TECHNICAL FIELD
[0001] The present invention relates to an anti-glare film used in various displays (e.g.,
a liquid crystal display) for computers, word processors, televisions and others,
a process for producing the same, and a display apparatus comprising (or equipped
with) the anti-glare film.
BACKGROUND ART
[0002] Recently, various displays such as a liquid crystal display, a plasma display, an
organic EL (electroluminescence) display, an inorganic EL display and a FED (field
emission display) have been developed. In particular, remarkable progress as a display
apparatus has been made in the liquid crystal display for television (TV) application
or movie display application, and the liquid crystal display has been rapidly popularized.
For example, the development of a liquid crystal material having a high-speed responsiveness
or the improvement of a drive system such as overdrive has overcome conventional poor
movie display in the liquid crystal, and the innovation of industrial technology corresponding
to the increase in display size has progressed.
[0003] In these displays, a treatment for inhibiting reflection of an exterior light is
usually subjected to a surface thereof in application that regards image quality as
important (e.g., a television and a monitor) and application that uses in the open
air with a strong exterior light (e.g., a video camera). One of the means is an anti-glare
treatment. For example, a surface of a liquid crystal display is usually subjected
to the anti-glare treatment. The anti-glare treatment forms a finely uneven structure
on the surface of the display so as to have effects on scattering of a reflected light
from the surface and blurring of a reflected image on the surface. Therefore, in the
anti-glare layer, different from a clear anti-reflection film, since shapes of viewer
and background are not reflected, the reflected light is hard to get in the way of
a projected image (or screen image) on the display.
[0004] For example, Japanese Patent Application Laid-Open No.
337734/1999 (
JP-11-337734A, Patent Document 1) discloses an antiglare-treated layer having an uneven structure
on a surface thereof, the layer being used as a surface-treated layer formed on a
surface of a polarizing film being preferable for a material of a liquid crystal cell.
This document mentions that the antiglare-treated layer is formed by coating (e.g.,
spin-coating) a resin solution in which fine particles having a high refraction index
are dispersed, or by coating (e.g., spin-coating) only an acrylic resin and then directly
imparting irregularity to the surface mechanically or chemically.
[0005] Japanese Patent Application Laid-Open No.
215307/2001 (
JP-2001-215307A, Patent Document 2) discloses an anti-glare layer containing a transparent fine particle
having a mean particle size of 15 µm in a coat layer whose thickness is not less than
twice of the mean particle size, wherein the anti-glare layer has a surface having
a finely uneven structure through unevenly distributing the transparent fine particles
in one side being in touch with air of the coat layer.
[0006] However, these anti-glare layers give an uneven structure on a film surface for imparting
anti-glareness to the film, and enhances scattering of light from the surface accordingly.
As a result, a part which originally appears to be black washes out (or becomes whitish)
by incidence of the scattered light. That is, in a place where a strong exterior light
shines, a screen becomes wholly whitish (whitening) and lacks contrast property. In
particular, in the television (TV) application, the recent home theater boom serves
as a tail wind for requirement of a contrasty projected image in which black is firmer.
Further, in the process using such fine particles, it is difficult to produce an anti-glare
layer which can impart anisotropy to a light-scattering direction.
[0007] Japanese Patent Application Laid-Open No.
27920/1995 (
JP-7-27920A, Patent Document 3) discloses a polyethylene terephthalate film for attaching to
a polarizing plate which is used for a surface of various displays such as word processors,
computers and televisions, particularly liquid crystal displays, wherein the polyethylene
terephthalate film is antiglare-treated by patterning of a pre-patterned film having
a finely uneven structure on a surface thereof. This document describes that the anti-glare
layer having a finely uneven structure on a surface thereof is obtained by coating
an ionizing radiation-curable resin composition on the polyethylene terephthalate
film, laminating a patterned matt film having a finely uneven structure on a surface
thereof on the coated resin composition in the uncured state, irradiating ionizing
radiation on the laminated matter to completely cure the coat, and separating the
patterned matt film from the completely cured coat.
[0008] In a method using such a patterned film, however, it is difficult to form a finely
uneven structure having anisotropy. Moreover, since it is difficult to produce such
a matt patterned film itself, the anti-glare film is low in high-volume production
capability. Further, it has been also known that such artificial impartment of a regular
arrangement to the surface of the anti-glare layer unescapably brings about interference
of the ref lected light, and then induces moire (formation of a rainbow pattern).
[0009] Japanese Patent Application Laid-Open No.
126495 /2004 (
JP-2004-126495A, Patent Document 4) discloses an anti-glare film comprising at least an anti-glare
layer, wherein the anti-glare layer has an uneven structure on a surface thereof,
and the anti-glare film isotropically transmits and scatters an incident light to
show the maximum value of the scattered light intensity at a scattering angle of 0.1
to 10°, and has a total light transmittance of 70 to 100%. This document describes
that, in a process which comprises preparing a solution of at least one polymer and
at least one curable resin precursor uniformly dissolved in a solvent and evaporating
the solvent from the solution to produce a sheet, spinodal decomposition under an
appropriate condition followed by curing the precursor ensures a phase-separation
structure having regularity and an uneven surface structure corresponding to the phase-separation
structure, and that attachment of such an anti-glare layer having a regular phase-separation
structure to a display apparatus ensures a clear image quality without blur of characters
and concurrently realizes good anti-glare effects without washing out or whitening
(white blur). Further, this document mentions that attachment of the film to a high-definition
display apparatus effectively eliminates dazzle in the display surface and ensures
high-performance anti-glaring function.
[0010] However, since the anti-glare film scatters light isotropically, a scattered reflected-light
causes deterioration in contrast property. Moreover, also in the process, it is difficult
to control phase separability. Further, since slight variation of a lot number of
material, a polymer formulation and other factors remarkably changes the size of the
phase-separation structure, it is difficult to produce an anti-glare sheet stably.
Patent Document 1: JP-11-337734A (Claims 1, 4 and 8, and paragraph number [0001])
Patent Document 2: JP-2001-215307A (Claim 1, and paragraph number [0012])
Patent Document 3: JP-7-27920A (Claims 1 and 3, and paragraph numbers [0001] and [0020])
Patent Document 4: JP-2004-126495A (Claims 1 and 21, and paragraph number [0090])
DISCLOSURE OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0011] It is therefore an object of the present invention to provide an anti-glare film
which inhibits reflection of an exterior light or dazzle and makes a display image
clear (or sharp), a process for producing the anti-glare film, and a display apparatus
comprising (or equipped with) the anti-glare film.
[0012] It is another object of the present invention to provide an anti-glare film which
reduces washing out or whitening (white blur) and makes a display image high contrast,
a process for producing the anti-glare film, and a display apparatus comprising (or
equipped with) the anti-glare film.
[0013] It is still another object of the present invention to provide an anti-glare film
which is highinanti-glareness and inhibits formation of a rainbow pattern (moire)
caused by interference of a reflected light, a process for producing the anti-glare
film, and a display apparatus comprising (or equipped with) the anti-glare film.
[0014] It is a further object of the present invention to provide a process for efficiently
and stably producing an anti-glare film which inhibits reflection of an exterior light
or dazzle and makes a display image contrasty and clear (or sharp).
MEANS TO SOLVE THE PROBLEMS
[0015] The inventors of the present invention made intensive studies to achieve the above
objects and finally found that a film having anisotropy in image clarity is prepared
by forming an uneven part comprising a plurality of domains and a matrix by phase
separation of polymers, and a variety of displays equipped with the film ensures a
clear (or sharp) image display, in which reflection of an exterior light or dazzle
is inhibited. The present invention was accomplished based on the above findings.
[0016] That is, the anti-glare film of the present invention comprises an anti-glare layer
which comprises a matrix comprising a polymer, and a plurality of domains which are
phase-separated from the matrix and comprise a polymer, wherein the domains and the
matrix form an uneven surface in the anti-glare layer, and the film varies an image
clarity measured by an image clarity measuring apparatus provided with an optical
slit depending on an installation direction of the film with respect to the optical
slit. For example, in an image clarity measured by an image clarity measuring apparatus
provided with an optical slit of 0.5 mm width, the difference (absolute value) of
the image clarity before and after changing the installation direction of the film
with respect to the optical slit by 90 degrees may be about 1 to 30. The film may
have anisotropy in a scattered intensity of a reflected light from the film surface.
In the film, at least one uneven part (or site) generated by phase separation may
be formed within the domain(s). The anti-glare layer may be a cured product of at
least one polymer and at least one curable resin precursor. Moreover, the film may
have an uneven surface formed (or hardened) by curing the curable resin precursor.
The polymer may comprise a plurality of polymers capable of phase separation from
each other [e.g., a cellulose derivative and at least one resin selected from the
group consisting of a styrenic resin, a (meth)acrylic resin, an alicyclic olefinic
resin, a polycarbonate-series resin, and a polyester-series resin] , and the curable
resin precursor may be compatible with at least one polymer of the plurality of polymers.
At least one polymer of the plurality of polymers may have a functional group participating
in a curing reaction of the curable resin precursor [e.g., a polymerizable group such
as a (meth)acryloyl group]. The anti-glare film of the present invention may further
comprise a support comprising a transparent polymer film, and the anti-glare layer
may be formed on the support. Moreover, in the anti-glare film of the present invention,
a resin layer having a low refraction index may be further formed on the anti-glare
layer. The resin layer having a low refraction index may comprise a resin having a
refraction index of 1.3 to 1.47. In the anti-glare film of the present invention,
the total light transmittance may be about 70 to 100%, the haze may be about 1 to
30%, and the image (transmitted image) clarity measured by an image clarity measuring
apparatus provided with an optical slit of 0.5 mm width may be about 10 to 70%. Moreover,
in the anti-glare film of the present invention, when a light enters and penetrates
the anti-glare film, part of the incident light may generate grating diffraction at
an angle of 0.01 to 1°; and the ratio of a scattered light intensity at an emission
angle of 30° (I
30) relative to a light intensity at an emission angle of 0° (I
0) in a scattered light profile (I
30/I
0) may be in the range of 0.00001 to 0.001%. Accordingly, the anti-glare film of the
present invention is suitable for a display device or apparatus such as a liquid crystal
display apparatus, a cathode ray tube display, an organic electroluminescence (EL)
display, a field emission display, a surface-conduction electron-emitter display,
a rear projection television display, a plasma display or a touch panel-equipped input
device.
[0017] The present invention also includes a process for producing the anti-glare film,
which comprises tilting a wet coating film comprising a solution containing at least
one polymer, at least one curable resin precursor and a solvent with respect to the
horizontal plane, and generating a cellular rotating convection in the wet coating
film in a step for drying the wet coating film. The production process may be, particularly,
a process which comprises coating a solution containing a plurality of polymers capable
of phase separation from each other, at least one curable resin precursor and a solvent
having a boiling point of not lower than 100°C on a support, placing the resulting
wet coating film at a slope of 10 to 90 degrees with respect to the horizontal plane,
then generating cellular rotating convection in the wet coating film in a step for
drying the wet coating film, and then curing the coating film. Moreover, the solvent
may comprise at least two solvent components with different boiling points. Further,
the coating film may be cured by an action of at least one selected from the group
consisting of an actinic ray and a thermic ray.
EFFECTS OF THE INVENTION
[0018] According to the present invention, since an uneven structure having anisotropy in
image clarity is formed on the surface of the anti-glare film, various displays equipped
with the film realizes display of a clear or sharp image in which reflection of an
exterior light or dazzle is inhibited. Moreover, these displays can display a high-contrast
image in which washing out or whitening (white blur) is reduced. Further, the film
is high in anti-glareness and can inhibit formation of a rainbow pattern (moire) caused
by interference of a reflected light. In particular, according to the present invention,
an anti-glare film having such properties can be efficiently and stably produced.
That is, since the present invention ensures convenient production of an excellent
anti-glare film with a high productivity, the present invention is industrially advantageous.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019]
[Fig. 1] Fig. 1 is a schematic view illustrating an apparatus for measuring a transmitted
scattering profile (an angle distribution of a transmitted scattered-light).
DETAILED DESCRIPTION OF THE INVENTION
[Anti-glare film]
[0020] The anti-glare film of the present invention comprises an anti-glare layer. The anti-glare
layer is usually formed on a support. Moreover, on the anti-glare layer of the anti-glare
film, a resin layer having a low refraction index (a low refraction index layer) may
be further formed.
