1
SPECIFICATION
PLASTIC POLARIZED LENS, METHOD FOR PRODUCING THE SAME, AND
POLARIZED FILM
5
TECHNICAL FIELD
[0001]
The present invention relates to a plastic polarized lens., a
method for producing the same, and a polarized film.
10
BACKGROUND ART
[0002]
A polarized lens can prevent transmission of reflected light.
Therefore, it is used for, for example, protecting eyes by
15 intercepting strong reflected light outdoors such as on a skiing
area or in fishing, and for securing safety during driving a car
by intercepting reflected light from a car traveling in the opposite
direction.
[0003]
20 For a plastic polarized lens, two kinds of polarized lens, that
is, a polarized lens with a polarized film laid on the surface of
the plastic lens material, and a sandwich structured polarized lens
with a polarized film within the plastic lens material, have been
proposed. The polarized lens with a polarized film laid on the
25 surface of the plastic lens material (for example, Japanese Patent
Laid-Open Application No. 09-258009 (Patent Document 1)) can make
the thickness of the lens smaller, but has a serious disadvantage
5
2
that the polarized film is liable to be peeled off from the lens
material during a periphery polishing process (a process of
polishing the edges of the lens to match a predetermined shape) .
[0004]
A resin used for a polarized film constituting a polarized lens
has been hitherto essentially limited to polyvinyl alcohols. The
polarized film is produced by uniaxial stretching of a polyvinyl
alcohol film after adding iodine or a dichroic dye to make a film
having molecular orientation in a uniaxial direction. A method of
10 producing a polarized lens composed of a polarized polyvinyl alcohol
film is disclosed, for example, in the pamphlet of WO 04/099859
(Patent Document 2) .
However, a polarized lens prepared using a polarized polyvinyl
alcohol film has a disadvantage of gradual invasion of moisture from
15 the edge of the lens, or due to the environment from the peripheral
portion of the lens toward the central portion and thus,
deterioration develops over time.
[0005]
In order to improve the above-described disadvantages, the
20 pamphlet of WO 02/073291 (Patent Document 3) has proposed a
polarized lens using a lens material including an impact-resistant
polyurethane resin obtained from a diamine and an -isocyanate
prepolymer, and a polarized polyethylene terephthalate film.
[0006]
25 However, this polarized lens has a disadvantage that the
polarized film contained in the lens is clearly visible from outside,
which gives an uncomfortable feeling to a person who wears the
3
eyeglasses containing this lens. In addition, since a composition
formed by mixing a diamine and an isocyanate prepolymer has a high
viscosity as well as a short pot life, inj ection of the composition
into a lens casting mold having a fixed polarized film therein is
5 troublesome, and the production of a thin lens has been extremely
difficult.
[0007]
Therefore, in the plastic polarized lenses in the related art,
there has been a demand for a plastic polarized lens, which has
10 suppressed occurrence of the peeling-off of the polarized film
during a downstream process of polishing the periphery of the lens,
excellent water resistance, and suppressed uncomfortable feeling
during wearing, and is capable of producing a thin product or the
like.
15 [0008]
On the other hand, it is desired to improve the contrast of
an object to be viewed through the lens, in order to clarify the
outlines and the colors of an obj ect, and thus reduce visual fatigue
regarding spectacle lenses. In order to improve the contrast, it
20 is necessary to selectively shield (or cut) as far as possible a
wavelength band which easily gives glare. For example, it is known
that a neodymium compound can absorb visible light in the vicinity
of 585 nm with high selectivity, and a spectacle lens including the
neodymium compound improves the contrast. Improvement of the
25 contrast of the object by a rare earth metal compound such as a
neodymium compound is attributable to extremely sharp peak shapes
of the absorption spectrum in the absorption wavelength band in the
4 • visible light region, that is, the absorption wavelength range is
narrow and the wavelength selectivity is high. By such high
wavelength selectivity, effects of a high transmission in a
wavelength band requiring visibility and the wavelength band
5 adversely affecting the glare being selectively absorbed can be
obtained. Thus, by using a rare earth metal compound such as a
neodymium compound, the contrast is improved, and thus, it is
possible to obtain a spectacle lens having excellent visibility.
[0009]
10 Furthermore, in addition to the rare earth metal compound such
as typically a neodymium compound, it is also known that a specific
organic coloring agent improves the contrast property of a spectacle
lens. Examples of such organic coloring agents include a
tetraazaporphyrin compound. The tetraazaporphyrin compound can
15 provide excellent anti-glare performance and improvement of a
contrast property for the spectacle lens, in a similar manner to
the neodymium compound. That is, since a bright view field can be
ensured with good light transmittance in the area excepting that
of around 585 nm, derived from the sharpness of the peaks in the
20 specific absorption wavelength, spectacle lenses having an
extremely high balance of antiglare properties and visibility
(contrast 'property) can be provided. In the case of using the
organic coloring agent, a method in which an organic coloring agent
is dissolved in a monomer composition in advance, followed by
25 performing polymerization to obtain a lens is described in Examples
of Japanese Patent Laid-Open Application No. 2008-134628 (Patent
Document 4). Further, a plastic lens obtained by polymerizing a
•
5
5
monomer composition having an organic coloring agent dissolved
therein is disclosed in Examples of Patent Document 4, and a plastic
lens obtained by laminating a base layer including the monomer
composition on a polarized film is not specifically disclosed
therein.
[0010]
In Patent Document 4, an organic coloring compound that
improves a contrast property is directly dissolved in a monomer
composition and polymerized to form lens materials. Thus,
10 according to the type of the monomers, particularly, there may be
cases where the-functions of the organic coloring compound are
damaged due to the interaction with the monomers or the reactions
during a polymerization reaction. Further, there are cases where
for lenses for vision correction, there is a large difference in
15 the thickness between the central portion and the peripheral portion,
and in the case where the organic coloring compound is incorporated
in the lens material itself, there have been cases where the color
intensity in the central portion and the peripheral portion varies
due to the coloration derived from the organic coloring compound.
20 As it is used for vision correction of the intensity, the difference
in the thickness between the central portion and the peripheral
portion increases, and accordingly, such a tendency gets more
remarkable. In this way, a polarized lens having a partially
different thickness has changed in the color intensity in the
25 portion, and accordingly, it has room for improvement in appearance.
For example, in Examples of Patent Document 4, an organic coloring
agent is directly dissolved in a monomer composition, and further,
.. 6
all of the lenses prepared in Examples are a Plano lens (a lens having
a small difference in the thickness between the central portion and
the peripheral portion). Accordingly, there is a desire for
development of a lens having an improved contrast property, which
5 can correspond to the lenses for vision correction.
10
RELATED DOCUMENTS
PATENT DOCUMENTS
[0011]
[Patent Document 1] Japanese Patent Laid-Open Application No.
09-258009
[Patent Document 2] Pamphlet of International Publication WO
04/099859
[Patent Document 3] Pamphlet of International Publication WO
15 02/073291
20
[Patent Document 4] Japanese Patent Laid-Open Application No.
2008-134618
[Patent Document 5] Pamphlet of International Publication WO
96/00247
[Patent Document 6] Japanese Patent Laid-Open Application No.
05-5860
[Patent Document 7] Japanese Patent Laid-Open Application No.
05-45610
25 DISCLOSURE OF THE INVENTION
[0012]
The present invention has been made by taking the above
• 7
problems in the related art into consideration, and provides a
plastic polarized lens with an improved contrast property and
excellent appearance, water resistance, processability, or the like,
and a method of producing the same. In addition, the present
5 invention provides a polarized film having a polarizing function
provided therewith and capable of providing a high contrast
property.
[0013 ]
That is, the prese~t invention will be described below.
10 [0014]
(1) A plastic polarized lens comprising:
a polarized film and
layers comprising a thiourethane-based resin stacked over both
surfaces of the polarized film,compound represented by the
15 following general formula (1) :
[0015]
A4
~
N
~ A6 A3 ~
N N
~ /;
~ A7
N ( 1 )
A1 A8
[0016]
In the formula (1), Al to As each independently represent a
20 hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy
group, an amino group, a carboxyl group, a sulfone group, a linear,
8
branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy
group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20
carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms,
a dialkylamino group having 2 to 20 carbon atoms, an aralkyl group
5 having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon
atoms, a heteroaryl group, an alkylthio group having 1 to 20 carbon
atoms, or an arylthio group having 1 to 20 carbon atoms, or may form
a ring other than an aromatic ring through a linking group, and M
represents two hydrogen atoms, a divalent metal atom, a trivalent
10 mono-substituted metal atom, a tetravalent di-substituted metal
atom, or an oxy metal.
[0017]
(2) The plastic polarized lens as described in (1) as above,
wherein the organic coloring compound is represented by the
15 following general formula (la):
[0018]
(1 a)
[0019]
In the formula (la), t-C4Hg represents a tertiary butyl group.
20 Four tertiary butyl groups correspond to Al or Az, A3 or A4' As or
A6' and A7 or As, respectively, in the formula (1), and represent
a position isomer structure. Further, four groups that are not
5
9
tertiary butyl groups in Al to As represent a hydrogen atom. M
represents a divalent copper atom, a divalent palladium atom, or
divalent vanadium oxide (-V(=O)-).
[0020]
(3) The plastic polarized lens as described in (1) or (2) as
above, wherein the polarized film is comprised of a thermoplastic
polyester.
[0021]
(4) The plastic polarized lens as described in anyone of (1)
10 to (3) as above, wherein the organic coloring compound is contained
in an amount of 50 to 7000 ppm in the polarized film.
[0022]
(5) The plastic polarized lens as described in anyone of (1)
to (4) as above, wherein the thiourethane-based resin is obtained
15 by reacting
(A) at least one kind of isocyanate compounds selected from
the group consisting of a polyisocyanate compound, an isocyanate
compound having an isothiocyanate group, and a polyisothiocyanate
compound with
20 (B) at least one kind of active hydrogen compounds selected
from the group consisting of thiol compounds and polythiol compounds
having a hydroxy group.
[0023]
(6) The plastic polarized lens as described in anyone of (3)
25 to (5) as above, wherein the polarized film is formed under the
condition of the temperature T1 represented by the following
formula:
5
10 • Glass transition temperature of the thermoplastic
polyester+20°C ~ Tl ~ Glass transition temperature of the
thermoplastic polyester+120°C.
[0024]
(7) The plastic polarized lens as described in anyone of (1)
to (6) as above, wherein the formation or surface modification
treatment of the adhesive layer is carried over at least one surface
of the polarized film.
[0025]
10 (8) The plastic polarized lens as described in anyone of (3)
to (7) as above, wherein the thermoplastic polyester is a
polyethylene terephthalate.
[0026]
(9) The plastic polarized lens as described in anyone of (5)
15 to (8) as above, wherein the isocyanate compound (A) is a
diisocyanate compound and the active hydrogen compound (B) is a
polythiol compound.
[0027]
(10) The plastic polarized lens as described in anyone of (5)
20 to (9) as above, wherein the isocyanate compound (A) is at least
one kind of diisocyanate compound selected from the group consisting
of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and mxylylene
diisocyanate, and
25 the active hydrogen compound (B) is at least one kind of
polythiol compound selected from the group consisting of
pentaerythritoltetrakis(3-mercaptopropionate),
10
15
11 • 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6, 9-trithiaundecane, and
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.
5 [0028]
(11) The plastic polarized lens as described in anyone of (1)
to (10) as above, wherein the refractive index at e-line of the
thiourethane-based resin is in a range of 1.57 to 1.70.
[0029]
(12) The plastic polarized lens as described in anyone of (1)
to (10) as above, wherein the refractive index at e-line of the
thiourethane-based resin is in a range of 1.59 to 1.70.
[0030]
(13) Amethod of producing a plastic polarized lens, including:
producing a resin film containing an organic coloring compound
represented by the following general formula (1),
shaping the resin film to obtain a polarized film,
fixing the polarized film in a lens casting mold in a state
in which the polarized film is apart from the mold,
20 injecting a monomer mixture into the space between both
surfaces of the polarized film and the mold, and
stacking layers comprising a thiourethane-based resin over
both surfaces of the polarized film by polymerizing and curing the
monomer mixture.
25 [0031]
12
A4
A5
~
N
~ A6
A3
~
N N
~ /;
~ A7
N ( 1 )
A1
As
[0032]
In the formula (1), Al to As each independently represent a
hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy
5 group, an amino group, a carboxyl group, a sulfone group, a linear,
branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy
group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20
carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms,
a dialkylamino group having 2 to 20 carbon atoms, an aralkyl group
10 having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon
atoms, a heteroaryl group, an alkylthio group having 1 to 20 carbon
atoms, or an arylthio group having 1 to 20 carbon atoms, or may form
a ring other than an aromatic ring through a linking group, and M
represents two hydrogen atoms, a divalent metal atom, a trivalent
15 mono-substituted metal atom, a tetravalent di-substituted metal
atom, or an oxy metal) .
[0033 ]
(14) The method of producing a plastic polarized lens as
described in (13) as above, wherein the organic coloring compound
20 is represented by the following general formula (la):
[0034]
• 13
(1 a)
In the formula (la), t-C4Hg represents a tertiary butyl group.
Four tertiary butyl groups correspond to Al or Az, A3 or A4, As or
A6, and A7 or As, respectively, in the formula (1), and represent
5 a position isomer structure. Further, four groups that are not
tertiary butyl groups in Al to As represent a hydrogen atom. M
represents a divalent copper atom, a divalent palladium atom, or
divalent vanadium oxide (-V(=O)-).
[0035 ]
10 (15) The method of producing a plastic polarized lens as
described in (13) or (14) as above, wherein the resin film is a
thermoplastic polyester film.
[0036]
(16) The method of producing a plastic polarized lens as
15 described in (15) as above, wherein the shaping the resin film
includes:
shaping the thermoplastic polyester film under the temperature
condition of the glass transition temperature of the thermoplastic
polyester+20°C or higher and the glass transition temperature+120°C
20 or lower.
[0037]
(17) The method of producing a plastic polarized lens as
14 • described in anyone of (13) to (16) as above, wherein the monomer
mixture includes:
(A) at least one kind of isocyanate compounds selected from
the group consisting of a polyisocyanate compound, an isocyanate
5 compound having an isothiocyanate group, and a polyisothiocyanate
compound,
(8) at least one kind of active hydrogen compound selected from
the group consisting of thio1 compounds and polythio1 compounds
having a hydroxy group.
10 [0038]
(18) The method of producing a plastic polarized lens as
described in anyone of (13) to (17) as above, further including:
subjecting at least one surface of the polarized film to a
surface modification treatment before the fixing the polarized
15 film.
[0039]
(19) The method of producing a plastic polarized lens as
described in anyone of (13) to (18) as above, further including:
forming an adhesive layer over at least one surface of the
20 polarized film before the step of fixing the polarized film.
[0040]
(20) The method of producing a plastic polarized lens as
described in anyone of (13) to (18), further including:
subjecting at least one surface of the polarized film to a
25 surface modification treatment; and
forming an adhesive layer over the surface that has been
subjected to a surface modification treatment,
15 • before the fixing the polarized film.
[0041]
(21) The method of producing a plastic polarized lens as
described in anyone of (15) to (20) as above, wherein the
5 thermoplastic polyester is a polyethylene terephthalate.
[0042]
(22) The method of producing a plastic polarized lens as
described in anyone of (17) to (21) as above, wherein the isocyanate
compound (A) is a diisocyanate compound and the active hydrogen
10 compound (B) is a polythiol compound.
[0043]
(23) The method of producing a plastic polarized lens as
described in anyone of (17) to (22) as above, wherein the isocyanate
compound (A) is at least one kind of diisocyanate compounds selected
15 from the group consisting of
2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and mxylylene
diisocyanate, and
the active hydrogen compound (B) is at least one kind of
20 polythiol compounds selected from the group consisting of
pentaerythritoltetrakis(3-mercaptopropionate),
4-mercaptomethyl-l,S-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane, and
25 4,S-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane.
[0044]
(24) The method of producing a plastic polarized lens as
5
16
described in anyone of (13) to (23) as above, wherein the viscosity
at 20°C of the monomer mixture is 200 mPa· s or less in the inj ecting
step.
[0045]
(25) A polarized film including a resin containing an organic
coloring compound represented by the following general formula (1) :
[0046]
N~
A,
( 1 )
10
[0047]
In the formula (1), Al to As each independently represent a
hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy
group, an amino group, a carboxyl group, a sulfone group, a linear,
branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy
group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20
15 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms,
a dialkylamino group having 2 to 20 carbon atoms, an aralkyl group
having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon
atoms, a heteroaryl group, an alkylthio group having 1 to 20 carbon
atoms, or an arylthio group having 1 to 20 carbon atoms, or may form
20 a ring other than an aromatic ring through a linking group, and M
represents two hydrogen atoms, a divalent metal atom, a trivalent
17 • mono-substituted metal atom, a tetravalent di-substituted metal
atom, or an oxy metal.
