent
base material, characterized in that
[0018] the at least one functional layer is in contact with the low
refractive index layer and comprises a binder and a leveling agent
A having neither functional groups that react under ionizing
radiation nor polar groups that react under heat, and
[0019] the low refractive index layer comprises, in addition to a
binder and a leveling agent B that is crosslinked at least with the
binder, the leveling agent A that has migrated from the at least
one functional layer, and that the migrated leveling agent A and
the leveling agent B are uniformly distributed on the surface of
the low refractive index layer.
[0020] Throughout the present specification, the term
"non-reactive" may be used to mean having neither functional groups
that react with ionizing radiation nor polar groups that react with
heat. Also throughout the present specification, the term
"reactive" will be used to mean having functional groups that react
with ionizing radiation or polar groups that react with heat.
[0021] The process for production of an antireflection film
according to the invention is a process for production of an
antireflection film comprising at least one functional layer and a
low refractive index layer laminated in that order on a transparent
base material,
[0022] characterized by coating the transparent base material or a
functional layer preformed thereover with a functional
layer-forming composition comprising a leveling agent A having
neither functional groups that react under ionizing radiation nor
polar groups that react under heat, and a binder, and half-curing
it to form a functional layer in contact with the low refractive
index layer, and further coating the functional layer in half-cured
state with a low refractive index layer-forming composition
comprising a binder and a leveling agent B which is reactive at
least with the binder, and then completing the curing to form the
low refractive index layer.
[0023] The functional layer in contact with the low refractive
index layer in the antireflection film of the invention may be a
primer layer, antistatic layer, high refractive index layer,
anti-glare layer or hard coat layer, or a layer that simultaneously
exhibits these functions.
[0024] The leveling agent has the function of improving the
flatness (smoothness) of the surface of the layer containing the
leveling agent, and appropriate selection of the type of leveling
agent will help impart the surface of the functional layer (for
example, the aforementioned layer such as a hard coat layer) or low
refractive index layer with slidability that can contribute to
enhanced antifouling properties and mar-proofness. If the leveling
agent in the low refractive index layer and hard coat layer is a
type such as mentioned above, aggregation of two (or more) types of
leveling agents in the low refractive index layer will be avoided,
thus providing an effect of preventing transparency reduction due
to layer opacity or haze increase.
[0025] Leveling agent A in the antireflection film of the invention
is non-reactive, and it is preferably a non-reactive fluorine-based
leveling agent. More preferably, it is a fluorinated compound with
a fluorinated alkyl group represented by the formula
F(CF.sub.2).sub.2nCH.sub.2CH.sub.2-- (where n is an integer of
1-10). Most preferably, the fluorinated alkyl group is a perfluoro
group.
[0026] Leveling agent B in the antireflection film of the invention
has reactivity at least for the binder in the low refractive index
layer, and it is preferably a reactive silicon-based leveling
agent. More preferably, it is a compound represented by the
following chemical formula (1).
##STR00001##
(wherein R.sup.a represents a C.sub.1-20 alkyl group, R.sup.b
represents a C.sub.1-20 alkyl, C.sub.1-3 alkoxy or
polyether-modified group which is either unsubstituted or
substituted with an amino, epoxy, carboxyl, hydroxyl, acryloyl
and/or methacryloyl group, and each R.sup.a and R.sup.b may be the
same or different; m represents an integer of 0-200; and n
represents an integer of 0-200).
[0027] Most preferably, the leveling agent A in the antireflection
film of the invention is a non-reactive fluorine-based leveling
agent and the leveling agent B is a reactive silicon-based leveling
agent. In this case, the fluorine-based leveling agent as leveling
agent A will easily migrate from the functional layer in contact
with the low refractive index layer, into the low refractive index
layer, and the low refractive index layer will therefore contain
the non-reactive fluorine-based leveling agent and the reactive
silicon-based leveling agent, thus being imparted with an
antifouling property, fingerprint wiping and mar-proofness.
[0028] The low refractive index layer in the antireflection film of
the invention preferably further contains reactive hollow particles
that are crosslinked with the binder in order to reduce the
refractive index of the low refractive index layer. The low
refractive index layer in the antireflection film of the invention
preferably still further contains reactive solid particles that are
crosslinked with at least the binder in order to improve the
hardness of the low refractive index layer.
[0029] The hard coat layer in the antireflection film of the
invention preferably further contains reactive inorganic fine
particles that are crosslinked with at least the binder, preferably
with solid particles as the reactive inorganic fine particles, in
order to improve the hardness of the hard coat layer.
[0030] In the antireflection film according to the invention,
preferably the film thickness of the functional layer is from 0.1
.mu.m to 30 .mu.m, and the leveling agent A is present at from 0.01
wt % to 5 wt % based on the total weight of the binder of the
functional layer.
[0031] In the antireflection film according to the invention,
preferably the film thickness of the low refractive index layer in
the antireflection film according to the invention is from 0.05
.mu.m to 0.15 .mu.m, and the film thickness of the hard coat layer
is from 5 .mu.m to 30 .mu.m, in order to obtain sufficient
antireflection and mar-proofness.
[0032] Particularly, satisfactory antifouling properties can be
obtained for the antireflection film of the invention if the water
contact angle of the low refractive index layer surface is
95.degree.-120.degree..
[0033] In the antireflection film according to the invention, a
migration layer that is composed of the mingled functional layer
(particularly hard coat layer) and low refractive index layer is
preferably present at their boundary. If a migration layer is
present, the component forming the low refractive index layer will
infiltrate the region of the functional layer adjacent to the
migration layer while the component forming the functional layer
will infiltrate the region of the low refractive index layer
adjacent to the migration layer, thus increasing the adhesiveness
between the functional layer and the low refractive index
layer.
[0034] For the process for production of an antireflection film
according to the invention, the functional layer in contact with
the low refractive index layer may be a primer layer, antistatic
layer, high refractive index layer, anti-glare layer or hard coat
layer, or a layer that simultaneously exhibits these functions.
[0035] In the process for production of an antireflection film
according to the invention, the leveling agent A migrates to the
surface of the low refractive index layer so that the leveling
agent A and the leveling agent B are uniformly distributed on the
surface of the low refractive index layer.
[0036] In the process for production of an antireflection film
according to the invention, the leveling agent A is non-reactive,
and it is preferably a non-reactive fluorine-based leveling agent.
More preferably, it is a fluorinated compound with a fluorinated
alkyl group represented by the formula
F(CF.sub.2).sub.2nCH.sub.2CH.sub.2-- (where n is an integer of
1-10). Most preferably, the fluorinated alkyl group is a perfluoro
group.
[0037] In the process for production of an antireflection film
according to the invention, the leveling agent B has reactivity at
least with the binder in the low refractive index layer, and it is
preferably a reactive silicon-based leveling agent. More
preferably, it is a compound represented by the following chemical
formula (1).
##STR00002##
(wherein R.sup.a represents a C.sub.1-20 alkyl group, R.sup.b
represents a C.sub.1-20 alkyl, C.sub.1-3 alkoxy or
polyether-modified group which is either unsubstituted or
substituted with an amino, epoxy, carboxyl, hydroxyl, acryloyl
and/or methacryloyl group, and each R.sup.a and R.sup.b may be the
same or different; m represents an integer of 0-200; and n
represents an integer of 0-200).
[0038] In the process for production of an antireflection film
according to the invention, most preferably the leveling agent A is
a non-reactive fluorine-based leveling agent and the leveling agent
B is a reactive silicon-based leveling agent. In this case, the
non-reactive fluorine-based leveling agent as leveling agent A will
easily migrate from the functional layer in contact with the low
refractive index layer, into the low refractive index layer, and
the low refractive index layer will therefore contain the
non-reactive fluorine-based leveling agent and the reactive
silicon-based leveling agent, in particular having the non-reactive
fluorine-based leveling agent and reactive silicon-based leveling
agent uniformly distributed at its surface, and thus being imparted
with antifouling properties, fingerprint wiping and
mar-proofness.
[0039] In the process for production of an antireflection film
according to the invention, the low refractive index layer-forming
composition preferably further comprises reactive hollow particles
that have crosslinking reactivity with at least the binder in order
to reduce the refractive index of the low refractive index
layer.
[0040] In the process for production of an antireflection film
according to the invention, the low refractive index layer-forming
composition preferably further comprises reactive solid particles
that have crosslinking reactivity with at least the binder, in
order to improve the hardness of the low refractive index
layer.
[0041] For the process for production of an antireflection film
according to the invention, in order to ensure that the leveling
agent A and the leveling agent B are uniformly distributed at the
surface of the low refractive index layer, it is preferred to form
a migration cured layer (cured migration layer) at the interface
between the low refractive index layer and the functional layer.
The cured migration layer is effective for ensuring that the
leveling agent A and the leveling agent B are uniformly distributed
at the surface, thus imparting an antifouling property and
mar-proofness to the surface of the low refractive index layer.
[0042] In the process for production of an antireflection film
according to the invention, preferably the surfaces of the reactive
hollow particle and the surfaces of the reactive solid particles
are modified with crosslink-forming groups which comprise a bonding
group for the particle surfaces, a spacer portion and an ionizing
radiation curable group, and preferably the crosslink-forming
groups of the reactive hollow particle surfaces and the
crosslink-forming groups of the reactive solid particle surfaces
either have the same structure or, even if they have differing
structures, the structures are similar in that the ionizing
radiation curable groups have the same backbone and differ only in
the presence or absence of one C.sub.1-3 hydrocarbon group, the
bonding groups for the particle surfaces have the same backbone and
differ only in the presence or absence of one C.sub.1-3 hydrocarbon
group, and the spacer portions have the same backbone and differ
only in the presence or absence of one C.sub.1-3 hydrocarbon group
or one functional group with 1-3 constituting atoms including
heteroatoms and excluding hydrogen, or differ only in 1-2 carbons
for the carbon chain length of the backbone, so that the hollow
particles and solid particles will be uniformly dispersed and the
mar-proofness of the low refractive index layer will be
improved.
[0043] In the process for production of an antireflection film
according to the invention, the hard coat layer-forming composition
preferably further comprises reactive inorganic fine particles that
have crosslinking reactivity with at least the binder, preferably
with reactive solid particles as the reactive inorganic fine
particles in order to improve the hardness of the hard coat
layer.
EFFECT OF THE INVENTION
[0044] The antireflection film of the invention has excellent
antifouling properties, excellent fingerprint wiping and excellent
mar-proofness on the surface of the low refractive index layer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0045] The antireflection film of the invention is an
antireflection film comprising at least one functional layer and a
low refractive index layer laminated in that order on a transparent
base material,
characterized in that
[0046] the at least one functional layer is in contact with the low
refractive index layer and comprises a binder and a leveling agent
A having neither functional groups that react under ionizing
radiation nor polar groups that react under heat, and
[0047] the low refractive index layer comprises, in addition to a
binder and a leveling agent B that is crosslinked at least with the
binder, the leveling agent A that has migrated from the at least
one functional layer, and the migrated leveling agent A and the
leveling agent B are uniformly distributed on the surface of the
low refractive index layer.
[0048] The process for production of an antireflection film
according to the invention is a process for production of an
antireflection film comprising at least one functional layer and a
low refractive index layer laminated in that order on a transparent
base material, characterized by coating the transparent base
material or a preformed functional layer with a functional
layer-forming composition comprising a leveling agent A having
neither functional groups that react under ionizing radiation nor
polar groups that react under heat, and a binder, and half-curing
it to form a functional layer in contact with the low refractive
index layer,
[0049] and further coating the half-cured functional layer with a
low refractive index layer-forming composition comprising a binder
and a leveling agent B which is reactive at least with the binder,
and then completing the curing to form a low refractive index
layer.
[0050] The term "functional layer" for the purpose of the invention
means a layer with some function, that when laminated on a
transparent base material produces an optical laminate that is more
satisfactory than the base material itself. As examples of
functional layers, there may be mentioned hard coat layers that
impart hardness to base materials, primer layers that improve the
adhesiveness between low refractive index layers and base
materials, antistatic layers that impart antistatic performance and
high refractive index layers that improve anti-reflection
properties, as well as antistatic high refractive index layers,
high-refractive-index hard coat layers, antistatic hard coat
layers, and antistatic high-refractive-index hard coat layers, that
exhibit combined performance, either as monolayers or
multilayers.
[0051] The preferred film thickness of the functional layer is from
0.1 .mu.m to 30 .mu.m, and in that film thickness range, the
concentration of leveling agent A that allows optimum migration is
from 0.01 wt % to 5 wt % based on the total weight of the binder
component of the functional layer. A concentration of greater than
0.01 wt % will allow migration to the low refractive index layer
surface so that the desired antifouling performance is exhibited,
but a concentration of greater than 5 wt % will result in excessive
migration, causing increased haze and opacity.
[0052] The term "binder" for the purpose of the invention means a
compound that comprises as an essential component, a polymerizable
compound such as a monomer or oligomer with a functional group that
reacts under ionizing radiation or a polar group that reacts under
heat, with inclusion of a non-polymerizable polymer or
polymerization initiator if necessary, and which after curing forms
a matrix for the functional layer or low refractive index
layer.
[0053] The term "uniformly distributed" for the purpose of the
invention means that two or more leveling agents are present on the
surface of the layer at a level that, despite some aggregation of
similar leveling agents, does not produce phase separation between
different leveling agents, and without causing opacity or haze.
According to the invention, the leveling agent A and the leveling
agent B are most satisfactorily in an uniformly distributed state
on the surface of the low refractive index layer. Specifically,
this means that leveling agents A and B are in a state of
essentially homogeneous admixture, or in a state that each leveling
agent, even if areas of aggregation are present, is mixed at a
level that does not produce opacity in the low refractive index
layer.
[0054] According to the invention, the term "half-cured" refers to
a state in which some of the curable groups of the curable resin in
the binder remain without being cured, so that the curing is
incomplete. In this state, the solvent of the coating composition
(coating solution) penetrates more easily and the resin components
of the hard coat layer and low refractive index layer migrate
through the half-cured migration layer (the boundary between the
hard coat layer and the low refractive index layer) into the other
layer, particularly with migration into the low refractive index
layer by the leveling agent A that is non-reactive with the binder
and has migrated into the low refractive index layer of the hard
coat layer.
[0055] The leveling agent used in the invention has the function of
improving the flatness (smoothness) of the surface of the layer
containing said leveling agent, and appropriate selection of the
type of leveling agent will help impart the surface of the hard
coat layer or low refractive index layer with slidability that can
contribute to enhanced antifouling properties and mar-proofness. If
the leveling agent in the low refractive index layer and hard coat
layer is a type such as the one mentioned above, aggregation and
phase separation of different leveling agents in the low refractive
index layer will be avoided, thus providing an effect of preventing
transparency reduction due to layer opacity or haze increase.
[0056] Normally, the leveling agents will undergo phase separation
if two (or more) different types of leveling agents are simply
included in the hard coat layer-forming composition and low
refractive index layer-forming composition and mixed in the
composition before coating, or the final necessary function
(antifouling property, fingerprint wiping, mar-proofness) may not
be obtained, but migration of one of the leveling agents through a
half-cured state allows the two different leveling agents (leveling
agent A and leveling agent B) in the low refractive index layer to
be evenly dispersed without phase separation and opacity, and
particularly to be uniformly distributed on the surface of the low
refractive index layer. While the reason for this is not fully
understood, it is believed that when two or more different leveling
agents are normally used in combination, each leveling agent is in
the state of capable of moving (migrating) freely and similar
leveling agents aggregate from the evenly dispersed state and
produce phase separation, but by being in a half-curing state, the
leveling agent B that has reactivity at least with the binder in
the low refractive index layer-forming composition undergoes
crosslinking reaction with the binder or leveling agent in the
curing or cured low refractive index layer, thus impeding its
movement (migration), while the leveling agent A moves (migrates)
from the half-cured hard coat layer toward the surface of the low
refractive index layer through the gaps, allowing it to be
uniformly distributed on the surface.
[0057] A preferred construction for the antireflection film of the
invention may be the basic structure of base material/hard coat
layer/low refractive index layer, but the antireflection film may
also be formed with monolayers or multilayer lamination with
various functional layers in different orders between the base
material and the low refractive index layer, such as:
base material/primer layer/hard coat layer/low refractive index
layer base material/hard coat layer/high refractive index layer/low
refractive index layer, base material/antistatic layer/hard coat
layer/low refractive index layer, base material/hard coat
layer/antistatic layer/low refractive index layer, base
material/hard coat layer 1/hard coat layer 2/low refractive index
layer, and such laminates with different structures are also within
the scope of the invention. The basic construction of base
material/hard coat layer/low refractive index layer will be
described for convenience for the detailed explanation of the
invention.
[0058] FIG. 1 is a schematic diagram showing a cross-sectional view
of an embodiment of the basic construction of an antireflection
film according to the invention. For convenience, the
cross-sectional view in FIG. 1 shows the thickness direction
(vertical direction in the drawing) magnified over the dimension in
the direction of the plane (horizontal direction in the drawing).
The antireflection film 1 shown in FIG. 1 has a hard coat layer 20
and a low refractive index layer 30 adjacent to the hard coat
layer, formed on one side of a transparent base material 10, in
that order nearer from the transparent base material. A migration
layer 40 that has resulted from the hard coat layer 20 and the low
refractive index layer 30 mingled with each other will usually be
situated between them.
[0059] The transparent base material, hard coat layer, low
refractive index layer and migration layer forming the
antireflection film of the invention will now be explained in
order.
1. Transparent Base Material
[0060] The materials of the transparent base material are not
particularly restricted, and any ordinary materials conventionally
used for antireflection films may be employed, and materials
composed principally of cellulose acetate, cycloolefin polymer,
acrylate-based polymer, or polyesters are preferable, for example.
Here, "composed principally of" means that the component has the
highest content among the constituent components of the base
material.
[0061] As specific examples of cellulose acylates, there may be
mentioned cellulose triacetate, cellulose diacetate and cellulose
acetate butyrate. As examples of cycloolefin polymers, there may be
mentioned norbornane-based copolymers, monocyclic olefin-based
copolymers, cyclic conjugated diene-based polymers, vinylalicyclic
hydrocarbon-based copolymer resins and the like. More specifically,
there may be mentioned ZEONEX or ZEONOR (norbornane-based resin) by
Zeon Corp., SUMILITE FS-1700 by Sumitomo Bakelite Co., Ltd., ARTON
(modified norbornane-based resin) by JSR Corp., APEL (cyclic olefin
copolymer) by Mitsui Chemicals, Inc., Topas (cyclic olefin
copolymer) by Ticona and the OPTOREZ OZ-1000 series (alicyclic
acrylic resins) by Hitachi Chemical Co., Ltd. As specific examples
of acrylate-based polymers, there may be mentioned polymethyl
(meth)acrylate, polyethyl (meth)acrylate, methyl (meth)acrylate,
butyl (meth)acrylate copolymer and the like. As specific examples
of polyesters, there may be mentioned polyethylene terephthalate
and polyethylene naphthalate.
[0062] The term "(meth)acryloyl" used throughout the present
specification refers to acryloyl and/or methacryloyl, the term
"(meth)acrylate" refers to acrylate and/or methacrylate, and
"(meth)acryl" refers to acryl and/or methacryl. The term "light"
used throughout the present specification refers not only to
visible light and electromagnetic waves with wavelengths in the
non-visible light range, but also particle beams such as electron
beams and radiation or ionizing radiation that include
electromagnetic waves and particle beams.
[0063] When the transparent base material is used as a thin, highly
flexible film for the invention, the thickness will normally be
from 20 .mu.m to 300 .mu.m, and preferably from 30 .mu.m to 200
.mu.m. During formation of the hard coat layer on the transparent
base material, the transparent base material may be subjected to
physical treatment such as corona discharge treatment or oxidation
treatment, or coating with a coating agent such as an anchoring
agent or primer, in order to improve the adhesive property.
2. Hard Coat Layer
[0064] The hard coat layer used in the invention is a layer that
imparts hardness to the antireflection film of the invention. The
hard coat layer comprises a cured product of a hard coat
layer-forming composition containing, as essential components, a
curable binder containing at least a curable resin, and at least
one type of non-reactive leveling agent (leveling agent A). The
hard coat layer preferably contains inorganic fine particles in
order to impart mar-proofness to the hard coat layer, and the
inorganic fine particles are preferably reactive inorganic fine
particles with reactive functional groups that are capable of
crosslinking with at least the binder (matrix), as the curable
resin that forms the hard coat layer. The curable resin of the hard
coat layer, therefore, preferably is a curable resin (binder
component) with reactive functional groups capable of crosslinking
with the reactive functional groups of the reactive inorganic fine
particles. The formation of the cured product by crosslinking
between the reactive inorganic fine particles and the curable resin
can further improve the mar-proofness of the hard coat layer.
[0065] As a preferred embodiment of the hard coat layer of the
invention, there will now be described a hard coat layer-forming
composition comprising components that include reactive inorganic
fine particles A containing a reactive functional group (a) and the
binder C that imparts adhesiveness to the base material and
adjacent layers, and at least one type of non-reactive leveling
agent A.
[0066] A "hard coat layer" is, generally, a layer that exhibits a
hardness of at least "H" in a pencil hardness test according to
JISK5600-5-4 (1999), but a hard coat layer used in the invention
preferably has a hard coat layer surface hardness of at least "3H"
in a pencil hardness test.
[0067] The film thickness of the hard coat layer is preferably from
5 .mu.m to 30 .mu.m from the viewpoint of mar-proofness.
[0068] The construction materials of the hard coat layer of the
invention will now be described.
2-1. Reactive Inorganic Fine Particles A
[0069] Inorganic fine particles are commonly included in hard coat
layers to maintain transparency while improving mar-proofness. The
inorganic fine particles with crosslinking reactivity undergo
crosslinking reaction with the curable binder to form a crosslinked
structure, to further improve the hard coat properties. The
reactive inorganic fine particles A are inorganic fine particles
having an organic component covering at least part of the surfaces
of the inorganic fine particles serving as the core, and having
reactive functional groups on the surfaces introduced by the
aforementioned organic component. The reactive inorganic fine
particles A include those having two or more inorganic fine
particles as the core per particle. The reactive inorganic fine
particles A may be reduced in particle size to increase the points
of crosslinking in the matrix, with respect to their contents.
[0070] In order to notably improve the hardness for adequate
mar-proofness of the hard coat layer of the invention, it
preferably contains reactive inorganic fine particles A having an
organic component covering at least part of the surface and having
reactive functional groups (a) introduced by the organic component.
The reactive inorganic fine particles A may also impart a function
to the hard coat layer, and may be appropriately selected according
to the purpose.
[0071] As examples of inorganic fine particles, there may be
mentioned metal oxide fine particles such as silica, aluminum
oxide, zirconia, titania, zinc oxide, germanium oxide, indium
oxide, tin oxide, indium tin oxide, (ITO), antimony oxide or cerium
oxide, and metal fluoride fine particles such as magnesium fluoride
or sodium fluoride. There may also be used metal fine particles,
metal sulfide fine particles or metal nitride fine particles.