(Support)
[0021] As the support, there may be used a support having light transmittance properties,
for example, a transparent support such as a synthetic resin film. Moreover, the support
having light transmittance properties may comprise a transparent polymer film for
forming an optical member.
[0022] As the transparent support (or substrate sheet), there may be exemplified a resin
sheet in addition to glass and ceramics. As a resin constituting the transparent support,
the resin similar to that of the after-mentioned anti-glare layer may be used. The
preferred transparent support includes a transparent polymer film, for example, a
film formed with a cellulose derivative [e.g., a cellulose acetate such as a cellulose
triacetate (TAG) or a cellulose diacetate], a polyester-series resin [e.g., a polyethylene
terephthalate (PET), a polybutylene terephthalate (PBT), and a polyarylate-seriesresin],a
polysulfone-series resin [e.g., a polysulfone, and a polyether sulfone (PES)], a polyether
ketone-series resin [e.g., a polyether ketone (PEK), and a polyether ether ketone
(PEEK)], a polycarbonate-series resin (PC), a polyolefinic resin (e.g., a polyethylene,
and a polypropylene), a cyclic polyolefinic resin (e.g., ARTON, ZEONEX), a halogen-containing
resin (e.g., a polyvinylidene chloride), a (meth)acrylic resin, a styrenic resin (e.g.,
a polystyrene), a vinyl acetate-or vinyl alcohol-series resin (e.g., a polyvinyl alcohol)
and others. The transparent support may be stretched monoaxially or biaxially, and
the transparent support having optical isotropy is preferred. The preferred transparent
support is a support sheet or film having a low birefringence index. The optically
isotropic transparent support may include a non-stretched sheet or film, and for example,
may include a sheet or film formed from a polyester (e.g., a PET, and a PBT), a cellulose
ester, in particular a cellulose acetate (e.g., a cellulose acetate such as a cellulose
diacetate or a cellulose triacetate, a cellulose acetate C
3-4acylate such as a cellulose acetate propionate or a cellulose acetate butyrate) or
the like. The thickness of the support having a two-dimensional structure may be selected
within the range of, for example, about 5 to 2000 µm, preferably about 15 to 1000
µm, and more preferably about 20 to 500 µm.
(Anti-glare layer)
[0023] The anti-glare layer comprises a polymer. In particular, in the present invention,
a polymer and a curable resin precursor may be used in combination for improving abrasion
resistance. In such a case, the anti-glare layer may comprise a cured product of at
least one polymer and at least one curable resin precursor. The anti-glare layer produced
by such a process provides a regular or periodic uneven surface in the film by curing
the curable resin.
(1) Polymer component
[0024] As a polymer component, a thermoplastic resin is usually employed. As the thermoplastic
resin, there may be exemplified a styrenic resin, a (meth)acrylic resin, an organic
acid vinyl ester-series resin, a vinyl ether-series resin,a halogen-containing resin,an
olefinic resin (including an alicyclic olefinic resin), a polycarbonate-series resin,
a polyester-series resin, a polyamide-series resin, a thermoplastic polyurethane resin,
a polysulfone-series resin (e.g., a polyether sulfone, and a polysulfone), a polyphenylene
ether-series resin (e.g., a polymer of 2,6-xylenol), a cellulose derivative (e.g.,
a cellulose ester, a cellulose carbamate, and a cellulose ether), a silicone resin
(e.g., a polydimethylsiloxane, and a polymethylphenylsiloxane), a rubber or elastomer
(e.g., a diene-series rubber such as a polybutadiene or a polyisoprene, a styrene-butadiene
copolymer, an acrylonitrile-butadiene copolymer, an acrylic rubber, a urethane rubber,
and a silicone rubber), and the like. These thermoplastic resins may be used singly
or in combination.
[0025] The styrenic resin may include a homo- or copolymer of a styrenic monomer (e.g. a
polystyrene, a styrene-α-methylstyrene copolymer, and a styrene-vinyl toluene copolymer)
and a copolymer of a styrenic monomer and other polymerizable monomer [e.g., a (meth)acrylic
monomer, maleic anhydride, a maleimide-series monomer, and a diene]. The styrenic
copolymer may include, for example, a styrene-acrylonitrile copolymer (AS resin),
a copolymer of styrene and a (meth)acrylic monomer [e.g., a styrene-methyl methacrylate
copolymer, a styrene-methyl methacrylate-(meth)acrylate copolymer, and a styrene-methyl
methacrylate- (meth) acrylic acid copolymer], and a styrene-maleic anhydride copolymer.
The preferred styrenic resin includes a polystyrene, a copolymer of styrene and a
(meth)acrylic monomer [e.g., a copolymer comprising styrene and methyl methacrylate
as a main component, such as a styrene-methyl methacrylate copolymer], an AS resin,
a styrene-butadiene copolymer and the like.
[0026] As the (meth)acrylic resin, a homo- or copolymer of a (meth)acrylic monomer, and
a copolymer of a (meth)acrylic monomer and a copolymerizable monomer may be employed.
As the (meth)acrylic monomer, there may be mentioned, for example, (meth)acrylic acid;
a C
1-10alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate,
t-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate
or 2-ethylhexyl (meth)acrylate; an aryl (meth)acrylate such as phenyl (meth)acrylate;
a hydroxyalkyl (meth)acrylate such as hydroxyethyl (meth)acrylate or hydroxypropyl
(meth)acrylate; glycidyl (meth)acrylate; an N,N-dialkylaminoalkyl (meth)acrylate;
(meth)acrylonitrile; a (meth)acrylate having an alicyclic hydrocarbon group such as
tricyclodecane. The copolymerizable monomer may include the above styrenic monomer,
a vinyl ester-series monomer, maleic anhydride, maleic acid, and fumaric acid. These
monomers may be used singly or in combination.
[0027] As the (meth)acrylic resin, there may be mentioned, for example, a poly(meth)acrylate
such as a poly(methyl methacrylate), a methyl methacrylate-(meth)acrylic acid copolymer,
a methyl methacrylate-(meth)acrylate copolymer, a methyl methacrylate-acrylate-(meth)acrylic
acid copolymer, and a (meth)acrylate-styrene copolymer (MS resin). The preferred (meth)acrylic
resin includes a methyl methacrylate-series resin containing a poly(C
1-6alkyl (meth)acrylate) such as a poly(methyl (meth)acrylate), particularly methyl methacrylate,
as a main component (about 50 to 100% by weight, and preferably about 70 to 100% by
weight).
[0028] As the organic acid vinyl ester-series resin, there may be mentioned a homo- or copolymer
of a vinyl ester-series monomer (e.g., a polyvinyl acetate, and a polyvinyl propionate),
a copolymer of a vinyl ester-series monomer and a copolymerizable monomer (e.g., an
ethylene-vinyl acetate copolymer, a vinyl acetate-vinyl chloride copolymer, and a
vinyl acetate-(meth)acrylate copolymer), or a derivative thereof. The derivative of
the vinyl ester-series resin may include a polyvinyl alcohol, an ethylene-vinyl alcohol
copolymer, a polyvinyl acetal resin, and the like.
[0029] As the vinyl ether-series resin, a homo- or copolymer of a vinyl C
1-10alkyl ether such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether or vinyl
t-butyl ether, and a copolymer of a vinyl C
1-10alkyl ether and a copolymerizable monomer (e.g., a vinyl alkyl ether-maleic anhydride
copolymer).
[0030] The halogen-containing resin may include a polyvinyl chloride, a polyvinylidene fluoride,
a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-(meth)acrylate copolymer,
a vinylidene chloride-(meth)acrylate copolymer, and the like.
[0031] The olefinic resin may include, for example, an olefinic homopolymer such as a polyethylene
or a polypropylene, and a copolymer such as an ethylene-vinyl acetate copolymer, an
ethylene-vinyl alcohol copolymer, an ethylene-(meth)acrylic acid copolymer or an ethylene-(meth)acrylate
copolymer. As the alicyclic olefinic resin, there may be mentioned a homo- or copolymer
of a cyclic olefin such as norbornene or dicyclopentadiene (e.g., a polymer having
an alicyclic hydrocarbon group such as tricyclodecane which is sterically rigid),
a copolymer of the cyclic olefin and a copolymerizable monomer (e.g., an ethylene-norbornene
copolymer, and a propylene-norbornene copolymer). The alicyclic olefinic resin is
available as, for example, the trade name "ARTON", the trade name "ZEONEX" and the
like.
[0032] The polycarbonate-series resin may include an aromatic polycarbonate based on a bisphenol
(e.g., bisphenol A), an aliphatic polycarbonate such as diethylene glycol bisallyl
carbonate, and others.
[0033] The polyester-series resin may include an aromatic polyester obtainable from an aromatic
dicarboxylic acid such as terephthalic acid [for example, a homopolyester, e.g., a
polyC
2-4alkylene terephthalate such as a polyethylene terephthalate or a polybutylene terephthalate,
a polyC
2-4alkylene naphthalate, and a copolyester comprising a C
2-4alkylene arylate unit (a C
2-4alkylene terephthalate unit and/or a C
2-4alkylene naphthalate unit) as a main component (e.g., not less than 50% by weight)].
The copolyester may include a copolyester in which, in constituting units of a polyC
2-4alkylene arylate, part of C
2-4alkylene glycols is substituted with a polyoxyC
2-4alkylene glycol, a C
6-10alkylene glycol, an alicyclic diol (e.g., cyclohexane dimethanol, and hydrogenated
bisphenol A), a diol having an aromatic ring (e.g., 9,9-bis (4-(2-hydroxyethoxy)phenyl)
fluorene having a fluorenone side chain, a bisphenol A, a bisphenol A-alkylene oxide
adduct) or the like, and a copolyester in which, in constituting units, part of aromatic
dicarboxylic acids is substituted with an unsymmetric aromatic dicarboxylic acid such
as phthalic acid or isophthalic acid, an aliphatic C
6-12dicarboxylic acid such as adipic acid, or the like. The polyester-series resin may
also include a polyarylate-series resin, an aliphatic polyester obtainable from an
aliphatic dicarboxylic acid such as adipic acid, and a homo- or copolymer of a lactone
such as ε-caprolactone. The preferred polyester-series resin is usually a non-crystalline
resin, such as a non-crystalline copolyester (e.g., a C
2-4alkylene arylate-series copolyester).
[0034] The polyamide-series resin may include an aliphatic polyamide such as nylon 46, nylon
6, nylon 66, nylon 610, nylon 612, nylon 11 or nylon 12, and a polyamide obtainable
from a dicarboxylic acid (e.g., terephthalic acid, isophthalic acid, and adipic acid)
and a diamine (e.g., hexamethylenediamine, and metaxylylenediamine). The polyamide-series
resin may be a homo- or copolymer of a lactam such as ε-caprolactam, and is not limited
to a homopolyamide but may be a copolyamide.
[0035] Among the cellulose derivatives, the cellulose ester may include, for example, an
aliphatic organic acid ester of a cellulose (e.g., a C
1-6oraganic acid ester of a cellulose such as a cellulose acetate (e.g., a cellulose
diacetate, and a cellulose triacetate), a cellulose propionate, a cellulose butyrate,
a cellulose acetate propionate, or a cellulose acetate butyrate), an aromatic organic
acid ester of a cellulose (e.g. a C
7-12aromatic carboxylic acid ester of a cellulose such as a cellulose phthalate or a cellulose
benzoate) , an inorganic acid ester of a cellulose (e.g., a cellulose phosphate, and
a cellulose sulfate), and may be a mixed acid ester of a cellulose such as a cellulose
acetate nitrate. The cellulose derivative may also include a cellulose carbamate (e.g.
a cellulose phenylcarbamate), a cellulose ether (e.g., a cyanoethylcellulose; a hydroxyC
2-4alkyl cellulose such as a hydroxyethyl cellulose or a hydroxypropyl cellulose; a C
1-6alkyl cellulose such as a methyl cellulose or an ethyl cellulose; a carboxymethyl
cellulose or a salt thereof, a benzyl cellulose, and an acetyl alkyl cellulose).