[0048]
(26) The polarized film as described in (25) as above, wherein
5 the organic coloring compound is represented by the following
general formula (la):
[0049]
(1 a)
10
[0050]
In the formula (la), t-C4Hg represents a tertiary butyl group.
Four tertiary butyl groups correspond to Al or A2, A3 or A4' As or
A6, and A7 or As, respectively, in the formula (1), and represent
a position isomer structure. Further, four groups that are not
tertiary butyl groups in Al to As represent a hydrogen atom. M
15 represents a divalent copper atom, a divalent palladium atom, or
divalent vanadium oxide (-V(=O)-).
[0051]
(27) The polarized film as described in (25) or (26) as above,
wherein the resin is a thermoplastic polyester.
20 [0052]
(28) The polarized film as described in anyone of (25) to (27)
15
25
18
as above, wherein the organic coloring compound is contained in the
amount of 50 to 7000 ppm in the polarized film.
[0053 ]
(29) The polarized film as described in (27) or (28) as above,
5 wherein the thermoplastic polyester is a polyethylene
terephthalate.
[0054]
(30) The polarized film as described in anyone of (25) to (29)
as above, which is used in a plastic polarized lens having layers
10 including a thiourethane-based resin laminated over both surfaces
of the polarized film.
[0055]
(31) A method for producing the polarized film as described
in (30) as above, including:
producing a resin film containing the organic coloring
compound; and
shaping the resin film.
[0056]
(32) The method for producing the polarized film as described
20 in (31) as above, wherein the resin film is a thermoplastic polyester
film.
[0057]
(33) The method for producing the polarized film as described
in (32) as above, wherein the step of shaping the resin film includes:
shaping the thermoplastic polyester film under the temperature
condition of the glass transition temperature of the thermoplastic
polyester+20°C or higher and the glass transition temperature+120°C
19
or lower.
[0058]
In the present invention, the "high-contrast property" means
visual characteristics that when an object is observed through a
5 plastic polarized lens visually, the color, the brightness, and the
outline of the object can be clearly perceived and there is clear
distinction between the obj ect and the obj ect or between the obj ect
and the background.
[0059]
10 The plastic polarized lens of the present invention has an
improved contrast property allowing clear perception of color
contrast or the outline of an object, and thus, the visibility is
excellent as well as the visual fatigue is reduced. Further, since
the polarized film itself contains a predetermined organic coloring
15 compound, partial color difference attributable to difference in
the thickness of lenses is suppressed, and the appearance is
improved even when applied to a lens having partially different
thickness, such as a lens for vision correction. In addition, since
the plastic polarized lens has excellent water resistance, time
20 deterioration is inhibited. Further, it has an excellent
construction for processing characteristics, and thus, it is
capable of providing a thinner lens and suitable for mass production.
The plastic polarized lens provided with such characteristics is
particularly useful as a polarized lens for spectacles.
25 Furthermore, the method for producing the plastic polarized
lens of the present invention is.
In addition, the polarized film of the present invention can
20
provide a polarizing function and can be provided with a high
contrast property, and can be suitably used particularly for a
polarized lens.
5 BRIEF DESCRIPTION OF THE DRAWINGS
[0060]
Fig. 1 is a cross-sectional view schematically showing a
plastic polarized lens according to an embodiment.
Fig. 2 is a cross-sectional view schematically showing a lens
10 casting mold according to an embodiment.
Fig. 3 is a chart showing a transmission spectrum of the
polarized film produced in Example 1.
DESCRIPTION OF EMBODIMENTS
15 [0061]
Hereinbelow, the embodiments of the present invention will be
described with reference to the drawings. Further, in all the
drawings, the same sYmbols are attached to the same components and
the explanations thereof will not be repeated.
20 [0062]
As shown in Fig. 1, the plastic polarized lens 10 of the present
embodiment has resin layers (plastic lenses) 14a and 14b including
a thiourethane-based resin on both surfaces of a polarized film 12.
The polarized film 12 contains an organic coloring compound.
25 [0063]
The thermoplastic resin as a resin constituting the polarized
film is not particularly limited, and examples thereof include a
21
thermoplastic polyolefin, a thermoplastic polyimide, and a
thermoplastic polyester. From the viewpoints of water resistance,
heat resistance, and mold processability, the thermoplastic
polyester is preferable.
5 . As the thermoplastic polyester, specifically, polyethylene
terephthalate, polyethylene naphthalate, polybutylene
terephthalate, or the like can be used, and from the viewpoint of
the effects above, polyethylene terephthalate is particularly
preferable. Those modified by an approach, such as addition of
10 copolymerization components are also included.
[0064]
As the organic coloring compound in the present embodiment,
those which are insoluble in water and do not cause decomposition,
discoloration, or the like at the melting point of the resin
15 constituting the polarized film are used. In the present embodiment,
those which do not cause decomposition, discoloration, or the like
at the melting point of the thermoplastic polyester are preferable,
and a compound having a porphyrin skeleton can be used.
[0065]
20 As the compound having a porphyrin skeleton, specifically, a
tetraazaporphyrin compound represented by the following general
formula (1) is preferably used.
[0066]
22
A4 A5
~
N
A3 ~ ~ A6
N N
~ /;
~ A7
N ( 1 )
A1 As
[0067]
In the formula (1), Al to As each independently represent a
hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy
5 group, an amino group, a carboxyl group, a sulfone group, a linear,
branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy
group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20
carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms,
a dialkylamino group having 2 to 20 carbon atoms, an aralkyl group
10 having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon
atoms, a heteroaryl group, an alkylthio group having 1 to 20 carbon
atoms, or an arylthio group having 1 to 20 carbon atoms, or may form
a ring other than an aromatic ring through a linking group. As Al
to As, a linear, branched, or cyclic alkyl group having 1 to 20 carbon
15 atoms is preferable, a linear or branched alkyl group having 1 to
20 carbon atoms is more preferable, and a linear or branched alkyl
group having 2 to 10 carbon atoms is particularly preferable.
M represents two hydrogen atoms, a divalent metal atom, a
trivalent mono-substituted metal atom, a tetravalent
20 di-substituted metal atom, or an oxy metal) .
[0068]
•
25
23
Examples of the divalent metal atom include Cu (II), Zn (II),
Co (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg
(II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II),
and Sn (II).
5 [0069]
Examples of the trivalent mono-substituted metal atom include
Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-F, Ga-I, Ga-Br, In-Cl, In-Br,
In-I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F, Al-C6Hs, Al-C6H4 (CH3), In-C6Hs,
In-C6H4(CH3), In-C6HS, Mn(OH), Mn(OC6HS), Mn(OSi(CH3)3), Fe-Cl, and
10 Ru-Cl.
[0070]
Examples of the tetravalent di-substituted metal atom include
CrClz, SiClz, SiBr2, SiFz, SiI2, ZrC12, GeC12, GeBr2, GeI2, GeF2, SnC12,
SnBrz, SnF2, TiC12, TiBr2, TiF2, Si (OH) 2, Ge (OH) 2, Zr (OH) 2, Mn (OH) 2,
15 Sn (OH) 2, TiRz, CrRz, SiR2, SnR2, GeR2 (in which R represents an alkyl
group, a phenyl group, a naphthyl group, or a derivative thereof),
Si(OR')z, Sn(OR')2, Ge(OR')z, Ti(OR')2, Cr(OR')2 (in which R'
represents an alkyl group, a phenyl group, a naphthyl group, a
trialkylsilyl group, a dialkylalkoxysilyl group, or a derivative
20 thereof), Sn(SR")2, and Ge(SR")2 (in which R" represents an alkyl
group, a phenyl group, a naphthyl group, or a derivative thereof) .
[0071]
Examples of the oxy metal include vanadium oxide (-V(=O)-),
manganese oxide (-Mn(=O)-), and titanium oxide (-Ti(=O)-).
As M, a divalent metal atom or an oxy metal is preferable, a
copper atom (Cu (II)), a palladium atom (Pd (II) ), or vanadium oxide
(-V(=O)-) is more preferable, and a copper atom (Cu (II)) is
• 24
particularly preferable.
[0072]
By using the tetraazaporphyrin compound represented by the
general formula (1) as an organic coloring compound, it is possible
5 to perceive the color contrast or the outline of an object clearly,
and improve the contrast property, and therefore, a plastic
polarized lens having excellent visibility as well as reduced vision
fatigue can be provided.
[0073]
10 As the tetraazaporphyrin compound represented by the general
formula (1), a tetraazaporphyrin compound represented by the
following general formula (la) is preferably used.
[0074]
15
(1 a)
In the formula (la), t-C4Hg represents a tertiary butyl group.
Four tertiary butyl groups correspond to Al or A2' A3 or A4' As or
A6' and A7 or As, respectively, in the formula (1), and represent
20 a position isomer structure. Further, four groups (Al or A2' A3 or
A4' As or A6' and A7 or As) that are not tertiary butyl groups in
Al to As represent a hydrogen atom. Mrepresents a divalent copper
25
atom, a divalent palladium atom, or divalent vanadium oxide
(-V(=O) -).
As the tetraazaporphyrin compound represented by the general
formula (1) or (la) , compounds represented by the following formulae
5 (2) to (4) can be used.
[0076]
t-C4Hg
~ N::qt-C
4
H
9
~ N N--
~ /'
N /CU N
~ /' )j N N
\ //
t-C4Hg
N t-C ( 2 ) 4Hg
[0077]
N
~
t-C4H9
10 [0078]
.r;::;
N
t-C4H9
N
)
t-C4H9
( 3)
( 4)
hN
t-C4Hg
26
N
~
t-C4Hg
[0079]
In the formulae (2) to (4), t-C4Hg represents a tertiary butyl
•
group. These four tertiary butyl groups correspond to Al or A2' A3
5 or A4 , As or A6' and A7 or As, respectively, in the formula (1), and
represent a position isomer structure. Further, Al to As that are
not tertiary butyl groups represent a hydrogen atom. Further, in
the formula (2), Cu represents divalent copper, in the formula (3),
Pd represents divalent palladium, and in the formula (4), v=o
10 represents divalent vanadium oxide.·
[0080]
These compounds can be produced by, for example, the method
described in Japanese Patent Laid-Open Application No. 11-116574,
Japanese Patent Laid-Open Application No. 11-130971, Japanese
15 Patent Laid-Open Application No. 2006-321925, Japanese Patent
Laid-Open Application No. 2007-099744, or the like.
[0081]
As the tetraazaporphyrin compound, a
tetra-t-butyl-tetraazaporphyrin-copper complex represented by the
20 formula (2) is preferably used from the viewpoints of the effects
above.
27
[0082]
As for the content of the organic coloring compound, the
preferable amount varies depending on the thickness of the polarized
film 12, and can be appropriately determined by the thickness, but
5 it is preferably contained in the amount of 50 to 7000 ppm, more
preferably 50 to 2000 ppm, and still more preferably 50 to 500 ppm,
in the polarized film 12.
[0083]
In the case where the content of the organic coloring compound
10 in the polarized film is less than 50 ppm, there is a room for
improvement in the contrast, whereas if the content is more than
7000 ppm, the contrast becomes strong, and thus, in some cases, there
are cases of feeling sickness when wearing spectacles made with a
polarized lens including polarized film. That is, by incorporating
15 the organic coloring compound in the above-described amount into
the polarized film 12, it is possible to perceive the color contrast
and the outline of an obj ect more clearly and the contrast property
is particularly improved. Accordingly, it is possible to provide
a plastic polarized lens with a high contrast property, having
20 excellent visibility as well as particularly reduced vision
fatigue.
[0084]
The polarized film 12 is obtained by shaping a resin film
containing an organic coloring compound. The forming step can be
25 carried out by an ordinary method. In the present embodiment, it
is preferable to use a thermoplastic polyester film as a resin film,
and in this case, the thermoplastic polyester film containing an
5
28
organic coloring compound is preferably a film formed under the
condition of a temperature Tl represented by the following formula:
(Formula) Glass transition temperature of the thermoplastic
polyester+20°C~Tl~Glasstransition temperature of the
thermoplastic polyester+120°C
[0085]
In the related art, in order to prepare a large number of
polarized lenses industrially, it is necessary to polish the outer
circumference of a lens after polymerization with an edger or the
10 like, and in this case, the polarized film and the lens base material
sometimes peel away from each other. Accordingly, there has been
a demand for a polarized lens having excellent adhesiveness between
a polarized film and a plastic lens, which suppresses the
peeling-off and is capable of producing a polarized lens
15 industrially with a high yield.
The polarized film 12 of the present embodiment is formed in
a desired curvature under this temperature condition, using a
thermoplastic polyester film as a resin film, and thus it has
excellent adhesiveness to the resin layers 14a and 14b. Therefore,
20 the plastic polarized lens of the present embodiment has excellent
productivity and is appropriate for mass production.
[0086]
Furthermore, the plastic polarized lens of the present
embodiment, in which thiourethane-based resin layers 14a and 14b
25 including a thiourethane-based resin are laminated on both surfaces
of the polarized film 12, has excellent water resistance, suppressed
uncomfortable feeling on wearing, capability of providing a thin
29
lens, and further, suppressed peeling-off of the polarized film
during a downstream process of polishing the periphery. That is,
it is excellent in the balance of these characteristics. This
effect is exhibited clear in the case of using the polarized film
5 12 including a thermoplastic polyester.
[0087]
In addition, in the present embodiment, a surface modification
treatment may be carried out on at least one surface of the polarized
film 12 or an adhesive layer may be provided thereon, and further,
10 the surface modification treatment and the formation of an adhesive
layer may be carried out sequentially. By this, the adhesiveness
of the polarized film 12 and the resin layers 14a and 14b including
the thiourethane-based resin, can be improved. Examples of the
adhesive layer include a layer including a urethane-based resin
15 containing a polyhydroxy compound-derived structural unit and a
polyisocyanate compound-derived structural unit, and examples of
the surface modification treatment include a plasma treatment on
a film surface.
[0088]
20 The method of producing the plastic polarized lens will be
described below.
[0089]

The method of producing the plastic polarized lens of the
25 present embodiment includes the following steps.
(a) a step of producing the resin film including the
above-described organic coloring compound;
30
(b) a step of shaping the resin film to produce a polarized
film;
(c) a step of fixing the polarized film in a lens casting mold
in a state in which the polarized film is apart from the mold;
5 (d) a step of inj ecting a mixture into the space between both
surfaces of the polarized film and the mold; and
(e) a step of polymerization and curing the mixture and
laminating layers including a thiourethane-based resin on both
surfaces of the polarized film.
10 The respective steps will be described in the order below.
[0090]
(a) Step of Preparing Resin Film Including Above-Described
Organic Coloring Compound
For the polarized film provided with the high-contrast
15 property of the present embodiment, a specific amount of a
water-insoluble dye including at least one dichroic dye is added
to a resin, and the organic coloring compound is added thereto in
an amount calculated to give the above-described amount in the
polarized film and mixed to obtain a resin composition. This resin
20 composition is molded to a film shape by a predetermined method.
Then, the obtained film is stretched in the uniaxial direction, and
then subjected to a heating treatment at a predetermined temperature
to prepare a polarized film. Further, in the present embodiment,
it is preferable to use a thermoplastic polyester as a resin.
25 [0091]
As the dichroic dye used in the present embodiment, a direct
dye that is soluble in water is not preferable and anyone may be
31
appropriately selected from water-insoluble known dyes that are
disperse dyes and acidic dyes. Specific examples thereof include
anthraquinone-based coloring agents, quinophthalone-based
coloring agents, and azo-based coloring agents. Further, it is
5 preferable that the coloring agent do not cause deterioration such
as decomposition and discoloration at the melting point of a
polyester-based resin base material. Examples of the dichroic dye
include dyes disclosed in Patent Application Publication No.
04-30986, Japanese Patent Laid-Open Application No. 61-087757,
10 Japanese Patent Laid-Open Application No. 61-285259, Japanese
Patent Laid-Open Application No. 62-270664, Japanese Patent
Laid-Open Application No. 62-275163, Japanese Patent Laid-Open
Application No. 01-103667, and the like.
Preferred examples of these derivatives include the exemplary
15 compounds represented by the formulae (5), (6), (7), and (8).
[0092]
[0093]
o
N:(JrC",
(5 )
20 [0094]
(6 )
32
o NH:.!
( 7 )
[0095]
[0096]
o NHz
(8 )
5 Considering the polarization degree of the polarized film, the
light transmission rate, or the like, the addition amount of the
dichroic dye is preferably from 0.005 to 4 parts by weight with
respect to 100 parts by weight of the resin.
When the polarized film of the present embodiment is prepared,
10 the resin and the organic coloring compound may be mixed with the
dichroic dye to give a resin composition. In order to give a favored
color, a plurality of generally used coloring agents may be added.
[0097]
The method for producing the resin composition is not
15 particularly limited, but examples thereof include methods for
mixing both using a known ribbon blender, a tumbler mixer, and the
like. The mixing temperature does not interfere with the
temperature around room temperature. If necessary, other
additives such as an ultraviolet ray absorbent may be added. The
33
method for forming a film with a resin composition including an
organic coloring compound and a dichroic dye is not particularly
limited, and known methods may be included. For example, the film
is formed by a T-die extrusion method using a known uniaxial or
5 biaxial extruder, or an inflation extrusion method. Typically, the
temperature for forming a film is in a range of the melting
temperature to lower than the decomposition temperature of the
resin.