[0072] Silica and aluminum oxide are preferred from the viewpoint
of achieving high hardness. In order to achieve a relatively high
refractive index layer for the hard coat layer relative to the
adjacent low refractive index layer, fine particles such as
zirconia, titania or antimony oxide may be appropriately selected
to increase the refractive index during film formation. When it is
desired to impart antistatic or conductive properties, indium tin
oxide (ITO), tin oxide or the like may be appropriately selected
for use. These may be used either alone or in combinations of two
or more.
[0073] The surfaces of the inorganic fine particles normally have
groups that cannot exist in that form inside the inorganic fine
particles. These surface groups usually are relatively reactive
functional groups. For example, in the case of a metal oxide they
will be hydroxyl and oxy groups; in the case of a metal sulfide
they will be thiol and thio groups; and in the case of a nitride
they will be amino group, amide and imide groups.
[0074] The reactive inorganic fine particles A according to the
invention are preferably solid particles without voids or a porous
structure in the particle interiors, rather than particles with
voids or a porous structure in the particle interiors, such as
hollow particles. Hollow particles have voids or a porous
composition in the particle interiors, and therefore exhibit lower
hardness than solid particles. Consequently, the reactive inorganic
fine particles A preferably employ solid particles that have high
hardness.
[0075] The reactive inorganic fine particles A used in the
invention have an organic component covering at least part of the
surfaces, and have reactive functional groups on the surfaces
introduced by the aforementioned organic component. Here, the
organic component is a carbon-containing component. Modes wherein
the organic component covers at least part of the surfaces include
a mode in which a compound containing an organic component such as
a silane coupling agent is reacted with the hydroxyl groups present
on the surfaces of metal oxide fine particles, bonding the organic
component to part of the surfaces, a mode in which an organic
component is attached to the hydroxyl groups on the surfaces of
metal oxide fine particles by interaction such as hydrogen bonding,
and a mode in which one or more inorganic fine particles are
included in the polymer particles.
[0076] The covering organic component inhibits aggregation between
the inorganic fine particles and increases the number of reactive
functional groups introduced to the inorganic fine particle
surfaces, thus improving the film hardness, and therefore, they
preferably cover essentially the entirety of the particle surfaces.
From this viewpoint, the organic component covering the inorganic
fine particles is preferably included to the reactive inorganic
fine particles A to at greater than 1.00.times.10.sup.-3 g/m.sup.2.
For the mode where the organic component is attached or bonded to
the inorganic fine particle surfaces, the organic component
covering the inorganic fine particles is more preferably included
in the reactive inorganic fine particles A at greater than
2.00.times.10.sup.-3 g/m.sup.2 and even more preferably it is
included in the reactive inorganic fine particles A at greater than
3.50.times.10.sup.-3 g/m.sup.2. For the mode where inorganic fine
particles are included in the polymer particles, the organic
component covering the inorganic fine particles is more preferably
is included in the reactive inorganic fine particles A at greater
than 3.50.times.10.sup.-3 g/m.sup.2, and even more preferably it is
included in the reactive inorganic fine particles A at greater than
5.50.times.10.sup.-3 g/m.sup.2.
[0077] Normally, the proportion of the covering organic component
can be determined, for example, by thermogravimetric analysis in
air from room temperature to usually 800.degree. C., as the
constant mass value of weight reduction when the dry powder has
undergone complete combustion in air.
[0078] The amount of organic component per unit area is determined
by the following method. First, using differential thermogravimetry
(DTG), the organic component weight is measured and divided by the
inorganic component weight (organic component weight/inorganic
component weight). Next, the volume of the entire inorganic
component is calculated from the inorganic component weight and the
specific gravity of the inorganic fine particles used. Assuming
that the inorganic fine particles are spherical before covering,
the volume and surface area per inorganic fine particle before
covering are calculated from the mean particle size of the
inorganic fine particles before covering. The volume of the entire
inorganic component is then divided by the volume per inorganic
fine particle before covering, to determine the number of reactive
inorganic fine particles A. Further, dividing the organic component
weight by the number of reactive inorganic fine particles A gives
the amount of organic component per reactive inorganic fine
particle A. Finally, the organic component weight per reactive
inorganic fine particle A is divided by the surface area per
inorganic fine particle before covering, to determine the amount of
organic component per unit area.
[0079] From the viewpoint of improving hardness, the mean particle
size of the reactive inorganic fine particles A is from 3 nm to 100
nm, preferably from 5 nm to 80 nm and even more preferably from 10
nm to 70 nm. From the viewpoint of improving hardness while
maintaining the recovery for the resin alone without impairing
transparency, the inorganic fine particles preferably have a narrow
particle size distribution and are monodispersed.
[0080] For the hard coat layer of the invention, the mean particle
size is the 50% particle size (d50: median diameter), where the
particles in the solution are measured by the dynamic light
scattering method and the particle size distribution is expressed
as cumulative distribution. The mean particle size can be measured
using a Microtrac particle size analyzer by Nikkiso Co., Ltd.
[0081] The fine particles according to the invention may be
aggregated particles, and when they are aggregated particles, the
secondary particle size must be within the specified range.
[0082] As a method for preparing the reactive inorganic fine
particles A having an organic component covering at least part of
their surfaces and having reactive functional groups on the
surfaces introduced by the aforementioned organic component, there
may be used any conventional method appropriately selected
depending on the reactive functional group (a) that is to be
introduced into the inorganic fine particles.
[0083] Particularly according to the invention, the covering
organic component can be included in the reactive inorganic fine
particles A in an amount of greater than 1.00.times.10.sup.-3
g/m.sup.2 unit area of the inorganic fine particles before
covering, and from the viewpoint of inhibiting aggregation of the
inorganic fine particles and improving the film hardness, it is
preferred to select one of the following types of inorganic fine
particles (i) (ii) and (iii) as appropriate.
[0084] (i) Inorganic fine particles having reactive functional
groups on their surfaces, obtained by dispersing inorganic fine
particles in water and/or an organic solvent as the dispersing
medium, in the presence of one or more surface-modifying compounds
with a molecular weight of less than 500, selected from the group
consisting of saturated or unsaturated carboxylic acids, acid
anhydrides, acid chlorides, esters or acid amides corresponding to
the carboxylic acids, amino acids, imines, nitrites, isonitriles,
epoxy compounds, amines, .beta.-dicarbonyl compounds, silanes and
functional group-containing metal compounds.
[0085] (ii) Inorganic fine particles having reactive functional
groups on their surfaces, obtained by discharging a monomer
comprising inorganic fine particles with particle sizes of from 3
nm to 100 nm dispersed in a hydrophobic vinyl monomer, into water
through a hydrophilized porous membrane, to form an aqueous
dispersion of inorganic fine particle-dispersed monomer droplets,
and then polymerizing the dispersion.
[0086] (iii) Inorganic fine particles having reactive functional
groups on their surfaces, obtained by bonding metal oxide fine
particles with a compound containing the reactive functional group
introduced into the inorganic fine particles before covering, a
group represented by chemical formula (2) below and a silanol group
or a group that produces a silanol group upon hydrolysis.
-Q.sup.1-C(=Q.sup.2)-NH-- Chemical formula (2)
(In chemical formula (2), Q.sup.1 represents NH, O (oxygen atom) or
S (sulfur atom), and Q.sup.2 represents O or S).
[0087] Reactive inorganic fine particles A suitable for use
according to the invention will now be described.
[0088] (i) Inorganic fine particles having reactive functional
groups on their surfaces, obtained by dispersing inorganic fine
particles in water and/or an organic solvent as the dispersing
medium, in the presence of one or more surface-modifying compounds
with a molecular weight of less than 500, selected from the group
consisting of saturated or unsaturated carboxylic acids, acid
anhydrides, acid chlorides, esters or acid amides corresponding to
the carboxylic acids, amino acids, imines, nitriles, isonitriles,
epoxy compounds, amines, .beta.-dicarbonyl compounds, silanes and
functional group-containing metal compounds.
[0089] Using reactive inorganic fine particles A of (i) above is
advantageous in that the film hardness can be improved without
lowering the organic component content.
[0090] The surface-modifying compound used for the reactive
inorganic fine particles A of (i) above has a functional group that
can chemically bond with a group on the surfaces of the inorganic
fine particles under dispersion conditions, such as a carboxyl
group, acid anhydride group, acid chloride group, acid amid group,
ester, imino, nitrile, isonitrile, hydroxyl, thiol or epoxy group,
primary, secondary or tertiary amino group, Si--OH group or silane
hydrolyzable residue, or a C--H acid group such as a
.beta.-dicarbonyl compound. Here, the chemical bonding may,
preferably, be a covalent bonding, ionic bonding or coordination
bonding, or even hydrogen bonding. Coordination bonding may be in
the formation of a complex. For example, Bronsted or Lewis
acid-base material reaction, complex formation or esterification
occurs between the functional groups of the surface-modifying
compound and the groups on the inorganic fine particle surfaces.
Surface-modifying compounds used for the reactive inorganic fine
particles A of (i) above may be used alone or in combinations of
two or more.
[0091] In addition to the at least one functional groups
(hereinafter referred to as "first functional group") that can
participate in chemical bonding with groups on the surfaces of the
inorganic fine particles, the surface-modifying compound will also
generally have molecular residues that can impart new properties to
the inorganic fine particles after bonding to the surface-modifying
compound via the functional groups. The molecular residues, or a
portion of them, may be hydrophobic or hydrophilic and may serve
for stabilization, compatibilization or activation of the inorganic
fine particles, for example.
[0092] As examples of hydrophobic molecular residues, there may be
mentioned alkyl, aryl, alkallyl, aralkyl and fluorine-containing
alkyl groups that can produce inactivation or repulsion. As
hydrophilic groups, there may be mentioned hydroxy, alkoxy and
polyester groups.
[0093] The surface-introduced reactive functional group (a) that
allows the reactive inorganic fine particles A to react with the
binder C described hereunder is appropriately selected depending on
the binder C. The reactive functional group (a) may be desirably a
polymerizable unsaturated group for use, and preferably it is a
photocuring unsaturated group and more preferably an ionizing
radiation-curing unsaturated group. As specific examples, there may
be mentioned ethylenic double bond-containing groups such as
(meth)acryloyl, vinyl and allyl, and epoxy groups.
[0094] When the molecular residue of the surface-modifying compound
contains the reactive functional group (a) that can react with the
binder C, the first functional group in the surface-modifying
compound can be reacted with the inorganic fine particle surfaces
to introduce the reactive functional group (a) that can react with
the binder C onto the surfaces of the reactive inorganic fine
particles A of (i) above. For example, surface-modifying compounds
with polymerizable unsaturated groups may be mentioned as suitable
groups in addition to the first functional group.
[0095] Alternatively, the reactive functional group (a) that can
react with the binder C may be introduced onto the surfaces of the
reactive inorganic fine particles A of (i) above by including a
second reactive functional group in the molecular residues of the
surface-modifying compound and using the second reactive functional
group as a scaffold. For example, preferably a group that can
undergo hydrogen bonding (hydrogen bond-forming group) such as a
hydroxyl or oxy group may be introduced as the second reactive
functional group and the hydrogen bond-forming group of another
surface-modifying compound reacted with the hydrogen bond-forming
group introduced onto the fine particle surfaces, to introduce the
reactive functional group (a) that can react with the binder C.
That is, a preferred example of the surface-modifying compound is a
compound with a hydrogen bond-forming group used in combination
with the reactive functional group (a) that can react with the
binder C, such as a polymerizable unsaturated group, and a compound
with a hydrogen bond-forming group. As specific examples of
hydrogen bond-forming groups, there may be mentioned functional
groups such as hydroxyl, carboxyl, epoxy, glycidyl and amide
groups, or amide bonds. An amide bond is one containing --NHC(O) or
>NC(O)-- in the bonding unit. Preferred among these for the
hydrogen bond-forming group used in the surface-modifying compound
of the invention are carboxyl, hydroxyl and amide groups.
[0096] The surface-modifying compound used in the reactive
inorganic fine particles A of (i) above has a molecular weight of
less than 500, more preferably less than 400 and especially not
exceeding 200. By using such a low molecular weight, it is possible
to rapidly occupy the fine particle surfaces and prevent
aggregation between the inorganic fine particles.
[0097] The surface-modifying compound used in the reactive
inorganic fine particles A of (i) above is preferably a liquid
under the reaction conditions used to modify the surfaces, and is
preferably soluble or at least emulsifiable in a dispersing medium.
More preferably, it is soluble in the dispersing medium and
uniformly distributed as dissociated molecules or molecular ions in
the dispersing medium.
[0098] As saturated or unsaturated carboxylic acids, there may be
mentioned those with 1-24 carbon atoms, such as formic acid, acetic
acid, propionic acid, butyric acid, valeric acid, caproic acid,
acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic
acid, succinic acid, glutaric acid, oxalic acid, maleic acid,
fumaric acid, itaconic acid and stearic acid, as well as their
corresponding acid anhydrides, chlorides, esters and amides, and
caprolactam may be mentioned as an example. Using an unsaturated
carboxylic acid allows introduction of a polymerizable unsaturated
group.
[0099] Preferred amines are those having the chemical formula
Q.sub.3-nNH.sub.n (n=0, 1 or 2), where each residue Q independently
represents alkyl with 1-12, especially 1-6 and preferably 1-4
carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl or
butyl) or aryl, alkallyl or aralkyl with 6-24 carbon atoms (for
example, phenyl, naphthyl, tolyl or benzyl). Polyalkyleneamines may
be mentioned as examples of preferred amines, and specifically
methylamine, dimethylamine, trimethylamine, ethylamine, aniline,
N-methylaniline, diphenylamine, triphenylamine, toluidine,
ethylenediamine and diethylenetriamine.
[0100] Preferred .beta.-dicarbonyl compounds have 4-12 and
especially 5-8 carbon atoms, and as examples there may be mentioned
diketones (acetylacetone and the like), 2,3-hexanedione,
3,5-heptanedione, acetoacetic acid, acetoacetic
acid-C.sub.1-C.sub.4-alkyl esters (ethyl acetoacetate ester and the
like), diacetyl and acetonylacetone.
[0101] As examples of amino acids, there may be mentioned
.beta.-alanine, glycine, valine, aminocaproic acid, leucine and
isoleucine.
[0102] Preferred silanes are hydrolyzable organosilanes with at
least one hydrolyzable group or hydroxy group and at least one
non-hydrolyzable residue. As examples of hydrolyzable groups, there
may be mentioned halogen, alkoxy and acyloxy groups. As
non-hydrolyzable residues, there may be used non-hydrolyzable
residues with a reactive functional group (a) and/or without a
reactive functional group (a). A silane partially containing at
least a fluorine-substituted organic residue may also be used.
[0103] There are no particular restrictions on the silane used, and
as examples there may be mentioned CH.sub.2.dbd.CHSi
(OOCCH.sub.3).sub.3, CH.sub.2.dbd.CHSiCl.sub.3, CH.sub.2.dbd.CHSi
(OC.sub.2H.sub.5).sub.3, CH.sub.2.dbd.CH--Si
(OC.sub.2H.sub.4OCH.sub.3).sub.3, CH.sub.2.dbd.CH--CH.sub.2--Si
(OC.sub.2H.sub.5).sub.3, CH.sub.2.dbd.CH--CH.sub.2--Si
(OOCCH.sub.3).sub.3, .gamma.-glycidyloxypropyltrimethoxysilane
(GPTS), .gamma.-glycidyloxypropyldimethylchlorosilane,
3-aminopropyltrimethoxysilane (APTS), 3-aminopropyltriethoxysilane
(APTES), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N--[N'-(2'-aminoethyl)-2-aminoethyl]-3-aminopropyltrimethoxysilane,
hydroxymethyltrimethoxysilane,
2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane,
bis-(hydroxyethyl)-3-aminopropyltriethoxysilane,
N-hydroxyethyl-N-methylaminopropyltriethoxysilane,
3-(meth)acryloxypropyltriethoxysilane and
3-(meth)acryloxypropyltrimethoxysilane.
[0104] As metal compounds with functional groups, there may be
mentioned metal compounds with a metal M from Groups IIIA-VA and/or
Groups IIB-IVB of the Periodic Table. Alkoxides of zirconium and
titanium: M(OR)4 (M=Ti, Zr) (wherein a portion of the OR groups are
substituted with a completing agent such as a .beta.-dicarbonyl
compound or monocarboxylic acid) may also be mentioned. Using a
compound with a polymerizable unsaturated group (such as
methacrylic acid) as a completing agent allows introduction of a
polymerizable unsaturated group.
[0105] The dispersing medium used is preferably water and/or an
organic solvent. Distilled water (pure) is particularly preferred
as the dispersing medium. Polar and non-polar aprotic solvents are
preferred as organic solvents. As examples there may be mentioned
alcohols including aliphatic alcohols with 1-6 carbon atoms
(especially methanol, ethanol, n- and i-propanol and butanol);
ketones such as acetone and butanone; esters such as ethyl acetate;
ethers such as diethyl ether, tetrahydrofuran and tetrahydropyran;
amides such as dimethylacetamide and dimethylformamide; sulfoxides
and sulfones such as sulfolane and dimethyl sulfoxide; and
aliphatic (optionally halogenated) hydrocarbons such as pentane,
hexane and cyclohexane. These dispersing media may also be used as
mixtures.
[0106] The dispersing medium preferably has a boiling point
allowing it to be easily removed by distillation (optionally under
reduced pressure), and it is preferably a solvent with a boiling
point of lower than 200.degree. C. and especially lower than
150.degree. C.
[0107] For preparation of the reactive inorganic fine particles A
of (i), the concentration of the dispersing medium will normally be
40-90 wt %, preferably 50-80 wt % and especially 55-75 wt %. The
remaining dispersion will be composed of untreated inorganic fine
particles and the aforementioned surface-modifying compound. The
weight ratio of the inorganic fine particles/surface-modifying
compound is preferably 100:1-4:1, more preferably 50:1-8:1 and even
more preferably 25:1-10:1. Preparation of the reactive inorganic
fine particles A of (i) is preferably carried out at from room
temperature (about 20.degree. C.) to the boiling point of the
dispersing medium. Most preferably, the dispersion temperature is
50-100.degree. C. The dispersion time will depend on the type of
material used, but generally it is from several minutes to several
hours, and for example, 1-24 hours.
[0108] (ii) Inorganic fine particles having reactive functional
groups on their surfaces, obtained by discharging a monomer
comprising inorganic fine particles with particle sizes from 3 nm
to 100 nm dispersed in a hydrophobic vinyl monomer, into water
through a hydrophilized porous membrane, to form an aqueous
dispersion of inorganic fine particle-dispersed monomer droplets,
and then polymerizing the dispersion.
[0109] Using reactive inorganic fine particles A according to (ii)
above is advantageous from the viewpoint of the particle size
distribution, in that the monodisperse property is increased and
irregular performance when coarse particles are present can be
minimized.
[0110] Since the reactive inorganic fine particles A used in the
invention are inorganic fine particles with an organic component
covering at least part of the surfaces and thus having reactive
functional groups on their surfaces which are introduced by the
organic component, either the reactive functional group (a) or a
different reactive functional group that allows subsequent
introduction of the desired reactive functional group (a) is
included in the hydrophobic vinyl monomer used for polymerization
during production of the reactive inorganic fine particles A of
type (ii). For example, a hydrophobic vinyl monomer already
containing a carboxyl group may be polymerized, and then glycidyl
methacrylate reacted with the carboxyl group to introduce a
polymerizable unsaturated group.
[0111] As specific examples of hydrophobic vinyl monomers, there
may be mentioned aromatic vinyl compounds such as styrene,
vinyltoluene, .alpha.-methylstyrene and divinylbenzene; unsaturated
carboxylic acid esters such as methyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl
(meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate,
2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl
(meth)acrylate, benzyl (meth)acrylate, (poly)ethylene glycol mono-
or di(meth)acrylate, (poly)propylene glycol mono- or
di(meth)acrylate, 1,4-butanediol mono- or di-(meth)acrylate,
trimethylolpropane mono-, di- or tri-(meth)acrylate and the like;
allyl compounds such as diallyl phthalate, diallylacrylamide,
triallyl (iso)cyanurate, triallyl-trimellitate, and
(poly)oxyalkyleneglycol di(meth)acrylates such as
(poly)ethyleneglycol di(meth)acrylate and (poly)-propyleneglycol
di(meth)acrylate. There may also be mentioned conjugated diene
compounds such as butadiene, isoprene and chloroprene. There may
further be mentioned reactive functional group-containing monomers
such as acrylic acid, methacrylic acid, itaconic acid, fumaric
acid, glycidyl methacrylate, vinylpyridine, diethylaminoethyl
acrylate, N-methylmethacrylamide and acrylonitrile. Among these,
monomers with high water-solubility such as acrylic acid,
methacrylic acid and itaconic acid have high water solubility
overall as monomers, and may be used in ranges that do not produce
oil-droplet monomer emulsions in water.
[0112] The inorganic fine particles used for (ii) must have small
particle sizes and must disperse satisfactorily in hydrophobic
vinyl monomers. The particle sizes of the inorganic fine particles
used are preferably less than 100 nm, preferably from 5 nm to 80
nm, and more preferably from 10 nm to 70 nm. If the inorganic fine
particles are poorly compatible with the hydrophobic vinyl monomer,
it is preferred for the fine particle surfaces to be subjected to
prior surface treatment. Surface treatment may employ a known
method such as dispersing agent treatment whereby a pigment
dispersant is adsorbed onto the fine particle surfaces, coupling
agent treatment with a silane coupling agent or titanate coupling
agent, or polymer coating treatment by capsule polymerization or
the like.
[0113] In order to emulsify the inorganic fine particle-dispersed
hydrophobic vinyl monomer in water for (ii), it is discharged into
water through a hydrophilized porous membrane. The pores must have
a mean pore size of 0.01-5 .mu.m and must have uniform pore sizes,
and must run from the front to the back of the membrane. Glass is
preferred as the material for the membrane, and specific examples
include porous glass (SPG: Shirasu Porous Glass) obtained by
microphase separation (by heat treatment) of
SiO.sub.2--Al.sub.2O.sub.3--B.sub.2O.sub.3--CaO glass prepared by
firing Shirasu volcanic ash as the main starting material, and
dissolving, removing the boric acid-rich phase with an acid.
[0114] For (ii) above, a surfactant or water-soluble polymer must
be present as a stabilizer for the monomer droplets in the aqueous
phase into which the inorganic fine particle-containing hydrophobic
vinyl monomer is extruded through the porous membrane. If no
stabilizer is used, the monomer droplets discharged through the
membrane will fuse together, resulting in a wide particle size
distribution. Preferred stabilizers include water-soluble
polymer-based stabilizers such as polyvinyl alcohol,
hydroxypropylcellulose and polyvinylpyrrolidone, for monomer
droplets of about 1 .mu.m or greater, and preferably an anionic
surfactant or nonionic emulsifier is also added. For example, a
combination of sodium lauryl sulfate as an emulsifier and
1-hexadecanol as a co-emulsifier firmly adsorbs onto the droplet
surfaces to provide a significant stabilizing effect, and is
particularly preferred as the stabilizer for (ii).