[0036] The preferred thermoplastic resin includes, for example, a styrenic resin, a (meth)acrylic
resin, a vinyl acetate-series resin, a vinyl ether-series resin, a halogen-containing
resin, an alicyclic olefinic resin, a polycarbonate-series resin, a polyester-series
resin, a polyamide-series resin, a cellulose derivative, a silicone-series resin,
and a rubber or elastomer, and the like. As the thermoplastic resin, there is usually
employed a resin which is non-crystalline and is soluble in an organic solvent (particularly
a common solvent for dissolving a plurality of polymers and curable compounds). In
particular, a resin which is excellent in moldability or film-forming (film-formable)
properties, transparency, and weather resistance [for example, a styrenic resin, a
(meth)acrylic resin, an alicyclic olefinic resin, a polyester-series resin, and a
cellulose derivative (e.g., a cellulose ester)] is preferred. In particular, in the
present invention, the cellulose derivative is preferred as the thermoplastic resin.
Since the cellulose derivative is a semisynthetic polymer and is different in dissolution
behavior from other resin or a curable resin precursor, the cellulose derivative has
very good phase separability.
[0037] As the polymer (or thermoplastic resin), there may be also used a polymer having
a functional group participating (or reacting) in a curing reaction (or a functional
group capable of reacting with the curable precursor). Such a polymer may have the
functional group in a main chain thereof, or in a side chain thereof. The functional
group may be introduced into a main chain of the polymer with co-polymerization, co-condensation
or the like, and is usually introduced into a side chain of the polymer. Such a functional
group may include a condensable or reactive functional group (for example, a hydroxyl
group, an acid anhydride group, a carboxyl group, an amino or imino group, an epoxy
group, a glycidyl group, and an isocyanate group), a polymerizable functional group
[for example, a C
2-6alkenyl group such as vinyl, propenyl, isopropenyl, butenyl or allyl, a C
2-6alkynyl group such as ethynyl, propynyl or butynyl, a C
2-6alkenylidene group such as vinylidene, or a functional group having the polymerizable
functional group(s) (e.g., (meth)acryloyl group)], and others. Among these functional
groups, the polymerizable functional group is preferred.
[0038] The thermoplastic resin having a polymerizable group in a side chain thereof may
for example be produced by allowing to react (i) a thermoplastic resin having a reactive
group (e.g., a group similar to the functional group exemplified in the paragraph
of the condensable or reactive functional group) with (ii) a compound (polymerizable
compound) having a group (reactive group) reactive to the reactive group of the thermoplastic
resin, and a polymerizable functional group to introduce the polymerizable functional
group of the compound (ii) into the thermoplastic resin.
[0039] Examples of the thermoplastic resin (i) having the reactive group may include a thermoplastic
resin having a carboxyl group or an acid anhydride group thereof [for example, a (meth)acrylic
resin (e.g., a (meth)acrylic acid-(meth)acrylate copolymer such as a methyl methacrylate-(meth)acrylic
acid copolymer, and a methyl methacrylate-acrylate-(meth)acrylic acid copolymer),
a polyester-series resin or polyamide-series resin having a terminal carboxyl group],
a thermoplastic resin having a hydroxyl group [for example, a (meth)acrylic resin
(e.g., a (meth)acrylate-hydroxyalkyl (meth)acrylate copolymer), a polyester-series
resin or polyurethane-series resin having a terminal hydroxyl group, a cellulose derivative
(e.g., a hydroxyC
2-4alkyl cellulose such as a hydroxyethyl cellulose or a hydroxypropyl cellulose),a polyamide-series
resin (e.g., an N-methylolacrylamide copolymer)], a thermoplastic resin having an
amino group (e.g., a polyamide-series resin having a terminal amino group), and a
thermoplastic resin having an epoxy group [e.g., a (meth)acrylic resin or polyester-series
resin having an epoxy group (such as a glycidyl group)]. Moreover, as the thermoplastic
resin (i) having the reactive group, there may be used a resin obtained by introducing
the reactive group into a thermoplastic resin (such as a styrenic resin or an olefinic
resin, and an alicyclic olefinic resin) with co-polymerization or graft polymerization.
Among these thermoplastic resins (i), a thermoplastic resin having a carboxyl group
or an acid anhydride group thereof, a hydroxyl group or a glycidyl group (particularly
a carboxyl group or an acid anhydride group thereof), as a reactive group, is preferred.
Incidentally, among the (meth)acrylic resins, the copolymer preferably contains (meth)acrylic
acid at a proportion of not less than 50 mol%. These thermoplastic resins (i) may
be used singly or in combination.
[0040] The reactive group of the polymerizable compound (ii) may include a group reactive
to the reactive group of the thermoplastic resin (i), for example, may include a functional
group similar to the condensable or reactive functional group exemplified in the paragraph
of the functional group of the polymer mentioned above.
[0041] Examples of the polymerizable compound (ii) may include a polymerizable compound
having an epoxy group [e.g., an epoxy group-containing (meth)acrylate (an epoxyC
3-8alkyl (meth)acrylate such as glycidyl (meth)acrylate or 1,2-epoxybutyl (meth)acrylate;
an epoxycycloC
5-8alkenyl (meth)acrylate such as epoxycyclohexenyl (meth)acrylate), and allyl glycidyl
ether], a compound having a hydroxyl group [for example, a hydroxyl group-containing
(meth)acrylate, e.g., a hydroxyC
2-4alkyl (meth)acrylate such as hydroxypropyl (meth)acrylate; a C
2-6alkylene glycol mono(meth)acrylate such as ethylene glycol mono(meth)acrylate], a
polymerizable compound having an amino group [e.g., an amino group-containing (meth)acrylate
(such as a C
3-6alkenylamine such as allylamine); an aminostyrene such as 4-aminostyrene or diaminostyrene],
a polymerizable compound having an isocyanate group [e.g., a (poly)urethane (meth)acrylate,
or vinylisocyanate], and a polymerizable compound having a carboxyl group or an acid
anhydride group thereof [e.g., an unsaturated carboxylic acid or an anhydride thereof,
such as (meth)acrylic acid or maleic anhydride]. These polymerizable compounds (ii)
may be used singly or in combination.
[0042] Incidentally, the combination of the reactive group of the thermoplastic resin (i)
with the reactive group of the polymerizable compound (ii) may include, for example,
the following combinations.
[0043]
(i-1) the reactive group of the thermoplastic resin (i): carboxyl group or acid anhydride
group thereof,
the reactive group of the polymerizable compound (ii): epoxy group, hydroxyl group,
amino group, isocyanate group;
(i-2) the reactive group of the thermoplastic resin (i): hydroxyl group,
the reactive group of the polymerizable compound (ii): carboxyl group or acid anhydride
group thereof, isocyanate group;
(i-3) the reactive group of the thermoplastic resin (i): amino group,
the reactive group of the polymerizable compound (ii): carboxyl group or acid anhydride
group thereof, epoxy group, isocyanate group; and
(i-4) the reactive group of the thermoplastic resin (i): epoxy group,
the reactive group of the polymerizable compound (ii): carboxyl group or acid anhydride
group thereof, amino group.
[0044] Among the polymerizable compounds (ii), an epoxy group-containing polymerizable compound
(such as an epoxy group-containing (meth)acrylate) is particularly preferred.
[0045] The functional group-containing polymer, e.g., a polymer in which a polymerizable
unsaturated group is introduced into part of carboxyl groups in a (meth)acrylic resin,
is for example available as "CYCLOMER-P" from Daicel Chemical Industries, Ltd. Incidentally,
"CYCLOMER-P" is a (meth)acrylic polymer in which epoxy group(s) of 3,4-epoxycyclohexenylmethyl
acrylate is allowed to react with part of carboxyl groups in a (meth)acrylic acid-(meth)acrylate
copolymer for introducing photo-polymerizable unsaturated group (s) in the side chain.
[0046] The amount of the functional group (particularly the polymerizable group), which
participates in (or associates with) a curing reaction and is introduced into the
thermoplastic resin, is about 0. 001 to 10 mol, preferably about 0.01 to 5 mol and
more preferably about 0.02 to 3 mol relative to 1 kg of the thermoplastic resin.
[0047] These polymers may be used in a suitable combination. That is, the polymer may comprise
a plurality of polymers. The plurality of polymers may be capable of phase separation
from each other (in the absence of a solvent), or may be capable of phase separation
in a liquid phase before complete evaporation of a solvent. Moreover, the plurality
of polymers may be incompatible with each other. In the case of combining a plurality
of polymers, the combination of a first polymer with a second polymer is not particularly
limited, and a plurality of polymers incompatible with each other in the neighborhood
of a processing temperature, for example two polymers incompatible with each other,
may be used in a suitable combination. For example, in the case where the first polymer
is a styrenic resin (e.g., a polystyrene, and a styrene-acrylonitrile copolymer),
the second polymer may be a cellulose derivative (e.g., a cellulose ester such as
a cellulose acetate propionate), a (meth) acrylic resin (e.g. , a poly(methyl methacrylate)),
an alicyclic olefinic resin (e.g., a polymer obtained by using norbornene asa monomer),a
polycarbonate-series resin, a polyester-series resin (e.g., the above-mentioned polyC
2-4alkylene arylate-series copolyester), and others. Moreover, for example, in the case
where the first polymer is a cellulose derivative (e.g., a cellulose ester such as
cellulose acetate propionate), the second polymer may be a styrenic resin (e.g., a
polystyrene, and a styrene-acrylonitrile copolymer), a (meth)acrylic resin, an alicyclic
olefinic resin (e.g., a polymer obtained by using norbornene asa monomer),a polycarbonate-seriesresin,
a polyester-series resin (e.g., the above-mentioned polyC
2-4alkylene arylate-series copolyester), and others. In the combination of a plurality
of resins, there may be used at least a cellulose ester (for example, a C
2-4aliphatic carboxylic acid ester of a cellulose such as a cellulose diacetate, a cellulose
triacetate, a cellulose acetate propionate or a cellulose acetate butyrate).
[0048] The glass transition temperature of the polymer may for example be selected within
the range of about -100°C to 250°C, preferably about -50°C to 230°C, andmorepreferably
about 0°C to 200°C (for example, about 50°C to 180°C).
[0049] It is advantageous from the viewpoint of surface hardness that the glass transition
temperature is not lower than 50°C (e.g., about 70°C to 200°C) and preferably not
lower than 100°C (e.g., about 100°C to 170°C). The weight-average molecular weight
of the polymer may for example be selected within the range of not more than 1,000,000,
and preferably about 1,000 to 500,000.
[0050] An uneven surface having projections formed by rotating convection (for example,
an uneven surface having projections due to phase-separation structure which is controlled
in arrangement and size by convection cell) is finally cured by an actinic ray (e.g.
, an ultraviolet ray, and an electron beam), a thermic ray, or others so that a cured
resin is formed. Accordingly, such a cured resin can impart abrasion resistance (hardcoat
property) to the anti-glare film, and can improve durability of the anti-glare film.
[0051] From the viewpoint of abrasion resistance after curing, at least one of the plurality
of polymers, e.g., one of polymers incompatible with each other (in the case of using
a first resin with a second resin in combination, particularly both polymers) is preferably
a polymer having a functional group, reactive to the curable resin precursor, in a
side chain thereof.
[0052] The ratio (weight ratio) of the first polymer relative to the second polymer [the
former/the latter] may be, for example, selected within the range of about 1/99 to
99/1, preferably about 5/95 to 95/5 and more preferably about 10/90 to 90/10, and
is usually about 20/80 to 80/20, particularly about 30/70 to 70/30. In particular,
in the case of using a cellulose derivative as the first polymer, the ratio (weight
ratio) of the first polymer relative to the second polymer [the former/the latter]
is, for example, about 1/99 to 30/70, preferably about 5/95 to 28/72, and more preferably
about 10/90 to 27/73 (particularly, about 15/85 to 25/75).
[0053] Incidentally, the polymer for forming a phase-separation structure may comprise the
thermoplastic resin or other polymer (s) in addition to the above-mentioned two polymers
incompatible with each other.
(2) Curable resin precursor
[0054] As the curable resin precursor, there may be used various curable compounds having
a reactive functional group by a thermic ray or an actinic ray (e.g., an ultraviolet
ray, and an electron beam), and being capable of forming a resin (particularly a cured
or crosslinked resin) by curing or crosslinking with heat or an actinic ray.