[0098]
10 Subsequently, the obtained film is stretched in the uniaxial
direction. The stretching method is not particularly limited, and
carried out by a known method. Usually, for the stretching
condition, the stretching is carried out in a range of the glass
transition temperature of the resin to lower than the melting
15 temperature to 2 to 10 times in a uniaxial direction. The stretching
direction may be a machine direction or may be a direction
perpendicular to the machine direction. Further, by carrying out
an annealing treatment in the stretching direction in the fixed
state, a polarized film can be obtained.. The annealing treatment
20 may be carried out at any time of during curve processing and after
curve processing. The annealing treatment method is not
particularly limited, and carried out by a known method. Usually,
the annealing treatment is carried out in the temperature range of
the crystallization temperature to lower than the melting
25 temperature of the resin, for 5 seconds to 30 minutes, in the
stretching direction in the fixed state.
[0099]
34
(b) Step of Forming Resin Film to Produce Polarized Film
[0100]
Shaping of the resin film can be usually carried out by an
ordinary method. Examples of the shaping method include vacuum
5 shaping, pressurization shaping, vacuum-pressurization shaping,
and press shaping. In these methods, the temperature of the resin
film is adjusted to a predetermined temperature range, and the resin
film is shaped into a desired curvature shape. In the method for
shaping the resin film, conditions such as the shaping pressure and
10 the shaping time are appropriately adjusted in correspondence to
the shaping method, the temperature during the shaping, a production
apparatus, and the like. In addition, the resin film may be heated
to a predetermined temperature before shaping with a die and the
like.
15 [0101]
The shaping of the thermoplastic polyester film can be
performed under a temperature condition of the glass transition
temperature of the thermoplastic polyester+20°C or higher, the
glass transition temperature of the thermoplastic polyester+120°C
20 or lower, preferably under a temperature condition of the glass
transition temperature of the thermoplastic polyester+20°C or
higher, the glass transition temperature of the thermoplastic
polyester+100°C or lower, and still more preferably under a
temperature condition of the glass transition temperature of the
25 thermoplastic polyester+40°C or higher, the glass transition
temperature of the thermoplastic polyester+100°C or lower. As for
the method for shaping the thermoplastic polyester film, a typical
35
method can be used as long as the film is heated at the
above-mentioned temperature and can be given a desired curvature
shape.
[0102]
5 With the above-described temperature, the adhesiveness
between the polarized film including a thermoplastic polyester and
the layer including a thiourethane-based resin is excellent,
regardless of the presence or absence of the adhesive layer.
[0103]
10 In the case where the thermoplastic polyester is, for example
a polyethylene terephthalate containing an organic coloring
compound, the glass transition temperature is 74°C, and thus, the
shaping can be carried out under a temperature condition of 94°C
or higher and 194°C and lower, preferably under a temperature
15 condition of 94°C or higher and 174°C or lower, and more preferably
under a temperature condition of 114°C or higher and 174°C or lower.
The glass transition temperature of the thermoplastic
polyester can be generally measured by means of a DSC (differential
scanning calorimeter).
20 [0104]
Examples of the shaping method include the above-mentioned
methods. In the shaping method, by adjusting the temperature of
the thermoplastic polyester film to the temperature range and
shaping the film into a desired curvature shape, the adhesiveness
25 between the polarized film including the thermoplastic polyester
film and the plastic lens can be improved.
[0105]
36
By the production method of the present embodiment including
the shaping step, the adhesiveness between the polarized film and
the plastic lens is improved, the peeling-off in the outer
circumference polishing step is suppressed, and the productivity
5 of the plastic polarized lens is improved. That is, a polarized
lens can be prepared industrially with a high yield.
In addition, by the production of the present embodiment, the
adhesiveness between the polarized film and the plastic lens is
provided or improved by a simple method, and therefore, there is
10 no need to separately provide a step of improving the adhesiveness
and a plastic polarized lens having excellent adhesiveness can be
obtained by a simple method. Further, a step carried out to improve
the adhesiveness is not excluded.
[0106]
15 In the present embodiment, a surface modification treatment
may be carried out or an adhesive layer may be provided separately
on at least one surface of the resin film or polarized film, and
further, the surface modification treatment and the formation of
an adhesive layer may be carried out in this order. By this, the
20 adhesiveness of the polarized film 12 and the resin layers 14a and
14b including the thiourethane-based resin can be further improved.
Preferred examples of the adhesive layer include a layer including
a urethane-based resin containing a polyhydroxy compound-derived
structural unit and a polyisocyanate-derived structural unit, or
25 a layer including an acrylic acid ester polymer-based resin which
may contain a functional group, and examples of the surface
modification treatment include plasma treatment and corona
37
discharge treatment of the film surface.
[0107]
Before providing an adhesive layer on the polarized film
surface, at least one kind of pretreatments selected from those such
5 as gas or chemical solution treatment, corona discharge treatment,
plasma treatment, ultraviolet ray irradiation treatment, electron
beam irradiation treatment, surface roughening treatment, and
firing treatment may be carried out on the polarized film in advance.
[0108]
10 In the present embodiment, a coating agent is usually used to
form the adhesive layer on the polarized film. The coating agent
may contain no solvent, but a solvent-based or dispersion-based
coating agent including an appropriate solvent is preferred.
[0109]
15 The solvent can be selected from alcohol compounds such as
methanol, ethanol, and isopropanol, aromatic compounds such as
toluene and xylene, ester compounds such as ethyl acetate, ketone
compounds such as acetone, methyl ethyl ketone, and methyl isobutyl
ketone, halogen compounds such as dichloromethane, and the like,
20 and the solvent may be used alone or combination of two or more kinds
thereof. As the alcohol compounds, isopropanol is preferably used.
[0110]
The concentration of the coating agent in terms of the resin
is from 0.1 to 50% by weight, preferably from 1 to 50% by weight,
25 and more preferably 3 to 30% by weight. When it is more than 50%
by weight, the temporal stability of the coating solution becomes
deficient, the existence of the coated layer becomes visible because
5
38
the coated layer thickens due to too much urethane resin being coated,
or a decrease in adhesiveness may occur due to peel-off within the
coated layer. On the other hand, when it is less than 0.1% by weight,
the effect of improvement of the adhesiveness between the film and
the urethane resin base material cannot be fully obtained.
[0111]
The thickness of the coated layer should be 30 to 0.001 ~,
preferably 10 to 0.01 pm, and more preferably 5 to 0.05 pm.
[0112]
10 In the present embodiment, the coating agent is coated as
necessary on both surfaces of the polarized film, and the coating
solution portion which has fluidicity on the film is removed from
the film as necessary and dried. There is no particular limit on
the drying temperature, but it is usually in a range of 5 to 100 o e,
15 preferably 20 to 100 o e, more preferably 20 to 80 °e, and particularly
preferably 20 to 60 o e, or these temperatures may be combined and
heating can be performed in steps.
[0113]
The drying time is set depending on the solvent used, the drying
20 temperature, the blowing conditions, and the like, and is not
particularly limited, but it is usually in the rage of 1 minute to
48 hours, and more preferably 10 minutes to 24 hours.
[0114]
In the present embodiment, the method for forming the adhesive
25 layer on the polarized film is not particularly limited. However,
the methods are largely classified into a method in which the
polarized film is treated with a coating agent and then processed
39
to have curvature, a method in which the polarized film is processed
to have curvature and then treated with a coating agent, or a method
including a combination of both, but anyone of the methods can be
employed, and according to each situation, a conventionally known
5 method such as a roll-coating method, a spin-coating method, a
spray-coating method, a bar-coating method, and a dipping method
or the like may be used. After drying, the coating can be performed
once or more, and the types of the coating solutions used each time
may be the same as or different from each other. Typically, the
10 object of the present embodiment can be achieved by one instance
of coating and drying without repeated coating.
[0115]
After coating the polarized film with the above-mentioned
coating agent as necessary, drying and/or heat treatment is carried
15 out as necessary. The applied temperature upon application of the
drying and/or heat treatment is not particularly limited as long
as it does not substantially deteriorate the performance of the
polarized film. After coating the resin on the polarized film, an
active energy line may be irradiated thereon. Examples of the
20 active energy line include ultraviolet rays and an electron beam.
[0116]
Preferred examples of the urethane-based resin used as the
coating agent is a polymer including a polyhydroxy compound-derived
structural unit and a polyisocyanate-derived structural unit.
25 Examples of the polyhydroxy compound include polyester diol,
polyether diol, polythioether diol, polylactone diol, and
polyacetal diol. Among them, polyester diol and polyether diol are
• 40
preferable, and polyester diol is particularly preferable.
[0117]
Examples of the polyester diol include polyesters having a
hydroxyl group at the terminal, which can be obtained by reacting
5 diols or polyhydric alcohols, for example saturated polyhydric
alcohols such as ethylene glycol, propylene glycol, butylene glycol,
diethylene glycol, neopentyl glycol, hexamethylene glycol,
trimethylolpropane, and 3-methyl 1,5-pentanediol or unsaturated
polyhydric alcohols such as butanediol, or a mixture thereof, with
10 organic dicarboxylic acids, for example, saturated aliphatic acids
such as adipic acid and sebacic acid, unsaturated aliphatic acids
such as maleic acid and fumaric acid, aromatic carboxylic acids such
as isophthalic acid, phthalic acid, and terephthalic acid, or
anhydrides thereof, or a mixture thereof; and polyesters obtained
15 by ring-opening polymerization of lactones such as caprolactam and
methylcaprolactone with diols.
[0118]
Specific examples of the polyether diol include a polymer or
copolymer having a hydroxyl group at the terminal, which is obtained
20 by ring-opening polymerization or ring-opening copolymerization of
ethylene oxide, propylene oxide, epichlorohydrin, oxacyclobutane,
substituted oxacyclobutane, and tetrahydrofuran; and a mixture
thereof.
[0119]
25 Examples of the polyisocyanate which is a monomer of the
above-mentioned urethane-based resin include 1,4-tetramethylene
diisocyanate, 1,6-hexamethylene diisocyanate, 1,8-octamethylene
41
diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexylene
diisocyanate, tolylene diisocyanate, 1,3-phenylene diisocyanate,
4,4'-methylenebis(cyclohexyl isocyanate), 4,4'-diphenylmethane
diisocyanate, isophorone diisocyanate, and triphenylmethane
5 triisocyanate, and at least one kind or at least two kinds thereof
can be selected and used.
[0120]
Among them, 1,6-hexamethylene diisocyanate,
1,4-cyclohexylene diisocyanate, tolylene diisocyanate,
10 1,3-phenylene diisocyanate, 4,4'-methylenebis(cyclohexyl
isocyanate), 4,4'-diphenylmethane diisocyanate, and isophorone
diisocyanate are particularly preferable.
[0121]
The polyhydroxy compound and polyisocyanate which constitute
15 the urethane-based resin can be suitably selected from these
examples and combined together. Among them, the polyhydroxy
compound is preferably polyester diol, more preferably polyester
diol composed of adipic acid, butylene glycol and 3-methyl
1,5-pentanediol. On the other hand, the isocyanate component is
20 preferably isophorone diisocyanate. From the viewpoint of
adhesiveness between the film and the resin base material, this
combination is particularly preferable.
[0122]
The acrylic acid ester polymer-based resin which may have a
25 functional group used as the coating agent may be a reaction-curable
one or a non-reactive one, among which the non-reactive one is more
preferable.
.. 42
Examples of the acrylic acid ester polymer-based resin which
may have a functional group include a linear or branched, noncyclic
or cyclic, or non-aromatic or aromatic alcohol or a copolymer of
a (meth)acrylic acid ester monomer comprised of phenol and
5 (meth)acrylic acid. Here, the (meth)acrylic acid represents
acrylic acid or methacrylic acid. The (meth)acrylic acid ester
monomer substantially has one or more (meth)acrylic acid ester
groups in one molecule, but mono (meth) acrylic acid ester monomers
substantially having one (meth) acrylic acid ester group are more
10 preferable.
[0123]
Specific examples of the mono (meth) acrylic acid ester monomer
include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl
(meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
15 isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl
(meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl
(meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate,
isobornyl (meth) acrylate, norbornane (meth) acrylate, benzyl
(meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic acid
20 esters of methoxypolyethylene glycol, (meth) acrylic acid esters of
methoxypolypropylene glycol, and (meth)acrylic acid esters of
phenoxypolyethyl glycol.
Among these, methyl (meth) acrylate, isobutyl (meth) acrylate,
and the like are preferably used.
25 [0124]
Examples of the functional group of the acrylic acid ester
polymer having a functional group include a carboxylic acid group,
•
20
43
a hydroxyl group, a glycidyl group, an amide group, and an anhydride
group, and the polymer has one or more functional groups.
Examples of the monomer functional group constituting the
acrylic acid ester polymer having a functional group include
5 ethylenically unsaturated carboxylic acids such as (meth)acrylic
acid, itaconic acid, fumaric acid, (meth)acrylic acid ester of
2-hydroxyethylphthalic acid, and (meth)acrylic acid ester of
2-hydroxyethylsuccinic acid, ethylenically unsaturated sulfonic
acids such as 2-sulfoethyl (meth)acrylic acid, ethylenically
10 unsaturated phosphonic acids such as vinylphosphonic acid,
2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,
hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate,
methaglycidyl (meth) acrylate, (meth) acrylic acid amide, mono- or
dialkyl-substituted (meth) acrylic acid amide, dimethylaminoethyl
15 (meth)acrylic acid amide, N-methylol (meth) acrylic acid amide,
N-vinylpyrrolidone, N-vinylcaprolactam, and alkyl vinyl ethers.
Among these, 2-hydroxyethyl (meth) acrylate and the like are
preferably used.
[0125]
The acrylic acid ester polymer having a functional group is
constituted with one or more monomers selected from the monomers
having the above-described functional groups, in addition to one
or more of the above-described (meth) acrylic acid ester monomers.
The monomers constituting a copolymer of the (meth)acrylic
25 acid ester monomers may include vinyl monomers within a range not
interfering with the range of the present invention, and examples
of the vinyl monomers include vinyl esters such as vinyl acetate
•
5
44
and vinyl propionate, substituted or unsubstituted styrenes such
as styrene and a-methylstyrene, and vinyl halides. The amount of
the vinyl monomer is preferably in a range of 0 to 40 parts by weight,
more preferably 0 to 20 parts by weight, still more preferably 0
to 10 parts by weight, and particularly preferably 0 to 5 parts by
weight, based on 100 parts by weight of the monomers constituting
the copolymer of the (meth)acrylic acid ester monomers.
[0126]
Specific examples of the gas or chemical treatment as described
10 above include gas treatments using ozone, halogen gas, chlorine
dioxide, or the like, or chemical solution treatments using
oxidizing agents or reducing agents such as sodium hypochlorite,
alkali metal hydroxides, alkaline earth metal hydroxides, sodium
metals, sulfuric acid, nitric acid and the like, or acid radicals
15 and bases. In the chemical solution treatment, the oxidizing agents
and reducing agents, or the acid radicals and bases are typically
dissolved in water, alcohol, liquid ammonia, or the like and
employed in a liquid state.
[0127]
20 When the chemical for the treatment is alkali metal hydroxides
and/or alkaline earth metal hydroxides, examples of the alkali metal
hydroxides include lithium hydroxide, sodium hydroxide, and
potassium hydroxide, examples of the alkaline earth metal hydroxide
include magnesium hydroxide, calcium hydroxide, and barium
25 hydroxide, and at least one kind of these may be selected and used.
Among them, sodium hydroxide and potassium hydroxide are preferable,
and sodium hydroxide is particularly preferable.
45
[0128]
It is preferable that the alkali metal hydroxides and/or
alkaline earth metal hydroxides be used as the solution; and
examples of the solvent for the solutions include water and/or
5 organic solvents and examples of the organic solvent include
methanol, ethanol, and isopropanol.
[0129]
The concentration of the solution is suitably in a range of
5 to 55% by weight, and preferably 10 to 45% by weight; and the
10 temperature of the solution is suitably in a range of 0 to 95°C,
preferably 20 to 90°C, and more preferably ·30 to 80°C.
[0130]
The pretreatment by the alkali metal hydroxide and/or the
alkaline earth metal hydroxide in the present embodiment can be
15 carried out by bringing the solution, which is within the
above-mentioned solution concentration and solution temperature
range, into contact with one side or both sides of the polarized
film for a predetermined period of time. As the method of contact,
there are no particular limits, and for example, a method of
20 immersing of the polarized film into the solution, or contacting
with the polarized film by showering or surface-flowing can be
suggested. Among them, the method of immersing the polarized film
into the solution is preferable. During this time, in order to
uniformize the concentration and the temperature of the solution,
25 methods such as stirring, convection current flowing, and jet
flowing can be adopted. The time period of contact is not
particularly limited, but it is preferably in a range of 1 minute
46
to 24 hours, more preferably 5 minutes to 10 hours, and particularly
preferably 5 minutes to 5 hours.