[0115] In most cases, an oil-soluble radical initiator is used for
polymerization of the aqueous dispersion of emulsified inorganic
fine particle-containing monomer droplets, for (ii) above. As
examples of initiators to be used as oil-soluble radical
initiators, there may be mentioned azo-based initiators such as
azobisisobutyronitrile, aromatic peroxides such as benzoyl peroxide
and 2,4-dichlorbenzoyl peroxide, and aliphatic peroxides such as
isobutyl peroxide, diisopropylperoxy dicarbonate and
di(2-ethylhexylperoxy) dicarbonate. These may be used by
dissolution in the monomer phase before emulsification. A
water-soluble radical polymerization inhibitor such as hydroquinone
or iron chloride may also be added.
[0116] (iii) Inorganic fine particles having reactive functional
groups on their surfaces, obtained by bonding metal oxide fine
particles, as inorganic fine particles to serve as the core, with a
compound containing the reactive functional group introduced into
the inorganic fine particles before covering, a group represented
by chemical formula (2) below and a silanol group or a group that
produces a silanol group by hydrolysis.
-Q.sup.1-C(=Q.sup.2)-NH-- Chemical Formula (2)
(In chemical formula (2), Q.sup.1 represents NH, O (oxygen atom) or
S (sulfur atom), and Q.sup.2 represents O or S).
[0117] Using the reactive inorganic fine particles A of (iii) above
is advantageous in that the organic component is increased and the
dispersibility and film strength are further increased.
[0118] First, compounds containing a group represented by chemical
formula (2) above and a silanol group or a group that produces a
silanol group by hydrolysis (hereinafter also referred to as
"reactive functional group-modified hydrolyzable silane") will be
explained as a reactive functional group to be introduced into the
inorganic fine particles before covering.
[0119] The reactive functional group (a) to be introduced into the
inorganic fine particles, in the reactive functional group-modified
hydrolyzable silane, is not particularly restricted so long as it
is appropriately selected to be reactive with the binder C. It is
one that is appropriate for introduction of the polymerizable
unsaturated group.
[0120] In the reactive functional group-modified hydrolyzable
silane, the group [-Q.sup.1-C(=Q.sup.2)-NH--] represented by
chemical formula (2) above includes, specifically, the six groups
[--O--C(.dbd.O)--NH--], [--O--C(.dbd.S)--NH--],
[--S--C(.dbd.O)--NH--], [--NH--C(.dbd.O)--NH--],
[--NH--C(.dbd.S)--NH--] and [--S--C(.dbd.S)--NH--].
[0121] These groups may be used either alone or in combinations of
two or more. From the viewpoint of thermostability, it is preferred
to use at least one from among the groups [--O--C(.dbd.O)--NH--],
[--O--C(.dbd.S)--NH--] and [--S--C(.dbd.O)--NH--]. A group
[-Q.sup.1-C(=Q.sup.2)-NH--] represented by chemical formula (2)
generates suitable cohesion by hydrogen bonding between molecules
to achieve curing, and thereby imparts properties such as excellent
mechanical strength, adhesiveness with base materials and heat
resistance.
[0122] As groups that produce silanol groups by hydrolysis, there
may be mentioned alkoxy groups, aryloxy groups, acetoxy groups,
amino groups and halogen atoms on silicon atoms, with alkoxysilyl
and aryloxysilyl groups being preferred. The silanol group or the
group that produces a silanol group by hydrolysis can bond with the
metal oxide fine particles either by condensation reaction or by
condensation reaction following hydrolysis.
[0123] As specific preferred examples of reactive functional
group-modified hydrolyzable silanes, there may be mentioned
compounds represented by chemical formula (3) below.
##STR00003##
[0124] In chemical formula (3), R.sup.c and R.sup.d may be the same
or different and represent hydrogen atoms or C.sub.1-C.sub.8 alkyl
or aryl groups, and as examples there may be mentioned methyl,
ethyl, propyl, butyl, octyl, phenyl and xylyl. The letter s
represents 1, 2 or 3.
[0125] As examples of groups represented by
[(R.sup.cO).sub.sR.sup.d.sub.3-sSi--], there may be mentioned
trimethoxysilyl, triethoxysilyl, triphenoxysilyl,
methyldimethoxysilyl and dimethyl-methoxysilyl. Trimethoxysilyl and
triethoxysilyl are preferred among such groups.
[0126] R.sup.e is a divalent organic group with a C.sub.1-C.sub.12
aliphatic or aromatic structure, and it may also include a
straight-chain, branched or cyclic structure. As examples of such
organic groups, there may be mentioned methylene, ethylene,
propylene, butylene, hexamethylene, cyclohexylene, phenylene,
xylylene and dodecamethylene. Preferred among these are methylene,
propylene, cyclohexylene and phenylene.
[0127] R.sup.f is a divalent organic group, and it will generally
be selected from among divalent organic groups with molecular
weights of from 14 to 10,000 and preferably molecular weights of
from 76 to 500. As examples there may be mentioned straight-chain
polyalkylene groups such as hexamethylene, octamethylene and
dodecamethylene; alicyclic or polycyclic divalent organic groups
such as cyclohexylene and norbornylene; divalent aromatic groups
such as phenylene, naphthylene, biphenylene and polyphenylene; and
alkyl group-substituted or aryl group-substituted forms of the
foregoing. These divalent organic groups may include atomic groups
containing elements other than carbon and hydrogen, and may also
include polyether bonds, polyester bonds, polyamide bonds and
polycarbonate bonds, as well as groups represented by chemical
formula (2) above.
[0128] R.sup.g is a (t+1)-valent organic group, and is preferably
selected from among straight-chain, branched or cyclic saturated
hydrocarbon and unsaturated hydrocarbon groups.
[0129] Y' represents a monovalent organic group with a reactive
functional group. It may also be the aforementioned reactive
functional group itself. For example, when the reactive functional
group (a) is selected from among polymerizable unsaturated groups,
there may be mentioned (meth)acryloyl(oxy), vinyl(oxy),
propenyl(oxy), butadienyl(oxy), styryl(oxy), ethynyl(oxy),
cinnamoyl(oxy), maleate and (meth)acrylamide groups. The letter t
is a positive integer of preferably 1-20, even more preferably 1-10
and most preferably 1-5.
[0130] Synthesis of the reactive functional group-modified
hydrolyzable silane used in the invention may be accomplished by
the method described in Japanese Unexamined Patent Publication HEI
No. 9-100111, for example. Specifically, a polymerizable
unsaturated group, for example, may be introduced by (I) addition
reaction between a mercaptoalkoxysilane, a polyisocyanate compound
and an active hydrogen group-containing polymerizable unsaturated
compound that can react with isocyanate groups. It may also be
accomplished by (II) direct reaction between a compound with
alkoxysilyl and isocyanate groups in its molecule, and the active
hydrogen group-containing polymerizable unsaturated compound. It
can also be accomplished by (III) direct synthesis by addition
reaction between a compound with polymerizable unsaturated and
isocyanate groups in its molecule, and a mercaptoalkoxysilane or
aminosilane.
[0131] For production of the reactive inorganic fine particles A of
(iii) above, there may be selected a method in which the reactive
functional group-modified hydrolyzable silane is subjected to a
separate hydrolysis procedure, and then mixed with inorganic fine
particles, heated and stirred, a method in which hydrolysis of the
reactive functional group-modified hydrolyzable silane is carried
out in the presence of the inorganic fine particles, or a method in
which the surface treatment of the inorganic fine particles is
carried out in the presence of another component such as a
polyvalent unsaturated organic compound, monovalent unsaturated
organic compound, radiation polymerization initiator or the like,
but hydrolysis of the reactive functional group-modified
hydrolyzable silane in the presence of the inorganic fine particles
is the preferred method.
[0132] The temperature for production of the reactive inorganic
fine particles A of (iii) is normally from 20.degree. C. to
150.degree. C., and the treatment time is in the range of 5
minutes-24 hours.
[0133] In order to accelerate the hydrolysis, an acid, salt or base
material may be added as a catalyst. As suitable acids, there may
be mentioned organic acids and unsaturated organic acids; and as
suitable base materials, there may be mentioned tertiary amines and
quaternary ammonium hydroxide. These acid or base material
catalysts may be added at 0.001-1.0 wt % and preferably 0.01-0.1 wt
% based on the reactive functional group-modified hydrolyzable
silane.
[0134] The reactive inorganic fine particles A for use may be
powdered fine particles containing no dispersing medium, but from
the viewpoint of omitting the dispersion step and increasing
productivity, the fine particles are preferably in the form of a
solvent-dispersed sol.
[0135] The content of the reactive inorganic fine particles A is
preferably 5-70 wt % and more preferably 20-60 wt % based on the
total solid content of the hard coat layer. At less than 5 wt % the
hardness of the hard coat layer surface may not be sufficient, and
at more than 70 wt % the adhesiveness at the interface between the
hard coat layer and transparent base material may be
insufficient.
2-2. Curable Binder System for Hard Coat Layer
[0136] The constituent components of the curable binder system for
the hard coat layer of the invention are those other than the
reactive inorganic fine particles A and the at least one leveling
agent A as an essential component of the hard coat layer, and they
include the essential component binder C as a curable resin, if
necessary a curable binder component other than the binder C, a
polymer component, a polymerization initiator, etc., which
represent what becomes the matrix of the hard coat layer after
curing.
2-2-1. Binder C
[0137] The binder C used in the invention is a curable resin that
serves as part of the matrix when cured. The binder C preferably
has a reactive functional group (b) with crosslinking reactivity
for the reactive functional group (a) of the reactive inorganic
fine particles A. If the binder C has the reactive functional group
(b), the reactive functional group (a) and reactive functional
group (b) will undergo crosslinking to form a network structure.
This will enhance the hardness of the hard coat layer. The binder C
preferably has three or more reactive functional groups (b) per
molecule in order to obtain sufficient crosslinkability. The
reactive functional group (b) for use may be a polymerizable
unsaturated group, and preferably it is a photocuring unsaturated
group and more preferably an ionizing radiation-curing unsaturated
group. As specific examples, there may be mentioned ethylenic
double bond-containing groups such as (meth)acryloyl, vinyl and
allyl, and epoxy groups.
[0138] The curable organic resin of the binder C is preferably
translucent to allow transmission of light as a coated film, and
there may be appropriately employed ionizing radiation curable
resins, as resins that cure by ionizing radiation, typically
ultraviolet rays or an electron beam, as well as other publicly
known curable resins, depending on the required performance. As
ionizing radiation curable resins, there may be mentioned
acrylate-based, oxetane-based and silicone-based resins.
[0139] From the viewpoint of increasing the hardness of the hard
coat layer of the invention, it is preferred to use a combination
of Polymer D containing polyalkylene oxide chains, represented by
chemical formula (4) below, and Compound E having two or more
reactive functional groups and having a molecular weight of less
than 10,000.
[0140] Polymer D, Compound E and the reactive inorganic fine
particles A are mutually reactive, and since Polymer C undergoes
crosslinking with both Compound E and the reactive inorganic fine
particles A, it may be expected to provide sufficient mar-proofness
to the hard coat layer.
2-2-1-1. Polyalkylene Oxide Chain-Containing Polymer D Represented
by Chemical Formula (4)
[0141] The polyalkylene oxide chain-containing Polymer D is
represented by chemical formula (4) below, and it is a polyalkylene
oxide chain-containing polymer having three or more reactive
functional groups (b) at the ends and having a molecular weight of
greater than 1000.
##STR00004##
[0142] In chemical formula (4), X is a C.sub.3-10 (not counting
substituents) trivalent or greater organic group comprising one or
a combination of straight-chain, branched or cyclic hydrocarbon
chains, where the hydrocarbon chains optionally have substituents
and heteroatoms are optionally present between the hydrocarbon
chains. The letter k represents an integer of 3-10. L.sub.1-L.sub.k
each independently represents a divalent group including one or
more selected from the group consisting of ether bonds, ester bonds
and urethane bonds, or a direct bond. R.sub.1-R.sub.k each
independently represents a C.sub.1-4 straight-chain or branched
hydrocarbon group. The symbols n1, n2 . . . nk are each independent
integers. Y.sub.1-Y.sub.k each independently represents a compound
residue with one or more reactive functional groups (b).
[0143] In the polyalkylene oxide chain-containing Polymer D
represented by chemical formula (4), X corresponds to a short main
chain with k bifurcation points from which the (O--R.sub.k).sub.nk
portions of the linear polyalkylene oxide side chains extend.
[0144] Such hydrocarbon chains include saturated hydrocarbons such
as --CH.sub.2-- and unsaturated hydrocarbons such as --CH.dbd.CH--.
Cyclic hydrocarbon chains may consist of alicyclic compounds or
aromatic compounds. Heteroatoms such as O or S may be present
between the hydrocarbon chains, and ether bonds, thioether bonds,
ester bonds or urethane bonds may also be present between the
hydrocarbon chains. The hydrocarbon chains branching from
straight-chain or cyclic hydrocarbon chains via heteroatoms are
counted in the number of carbon atoms of the substituents explained
hereunder.
[0145] As substituents that may be optionally present on the
hydrocarbon chains, there may be mentioned, specifically, halogen
atoms, hydroxyl, carboxyl, amino, epoxy, isocyanate, mercapto,
cyano, silyl, silanol, nitro, acetyl, acetoxy, sulfone groups and
the like, with no particular restriction to these. The substituents
that are optionally present on the hydrocarbon chains may include
hydrocarbon chains branched from the aforementioned straight-chain
or cyclic hydrocarbon chains via heteroatoms, and as examples,
there may be mentioned alkoxy groups (RO--, where R is a saturated
or unsaturated straight-chain, branched or cyclic hydrocarbon
chain), alkylthioether groups (RS--, where R is a saturated or
unsaturated straight-chain, branched or cyclic hydrocarbon chain)
and alkyl ester groups (RCOO--, where R is a saturated or
unsaturated straight-chain, branched or cyclic hydrocarbon
chain).
[0146] X is a C.sub.3-10 (not counting the substituents) trivalent
or greater organic group. If the number of carbon atoms excluding
the substituents in X is less than three, it will be difficult for
three or more of the linear polyalkylene oxide side chain
(O--R.sub.k).sub.nk portions to be present. On the other hand, if
the number of carbon atoms excluding substituents in X is greater
than 10, there will be more flexible sections and the hardness of
the cured film will be undesirably lowered. The number of carbon
atoms excluding substituents is preferably 3-7 and even more
preferably 3-5.
[0147] X is not particularly restricted so long as these conditions
are satisfied. For example, it may have any of the following
structures.
##STR00005##
[0148] As preferred structures among these, there may be mentioned
structures (x-1), (x-2), (x-3) and (x-7).
[0149] As starting materials for X, there are preferably used
C.sub.3-10 polyhydric alcohols having three or more hydroxyl groups
in the molecule, such as 1,2,3-propanetriol (glycerol),
trimethylolpropane, pentaerythritol and dipentaerythritol,
C.sub.3-10 polybasic carboxylic acids having three or more carboxyl
groups in the molecule, and C.sub.3-10 polyvalent amine acids
having three or more amino groups in the molecule.
[0150] In chemical formula (4), k represents the number of
polyalkylene oxide chains (O--R.sub.k).sub.nk in the molecule, and
it is an integer of 3-10. If k is less than 3, i.e. two
polyalkylene oxide chains are present, sufficient hardness will not
be obtained. If k exceeds 10, there will be more flexible sections
and the hardness of the cured film will be undesirably lowered. The
value of k is preferably 3-7 and even more preferably 3-5.
[0151] In chemical formula (4), L1-Lk each independently represents
a divalent group including one or more selected from the group
consisting of ether bonds, ester bonds and urethane bonds, or a
direct bond. The divalent group including one or more selected from
the group consisting of ether bonds, ester bonds and urethane bonds
may be an ether bond (--O--), ester bond (--COO--) or urethane bond
(--NHCOO--). These bonds facilitate propagation of the molecular
chains with a high degree of freedom, and can therefore provide
compatibility with other resin components.
[0152] As examples of divalent groups including one or more
selected from the group consisting of ether bonds, ester bonds and
urethane bonds, there may be mentioned --O--R--O--,
--O(C.dbd.O)--R--O--, --O(C.dbd.O)--R--(C.dbd.O)O--,
--(C.dbd.O)O--R--O--, --(C.dbd.O)O--R--(C.dbd.O)O--,
--(C.dbd.O)O--R--O(C.dbd.O)--, --NHCOO--R--O--,
--NHCOO--R--O(C.dbd.O)NH--, --O(C.dbd.O)NH--R--O--,
--O(C.dbd.O)NH--R--O(C.dbd.O)NH--, --NHCOO--R--O(C.dbd.O)NH--,
--NHCOO--R--(C.dbd.O)O--, --O(C.dbd.O)NH--R--(C.dbd.O)O--,
--NHCOO--R--O(C.dbd.O)-- and --O(C.dbd.O)NH--R--O(C.dbd.O)--. Here,
R represents a saturated or unsaturated straight-chain, branched or
cyclic hydrocarbon chain.
[0153] As specific examples of such divalent groups, there may be
mentioned residues with the exclusion of an active hydrogen from
diols such as (poly)ethylene glycol and (poly)propylene glycol,
dicarboxylic acids such as fumaric acid, maleic acid and succinic
acid, or diisocyanates such as tolylene diisocyanate, hexamethylene
diisocyanate and isoboron diisocyanate, although there is no
limitation to these.
[0154] In chemical formula (4), (O--R.sub.k).sub.nk is a
polyalkylene oxide chain, i.e. a linear side chain with alkylene
oxide as the repeating unit. Here, R.sub.1-R.sub.k each
independently represents a C.sub.1-4 straight-chain or branched
hydrocarbon group. As alkylene oxides, there may be mentioned
methylene oxide, ethylene oxide, propylene oxide and isobutylene
oxide, with ethylene oxide and propylene oxide (C.sub.2-3
straight-chain or branched hydrocarbon groups) being preferred.
[0155] The symbols n1, n2 . . . nk for the number of repeating
units of the alkylene oxide R.sub.k--O are all independent
integers. The symbols n1, n2 . . . nk are not particularly
restricted so long as the weight-average molecular weight of the
entire molecule is greater than 1000. The symbols n1, n2 . . . nk
may be different, but the chain lengths are preferably similar from
the viewpoint of maintaining the hardness of the formed hard coat
layer while inhibiting cracking. Thus, the difference between n1,
n2 . . . nk is preferably about 0-100, more preferably about 0-50
and most preferably about 0-10. From the viewpoint of maintaining
the hardness of the formed hard coat layer while inhibiting
cracking, n1, n2 . . . nk are preferably each integers of 2-500 and
more preferably integers of 2-300.
[0156] Y.sub.1-Y.sub.k each independently represents a reactive
functional group (b) or a compound residue with one or more
reactive functional groups (b). This will ensure that three or more
reactive functional groups (b) are at the ends of the polyalkylene
oxide chain-containing polymer.
[0157] As examples of Y.sub.1-Y.sub.k when Y.sub.1-Y.sub.k are
reactive functional groups (b), there may be mentioned
polymerizable unsaturated groups such as (meth)acryloyl.
[0158] As examples of reactive functional groups (b) when
Y.sub.1-Y.sub.k are compound residues with one or more reactive
functional groups (b), there may be mentioned polymerizable
unsaturated groups such as (meth)acryloyl, (meth)acryloyloxy, vinyl
group (CH.sub.2.dbd.CH--) and CH.sub.2.dbd.CR-- (where R is a
hydrocarbon group). The compound residue is not particularly
restricted so long as the reactive functional group (b) is
appropriately selected for reaction with Compound D described
hereunder and the reactive inorganic fine particles A. When
Y.sub.1-Y.sub.k are compound residues, the number of reactive
functional groups (b) in Y.sub.1-Y.sub.k may be one, although two
or more can further increase the crosslink density and are
preferred from the viewpoint of hardness of the hard coat
layer.
[0159] When Y.sub.1-Y.sub.k are compound residues with one or more
reactive functional groups (b), the compound residues are residues
with the exclusion of the reactive substituent or a portion of the
reactive substituent (hydrogen, etc.) from a compound with at least
one reactive functional groups (b) and another reactive substituent
different from the reactive functional groups (b).
[0160] As examples of compound residues with ethylenic unsaturated
groups, there may be mentioned, specifically, residues with the
exclusion of a reactive substituent or a portion of a reactive
substituent (hydrogen, etc.), other than the ethylenic unsaturated
groups of the following compounds. For examples, there may be
mentioned (meth)-acrylic acid, hydroxyethyl(meth)acrylate,
hydroxypropyl-(meth)acrylate and pentaerythritol tri(meth)acrylate,
with no limitation to these.
[0161] The molecular weight of the polyalkylene oxide
chain-containing Polymer D in the invention is preferably greater
than 1000, even more preferably greater than 5000 and most
preferably greater than 10,000, from the viewpoint of imparting
flexibility to the cured film and preventing cracks.
[0162] As examples of commercially available products that include
a polyalkylene oxide chain-containing Polymer D represented by
chemical formula (4) above, there may be mentioned the trade name
BEAMSET 371 (product of Arakawa Chemical Industries, Ltd.), and the
trade name DIABEAM UK-4153 (product of Mitsubishi Rayon Co., Ltd.;
in chemical formula (4), X is (x-7), k is 3, L.sub.1-L.sub.3 are
each direct bonds, R.sub.1-R.sub.3 is ethylene, the total of n1, n2
and n3 is 20, and Y.sub.1-Y.sub.3 are acryloyloxy groups).
[0163] The content of Polymer D is preferably 5-100 parts by weight
and more preferably 10-50 parts by weight based on 100 parts by
weight of Compound E described hereunder. If the content of Polymer
D is 5 parts by weight or greater based on 100 parts by weight of
Compound E described hereunder, it will be possible to impart
flexibility and recovery properties to the cured film, while if it
is 100 parts or less by weight it will be possible to maintain the
hardness of the cured film.
2-2-1-2. Compound E Having Two or More Reactive Functional Groups
(b) and Having a Molecular Weight of Less than 10,000
[0164] Compound E, which has two or more reactive functional groups
(b) and a molecular weight of less than 10,000, together with the
reactive inorganic fine particles A described above, improves the
hardness of the cured resin composition film and provides a
function of imparting sufficient mar-proofness. Compounds with the
structure of Polymer D above are excluded from Compound E having
two or more reactive functional groups (b) and a molecular weight
of less than 10,000.
[0165] Compound E according to the invention may be appropriately
selected from among a wide range of compounds having reactive
functional groups (b) that can react with each other in the
combination of Polymer D and the reactive inorganic fine particles
A, and having sufficient mar-proofness. Compound E may be of a
single type, or an appropriate mixture of two or more types.
[0166] Compound E having two or more reactive functional groups (b)
and a molecular weight of less than 10,000 preferably has three or
more reactive functional groups (b) in the molecule from the
viewpoint of increasing the crosslink density of the cured film and
imparting hardness. When Compound E is an oligomer with a molecular
weight distribution, the number of reactive functional groups (b)
is the average number.
[0167] The molecular weight of Compound E is preferably less than
5000 from the viewpoint of improving hardness.
[0168] Concrete examples will now be provided, with the
understanding that Compound E used in the invention is not limited
to these examples.