[0055] For example, as the resin precursor, there may be mentioned a thermosetting compound
or resin [a low molecular weight compound (or prepolymer such as a low molecular weight
resin (e.g., an epoxy-series resin, an unsaturated polyester-series resin, a urethane-series
resin, and a silicone-series resin)) having an epoxy group, an isocyanate group, an
alkoxysilyl group, a silanol group, a polymerizable group (such as vinyl group, allyl
group, and (meth)acryloyl group), or others], and a photo-curable compound which is
curable with an actinic ray (such as ultraviolet ray) (e.g., an ultraviolet curable
compound such as a photo-curable monomer, oligomer, or prepolymer). The photo-curable
compound may be an EB (electron beam) curable compound, or others. Incidentally, a
photo-curable compound such as a photo-curable monomer, a photo-curable oligomer,
or a photo-curable resin which may have low molecular weight is sometimes simply referred
to as "photo-curable resin". These curable resin precursors may be used singly or
in combination.
[0056] The photo-curable compound usually has a photo-curable group, for example, a polymerizable
group (e.g., vinyl group, allyl group, (meth)acryloyl group) or a photosensitive group
(e.g., cinnamoyl group), and in particular, is preferably a photo-curable compound
having a polymerizable group [e.g., a monomer, an oligomer (or resin, particularly
a low molecular weight resin)]. These photo-curable compounds may be used singly or
in combination.
[0057] Among the photo-curable compounds having a polymerizable group, as the monomer, for
example, there may be exemplified a monofunctional monomer [for example, a (meth)acrylic
monomer such as a (meth)acrylic ester, e.g., an alkyl (meth)acrylate (e.g., a C
1-6alkyl (meth)acrylate such as methyl (meth)acrylate), a cycloalkyl (meth)acrylate,
a (meth)acrylate having a crosslinked cyclic hydrocarbon group (e.g., isobornyl (meth)acrylate,
and adamantyl (meth)acrylate), glycidyl (meth)acrylate; a vinyl-series monomer such
as a vinyl ester (e.g., vinyl acetate) or vinylpyrrolidone], a polyfunctional monomer
having at least two polymerizable unsaturated bonds [for example, an alkylene glycol
di(meth)acrylate such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate,
butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, or hexanediol di(meth)acrylate;
a (poly)oxyalkylene glycol di(meth)acrylate such as diethylene glycol di(meth)acrylate,
dipropylene glycol di(meth)acrylate, or a polyoxytetramethylene glycol di(meth)acrylate;
a di(meth)acrylate having a crosslinked cyclic hydrocarbon group (e.g., tricyclodecane
dimethanol di(meth)acrylate, and adamantane di(meth)acrylate); and a polyfunctional
monomer having about 3 to 6 polymerizable unsaturated bonds (e.g., trimethylol propane
tri(meth)acrylate, trimethylol ethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate,
pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate)].
[0058] Among the photo-curable compounds having a polymerizable group, examples of the oligomer
or resin may include a (meth)acrylate of a bisphenol A added with an alkylene oxide,
an epoxy (meth)acrylate (e.g., a bisphenol A-based epoxy (meth)acrylate, and a novolak-based
epoxy (meth)acrylate), a polyester (meth)acrylate (e.g., an aliphatic polyester-based
(meth)acrylate, and an aromatic polyester-based (meth)acrylate), a (poly)urethane
(meth)acrylate (e.g., a polyester-based urethane (meth)acrylate, and a polyether-based
urethane (meth)acrylate), a silicone (meth)acrylate, and others.
[0059] The preferred curable resin precursor includes a photo-curable compound curable in
a short time, for example, an ultraviolet curable compound (e.g., a monomer, an oligomer,
and a resin which may be a low molecular weight resin), and an EB curable compound.
In particular, a practically advantageous resin precursor is an ultraviolet curable
monomer, or an ultraviolet curable resin. Further, to improve resistance such as abrasion
resistance, the photo-curable resin is preferably a compound having polymerizable
unsaturated bonds of not less than 2 (preferably about 2 to 6, and more preferably
about 2 to 4) in the molecule.
[0060] The molecular weight of the curable resin precursor is, allowing for compatibility
to the polymer, not more than about 5000 (e.g., about 100 to 5000), preferably not
more than about 2000 (e.g., about 150 to 2000), and more preferably not more than
about 1000 (e.g., about 200 to 1000).
[0061] The curable resin precursor may be used in combination with a curing agent depending
on the variety. For example, a thermosetting resin precursor may be used in combination
with a curing agent such as an amine or a polyfunctional carboxylic acid (or polycarboxylic
acid), or a photo-curable resin precursor may be used in combination with a photopolymerization
initiator.
[0062] As the photopolymerization initiator, there may be exemplified a conventional component,
e.g., an acetophenone, a propiophenone, a benzyl, a benzoin, a benzophenone, a thioxanthone,
an acylphosphine oxide, and others.
[0063] The content of the curing agent (such as a photo curing agent) relative to 100 parts
by weight of the curable resin precursor is about 0.1 to 20 parts by weight, preferably
about 0.5 to 10 parts by weight, and more preferably about 1 to 8 parts by weight
(particularly about 1 to 5 parts by weight), and may be about 3 to 8 parts by weight.
[0064] Further, the curable resin precursor may contain a curing accelerator or a crosslinking
agent. For example, the photo-curable resin precursor may be used in combination with
a photo-curing accelerator, e.g., a tertiary amine (e.g., a dialkylaminobenzoic ester)
or a phosphine-series photopolymerization accelerator.
[0065] In the present invention, among at least one polymer and at least one curable resin
precursor, at least two components are preferably used in such a combination as they
are phase-separated with each other in the neighborhood of a processing temperature.
As such a combination, for example, there may be mentioned (a) a combination in which
a plurality of polymers are incompatible with each other and form a phase separation,
(b) a combination in which a polymer and a curable resin precursor are incompatible
with each other and form a phase separation, (c) a combination in which a plurality
of curable resin precursors are incompatible with each other and form a phase separation,
and other combinations. Among these combinations, (a) the combination of a plurality
of polymers or (b) the combination of a polymer with a curable resin precursor is
usually employed, and (a) the combination of a plurality of polymers is particularly
preferred. In the case where both components to be phase-separated have high compatibility,
both components fail to generate effective phase separation during a drying step for
evaporating the solvent, and as a result the layer obtained therefrom deteriorates
functions as an anti-glare layer.
[0066] Incidentally, the thermoplastic resin and the curable resin precursor (or cured resin)
are usually incompatible with each other. When the polymer and the curable resin precursor
are incompatible with each other and are phase-separated, a plurality of polymers
may be used as the polymer. In the case of using a plurality of polymers, at least
one polymer needs only to be incompatible with the resin precursor (or cured resin),
and other polymer(s) may be compatible with the resin precursor.
[0067] Moreover, the above-mentioned combination may be a combination of two thermoplastic
resins incompatible with each other and a curable compound (in particular a monomer
or oligomer having a plurality of curable functional groups). Further, from the viewpoint
of abrasion resistance after curing, one polymer of the above-mentioned incompatible
thermoplastic resins (particularly both polymers) may be a thermoplastic resin having
a functional group participating in a curing reaction (a functional group participating
in curing of the curable resin precursor).
[0068] In the case where the polymer comprises a plurality of polymers incompatible with
each other to form phase separation, it is preferred that the curable resin precursor
is compatible with at least one polymer in the neighborhood of a processing temperature,
among a plurality of polymers incompatible with each other. That is, when a plurality
of polymers incompatible with each other comprise, for example, a first polymer and
a second polymer, the curable resin precursor needs only to be compatible with at
least one resin of the first polymer and the second polymer, or may be compatible
with both polymer components. In the case where the curable resin precursor is compatible
with both polymer components, at least two phases which are phase-separated may be
obtained, one phase comprises a mixture containing the first polymer and the curable
resin precursor as main components, and the other phase comprises a mixture containing
the second polymer and the curable resin precursor as main components.
[0069] In the case where a plurality of polymers to be selected have high compatibility,
the polymers fail to generate effective phase separation among themselves during a
drying step for evaporating the solvent, and as a result the layer obtained therefrom
deteriorates functions as an anti-glare film.
[0070] The curable monomer and a plurality of polymers incompatible with each other are
used in such a combination that at least one polymer and the curable monomer are compatible
with each other in the neighborhood of a processing temperature. That is, when a plurality
of polymers incompatible with each other comprise, for example, a polymer A and a
polymer B, the curable monomer needs only to be compatible with at least one of the
polymer A and the polymer B, or may be preferably compatible with both polymer components.
In the case where the curable monomer is compatible with both polymer components,
at least two phases which are phase-separated are obtained, one phase comprises a
mixture containing the polymer A and the curable monomer as main components, and the
other phase comprises a mixture containing the polymer B and the curable monomer as
main components.
[0071] Incidentally, each of the phase separability among a plurality of polymers, and the
phase separability among the polymer and the curable monomer can be judged conveniently
by visually conforming whether the residual solid content becomes clouded or not during
a step of preparing a uniform solution with a good solvent to both components and
gradually evaporating the solvent.
[0072] Further, the polymer and a cured or crosslinked resin obtained by curing the resin
precursor are usually different from each other in refraction index. Moreover, the
plurality of polymers (the first polymer and the second polymer) is also different
from each other in refraction index. The difference in the refraction index between
the polymer and the cured or crosslinked resin, or the difference in the refraction
index between the plurality of polymers (the first polymer and the second polymer)
may for example be about 0.001 to 0.2, and preferably about 0.05 to 0.15.
[0073] With the progress of the phase separation, the bicontinuous structure is formed.
On further proceeding the phase separation, the continuous phase becomes discontinuous
owing to its own surface tension to change into the droplet phase structure (e.g.,
an islands-in-the-sea structure containing independent phases such as ball-like shape,
spherical shape, discotic shape, oval-sphere shape or rectangular prism shape). Therefore,
an intermediate structure of the bicontinuous phase structure and the drop phase structure
(i.e. , a phase structure in a transitional state from the bicontinuous phase to the
drop phase) can also be formed by varying the degree of phase separation. The phase-separation
structure in the anti-glare layer in the present invention may be an islands-in-the-sea
structure (a droplet phase structure, or a phase structure in which one phase is independent
or isolated) or a bicontinuous phase structure (or a mesh structure), or may be an
intermediate structure being a coexistent state of a bicontinuous phase structure
and a droplet phase structure. The phase-separation structure realizes the formation
of a finely uneven structure on the surface of thus obtained anti-glare film after
drying of the solvent.
[0074] Thus, the anti-glare layer having an uneven surface formed by phase separation contains
no fine particle which leads to scattering in the interior of the layer, differently
from an anti-glare layer obtained by a method which comprises dispersing a fine particle
to form an uneven surface. Therefore, the haze in the interior of the layer (the internal
haze leading to scattering in the interior of the layer) is low, for example, may
be about 0 to 1%, preferably about 0 to 0.8% (e.g., about 0.01 to 0.8%), and more
preferably about 0 to 0.5% (e.g., 0.1 to 0.5%). Incidentally, the internal haze can
be determined by coating a resin layer on the anti-glare layer or pasting a smooth
transparent film on the uneven surface of the anti-glare layer through a transparent
adhesive layer so as to planarize the uneven surface of the anti-glare layer, and
measuring a haze of the planarized matter.
[0075] In the phase-separation structure, it is advantageous from the viewpoint of forming
the uneven surface structure and of enhancing the surface hardness that the structure
forms a droplet phase structure having at least an island domain. Incidentally, when
the phase-separation structure comprising a polymer and the above-mentioned precursor
(or cured resin) forms an islands-in-the-sea structure, the polymer component may
form a sea phase. It is however advantageous from the viewpoint of surface hardness
that the polymer component forms island domains. The formation of the island domains
realizes a finely uneven structure on the surface of thus obtained anti-glare layer
after drying. In particular, in the present invention, the island domain may be a
deformed (or irregular) shape (e.g., a long shape such as oval- sphere shape or rectangular
prism shape) for having anisotropy in image clarity and light scattered intensity.
Further, these deformed island domains may be partly united with each other to form
a mountain range-like domain.