[0131]
In order to bring the alkali metal hydroxide and/or the
5 alkaline earth metal hydroxide solution into contact with the
polarized film, physical stimulation such as ultrasound sonication
or vibration may be used in combination therewith.
[0132]
For the purpose of improving the wetting of the polarized film
10 with the solution, the alkali metal hydroxide and/or alkaline earth
metal hydroxide solution may contain anionic or nonionic
surfactants, and the like.
[0133 ]
When a solution of the alkali metal hydroxide and/or the
15 alkaline earth metal hydroxide is brought in contact with the
polarized film, the solution concentration, the solution
temperature, and the contact time can be appropriately selected and
carried out within a range substantially not interfering with the
optical characteristics of the polarized film.
20 [0134]
After a solution of the alkali metal hydroxide and/or the
alkaline earth metal hydroxide is brought in contact with the
polarized film, the polarized film is pulled out of the solution,
and as necessary, the washing and drying of the polarized film may
25 be carried out with water and/or organic solvents such as methanol,
ethanol, isopropanol, acetone, and methyl ethyl ketone.
[0135]
47
The corona discharge treatment mentioned above is a kind of
gas discharge, in which the gas molecules ionize to exhibit
conductivity and uses the phenomenon in which the film surface is
activated by the ion flows, which is a surface treatment technique
5 employed widely. Examples of the gas for the discharge treatment
include air, but the gas may be gases such as nitrogen, carbon dioxide,
and ammonia gas. The corona discharge treatment can be achieved,
for example, by a method of treating the polarized film surface using
the corona generated by applying voltage to electrodes of a known
10 high frequency generation apparatus. The corona discharge
treatment strength should be preferably 1 to 500 W·min/m2
, and more
preferably 5 to 400 W·min/m2
•
[0136]
Examples of the plasma treatment include a normal pressure
15 plasma treatment and a vacuum plasma treatment (low temperature
plasma treatment).
In the normal pressure plasma treatment, the discharge
treatment is carried out within a single or mixed gas atmosphere
such as air, water vapor, argon, nitrogen, helium, carbon dioxide,
20 carbon monoxide, alcohols such as IPA, and carboxylic acids such
as acrylic acid.
The vacuum plasma treatment can be carried out with a reduced
pressure, for example, by placing the polarized film inside a
discharge treatment apparatus of an internal electrode type which
25 has counter electrodes composed of a drum-shaped electrode and
plural rod-shaped electrodes, and under a treatment gas atmosphere
of 0.001 to 50 Torr, preferably 0.01 to 10 Torr, and more preferably
48
5
0.02 to 1 Torr, supplying a high voltage of direct current or
alternating current between the electrodes and discharging,
generating plasma of the treatment gas, and exposing the polarized
film surface thereto. Although the treatment conditions of the
vacuum plasma treatment depend on the treatment apparatus, the type
of treatment gas, the pressure, the frequency of the power source
and the like, the preferable conditions may be set suitably.
Examples of the gas for treatment include argon, nitrogen, helium,
carbon dioxide, carbon monoxide, air, water vapor, alcohols such
10 as IPA, and carboxylic acids such as acrylic acid. These may be
•
used alone or in a mixture thereof.
[0137]
(c) Step of Fixing the Polarized Film in Lens Casting Mold in
State in which Polarized Film is Apart from Mold
15 [0138]
As shown in Fig. 2, the plastic polarized lens of the present
embodiment is obtained by injecting a mixture of a specific
isocyanate compound and a specific active hydrogen compound into
a lens casting mold 20 where the polarized film 12 is fixed thereto,
20 and performing polymerization and curing.
The lens casting mold 20 is generally constituted with two
molds 22a and 22b, maintained by a gasket 22c.
As the material of the gasket 22c, polyvinyl chloride, a vinyl
ethylene-acetate copolymer, an ethylene-ethyl acrylate copolymer,
25 an ethylene-propylene copolymer, an ethylene-propylene-diene
copolymer, a polyurethane elastomer, a fluorine rubber, or a soft
elastic resin in which polypropylene is blended with them is used.
49
A material which does not swell or elute with respect to a mixture
of a specific isocyanate compound and a specific active hydrogen
compound employed in the present embodiment is preferred.
Examples of the material of the mold 22a and 22b include glass
5 and metal, and glass is usually used. A mold releasing agent may
be coated on molds 22a and 22b in advance in order to improve the
mold-releasing property of the obtained lens. In addition, a
coating solution which affords a hard coating ability to the lens
material may be coated on the molds in advance.
10 [0139]
Inside the space of the lens casting mold 20, the polarized
film 12 is installed so that the film surface is parallel to the
inner surface of the front side mold 22a which it faces. Between
the polarized film 12 and the molds 22a and 22b, space portions 24a
15 and 24b are formed, respectively. The separated distance "aU of
the space portions 24a and 24b where the space is the narrowest is
about 0.2 to 2.0 mm.
Since the mixture of the (A) isocyanate compound and the (B)
active hydrogen compound having a thiol group is used in the present
20 embodiment, viscosity is low during injection and thus, the mixture
can be injected easily even into the above-mentioned spaces of
intervals.
[0140J
(d) Step of Inj ecting Mixture in Spaces Between Both Surfaces
25 of Polarized Film and Mold.
[0141]
Subsequently, inside the space of the lens casting mold 20,
50
at the two space portions 24a and 24b between the molds 22a and 22b
and the polarized film 12, the mixture of (A) a specific isocyanate
compound and (B) a specific active hydrogen compound is injected
by a predetermined injection unit.
5 [0142]
The (A) isocyanate compound used in the present embodiment
includes a compound having an isothiocyanate group, and
specifically, it is a compound of one or more kinds or two or more
kinds selected from a polyisocyanate compound, an isocyanate
10 compound having an isothiocyanate group, and a polyisothiocyanate
compound.
[0143]
Examples of the polyisocyanate compounds include:
aliphatic polyisocyanate compounds such as hexamethylene
15 diisocyanate, 2,2,4-trimethylhexane diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate, lysine
diisocyanatomethyl ester, lysine triisocyanate, m- xylylene
diisocyanate, a,a,a',a'-tetramethylxylene diisocyanate
bis(isocyanatomethyl)naphthalene, mesitylylene triisocyanate,
20 bis(isocyanatomethyl) sulfide, bis(isocyanatoethyl)sulfide,
bis(isocyanatomethyl)disulfide, bis(isocyanatoethyl)disulfide,
bis(isocyanatomethylthio)methane,
bis(isocyanatoethylthio)methane, bis(isocyanatoethylthio)ethane,
and bis(isocyanatomethylthio)ethane;
25 alicyclic polyisocyanate compounds such as isophorone.
diisocyanate, bis (isocyanatomethyl) cyclohexane,
dicyclohexylmethane diisocyanate, cyclohexane diisocyanate,
10
Sl
S
methylcyclohexane diisocyanate,
dicyclohexyldimethylmethaneisocyanate,
2,S-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
3,S-bis(isocyanatomethyl)tricyclodecane,
3,9-bis(isocyanatomethyl)tricyclodecane,
4,S-bis(isocyanatomethyl)tricyclodecane, and
4,9-bis(isocyanatomethyl)tricyclodecane;
aromatic polyisocyanate compounds such as phenylene
diisocyanate, diphenylsulfide-4,4-diisocyanate; and
heterocyclic polyisocyanate compounds such as
2,S-diisocyanatothiophene, 2,S-bis(isocyanatomethyl)thiophene,
2,S-diisocyanatotetrahydrothiophene,
2,S-bis(isocyanatomethyl)tetrahydrothiophene,
IS 3,4-bis(isocyanatomethyl)tetrahydrothiophene,
•
2,S-diisocyanato-l,4-dithiane,
2,S-bis (isocyanatomethyl)-l, 4-dithiane,
4,S-diisocyanato-l,3-dithiolane, and
4,S-bis(isocyanatomethyl)-1,3-dithiolane, but are not limited to
20 the exemplary compounds.
[0144]
As isocyanate compounds having an isothiocyanate group, for
example, there are the polyisocyanate compounds exemplified above
which have a part of the isocyanate group replaced with the
2S isothiocyanate.group, but are not limited to these.
[014S]
Examples of the polyisothiocyanate compounds include:
S2
aliphatic polyisothiocyanate compounds such as
hexamethylenediisothiocyanate, lysine diisothiocyanatomethyl
ester, lysine triisothiocyanate, m- xylylene diisothiocyanate,
bis (isothiocyanatoethyl) sulfide,
S bis (isothiocyanatomethyl) sulfide, and
bis(isothiocyanatoethyl)disulfide and the like;
alicyclic polyisothiocyanate compounds such as isophorone
diisothiocyanate, bis(isothiocyanatomethyl)cyclohexane,
dicyclohexylmethane diisothiocyanate, cyclohexane
10 diisothiocyanate, methylcyclohexane diisothiocyanate,
2,S-bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane,
3,S-bis(isothiocyanatomethyl)tricyclodecane,
3,9-bis(isothiocyanatomethyl)tricyclodecane,
IS 4,S-bis(isothiocyanatomethyl)tricyclodecane, and
4,9-bis(isothiocyanatomethyl)tricyclodecane;
aromatic polyisothiocyanate compounds such as
diphenyldisulfide-4,4-diisothiocyanate; and
sulfur-containing heterocyclic polyisothiocyanate compounds
20 such as 2,S-diisothiocyanatothiophene,
2,S-bis(isothiocyanatomethyl)thiophene,
2,S-diisothiocyanatotetrahydrothiophene,
2,S-bis(isothiocyanatomethyl)tetrahydrothiophene,
3,4-bis(isothiocyanatomethyl)tetrahydrothiophene,
2S 2, S-diisothiocyanato-l,4-dithiane,
2,S-bis(isothiocyanatomethyl)-1,4-dithiane,
4, S-diisothiocyanato-l,3-dithiolane, and
25
53
4, 5-bis (isothiocyanatomethyl) -1, 3-dithiolane, but are not limited
to the exemplary compounds.
[0146]
Furthermore, these isocyanate compounds substituted with
5 halogen such as chlorine, bromine and the like, with an alkyl group,
an alkoxy group, a nitro group, or modified with polyhydric alcohol
prepolymer, carbodiimide, urea, biuret, or a dimerization or
trimerization reaction product of the isocyanate compounds may be
used. These isocyanate compounds may be used alone or in mixture
10 of'j:wo or more kinds thereof.
[0147]
Among these isocyanate compounds, in view of high availability,
cost, performance of the obtained resin, or the like, a diisocyanate
compound is preferably used. For example, hexamethylene
15 diisocyanate, isophorone diisocyanate,
bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane
diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, m- xylylene
diisocyanate, and 2,5-bis(isocyanatomethyl)-1,4-dithiane are
20 preferably used, and
2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and mxylylene
diisocyanate are particularly preferably used.
[0148]
The (B) active hydrogen compound used in the present embodiment
is an active hydrogen compound of one or more kinds or two or more
kinds selected from thiol compounds or polythiol compounds having
54
a hydroxyl group.
[0149]
Examples of the thiol compounds having a hydroxyl group
include:
5 2-mercaptoethanol, 3-mercapto-1,2-propandiol, glycerin
bis(mercaptoacetate), 4-mercaptophenol,
2,3-dimercapto-1-propanol, pentaerythritol
tris(3-mercaptopropionate), and pentaerythritol
tris(thioglycolate), but are not limited to the exemplary
10 compounds.
[0150]
Example of the polythiol compounds include:
aliphatic polythiol compounds such as methanedithiol,
1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol,
15 bis (2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane,
diethylene glycol bis(2-mercaptoacetate), diethylene glycol
bis(3-mercaptopropionate), ethylene glycol
bis(2-mercaptoacetate), ethylene glycol
bis(3-mercaptopropionate), trimethylolpropane
20 tris(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolethane
tris(2-mercaptoacetate), trimethylolethane
tris(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
25 tetrakis(3-mercaptopropionate), bis(mercaptomethyl)sulfide,
bis(mercaptomethyl)disulfide, bis(mercaptoethyl) sulfide,
bis(mercaptoethyl)disulfide, bis (mercaptopropyl) sulfide,
55
bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane,
bis(3-mercaptopropylthio)methane,
1,2-bis(mercaptomethylthio)ethane,
1,2-bis(2-mercaptoethylthio)ethane,
5 1,2-bis(3-mercaptopropylthio)ethane,
1,2,3-tris(mercaptomethylthio)propane,
1,2,3-tris(2-mercaptoethylthio)propane,
1,2,3-tris(3-mercaptopropylthio)propane,
4-mercaptomethyl-l,S-dimercapto-3,6-dithiaoctane,
10 5,7-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane,
4,S-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane,
tetrakis(mercaptomethylthiomethyl)methane,
tetrakis(2-mercaptoethylthiomethyl)methane,
15 tetrakis(3-mercaptopropylthiomethyl)methane,
bis(2,3-dimercaptopropyl) sulfide,
2, 5-dimercaptomethyl-l,4-dithiane, 2,S-dimercapto-l,4-dithiane,
2,5-dimercaptomethyl-2,5-dimethyl-l,4-dithiane and esters of
thioglycolic acid and mercaptopropionic acid,
20 hydroxymethylsulfide bis(2-mercaptoacetate),
hydroxymethylsulfide bis(3-mercaptopropionate),
hydroxyethylsulfide bis(2-mercaptoacetate), hydroxyethylsulfide
bis(3-mercaptopropionate), hydroxymethyldisulfide
bis(2-mercaptoacetate), hydroxymethyldisulfide
25 bis(3-mercaptopropionate), hydroxyethyldisulfide
bis(2-mercaptoacetate), hydroxyethyldisulfide
bis(3-mercaptopropionate), 2-mercaptoethyl ether
56
bis(2-mercaptoacetate), 2-mercaptoethyl ether
bis(3-mercaptopropionate), thiodiglycolate bis(2-mercaptoethyl
ester), thiodipropionate bis(2-mercaptoethyl ester),
dithiodiglycolate bis(2-mercaptoethyl ester), dithiodipropionate
5 bis(2-mercaptoethyl ester),
1,1, 3,3-tetrakis (mercaptomethylthio) propane,
1,1,2,2-tetrakis(mercaptomethylthio)ethane,
4,6-bis(mercaptomethyLthio)-1,3-dithiacyclohexane,
tris(mercaptomethylthio)methane, and
10 tris(mercaptoethylthio)methane;
aromatic polythiol compounds such as 1,2-dimercaptobenzene,
1,3-dimercaptobenzene, 1,4-dimercaptobenzene,
1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene,
1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene,
15 1, 3-bis (mercaptoethyl) benzene, 1,4-bis(mercaptoethyl)benzene,
1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene,
1,3,5-tris(mercaptomethyleneoxy)benzene,
1,3,5-tris(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol,
3,4-toluenedithiol, 1,5-naphthalenedithiol, and
20 2,6-naphthalenedithiol; and
heterocyclic polythiol compounds such as
2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol,
bismuthiol, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, but are
25 not limited to the exemplary compounds.
[0151]
In addition, an oligomer of the above active hydrogen compounds
57
or those substituted with halogen such as chlorine and bromine or
the like may be used. These active hydrogen compounds may be used
alone or in mixture of two or more kinds thereof.
[0152]
5 Among these active hydrogen compounds, in view of high
availability, cost, performance of the obtained resin, or the like,
polythiol compounds are preferably used. For example,
pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), bis(mercaptoethyl)sulfide,
10 4-mercaptomethyl-1,S-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,S-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
2,5-dimercaptomethyl-1,4-dithiane,
15 1, 1, 3,3-tetrakis (mercaptomethylthio) propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane are
preferably used, and pentaerythritol
tetrakis(3-mercaptopropionate),
20 4-mercaptomethyl-1,S-dimercapto-3,6-dithiaoctane,
5, 7-dimercaptomethyl-1,11-dimercapto-3,6, 9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
4,S-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane are
particularly preferably used.
25 [0153]
Moreover, the (A) isocyanate compound used in the present
embodiment may be preliminarily partially reacted with the (B)
58
active hydrogen compound in advance. Additionally, the (B) active
hydrogen compound used in the present embodiment may be
preliminarily partially reacted with the (A) isocyanate compound
in advance.
5 [0154]
In addition to the (A) isocyanate compound and (B) active
hydrogen compound, in order to modify the resin, a resin modifier
such as a hydroxy compound, an epoxy compound, an episulfide
compound, an organic acid and its anhydride, and an olefin compound
10 including a (meth) acrylate compound may be added. Herein, the resin
modifier is a compound which adjusts or improves physical properties
such as a refractive index, an Abbe's number, the heat resistance,
and the specific gravity of a thiourethane-based resin, and
mechanical strength such as impact strength of the
15 thiourethane-based resin.