[0169] As specific examples compounds with polymerizable
unsaturated groups, there may be mentioned polyfunctional
(meth)acrylate-based monomers with two or more polymerizable
unsaturated groups in the molecule, for example, difunctional
(meth)acrylate compounds such as 1,6-hexanediol di(meth)acrylate,
neopentylglycol di(meth)acrylate, ethyleneglycol di(meth)acrylate
and isocyanuric acid-ethylene oxide-modified di(meth)acrylate;
trifunctional (meth)acrylate compounds such as trimethylolpropane
tri(meth)acrylate and its EO, PO and epichlorhydrin-modified
products, pentaerythritol tri(meth)acrylate, glycerol
tri(meth)acrylate and its EO, PO and epichlorhydrin-modified
products, isocyanuric acid/EO-modified tri(meth)acrylate (ARONIX
M-315 by ToaGosei Co., Ltd.), tris(meth)acryloyloxyethyl phosphate,
(2,2,2-tri-(meth)acryloyloxymethyl)ethyl hydrogenphthalate, and
glycerol tri(meth)acrylate and its EO, PO and
epichlorhydrin-modified products; tetrafunctional (meth)acrylate
compounds such as pentaerythritol tetra(meth)acrylate and its EO,
PO and epichlorhydrin-modified products, and ditrimethylolpropane
tetra(meth)acrylate; pentafunctional (meth)acrylate compounds such
as dipentaerythritol penta(meth)acrylate and its EO, PO,
epichlorhydrin, fatty acid, alkyl and urethane-modified products;
and hexafunctional (meth)acrylate compounds such as
dipentaerythritol hexa(meth)acrylate and its EO, PO,
epichlorhydrin, fatty acid, alkyl and urethane-modified products,
and sorbitol hexa(meth)acrylate and its EO, PO, epichlorhydrin,
fatty acid, alkyl and urethane-modified products.
[0170] As examples of (meth)acrylate-based oligomers (or
prepolymers), there may be mentioned epoxy (meth)acrylates obtained
by addition reaction between glycidyl ethers and monomers with
(meth)acrylic acid or carboxylic acid groups; urethane
(meth)acrylates obtained by addition reaction between polyol and
polyisocyanate reaction products and hydroxyl-containing
(meth)acrylates, polyester acrylates obtained by esterification of
(meth)acrylic acid with polyester polyols composed of polyols and
polybasic acids; and polybutadiene (meth)acrylates which are
(meth)acrylic compounds with polybutadiene or hydrogenated
polybutadiene backbones. When the reactive functional groups (b) of
the essential components according to the invention are
polymerizable unsaturated groups, urethane (meth)acrylate is
preferably used from the viewpoint of imparting hardness and
flexibility to the cured film.
[0171] As examples of glycidyl ethers to be used for the
aforementioned epoxy (meth)acrylates, there may be mentioned
1,6-hexanediglycidyl ether, polyethyleneglycolglycidyl ether,
bisphenol A epoxy resin, naphthalene-based epoxy resin, cardo epoxy
resins, glycerol triglycidyl ether and phenol-novolac-type epoxy
resins.
[0172] As examples of polyols to be used for the aforementioned
urethane (meth)acrylates, there may be mentioned
1,6-hexanediglycidyl ether, polyethylene glycol, polypropylene
glycol, polytetramethylene glycol, polycaprolactonediol,
polycarbonatediol, polybutadiene polyol and polyester diol. As
polyisocyanates to be used for the aforementioned urethane
(meth)acrylates, there may be mentioned tolylene diisocyanate,
xylylene diisocyanate, diphenylmethane diisocyanate,
tetramethylxylene diisocyanate, hexamethylene diisocyanate,
isophorone diisocyanate and dicyclohexylmethane diisocyanate. As
hydroxyl-containing (meth)acrylates to be used for the
aforementioned urethane (meth)acrylates, there may be mentioned
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
4-hydroxybutyl (meth)acrylate, pentaerythritol (meth)acrylate and
caprolactone-modified 2-hydroxyethyl (meth)acrylate.
[0173] As examples of polyols for formation of polyester polyols to
be used for the aforementioned polyester acrylates, there may be
mentioned ethylene glycol, polyethylene glycol, propylene glycol,
polypropylene glycol, neopentyl glycol, 1,4-butanediol,
trimethylolpropane and pentaerythritol, and as examples of
polybasic acids, there may be mentioned succinic acid, adipic acid,
sebacic acid, phthalic acid, isophthalic acid, terephthalic acid,
trimellitic acid and pyromellitic acid.
[0174] As Compound E to be used in the invention, there may also be
used polymers represented by chemical formula (5) below, having a
molecular weight of less than 10,000.
##STR00006##
[0175] In chemical formula (5), L' represents a C.sub.1-10 linking
group and q represents 0 or 1. R represents hydrogen or a methyl
group. E represents any vinyl monomer polymerization unit, and it
may consist of a single component or more than one component. The
letters o and p represent the molar percentages of each
polymerization unit. The letter p may also be 0.
[0176] In chemical formula (5), L' represents a C.sub.1-10 linking
group, more preferably a C.sub.1-6 linking group and most
preferably a C.sub.2-4 linking group, and it may have a
straight-chain or branched structure, or even a cyclic structure,
and may also contain heteroatoms selected from among O, N and
S.
[0177] As preferred examples of the linking group L' in chemical
formula (5), there may be mentioned *-(CH.sub.2).sub.2--O-**,
*-(CH.sub.2).sub.2--NH-**, *-(CH.sub.2).sub.4--O-**,
*-(CH.sub.2).sub.6--O-**, *-(CH.sub.2).sub.2--O--(CH).sub.2--O-**,
*-CONH--(CH.sub.2).sub.3--O-**, *-CH.sub.2CH(OH)CH.sub.2--O-**,
*-CH.sub.2CH.sub.2OCONH(CH.sub.2).sub.3--O-**. Here, the "*" symbol
denotes linking sites on the main chain of the polymer, and "**"
denotes linking sites on the (meth)acryloyl group end.
[0178] In chemical formula (5), R represents hydrogen or a methyl
group, but it is more preferably hydrogen from the viewpoint of
curing reactivity. Also in chemical formula (5), o may be 100 mol
%, i.e. it may be a single polymer. Even if o is 100 mol %, it may
be a copolymer obtained using a mixture of two or more different
polymerization units containing (meth)acryloyl groups represented
by o mol %. The ratio of o and p is not particularly restricted,
and may be appropriately selected from the viewpoint of hardness,
solubility in solvents, transparency and the like.
[0179] In chemical formula (5), E represents any vinyl monomer
polymerization unit, and is not particularly restricted and may be
appropriately selected from the viewpoint of hardness, solubility
in solvents, transparency and the like, while it may also be
composed of a single or multiple vinyl monomers, depending on the
purpose.
[0180] Specifically, there may be mentioned vinyl ethers such as
methylvinyl ether, ethylvinyl ether, t-butylvinyl ether,
cyclohexylvinyl ether, isopropylvinyl ether, hydroxyethylvinyl
ether, hydroxybutylvinyl ether, glycidylvinyl ether and allylvinyl
ether; vinyl esters such as vinyl acetate, vinyl propionate and
vinyl butyrate; (meth)acrylates such as methyl (meth)acrylate,
ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, glycidyl
methacrylate, allyl (meth)acrylate and
(meth)acryloyloxy-propyltrimethoxysilane; styrene derivatives such
as styrene and p-hydroxymethylstyrene; and unsaturated carboxylic
acids such as crotonic acid, maleic acid and itaconic acid, as well
as derivatives thereof.
[0181] There may also be used reactive oligomers with
weight-average molecular weights of less than 10,000 and having
ethylenic double bond groups at the ends or on side chains. As
reactive oligomers, there may be mentioned ones whose backbone
components are polymethyl (meth)acrylate, polystyrene, polybutyl
(meth)acrylate, poly-(acrylonitrile/styrene), poly(2-hydroxymethyl
(meth)-acrylate/methyl (meth)acrylate) or poly(2-hydroxymethyl
(meth)acrylate/butyl (meth)acrylate), as well as copolymers of
these resins with silicone resins.
[0182] Commercially available products may be used for the
aforementioned compounds. As urethane acrylates with weight-average
molecular weights of less than 10,000 and having two or more
polymerizable unsaturated groups, there may be mentioned AH-600,
AT-600, UA-306H, UA-306T and UA-306I, trade names of Kyoeisha
Chemical Co., Ltd.; UV-1700B, UV-3000B, UV-3200B, UV-6300B,
UV-6330B and UV-7000B, trade names of Nippon Synthetic Chemical
Industry Co., Ltd.; BEAMSET 500 Series (502H, 504H, 550B), trade
names of Arakawa Chemical Industries, Ltd.; U-6HA, U-15HA, UA-32P
and U-324A, trade names of Shin-Nakamura Chemical Co., Ltd.; and
M-9050, trade name of ToaGosei Co., Ltd. Urethane (meth)acrylates
among the above that are preferred for combination with Polymer D
according to the invention include urethane (meth)acrylates
obtained by reacting isophorone diisocyanate monomers or multimers
with pentaerythritol polyfunctional acrylate and dipentaerythritol
polyfunctional acrylate. As an example of a commercially available
urethane (meth)acrylates, there may be mentioned the trade name
UV-1700B (product of Nippon Synthetic Chemical Industry Co.,
Ltd.).
[0183] As epoxy acrylates with weight-average molecular weights of
less than 10,000 and having two or more polymerizable unsaturated
groups, there may be mentioned the SP Series (SP-4060, 1450) and VR
Series (VR-60, 1950; VR-90, 1100), trade names of Showa HighPolymer
Co., Ltd.; UV-9100B and UV-9170B, trade names of Nippon Synthetic
Chemical Industry Co., Ltd.; and EA-6320/PGMAc and EA-6340/PGMAc,
trade names of Shin-Nakamura Chemical Co., Ltd.
[0184] As reactive oligomers with weight-average molecular weights
of less than 10,000 and having two or more polymerizable
unsaturated groups, there may be mentioned the Macromonomer Series
AA-6, AS-6, AB-6 and AA-714SK, trade names of ToaGosei Co.,
Ltd.
2-3. Leveling Agent A of Hard Coat Layer
[0185] According to the invention, the leveling agent is an
essential component of the hard coat layer, and at least one type
thereof is a (non-reactive) leveling agent A that has neither
functional groups that react under ionizing radiation nor polar
groups that react under heat. It will therefore lack reactivity
with any of the components contained in the hard coat or other
layers, especially the low refractive index layer. It has the
function of improving the flatness (smoothness) of the surface of
the layer containing the leveling agent, and appropriate selection
of the type of leveling agent will help impart the surface of the
hard coat layer or low refractive index layer with functions such
as antifouling properties, fingerprint wiping and
mar-proofness.
[0186] As such leveling agents, there may be mentioned
fluorine-based leveling agents, silicon-based leveling agents and
olefin-based leveling agents, and as mentioned above, at least one
type of leveling agent A is characterized by being
non-reactive.
[0187] One leveling agent or a mixture of two or more different
ones may be used in the curable binder system of the hard coat
layer. Particularly preferred as leveling agents A to be included
in the curable binder system of the hard coat layer are fluorinated
compounds containing perfluoro groups.
[0188] According to the invention, a non-reactive fluorine-based
leveling agent is a compound that necessarily contains a
fluorinated alkyl group, and it is a non-reactive compound
containing absolutely no functional groups that can react under
ionizing radiation or heat. If the molecular weight of the
non-reactive fluorine-based leveling agent is too low, it will tend
to cause repulsion during coating and hamper workability, while if
the molecular weight is too high, the compatibility with the binder
in the hard coat layer-forming composition will be impaired, making
it impossible to obtain a satisfactory coated film. The
weight-average molecular weight will, therefore, usually be
5000-500,000, preferably 10,000-300,000 and more preferably
20,000-200,000. The weight-average molecular weight may be measured
by gel permeation chromatography (GPC), based on polystyrene. The
solvent in the GPC mobile phase for use may be tetrahydrofuran or
chloroform. The measuring column may be a combination of
commercially available columns for tetrahydrofuran or chloroform.
As examples of commercially available columns for tetrahydrofuran,
there may be mentioned Shodex GPC KF-801, GPC KF-802, GPC KF-803,
GPC KF-804, GPC KF-805, GPC KF-806 and GPC-KF800D (all trade names
of the products of Showa Denko K.K.). The detectors used may be an
RI (differential refractive index) detector and a UV detector. The
solvent, column and detectors may be used in a GPC system such as
Shodex GPC-101 (product of Showa Denko K.K.) for appropriate
measurement of the weight-average molecular weight.
[0189] The fluorine-based leveling agent is preferably a
fluorinated compound with a fluorinated alkyl group represented by
the general formula F(CF.sub.2).sub.2nCH.sub.2CH.sub.2-- (where n
is an integer of 1-10). The fluorinated alkyl group may either be a
perfluoroalkyl group wherein all of the hydrogens of the alkyl
group are replaced with fluorine atoms, or a group wherein a
portion of the hydrogens of the alkyl group are replaced with
fluorine atoms (for example, HCF.sub.2CF.sub.2CF.sub.2CF.sub.2--),
and it may be straight-chain or branched. The fluorinated alkyl
group may also contain oxygen atoms (for example,
CF.sub.3--(OCF.sub.2CF.sub.2).sub.2--).
[0190] As the fluorinated compounds, there may be mentioned,
specifically, compounds represented by the following general
formula:
(A)w-(B)x-(C)y-CF.sub.3
(wherein
[0191] A represents one or more groups selected from the group
consisting of CF.sub.2, CFCF.sub.2, C(CF.sub.2).sub.2 and
(CF.sub.2).sub.2nCH.sub.2CH.sub.2,
[0192] B represents one or more groups selected from the group
consisting of OCF.sub.2CF.sub.2, OCF.sub.2CF(CF.sub.2),
OCF.sub.2C(CF.sub.2).sub.2, OCF (CF.sub.2) CF (CF.sub.2), OCF
(CF.sub.2) C(CF.sub.2).sub.2, OC(CF.sub.2).sub.2CF (CF.sub.2) and
OC(CF.sub.2).sub.2C(CF.sub.2).sub.2,
[0193] C represents one or more groups selected from the group
consisting of OCH.sub.2CH.sub.2, OCH.sub.2CH.sub.2CH.sub.2 and
OC(O) (CH.sub.2)z, and
[0194] w, x, y and z represent integers of 0-50).
[0195] The number of carbon atoms in the fluorinated alkyl group is
normally an integer of 1-20, preferably of 3-12 and most preferably
of 6-10, from the viewpoint of achieving high surface-active
performance. It is preferably a straight-chain perfluoroalkyl
group. Higher fluorine atom content in the compound will result in
more excellent surface-active performance, but because surfactants
with high fluorine atom contents have poor compatibility with
resins and solvents, the fluorine atom content of the leveling
agent compound will usually be 5-50%, preferably 7-35% and most
preferably 10-30 wt %. The fluorine atom content may be calculated
by burning the leveling agent compound for decomposition,
extracting the decomposition product with water or alkali water,
and quantifying the fluorine ion concentration by ion
chromatography.
[0196] As examples of commercially available fluorinated compounds
that satisfy the structure and performance described above, there
may be mentioned among others, the MEGAFAC Series (MCF350-5, F445,
F444, F455, F178, F470, F475, F479, F477, TF1025, F478, F178K) by
Dainippon Ink & Chemicals, Inc., as well as the TSF Series by
Momentive Materials Performance, Inc. Japan Joint Venture (Toshiba
Silicone), the X22 Series and KF Series by Shin-Etsu Chemical Co.,
Ltd., and the SILOPRENE Series by Chisso Corp.
[0197] The total content of the leveling agent in the curable
binder system of the hard coat layer is preferably from 0.01 wt %
to 5 wt % and more preferably from 0.03 wt % to 2 wt % based on the
total weight of the binder when no reactive inorganic fine
particles A are present, or based on the total weight of the
reactive inorganic fine particles A and binder C. A content of
greater than 0.01 wt % can impart sufficient flatness (smoothness)
to the hard coat layer surface. A content of greater than 5 wt %
will increase the amount of leveling agent A that migrates into the
low refractive index layer described hereunder and tend to cause
phase separation with the leveling agent B in the low refractive
index layer-forming composition described hereunder, at the low
refractive index layer surface, thus undesirably lowering the
transparency due to increased opacity and haze of the low
refractive index layer. By limiting the leveling agent content to
from 0.03 wt % to 2 wt %, a portion of the leveling agent A in the
hard coat layer-forming composition will migrate into the surface
of the low refractive index layer and become uniformly distributed,
when the hard coat layer is half-cured, the half-cured hard coat
layer is subsequently coated with the low refractive index
layer-forming composition described hereunder and then fully cured.
This will allow the antireflection film composed of the hard coat
layer and low refractive index layer to exhibit excellent
antifouling properties, fingerprint wiping and mar-proofness on the
film surface.
[0198] According to the invention, the concentration of the
leveling agent may be measured using an XPS (X-ray Photoelectron
Spectroscopy) apparatus (VG Theta Probe) by Thermo Electron Corp.,
for example.
2-3-1. Polymerization Initiator
[0199] According to the invention, radical polymerization
initiators, cationic polymerization initiators and radical and
cationic polymerization initiator combinations may be appropriately
selected for use as components in the curable binder system, as
necessary in order to initiate or promote polymerization of the
radical-polymerizing functional groups or cationic polymerizable
functional groups. These polymerization initiators are decomposed
by light irradiation and/or heat to generate radicals or cations
and promote radical polymerization and cationic polymerization.
[0200] The radical polymerization initiator may be one capable of
under light irradiation and/or heat releasing a substance that
initiates radical polymerization. As examples of photoradical
polymerization initiators, there may be mentioned imidazole
derivatives, bisimidazole derivatives, N-arylglycine derivatives,
organic azide compounds, titanocenes, aluminate complexes, organic
peroxides, N-alkoxypyridinium salts, thioxanthone derivatives and
the like, and more specifically,
1,3-di(tert-butyldioxycarbonyl)benzophenone,
3,3',4,4'-tetrakis-(tert-butyldioxycarbonyl)benzophenone,
3-phenyl-5-isooxazolone, 2-mercaptobenzimidazole,
bis(2,4,5-triphenyl)-imidazole,
2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE 651, trade name of
Ciba Specialty Chemicals Co., Ltd.),
1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184, trade name of
Ciba Specialty Chemicals Co., Ltd.),
2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one
(IRGACURE 369, trade name of Ciba Specialty Chemicals Co., Ltd.)
and
bis(.eta.5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-
-phenyl)titanium) (IRGACURE 784, trade name of Ciba Specialty
Chemicals Co., Ltd.), although there is no limitation to these.
[0201] The cationic polymerization initiator may be one capable of
under light irradiation and/or heat releasing a substance that
initiates cationic polymerization. As examples of cationic
polymerization initiators, there may be mentioned sulfonic acid
esters, imide sulfonates, dialkyl-4-hydroxysulfonium salts,
aryl-p-nitrobenzyl sulfonate esters, silanol-aluminum complexes,
(.eta.16-benzene)(.eta.15-cyclopentadienyl)iron(II) and the like,
and more specifically, benzoin tosylate, 2,5-dinitrobenzyl tosylate
and N-tosyphthalic acid imide, although there is no limitation to
these.
[0202] Examples of radical polymerization initiators, which may
also be used as cationic polymerization initiators, include
aromatic iodonium salts, aromatic sulfonium salts, aromatic
diazonium salts, aromatic phosphonium salts, triazine compounds,
iron arene complexes and the like, and more specifically iodonium
salts including chlorides, bromides, fluoroborates,
hexafluorophosphates and hexafluoroantimonates of iodoniums such as
diphenyliodonium, ditolyliodonium, bis(p-tert-butylphenyl)iodonium
and bis(p-chlorophenyl)iodonium, sulfonium salts including
chlorides, bromides, fluoroborates, hexafluorophosphates and
hexafluoroantimonates of sulfoniums such as triphenyl-sulfonium,
4-tert-butyltriphenylsulfonium and tris(4-methylphenyl)sulfonium,
and 2,4,6-substituted-1,3,5-triazine compounds such as
2,4,6-tris(trichloromethyl)-1,3,5-triazine,
2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine and
2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine.
2-3-2. Other Components
[0203] The hard coat layer of the invention may also contain
antistatic agents and anti-glare agents as other components to be
added to the curable binder system as appropriate. Various
additives such as sensitizing agents may also be included.
Including an antistatic agent and/or anti-glare agent can further
impart an antistatic property and/or anti-glare property to the
hard coat layer of the invention.
2-4. Hard Coat Layer-Forming Composition
[0204] The hard coat layer-forming composition is prepared by
dispersing the mixture of the curable resin and the at least one
leveling agent (leveling agent A) as the essential components, in
admixture with desired components as necessary, in a solvent by an
ordinary preparation method. The composition may then be coated on
a transparent base material and dried and cured to form a hard coat
layer. A method for preparing the solvent and the hard coat
layer-forming composition will now be explained.
2-4-1. Solvent
[0205] As specific examples of solvents, there may be mentioned
alcohols such as methanol, ethanol, isopropyl alcohol, butanol,
isobutyl alcohol, methyl glycol, methyl glycol acetate,
methylcellosolve, ethylcellosolve and butylcellosolve; ketones such
as acetone, methyl ethyl ketone, methyl isobutyl ketone,
cyclohexanone and diacetone alcohol; esters such as methyl formate,
methyl acetate, ethyl acetate, ethyl lactate and butyl acetate;
nitrogen-containing compounds such as nitromethane,
N-methylpyrrolidone and N,N-dimethylformamide; ethers such as
diisopropyl ether, tetrahydrofuran, dioxane and dioxolane;
halogenated hydrocarbons such as methylene chloride, chloroform,
trichloroethane and tetrachloroethane; and other solvents such as
dimethyl sulfoxide and propylene carbonate; as well as mixtures of
the foregoing. As more preferred solvents, there may be mentioned
methyl acetate, ethyl acetate, butyl acetate and methyl ethyl
ketone.
[0206] Particularly preferred for use among these solvents are
ketone-based organic solvents. Preparing the coating solution using
a ketone-based solvent will facilitate thin and even coating onto
the surface of transparent base materials or hard coat layers, and
the evaporation rate of the solvent after coating will be suitable
enough to prevent drying irregularities, thus facilitating
formation of large-area coated films with uniform thicknesses.
[0207] As ketone-based solvents, there may be mentioned simple
solvents comprising one type of ketone, mixed solvents comprising
two or more ketones, and complex mixed solvents that contain other
solvents in addition to one or more ketone-based solvents and that
still retain the properties of the ketone solvents. Complex mixed
solvents are preferred among these, in which case the ketone-based
solvents are preferably used in a proportion of greater than 70 wt
% and especially greater than 80 wt % of the total solvent.
2-4-2. Preparation of Hard Coat Layer-Forming Composition
[0208] The hard coat layer-forming composition is usually prepared
by mixing the curable resin and the at least one leveling agent
(leveling agent A) as the essential components, in admixture with
desired components as necessary, with a solvent by an ordinary
preparation method, and dispersing the mixture. The mixing and
dispersion may be carried out using a paint shaker or bead
mill.