[0076] The ratio (weight ratio) of the polymer relative to the curable resin precursor is
not particularly limited to a specific one, and for example, the polymer/the curable
resin precursor may be selected within the range of about 5/95 to 95/5. From the viewpoint
of surface hardness, the ratio (weight ratio) is preferably about 5/95 to 60/40, more
preferably about 10/90 to 50/50, and particularly about 10/90 to 40/60. In particular,
in the case of using a cellulose derivative in whole or part of the polymer, the ratio
(weight ratio) of the polymer relative to the curable resin precursor [the former/the
latter] is, for example, about 10/90 to 80/20, preferably about 20/80 to 70/30, and
more preferably about 30/70 to 50/50.
[0077] The thickness of the anti-glare layer may for example be about 0.3 to 20 µm, preferably
about 1 to 18 µm (e.g., about 3 to 16 µm), and usually about 5 to 15 µm (particularly
about 7 to 13 µm).
(Low refraction index layer)
[0078] The low refraction index layer comprises a resin having a low refraction index (or
a low refraction index resin). By laminating the low refraction index layer on at
least one side of the anti-glare layer, when the low refraction index layer is disposed
so that the layer becomes the top layer in an optical member or others, it can be
effectively inhibited that an external light (e.g., an exterior light source) is reflected
in the surface of the anti-glare film.
[0079] The refraction index of the low refraction index resin may for example be about 1.30
to 1.49, preferably about 1.36 to 1.49, and more preferably about 1.38 to 1.48.
[0080] Examples of the low refraction index resin may include a methylpentene resin, a diethylene
glycol bis(allylcarbonate) resin, and a fluorine-containing resin such as a polyvinylidene
fluoride (PVDF) or a polyvinylfluoride (PVF). Moreover, usually the low refraction
index layer preferably contains a fluorine-containing compound. In the case of using
the fluorine-containing compound, since the refraction index of the low refraction
index layer can be reduced, the refraction index can be suitably selected.
[0081] The fluorine-containing compound may include a fluorine-containing resin precursor
which has a fluorine atom, and a reactive functional group (e.g., a curable group
such as a crosslinkable group or a polymerizable group) by heat or an actinic ray
(e.g., an ultraviolet ray or an electron beam) or the like, and can be cured or crosslinked
by heat or an actinic ray or the like to form a fluorine-containing resin (particularly
a cured or crosslinked resin).
[0082] Examples of such a fluorine-containing resin precursor may include a fluorine atom-containing
thermosetting compound or resin [a low molecular weight compound which has a fluorine
atom, and a reactive group (e.g., an epoxy group, an isocyanate group, a carboxyl
group, a hydroxyl group), a polymerizable group (e.g., a vinyl group, an allyl group,
a (meth)acryloyl group) or others], a fluorine atom-containing photo-curable compound
or resin which is curable by an actinic ray such as an ultraviolet ray (for example,
an ultraviolet ray-curable compound such as a photo-curable fluorine-containing monomer
or oligomer), and others.
[0083] As the thermosetting compound or resin, there may be mentioned, for example, a low
molecular weight resin obtained by using at least a fluorine-containing monomer, e.g.,
an epoxy-series fluorine-containing resin obtained by using a fluorine-containing
polyol (particularly a diol) instead of part or all of polyol components as a constituting
monomer; in the same way, an unsaturated polyester-series fluorine-containing resin
obtained by using a fluorine atom-containing polyol and/or fluorine atom-containing
polycarboxylic acid component instead of part or all of polyol and/or polycarboxylic
acid component(s); a urethane-series fluorine-containing resin obtained by using a
fluorine atom-containing polyol and/or polyisocyanate component instead of part or
all of polyol and/or polyisocyanate component(s); and others. These thermosetting
compounds or resins may be used singly or in combination.
[0084] The photo-curable compound may include, for example, a monomer, an oligomer (or a
resin, in particular a low molecular weight resin). Examples of the monomer may include
a fluorine atom-containing monomer corresponding to the monofunctional monomer and
polyfunctional monomer exemplified in the paragraph of the anti-glare layer mentioned
above [e.g., a monofunctional monomer such as a fluorine atom-containing (meth)acrylic
monomer (such as a fluorinated alkyl ester of (meth)acrylic acid), or a vinyl-series
monomer (such as a fluoroolefin); and a di(meth)acrylate of a fluorinated alkylene
glycol such as 1-fluoro-1,2-di(meth)acryloyloxyethylenel. Moreover, as the oligomer
or resin, a fluorine atom-containing oligomer or resin corresponding to the oligomer
or resin exemplified in the paragraph of the anti-glare layer may be used. These photo-curable
compounds may be used singly or in combination.
[0085] The curable precursor for the fluorine-containing resin is, for example, procurable
in the form of a liquid solution (coating liquid). For example, such a coating liquid
may be available as "TT1006A" and "JN7215" manufactured by Japan Synthetic Rubber
Co. , Ltd., "DEFENSA TR-330" manufactured by Dainippon Ink And Chemicals, Inc. , or
others.
[0086] The thickness of the low refraction index layer may for example be about 0.05 to
2 µm, preferably about 0.06 to 1 µm (e. g. , about 0.08 to 0.5 µm), and more preferably
about 0.1 to 0.3 µm.
(Anti-glare film)
[0087] In the anti-glare film of the present invention, the anti-glare layer comprises a
plurality of domains and a matrix which are phase-separated from each other, and the
domains and the matrix form an uneven surface. The domain is a closed uneven (loop)
region, and usually, it is sufficient that the loop (exterior loop) is almost closed.
Moreover, almost all of the domains may be independent, or some adjacent domains may
be connected with each other through a long and slender (or narrow) connection part.
[0088] That is, in the present invention, the anti-glare film has an uneven surface formed
as convection cells (exterior loops) at a relatively controlled interval corresponding
to arrangement of convection cells. The uneven surface formed by cellular rotating
convection usually has substantial regularity or periodicity. For example, the mean
distance between two adjacent projections (Sm) may be about 20 to 300 µm, and is preferably
about 25 to 250 µm and more preferably about 30 to 200 µm. The mean distance between
two adjacent projections (Sm) is, for example, controllable by the thickness of the
coating film when convection is generated.
[0089] As the surface roughness of the anti-glare film, the centerline average roughness
(Ra) may be, for example, about 0.05 to 0.5 µm, preferably about 0.06 to 0.4 µm, and
more preferably about 0.07 to 0.25 µm (particularly about 0.08 to 0.22 µm). Moreover,
in the case where the anti-glare film has the low refraction index layer, it is preferred
that the film having the coated low refraction index layer has a centerline average
roughness in this range.
[0090] In particular, the anti-glare film of the present invention has anisotropy, and for
example, the image (transmitted image) clarity measured by an image clarity measuring
apparatus provided with an optical slit varies depending on an installation direction
of the film with respect to the optical slit. Specifically, in the image clarity measured
by an image clarity measuring apparatus provided with an optical slit of 0.5 mm width,
the difference (absolute value) of the image clarity before and after changing the
installation direction of the film with respect to the optical slit by 90 degrees
may be, for example, about 1 to 30, preferably about 5 to 28, and more preferably
about 10 to 26 (particularly about 15 to 25). Such a film is usually produced by tilting
a wet coating film with respect to the horizontal plane as mentioned below. In the
obtained film, probably because of anisotropy imparted by a gravitational action,
the image clarity in the case of installing the film so that the direction parallel
to the gravitated direction is parallel to the teeth direction of the optical slit
is larger than that in the case of installing the film so that the direction parallel
to the gravitated direction is perpendicular to the teeth direction of the optical
slit.
[0091] The image clarity is a measure for quantifying defocusing or distortion of a light
transmitted through a film. The image clarity is obtained by measuring a transmitted
light from a film through a movable optical slit, and calculating amount of light
in both a light part and a dark part of the optical slit. That is, in the case where
a transmitted light is defocused by a film, the slit image formed on the optical slit
becomes thicker, and as a result the amount of light in the transmitting part is not
more than 100%. On the other hand, in the non-transmitting part, the amount of light
is not less than 0% due to leakage of light. The value C of the image clarity is defined
by the following formula according to the maximum value M of the transmitted light
in the transparent part of the optical slit, and the minimumvalue m of the transmitted
light in the opaque part thereof.
[0092] 
That is, the closer the value C comes to 100%, the lower the image defocusing depending
on the anti-glare film is. [reference; Suga and Mitamura, Tosou Gijutsu, July, 1985].
[0093] As an apparatus for measuring the image clarity, there may be used an image clarity
measuring apparatus (ICM-1DP, manufactured by Suga Test Instruments Co. , Ltd.). As
the optical slit, there may be used an optical slit of 0.125 mm to 2 mm width.
[0094] In the same way, the anti-glare film of the present invention also has anisotropy
in a scattered intensity of a reflected light from the film surface. That is, in the
film obtained by the above-mentioned process, the scattered light intensity of the
reflection from the film surface in the direction perpendicular to the gravitated
direction is larger than that in the gravitated direction.
[0095] Further, on the anti-glare film of the present invention, an uneven surface is formed
at an interval corresponding to the arrangement of convection in production of the
anti-glare layer. Therefore, in a film comprising an anti-glare layer formed from
cellular convection having a relatively high regularity, when a light enters the film,
part of the transmitted light is diffracted corresponding to the arrangement state.
The diffraction pattern of the anti-glare film of the present invention may be a pattern
which has been known about the relationship between an arrangement and a diffraction
pattern. Preferably, regarding the diffraction pattern, the scattered intensity may
appear at two spots diagonally (at equal distances from the center and oppositely
each other on the line containing the center).
[0096] Furthermore, in the anti-glare film of the present invention, at least one uneven
part (internal cell) generated by phase separation may be formed within the domain.
The uneven part may be formed as a raised part (minute raised region) protruded by
a rising flow or a depressed part (minute depressed region) or caved by a rising flow
at a position corresponding to a central part or peripheral part of the convection
cell. This uneven part is also a closed loop (interior loop), and usually, the interior
loop may be almost closed. Moreover, the interior loop is independent in many cases.
Some adjacent loops may be connected with each other through a long and slender (or
narrow) connection part. In particular, one to several (e.g., about 1 to 3) uneven
part(s) (particularly punctiform raised part(s)) may be formed within one domain.
The shape of the uneven part (interior loop) (the two-dimensional shape of the film
surface, or the outline of the border between the interior loop and the exterior loop)
is not particularly limited to a specific one, and is amorphous, a circular form,
an oval form, a polygonal form, and others. The shape is usually a circular form or
an oval form. Incidentally, in the case where a minute uneven part is formed inside
each convection cell by a rising flow or phase-separation structure, the light scattering
property of the film is improved, as a result, dazzle of a reflection image can be
inhibited. Further, such a formation of a minute uneven part inside each convection
cell is particularly preferred since each distance between interior loops of the cells
becomes equally so that the domain forms a uniform uneven shape.
[0097] The size (diameter) of the interior loop (minute uneven part) may be, for example,
about 3 to 150 µm, and is preferably about 5 to 100 µm and more preferably about 10
to 50 µm (particularly about 15 to 40 µm). The area ratio of the interior loop is
about 1 to 80%, preferably about 3 to 50% and more preferably about 5 to 40% (particularly
about 10 to 30%) relative to the exterior loop area.
[0098] When a light enters and penetrates the anti-glare film of the present invention,
part of the incident light generates grating diffraction at a certain angle with respect
to the incident light (about 0.3°) (diffraction angle). Specifically, such a diffraction
angle is , for example, about 0.01 to 1°, preferably about 0.05 to 0.8°, and more
preferably about 0.1 to 0.7° (particularly about 0.15 to 0.5°).
[0099] The total light transmittance of the anti-glare film of the present invention is,
for example, about 70 to 100%, preferably about 80 to 99%, and more preferably about
85 to 98% (particularly, about 88 to 97%).
[0100] The haze of the anti-glare film of the present invention is about 1 to 50%, preferably
about 2 to 40%, and more preferably about 3 to 35% (particularly, about 5 to 30%).
Moreover, in the case where the film comprises the low refraction index layer coated
on the anti-glare layer, the haze of the film shows a lowering of about 1 to 10% compared
with that of a film comprising the anti-glare layer alone. The haze of a film comprising
the anti-glare layer and the low refraction index layer in combination is, for example,
about 1 to 30%, preferably about 2 to 25%, more preferably about 2 to 20%, and usually
about 3 to 15%. In the case of forming the low refraction index layer, it is preferred
to adjust the haze of the anti-glare layer in consideration of the lowering of the
haze.