[0155]
Examples of the hydroxy compound that is used as the resin
modifier include:
diethylene glycol, triethylene glycol, dipropylene glycol,
20 tripropylene glycol, 1,4-butanediol, thiodiethanol,
dithiodiethanol, glycerin, trimethylolpropane, pentaerythritol,
and an oligomer thereof, but are not limited to the exemplary
compounds.
[0156]
25 Examples of the epoxy compound which can be added as the resin
modifier include:
phenol-based epoxy compounds which can be obtained by
59
condensation reactions between polyhydric phenol compounds such as
bisphenol A glycidyl ether, and epihalohydrin compounds;
alcohol-based epoxy compounds which can be obtained by
condensation between polyhydric alcohol compounds such as
5 hydrogenated bisphenol A glycidyl ether, and epihalohydrin
compounds;
glycidyl ester-based epoxy compounds which can be obtained by
condensation between multivalent organic acid compounds such as
3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate,
10 and epihalohydrin compounds;
amine-based epoxy compounds which can be obtained by
condensation between primary and secondary diamine compounds and
epihalohydrin compounds; and
aliphatic multivalent epoxy compounds such as
15 vinylcyclohexenediepoxide, but are not limited to the exemplary
compounds.
[0157]
Examples of the episulfide compound which can be added as the
resin modifier include:
20 2, 3-epithiopropylthio compounds of chain aliphatic compounds
such as bis (2,3-epithiopropylthio) sulfide,
bis(2,3-epithiopropylthio)disulfide,
bis(2,3-epithiopropylthio)methane,
1,2-bis(2,3-epithiopropylthio)ethane, and
25 1,5-bis(2,3-epithiopropylthio)-3-thiapentane;
2,3-epithiopropylthio compounds having alicyclic compounds
and heterocyclic rings such as
10
60
1,3-bis(2,3-epithiopropylthio)cyclohexane, and
2,5-bis(2,3-epithiopropylthiomethyl)-1,4-dithiane; and
aromatic 2,3-epithiopropylthio compounds such as
1, 3-bis (2, 3-epithiopropylthio) benzene, and
5 1, 4-bis (2, 3-epithiopropylthio) benzene, but are not limited to the
exemplary compounds.
[0158]
Examples of the organic acid and anhydride thereof which can
be added as the resin modifier include:
thiodiglycolic acid, thiodipropionic acid, dithiodipropionic
acid, phthalic anhydride, hexahydrophthalic anhydride,
methylhexahydrophthalic anhydride, methyltetrahydrophthalic
anhydride, maleic anhydride, trimellitic anhydride, and
pyromellitic anhydride, but are not limited to the exemplary
15 compounds.
[0159]
Examples of the olefin compound which can be added as the resin
modifier include:
(meth)acrylate compounds such as benzyl acrylate, benzyl
20 methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl
acrylate, glycidyl methacrylate, phenoxyethyl acrylate,
phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol
diacrylate, ethylene glycol dimethacrylate, diethylene glycol
25 diacrylate, diethylene glycol dimethacrylate, triethylene glycol
diacrylate, triethylene glycol dimethacrylate, neopentyl glycol
diacrylate, neopentyl glycol dimethacrylate, ethylene glycol
61
5
bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate,
bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F
diacrylate, bisphenol F dimethacrylate, trimethylolpropane
triacrylate, trimethylolpropane trimethacrylate, glycerol
diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate,
pentaerythritol tetracrylate, pentaerythritol tetramethacrylate,
xylenedithiol diacrylate, xylenedithiol dimethacrylate,
mercaptoethylsulfide diacrylate, and mercaptoethylsulfide
dimethacrylate;
10 allyl compounds such as allylglycidyl ether, diallyl phthalate,
diallyl terephthalate, diallyl isophthalate and diethylene glycol
bisallylcarbonate; and
•
vinyl compounds such as styrene, chlorostyrene, methylstyrene,
bromostyrene, dibromostyrene, divinylbenzene and
15 3, 9-divinylspirobi (m-dioxane) , but are not limited to the exemplary
compounds.
[0160]
These resin modifiers may be used alone or in mixture of two
or more kinds thereof.
20 [0161]
The ratio of the (A) isocyanate compound and the (B) active
hydrogen compound (including the hydroxy compounds which are the
modifiers) to be used in the present embodiment, in terms of the
molar ratio of functional groups (NCO+NCS) / (SH+OH), is normally in
25 a range of 0.8 to 1.5, and preferably in a range of 0.9 to 1.2.
[0162 ]
The (A) isocyanate compound and the (B) active hydrogen
62
compound used in the present embodiment are selected considering
high availability, cost, high handleability, and performance of the
obtained resin, or the like.
The important factor in the high handleability is the viscosity
5 of the mixture during injection. The viscosity during injection
is determined by the combination of the (A) isocyanate compound and
the (B) active hydrogen compound (when employing the resin modifier,
this includes the type and amount of the resin modifie~;
furthermore, when employing a catalyst, this includes the type and
10 amount of the catalyst), but when the viscosity is too high, the
production of the polarized lens becomes difficult since it is
difficult to inject into the narrow space portions 24a and 24b
located between the glass molds 22a and 22b and the polarized film
12 inside the space of the lens casting mold 20. Typically, the
15 viscosity during injection should be preferably a measurement of
200 mPa·s or less at 20°C, and for producing a lens with very thin
central thickness, an even lower viscosity of, for example, 100
mPa·s or less is preferable. The viscosity of the mixture is
measured by using a B type viscometer at a solution temperature of
20 20°C.
As for the performance of the resin to be considered, the
refractive index is important, and those having a high refractive
index can be used appropriately. For example, a combination of the
(A) isocyanate compound and the (B) active hydrogen compound (when
25 employing the resin modifier, this includes the type and amount of
the resin modifier), which can obtain a resin having a refractive
index typically in a range of 1.57 to 1.70, preferably in a range
• 63
of 1.59 to 1.70, and more preferably in a range of 1.65 to 1.68 when
its refractive index is measured by an e-beam is preferable. If
the refractive index is too small, it is believed that the film inside
the polarized lens becomes obvious, and the appearance becomes poor.
5 [0163]
The same mixture of the (A) isocyanate compound and the (B)
active hydrogen compound used in the present embodiment is typically
used on both sides of the polarized film, but there is no problem
in using different mixtures.
10 [0164]
When curing and forming the mixture of the (A) isocyanate
compound and the (B) active hydrogen compound, as in the known
forming method, materials such as catalysts such as dibutyl tin
dichloride, ultraviolet ray absorbing agents such as a
15 benzotriazole-based agent, internal mold releasing agents such as
acidic phosphate ester, photostabilizers, antioxidants, reaction
initiators such as a radical reaction initiator, chain elongators,
,
cross-linking agents, anticoloring agents, oil-soluble dyes, and
fillers may be added, as necessary.
20 [0165]
When producing an injection solution by mixing a reaction
catalyst, mold releasing agents or other additives with the (A)
isocyanate compound and the (B) active hydrogen compound, the adding
of the catalyst, the mold releasing agents or other additives are
25 also dependent on the solubility of the (A) isocyanate compound and
the (B) active hydrogen compound, but the additives may be added
and dissolved in the (A) isocyanate compound in advance, added and
64
5
dissolved in the (B) active hydrogen compound in advance, or added
and dissolved in the mixture of the (A) isocyanate compound and the
(B) active hydrogen compound. In addition, there is no problem in
dissolving the additive in a part of the (A) isocyanate compound
or the (B) active hydrogen compound each used to produce a master
solution and then adding the additive to the mixture. The adding
order is not limited by the exemplary methods, and is appropriately
selected on the basis of operability, safety, convenience, or the
like.
10 Mixing is generally carried out at a temperature of 30°C or
lower. From the viewpoint of the pot life of the mixture, lower
"
temperatures are sometimes preferred. Additionally, when
additives such as a catalyst and a mold releasing agent do not exhibit
preferable solubility with the (A) isocyanate compound or the (B)
15 active hydrogen compound, they may be heated in advance and then
dissolved in the (A) isocyanate compound, the (B) active hydrogen
compound, or a mixture thereof.
In addition, depending on the physical properties required for
the obtained plastic lens, carrying out a degassing treatment under
20 reduced pressure or a filtration treatment under increased pressure
and reduced pressure as necessary may be preferable in many cases.
[016·6 ]
(e) Step of Polymerization and Curing Mixture and Laminating
Layers Including Thiourethane-Based Resin on Both Surfaces of
25 Polarized Film
[0167]
Subsequently, the lens casting mold wherein the polarized film
65
is fixed, into which the mixture of the (A) isocyanate compound and
the (B) active hydrogen compound has been injected, is cured and
formed inside a heating apparatus, such as in an oven and under water,
by a predetermined temperature program for several hours to several
5 tens of hours.
[0168]
The polymerizing and curing temperature cannot be limited
since the conditions differ depending on the composition of the
mixture, the type of a catalyst, the shape of a mold, or the like,
10 but it is carried out at a temperature of -50 to 200°C for 1 to 100
hours.
Typically, it is common to start at a temperature range of 5°C
to 40°C, slowly raising the temperature to a range of 80 °c to 130°C,
and then heating at that temperature for 1 hour to 4 hours.
15 [0169]
After the completion of the curing and forming, the plastic
polarized lens of the present embodiment, as shown in Fig. 1, can
be obtained by taking it out of the lens casting mold. In this
plastic polarized lens 10, the resin layer 14a, the polarized film
20 12 and the resin layer 14b are laminated, respectively. Due to this
structure, the peel-off of the polarized film 12 from the lens
material during the outer circumference polishing process can be
suppressed, and the polarized lens can be mass-produced
industrially.
25 [0170]
In the plastic polarized lens of the present embodiment, it
is preferable to heat the released lens for an annealing treatment
••....
66
,) '7
in order to lessen the strain caused by the polymerization.
annealing temperature is usuaily in a range of 80 to 150°C,
The
preferably in a range of 100 to 130°C, and more preferably in a range
of 110 to 130°C. The annealing time is usually in a range of 0.5
5 to 5 hours, and preferably in a range of 1 to 4 hours.
[0171]
The plastic polarized lens -"of the present embodiment is used
having coated layer(s) formed on one surface or both surfaces as
necessary. Examples of the coated layers include primer layers,
10 hard coated layers, antireflection film layers, antifog coated
. layers, antipollutant layers, and water-repellent layers. These
coated layers can be each used alone or as multi-layers with plural
coated layers. When forming the coated layers on both surfaces,
the same coated layer may be formed on each surface, or different
15 coated layers may be formed thereon.
[0172]
Along with these coated layers, ultraviolet ray absorbing
agents for protecting the lens or the eyes from ultraviolet rays,
infrared absorbing agents for protecting the eyes from infrared rays,
20 photostabilizers or antioxidants for improving the weathering
resistance of the lens, dyes or pigments for the purpose of improving
the fashionability of the lens, and photochromic dyes or
photochromic pigments, antistatic agents, and other known additives
for improving the performance of the lens may be co-opted. 'Various
.25 leveling agents may be used for the purpose of improving the coating
characteristics.
[0173]
J
67
-
The primer layer is generally formed between the polarized lens
base material (thiourethane-based resin) and the hard coated layer
for the purpose of improving the adhesiveness of the hard coated
layer or the impact resistance of the polarized lens, and the film
5 thickness is usually about 0.1 to 10 pm.
[0174]
'..
The primer layer is, for example, formed by a coating method
or a dry method. In the coating method, the primer composition is
coated by a well-known coating method such as spin coating, dip
10 coating and the like, and then it is solidified to form a primer
. layer. In the dry method, it is formed by a known dry method such
as the CVD method and a vacuum plating method. When forming the
primer layer, pretreatments of the lens surface such as an alkali
treatment, a plasma treatment, and an ultraviolet ray treatment for
15 the purpose of improving the adhesiveness may be carried out as
necessary.
[0175]
As the primer composition, materials which provide high
adhesiveness between the solidified primer layer and the lens base
20 material (thiourethane-based resin) are preferred, and typically,
primer compositions having a urethane-based resin, an epoxy-based
t'(\ e, IQfl1 il\L
resin, a polyester-based resin, a ~ .. I-based resin, and
polyvinylacetal as main ingredients are used. The primer
composition can be used without a solvent, but an appropriate
25 solvent which does not affect the lens may be used for the purpose
•
of adjusting the viscosity of the composition, and the like.
[0176]
J
The hard coated layer is a coated layer which aims to provide
the lens surface with functions such as abrasion resistance, wear
resistance, moisture resistance, hot water resistance, heat
resistance, and weathering resistance, and its layer thickness is
5 usually about 0.3 to 30 11m.
[0177]
The hard coated layer is typically formed by curing after
coating the hard coating composition by known coating methods such
as a spin coating method, dip coating method and the like. As the
10 curing method, there are heat curing methods and curing methods by
irradiation of energy lines such as ultraviolet rays, visible light
and the like. When forming the hard coated layer, pretreatments
of the coated surface (the lens base material or the primer layer)
such as an alkali treatment, a plasma treatment, and an ultraviolet
15 ray treatment for the purpose of improving the adhesiveness may be
carried out as necessary.
•
68
[0178]
As hard coating compositions, in general, the mixture of
organic silicone compounds having curability and fine oxide
20 particles (including complex fine oxide particles) of Si, Al, Sn,
Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, Ti, or the like is frequently
used. Besides these, amines, amino acids, metal acetyl acetonate
complexes, organic acid metal salts, perchloric acids, salts of
perchloric acids, acids, metal chlorides, multifunctional epoxy
25 compounds, or the like may be used. The hard coating composition
can be used without a solvent, but an appropriate solvent which does
not affect the lens may be used.
•
69
[0179]
The antireflection layer is typically formed on the hard coated
layer as necessary. The antireflection layer may be
inorganic-based or organic-based. Generally, the inorganic-based
5 antireflection layer is frequently formed by dry methods such as
a vacuum plating method, a sputtering method, an ion plating method,
an ion beam assisting method, and a CVD method, which employ
inorganic oxides such as SiOz and TiOz. Generally, the
organic-based antireflection layer is frequently formed by a wet
10 method which employs organosilicone compounds and compositions
including silica-based fine particles having internal cavities.
[0180]
The antireflection layer may be a single layered or
multi-layered, but when used as a single layer, it is preferable
15 for its refractive index to be lower than the refractive index of
the hard coated layer by 0.1 or more. The multi-layered
anti-refractive layer is preferable in order to effectively realize
the antireflection function, and in this case, low refractive index
layers and high refractive index layers are typically laminated
20 alternatively. In this case, it is also preferable that the
refractive index difference between the low refractive index layer
and the high refractive index layer be 0.1 or more. Examples of
the high refractive index layer include films of ZnO, TiOz, CeOz,
SbzOs, SnOz, ZrOz, TazOs, or the like, and examples of the low
25 refractive index layer include a SiOz film. The thickness of the
layer is usually about 50 to 150 nm.
[0181]
5
•
70
In addition, the plastic polarized lens of the present
invention may be subjected to rear side polishing, an antistatic
treatment, a dye treatment, a light modulation treatment, or the
like as necessary.
[0182]

The polarized film of the present embodiment is a resin film
containing an organic coloring compound. Specifically, ones
having the same composition as the polarized film 12 used in the
10 plastic. polarized lens 10 of the present embodiment can be used.
Through this polarized film, it is possible to perceive clearly the
color contrast and the outline of an object and the contrast property
is improved, and therefore, by using it in the optical applications
such as lenses or goggles, the effects of excellent visibility and
15 reduced vision fatigue can be obtained.
[0183]
The polarized film of the present embodiment can be obtained
by the same method as the (a) step in the method of producing the
plastic polarized lens of the present embodiment. That is, first,
20 predetermined amounts of a water-insoluble dye containing at least
one kind of dichroic dye and an organic coloring compound are added
to the predetermined resin and mixed in to obtain a resin composition.
Further, after molding the resin composition into a film form by
a predetermined method, the obtained film is stretched in a uniaxial
25 direction and then subjected to a heat treatment at a predetermined
temperature to produce a polarized film. In the present embodiment,
the film thus obtained can also be used as a polarized film.
71
In addition, as in the present embodiment, when used in a
polarized lens having plastic lenses (resin layers) laminated on
both sides of the polarized film, it is preferable to carry out the
following shaping step (curvature processing) in the polarized
5 film.
[0184]
The method for curvature processing is not particularly
limited, and general press molding, vacuum molding, or the like is
used. For the purpose of preventing scratches on the polarized film
10 during the curvature processing, a protective film may be laminated
on one surface or both surfaces of the polarized film for processing.
The protective film is not particularly limited as long as it does
not leave glue when peeled off from the polarized film after the
curvature processing.
15 [0185]
As the temperature of carrying out the curvature processing,
in the case of using a polarized film that has been subjected to
an annealing treatment in advance, a temperature range of the
crystallization temperature of the resin to lower than the melting
20 temperature is preferred. In the case of using a polarized film
that has not been subjected to an annealing treatme_.nt, a temperature
range of the glass transition temperature of the resin to lower than
the melting temperature is preferred. Curvature processing with
the polarized film that has not been subjected to an annealing
25 treatment is preferred to perform the annealing treatment after the
curvature processing in order to give dimensional stability.