3. Low Refractive Index Layer
[0209] The low refractive index layer of the invention has a lower
refractive index than the hard coat layer that is adjacent to the
transparent base material side, and it has the function of
increasing the visibility of the antireflection film comprising the
hard coat layer and the low refractive index layer.
[0210] The low refractive index layer of the invention is obtained
by coating, drying and curing the low refractive index
layer-forming composition described hereunder, and it contains at
least a curable binder containing a curable resin, and two or more
leveling agents, as essential components of the layer. Of the two
different leveling agents, at least one is the same as the one
contained in the hard coat layer, i.e. leveling agent A, and at
least one is leveling agent B which is reactive with the binder and
crosslinks with the binder during the curing described hereunder.
The low refractive index layer of the invention is obtained by
half-curing the hard coat layer, and then coating the hard coat
layer with the low refractive index layer-forming composition and
fully curing the half-cured hard coat layer and the low refractive
index layer-forming composition. At this time, the leveling agent A
in the hard coat layer migrates from the half-cured hard coat layer
into the low refractive index layer.
[0211] The curable resin of the low refractive index layer is
preferably an ionizing radiation-curable resin (binder component).
In order to lower the refractive index of the low refractive index
layer, it is preferred to include low refractive index fine
particles, and using hollow fine particles as the low refractive
index fine particles is preferred in order to help lower the
refractive index. Solid fine particles are also preferably included
to increase the hardness of the low refractive index layer, which
is insufficient with hollow fine particles alone.
[0212] As hollow fine particles and solid fine particles, there are
preferably used reactive hollow fine particles and reactive solid
fine particles modified with crosslink-forming groups on the
surfaces of the fine particles that allow formation of crosslinking
with the ionizing radiation curable resin, in order to improve the
hardness of the low refractive index layer. Most preferably, the
crosslink-forming groups of the reactive hollow fine particle
surfaces and the crosslink-forming groups of the reactive solid
fine particle surfaces either have the same structure or, even if
they have differing structures, the structures are similar in that
the ionizing radiation curable groups have the same backbone and
differ only in the presence or absence of one C.sub.1-3 hydrocarbon
group, the bonding groups for the particle surfaces have the same
backbone and differ only in the presence or absence of one
C.sub.1-3 hydrocarbon group, and the spacer portions have the same
backbone and differ only in the presence or absence of one
C.sub.1-3 hydrocarbon group or one functional group with 1-3
constituting atoms including heteroatoms and excluding hydrogen, or
differ only in 1-2 carbons for the carbon chain length of the
backbone. Such crosslink-forming groups help prevent aggregation
between the reactive hollow fine particles and aggregation between
the reactive solid fine particles, so that the reactive hollow fine
particles and the reactive solid fine particles will pack more
evenly and densely to improve the hardness of the low refractive
index layer.
[0213] As a preferred example for the low refractive index layer of
the invention, there will now be described a low refractive index
layer-forming composition comprising hollow fine particles and
solid fine particles having the particle surfaces modified by
crosslink-forming groups with numerous intersections, an ionizing
radiation curable resin, and a curable binder containing at least
one type of leveling agent B.
[0214] The low refractive index layer of the invention preferably
has a refractive index of less than 1.45. A refractive index in
this range can yield a low refractive index layer with
anti-reflection performance that is satisfactory for practical use.
The refractive index may be controlled by appropriate adjustment of
the type of ionizing radiation curable resin, the materials and
sizes of the hollow fine particles and solid fine particles and the
mixing ratio of each material included in the low refractive index
layer. The refractive index is preferably near the refractive index
of air (=1), but in practice the lower limit for the refractive
index will be 1.1. The refractive index may be measured by a known
method in the prior art without any particular restrictions. For
example, it may be calculated by simulation from a reflectance
curve obtained using a spectrophotometer, or by measurement using
an ellipsometer.
[0215] For the low refractive index layer of the invention, the
mean particle size is the 50% particle size (d50: median diameter),
where the particles in the solution are measured by the dynamic
light scattering method before curing and the particle size
distribution is expressed as cumulative distribution. The mean
particle size can be measured using a Microtrac particle size
analyzer by Nikkiso Co., Ltd. The mean particle size in the film
can be measured using a transmission electron microscope (TEM).
Specifically, the particles are observed at 50-2,000,000.times.
magnification, and the average value for 100 observed particles is
recorded as the mean particle size.
[0216] The film thickness of the low refractive index layer is
preferably from 0.05 .mu.m to 0.15 .mu.m from the viewpoint of
mar-proofness.
[0217] The structural materials of the low refractive index layer
of the invention will now be described.
3-1-1. Hollow Fine Particles
[0218] The hollow fine particles of the invention are fine
particles having an outer shell layer, where the interior
surrounded by the outer shell layer is porous or hollow. Air
(refractive index: 1) is present in the porous or hollow sections,
and inclusion of hollow fine particles to the low refractive index
layer can reduce the refractive index of the layer.
[0219] The material of the hollow fine particles of the invention
may be inorganic or organic. An inorganic material is preferred in
consideration of productivity and strength. In this case, the outer
shell layer is formed of an inorganic material.
[0220] When the hollow fine particles are formed of an inorganic
material, the material of the hollow fine particles is preferably
at least one selected from the group consisting of metal oxides,
metal nitrides, metal sulfides and metal halides. Using such
materials for the hollow fine particles will yield fine particles
having outer shells with high strength that are resistant to
crushing by external pressure. More preferably, the material of the
hollow fine particles is a metal oxide or metal halide, and most
preferably a metal oxide or metal fluoride. Using such materials
can provide hollow fine particles with high strength and a low
refractive index.
[0221] As metal elements to be used in metal oxides, there are
preferred Na, K, Mg, Ca, Ba, Al, Si and B, with Mg, Ca, Al and Si
being more preferred. Using such metal elements will result in a
low refractive index and can yield hollow fine particles that are
easier to produce than with other elements. One type of metal
element may be used, or two or more different ones may be used in
combination.
[0222] As specific preferred examples of organic fine particles
with voids there may be mentioned hollow polymer fine particles
prepared by the technique disclosed in Japanese Unexamined Patent
Publication No. 2002-80503.
[0223] When the hollow fine particles of the invention are formed
of a metal oxide, it is particularly preferred to use hollow fine
particles composed of silica (silicon dioxide: SiO.sub.2), in
consideration of the material refractive index and productivity.
Hollow silica fine particles have fine voids in the interiors, and
air having a refractive index of 1 is also present in the fine
particle interiors. Consequently, the refractive indexes of the
fine particles themselves are lower than the solid fine particles
and the ionizing radiation curable resin, thus allowing the
refractive index of the refractive index layer containing the fine
particles to be reduced. In other words, the hollow silica fine
particles with voids have a refractive index as low as 1.20-1.45
compared to hollow silica fine particles containing no air in the
interior (refractive index n=.about.1.46), thus allowing the
refractive index of the refractive index layer to be no greater
than 1.45.
[0224] The thickness of the outer shell layers of the hollow fine
particles of the invention is normally greater than 1 nm, and is
preferably greater than 2 nm. An outer shell layer thickness in
this range permits satisfactory covering of the fine particles, and
can prevent infiltration of other components such as the ionizing
radiation curable resin into the fine particles. As a result, the
hollow or porous structure in the interiors is not reduced, making
it easier to obtain the effect of the low refractive index. The
thickness of the outer shell layers of the hollow fine particles is
also usually less than 30 nm and is preferably less than 20 nm. An
outer shell layer thickness in this range can provide a low
refractive index effect without lowering the porosity of the fine
particles.
3-1-2. Process for Production of Hollow Fine Particles
[0225] An example of a process for production of hollow silica fine
particles will now be explained, as a process for production of
hollow fine particles.
[0226] The type of hollow silica fine particles is not particularly
restricted so long as they have a refractive index of less than
1.44. As such hollow silica fine particles, there may be mentioned
the complex oxide sol or hollow silica fine particles disclosed in
Japanese Unexamined Patent Publication HEI No. 7-133105 and
Japanese Unexamined Patent Publication No. 2001-233611, for
example. Such hollow silica fine particles may be produced,
specifically, by the following first to third steps, as well as by
the fourth step, described below.
[0227] As the first step, separate aqueous alkali solutions of a
silica starting material and inorganic oxide starting material
other than silica are prepared, or a mixed aqueous solution
containing both starting materials is prepared. The aqueous
solution is then gradually added to an aqueous alkali solution with
a pH of greater than 10 while stirring, according to the proportion
desired for the complex oxide. This yields colloidal particles
composed of the complex oxide. A dispersion containing seed
particles may be used as the starting material instead of the first
step.
[0228] As used herein, seed particles are particles that can be
used to form a hollow or porous structure during preparation of
hollow fine particles, and the particles are used as seed to grow
the particles into nucleus particles. Next, all or a portion of the
nucleus particles are removed in the second step to form the hollow
or porous structure. Using seed particles facilitates control of
the particle sizes of the growing particles, to obtain fine nucleus
particles with uniform particle sizes.
[0229] Next, in the second step, at least some of the elements
other than silicon and oxygen are selectively removed from the
colloidal particles composed of the complex oxide obtained in the
previous step. Specifically, the elements in the complex oxide are
removed by dissolution using a mineral acid or organic acid, or
they are contacted with a cation-exchange resin for ion exchange
removal. This yields colloidal particles of the complex oxide
having a portion of the elements removed.
[0230] Subsequently, in the third step, a hydrolyzable organic
silicon compound or silicic acid solution is added to the colloidal
particles of the complex oxide from which a portion of the elements
have been removed and which has been obtained in the previous step,
to cover the surfaces of the colloidal particles with a polymer of
the hydrolyzable organic silicon compound or silicic acid solution.
This produces silica fine particles as a complex oxide sol, as
described in the publications mentioned above.
[0231] As hydrolyzable organic silicon compounds, there may be used
alkoxysilanes represented by the general formula R.sub.nSi
(OR').sub.4-n (where R and R' represent hydrocarbon groups such as
alkyl, aryl, vinyl or acryl, and n=0, 1, 2 or 3). Most preferred
for use are tetraalkoxysilanes such as tetramethoxysilane,
tetraethoxysilane and tetraisopropoxy-silane.
[0232] The method of addition may involve, for example, adding a
solution containing a small amount of an alkali or acid added as a
catalyst to a mixture of the alkoxysilane, purified water and
alcohol, to the colloidal particles obtained in the second step,
and hydrolyzing the alkoxysilane to produce a silicic acid polymer
that is deposited on the surfaces of the colloidal particles. The
alkoxysilane, alcohol and catalyst may also be added simultaneously
to the colloidal particles. As alkali catalysts, there may be used
ammonia, alkali metal hydroxides and amines. As acid catalysts,
there may be used various inorganic acids and organic acids.
[0233] When the dispersing medium for the colloidal particles is
water alone, or when the proportion of water with respect to the
organic solvent is high, coating treatment can be accomplished with
a silicic acid solution. A silicic acid solution is an aqueous
solution of a low silicic acid polymer that has been dealkalized by
ion exchange treatment of an aqueous solution of an alkali metal
silicate such as water glass. When a silicic acid solution is used,
a prescribed amount of the silicic acid solution is added to the
colloidal particles and an alkali is simultaneously added for
polymerization and gelling of the silicic acid solution, whereby
the silicic acid polymer is deposited onto the colloidal particle
surfaces. The silicic acid solution may also be used in combination
with the alkoxysilane for coating treatment. The amount of organic
silicon compound or silicic acid solution added is an amount
sufficient to cover the surfaces of the colloidal particles with
each polymer.
[0234] As a fourth step, the silica fine particles obtained from
the third step are preferably subjected to hydrothermal treatment
at 50-300.degree. C. A hydrothermal treatment temperature of
50.degree. C. or higher will effectively lower the content of the
alkali metal oxide and/or ammonia in the finally obtained silica
fine particles or silica fine particles dispersion, thus improving
the shelf life of the coating solution and the strength of the
coating. Also, limiting the hydrothermal treatment temperature to
300.degree. C. or lower will improve the shelf life of the coating
solution and the strength of the coating, and will prevent
aggregation of the silica fine particles.
[0235] The silica fine particles obtained up to the third step will
tend to have low molecular compounds as ionic impurities on the
fine particle surfaces. The ionic impurities are those present in
the fine particle starting material and derived from the additives
added during the production steps. Removing the ionic impurities by
hydrothermal treatment in the fourth step will help limit the level
of impurities on the silica fine particle surfaces to below the
prescribed level.
[0236] Specifically, the content of alkali metal oxides in the
silica fine particles is preferably less than 10 ppm, even more
preferably less than 5 ppm and most preferably less than 2 ppm. The
alkali metal oxide content is most preferably less 5 ppm in order
to improve the stability of the coating solution containing the
silica fine particles. This will limit increase in the viscosity of
the coating solution even when the coating solution is stored for
long periods, thus resulting in an excellent shelf life. If the
alkali metal oxide content is within the range specified above, it
is presumed that this will more reliably produce reaction between
the silica fine particle surfaces and the compound such as a silane
coupling agent used to introduce the crosslink-forming groups, thus
resulting in improved strength of the refractive index layer (this
will be described below in regard to the silane coupling agent).
Also, by limiting the alkali metal oxide content to less than 10
ppm, it is possible to improve the film formability and the
strength of the obtained film. The alkali metal oxide content is
the content of M.sub.2O (where M represents an alkali metal
element), and it can usually be measured by atomic absorption or
ICP MS.
[0237] The content of ammonia (including ammonium ion) in the
silica fine particles is preferably less than 2000 ppm, even more
preferably less than 1500 ppm and most preferably less than 1000
ppm. The ammonia content is most preferably less than 1500 ppm in
order to improve the stability of the coating solution containing
the silica fine particles. This will limit increase in the
viscosity of the coating solution even when the coating solution is
stored for long periods, thus resulting in excellent shelf life. If
the ammonia content is within the range specified above, it is
presumed that this will more reliably produce reaction between the
silica fine particle surfaces and the compound such as a silane
coupling agent used to introduce the crosslink-forming groups, thus
resulting in improved strength of the refractive index layer. Also,
by limiting the ammonia content to less than 2000 ppm, it is
possible to improve the film formability and the strength of the
obtained film. The content of ammonia (including ammonium ions) in
the silica fine particles is the content as NH3, and it can usually
be measured by chemical analysis.
[0238] The fourth step (hydrothermal treatment step) can be
repeated several times in order to limit the content of impurity
compounds in the silica fine particles to the range specified
above. By repeating hydrothermal treatment, it is possible to
reduce the content of alkali metal oxides and/or ammonia (including
ammonium ions) in the obtained silica-based fine particles.
3-2-1. Solid Fine Particles
[0239] The solid fine particles of the invention are fine particles
without pores or hollow sections in the fine particles. Because
they lack voids, they are more resistant to pressure exerted on the
fine particles (external pressure) than hollow fine particles, and
thus have excellent pressure resistance. They can, therefore,
improve the mar-proofness of the refractive index layer containing
the solid fine particles.
[0240] The material of the solid fine particles of the invention
may be inorganic or organic. An inorganic material is preferably
used from the viewpoint of improving the strength of the refractive
index layer against pressing force.
[0241] When the solid fine particles are formed of an inorganic
material, the material of the solid fine particles is preferably at
least one selected from the group consisting of metal oxides, metal
nitrides, metal sulfides and metal halides. Using such materials
for the solid fine particles can stably yield high-strength fine
particles.
[0242] More preferably, the material of the solid fine particles is
a metal oxide or metal halide, and most preferably a metal oxide or
metal fluoride. Using such materials can further lower the
refractive index, and provide more satisfactory performance as an
anti-reflection layer.
[0243] As metal elements to be used for metal oxides, there are
preferred Na, K, Mg, Ca, Ba, Al, Si and B, with Mg, Ca, Al and Si
being more preferred. Using such metal elements can increase the
strength and lower the refractive index. One type of metal element
may be used, or two or more different ones may be used in
combination.
[0244] According to the invention, the refractive index of the
solid fine particles is preferably lower than the refractive index
of the ionizing radiation curable resin in order to further lower
the refractive index of the refractive index layer. The refractive
index of silica (SiO.sub.2) is 1.42-1.46, which is lower than the
refractive index of 1.49-1.55 for an acrylic-based resin that is
preferably used as the ionizing radiation curable resin. Therefore,
silica (SiO.sub.2) is most preferably used as the material of the
solid fine particles.
3-2-2. Process for Production of Solid Fine Particles
[0245] The solid fine particles may be produced by a known
production process in the prior art As examples of such processes,
there may be mentioned chemical processes such as sol-gel processes
and physical processes such as gas vapor deposition processes.
3-3. Relationship Between Reactive Hollow Fine Particles and
Reactive Solid Fine Particles
[0246] According to one embodiment of the low refractive index
layer of the invention, the mean particle size F of the reactive
solid fine particles and the mean particle size G of the reactive
hollow fine particles in the low refractive index layer preferably
have the following relationship:
10 nm.ltoreq.F.ltoreq.40 nm;
30 nm.ltoreq.G.ltoreq.60 nm; and
F.ltoreq.G
and more preferably F+10.ltoreq.G.
[0247] The low refractive index layer of the invention preferably
contains 5-50 parts by weight of hollow fine particles based on 100
parts by weight of solid fine particles. Within this range, the
reactive solid fine particles fill in the gaps between the reactive
hollow fine particles in the low refractive index layer, thus
allowing more dense packing and providing a particularly high
effect of improving the mar-proofness and especially steel wool
resistance of the layer surface.
[0248] According to another embodiment of the low refractive index
layer of the invention, the mean particle size F of the reactive
solid fine particles and the mean particle size G of the reactive
hollow fine particles in the low refractive index layer preferably
have the following relationship:
30 nm<F.ltoreq.100 nm;
30 nm.ltoreq.G.ltoreq.60 nm; and
F>G
and more preferably F.gtoreq.G+10.
[0249] The low refractive index layer of the invention preferably
contains 5-50 parts by weight of hollow fine particles based on
solid fine particles. This will increase the volume occupancy of
the solid fine particles in the low refractive index layer,
resulting in a notably high effect of reducing the reflectance of
the low refractive index layer.
[0250] With hollow fine particles and solid fine particles used in
conventional surface treatment, larger sizes of the solid fine
particles than the hollow fine particles tend to produce
aggregation between the similar fine particles because of the low
affinity between different fine particles, and consequently, the
haze of the refractive index layer surface is increased. In
contrast, using hollow fine particles and solid fine particles with
surface treatment according to the invention allows high affinity
even between different fine particles even when the solid fine
particles are larger than the hollow fine particles, thus providing
increased homogeneity and more dense packing in the layer.
Moreover, since fine particles with large particle sizes are
combined, the gaps between fine particles are increased and air
becomes included. Consequently, the low refractive index layer of
the invention satisfying the aforementioned ranges exhibits a
particularly high effect of reflectance reduction.
3-4. Crosslink-Forming Group
[0251] The fine particle surfaces of the hollow fine particles and
solid fine particles according to the invention either have the
same structure or, even if they have differing structures, the
structures are modified with crosslink-forming groups that are
similar in that the ionizing radiation curable groups have the same
backbone and differ only in the presence or absence of one
C.sub.1-3 hydrocarbon group, the bonding groups for the fine
particle surfaces have the same backbone and differ only in the
presence or absence of one C.sub.1-3 hydrocarbon group among the
groups other than the spacers bonded to the bonding groups, and the
spacer portions have the same backbone and differ only in the
presence or absence of one C.sub.1-3 hydrocarbon group or one
functional group with 1-3 constituting atoms including heteroatoms
and excluding hydrogen, or differ only in 1-2 carbons for the
carbon chain length of the backbone. Coupling agents are examples
of compounds for introduction of crosslink-forming groups into the
fine particle surfaces, and silane coupling agents are preferred
coupling agents. A silane coupling agent is composed of a bonding
group for the fine particle surfaces, a space portion and an
ionizing radiation curable group.
[0252] The solid fine particles and hollow fine particles having
crosslink-forming groups help prevent aggregation between reactive
hollow fine particles and aggregation between reactive solid fine
particles, so that the reactive hollow fine particles and reactive
solid fine particles will pack more evenly and densely to improve
the hardness of the low refractive index layer.
[0253] As preferred silane coupling agents for use in the
invention, there may be mentioned
3-methacryloxypropyltrimethoxysilane,
3-methacryloxypropyltriethoxysilane,
3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane,
3-methacryloxypropylmethyldimethoxysilane,
3-methacryloxypropylmethyldiethoxysilane,
2-methacryloxypropyltrimethoxysilane and
2-methacryloxypropyltriethoxysilane.
3-4-1. Bonding Group
[0254] Bonding groups are sites where the crosslink-forming groups
bond to the hollow fine particles and solid fine particles, and
they are groups that can form covalent bonds between the hollow
fine particles and solid fine particles. As a specific example with
3-methacryloxypropyltrimethoxysilane as the silane coupling agent,
the --Si(OCH.sub.3).sub.3 portion 2 of the
3-methacryloxypropyltrimethoxysilane as the silane coupling agent 1
in chemical formula (6) below reacts by hydrolysis to form a
bonding group.
##STR00007##
3-4-2. Spacer Portion
[0255] The spacer portion according to the invention is a site in
the crosslink-forming group that connects the bonding group with
the ionizing radiation curable group described below, and it has
the function of imparting the crosslink-forming group with affinity
for the ionizing radiation curable resin which is composed of an
organic component. As a specific example with
3-methacryloxy-propyltrimethoxysilane as the silane coupling agent,
the --COO(CH.sub.2).sub.3 portion 3 of the
3-methacryloxypropyl-trimethoxysilane as the silane coupling agent
1 in chemical formula (6) above corresponds to the spacer
portion.
3-4-3. Ionizing Radiation Curable Group
[0256] The ionizing radiation curable group according to the
invention is a functional group that, under ionizing radiation,
promotes polymerization reaction or crosslinking reaction with the
ionizing radiation curable resin as an essential component for
forming the low refraction layer, to accomplish curing. The curable
group has the function of improving the refractive index layer
strength by polymerization with the ionizing radiation curable
resin.
[0257] As examples of such ionizing radiation curable groups, there
may be mentioned groups that undergo such reactions as
polymerization reactions including photoradical polymerization,
photocationic polymerization or photoanionic polymerization, or
addition polymerization and condensation polymerization that
proceed by photodimerization. In particular, groups with ethylenic
unsaturated bonds such as (meth)acryloyl, vinyl and allyl can
undergo photoradical polymerization reaction by exposure to
ionizing radiation such as ultraviolet rays or an electron beam,
either directly or indirectly by the action of an initiator, and
therefore their handling, including handling in the photocuring
step, is easier. Among these, (meth)acryloyl is preferred as the
ionizing radiation curable group since it allows excellent
productivity and facilitates control of the mechanical strength of
the cured refractive index layer.
[0258] In a specific example with
3-methacryloxy-propyltrimethoxysilane as the silane coupling agent,
the CH.sub.2.dbd.C(CH.sub.3)-- portion 4 of the
3-methacryloxypropyltrimethoxy-silane as the silane coupling agent
1 in chemical formula (6) above corresponds to the ionizing
radiation curable group.
[0259] FIGS. 2 and 3 are schematic drawings of the mechanism of
modification of the fine particle surfaces by the crosslink-forming
groups, for a case where a silane coupling agent is used as the
compound for introduction of the crosslink-forming group.