[0101] The haze and the total light transmittance can be measured with a NDH-300A haze meter
manufactured by Nippon Denshoku Industries Co. , Ltd. in accordance with JIS K7105.
[0102] The image clarity of the anti-glare film of the present invention is, in the case
of using an optical slit of 0.5 mm width, about 10 to 70%, preferably about 15 to
60% and more preferably about 20 to 50% (particularly about 25 to 45%). In the case
of using an optical slit of 0.25 mm width, the image clarity is about 10 to 70%, preferably
about 20 to 60% and more preferably about 25 to 50%. In the case where the image clarity
is within the range, the outline (or contour) of reflection can be enough blurred
so that excellent anti-glareness can be imparted to the film. Too high image clarity
deteriorates an effect on inhibition of reflection. On the other hand, too small image
clarity inhibits the above-mentioned reflection but deteriorates clearness (or sharpness)
of image.
[0103] In the anti-glare film of the present invention, for achieving desired visibility
(particularly, for improving sharpness of image), the ratio of the scattered light
intensity at an emission angle of 30° (I
30) relative to the light intensity at an emission angle of 0° (I
0) in a scattered light profile (I
30/I
0) is adjusted to be within the range of 0.00001 to 0.001%. The ratio of the light
scattered intensity (I
30/I
0) is preferably about 0.00003 to 0.0009%, and more preferably about 0.00005 to 0.0008%
(particularly about 0.00007 to 0.0007%).
[0104] Further, in terms of improving image sharpness, the ratio of the scattered light
intensity at an emission angle of 10° (I
10) relative to the light intensity at an emission angle of 0° (I
0) in a scattered light profile (I
10/I
0) is, for example, about 0.0001 to 0.1%, preferably about 0.0003 to 0.008%, and more
preferably about 0.0005 to 0.005%.
[0105] The scattered light profile about the anti-glare film may be measured by using a
goniophotometer, for example, a commercially available automatic goniophotometer (GP-200
type, manufactured by Murakami Color Research Laboratory). For example, the angle
distribution of the light transmitted through the anti-glare film can be measured
by means of a measuring equipment comprising a laser beam source 1 such as He-Ne laser,
andabeamreceiver 4 set on a goniophotometer, as shown in Fig. 1. In the embodiment,
the relationship between the scattered light intensity and the scattering angle θ
is determined by irradiating a sample 3 with a laser beam from the laser beam source
1 through an ND filter 2, and detecting the scattered light from the sample by means
of a detector (beam receiver) 4 which is capable of varying an angle at a scattering
angle θ relative to a light path of the laser beam and comprises a photomultiplier.
As such an equipment, an automatic measuring equipment for laser beam scatteration
(manufactured by NEOARK Corporation) is utilizable.
[Process for producing anti-glare film]
[0106] The anti-glare film of the present invention may be produced by tilting a wet coating
film which comprises a solution containing at least one polymer, at least one curable
resin precursor and a solvent with respect to the horizontal plane, and generating
a cellular rotating convection in the wet coating film in a step for drying the wet
(undried) coating film. More specifically, the production may be usually carried out
by coating the solution on a support, tilting the resulting wet coating film, and
evaporating the solvent from the coating film. Further, the preferred process comprises
coating a solution containing a plurality of polymers capable of phase separation
from each other, at least one curable resin precursor and a solvent having a boiling
point of not lower than 100°C on a support, placing the resulting wet coating film
with the wet coating film tilted with respect to the horizontal plane, generating
cellular rotating convection (convection cell) in the wet coating film in a step for
drying the wet coating film, and then curing the coating film to give an anti-glare
film. Incidentally, in the case of using a separable support as the support, the coating
film may be released (or separated) from the support to give an anti-glare membrane.
(Cellular rotating convection)
[0107] In the present invention, the regular or periodic uneven surface is formed in the
film by coating the solution, and raising the surface of the coating film by a cellular
rotating convection. In general, evaporation of the solvent for dryness and cooling
of near the surface of the coating film by vaporization heat induce a temperature
difference beyond the criticality between the upper and lower layers of the coating
film, as a result the rotating convection is generated. Such a convection is referred
to as Benard convection. Moreover, Benard convection is discovered by Benard and theoretically
systematized by Rayleigh, therefore the convection is also referred to as Benard-Rayleigh
convection. The critical temperature difference (ΔT) is determined by the thickness
of the coating film (d), the coefficient of kinematic viscosity of the coating film
(solution) (v), the thermal diffusibility of the coating film (κ), the coefficient
of cubical expansion of the coating film (α) and the gravitational acceleration (g).
The convection is generated when the Rayleigh number (Ra) defined by the following
formula exceeds a certain critical value.
[0108] 
The generated convection regularly repeats upstroke and downstroke so that the surface
of the film has a regular or periodic unevenness arranged in a cell-like form. It
is known that the aspect ratio of the cell (the coated direction/the thick direction)
is about 2/1 to 3/1.
[0109] Moreover, the mode of the cellular rotating convection is not particularly limited
to a specific one, and may be other convection mode. For example, the mode of the
cellular rotating convection may be Marangoni convection (density convection) due
to inhomogeneously distributed surface tension.
(Combination of convection and phase separation)
[0110] In the present invention, as mentioned above, the uneven surface is formed by generating
rotating convection to give convection flow and concentration difference in solid
content. Together with such convection, two components having phase separability from
each other (at least two components among polymers and curable resin precursors) may
be phase-separated by using a solution containing the components to form a phase-separation
structure. Although the details of mechanism in combination of convection and phase
separation are not yet elucidated, the mechanism can be presumed as follows.
[0111] By combining convection and phase separation, firstly convection cells are generated
after coating. Next, phase separation is developed within each of the convection cells.
The phase-separation structure grows to an enormous size with time, and the growth
of the phase separation is stopped in the wall of the convection cell. As a result,
the interval of the phase separation structure is controlled depending on the size
and arrangement of the convection cell, and the phase-separation structure is accompanied
by forming an uneven pattern (or part) having a good size and height. That is, an
anti-glare film in which the shape, arrangement and size of the uneven pattern (or
part) are sufficiently controlled can be obtained.
(Solvent)
[0112] In the present invention, the convection or phase separation may be conducted by
evaporating the solvent from the solution containing the polymer and the curable resin
precursor. In particular, among components contained in the solution, the solvent
is absolutely necessary to generate convection stably. The reason is that the solvent
has an action for lowering a surface temperature of a coating film by vaporization
heat due to evaporation, and further has fluidity for flowing and circulating generated
convection without stagnation.
[0113] The solvent may be selected depending on the species and solubility of the polymer
and curable resin precursor to be used. In the case of a mixed solvent, at least one
solvent component needs only to be a solvent for uniformly dissolving a solid content
(a plurality of polymers and curable resin precursor(s), a reaction initiator, other
additive(s)). As such a solvent, there may be mentioned, for example, a ketone (e.g.
, acetone, methyl ethyl ketone, methyl isobutyl ketone,and cyclohexanone), an ether
(e.g., dioxane, and tetrahydrofuran), an aliphatic hydrocarbon (e.g., hexane), an
alicyclic hydrocarbon (e.g., cyclohexane), an aromatic hydrocarbon (e.g., toluene,
and xylene), a carbon halide (e.g., dichloromethane, and dichloroethane), an ester
(e.g., methyl acetate, ethyl acetate, and butyl acetate), water, an alcohol (e.g.,
ethanol, isopropanol, butanol, and cyclohexanol), a cellosolve (e.g., methyl cellosolve,
and ethyl cellosolve), a cellosolve acetate, a sulfoxide (e.g., dimethyl sulfoxide),
and an amide (e.g., dimethylformamide, and dimethyhlacetamide). These solvents may
be used singly or in combination.
[0114] Incidentally, Japanese Patent Application Laid-Open No.
126495/2004 (
JP-2004-126495A) discloses, as is the case with the present invention, a process for producing a
sheet, which comprises evaporating a solvent from a solution containing at least one
polymer and at least one curable resin precursor uniformly dissolved in the solvent,
wherein an anti-glare layer is produced by spinodal decomposition under an appropriate
condition followed by curing the precursor. Although this document discloses a process
for forming an uneven surface of the anti-glare film by phase separation due to spinodal
decomposition, there is no description about cellular rotating convection.
[0115] In the present invention, in order to generate such a convection cell, it is preferred
to use a solvent having a boiling point of not lower than 100°C at an atmospheric
pressure as a solvent. Further, to generate the convection cell, the solvent preferably
comprises at least two solvent components with different boiling points. Moreover,
the boiling point of the solvent component having a higher boiling point may be not
lower than 100°C, and is usually about 100 to 200°C, preferably about 105 to 150°C
and more preferably about 110 to 130°C. In particular, from the viewpoint of combining
convection cell and phase separation, the solvent preferably comprises at least one
solvent component having a boiling point of not lower than 100°C and at least one
solvent component having a boiling point of lower than 100°C in combination. In the
case of using such a mixed solvent, the solvent component having a lower boiling point
generates a temperature difference between the upper and lower layers of the coating
film due to evaporation, and the solvent component having a higher boiling point remains
in the coating film resulting in keeping of fluidity.
[0116] The solvent (or solvent component) having a boiling point of not lower than 100°C
at an atmospheric pressure may include, for example, an alcohol (e.g., a C
4-8alkyl alcohol such as butanol, pentyl alcohol or hexyl alcohol), an alkoxy alcohol
(e.g., a C
1-6alkoxyC
2-6alkyl alcohol such as methoxypropanol or butoxyethanol), an alkylene glycol (e.g.,
a C
2-4alkylene glycol such as ethylene glycol or propylene glycol), and a ketone (e.g.,
cyclohexanone). These solvents may be used singly or in combination. Among them, a
C
4-8alkyl alcohol such as butanol, a C
1-6alkoxyC
2-6alkyl alcohol such as methoxypropanol or butoxyethanol, and a C
2-4alkylene glycol such as ethylene glycol are preferred.
[0117] The ratio of the solvent components with different boiling points is not particularly
limited to a specific one. In the case of using a solvent component having a boiling
point of not lower than 100°C (a first solvent component) in combination with a solvent
component having a boiling point lower than 100°C (a second solvent component), the
ratio of the first solvent component relative to the second component (when each of
the first and second solvent components comprises a plurality of components, the ratio
is defined as a weight ratio of the total first solvent components relative to the
total second solvent components) may be, for example, about 10/90 to 70/30, preferably
about 10/90 to 50/50, and more preferably about 15/85 to 40/60 (particularly about
20/80 to 40/60).
[0118] Moreover, when a liquid mixture or coating liquid is coated on a transparent support,
a solvent in which the transparent support does not dissolve, corrode or swell may
be selected according to the species of the transparent support. For example, when
a cellulose triacetate film is employed as the transparent support, tetrahydrofuran,
methyl ethyl ketone, isopropanol, toluene or the like is used as a solvent for the
liquid mixture or the coating liquid and thus the anti-glare film can be formed without
deteriorating properties of the film.
(Viscosity and concentration of solution)
[0119] According to the present invention, in generation of convection, it is preferable
that the viscosity of the solution be moderately high for maintaining the uneven surface
due to convection, and it is preferable that the viscosity of the solution be moderately
low for flowing and circulating generated convection without stagnation. In order
to ensure such a viscosity of the solution, the solid content of the solution may
be, for example, about 5 to 50% by weight, preferably about 10 to 40% by weight, and
more preferably about 15 to 35% by weight.
(Coating thickness)
[0120] In order to generate cellular rotating convection with a desired size, the coating
thickness of the solution may be, for example, about 10 to 200 µm, preferably about
15 to 100 µm, and more preferably about 20 to 50 µm. With the use that the aspect
ratio of the convection cell becomes 2 to 3, an uneven surface (or uneven pattern)
in which the distance between adjacent projections is about 50 µm can be obtained
by coating of the solution on the support at a coating thickness of about 20 to 50
µm. The thickness of the coating film becomes thin due to evaporation of part of the
solvent (or solvent component) with a lower boiling point in the solution, and concurrently
the evaporation generates a temperature difference between the upper and the lower
layers of the coating film, as a result, cellular rotating convection having a size
of about 50 µm can be generated.