Generally, the curvature radius at a time of carrying out the
72
curvature processing is about 40 to 1000 mm.
[0186]
The temperature for the annealing treatment is preferably in
a range of 120°C to the melting temperature of the resin, considering
5 the situation where a lens is used, particularly the situation where
the lens is left in a vehicle.
Further, in the case where a polarized film using a
thermoplastic polyester as a resin is used in the polarized lens
of the present embodiment, it is preferable to carry out the
10 curvature processing of the thermoplastic polyester film under the
temperature conditions of the glass transition temperature of the
thermoplastic polyester+20°C or higher and the glass transition
temperature+120°C or lower, from the viewpoint of adhesiveness to
the thiourethane-based resin.
15 [0187]
In the case where the plastic polarized film according to the
present embodiment is used in a polarized lens, a surface
modification treatment may be carried out on at least one surface
of the polarized film after carrying out the curvature processing,
20 or an adhesive layer may be provided separately. Otherwise, the
surface modification treatment and the formation of the adhesive
layer may be carried out in this order. By these, the adhesiveness
to a resin layer including the polarized film and the
thiourethane-based resin can be improved. Examples of the adhesive
25 layer include layers including a urethane-based resin containing
a polyhydroxy compound-derived structural unit and a
polyisocyanate-derived structural unit, and examples of the surface
•
73
modification treatment include a plasma treatment of the film
surface.
Further, a polarized lens can be obtained by inserting the
polarized film that has been subjected to curvature processing
5 between the two molds holding a gasket, injecting a thermosetting
resin, and then molding at a temperature set to a required
temperature over several hours to several tens of hours.
[0188]
By using the polarized film of the present embodiment in the
10 polarized lens, the color contrast or the outline of an obj ect can
be perceived clearly and the contrast property is improved, and
therefore, the visibility is excellent and the vision fatigue is
reduced. In addition, the polarized film of the present embodiment
can be developed not only for the lens alone, but also for other
15 contrast-improving applications such as goggles and shields of
helmets.
[0189]
[Examples]
Below, the present invention will be described in more detail
20 by way of examples, but is not limited to the present invention.
In addition, performance tests on the polarized lens were carried
out in the following methods.
[0190]
(A) Contrast Property
25 In the outdoors, an object was observed visually through the
obtained polarized lens and evaluated based on the following
criteria.
10
• 74
A: The outline of the object is clear and the color contrast
is high.
B: The outline of the obj ect is unclear and the color contrast
is low.
5 [0191]
(B) Hue of Lens
The difference in the hues between the central portion and the
peripheral portion of the obtained polarized lens in -60 was
visually evaluated according to the following criteria.
A: The hues of the central portion and the peripheral portion
are the same.
B: The hues of the central portion and the peripheral portion
are different.
15
[0192]
(C) Adhesiveness of Polarized Film
This is an evaluation which determines whether the
adhesiveness between the cured lens material and the polarized film
is excellent or not in the polarized lens after the forming.
The test is carried out by striking the obtained lens with a
20 hammer. At this time, if the adhesiveness between the polarized
film and the cured lens material is insufficient, peeling off of
the polarized film occurs. In other words, by observing the
peeling-off state of the laminated portion between the cured lens
material of the destroyed lens and the polarized film, and the
25 existence/nonexistence of the peeled-off layer in the destroyed
portion, the adhesion state was evaluated by the following criteria.
A: Among the destroyed portions, there are no confirmed
75
~ positions where the layers are peeled off.
B: Among the destroyed portions, most points are confirmed as
not having any peeling off in the layers, but some positions are
confirmed as having minute areas of peeling off in the layers.
5 c: Among the destroyed portions, there are numerous confirmed
positions where the layers are peeled off.
[0193]
(D) Poor Visibility of Polarized Film in Lens
Although the visibility may be evaluated under the light in
10 a normal life environment, in order to simplify the environmental
light factors as much as possible, the evaluation was made according
to the following method.
In a dark room where other light sources may be neglected, the
polarized lens to be tested was placed at a position about 150 cm
15 below a lighted fluorescent lamp with a length of about 120 cm and
of 37 watts set above, the image of the fluorescent lamp was observed
by looking at the concave surface of the lens from the direction
as vertical as possible to the surface, at about 30 cm above the
lens, having the lens in the horizontal position with the concave
20 face of the lens turned toward the lamp, while supporting a side
face of the lens by hand so that no hindrance existed on both side
faces of the lens. In addition, the image was observed while
slightly changing the angle of the lens from a horizontal position.
Two kinds of clear, large and small images were observed in common,
25 but when the polarized film was conspicuous, another vague image
could be observed. Poor visibility of the polarized film was rated
according to the following criteria:
76
A: Almost no vague image is seen.
B: A vague image is slightly seen but not expanded.
C: A vague image fluctuates, and is expanded and conspicuous.
[0194]
5 (E) Water Resistance
The polarized lens to be tested was dipped in a constant
temperature water bath kept at 60°C, and at each of predetermined
intervals, 3 kinds of lenses were taken out and changes were observed.
When water-resistance was not sufficient, whitening or
10 discoloration-like deterioration was observed progressing from the
peripheral portion to the central portion of the lens with time of
dipping (data obtained after 4 hours, 3 days, and 7 days). The
length of the deteriorated part from the peripheral portion to the
central portion of the lens was measured in millimeters using a
15 vernier caliper.
[0195]
(F) Refractive Index of Lens Material
Separately, the refractive index at e-line of a piece of a resin
(the lens material) molded without the use of the polarized film
20 was measured at 20°C using a Pulfrich refractometer.
[0196]
In the present Example, the following raw materials were used.
(Organic Coloring Compound)
Organic coloring compound A: The tetra-t-butyl
25 tetraazaporphyrin-copper complex represented by the formula (2) was
used.
[0197]
77
(Dichroic Dye)
Dichroic dye A: The dichroic dye represented by the formula
(5) was used.
Dichroic dye B: The dichroic dye represented by the formula
5 (6) was used.
Dichroic dye C: The dichroic dye represented by the formula
(7) was used.
Dichroic dye D: The dichroic dye represented by the formula
(8) was used.
10 Dichroic dye E: The dichroic dye represented by the formula
(9) was used.
[0198]
Br
OH 0
(9)
[0199]
15 Dichroic dye F: The dichroic dye repr~sented by the formula
(10) was used.
o OH
(10)
[0200]
Dichroic dye G: The dichroic dye represented by the formula
20 (11) was used.
.. 78
CI
CI
(11)
[0201]
(12)
o NH
5
Dichroic dye H: The dichroic dye represented by the formula
(12) was used.
o
[0202]
(Example 1)

0.0150 parts by weight of organic coloring compound A, and
10 suitable blending amounts of the dichroic dyes A to H were prepared
to give a desired color tone, and mixed with 100 parts by weight
of a polyethylene terephthalate resin. The resin made molten using
a T die film molding machine was cast by T die and molded into a
film, and the film was subjected to a 4-times stretching operation
15 to obtain a polarized film having a thickness of 140~. The
polarized film contained 134 ppm of the organic coloring compound
A.
[0203]

20 The absorbance of the obtained polarized film ,was measured
using an absorbance measurement device, UV/VIS SPECTROMETER V-550,
•
79
manufactured by JASCO Inc .. The measurement results are shown in
Fig. 3. As shown in Fig. 3, there was a peak of maximum absorption
at 588 nm. In addition, the polarized film had polarization
characteristics.
5 The glass transition temperature of the polyethylene
terephthalate-made polarized film as obtained above, which was
provided with an antiglare property was measured by the following
manner.
Furthermore, the polarized film was made into a 4.30 mg-cut
10 measurement sample. Using a differential scanning calorimeter
DSC-60 manufactured by Shimadzu Corporation, the glass transition
temperature was measured by raising the temperature using a heating
rate giving a rate of temperature increase of 10°C/min. The glass
transition temperature of the polarized film was 70.7°C
15 (intersection point method) from the inflection point in the chart.
In addition, the melting point was 253.8°C (peak top).
[0204]
(Example 2)

The polyethylene terephthalate-made polarized film obtained
above in Example 1 [glass transition temperature: 70.7°C]
(thickness 140 pm) was shaped in a curved shape of 2C (curve) at
a shaping temperature of 120°C by a heat pressing method. The
25 polarized film was prepared by cutting the polarized film to match
the mold size. This was inserted and installed inside the polarized
lens casting mold (glass mold set -5D with a front surface of 2C
5
• 80
and a rear surface of 6C) shown in Fig. 2.
On other hand, 50.6 parts by weight of m- xylylene diisocyanate,
49.4 parts by weight of a mixture of
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and
5,7-dimercaptomethyl-1,11-dimercapto-3,6, 9-trithiaundecane,
0.01 parts by weight of dibutyl tin dichloride as a curing promoting
agent, 0.1 parts by weight of Zelec UN (registered trademark,
manufactured by Stepan Company) as a mold releasing agent and 0.05
10 parts by weight of Seesorb 709 (manufactured by Shipro Kasei Kaisha,
Ltd.) as an ultraviolet ray absorbing agent were stirred and
dissolved, degassed under reduced pressure, and provided as the
monomer mixture for injection right after production. The
viscosity at 20°C after 1 hour of stirring and dissolving was 30
15 mPa·s. The viscosity of the monomer mixture for injection was
measured using a B type viscometer at a liquid temperature of 20°C.
Subsequently, on the two space portions 24a and 24b which are
divided by the glass molds 22a and 22b inside the lens casting mold
arid the polarized film 12, this monomer mixture was passed through
20 a 3 pm filter and filtered, and then passed through the tube for
injection. Furthermore, the separated distance "a" of the
narrowest space portion 24a, was about 0.5 ffiffi. After the inj ection,
the closed lens casting mold 20 was placed in a hot air circulating
oven, heated from 25°C to 120°C for 16 hours, and maintained at 120 °c
25 for 4 hours and slowly cooled down, and then the lens casting mold
was taken out from the oven. The lens was released from the lens
casting mold, subjected to an annealing treatment at 130°C for 2
• 81
hours to obtain a polarized lens.
The performance test results of the obtained polarized lens
are shown in Table 1.
The obtained -5D lens had a center thickness of 1.2 rom and a
5 edge thickness of 6.2 rom. When the lens was observed, there was
a significant difference in the thickness between the central
portion and the peripheral portion, but the color tone of the lens
was had almost no change and the lens had good appearance. Further,
when observed through the obtained lens, for example, the lines of
10 the branches of the trees under clear sky were very clear or the
contrast of green, yellow, and red colors was very high, and the
objects could be perceived clearly.
[0205 ]
(Comparative Example 1)
15
The polyethylene terephthalate-made polarized film
[manufactured by Mitsui Chemicals, Inc.: "POLASOLA (registered
trademark) ", glass transition temperature: 70.7 °C] (thickness 140
20 ]lm) was cut to match the mold size to prepare a polarized film. This
was inserted and installed inside the polarized lens casting mold
(glass mold set -5D with a front surface of 2C and a rear surface
of 6C) shown in Fig. 2.
On other hand, 50.6 parts by weight of m- xylylene diisocyanate,
25 49.4 parts by weight of a mixture of
4,S-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4, 7-dimercaptomethyl-1,11-dimercapto-3,6, 9-trithiaundecane and
25
82
5, 7-dimercaptomethyl-1,11-dimercapto-3,6, 9-trithiaundecane,
0.01 parts by weight of dibutyl tin dichloride as a curing promoting
agent, 0.1 parts by weight of Zelec UN (registered trademark,
manufactured by Stepan Company) as a mold releasing agent and 0.05
5 parts by weight of Seesorb 709 (manufactured by Shipro Kasei Kaisha,
Ltd.) as an ultraviolet ray absorbing agent were stirred and
dissolved, degassed under reduced pressure, and provided as the
monomer mixture for injection right after production. The
viscosity at 20°C after 1 hour of stirring and dissolving was 30
10 mPa' s.
Subsequently, on the two space portions 24a and 24b which are
divided by the glass molds 22a and 22b inside the lens casting mold
and the polarized film 12, this monomer mixture was passed through
a 3 pm filter and filtered, and then passed through the tube for
15 injection. Furthermore, the separated distance "a" of the
narrowest space portion 24a, was about 0.5 mm. After the injection,
the closed lens casting mold 20 was placed in a hot air circulating
oven, heated from 25°C to 120°C for 16 hours, and maintained at 120°C
for 4 hours and slowly cooled down, and then the lens casting mold
20 was taken out from the oven. The lens was released from the lens
casting mold, subjected to an annealing treatment at 130°C for 2
hours to obtain a polarized lens.
The performance test results of the obtained polarized lens
are shown in Table 1.
The obtained -5D lens had a center thickness of 1.2 mm and a
edge thickness of 6.2 mm. As compared with the polarized lens of
the present invention using the polarized film containing the
83
.. organic coloring compound in Example 2, the lines of the branches
of the trees under clear sky were not clear or the contrast of green,
yellow, and red colors was very high, and the obj ects could not be
perceived clearly.
5 [0206]
(Comparative Example 2)

The polyethylene terephthalate-made polarized film
10 [manufactured by Mitsui Chemicals, Inc.: "POLASOLA (registered
trademark) ", glasstransition temperature: 70. 7°C] (thickness 140
]lm) was cut to match the mold size to prepare a polarized film. This
was inserted and installed inside the polarized lens casting mold
(glass mold set -5D with a front surface 2C and a rear surface of
15 6C) shown in Fig. 2.
On other hand, 0.001 parts by weight of an organic coloring
compound A was added to 50.6 parts by weight of m- xylylene
diisocyanate to give a uniform solution while stirring, 49.4 parts
by weight of a mixture of
20 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6, 9-trithiaundecane and
5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane,
0.01 parts by weight of dibutyl tin dichloride as a curing promoting
agent, 0.1 parts by weight of Zelec UN (registered trademark,
25 manufactured by Stepan Company) as a mold releasing agent and 0.05
parts by weight of Seesorb 709 (manufactured by Shipro Kasei Kaisha,
Ltd.) as an ultraviolet ray absorbing agent were stirred and
84
~ dissolved, degassed under reduced pressure, and provided as the
monomer mixture for injection right after production. The
viscosity at 20°C after 1 hour of stirring and dissolving was 30
mPa·s.
5 Subsequently, on the two space portions 24a and 24b which are
divided by the glass molds 22a and 22b inside the lens casting mold
and the polarized film 12, this monomer mixture was passed through
a 3 ~m filter and filtered, and then passed through the tube for
-inj ection. Furthermore, the separated distance "a" of the
10 narrowest space portion 24a was about 0.5 rom. After the inj ection,
the closed lens casting mold 20 was placed in a hot air circulating
oven, heated from 25°C to 120°C for 16 hours, and maintained at 120 °c
for 4 hours and slowly cooled down, and then the lens casting mold
was taken out from the oven. The lens was released from the lens
15 casting mold, and subj ected to an annealing treatment at 130 °C for
2 hours to obtain a polarized lens.
The performance test results of the obtained polarized lens
are shown in Table 1.
The obtained -50 lens had a center thickness of 1.2 rom and a
20 edge thickness of 6.2 rom. When observed through the lens, for
example, the lines of the branches of the trees under clear sky were
very clear or the contrast of green, yellow, and red colors was very
high, and the objects could be perceived clearly. However, when
the lens itself was observed, there was a difference in the hue
25 between the central portion and the peripheral portion, the color
in the central portion is not thick, and thus, the lens had an
extremely poor appearance.
[0207]
[Table 1]
85
.,
Places Formin'g Viscosity (A) (B) (C) (D) (E) Water (F)
having temperature (mPa· s) at Contrast Color Adhesiveness Poor resistance Refractive
organic ( °C) 20°C after property of of polarized visibility (length (mm) of index of
coloring stirring lens film of deteriorated lens
compound and polarized portion from
contained dissolving film in peripheral portion
therein for 1 hour lens to central portion)
After After After
4 3 7
hours days days
Example 2 Polarized 120 30 A A A A 0 0 0 1. 67
film
Comparative Not 120 30 B A A A 0 0 0 1. 67
Example 1 present
Comparative Lens 120 30 A B A A 0 0 0 1. 67
Example 2 materials
86
[0208]
(Example 3)
The polyethylene terephthalate-made polarized film obtained
above in Example 1 [glass transition temperature: 70.7°C]
(thickness 140 pm) was subjected to a heating treatment in an oven
at 140°C for 15 minutes in advance, and then shaped in a curved shape
of 6C (curve) at a shaping temperature of 160°C by a heat pressing
method. The polarized film was cut to match the mold size, and then
the surface and the back surface of the polarized film were
irradiated with plasma for 20 seconds, respectively, using a surface
modification device by irradiation with plasma (PS-601 SW type:
manufactured by Wedge Co., Ltd.), washed with methanol, and then
air-dried. This was inserted and installed inside the polarized
lens casting mold (glass mold set with a front surface of 6C and
a rear surface of 6C, center thickness: 12 rom). Further, in the
same manner as in Example 2, the monomer mixture for inj ection was
injected, warmed from 25°C to 100°C in an oven over 16 hours, and
then kept at 100°C for 10 hours and gradually cooled. Then, the
lens casting mold was taken out from the oven. The lens was released
from the lens casting mold, and annealed at 115°C for 2 hours to
obtain a polarized lens in a semi-finished lens shape. Thereafter,
the rear surface was cut and polished to give a lens having a -6D
shape.