[0260] In FIG. 2, in the first stage, the silane coupling agent 101
undergoes hydrolysis 110 to produce crosslink-forming groups 102
with bonding groups, and then in the second stage, the
crosslink-forming groups 102 participate in hydrogen bonding 111
with the polar groups 103 on the fine particle surface, thus
forming crosslink-forming groups 104 by hydrogen bonding with the
polar groups on the fine particle surface.
[0261] Then in the third stage, the hydrogen bonded
crosslink-forming groups 104 are subjected to heating and
dehydration reaction 112 to produce the desired fine particle 105
with the surface modified with crosslink-forming groups.
[0262] In FIG. 3, in the first stage, the silane coupling agent 101
undergoes hydrolysis 110 to produce crosslink-forming groups 102
with bonding groups, and then in the second stage, the
crosslink-forming groups 102 participate in dehydrating
condensation reaction 113 to produce dehydration condensed
crosslink-forming groups 106.
[0263] Then in the third stage, the dehydration condensed
crosslink-forming groups 106 participate in hydrogen bonding 111
with the polar groups 103 on the fine particle surface to form a
dehydration condensed body 107 having crosslink-forming groups
hydrogen bonded with the polar groups on the fine particle
surface.
[0264] In the fourth stage, the dehydration condensed body 107 is
subjected to heating and dehydration reaction 112 to produce the
desired fine particle 108 having the surface modified with
dehydration condensed crosslink-forming groups.
[0265] The amount of silane coupling agent used for treatment of
the silica fine particles is preferably greater than 1 wt % and
more preferably greater than 2 wt % based on the silica fine
particles. This range will result in satisfactory affinity of the
silica fine particles for the ionizing radiation-curable resin. On
the other hand, the amount of silane coupling agent used for
treatment of the silica fine particles is preferably less than 200
wt % and more preferably less than 150 wt % based on the silica
fine particles. This range will satisfactorily suppress production
of free silane coupling agent that has not participated in
treatment of the silica fine particles, thus improving the recovery
property against external impacts and helping to prevent cracks and
damage.
[0266] The method of modifying the silica fine particle surfaces
with the silane coupling agent is not particularly restricted so
long as it can improve the dispersibility in the organic solvent
and the affinity with the ionizing radiation curable resin, and any
conventional treatment method may be employed. For example, a
prescribed amount of silane coupling agent may be added to a
dispersion of the silica fine particles, with acid treatment,
alkali treatment or heat treatment if necessary, for modification
of the silica fine particle surfaces.
[0267] When a silane coupling agent other than those mentioned
above is used, its suitability may be determined based on whether
the modified fine particle surfaces are hydrophobic or hydrophilic.
As a specific method of determining suitability, the silane
coupling agent may be used to modify the fine particle surfaces and
then dried, after which an agate mortar may be used to produce a
fine powder with a size of less than 1 mm, and its ability to float
on water determined.
[0268] According to the invention, it is not necessary to introduce
all of the silane coupling agent on the silica fine particle
surfaces, and some of it may exist as monomer or condensate in the
layer-forming composition containing the ionizing radiation curable
resin. Since the silane coupling agent has excellent affinity with
the ionizing radiation curable resin and silica fine particles, it
can stably disperse the silica fine particles in the composition.
The silane coupling agent becomes incorporated into the film and
acts as a crosslinking agent during curing by ionizing radiation or
heat, so that the performance of the refractive index layer can be
more easily improved than when the entire amount of the silane
coupling agent is introduced into the silica fine particle
surfaces.
[0269] The above explanation assumes that the hollow fine particles
and solid fine particles are formed by silica, but when the fine
particles are formed of a material other than silica, surface
modification that is suitable for each material may be carried
out.
[0270] Even compounds other than coupling agents may be used as
compounds for introduction of crosslink-forming groups according to
the invention, so long as they are provided with the properties
specified above.
3-5. Curable Binder System of Low Refractive Index Layer
[0271] The constituent components of the curable binder system of
the low refractive index layer according to the invention are those
other than the aforementioned reactive hollow fine particles,
reactive solid fine particles and the at least one leveling agent
(leveling agents B) of a different type from the leveling agent A
in the hard coat layer-forming composition, which contain as an
essential component, an ionizing radiation curable resin as the
curable resin in the binder, if necessary with a curable resin
other than the ionizing radiation curable resin, a
non-polymerizable polymer component, a polymerization initiator and
the like forming the matrix of the low refractive index layer after
curing.
3-5-1. Ionizing Radiation Curable Resin
[0272] According to the invention, the ionizing radiation curable
resin is a resin that can react and cure upon exposure to ionizing
radiation. The resin is preferably translucent to allow
transmission of light when formed into a coated film.
[0273] The content of the ionizing radiation curable resin in the
low refractive index layer is preferably greater than 10 wt %, even
more preferably greater than 20 wt % and most preferably greater
than 30 wt %. It is also preferably less than 70 wt %, even more
preferably less than 60 wt % and most preferably less than 50 wt %.
Within this range, sufficient film strength for practical use will
be exhibited while obtaining a low refractive index.
[0274] The material used to form the ionizing radiation curable
resin may be any material that has a suitable refractive index for
ensuring anti-reflection performance, that can ensure adhesion with
the optically transparent base material, and that can ensure
mechanical strength of the refractive index layer.
[0275] The ionizing radiation curable resin preferably contains a
compound with at least one hydrogen bond-forming group in the
molecule and with three or more ionizing radiation curable groups.
As a result, at least a portion of the cured ionizing radiation
curable resin will be formed of a compound with one or more
hydrogen bond-forming groups and three or more ionizing radiation
curable groups in the molecule.
[0276] Using a compound with an ionizing radiation curable group
that cures by ionizing radiation and a hydrogen bond-forming group
that thermosets alone or in combination with a curing agent, will
facilitate chemical bonding such as crosslinking in the coated film
and efficient curing of the coated film, when the low refractive
index layer-forming composition containing the ionizing radiation
curable resin has been coated and dried on the surface of the
coated article and subjected to ionizing radiation exposure and
heat. When the hollow fine particles and solid fine particles are
formed of inorganic fine particles (especially silica), the
hydroxyl groups on the surfaces of the fine particles and the
aforementioned compound will readily form covalent bonds, thus
helping to improve the strength of the low refractive index layer.
In this case, crosslinking will be formed between the hollow fine
particles or solid fine particles and the cured ionizing radiation
curable resin.
[0277] As examples of ionizing radiation curable groups to be used
in the compound with at least one hydrogen bond-forming group and
three or more ionizing radiation curable groups in the molecule,
there may be mentioned functional groups that undergo such
reactions as polymerization reactions including photoradical
polymerization, photocationic polymerization, and photoanionic
polymerization, or addition polymerization that proceed by
photodimerization, or condensation polymerization. In particular,
groups with ethylenic unsaturated bonds such as (meth)acryloyl,
vinyl and allyl can produce photoradical polymerization reaction by
exposure to ionizing radiation such as ultraviolet rays or an
electron beam, either directly or indirectly by the action of an
initiator, and therefore their handling, including handling in the
photocuring step, is easier. (Meth)acryloyl is preferred among such
functional groups since it has excellent productivity and
facilitates control of the mechanical strength of the cured
refractive index layer.
[0278] As examples of hydrogen bond-forming groups to be used in
the compound with at least one hydrogen bond-forming group and
three or more ionizing radiation curable groups in the molecule,
there may be mentioned alkoxy, hydroxyl, carboxyl, amino and epoxy
groups. Hydroxyl is preferred among such functional groups because
of its excellent affinity with inorganic fine particles (especially
silica) when the hollow fine particles or solid fine particles are
formed of inorganic fine particles, by which it can improve the
dispersibility of the inorganic fine particles in the ionizing
radiation curable resin. Hydroxyl groups are easily introduced into
the compound, and when the hollow fine particles or solid fine
particles are inorganic fine particles, adsorption onto the
hydroxyl groups on the fine particle surfaces results in even
dispersion in the coating solution and film. Therefore, the coating
solution life is extended and it is possible to form a film that is
resistant to loss of film transparency due to aggregation of hollow
fine particles or solid fine particles, and that is resistant to
reduction in film strength.
[0279] The compound with at least one hydrogen bond-forming group
and three or more ionizing radiation curable groups in the molecule
can normally be a compound with hydrogen bond-forming groups such
as hydroxyl groups. The hydrogen bond-forming groups may be present
in part of the monomer as by-products of synthesis. Specifically,
there may be mentioned di(meth)acrylates such as ethyleneglycol
di(meth)acrylate and pentaerythritol di(meth)acrylate monostearate;
tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate and
pentaerythritol tri(meth)acrylate; and polyfunctional
(meth)acrylates such as pentaerythritol tetra(meth)acrylate
derivatives and dipentaerythritol penta(meth)acrylates.
[0280] In addition to these, there may also preferably be used
oligomers containing hydrogen bond-forming groups and having a
number-average molecular weight (polystyrene-based number-average
molecular weight measured by GPC (Gel Permeation Chromatography))
of less than 20,000, such as epoxy acrylate resins with hydroxyl
residues (for example, EPOXY ESTER by Kyoeisha Chemical Co., Ltd.
or LIPOXY by Showa HighPolymer Co., Ltd.), urethane acrylate resins
(resins obtained by polyaddition of various monomers with
isocyanato and hydroxyl groups via urethane bonds; for example,
"SHIKOHR" by Nippon Synthetic Chemical Industry Co., Ltd. and
"URETHANE ACRYLATE" by Kyoeisha Chemical Co., Ltd.).
[0281] These monomers and oligomers have excellent effects of
increasing film crosslink density, and because their number-average
molecular weights are less than 20,000, they exhibit high
flowability and excellent coating suitability.
[0282] If necessary, there may also preferably be used (co)polymers
containing monomers with hydrogen bond-forming groups, which are
reactive polymers having number-average molecular weights of
greater than 20,000 and having (meth)acrylate groups on the main
chain or side chains. Such reactive polymers for use may be
commercially available products such as MACROMONOMER (product of
ToaGosei Co., Ltd.), or a copolymer of methyl methacrylate and
glycidyl methacrylate may be pre-polymerized and the glycidyl
groups of the copolymer and the carboxyl groups of methacrylic acid
or acrylic acid subsequently condensed to obtain a reactive polymer
with (meth)acrylate groups. According to the invention,
"(co)polymer" means a polymer and/or copolymer.
[0283] Also according to the invention, a monomer and/or oligomer
with a number-average molecular weight of less than 20,000 and a
polymer with a number-average molecular weight of more than 20,000
may appropriately be combined to easily adjust the various
properties of the refractive index layer.
[0284] The content of the compound with at least one hydrogen
bond-forming group and three or more ionizing radiation curable
groups in the molecule is preferably greater than 10 parts by
weight and even more preferably greater than 30 parts by weight,
based on 100 parts by weight of the ionizing radiation curable
resin. The content of the compound is also preferably less than 100
parts by weight based on 100 parts by weight of the coating
solution. The mechanical strength of the refractive index layer can
be increased if the content is within this range.
3-6. Leveling Agent of Low Refractive Index Layer
[0285] The low refractive index layer of the invention also
contains a leveling agent A in the hard coat layer-forming
composition in addition to the leveling agent B in the low
refractive index layer-forming composition before curing, for the
reasons explained above. The leveling agent B included in the
curable binder system of the low refractive index layer is
preferably a reactive silicon-based leveling agent exhibiting
reactivity with at least the binder and having compatibility with
any of the ionizing radiation-curable resin, reactive hollow fine
particles and reactive solid fine particles.
[0286] If the molecular weight of the reactive silicon-based
leveling agent is too low (a molecular weight of less than 5000),
it will not migrate easily into the layer surface and the function
will not be exhibited. If the molecular weight is too high (a
molecular weight of greater than 100,000), compatibility with the
binder in the low refractive index layer-forming composition will
be poor and a satisfactory coated film will not be obtained. The
weight-average molecular weight will, therefore, usually be
5000-100,000, preferably 10,000-50,000 and more preferably
10,000-20,000. The weight-average molecular weight may be measured
in the same manner as for the non-reactive fluorine-based leveling
agent mentioned above.
[0287] As silicon-based leveling agents, there are preferred
compounds having the structure represented by the following
chemical formula (1).
##STR00008##
[0288] In the formula, R.sup.a represents a C.sub.1-20 alkyl group
such as methyl or phenyl, R.sup.b represents a C.sub.1-20 alkyl,
C.sub.1-3 alkoxy or polyether-modified group which is either
unsubstituted or substituted with an amino, epoxy, carboxyl,
hydroxyl, acryloyl and/or methacryloyl group, and each R.sup.a and
R.sup.b may be the same or different. The letters m and n both
represent integers of 0-200.
[0289] In the compound represented by chemical formula (1), the a
groups, R groups and R.sup.a and R.sup.b groups may be mutually
identical or different. As an example, one R.sup.a in chemical
formula (1) may be methyl and the remaining R.sup.a groups ethyl,
and one R.sup.b may be propyl and the remaining R.sup.b groups
methyl. As another example, all of the R.sup.a groups in chemical
formula (1) may be methyl, and all of the R.sup.b groups may be
ethyl.
[0290] These silicon compounds may be used alone or in combinations
of two or more, depending on the expected effect. By appropriately
combining such compounds, it is possible to adjust the properties
including antifouling properties, water and oil repellency,
slidability, rubfastness, durability and leveling properties, in
order to exhibit the desired function.
[0291] Silicon compounds with a basic backbone having the chemical
formula shown above are generally known to have low surface tension
and exhibit excellent water-repellency and releasability, but
introducing various functional groups on the side chains or at the
ends can impart additional effects. For example, introduction of
amino, epoxy, carboxyl, hydroxyl, (meth)acryloyl or alkoxy groups
can improve reactivity, thus facilitating formation of crosslinking
by chemical reaction with the ionizing radiation-curable resin
(binder).
[0292] Such silicon compounds can be obtained as commercial
products, and for example, various modified silicone oils can be
purchased according to the desired purpose, such as the
polyether-modified silicone oil TSF4460 (trade name of GE Toshiba
Silicone) or X22-164E (trade name of Shin-Etsu Chemical Co.,
Ltd.).
[0293] The content of leveling agent B in the low refractive index
layer-forming composition is preferably from 0.01 wt % to 5 wt %,
and more preferably from 0.03 wt % to 3 wt %. A content of more
than 0.01 wt % can impart sufficient flatness and slidability to
the low refractive index layer surface. If it is more than 5 wt %,
phase separation will tend to occur with the leveling agent A which
migrates from the half-cured hard coat layer into the low
refractive index layer, and this will undesirably lead to reduced
transparency due to increased opacity and haze of the low
refractive index layer.
[0294] The low refractive index layer may also contain binder
components other than the ionizing radiation curable resin
described above, if necessary. In addition, the low refractive
index layer-forming composition described hereunder may further
contain components such as solvents, polymerization initiators,
curing agents, crosslinking agents, ultraviolet screeners,
ultraviolet absorbers and the like. Polymerization initiators and
curing agents will now be explained as examples of such
materials.
3-7. Other Components
[0295] A polymerization initiator is not necessarily required
according to the invention. However, when the ionizing radiation
curable resin and the ionizing radiation curable groups of other
optional binder components do not easily undergo direct
polymerization reaction by ionizing radiation exposure, a suitable
initiator is preferably used in consideration of the reaction
system comprising the reactive hollow fine particles, reactive
solid fine particles and other binder components.
[0296] For example, a photoradical polymerization initiator is used
when the ionizing radiation curable group of the ionizing
radiation-curable resin composition is a (meth)acryloyl group. As
examples of photoradical polymerization initiators, there may be
mentioned acetophenones, benzophenones, ketals, anthraquinones,
thioxanthones, azo compounds, peroxides, 2,3-dialkyldione
compounds, disulfide compounds, thiuram compounds, fluoroamine
compounds and the like. More specifically, there may be mentioned
1-hydroxy-cyclohexyl-phenyl-ketone,
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,
benzyldimethylketone,
1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one,
2-hydroxy-2-methyl-1-phenylpropan-1-one,
1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one,
2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-
-propan-1-one and benzophenone. Preferred among these are
1-hydroxy-cyclohexyl-phenyl-ketone, and
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one or
2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-
-propan-1-one, because they initiate and promote polymerization
reaction under ionizing radiation exposure. Any of the
aforementioned photoradical polymerization initiators may be used
alone, or in combination.
[0297] Commercial products may be used, such as the trade name
IRGACURE 127 (IRGACURE is a registered trade name) by Ciba
Specialty Chemicals, Inc. as
2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}--
2-methyl-propan-1-one.
[0298] When a photoradical polymerization initiator is used, it is
preferably added at from 3 parts by weight to 15 parts by weight
based on 100 parts by weight as the total of the binder composed
mainly of the ionizing radiation curable resin.
[0299] A curing agent is usually added to promote thermosetting
reaction of the hydrogen bond-forming groups present in part of the
ionizing radiation curable resin. When the hollow fine particles
and solid fine particles are formed of silica, and at least a
portion of the solid fine particles is to be used as
surface-treated silica fine particles, a curing agent is added to
promote thermosetting reaction of the silanol groups present on the
surface, the silane coupling agent used for the surface treatment
and the unreacted portion of the silane coupling agent
condensate.
[0300] When the thermosetting polar groups are hydroxyl groups, the
curing agent will usually be a compound with basic groups such as
methylolmelamine, or a compound with hydrolyzable groups that
generate hydroxyl groups by hydrolysis, such as a metal alkoxide.
Amine, nitrile, amide and isocyanate groups are preferred as basic
groups, and alkoxy groups are preferred as hydrolyzable groups. In
the latter case, aluminum compounds represented by chemical formula
(7) below and/or their derivatives are particularly preferred for
satisfactory compatibility with hydroxyl groups.
AlR.sub.3 Chemical formula (7)
[In chemical formula (7), the residues R.sub.3 may be the same or
different and may be halogens, alkyl with no greater than 10 and
preferably no greater than 4 carbon atoms, alkoxy, acyloxy or
hydroxy, all or some of which groups may be replaced with chelate
ligands.]
[0301] These compounds may be selected from among aluminum
compounds and/or oligomers and/or complexes derived therefrom, as
well as inorganic or organic acid aluminum salts.
[0302] Specifically, there may be mentioned aluminum-sec-butoxide,
aluminum-iso-propoxide, and their acetylacetones, ethyl
acetoacetates, alkanolamines or glycols, and complexes with their
derivatives.
[0303] When a curing agent is used, it is preferably added at from
0.05 part by weight to 30.0 parts by weight based on 100 parts by
weight of the curable binder system composed mainly of the ionizing
radiation curable resin.
3-8. Low Refractive Index Layer-Forming Composition
[0304] The low refractive index layer-forming composition is
prepared by dispersing a mixture of the ionizing radiation curable
resin and the at least one leveling agent B different from the
leveling agent A in the hard coat layer-forming composition, as the
essential components described above, with various desired
components as necessary, in a solvent by an ordinary preparation
method. The composition may then be coated on the half-cured hard
coat layer and dried and cured to form the low refractive index
layer. A method for preparing the solvent and the low refractive
index layer-forming composition will now be explained.
3-8-1. Solvent
[0305] When a relatively large amount of the ionizing radiation
curable resin is used as the binder, the monomer and/or oligomer in
the resin will be able to also function as a liquid medium, and
therefore a coating solution may be prepared without using a
solvent. Therefore, a solvent may be used to suitably dissolve and
disperse the solid components, and to adjust the concentration to
prepare a layer-forming composition with excellent coatability.
[0306] The solvent used to dissolve and disperse the solid
components of the low refractive index layer is not particularly
restricted, and there may be mentioned various organic solvents
including alcohols such as isopropyl alcohol, methanol and ethanol;
ketones such as methyl ethyl ketone, methyl isobutyl ketone and
cyclohexanone; esters such as ethyl acetate and butyl acetate;
halogenated hydrocarbons; and aromatic hydrocarbons such as toluene
and xylene; as well as mixtures of the foregoing.
[0307] Preferred for use among these solvents are ketone-based
organic solvents. Preparing the layer-forming composition using a
ketone-based solvent will facilitate thin and even coating onto the
surface of transparent base materials, and the evaporation rate of
the solvent after coating will be suitable enough to prevent drying
irregularities, thus facilitating formation of large-area coated
films with uniform thicknesses.
[0308] Another reason that ketone-based organic solvents are
preferred for the solvent is that they allow uniform coating and
prevent coating unevenness during formation of low refractive index
layers on hard coat layers having microirregularities on the
surface.
[0309] As ketone-based solvents, there may be mentioned a single
solvent comprising one type of ketone, a mixed solvent comprising
two or more different ketones, and a complex mixed solvent that
contains other solvents in addition to one or more different
ketone-based solvents and still retain the properties of the ketone
solvents. Complex mixed solvents are preferred among these, in
which case the ketone-based solvents are preferably used in a
proportion of greater than 70 wt % and especially greater than 80
wt % of the total solvent.
[0310] The amount of solvent may be appropriately adjusted to a
concentration that allows homogeneous dissolution and dispersion of
the components, prevents aggregation of the hollow fine particles
or solid fine particles even when allowed to stand after
preparation, and is not too dilute during coating. The amount of
solvent added is preferably reduced to prepare a high-concentration
composition, within a range that satisfies these conditions. This
will permit storage with small volumes and dilution to a suitable
concentration for use in the coating operation. By using the
solvent at 50-95.5 parts by weight with respect to 0.5-50 parts by
weight of the total solid content of the low refractive index
layer, and more preferably using the solvent at 70-90 parts by
weight with respect to 10-30 parts by weight of the total solid
content of the low refractive index layer, based on 100 parts by
weight of the total of the solid content and solvent in the low
refractive index layer, it is possible to obtain a low refractive
index layer-forming composition with particularly excellent
dispersion stability and suitability for long-term storage.
3-8-2. Preparation of Low Refractive Index Layer Composition
[0311] The low refractive index layer-forming composition will
usually be prepared by dispersing a mixture of the ionizing
radiation curable resin and the at least one leveling agent
(leveling agent B) different from the leveling agent A in the hard
coat layer-forming composition, as the essential components
described above, with various desired components as necessary, in a
solvent by an ordinary preparation method. The mixing and
dispersion may be accomplished using a paint shaker or bead
mill.
4. Migration Layer
[0312] The migration layer in the antireflection film of the
invention is the region where the hard coat layer and the low
refractive index layer are mingled with each other for its
formation. The migration layer is formed by coating one side of the
transparent base material with the hard coat layer-forming
composition and half-curing it, and then coating the half-cured
hard coat layer with the low refractive index layer-forming
composition and fully curing it. The migration layer forms in most
cases by the half-curing step.
[0313] The hard coat layer components and low refractive index
layer components infiltrate into the migration layer, producing an
effect of increasing the adhesiveness between the hard coat layer
and the low refractive index layer, and imparting mar-proofness.
When the difference in hardness between the hard coat layer and the
low refractive index layer is extreme (a hard coat layer and a soft
low refractive index layer), the formed migration layer has a
hardness that is intermediate between that of the hard coat layer
and the low refractive index layer and thus exhibits a cushion
property, thereby improving the mar-proofness of the low refractive
index layer without allowing stress to concentrate on the low
refractive index layer.
