SPECIFICATION
PLASTIC POLARIZED LENS AND METHOD OF PRODUCING THE SAME
TECHNICAL FIELD
[OOOl]
The present invention relates to a plastic polarized
lens and a method of producing the same.
BACKGROUND ART
[0002]
A polarized lens can prevent transmission of
reflected light. Therefore, it is used for protecting eyes
by intercepting a strong reflected light in outdoor such as
in a skiing ground or in fishing, and for securing safety
in driving a car by intercepting a reflected light from a
car running in the opposite direction.
[0003]
For a plastic polarized lens, two kinds of polarized
lens are proposed, namely, a polarized lens with a
polarized film laid on the surface of the lens material,
and a sandwich structured polarized lens with a polarized
film within the lens. The polarized lens with a polarized
film laid on the surface of the lens material (for example,
Japanese Patent Application Laid-Open No. H09-258009
(Patent Document 1)) can make the thickness of the lens
thin, but has a serious disadvantage that the polarized
film is liable to be peeled off from the lens material
during a periphery grinding process (a process of grinding
periphery of the lens to fit in a predetermined shape).
[0004]
A resin used for a polarized film composing a
polarized lens has been essentially limited so far to
polyvinyl alcohol. The polarized film is produced by a
uniaxial extension of polyvinyl alcohol film after adding
iodine or a dichroic dye to make a film having molecular
orientation in uniaxial direction. A method of producing a
polarized lens composed of a polarized polyvinyl alcohol
film is disclosed, for example, in the WO 2004/099859
(Patent Document 2) ) .
[0005]
However, the polarized lens produced by using a
polarized polyvinyl alcohol film has shortcomings of
gradual penetration of water from the rim of the lens and
causing deterioration from the periphery to the center of
the lens with time or due to the surrounding environment.
[0006]
In order to improve above-mentioned shortcomings, WO
02/073291 (Patent Document 3) proposed a polarized lens
using a lens material containing impact-resistant
polyurethane resin obtained from diamine and isocyanateprepolymer,
and a polarized film containing polyethylene
terephthalate.
[0007]
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 eyeglasses containing this lens.
Furthermore, as the composition of the mixture of diamine
and isocyanate prepolymer has a high viscosity and a short
pot life, injection of the composition to a lens mold with
a fixed polarized film therein is troublesome, and
production of a thin lens was particularly difficult.
[0008]
WO 2008/018168 (Patent Document 4) proposed a plastic
polarized lens in which a layer containing a thiourethanebased
resin obtained by reacting an isocyanate compound
with an active hydrogen compound is stacked on both
surfaces of a polarized film containing thermoplastic
polyester.
[00091
However, this polarized lens needed to be improved in
terms of peeling of the polarized film caused in the
periphery grinding process.
[OOlO]
Therefore, in the conventional plastic polarized lens,
there has been a demand for a plastic polarized lens having
reduced occurrence of peeling-off of the polarized film
during a periphery grinding process of the lens as a
downstream process and excellent water-resistance, giving
less uncomfortable feeling on wearing, and is capable of
producing a thin product.
RELATED DOCUMENT
PATENT DOCUMENT
[OOll]
[Patent Document 11 Japanese Unexamined Patent
Application Publication No. H9-258009
[Patent Document 21 WO 2004/099859
[Patent Document 31 WO 02/073291
[Patent Document 41 WO 2008/018168
DISCLOSURE OF THE INVENTION
[0012]
In addition, for industrially manufacturing a large
amount of polarized lenses, there is a demand for a
polarized lens which can be industrially manufactured with
excellent yield by inhibiting peeling of a polarized lens
caused when the periphery of a polymerized lens is grinded
with an edger or the like, and exhibits excellent adhesion
between a polarized film and a plastic lens.
[0013]
The present invention has been made to address the
above problems in the conventional art, has an object to
provide a plastic polarized lens with excellent
processability and showing excellent adhesion between a
polarized lens and a plastic lens, and a method of
producing the same.
[0014]
[I] A plastic polarized lens, comprising: a polarized
film containing thermoplastic polyester, a coat layer
containing a urethane-based resin comprised of a structural
unit derived from compound having hydroxyl group and a
structural unit derived from aromatic diisocyanate, which
is formed over at least one surface of the polarized film
and a substrate layer containing a thiourethane-based resin,
which is formed over at least the coat'layer of the coat
layer-attached polarized film.
[2] The plastic polarized lens according to [I],
wherein, the compound having hydroxyl group is a
trimethylolpropane and the aromatic diisocyanate is a
tolylene diisocyanate.
131 The plastic polarized lens according to 121,
wherein the coat layer further contains a silane coupling
agent.
[4] The plastic polarized lens according to [I],
wherein, the compound having hydroxyl group is a
polybutadiene having hydroxyl group on the terminal and the
aromatic diisocyanate is a diphenylmethane diisocyanate.
[5] The plastic polarized lens according to any one
of [I] to [4], wherein the coat layer and the substrate
layer are stacked in order over both surfaces of the
polarized film.
[6] The plastic polarized lens according to any one
of [I] to [5], wherein the thiourethane-based resin is
obtained by reacting isocyanate compound(s) (A) with active
hydrogen compound(s) (B) and wherein the isocyanate
compound(s) (A) is at lease one selected from a group
consisting of a polyisocyanate compound, an isocyanate
compound having an isothiocyanate group and a
polyisothiocyanate, and the active hydrogen compound(s) (B)
is at least one selected from a group consisting of a thiol
compound having a hydroxyl group and a polythiol compound.