The obtained -6D lens had a center thickness of 1.2 rom and a
edge thickness of 9.0 rom. The performance test results of the
polarized lens are shown in Table 2. The adhesiveness between the
lens and the polarized film was good, and deformation such as strain
87
could not be seen.
When the lens was observed, there was a significant difference
in the thickness between the central portion and the peripheral
portion, but there was almost no change in the color tone of the
lens and the lens had good appearance. Further, when observed
through the obtained lens, for example, the lines of the branches
of the trees under clear sky were very clear or the contrast of green,
yellow, and red colors was very high, and the objects could be
perceived clearly.
[0209]
(Example 4)
The polarized film was prepared by shaping and cutting the film
in the same manner as in Example 3 except that the shaping temperature
by heat pressing of the polarized film was set to 140°C to form a
curved shape of 2C (curve), and subjecting the surface and the back
surface of the polarized film to a corona discharge treatment in
a 400 Wset using a corona discharge surface treatment device
(CTW-0212 type: manufactured by Wedge Co., Ltd.).
Therefore, in the same manner as in Example 3, this was inserted
and installed inside the polarized lens casting mold (glass mold
set with a front surface of 2C and a rear surface of 4C, center
thickness: 10 mm). Further, in the same manner as in Example 3,
the monomer mixture was injected and subjected to a heating
treatment and curing in an oven, and gradually cooled. Then, the
lens was released from the lens casting mold and annealed to obtain
a polarized lens in a semi-finished lens shape. Thereafter, the
rear surface was cut and polished to give a lens having a -3D shape.
88
The obtained -3D lens had a center thickness of 1.2 rom and a edge
thickness of 3.6 rom. The performance test results of the polarized
lens are shown in Table 2. The adhesiveness between the lens and
the polarized film was good, and deformation such as strain could
not be seen.
When the lens was observed, there was a significant difference
in the thickness between the central portion and the peripheral
portion, but there was almost no change in the color tone of the
lens and the lens had good appearance. Further, when observed
through the obtained lens, for example, the lines of the branches
of the trees under clear sky were very clear or the contrast of green,
yellow, and red colors was very high, and the objects could be
perceived clearly.
[0210]
(Example 5)
The polarized film formed by shaping and cutting the polarized
film in the same manner as in Example 3 except that the shaping
temperature by heat pressing of the polarized film was set to 140°C
to form a curved shape of 4C (curve) was washed with methanol and
dried at 40°C. This film was dipped in an acryl-based adhesive
solution (SYNEDOL2263XB coating solution manufactured by CHEMISCHE
INDUSTRIE SYNRES NV. (HOLLAND)), taken out, then dried at 40°C, and
subjected to an acryl-based coating treatment.
Thereafter, in the same manner as in Example 3, this was
inserted and installed inside the polarized lens casting mold (glass
mold set with a front surface of 4C and a rear surface 6C, center
thickness: 11 rom). Further, in the same manner as in Example 3,
.. 89
the monomer mixture was injected and subjected to a heating
treatment and curing in an oven, and gradually cooled. Then, the
lens was released from the lens casting mold and annealed to obtain
a polarized lens in a semi-finished lens shape. Thereafter, the
rear surface was cut and polished to give a lens having a -5D shape.
The obtained -5D lens had a center thickness of 1.2 ffiffi and a edge
thickness of 6.6 ffiffi. The performance test results of the polarized
lens are shown in Table 2. The adhesiveness between the lens and
the polarized film was good, and deformation such as strain could
not be seen.
When the lens was observed, there was a significant difference
in the thickness between the central portion and the peripheral
portion, but there was almost no change in the color tone of the
lens and the lens had good appearance. Further, when observed
through the obtained lens, for example, the lines of the branches
of the trees under clear sky were very clear or the contrast of green,
yellow, and red colors was very high, and the objects could be
perceived clearly.
[0211]
(Example 6)
As a urethane-based coating, 100 parts by weight of SANPLENE
IB-422 (polyester-based polyurethane resin solution, manufactured
by Sanyo Chemical Industries, Ltd.) was dissolved in 330 parts by
weight of a mixture solvent with a weight ratio of 2:1 of methyl
ethyl ketone and isopropanol, and the urethane- based coating
solution was produced.
The polarized film before shaping by heat pressing was
90
maintained mostly horizontally while coating the surface of the film
with the above-described urethane-based coating solution that had
been prepared in advance using a #4 bar coater, and then dried in
a blower dry oven at 50°C for 5 minutes. Subsequently, the other
surface of the obtained film was peeled and the coating solution
was coated and dried in the same method as above.
The polarized film that had been urethane-coated was shaped
in a curved shape of 6C (curves) at a shaping temperature of 140°C
by a heat pressing method.
Thereafter, in the same manner as in Example 3, this was
inserted and installed inside the polarized lens casting mold (glass
mold set with a front surface of 6C and a rear surface of 6C, center
thickness: 12 mm). Further, in the same manner as in Example 3,
the monomer mixture was injected and subjected to a heating
treatment and curing in an oven, and gradually cooled. Then, the
lens was released from the lens casting mold and annealed to obtain
a polarized lens in a semi-finished lens shape. Thereafter, the
rear surface was cut and polished to give a lens having a -60 shape.
The obtained -60 lens had a center thickness of 1.2 mm and a edge
thickness of 9.0 mm. The performance test results of the polarized
lens are shown in Table 2. The adhesiveness between the lens and
the polarized film was good, and deformation such as strain could
not be seen.
When the IEms was observed, there was a significant difference
in the thickness between the central portion and the peripheral
portion, but there was almost no change in the color tone of the
lens and the lens had good appearance. Further, when observed
•
91
through the obtained lens, for example, the lines of the branches
of the trees under clear sky were very clear or the contrast of green,
yellow, and red colors was very high, and the objects could be
perceived clearly.
[0212]
(Example 7)
The surface and the back surface of the polarized film formed
by shaping and cutting the polarized film in the same manner as in
Example 3 except that the shaping temperature by heat pressing of
the polarized film was set to 140°C to form a curved shape of 6C
(curve) were irradiated with plasma for 20 seconds, respectively,
using a surface modification device by irradiation with plasma
(PS-601 SW type: manufactured by Wedge Co., Ltd.), washed with
methanol, and then dried at 40°C. This film was dipped in an
acryl-based adhesive solution (SYNEDOL2263XB coating solution
manufactured by CHEMISCHE INDUSTRIE SYNRES NV. (HOLLAND)), taken
out, then dried at 40°C, and subjected to an acryl-based coating
treatment.
Thereafter, in the same manner as in Example 3, this was
inserted and installed inside the polarized lens casting mold (glass
mold set with a front surface of 6C and a rear surface 6C, center
thickness: 12 rom). Further, in the same manner as in Example 3,
the monomer mixture was injected and subjected to a heating
treatment and curing in an oven, and gradually cooled. Then, the
lens was released from the lens casting mold and annealed to obtain
a polarized lens in a semi-finished lens shape. Thereafter, the
rear surface was cut and polished to give a lens having a -6D shape.
92
The obtained -6D lens had a center thickness of 1.2 mm and a edge
thickness of 9.0 mm. The performance test results of the polarized
lens are shown in Table 2. The adhesiveness between the lens and
the polarized film was good, and deformation such as strain could
not be seen.
When the lens was observed, there was a significant difference
in the thickness between the central portion and the peripheral
portion, but there was almost no change in the color tone of the
lens and the lens had good appearance. Further, when observed
through the obtained lens, for example, the lines of the branches
of the trees under clear sky were very clear or the contrast of green,
yellow, and red colors was very high, and the objects could be
perceived clearly.
[0213]
(Example 8)
The polarized film was prepared by shaping and cutting the film
in the same manner as in Example 3 except that the shaping temperature
by heat pressing of the polarized film was set to 140°C to form a
curved shape of 6C (curve), and the surface and the back surface
of the polarized film were subj ected to a corona discharge treatment
in a 400 Wset using a corona discharge surface treatment device
(CTW-0212 type: manufactured by Wedge Co., Ltd.). This film was
dipped in an acryl-based adhesive solution (SYNEDOL2263XB coating
solution manufactured by CHEMISCHE INDUSTRIE SYNRES NV. (HOLLAND)),
taken out, then dried at 40°C, and subjected to an acryl-based
coating treatment.
Thereafter, in the same manner as in Example 3, this was
•
93
inserted and installed inside the polarized lens casting mold (glass
mold set with a front surface of 6C and a rear surface of 6C, center
thickness: 12 mm). Further, in the same manner as in Example 3,
the monomer mixture for injection was injected, warmed from 2SoC
to 11SoC in an oven over 16 hours, and then kept at 11SoC for 10
hours and gradually cooled. Then, the lens casting mold was taken
out from the oven. The lens was released from the lens casting mold,
and annealed at 11S °c for 2 hours to obtain a polarized lens having
a semi-finished lens shape.
After the heat treatment and curing, and then slowly cooling,
the lens was released from the lens casing mold and annealed to obtain
a polarized lens in a semi-finished lens shape. Thereafter, the
rear surface was cut and polished to give a lens having a - 6D shape.
The obtained -6D lens had a center thickness of 1.2 mm and a edge
thickness of 9.0 mm. The performance test results of the polarized
lens are shown in Table 2. The adhesiveness between the lens and
the polarized film was good, and deformation such as strain could
not be seen.
When the lens was observed, there was a significant difference
in the thickness between the central portion and the peripheral
portion, but there was almost no change in the color tone of the
lens and the lens had good appearance. Further, when observed
through the obtained lens, for example, the lines of the branches
of the trees under clear sky were very clear or the contrast of green,
yellow, and red colors was very high, and the objects could be
perceived clearly.
94
[0214]
[Table 2]
•
Polarized Forming Surface Strain or (A) (B) (C) (D) (E) Water resistance (F)
film in temperature modification deformation Contrast Hue Adhesiveness of Poor (length (mm) of Refractive
the curve ( ·C) treatment of lens property of polarized film visibility deteriorated portion index of
shape lens of from peripheral lens
polarized portion to central
film in portion)
lens After After After
4 3 7
hours days days
Example 6C 160 Plasma No strain A A A A 0 0 0 1. 67
3 treatment No
deformation
Example 2C 140 Corona No strain A A A A 0 0 0 1. 67
4 discharge No
treatment deformation
Example 4C 140 Acryl-based No strain A A A A 0 0 0 1. 67
5 coating No
deformation
Example 6C 140 Urethane-based No strain A A A A 0 0 0 1. 67
6 coating No
deformation
Example 6C 140 Plasma No strain A A A A 0 0 0 1. 67
7 treatment No
Acryl-based deformation
coating
Example 6C 140 Corona No strain A A A A 0 0 0 1. 67
8 discharge No
treatment deformation
Acryl-based
coating
___mhgn_n_Jli,V~;~,,_,,""',Mh_"'A."'·;i:::A!?inq £iii JZ,; JA/UMh!UliJ& ,M n,@.(Q,,_iM,_Al;:s:mnMUWSiSiMiJid.;.L&Sil.,iLQlABA&.A:WMMRS&kAA1LihmGW4AMiMt4AiW!iWili .h A.b..a t&!k ,LM4l14&Ji)i,m& S ••.U c_mRS z; L
95
• [0215]
The present invention may include the embodiments below.
[0216]
(a1) A plastic polarized lens with a high contrast property,
5 in which the layers including a thiourethane-based resin containing
a thermoplastic polyester are laminated on both surfaces of the
polarized film,
wherein the polarized film contains an organic coloring compound
represented by the following general formula (1):
10 [0217]
( 1 )
[0218]
wherein Al to As each independently represent a hydrogen atom,
a halogen atom, a nitro group, a cyano group, a hydroxy group, an
15 amino group, a carboxyl group, a sulfone group, a linear, branched,
or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group
having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon
atoms, a monoa1kylamino group having 1 to 20 carbon atoms, a
dialkylamino group having 2 to 20 carbon atoms, an aralkyl group having
20 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a
heteroaryl group, an alkylthio group having 1 to 20 carbon atoms,
96
• or an arylthio group having 1 to 20 carbon atoms, or may form a ring
other than an aromatic ring through a linking group, and Mrepresents
two hydrogen atoms, a divalent metal atom, a trivalent
mono-substituted metal atom, a tetravalent di-substituted metal atom,
5 or an oxy metal.
[0219]
(a2) The plastic polarized lens with a high contrast property
as described in (a1), wherein the organic coloring compound is
represented by the following general formula (la):
(1 a)
wherein t-C4Hg represents a tertiary butyl group, four tertiary
butyl groups correspond to Al or A2, A3 or A4 , As or A6, and A7 or As,
15 respectively, in the formula (1), and represent a position isomer
structure, four groups that are not tertiary butyl groups in Al to
As represent a hydrogen atom. M represents a divalent copper atom,
a divalent palladium atom, or divalent vanadium oxide (-V(=O)-).
[0222]
20 (a3) The plastic polarized lens with a high contrast property
as described in (a1) or (a2), wherein the organic coloring compound
is contained in the amount of 50 to 7000 ppm in the polarized film.
5
97
• [0223]
(a4) The plastic polarized lens with a high contrast property
as described in anyone of (al) to (a3) , wherein the thiourethane-based
resin is obtained by reacting
(A) at least one kind of isocyanate compounds selected from the
group consisting of a polyisocyanate compound, an isocyanate compound
having an isothiocyanate group, and a polyisothiocyanate compound
with
(B) at least one kind of active hydrogen compounds selected from
10 the group consisting of thiol compounds and polythiol compounds
having a hydroxy group.
[0224]
(as) The plastic polarized lens with a high contrast property
as described in anyone of (al) to (a4), wherein the polarized film
15 is shaped under the condition of the temperature Tl represented by
the following formula:
(Formula) Glass transition temperature of the thermoplastic
polyester+20 °C~Tl~Glass transition temperature of the thermoplastic
polyester+120°C.
20 [0225]
(a6) The plastic polarized lens with a high contrast property
as described in anyone of (al) to (as), wherein the formation or
surface modification treatment of the adhesive layer is carried on
at least one surface of the polarized film.
25 [0226]
(a7) The plastic polarized lens with a high contrast property
as described in anyone of (al) to (a6), wherein the thermoplastic
is
98
~ polyester is a polyethylene terephthalate.
[0227]
(a8) The plastic polarized lens with a high contrast property
as described in anyone of (a4) to (a7), wherein the isocyanate
5 compound (A) is a diisocyanate compound and the active hydrogen
compound (B) is a polythiol compound.
[0228]
(a9) The plastic polarized lens with a high contrast property
as described in anyone of (a4) to (a8), wherein the isocyanate
10 compound (A) is at least one kind of diisocyanate compound selected
from the group consisting of
2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and m- xylylene
diisocyanate, and
the active hydrogen compound (B) is at least one kind of polythiol
compound selected from the group consisting of
pentaerythritoltetrakis(3-mercaptopropionate) ,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
20 4, 7-dimercaptomethyl-1,11-dimercapto-3,6, 9-trithiaundecane, and
4,8-dimercaptomethyl-1,11-dimercapto-3,6, 9-trithiaundecane.
[0229]
(a10) The plastic polarized lens with a high contrast property
as described in anyone of (a1) to (a9), wherein the refractive index
25 at e-line of the thiourethane-based resin is in a range of 1.57 to
1. 70.
[0230]
5
•
99
(all) The plastic polarized lens with a high contrast property
as described in anyone of (a1) to (a9), wherein the refractive index
at e-line of the thiourethane-based resin is in a range of 1.59 to
1. 70.
[0231]
(a12) A method of producing a plastic polarized lens with a high
contrast property, including:
producing a thermoplastic polyester film containing an organic
coloring compound represented by the following general formula (1),
10 shaping the thermoplastic polyester film under the temperature
condition of the glass transition temperature of the thermoplastic
polyester+20°C or higher and the glass transition temperature+120°C
or lower to obtain a polarized film,
fixing the polarized film in a lens casting mold in a state in
15 which the polarized film is apart from the mold,
injecting a monomer mixture into the space between both surfaces
of the polarized film and the mold, and
stacking layers comprising a thiourethane-based resin over both
surfaces of the polarized film by polymerizing and curing the monomer
20 mixture.
[0232]
100
•
[0233]
N
~
~
N ( 1 )
wherein Al to As each independently represent a hydrogen atom,
a halogen atom, a nitro group, a cyano group, a hydroxy group, an
5 amino group, a carboxyl group, a sulfone group, a linear, branched,
or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group
having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon
atoms, a monoalkylamino group having 1 to 20 carbon atoms, a
dialkylamino group having 2 to 20 carbon atoms, an aralkyl group having
10 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a
heteroaryl group, an alkylthio group having 1 to 20 carbon atoms,
or an arylthio group having 1 to 20 carbon atoms, or may form a ring
other than an aromatic ring through a linking group, and M represents
two hydrogen atoms, a divalent metal atom, a trivalent
15 mono-substituted metal atom, a tetravalent di-substituted metal atom,
or an oxy metal.