[0314] The migration layer can be confirmed by a TEM photograph of
the cross-section in the direction of thickness of the
antireflection film. In the TEM photograph, the migration layer is
seen as a regional layer differing in light and shade from the hard
coat layer and low refractive index layer.
5. Process for Production of Antireflection Film
[0315] The process for production of an antireflection film
according to the invention is characterized by coating one side of
a transparent base material with a hard coat layer-forming
composition comprising a binder and at least one leveling agent A,
and half-curing it, and then coating the half-cured hard coat layer
with a low refractive index layer-forming composition comprising a
binder and a leveling agent B that is different from the one
included in the hard coat layer-forming composition, and then
completing the curing.
[0316] In the half-cured state, the solvent of the composition
easily permeates and the leveling agent and components other than
the leveling agent composing the hard coat layer and low refractive
index layer migrate between the layers, through the half-cured
migration layer.
[0317] Normally, the leveling agents will undergo phase separation
if two (or more) different leveling agents are simply included in
the hard coat layer-forming composition and low refractive index
layer-forming composition and mixed in the composition before
coating, or the final necessary function (antifouling property,
fingerprint wiping, mar-proofness) may not be obtained, but
migration of one of the leveling agents through a half-cured state
allows the two different leveling agents (leveling agent A and
leveling agent B) in the low refractive index layer to be evenly
distributed without phase separation and opacity, and particularly
to be uniformly distributed on the surface of the low refractive
index layer. While the reason for this is not fully understood, it
is believed that when two or more different leveling agents are
normally used in combination, each leveling agent moves (migrates)
freely and similar leveling agents aggregate from the evenly
distributed state and produce phase separation, but by being in a
half-cured state, the leveling agent B that has reactivity at least
with the binder in the low refractive index layer-forming
composition undergoes crosslinking reaction with the binder or
leveling agent in the curing or cured low refractive index layer,
thus impeding its movement (migration), whereas the leveling agent
A moves (migrates) from the half-cured hard coat layer toward the
surface of the low refractive index layer, allowing it to be
uniformly distributed on the surface.
[0318] Therefore, when two or more different leveling agents are
used in combination, the process for production of a reflective
film according to the invention can reduce haze of the low
refractive index layer while adequately exhibiting the properties
of all the combined leveling agents (for example, leveling agents A
and B). As an example of lowering haze in a mirror-surface, clear
antireflection film with no irregularities on the surface, the haze
can be maintained at about the same level as a transparent base
material film (0.2-0.4%, measured according to JIS K-7136 using a
HM-150 Hazemeter (Murakami Color Research Laboratory Co., Ltd.)),
while exhibiting satisfactory anti-reflection performance or
transmittance.
[0319] The process for production of an antireflection film
according to the invention will now be explained in detail.
5-1. Coating of Hard Coat Layer-Forming Composition and Preparation
of Half-Cured Hard Coat Layer
[0320] A transparent base material is coated with the hard coat
layer-forming composition by bar coating or the like, and after
removing the solvent by drying, an ultraviolet irradiation
apparatus (light source: H bulb, product of Fusion UV Systems,
Japan) is used for half-curing of the hard coat layer by
ultraviolet irradiation at a dose of 10 mJ/cm.sup.2.
5-2. Coating of Low Refractive Index Layer-Forming Composition and
Full Curing of Hard Coat Layer and Low Refractive Index Layer
[0321] The half-cured hard coat layer is coated with the low
refractive index layer-forming composition by bar coating or the
like, and after removing the solvent by drying, an ultraviolet
irradiation apparatus (light source: H bulb, product of Fusion UV
Systems, Japan) is used for full curing of the hard coat layer and
low refractive index layer by ultraviolet irradiation at a dose of
200 mJ/cm.sup.2, to obtain an antireflection film.
[0322] The invention is not limited to the mode described above.
This mode was explained merely for illustration, and any mode that
has a construction essentially identical in terms of the technical
concept described in the claims of the present invention and
exhibits the same function and effect is also encompassed by the
technical scope of the invention.
EXAMPLES
[0323] The present invention will now be explained in further
detail through examples and comparative examples. However, it is to
be understood that the invention is not restricted by the examples.
The "parts" referred to throughout the examples are based on
weight, unless otherwise specified.
6-1. Preparation of Low Refractive Index Layer Particles
Production Example 1-1
Preparation of Surface-Modified Hollow Particles (Surface-Modified
Hollow Silica Fine Particles LM(1))
[0324] An isopropanol dispersion of hollow silica fine particles
with a mean particle size of 50 nm (product of Catalysts &
Chemicals Industrial Co., Ltd.), as hollow particles, was subjected
to solvent substitution from isopropyl alcohol to methyl isobutyl
ketone (hereinafter also abbreviated as MIBK) using a rotary
evaporator, to obtain a 20 wt % dispersion of silica fine
particles. Next, 5 wt % 3-methacryloxypropylmethyldimethoxysilane
was added to 100 wt % of the methyl isobutyl ketone dispersion, and
the mixture was heat treated at 50.degree. C. for 1 hour to obtain
a 20 wt % methyl isobutyl ketone dispersion of surface-treated
hollow silica fine particles.
[0325] The surface-modified hollow silica fine particles LM(1)
obtained in this manner were measured using a Microtrac particle
size analyzer by Nikkiso Co., Ltd. and were found to have a mean
particle size of d50=50 nm.
Production Example 1-2
Preparation of Surface-Modified Solid Particles (Surface-Modified
Solid Silica Fine Particles LS(1))
[0326] To 100 parts by weight of a methyl isobutyl ketone dispersed
silica sol with a mean particle size of 12 nm (MIBK-ST:, trade name
of Nissan Chemical Industries, Ltd.: silica solid content: 20 wt %)
as solid particles, there was added 5 wt %
3-methacryloxypropylmethyldimethoxysilane, and the mixture was heat
treated at 50.degree. C. for 1 hour to obtain a 20 wt % methyl
isobutyl ketone dispersion of surface-treated solid silica fine
particles.
[0327] The surface-modified solid silica fine particles LS(1)
obtained in this manner were measured using the aforementioned
particle size analyzer and were found to have a mean particle size
of d50=12 nm.
Production Example 2
6-2. Preparation of Reactive Inorganic Fine Particles A(1) for Hard
Coat Layer
[0328] (1) Removal of Surface Adsorbed ions
[0329] Water-dispersed colloidal silica with a particle size of 90
nm (SNOWTEX ZL, trade name of Nissan Chemical Industries, Ltd., pH
9-10) was subjected to ion exchange for 3 hours using 400 g of a
cation-exchange resin (DIAION SK1B, product of Mitsubishi Chemical
Corp.), and then 200 g of an anion exchange resin (DIAION SA20A,
product of Mitsubishi Chemical Corp.) was used for 3 hours of ion
exchange, followed by washing to obtain an aqueous dispersion of
inorganic fine particles with a solid concentration of 20 wt %.
[0330] The Na.sub.2O content of the inorganic fine particle aqueous
dispersion was 7 ppm for each inorganic fine particle.
(2) Surface Treatment (Introduction of Monofunctional Monomer)
[0331] To 10 g of the inorganic fine particle aqueous dispersion
treated in (1) above there were added 150 ml of isopropanol, 4.0 g
of 3,6,9-trioxadecanoic acid and 4.0 g of methacrylic acid, and the
mixture was stirred for 30 minutes.
[0332] The obtained mixture was stirred while heating at 60.degree.
C. for 5 hours, to obtain an inorganic fine particle dispersion
having methacryloyl groups introduced on the fine particle
surfaces. Distilled water and isopropanol were distilled off from
the obtained inorganic fine particle dispersion using a rotary
evaporator, and methyl ethyl ketone was added to avoid drying with
a final remaining water or isopropanol residue of 0.1 wt %, to
obtain a silica-dispersed methyl ethyl ketone solution with a solid
content of 50 wt %.
[0333] The reactive inorganic fine particles A(1) obtained in this
manner were measured using the aforementioned particle size
analyzer and were found to have a mean particle size of d50=90 nm.
The amount of organic component covering the fine particle surfaces
was 4.05.times.10.sup.-3 g/m.sup.2, as a result of measurement by
thermogravimetric analysis.
Production Example 3
6-3. Synthesis of Antistatic Agent
[0334] In a flask equipped with a stirrer, reflux condenser,
dropping funnel and nitrogen inlet tube, there were placed 50 parts
of an alkyl methacrylate (mixed alkyl ester comprising dodecyl
methacrylate and tridecyl methacrylate, average molecular weight:
263) (SLMA), 10 parts of methyl methacrylate (MMA), 40 parts of
N,N-dimethylaminoethyl methacrylate (DMMA) and 210 parts of
ethanol, with 1.2 parts of azobisisobutyronitrile as a catalyst,
and reaction was conducted at 80.degree. C. for 6 hours under a
nitrogen atmosphere. Upon completion of polymerization, 80 parts of
benzyl chloride was added dropwise to the obtained copolymer
solution, and further reaction at 60.degree. C. for 8 hours
produced an antistatic agent containing a cationic copolymer. The
number-average molecular weight of the antistatic agent measured by
GPC was 2,300.
Production Example 4
6-4-1. Preparation of Low Refractive Index Layer-Forming
Composition
[0335] A low refractive index layer-forming composition was
prepared by mixing the following components.
Surface-modified hollow silica fine particles LM(1) with a mean
particle size of d50=50 nm (methyl isobutyl ketone containing 20 wt
% hollow silica fine particles): 15.0 parts by weight
Surface-modified solid silica fine particles LS(1) with a mean
particle size of d50=12 nm (methyl isobutyl ketone containing 20 wt
% solid silica fine particles): 0.4 part by weight Ionizing
radiation curable resin 1: Pentaerythritol triacrylate (PETA): 1.2
parts by weight Ionizing radiation curable resin 2:
Dipentaerythritol hexaacrylate (DPHA): 0.4 part by weight Reactive
silicon-based leveling agent: X-22-164E (trade name of Shin-Etsu
Chemical Co., Ltd.): 0.15 part by weight Polymerization initiator:
IRGACURE 127 (trade name of Ciba Specialty Chemicals Co., Ltd.):
0.1 part by weight Solvent: Methyl isobutyl ketone: 83.5 parts by
weight
Production Example 5
6-4-2. Preparation of Low Refractive Index Layer-Forming
Composition
[0336] A low refractive index layer-forming composition was
prepared by mixing the following components.
Surface-modified hollow silica fine particles LM(1) with a mean
particle size of d50=50 nm (methyl isobutyl ketone containing 20 wt
% hollow silica fine particles): 15.0 parts by weight Ionizing
radiation curable resin 1: Pentaerythritol triacrylate (PETA): 0.68
part by weight Ionizing radiation curable resin 2: OPSTAR JM5010
(trade name of JSR: refractive index: 1.41, solid content: 10 wt %,
methyl ethyl ketone solution): 15.8 parts by weight Reactive
silicon-based leveling agent: X-22-164E: 0.15 part by weight
Polymerization initiator: IRGACURE 127: 0.1 part by weight Solvent:
Methyl isobutyl ketone: 68.5 parts by weight
Production Example 6
6-4-3. Preparation of Low Refractive Index Layer-Forming
Composition
[0337] A low refractive index layer-forming composition was
prepared by mixing the following components.
Surface-modified hollow silica fine particles LM(1) with a mean
particle size of d50=50 nm (methyl isobutyl ketone containing 20 wt
% hollow silica fine particles): 15.0 parts by weight Ionizing
radiation curable resin 1: Pentaerythritol triacrylate (PETA): 0.68
part by weight Ionizing radiation curable resin 2: OPSTAR JM5010:
15.8 parts by weight Non-reactive silicon-based leveling agent:
BYK-300 (trade name of Byk-Chemie Corp.): 0.15 part by weight
Polymerization initiator: IRGACURE 127: 0.1 part by weight Solvent:
Methyl isobutyl ketone: 68.5 parts by weight
Production Example 7
6-4-4. Preparation of Low Refractive Index Layer-Forming
Composition
[0338] The reactive silicon-based leveling agent components in the
composition of Production Example 4 were replaced by the following
to prepare a low refractive index layer-forming composition.
Surface-modified hollow silica fine particles LM(1) with a mean
particle size of d50=50 nm (methyl isobutyl ketone containing 20 wt
% hollow silica fine particles): 15.0 parts by weight
Surface-modified solid silica fine particles LS(1) with a mean
particle size of d50=12 nm (methyl isobutyl ketone containing 20 wt
% solid silica fine particles): 0.4 part by weight Ionizing
radiation curable resin 1: Pentaerythritol triacrylate (PETA): 1.2
part by weight Ionizing radiation curable resin 2:
Dipentaerythritol hexaacrylate (DPHA): 0.4 part by weight Reactive
silicon-based leveling agent: Polyether-modified silicone oil
TSF4460 (trade name of Momentive Materials Performance Japan,
Inc.): 0.15 part by weight Polymerization initiator: IRGACURE 127:
0.1 part by weight Solvent: Methyl isobutyl ketone: 83.5 parts by
weight
Production Example 8
6-4-5. Preparation of Low Refractive Index Layer-Forming
Composition
[0339] The non-reactive silicon-based leveling agent components in
the composition of Production Example 6 were replaced by the
following to prepare a low refractive index layer-forming
composition.
Surface-modified hollow silica fine particles LM(1) with a mean
particle size of d50=50 nm (methyl isobutyl ketone containing 20 wt
% hollow silica fine particles): 15.0 parts by weight Ionizing
radiation curable resin 1: Pentaerythritol triacrylate (PETA): 0.68
part by weight Ionizing radiation curable resin 2: OPSTAR JM5010:
15.8 parts by weight Non-reactive silicon-based leveling agent:
FM4421 (trade name of Chisso Corp.): 0.15 part by weight
Polymerization initiator: IRGACURE 127: 0.1 part by weight Solvent:
Methyl isobutyl ketone: 68.5 parts by weight
Production Example 9
6-4-6. Preparation of Low Refractive Index Layer-Forming
Composition
[0340] The non-reactive silicon-based leveling agent components in
the composition of Production Example 6 and their addition amounts
were replaced by the following to prepare a low refractive index
layer-forming composition.
Surface-modified hollow silica fine particles LM(1) with a mean
particle size of d50=50 nm (methyl isobutyl ketone containing 20 wt
% hollow silica fine particles): 15.0 parts by weight Ionizing
radiation curable resin 1: Pentaerythritol triacrylate (PETA): 0.68
part by weight Ionizing radiation curable resin 2: OPSTAR JM5010:
15.8 parts by weight Non-reactive fluorine-based leveling agent
(MEGAFAC MCF-445 (ethylene oxide-added, trade name of Dainippon Ink
and Chemicals, Inc.): 0.07 part by weight Non-reactive
silicon-based leveling agent: KF-6004 (polyether-modified, trade
name of Shin-Etsu Chemical Co., Ltd.): 0.07 part by weight
Polymerization initiator: IRGACURE 127: 0.1 part by weight Solvent:
Methyl isobutyl ketone: 68.5 parts by weight
Production Example 10
6-4-7. Preparation of Low Refractive Index Layer-Forming
Composition
[0341] The reactive silicon-based leveling agent components in the
composition of Production Example 4 were replaced by the following
to prepare a low refractive index layer-forming composition.
Surface-modified hollow silica fine particles LM(1) with a mean
particle size of d50=50 nm (methyl isobutyl ketone containing 20 wt
% hollow silica fine particles): 15.0 parts by weight
Surface-modified solid silica fine particles LS(1) with a mean
particle size of d50=12 nm (methyl isobutyl ketone containing 20 wt
% solid silica fine particles): 0.4 part by weight Ionizing
radiation curable resin 1: Pentaerythritol triacrylate (PETA): 1.2
parts by weight Ionizing radiation curable resin 2:
Dipentaerythritol hexaacrylate (DPHA): 0.4 part by weight Reactive
fluorine-based leveling agent: OPTOOL DAC (trade name of Daikin
Industries, Ltd.): 0.15 part by weight Polymerization initiator:
IRGACURE 127: 0.1 part by weight Solvent: Methyl isobutyl ketone:
83.5 parts by weight
Production Example 11
6-4-8. Preparation of Low Refractive Index Layer-Forming
Composition
[0342] A non-reactive fluorine-based leveling agent was added to
the components of Production Example 4 to prepare a low refractive
index layer-forming composition.
Surface-modified hollow silica sol LM(1) with a mean particle size
of d50=50 nm (methyl isobutyl ketone containing 20 wt % hollow
silica fine particles): 15.0 parts by weight Surface-modified solid
silica fine particles LS(1) with a mean particle size of d50=12 nm
(methyl isobutyl ketone containing 20 wt % solid silica fine
particles): 0.4 part by weight Ionizing radiation curable resin:
Pentaerythritol triacrylate (PETA): 1.2 parts by weight Ionizing
radiation curable resin: Dipentaerythritol hexaacrylate (DPHA): 0.4
part by weight Reactive silicon-based leveling agent: X-22-164E:
0.15 part by weight Non-reactive fluorine-based leveling agent:
MEGAFAC MCF-350 (trade name of Dainippon Ink and Chemicals, Inc.):
0.03 part by weight Polymerization initiator: IRGACURE 127: 0.1
part by weight Solvent: Methyl isobutyl ketone: 83.5 parts by
weight
Production Example 12
6-4-9. Preparation of Low Refractive Index Layer-Forming
Composition
[0343] A low refractive index layer-forming composition was
prepared, lacking only the reactive silicon-based leveling agent in
the composition of Production Example 4.
Surface-modified hollow silica sol LM(1) with a mean particle size
of d50=50 nm (methyl isobutyl ketone containing 20 wt % hollow
silica fine particles): 15.0 parts by weight Surface-modified solid
silica fine particles LS(1) with a mean particle size of d50=12 nm
(methyl isobutyl ketone containing 20 wt % solid silica fine
particles): 0.4 part by weight Ionizing radiation curable resin 1:
Pentaerythritol triacrylate (PETA): 1.2 part by weight Ionizing
radiation curable resin 2: Dipentaerythritol hexaacrylate (DPHA):
0.4 part by weight Polymerization initiator: IRGACURE 127: 0.1 part
by weight Solvent: Methyl isobutyl ketone: 83.5 parts by weight
Production Example 13
6-4-10. Preparation of Hard Coat Layer-Forming Composition
[0344] A hard coat layer-forming composition was prepared by mixing
the following components.
Reactive silica fine particles A (methyl isobutyl ketone containing
35 wt % solid silica fine particles): 25.0 parts by weight Binder
C: Urethane acrylate (SHIKOH UV1700-B: trade name of Nippon
Synthetic Chemical Industry Co., Ltd.): 25.0 parts by weight
Non-reactive fluorine-based leveling agent: MEGAFAC MCF-350: 0.03
part by weight Polymerization initiator: IRGACURE 184 (trade name
of Ciba Specialty Chemicals Co., Ltd.): 0.2 part by weight Solvent:
Methyl ethyl ketone: 49.8 parts by weight
Production Example 14
6-4-11. Preparation of Hard Coat Layer-Forming Composition
[0345] A hard coat layer-forming composition was prepared, lacking
only the non-reactive fluorine-based leveling agent in the
composition of Production Example 13.
Reactive silica fine particles A (methyl isobutyl ketone containing
35 wt % solid silica fine particles): 25.0 parts by weight Binder
C: Urethane acrylate (SHIKOH UV1700-B): 25.0 parts by weight
Polymerization initiator: IRGACURE 184: 0.2 part by weight Solvent:
Methyl ethyl ketone: 49.8 parts by weight
Production Example 15
6-4-12. Preparation of Hard Coat Layer-Forming Composition
[0346] A reactive silicon-based leveling agent was added to the
composition of Production Example 13 to prepare a hard coat
layer-forming composition.
Reactive silica fine particles A (methyl isobutyl ketone containing
35 wt % solid silica fine particles): 25.0 parts by weight Binder
C: Urethane acrylate (SHIKOH UV1700-B): 25.0 parts by weight
Reactive silicon-based leveling agent: X-22-164E: 0.15 part by
weight Non-reactive fluorine-based leveling agent: MEGAFAC MCF-350:
0.03 part by weight Polymerization initiator: IRGACURE 184: 0.2
part by weight Solvent: Methyl ethyl ketone: 49.8 parts by
weight
Production Example 16
6-4-13. Preparation of Hard Coat Layer-Forming Composition
[0347] A hard coat layer-forming composition was prepared by mixing
the following components.
Antistatic component synthesized in Production Example 3: 0.27 part
by weight Ionizing radiation curable resin 1: Pentaerythritol
triacrylate (PETA): 1.3 part by weight Ionizing radiation curable
resin 2: BS577 (trade name of Arakawa Chemical Industries, Ltd.):
1.3 part by weight Ionizing radiation curable resin 3: M9050 (trade
name of ToaGosei Co., Ltd.): 2.7 parts by weight Non-reactive
fluorine-based leveling agent: MEGAFAC MCF350: 0.1 part by weight
Polymerization initiator: IRGACURE 184: 0.22 part by weight
Solvent: Methyl ethyl ketone: 17 parts by weight
Production Example 17
6-4-14. Preparation of Hard Coat Layer-Forming Composition
[0348] A hard coat layer-forming composition was prepared, changing
only the non-reactive fluorine-based leveling agent in the
composition of Production Example 16.
Antistatic component synthesized in Production Example 3: 0.27 part
by weight Ionizing radiation curable resin: Pentaerythritol
triacrylate (PETA): 1.3 parts by weight Ionizing radiation curable
resin: BS577: 1.3 part by weight Ionizing radiation curable resin:
M9050: 2.7 parts by weight Non-reactive fluorine-based leveling
agent: MEGAFAC 178 (trade name of Dainippon Ink and Chemicals,
Inc.): 0.1 part by weight Polymerization initiator: IRGACURE 184:
0.22 part by weight Solvent: Methyl ethyl ketone: 17 parts by
weight
Production Example 18
6-4-15. Preparation of Hard Coat Layer-Forming Composition
[0349] A hard coat layer-forming composition was prepared, lacking
only the non-reactive fluorine-based leveling agent in the
composition of Production Example 16.
Antistatic component synthesized in Production Example 3: 0.27 part
by weight Ionizing radiation curable resin 1: Pentaerythritol
triacrylate (PETA): 1.3 parts by weight Ionizing radiation curable
resin 2: BS577: 1.3 parts by weight Ionizing radiation curable
resin 3: M9050: 2.7 parts by weight Polymerization initiator:
IRGACURE 184: 0.22 part by weight Solvent: Methyl ethyl ketone: 17
parts by weight
Production Example 19
6-4-16. Preparation of Hard Coat Layer-Forming Composition
[0350] A hard coat layer-forming composition was prepared by mixing
the following components.