(Method for imparting anisotropy)
[0121] In order to impart anisotropy to the anti-glare layer, the solution is coated on
the support, and then the resulting wet coating film is tilted at a predetermined
angle (e.g., about 30 to 90 degrees, preferably about 45 to 90 degrees, more preferably
about 60 to 90 degrees, and usually about 90 degrees) with respect to the horizontal
plane before curing the coating film (for example, in the drying step, or as a step
before the drying step).
[0122] The coating method may include a conventional manner, for example, a roll coater,
an air knife coater, a blade coater, a rod coater, a reverse coater, a bar coater,
a comma coater, a dip and squeeze coater, a die coater, a gravure coater, and a silkscreen
coater. Among these methods, a bar coater or a gravure coater is used widely. In general,
in the production of the anti-glare layer, cellular convection tends to be arranged
in a machine direction (a MD direction of the film, or a moving direction of a coater
such as bar coater). Therefore, with respect to a gravitational direction, it is preferred
to tilt the coating film toward a direction at which the plane direction of the coating
film, particularly the machine direction, is almost parallel with the gravitational
direction (that is, to hold the end of the coating film in the machine direction for
lifting and tilting).
[0123] As the method for imparting anisotropy, there is usually employed a method which
comprises forming a coating film on a support by such a coating method, and then tilting
the resulting wet coating film at an angle of almost 90 degrees (or almost perpendicular)
with respect to the horizontal plane, that is, tilting (raising) the resulting wet
coating film so that the plane direction of the coating film is almost parallel to
the gravitational direction, and placing the wet coating film for a predetermined
time to generate cellular rotating convection. Such a tilting step of the wet coating
film is preferably carried out immediately after coating the coating solution. Further,
although such a placing step may be conducted in the drying step (e.g., a heating
step using a dryer), the step is preferably carried out as a step before the drying
step, e.g., before putting the coating film in a dryer, at an ambient temperature
or room temperature (e.g., about 0 to 40°C and preferably about 5 to 30°C).
[0124] Specifically, the method may comprise coating a coating solution on a support film
by using a coater, lifting one end of the support film (particularly, one end in the
machine direction, that is, one side perpendicular to the machine direction), immediately
suspending the coated support film, leaving the coated support film for a predetermined
time, and putting the coated support film in a dryer. Moreover, in the case of using
a continuous coating machine, the method may comprise coating a coating solution on
a support, transferring the coated support so that the plane direction of the wet
coating film is almost parallel to the gravitational direction in the process of upward
transferring the support by a carrying machine (such as a conveyer) continuously,
and carrying the support in a drying furnace. Such a transferring is ensured by disposing
an entrance to the drying furnace in the upper side of the coater head.
[0125] In the case where the wet coating film is placed to the above-mentioned direction
so that the film is subjected to the gravitational action, it can be presumed that
the convection cell is longitudinally extended by a gravity, while the mechanism that
expresses anisotropy to the anti-glare layer is poorly understood. The time for placing
the wet coating film in the above-mentioned direction (usually, the time until put
the coated support in a dryer after placing the coated support) may be selected within
the range of about 1 second to 10 minutes, for example, is about 5 seconds to 5 minutes,
preferably about 10 to 60 seconds, and more preferably about 10 to 40 seconds (particularly
about 15 to 30 seconds).
[0126] In the present invention, the degree of anisotropy can be controlled by adjusting
the tilt angle, the placing time, the temperature, and others in such a method.
(Drying temperature)
[0127] The cellular rotating convection and phase separation is preferably induced by casting
or coating the solution, and then evaporating the solvent at a temperature lower than
the boiling point of the solvent [for example, at a temperature lower than a boiling
point of a solvent having a higher boiling point by about 1 to 120°C (preferably about
5 to 80°C and particularly about 10 to 60°C)]. For example, depending on the boiling
point of the solvent, the coating film may be dried at a temperature of about 30 to
200°C, preferably about 40 to 120°C and more preferably about 50 to 100°C.
[0128] Firstly, in order to generate cellular rotating convection, after casting or coating
the solution on the support, it is not preferable that the coating film be immediately
put in a dryer such as an oven for dryness, but preferable that the coating film be
put in a dryer after allowing the coating film to stand for a predetermined time (e.g.,
for about 1 second to 1 minute, preferably about 3 to 30 seconds and more preferably
about 5 to 20 seconds) at an ambient temperature or room temperature (e.g., about
0 to 40°C and preferably about 5 to 30°C) (particularly, after placing the wet coating
film with the wet coating film tilted with respect to the horizontal plane as mentioned
above).
[0129] Moreover, the dry air flow rate is not particularly limited to a specific one. In
the case where the air flow rate is too high, the coating film is dried and solidified
before enough generation of rotating convection. Accordingly, the dry air flow rate
may be not higher than 50 m/minute (e.g., about 1 to 50 m/minute), preferably about
1 to 30 m/minute and more preferably about 1 to 20 m/minute. The angle of the dry
wind blown against the anti-glare film is not particularly limited to a specific one.
For example, the angle may be parallel or perpendicular to the film.
[0130] In particular, for generating cellular rotating convection, it is preferred to dry
the coating film in the presence of a solvent under an external force which does not
inhibit formation of convection cell or an external force which does not inhibit convection
in a phase separation region, for example, under a calm or a low air flow rate. That
is, specifically, cellular rotating convection can be generated by heating the coating
film under a calm or low air flow rate (e.g. , about 0.1 to 8 m/minute, preferably
about 0.5 to 6 m/minute and more preferably about 1 to 5 m/minute) in a dryer having
the above-mentioned drying temperature. Incidentally, instead of drying the film under
a low air flow rate, the angle of the dry wind blown against the film may be set up
as a low angle, for example, not larger than 70°, preferably about 5 to 60° and more
preferably about 10 to 50°. The heating time under a calm or low air flow rate may
be, for example, about 1 second to 1 minute, preferably about 3 to 30 seconds and
more preferably about 5 to 20 seconds (particularly about 7 to 15 seconds).
(Curing treatment)
[0131] After drying the solution, the coating film is cured or crosslinked by a thermic
ray or an actinic ray (e.g., an ultraviolet ray, and an electron beam). The curing
process may be selected depending on the species of the curable resin precursor, and
a curing process by light irradiation such as an ultraviolet ray or an electron beam
is usually employed. The general-purpose light source for exposure is usually an ultraviolet
irradiation equipment. If necessary, light irradiation may be carried out under an
inert gas atmosphere.
(Process for producing low refraction index layer)
[0132] The process for forming the low refraction index layer is not particularly limited
to a specific one, and it is sufficient that a layer comprising at least the above-mentioned
resin-based material is formed on the anti-glare layer. The low refraction index layer
may be usually formed by coating or flow casting a coating liquid containing a low
refraction index component on the anti-glare layer, and curing the coating film with
heat (a thermal source) or an actinic ray.
[0133] The coating liquidmay usually comprise, in addition a low refraction index component
(e.g., a fluorine-containing compound), an organic solvent [e.g., an organic solvent
similar to a solvent exemplified in the paragraph of the anti-glare layer, depending
on the species of the low refraction index resin], and further a reactive diluent
[e.g., a (meth)acrylic monomer such as a polyfunctional (meth)acrylate]. Such a solvent
may be evaporated and removed together with formation of the coating film. In the
case where the solvent is a reactive diluent, the solvent may be cured by polymerization
along with curing of a fluorine-containing resin precursor. The coating liquid may
further comprise a curing agent [for example, a thermal polymerization initiator such
as an organic peroxide; a photopolymerization initiator (e.g., a ketone-series polymerization
initiator such as 1-hydroxy-cyclohexyl-phenyl-ketone)]. Moreover, the coating liquid
may comprise a crosslinking agent, or others.
[0134] The concentration of the solid content (a low refraction index component, a curable
compound, other additive(s)) in the coating liquid for a low refraction index layer
may be selected within such a range that coating properties or others are not deteriorated,
and for example, the concentration is about 0.1 to 50 wt.%, preferably 0.5 to 10 wt.%,
and more preferably 1 to 5 wt.%.
[Optical member]
[0135] The anti-glare film of the present invention has uniform and high-definition anti-glareness
because of having anisotropy about light scattering property and having an uneven
surface in which each raised part is uniformly controlled by cellular rotating convection.
Further, the anti-glare film has a high abrasion resistance (hardcoat property) and
can control an intensity distribution of a transmitted scattered-light. In particular,
the anti-glare film makes a scattered intensity at a particular angle range larger
with allowing a transmitted light to transmit and scatter anisotropically. Further,
the anti-glare film is excellent in clearness (or sharpness) of a transmitted image,
and reduces blur of characters in a display surface (or visual surface). Moreover,
in the case of forming a low refraction index layer on the anti-glare layer, reflection
of an external light can be efficiently inhibited in the surface of the low refraction
index layer. Therefore, the anti-glare film of the present invention is suitable for
application of an optical member or others, and the above-mentioned support may also
comprise a transparent polymer film for forming various optical members. The anti-glare
film obtained in combination with the transparent polymer film may be directly used
as an optical member, or may form an optical member in combination with an optical
element [for example, a variety of optical elements to be disposed into a light path,
e. g. , a polarizing plate, an optical retardation plate (or phase plate), and a light
guide plate (or light guide)]. That is, the anti-glare film may be disposed or laminated
on at least one light path surface of an optical element. For example, the anti-glare
film may be laminated on at least one surface of the optical retardation plate, or
may be disposed or laminated on an emerging surface (or emerge surface) of the light
guide plate.
[0136] The anti-glare film having imparted abrasion resistance can be also performed as
a protective film. The anti-glare film of the present invention is, therefore, suitable
for utilizing as a laminate (optical member) in which an anti-glare film is used instead
of at least one protective film among two protective films constituting a polarizing
plate, that is, as a laminate (optical member) in which an anti-glare film is laminated
on at least one surface of a polarizing plate.
[Display apparatus]
[0137] The anti-glare film of the present invention can be utilized for various display
apparatuses or devices such as a liquid crystal display (LCD) apparatus, a cathode
ray tube display, an organic or inorganic EL display, a field emission display (FED),
a surface-conduction electron-emitter display (SED), a rear projection television
display, a plasma display, and a touch panel-equipped display device. These display
apparatuses comprise the anti-glare film or the optical member (particularly, e.g.,
a laminate of a polarizing plate and an anti-glare film) as an optical element. In
particular, the anti-glare film can be preferably used for a liquid crystal display
apparatus and others because the anti-glare film can inhibit reflection even in the
case of being attached to a large-screen liquid crystal display apparatus such as
a high-definition or high-definitional liquid crystal display.
[0138] Incidentally, the liquid crystal display apparatus may be a reflection-mode (or reflective)
liquid crystal display apparatus using an external light (or outside light) for illuminating
a display unit comprising a liquid crystal cell, or may be a transmission-mode (or
transmissive) liquid crystal display apparatus comprising a backlight unit for illuminating
a display unit. In the reflection-mode liquid crystal display apparatus, the display
unit can be illuminated by taking in an incident light from the outside through the
display unit, and reflecting the transmitted incident light by a reflective member.
In the reflection-mode liquid crystal display apparatus, the anti-glare film or optical
member (particularly a laminate of a polarizing plate and an anti-glare film) can
be disposed in a light path in front of the reflective member. For example, the anti-glare
film or optical member can be disposed or laminated, for example, between the reflective
member and the display unit, or in front of the display unit.
[0139] In the transmission-mode liquid crystal display apparatus, the backlight unit may
comprise a light guide plate (e.g., a light guide plate having a wedge-shaped cross
section) for allowing a light from a light source (e.g., a tubular light source such
as a cold cathode tube, a point light source such as a light emitting diode) incident
from one side of the light guide plate and for allowing the incident light to emit
from the front emerging surface. Moreover, if necessary, a prism sheet may be disposed
in front of the light guide plate. Incidentally, a reflective member for allowing
a light obtained from the light source to reflect to the emerging surface side is
usually disposed on the reverse side of the light guide plate. In such a transmission-mode
liquid crystal display apparatus, the anti-glare film or the optical member may be
usually disposed or laminated into a light path in front of the light source. For
example, the anti-glare film or optical member can be disposed or laminated between
the light guide plate and the display unit, in front of the display unit, or others.