[0234]
(a13) The method of producing a plastic polarized lens with a
high contrast property as described in (a12), wherein the organic
20 coloring compound is represented by the following general formula
(la) :
•
101
[0235]
(1 a)
[0236]
wherein t-C4H9 represents a tertiary butyl group. Four tertiary
5 butyl groups correspond to Al or A2, A3 or A4, As or A6, and A7 or As,
respectively, in the formula (1), and represent a position isomer
structure. Further, four groups that are not tertiary butyl groups
in Al to As represent a hydrogen atom. Mrepresents a divalent copper
atom, a divalent palladium atom, or divalent vanadium oxide
10 (-V (=0) -) •
[0237]
(aI4) The method of producing a plastic polarized lens with a
high contrast property as described in (aI2) or (aI3), wherein the
monomer mixture includes:
15 (A) at least one kind of isocyanate compounds selected from the
group consisting of a polyisocyanate compound, an isocyanate compound
having an isothiocyanate group, and a polyisothiocyanate compound,
(B) at least one kind of active hydrogen compound selected from
the group consisting of thiol compounds and polythiol compounds
20 having a hydroxy group.
[0238]
(aI5) The method of producing a plastic polarized lens with a
15
102
.. high contrast property as described in anyone of (a12) to (a14),
including:
subj ecting at least one surface of the polarized film to a surface
modification treatment before the fixing the polarized film.
5 [0239]
(a16) The method of producing a plastic polarized lens with a
high contrast property as described in anyone of (a12) to (a15),
including:
forming an adhesive layer on at least one surface of the polarized
10 film before the fixing the polarized film.
[0240]
(a17) The method of producing a plastic polarized lens with a
high contrast property as described in anyone of (a12) to (a14),
including:
subjecting at least one surface of the polarized film to a surface
modification treatment, and
forming an adhesive layer on the surface that has been subj ected
to a surface modification treatment,
before the fixing the polarized film.
20 [0241]
(a18) The method of producing a plastic polarized lens with a
high contrast property as described in anyone of (a12) to (a17),
wherein the thermoplastic polyester is a polyethylene terephthalate.
[0242]
25 (a19) The method of producing a plastic polarized lens with a
high contrast property as described in anyone of (a14) to (a18),
wherein the isocyanate compound (A) is a diisocyanate compound and
10
103
4t the active hydrogen compound (B) is a polythiol compound.
[0243]
(a20) The method of producing a plastic polarized lens with a
high contrast property as described in anyone of (a14) to (a19),
5 wherein the isocyanate compound (A) is at least one kind of
diisocyanate compounds selected from the group consisting of
2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and m- xylylene
diisocyanate, and
the active hydrogen compound (B) is at least one kind of polythiol
compounds selected from the group consisting of
pentaerythritoltetrakis(3-mercaptopropionate),
4-mercaptomethyl-l,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-l,11-dimercapto-3,6, 9-trithiaundecane,
15 4,7-dimercaptomethyl-l,11-dimercapto-3,6, 9-trithiaundecane, and
4,8-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane.
[0244]
(a21) The method of producing a plastic polarized lens with a
high contrast property as described in anyone of (a14) to (a20),
20 wherein the viscosity at 20°C of the monomer mixture is 200 mPa·s
or less in the injecting step.
[0245]
(a22) A polarized film including a thermoplastic polyester
containing an organic coloring compound represented by the following
25 general formula (1):
[0246]
104
•
( 1 )
[0247]
wherein Al to As each independently represent a hydrogen atom,
a halogen atom, a nitro group, a cyano group, a hydroxy group, an
5 amino group, a carboxyl group, a sulfone group, a linear, branched,
or cyclic alkyl group having 1 to 20 ca~bon atoms, an alkoxy group
having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon
atoms, a monoalkylamino group having 1 to 20 carbon atoms, a
dialkylamino group having 2 to 20 carbon atoms, an aralkyl group having
10 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a
heteroaryl group, an alkylthio group having 1 to 20 carbon atoms,
or an arylthio group having 1 to 20 carbon atoms, or may form a ring.
other than an aromatic ring through a linking group, and Mrepresents
two hydrogen atoms, a divalent metal atom, a trivalent
15 mono-substituted metal atom, a tetravalent di-substituted metal atom,
or an oxy metal.
[0248]
(a23) The polarized film as described in (a22), wherein the
organic coloring compound is represented by the following general
20 formula (la):
[0249]
•
105
(1 a)
[0250]
wherein t-C4H9 represents a tertiary butyl group. Four tertiary
butyl groups correspond to Al or A2, A3 or A4, As or A6, and A7 or As,
5 respectively, in the formula (1), and represent a position isomer
structure. Further, four groups that are not tertiary butyl groups
in Al to As represent a hydrogen atom. Mrepresents a divalent copper
atom, a divalent palladium atom, or divalent vanadium oxide
(-V (=0) -) •
10 [0251]
(a24) The polarized film as described in (a22) or (a23), wherein
the organic coloring compound is contained in the amount of 50 to
7000 ppm in the polarized film.
[0252]
15 (a25) The polarized film as described in anyone of (a22) to
(a24), wherein the thermoplastic polyester is a polyethylene
terephthalate.
[0253]
(a26) The polarized film as described in anyone of (a22) to
20 (a25), which is used in the plastic polarized lens with a high contrast
property as described in anyone of (a1) to (all).
[0254]
5
106
~ (a27) A method for producing the polarized film as described
in (a26), including:
producing a thermoplastic polyester film containing the organic
coloring compound, and
shaping the thermoplastic polyester film under the temperature
condition of the glass transition temperature of the thermoplastic
polyester+20°C or higher and the glass transition temperature+120°C
or lower.

107
-. CLAIMS
1. A plastic polarized lens comprising:
a polarized film and
5
10
layers comprising a thiourethane-based resin stacked over both
surfaces of the polarized film,
wherein the polarized film contains an organic coloring compound
represented by the following general formula (1):
A4
~
N
~ A6
A3
\ N
"""/ N M
\ / /"'" N N
\ ~ A7
N ( 1 )
A1 As
wherein Al to As each independently represent a hydrogen atom,
a halogen atom, a nitro group, a cyano group, a hydroxy group, an
amino group, a carboxyl group, a sulfone group, a linear, branched,
or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group
having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon
15 atoms, a monoalkylamino group having 1 to 20 carbon atoms, a
dialkylamino group having 2 to 20 carbon atoms, an aralkyl group having
7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a
heteroaryl group, an alkylthio group having 1 to 20 carbon atoms,
or an arylthio group having 1 to 20 carbon atoms, or may form a ring
20 other than an aromatic ring through a linking group, and Mrepresents
108
two hydrogen atoms, a divalent metal atom, a trivalent
mono-substituted metal atom, a tetravalent di-substituted metal atom,
or an oxy metal.
5 2. The plastic polarized lens according to claim 1, wherein the
organic coloring compound is represented by the following general
formula (la):
(1 a)
wherein t-C4H9 represents a tertiary butyl group, four tertiary
10 butyl groups correspond to Al or A2, A3 or A4, As or A6, and A7 or As,
respectively in the formula (1), and represent a position isomer
structure, four groups that are not tertiary butyl groups in Al to
As represent a hydrogen atom; M represents a divalent copper atom,
a divalent palladium atom, or divalent vanadium oxide (-V(=O)-).
15
3. The plastic polarized lens according to claim 1 or 2, wherein
the polarized film is comprised of a thermoplastic polyester.
4. The plastic polarized lens according to anyone of claims 1 to
20 3, wherein the organic coloring compound is contained in the amount
of 50 to 7000 ppm in the polarized film.
109
5. The plastic polarized lens according to anyone of claims 1 to
4, wherein the thiourethane-based resin is obtained by reacting
(A) at lease one kind of isocyanate compounds selected from the
group consisting of a polyisocyanate compound, an isocyanate compound
5 having an isothiocyanate group, and a polyisothiocyanate compound
with
(B) at lease one kind of active hydrogen compounds selected from
the group consisting of thiol compounds and polythiol compounds
having a hydroxy group.
10
6. The plastic polarized lens according to anyone of claims 3 to
5, wherein the polarized film is shaped under the condition of the
temperature T1 represented by the following formula:
Glass transition temperature of the thermoplastic
15 polyester+20°C ~ T1 ~ Glass transition temperature of the
thermoplastic polyester+120°C.
7. The plastic polarized lens according to anyone of claims 1 to
6, wherein the formation of the adhesive layer or surface modification
20 treatment of the adhesive layer is carried over at least one surface
of the polarized film.
8. The plastic polarized lens according to anyone of claims 3 to
7, wherein the thermoplastic polyester is a polyethylene
25 terephthalate.
9. The plastic polarized lens according to anyone of claims 5 to
110
8, wherein the isocyanate compound (A) is a diisocyanate compound
and the active hydrogen compound (B) is a polythiol compound.
10. The plastic polarized lens according to anyone of claims 5 to
5 9, wherein the isocyanate compound (A) is at least one kind of
diisocyanate compound selected from the group consisting of
2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and m- xylylene
diisocyanate, and
10 the active hydrogen compound (B) is at least one kind of polythiol
compound selected from the group consisting of
pentaerythritoltetrakis(3-mercaptopropionate),
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
15 4,7-dimercaptomethyl-1,11-dimercapto-3,6, 9-trithiaundecane, and
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.
11. The plastic polarized lens according to anyone of claims 1 to
10, wherein the refractive index at e-line of the thiourethane-based
20 resin is in a range of 1.57 to 1.70.
12. The plastic polarized lens according to anyone of claims 1 to
10, wherein the refractive index at e-line of the thiourethane-based
resin is in a range of 1.59 to 1.70.
25
13. A method of producing a plastic polarized lens, comprising:
producing a resin film containing an organic coloring compound
111
5
.. represented by the following general formula (1);
shaping the resin film to obtain a polarized film;
fixing the polarized film in a lens casting mold in a state in
which the polarized film is apart from the mold;
inj ecting a monomer mixture into the space between both surfaces
of the polarized film and the mold; and
stacking layers comprising a thiourethane-based resin over both
surfaces of the polarized film by polymerizing and curing the monomer
mixture:
N
~ A6
N
/;
~ A7
N ( 1 )
As
N~
10
A1
wherein Al to As each independently represent a hydrogen atom,
a halogen atom, a nitro group, a cyano group, a hydroxy group, an
amino group, a carboxyl group, a sulfone group, a linear, branched,
or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group
15 having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon
atoms, a monoalkylamino group having 1 to 20 carbon atoms, a
dialkylamino group having 2 to 20 carbon atoms, an aralkyl group having
7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a
heteroaryl group, an alkylthio group having 1 to 20 carbon atoms,
20 or an arylthio group having 1 to 20 carbon atoms, or may form a ring
other than an aromatic ring through a linking group, and Mrepresents
112
1t two hydrogen atoms, a divalent metal atom, a trivalent
mono-substituted metal atom, a tetravalent di-substituted metal atom,
or an oxy metal) .
5 14. The method of producing a plastic polarized lens according
to claim 13, wherein the organic coloring compound is represented
by the following general formula (la):
(1 a)
wherein t-C4Hg represents a tertiary "butyl group, four tertiary
10 butyl groups correspond to A1 or A2, A3 or A4 , As or A6, and A7 or As,
respectively, in the formula (1), and represent a position isomer
structure, four groups that are not tertiary butyl groups in Al to
As represent a hydrogen atom; Mrepresents a divalent copper atom,
a divalent palladium atom, or divalent vanadium oxide (-V(=O)-).
15
15. The method of producing a plastic polarized lens according to
claim 13 or 14, wherein the resin film is a thermoplastic polyester
film.
20 16. The method of producing a plastic polarized lens according to
claim 15, wherein the shaping the resin film includes:
shaping the thermoplastic polyester film under the temperature
113
~ condition of the glass transition temperature of the thermoplastic
polyester+20°C or higher and the glass transition temperature+120°C
or lower.
5 17. The method of producing a plastic polarized lens according to
anyone of claims 13 to 16, wherein the monomer mixture includes:
(A) at least one kind of isocyanate compounds selected from the
group consisting of a polyisocyanate compound, an isocyanate compound
having an isothiocyanate group, and a polyisothiocyanate compound,
10 (B) at least one kind of active hydrogen compound selected from
the group consisting of thiol compounds and polythiol compounds
having a hydroxy group.
18. The method of producing a plastic polarized lens according to
15 anyone of claims 13 to 17, further comprising:
subjecting at least one surface of the polarized film to a surface
modification treatment before the fixing the polarized film.
19. The method of producing a plastic polarized lens according to
20 anyone of claims 13 to 18, further comprising:
forming an adhesive layer over at least one surface of the
polarized film before the fixing the polarized film.
20. The method of producing a plastic polarized lens according to
25 anyone of claims 13 to 18, further comprising:
subjecting at least one surface of the polarized film to a surface
modification treatment; and
20
114
1t forming an adhesive layer over the surface that has been
subjected to a surface modification treatment,
before the fixing the polarized film.
5 21. The method of producing a plastic polarized lens according to
anyone of claims 15 to 20, wherein the thermoplastic polyester is
a polyethylene terephthalate.
22. The metaod of producing a plastic polarized lens according to
10 anyone of claims 17 to 21, wherein the isocyanate compound (A) is
a diisocyanate compound and the active hydrogen compound (B) is a
polythiol compound.
23. The method of producing a plastic polarized lens according to
15 anyone of claims 17 to 22, wherein the isocyanate compound (A) is
at least one kind of diisocyanate compounds selected from the group
consisting of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and m- xylylene
diisocyanate, and
the active hydrogen compound (B) is at least one kind of polythiol
compounds selected from the group consisting of
pentaerythritoltetrakis(3-mercaptopropionate),
4-mercaptomethyl-l,S-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-l,11-dimercapto-3,6, 9-trithiaundecane,
25 4,7-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane, and
4,S-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane.
115
1t 24. The method of producing a plastic polarized lens according to
anyone of claims 13 to 23, wherein the viscosity at 20°C of the monomer
mixture is 200 mPa·s or less in the injecting step.
5 25. A polarized film comprising a resin containing an organic
coloring compound represented by the following general formula (1):
A5
N~~
N'" N-- /' N M N
~ /l} N N .
\ N~ ~ A7 ( 1 )
A, A8
wherein Al to As each independently represent a hydrogen atom,
a halogen atom, a nitro group, a cyano group, a hydroxy group, an
10 amino group, a carboxyl group, a sulfone group, a linear, branched,
or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group
having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon
atoms, a monoalkylamino group having 1 to 20 carbon atoms, a
dialkylamino group having 2 to 20 carbon atoms, an aralkyl group having
15 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a
heteroaryl group, an alkylthio group having 1 to 20 carbon atoms,
or an arylthio group having 1 to 20 carbon atoms, or may form a ring
other than an aromatic ring through a linking group, and Mrepresents
two hydrogen atoms, a divalent metal atom, a trivalent
20 mono-substituted metal a tom, a tetravalent di-substituted metal atom,
or an oxy metal.
•
116
26. The polarized film according to claim 25, wherein the organic
coloring compound is represented by the following general formula
(la) :
5
(1 a)
wherein t-C4Hg represents a tertiary butyl group, four tertiary
butyl groups correspond to Al or A2, A3 or A4, As or A6, and A7 or As,
respectively, in the formula (1), and represent a position isomer
structure, four groups that are not tertiary butyl groups in Al to
10 As represent a hydrogen atom; M represents a divalent copper atom,
a divalent palladium atom, or divalent vanadium oxide (-V(=O)-).
27. The polarized film according to claim 25 or 26, wherein the resin
is a thermoplastic polyester.
15
28. The polarized film according to anyone of claims 25 to 27, wherein
the organic coloring compound is contained in the amount of 50 to
7000 ppm in the polarized film.
20 29. The polarized film according to claim 27 or 28, wherein the
thermoplastic polyester is a polyethylene terephthalate.
•
r
- ---
117
..
30. The polarized film according to anyone of claims 25 to 29, which
is used in a plastic polarized lens having layers comprising a
thiourethane-based resin laminated over both surfaces of the
5 polarized film.
31. A method for producing the polarized film according to claim
30, comprising:
producing a resin film containing the organic coloring compound;
10 and
shaping the resin film.
32. The method for producing the polarized film according to claim
31, wherein the resin film is a thermoplastic polyester film.
15
33. The method for producing the polarized film according to claim
32, wherein the shaping the resin film includes:
shaping the thermoplastic polyester film under the temperature
condition of the glass transition temperature of the thermoplastic
20 polyester+20°C or higher and the glass transition temperature+120°C
or lower.
Dated this 28/02/2013 -
[SHRIMANT INGH]
OF REMFRY & SAGAR
ATTORNEY FOR THE APPLICANT ,-' .
., " -"'- ~ \: ..,:' -..