Antistatic component synthesized in Production Example 3: 0.27 part
by weight Ionizing radiation curable resin 1: Pentaerythritol
triacrylate (PETA): 1.3 parts by weight Ionizing radiation curable
resin 2: BS577: 1.3 parts by weight Ionizing radiation curable
resin 3: M9050: 2.7 parts by weight Reactive fluorine-based
leveling agent: FA-108 (trade name of Kyoeisha Chemical Co., Ltd.):
0.005 part by weight Polymerization initiator: IRGACURE 184: 0.22
part by weight Solvent: Methyl ethyl ketone: 17 parts by weight
Production Example 20
6-4-17. Preparation of Hard Coat Layer-Forming Composition
[0351] A hard coat layer-forming composition was prepared, changing
only the non-reactive fluorinated leveling agent in the composition
of Production Example 13.
Reactive silica fine particles A (methyl isobutyl ketone containing
35 wt % solid silica fine particles): 25.0 parts by weight Binder
C: Urethane acrylate (SHIKOH UV1700-B): 25.0 parts by weight
Non-reactive fluorine-based leveling agent: MEGAFAC F445 (trade
name of Dainippon Ink and Chemicals, Inc.): 0.03 part by weight
Polymerization initiator: IRGACURE 184: 0.2 part by weight Solvent:
Methyl ethyl ketone: 49.8 parts by weight
Production Example 21
6-4-18. Preparation of Hard Coat Layer-Forming Composition
[0352] A hard coat layer-forming composition was prepared, changing
only the non-reactive fluorinated leveling agent in the composition
of Production Example 13.
Reactive silica fine particles A (methyl isobutyl ketone containing
35 wt % solid silica fine particles): 25.0 parts by weight Binder
C: Urethane acrylate (SHIKOH UV1700-B): 25.0 parts by weight
Non-reactive silicon-based leveling agent: X-22-3710 (trade name of
Shin-Etsu Chemical Co., Ltd.): 0.03 part by weight Polymerization
initiator: IRGACURE 184: 0.2 part by weight Solvent: Methyl ethyl
ketone: 49.8 parts by weight
Production Example 22
6-4-19. Preparation of Hard Coat Layer-Forming Composition
[0353] A hard coat layer-forming composition was prepared by mixing
the following components.
Ionizing radiation curable resin: Dipentaerythritol hexaacrylate
(DPHA): 4 parts by weight Methyl ethyl ketone dispersion of
zirconia particles (UEP, product of Daiichi Kigenso Kagaku Kogyo
Co., Ltd., primary particle size: 20-30 nm) (solid content: 40%):
10 parts by weight Non-reactive fluorine-based leveling agent:
MEGAFAC MCF-350: 0.05 part by weight Solvent: Methyl ethyl ketone:
6 parts by weight
Example 1
6-5-1. Coating of Hard Coat Layer-Forming Composition and
Preparation of Half-Cured Hard Coat Layer
[0354] A hard coat layer-forming composition having the composition
of Production Example 13 above was bar coated onto an 80
.mu.m-thick triacetatecellulose (TAC) film (product of Fuji Film
Co.), and after removing the solvent by drying, an ultraviolet
irradiation apparatus (light source: H bulb, product of Fusion UV
Systems, Japan) was used for ultraviolet irradiation at a dose of
10 mJ/cm.sup.2, to obtain a half-cured hard coat layer.
6-5-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Hard Coat Layer and Low Refractive Index
Layer
[0355] The low refractive index layer-forming composition of
Production Example 4 was bar coated onto the obtained base
material/half-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the coated film, to obtain an
antireflection film having the construction: base material/hard
coat layer/low refractive index layer.
[0356] The film thickness of the low refractive index layer was set
so that the minimum value of the reflectance measured using a
spectrophotometer by Shimadzu Corp. (UV-3100PC) was near a
wavelength of 550 nm.
[0357] Since nearly all of the PETA and DPHA polymerizes, the
content of solid silica particles with respect to this ionizing
radiation curable resin may be considered to be essentially equal
to the content of solid silica particles with respect to the
ionizing radiation curable resin.
Example 2
6-6-1. Coating of Hard Coat Layer-Forming Composition and
Preparation of Half-Cured Hard Coat Layer
[0358] A hard coat layer-forming composition having the composition
of Production Example 16 above was bar coated onto an 80
.mu.m-thick triacetatecellulose (TAC) film, and after removing the
solvent by drying, the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 10
mJ/cm.sup.2, to obtain a half-cured hard coat layer.
6-6-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Hard Coat Layer and Low Refractive Index
Layer
[0359] The low refractive index layer-forming composition of
Production Example 5 was bar coated onto the obtained base
material/half-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the coated film, to obtain an
antireflection film having the construction: base material/hard
coat layer/low refractive index layer.
Example 3
6-7-1. Coating of Hard Coat Layer-Forming Composition and
Preparation of Half-Cured Hard Coat Layer
[0360] A hard coat layer-forming composition having the composition
of Production Example 22 above was bar coated onto a 100
.mu.m-thick polyethylene terephthalate (PET) film (A2401, product
of Toyobo, Ltd.), and after removing the solvent by drying, the
aforementioned ultraviolet irradiation apparatus was used for
ultraviolet irradiation at a dose of 10 mJ/cm.sup.2, to obtain a
half-cured hard coat layer.
6-7-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Hard Coat Layer and Low Refractive Index
Layer
[0361] The low refractive index layer-forming composition of
Production Example 5 was bar coated onto the obtained base
material/half-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the coated film, to obtain an
antireflection film having the construction: base material/hard
coat layer/low refractive index layer.
Example 4
6-8-1. Coating of Hard Coat Layer-Forming Composition and
Preparation of Half-Cured Hard Coat Layer
[0362] A hard coat layer-forming composition having the composition
of Production Example 20 above was bar coated onto an 80
.mu.m-thick triacetatecellulose (TAC) film, and after removing the
solvent by drying, the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 10
mJ/cm.sup.2, to obtain a half-cured hard coat layer.
6-8-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Hard Coat Layer and Low Refractive Index
Layer
[0363] The low refractive index layer-forming composition of
Production Example 7 was bar coated onto the obtained base
material/half-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the coated film, to obtain an
antireflection film having the construction: base material/hard
coat layer/low refractive index layer.
Example 5
6-9-1. Coating of Antistatic Hard Coat Layer-Forming Composition
and Preparation of Half-Cured Hard Coat Layer
[0364] An antistatic hard coat layer-forming composition having the
composition of Production Example 16 above was bar coated onto an
80 .mu.m-thick triacetatecellulose (TAC) film, and after removing
the solvent by drying, the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 10
mJ/cm.sup.2, to obtain a half-cured antistatic hard coat layer. The
film thickness of the obtained antistatic hard coat layer was 3
.mu.m.
6-9-2. Additional Coating of Hard Coat Layer-Forming Composition
and Preparation of Half-Cured Hard Coat Layer
[0365] The hard coat layer-forming composition of Production
Example 13 was bar coated onto the obtained base
material/antistatic hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 10
mJ/cm.sup.2 for further half-curing of the coated film, to obtain
the construction: base material/antistatic hard coat layer/hard
coat layer film. The total film thickness of the obtained two-layer
hard coat layer was 18 .mu.m.
6-9-3. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Two-Layer Hard Coat Layer and Low Refractive
Index Layer
[0366] The low refractive index layer-forming composition of
Production Example 4 was bar coated onto the obtained base
material/half-cured antistatic hard coat layer/half-cured hard coat
layer film and dried to remove the solvent, and then the
aforementioned ultraviolet irradiation apparatus was used for
ultraviolet irradiation at a dose of 200 mJ/cm.sup.2 to full curing
of the coated film, to obtain an antireflection film having the
construction: base material/antistatic hard coat layer/hard coat
layer/low refractive index layer. The film thickness of the
obtained low refractive index layer was 0.1 .mu.m.
[0367] Even with two hard coat layers, the overall performance was
satisfactory with no opacity, similar to a single layer.
Comparative Example 1
6-10-1. Coating of Hard Coat Layer-Forming Composition and
Formation of Fully-Cured Hard Coat Layer
[0368] A hard coat layer-forming composition having the composition
of Production Example 13 above was bar coated onto an 80
.mu.m-thick triacetatecellulose (TAC) film, and after removing the
solvent by drying, the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2, to obtain a fully-cured hard coat layer.
6-10-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Low Refractive Index Layer
[0369] The low refractive index layer-forming composition of
Production Example 4 was bar coated onto the obtained base
material/fully-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the low refractive index
layer-forming composition, to obtain an antireflection film having
the construction: base material/hard coat layer/low refractive
index layer.
[0370] Since the hard coat layer was fully cured, the non-reactive
fluorine-based leveling agent could not migrate and the fingerprint
wiping was reduced.
Comparative Example 2
6-11-1. Coating of Hard Coat Layer-Forming Composition and
Preparation of Half-Cured Hard Coat Layer
[0371] A hard coat layer-forming composition having the composition
of Production Example 15 above was bar coated onto an 80
.mu.m-thick triacetatecellulose (TAC) film, and after removing the
solvent by drying, the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 10
mJ/cm.sup.2, to obtain a half-cured hard coat layer.
6-11-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Hard Coat Layer and Low Refractive Index
Layer
[0372] The low refractive index layer-forming composition of
Production Example 12 was bar coated onto the obtained base
material/half-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the coated film, to obtain an
antireflection film having the construction: base material/hard
coat layer/low refractive index layer.
[0373] Since the reactive silicon-based leveling agent was present
in the hard coat layer, it could not migrate into the surface of
the low refractive index layer and the fingerprint wiping,
mar-proofness and antifouling property were reduced.
Comparative Example 3
6-12-1. Coating of Hard Coat Layer-Forming Composition and
Preparation of Half-Cured Hard Coat Layer
[0374] A hard coat layer-forming composition having the composition
of Production Example 14 above was bar coated onto an 80
.mu.m-thick triacetatecellulose (TAC) film, and after removing the
solvent by drying, the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 10
mJ/cm.sup.2, to obtain a half-cured hard coat layer.
6-12-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Hard Coat Layer and Low Refractive Index
Layer
[0375] The low refractive index layer-forming composition of
Production Example 11 was bar coated onto the obtained base
material/half-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the coated film, to obtain an
antireflection film having the construction: base material/hard
coat layer/low refractive index layer.
[0376] Since the non-reactive fluorine-based leveling agent and
reactive silicon-based leveling agent were both present in the low
refractive index layer, they were not uniformly distributed at the
surface, and therefore the overall performance was reduced and
opacity was exhibited due to lack of compatibility.
Comparative Example 4
6-13-1. Coating of Hard Coat Layer-Forming Composition and
Formation of Half-Cured Hard Coat Layer
[0377] A hard coat layer-forming composition having the composition
of Production Example 17 above was bar coated onto an 80
.mu.m-thick triacetatecellulose (TAC) film, and after removing the
solvent by drying, the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 10
mJ/cm.sup.2, to obtain a half-cured hard coat layer.
6-13-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Low Refractive Index Layer
[0378] The low refractive index layer-forming composition of
Production Example 6 was bar coated onto the obtained base
material/half-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the low refractive index
layer-forming composition, to obtain an antireflection film having
the construction: base material/hard coat layer/low refractive
index layer. Because the silicon-based leveling agent in the low
refractive index layer was non-reactive, the two different leveling
agents could not be uniformly distributed at the surface, the
overall performance was reduced, and opacity was exhibited due to
lack of compatibility with the migrating non-reactive F-type
leveling agent.
Comparative Example 5
6-14-1. Coating of Hard Coat Layer-Forming Composition and
Formation of Half-Cured Hard Coat Layer
[0379] A hard coat layer-forming composition having the composition
of Production Example 19 above was bar coated onto an 80
.mu.m-thick triacetatecellulose (TAC) film, and after removing the
solvent by drying, the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 10
mJ/cm.sup.2, to obtain a half-cured hard coat layer.
6-14-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Low Refractive Index Layer
[0380] The low refractive index layer-forming composition of
Production Example 8 was bar coated onto the obtained base
material/half-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the low refractive index
layer-forming composition, to obtain an antireflection film having
the construction: base material/hard coat layer/low refractive
index layer. Since the reactive fluorine-based leveling agent was
present in the hard coat, the fluorine-based leveling agent could
not migrate into the low refractive index layer surface and the
fingerprint wiping was reduced.
Comparative Example 6
6-15-1. Coating of Hard Coat Layer-Forming Composition and
Formation of Half-Cured Hard Coat Layer
[0381] A hard coat layer-forming composition having the composition
of Production Example 18 above was bar coated onto an 80
.mu.m-thick triacetatecellulose (TAC) film, and after removing the
solvent by drying, the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 10
mJ/cm.sup.2, to obtain a half-cured hard coat layer.
6-15-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Low Refractive Index Layer
[0382] The low refractive index layer-forming composition of
Production Example 9 was bar coated onto the obtained base
material/half-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the low refractive index
layer-forming composition, to obtain an antireflection film having
the construction: base material/hard coat layer/low refractive
index layer. Since the non-reactive fluorine-based leveling agent
and reactive silicon-based leveling agent were present in the low
refractive index layer, only the silicon-based leveling agent
readily entered the surface, resulting in a non-uniform condition
and reduced fingerprint wiping. No opacity was exhibited, due to
compatibility between the two different leveling agents.
Comparative Example 7
6-16-1. Coating of Hard Coat Layer-Forming Composition and
Formation of Half-Cured Hard Coat Layer
[0383] A hard coat layer-forming composition having the composition
of Production Example 21 above was bar coated onto an 80
.mu.m-thick triacetatecellulose (TAC) film, and after removing the
solvent by drying, the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 10
mJ/cm.sup.2, to obtain a half-cured hard coat layer.
6-16-2. Coating of Low Refractive Index Layer-Forming Composition
and Full Curing of Low Refractive Index Layer
[0384] The low refractive index layer-forming composition of
Production Example 10 was bar coated onto the obtained base
material/half-cured hard coat layer film and dried to remove the
solvent, and then the aforementioned ultraviolet irradiation
apparatus was used for ultraviolet irradiation at a dose of 200
mJ/cm.sup.2 to full curing of the low refractive index
layer-forming composition, to obtain an antireflection film having
the construction: base material/hard coat layer/low refractive
index layer.
[0385] Since the non-reactive silicon-based leveling agent was
present in the hard coat layer and the reactive fluorine-based
leveling agent was present in the low refractive index layer, the
fluorine-based leveling agent crosslinked with the binder, thus
further preventing it from entering the surface, and therefore only
the silicon-based leveling agent migrated into the low refractive
index layer surface from the hard coat layer; this was assumed to
be the cause of the reduced fingerprint wiping.
6-17-1. Rubfastness Evaluation Test (Steel Wool Resistance)
[0386] The obtained antireflection film was rubbed 20 times using
#0000 steel wool under a 200 g weight, and the presence of
scratches was visually examined. The evaluation was made on the
following scale.
.circleincircle.: Absolutely no scratch found. .largecircle.: Fine
scratches (no more than five) found. .DELTA.: Notable scratches,
but no peeling.
x: Peeling.
6-17-2. Antifouling Property Evaluation Test
[0387] An oil-based ink marker was used to draw on the obtained
antireflection film surface, and the condition after wiping with a
BENCOT M-3 by Asahi Kasei Corp. was observed. The evaluation was
made on the following scale.
.circleincircle.: Ink repelled and easily wiped off. .largecircle.:
Ink repelled, and wiped off with strong rubbing. .DELTA.: Portion
of ink remained without being wiped off. x: Ink could not be wiped
off.
6-17-3. Fingerprint Wiping Test
[0388] A fingerprint on the obtained antireflection film surface
was rubbed off using a BENCOT M-3 by Asahi Kasei Corp., and the
ease of removal was visually judged. The evaluation was made on the
following scale.
.largecircle.: Fingerprint completely removed. .DELTA.: Fingerprint
removed but with remaining trace, or trace removed but with initial
smearing of fingerprint. x: Fingerprint not removed.
6-17-4. Opacity Evaluation Test
[0389] The following evaluation was conducted to determine whether
the obtained antireflection film lacked opacity and had
satisfactory transparency. An optical pressure-sensitive adhesive
(for example, an acrylic pressure-sensitive adhesive for an optical
film, such as DA-1000 by Hitachi Chemical Co., Ltd.) was affixed to
a black acrylic sheet, and the following samples were prepared.
[0390] Reference sample: Black acrylic sheet/optical
pressure-sensitive/transparent base material film
[0391] Evaluation samples: Black acrylic sheet/optical
pressure-sensitive/transparent base material film/hard coat/low
refractive index layers (antireflection films prepared in examples
and comparative examples)
[0392] The samples prepared in the examples and comparative
examples were used as the evaluation samples, and visually observed
together with the reference sample, evaluating whether whiteness
was increased compared to the base material alone.
[0393] When the haze of the examples and comparative examples was
measured according to JIS K-7136 using a Hazemeter HM-150 (Murakami
Color Research Laboratory Co., Ltd.), the samples without opacity
in the opacity evaluation test were found to have hazes of
0.2-0.4%, whereas those with opacity had hazes of as high as 0.9%
in Comparative Example 3 and 0.7% in Comparative Example 4,
concurring with the visual examination that they were unusable as
products.
[0394] The evaluation results for the four tests described above
are shown in Table 1. Table 2 shows the relationship between the
antireflection films of the examples and comparative examples and
the methods of forming the hard coat layers and low refractive
index layers in each of the examples.
TABLE-US-00001 TABLE 1 Fingerprint Steel wool Antifouling wiping
resistance Opacity property Example 1 .largecircle.
.circleincircle. None .circleincircle. Comp. X .largecircle. None
.largecircle. Example 1 Comp. X .DELTA. None X Example 2 Comp. X X
Opacity .DELTA. Example 3 Example 2 .largecircle. .circleincircle.
None .circleincircle. Example 3 .largecircle. .circleincircle. None
.circleincircle. Example 4 .largecircle. .circleincircle. None
.circleincircle. Example 5 .largecircle. .circleincircle. None
.circleincircle. Comp. X X Opacity .DELTA. Example 4 Comp. X
.largecircle. None .largecircle. Example 5 Comp. .DELTA.
.largecircle. None .largecircle. Example 6 Comp. X .largecircle.
None .largecircle. Example 7
TABLE-US-00002 TABLE 2 Low refractive index Hard coat layer layer
production production process process Example 1 Production Example
13 Production Example 4 Comp. Example 1 Production Example 13
Production Example 4 Comp. Example 2 Production Example 15
Production Example 12 Comp. Example 3 Production Example 14
Production Example 11 Example 2 Production Example 16 Production
Example 5 Example 3 Production Example 22 Production Example 5
Example 4 Production Example 20 Production Example 7 Example 5
Production Example 16, Production Example 4 Production Example 13
Comp. Example 4 Production Example 17 Production Example 6 Comp.
Example 5 Production Example 19 Production Example 8 Comp. Example
6 Production Example 18 Production Example 9 Comp. Example 7
Production Example 21 Production Example 10
Reference Example
[0395] The construction of an antireflection film according to the
invention and a process for its production are shown schematically
in FIG. 4 and FIG. 5. FIG. 4 shows, at left, the half-cured state
of a base material/half-cured hard coat layer film that has been
half-cured after coating the hard coat layer-forming composition on
the transparent base material. The leveling agent A (indicated by
circles) is uniformly distributed in the hard coat layer. At the
right there is shown the base material/half-cured hard coat
layer/low refractive index layer film state obtained by coating the
base material/half-cured hard coat layer film with the low
refractive index layer. In this drawing, the leveling agent A in
the half-cured hard coat layer begins to migrate toward the top of
the drawing (i.e., the interface with the air). As it migrates, the
concentration of the leveling agent A is reduced in the base
material while it is increased in the low refractive index layer,
thus producing a concentration gradation in the layer. The leveling
agent B (indicated by triangles) is uniformly distributed in the
low refractive index layer.
[0396] FIG. 5 shows, at left, the fully curing state of the base
material/half-cured hard coat layer/low refractive index layer
film. This drawing depicts migration of the leveling agent A from
the hard coat layer which is in a half-cured state into the low
refractive index layer. Leveling agent B simultaneously undergoes
crosslinking with the binder in the low refractive index layer
while the non-crosslinked portions begin to migrate toward the
surface of the low refractive index layer. Leveling agent B becomes
concentrated at the surface, but because of the portions that have
undergone crosslinking and are unable to migrate, the concentration
of leveling agent B does not increase further after a fixed amount
has migrated to the surface. At right there is shown the fully
cured state of the base material/fully cured hard coat layer/low
refractive index layer film. Leveling agent A passes through the
gaps of the crosslinked sections of leveling agent B, and migrates
into the low refractive index layer and even to the surface. Thus,
leveling agent A permeates to the surface of the low refractive
index layer together with leveling agent B that is already present
there, thus forming a cured migration layer in which leveling
agents A and B are uniformly distributed. The surface of the low
refractive index layer is imparted with the performance of the
leveling agents A and B, and therefore exhibits an antifouling
property, fingerprint wiping and mar-proofness.
[0397] The construction of an antireflection film according to an
example of the prior art and a process for its production are shown
schematically in FIG. 6. FIG. 6 shows, at left, a state when a
composition for formation of a functional layer (for example, a
hard coat layer) on a transparent base material has been half-cured
and a low refractive index layer composition coated thereover. The
leveling agent A (indicated by circles) and leveling agent B
(indicated by triangles) are essentially uniformly distributed in
the low refractive index layer. At right there is shown the fully
cured state of the base material/functional layer/low refractive
index layer film. In the drawing, both leveling agents A and B have
migrated toward the interface with air (i.e., top of the drawing),
and the concentration of the leveling agents is reduced in the base
material while being increased at the interface with air, thus
producing a concentration gradation in the layer. Since silicon has
the property of more readily appearing at the surface of the low
refractive index layer than fluorine during curing, although the
reason for this is unclear, migration of the leveling agent B
(reactive silicon leveling agent) occurs more easily than the
leveling agent A (non-reactive F-based leveling agent), and
therefore the surface has a higher concentration of leveling agent
B. Consequently, leveling agent A does not appear as readily at the
surface, and it is essentially leveling agent B alone that is
present at the surface of the low refractive index layer.
Therefore, instead of exhibiting the performance of both leveling
agents A and B at the surface of the low refractive index layer,
only the performance of one leveling agent (that is, leveling agent
B) is exhibited, such that all of the properties including
antifouling property, fingerprint wiping and mar-proofness cannot
be expected.
BRIEF DESCRIPTION OF THE DRAWINGS
[0398] FIG. 1 is a schematic view of an example of the
cross-section of an antireflection film according to the
invention.
[0399] FIG. 2 is a schematic view of the mechanism for modification
of particle surfaces by crosslink-forming groups according to the
invention.
[0400] FIG. 3 is a schematic view of another mechanism for
modification of particle surfaces by crosslink-forming groups
according to the invention.
[0401] FIG. 4 is a schematic view of the construction of an
antireflection film according to the invention and a process for
its production (base material/half-cured hard coat layer/low
refractive index layer film and its formation).
[0402] FIG. 5 is a schematic view of the construction of an
antireflection film according to the invention and a process for
its production (base material/fully-cured hard coat layer/low
refractive index layer film and its formation).
[0403] FIG. 6 is a schematic view of the construction of an
antireflection film according to an example of the prior art and a
process for its production.
EXPLANATION OF SYMBOLS
[0404] 1 Antireflection film [0405] 10 Transparent base material
[0406] 20 Hard coat layer [0407] 30 Low refractive index layer
[0408] 40 Migration layer
* * * * *