INDUSTRIAL APPLICABILITY
[0140] The present invention is useful for a variety of application in need of anti-glareness
and light-scattering properties, e.g., for the optical member or an optical element
of a display apparatus such as a liquid crystal display apparatus (in particular,
a high-definition or high-definitional display apparatus).
EXAMPLES
[0141] The following examples are intended to describe this invention in further detail
and should by no means be interpreted as defining the scope of the invention.
Example 1
[0142] In a mixed solvent containing 24.7 parts by weight of methyl ethyl ketone (MEK) (boiling
point: 80°C), 5.2 parts by weight of 1-butanol (BuOH) (boiling point: 113°C) and 4.
5 parts by weight of 1-methoxy-2-propanol (boiling point: 119°C) were dissolved 5.88
parts by weight of an acrylic resin having a polymerizable unsaturated group (s) in
a side chain thereof [a compound in which 3,4-epoxycyclohexenylmethyl acrylate is
added to part of carboxyl groups in a (meth)acrylic acid-(meth)acrylate copolymer;manufactured
by Daicel Chemical Industries, Ltd., CYCLOMER-P (ACA) 320M, solid content: 44.2% by
weight, and solvent: 1-methoxy-2-propanol (MMPG) (boiling point: 119°C)], 0.8 part
by weight of a cellulose acetate propionate (acetylation degree = 2.5%, propionylation
degree = 46%, number average molecular weight in terms of polystyrene: 75,000; manufactured
by Eastman, Ltd., CAP-482-20), 3.3 parts by weight of a polyfunctional acrylic UV
curable monomer (manufactured by DAICEL-CYTEC Company, Ltd., DPHA), 3.3 parts by weight
of a polyfunctional acrylic UV curable monomer (manufacturedbyDAICEL-CYTECCompany,
Ltd., PETIA) and 0.5 part by weight of a photo initiator (manufactured by Ciba Specialty
Chemicals K.K., IRGACURE 184). Incidentally, the cellulose acetate propionate and
the acrylic resin are incompatible with each other, and the concentration of the resulting
solution is accompanied by phase separability. The solution was coated on a cellulose
triacetate film with the use of a wire bar #36, and then one end of the film (an end
of the film in the machine direction) was immediately lifted up and the film was suspended
vertically. The suspended film was held vertically for 30 seconds, and then the film
was immediately put in an explosion-proof oven at 80°C at a fan wind speed of 4 m/minute
and dried for one minute. Thereby a phase-separation structure was generated in a
convection cell, and an about 10.5 µm thick coat layer having an uneven surface structure
was formed. Following that, the coat layer was subjected to UV curing treatment for
about 30 seconds by irradiating ultraviolet ray derived from a metal halide lump (manufactured
by Eyegraphics Co., Ltd.) to form an anti-glare film having hardcoat property and
an uneven surface structure.
Example 2
[0143] In a mixed solvent containing 25 parts by weight of methyl ethyl ketone (MEK), 5.24
parts by weight of 1-butanol (BuOH) and 3 parts by weight of 1-methoxy-2-propanol
were dissolved 5.66 parts by weight of an acrylic resin having a polymerizable unsaturated
group(s) in a side chain thereof [a compound in which 3,4-epoxycyclohexenylmethyl
acrylate is added to part of carboxyl groups in a (meth)acrylic acid-(meth)acrylate
copolymer; manufactured by Daicel Chemical Industries, Ltd., CYCLOMER-P (ACA) 320M,
solid content: 44.2% by weight, and solvent: 1-methoxy-2-propanol (MMPG) (boiling
point: 119°C)], 0.6 part by weight of a cellulose acetate propionate (acetylation
degree = 2.5%, propionylation degree = 46%, number average molecular weight in terms
of polystyrene: 75,000; manufactured by Eastman, Ltd., CAP-482-20), 2.76 parts by
weight of a polyfunctional acrylic UV curable monomer (manufactured by DAICEL-CYTEC
Company, Ltd., DPHA), 2.76 parts by weight of a polyfunctional acrylic UV curable
monomer (manufactured by DAICEL-CYTEC Company, Ltd., PETIA) and 0.4 part by weight
of a photo initiator (manufactured by Ciba Specialty Chemicals K.K., IRGACURE 184).
The resulting solution was used for coating by a pilot machine. Incidentally, the
pilot machine is equipped with a coater head for a microgravure application (No. 45)
and a drying furnace (temperature: 70°C, fan wind speed: 4 m/minute) having a length
of 10 m. Further, the entrance to the drying furnace was positioned almost right above
the coater head, and the path of the film was as follows: the film was coated by the
coater head and was moved through a distance of 30 cm, the film was lifted up vertically
so that the film was allowed to stand vertically (in the state that the machine direction
of the film was almost parallel to the gravitational direction), the film was moved
(was moved upwards) through a distance of about 2 m, and then the film entered the
drying furnace. With the use of this pilot machine, the solution was coated on a cellulose
triacetate film at a linear velocity of 6 m/minute to form an about 10 µm thick coat
layer having an uneven surface structure. Following that, the coat layer fed from
the drying furnace was subjected to UV curing treatment for about 30 seconds by irradiating
ultraviolet ray derived from a metal halide lump (manufactured by Eyegraphics Co.,
Ltd.) to form an anti-glare film having hardcoat property and an uneven surface structure.
Comparative Example 1
[0144] A 10.5 µm thick coat layer was formed in the same manner as Example 1 except that
the cellulose triacetate film was allowed to stand for 30 seconds without suspending
vertically after coating the solution on the film and put in the explosion-proof oven
at 80°C at a fan wind speed of 4 m/minute. Following that, the coat layer was subjected
to UV curing treatment for about 30 seconds by irradiating ultraviolet ray derived
from a metal halide lump (manufactured by Eyegraphics Co., Ltd.) to form an anti-glare
film having hardcoat property and an uneven surface structure.
Example 3
[0145] A coating liquid containing a thermosetting fluorine-containing compound ("LR204-6"
manufactured by Nissan Chemical Industries, Ltd., solid content: 1% by weight) as
a low refraction index layer was coated on the coat layer, having hardcoat property
and an uneven surface structure, obtained in Example 1 with the use of a wire bar
#5. The coated product was dried, and then hot-cured (or heat-cured) at 90°C for 5
minutes to give a low-reflection anti-glare film.
Comparative Example 2
[0146] A coating liquid containing a thermosetting fluorine-containing compound ("LR204-6"
manufactured by Nissan Chemical Industries, Ltd., solid content: 1% by weight) as
a low refraction index layer was coated on the coat layer, having hardcoat property
and an uneven surface structure, obtained in Comparative Example 1 with the use of
a wire bar #5. The coated product was dried, and then hot-cured (or heat-cured) at
90°C for 5 minutes to give a low-reflection anti-glare film.
[0147] Each of anti-glare films obtained in above-mentioned Examples and Comparative Examples
was evaluated by the following items. The results are shown in Table 1.
[Total light transmittance and haze]
[0148] The total light transmittance and haze were measured by using a haze meter (manufactured
by Nippon Denshoku Industries Co., Ltd., trade name "NDH-5000W").
[Image clarity]
[0149] The image clarity of the anti-glare film was measured in accordance with JIS K7150
by using an image clarity measuring apparatus (manufactured by Suga Test Instruments
Co., Ltd., trade name "ICM-1DD") provided with an optical slit (the slit width = 0.25
mm, 0.5 mm). The image clarity was measured in the following two methods: (method
1) the film was installed so that the machine direction of the film was parallel to
the teeth direction of the optical slit, and (method 2) the film was installed so
that the machine direction of the film was perpendicular to the teeth direction of
the optical slit. The difference (absolute value) in image clarity between these methods
was calculated.
[Transmitted scattering profile]
[0150] Based on transmitted scattered-light intensities at emission angles of 0° and 30°
measured by using a goniophotometer (manufactured by Murakami Color Research Laboratory,
"GP-200"), the transmitted scattering profile (or property) of the anti-glare film
was determined as the ratio of these scattered-light intensities.
[Evaluation for mounting]
[0151] Regarding each of the anti-glare films, the back side of the film was subjected to
adhesion treatment, and the treated film was attached to a surface of a 20-inch VA
(vertically aligned) LCD panel (having a front luminance of 450 cd/m
2, a contrast of 400/1 and a resolution of 60 ppi) so that the machine direction (MD
direction) of the anti-glare layer was a direction perpendicular to the gravitational
direction (that is, the MD direction was parallel to the horizontal direction). Then,
dazzle and anti-glareness were evaluated by the following methods.
(Dazzle)
[0152] Green or white color image was displayed on the panel screen, and observed at a distance
of one meter from the screen. The visual evaluation on dazzle was conducted on the
basis of the following criteria.
[0153]
"A": No dazzles.
"B": Dazzle is recognized in a degree hardly recognizable.
"C" : Dazzle is recognized in a degree recognizable.
"D": Strong dazzle is recognized, and is very uncomfortable.
(Anti-glareness)
[0154] A fluorescent lamp was fixed to the ceiling so that the fluorescent lamp was positioned
at a distance of 5 meters in an obliquely upward direction from the panel screen.
The reflected light of the lamp on the surface of the LCD panel (power-off or black
display) was observed, and blurring of the reflected outline of the fluorescent lamp
was evaluated on the basis of the following criteria.
[0155]
"A": No reflected outline of the fluorescent lamp is recognized.
"B" : The reflected outline of the fluorescent lamp is slightly recognized in a degree
hardly recognizable.
"C": The reflected outline of the fluorescent lamp is recognized in a degree recognizable.
"D" : The strongly reflected outline of the fluorescent lamp is recognized, and is
very uncomfortable.
[0156] [Table 1]
Table 1
|
|
|
Ex. 1 |
Ex. 2 |
Com. Ex. 1 |
Ex. 3 |
Com. Ex. 2 |
Main solvent |
|
MEK |
MEK |
MEK |
MEK |
MEK |
Solvent having a boiling point of not lower than 100°C |
Species |
BuOH, MMPG |
BuOH, MMPG |
BuOH, MMPG |
BuOH, MMPG |
BuOH, MMPG |
Solvent ratio |
34% |
31% |
34% |
31% |
34% |
Drying furnace |
80°C Wind speed: 4 m/min. |
70°C Wind speed: 4 m/min. Furnace length: 10 m |
80°C Wind speed: 4 m/min. |
Same as Ex. 1 |
Same as Com. Ex. 1 |
Process from coating to drying |
Lifting up and suspending vertically, and holding for 30 sec. |
Moving upwards through a distance of 2 mby a continuous system (6 m/min.) |
Holding for 30 sec. without suspending vertically |
Same as Ex. 1 |
Same as Com. Ex. 1 |
Phase separability of solution |
Presence |
Presence |
Presence |
Presence |
Presence |
Low refraction index layer |
Absence |
Absence |
Absence |
Presence |
Presence |
Total light transmittance (%) |
90.5 |
90.5 |
90.5 |
93.2 |
93.2 |
Haze (%) |
8 |
12 |
9 |
6 |
7 |
Image clarity |
Method 1 |
0.5 mm |
35 |
30 |
38 |
39 |
42 |
(parallel) |
0.25 mm |
37 |
30 |
39 |
40 |
43 |
Method 2 |
0.5 mm |
46 |
51 |
38 |
49 |
42 |
(Perpendicular) |
0.25 mm |
47 |
52 |
39 |
51 |
43 |
Difference between methods 1 and 2 |
0.5 mm |
11 |
21 |
0 |
10 |
0 |
0.25 mm |
10 |
22 |
0 |
11 |
0 |
Transmitted scattered-light Intensity |
Intensity at 0° (I0) |
60000 |
57000 |
60000 |
64000 |
64000 |
Intensity at 30° (I30) |
0.15 |
0.12 |
0.14 |
0.09 |
0.10 |
Intensity ratio (I30/I0) |
0.00025% |
0.00021% |
0.00023% |
0.00014% |
0.00015% |
Evaluation for mounting |
Dazzle |
B |
B |
C |
B |
C |
Anti-glareness |
B |
A |
C |
A |
C |
[0157] As apparent from results in Table 1, the anti-glare films of Examples 1 to 3 have
no dazzle and are high in anti-glareness. On the other hand, in the anti-glare films
of Comparative Examples 1 and 2, both dazzle and reflection are recognized in a degree
recognizable.