[7] The plastic polarized lens according to any one
of [I] to [6], wherein the polarized film is shaped under a
condition of a temperature T represented by the following
formula,
(Formula) glass transition temperature of
thermoplastic polyester +5"C I T I melting point of
thermoplastic polyester.
[8] The plastic polarized lens according to any one
of [I] to [7], wherein the polarized film is a polyethylene
terephthalate film.
[9] The plastic polarized lens according to any one
of [6] to [8], wherein the isocyanate compound(s) (A) is at
least one of diisocyanate compounds selected from a group
consisting of m-xylylene diisocyanate, 2,4-tolylene
diisocyanate, 2,6-tolylene diisocyanate, 4,4'-
diphenylmethane diisocyanate, 2,5-bis(isocyanatomethy1)-
bicyclo l2.2.11 -heptane, 2,6-bis (isocyanatomethyl)-
bicyclo [2.2.1] -heptane, bis (4-isocyanatocyclohexyl)methane,
1,3-bis(isocyanatomethyl)cyclohexane, 1,4-
bis(isocyanatomethyl)cyclohexane, and hexamethylene
diisocyanate, and the active hydrogen compound(s) (B) is at
least one of polythiol compounds selected from a group
consisting of pentaerythritol tetrakis(3-
mercaptopropionate), 5,7-dimercaptomethyl-1,ll-dimercapto-
3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,lldimercapto-
3,6,9-trithiaundecane, 4,8-dimercaptomethyl-
1,ll-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-
1,8-dimercapto-3,6-dithiaoctane, 2,5-dimercaptomethyl-1,4-
dithiane, 1,1,3,3-tetrakis (mercaptomethylthio)p ropane, 4,6-
bis(mercaptomethy1thio)-1,3-dithiane, and 2-(2,2-
bis(mercaptomethy1thio)ethyl)-1,3-dithietane.
[lo] The plastic polarized lens according to [2] or
[3], wherein a refractive index at e-line of the
thiourethane-based resin is in a range of 1.50 to 1.70.
[0015]
[Ill A method of producing a plastic polarized lens,
comprising: forming a coat layer containing a urethanebased
resin comprised of a structural unit derived from
compound having hydroxyl group and a structural unit
derived from aromatic diisocyanate, over at least one
surface of a polarized film containing thermoplastic
polyester; fixing the coat layer-attached polarized film
into a lens casting mold, in a state separated from an
inner surface of the mold; injecting a monomer mixture into
a gap between at least the coat layer of the coat layerattached
polarized film and the inner surface of the mold;
and stacking a 'substrate layer containing a thiourethanebased
resin over at least the coat layer of the coat layerattached
polarized film by polymerizing and curing the
monomer mixture.
[I21 The method of producing a plastic polarized lens
according to [Ill, wherein, the compound having hydroxyl
group is a trimethylolpropane and the aromatic diisocyanate
is a tolylene diisocyanate.
[I31 The method of producing a plastic polarized lens
according to [12], wherein the coat layer further contains
a silane coupling agent.
[I41 The method of producing a plastic polarized lens
according to [Ill, wherein, the compound having hydroxyl
group is a polybutadiene having hydroxyl group on the
terminal and the aromatic diisocyanate is a diphenylmethane
diisocyanate.
[15] The method of producing a plastic polarized lens
according to any one of [ll] to [14], wherein the forming a
coat layer includes forming the coat layer over both
surfaces of the polarized film.
[16] The method of producing a plastic polarized lens
according to any one of [ll] to [15], further comprising:
shaping the polarized film under a condition of a
temperature equal to or higher than a glass transition
temperature of thermoplastic polyester +5'C and equal to or
lower than a melting point of thermoplastic polyester,
before the forming a coat layer.
[17] The method of producing a plastic polarized lens
according to [12] or [13], further comprising: a step of
shaping the polarized film under a condition of a
temperature equal to or higher than a glass transition
temperature of thermoplastic polyester +5'C and equal to or
lower than a melting point of thermoplastic polyester,
after the forming a coat layer.
[18] The method of producing a plastic polarized lens
according to [12], [I31 or [17], wherein, in the injecting
a monomer mixture, a viscosity at 20°C of the monomer
mixture is not more than 200 mPa.s.
[0016]
[19] A urethane-based resin-coated polarized film
comprising: a polarized film containing thermoplastic
polyester and a coat layer containing a urethane-based
resin comprised of a structural unit derived from compound
having hydroxyl group and a structural unit derived from
aromatic diisocyanate, which is formed over at least one
surface of the polarized film.
[20] The urethane-based resin-coated polarized film
according to [19], wherein, the compound having hydroxyl
group is a trimethylolpropane and the aromatic diisocyanate
is a tolylene diisocyanate.
[21] The urethane-based resin-coated polarized film
according to [20], wherein the coat layer further contains
a silane coupling agent.
[22] The urethane-based resin-coated polarized film
according to [19], wherein, the compound having hydroxyl
group is a polybutadiene having a hydroxyl group on the
terminal and the aromatic diisocyanate is a diphenylmethane
diisocyanate.
[0017]
[23] A method of producing a urethane-based resincoated
polarized film, comprising: forming a coat layer
containing a urethane-based resin comprised of a structural
unit derived from compound having hydroxyl group and a
structural unit derived from aromatic diisocyanate, over at
least one surface of a polarized film containing
thermoplastic polyester.
[24] The method of producing a urethane-based resincoated
polarized film according to 1231, wherein, the
compound having hydroxyl group is a trimethylolpropane and
the aromatic diisocyanate is a tolylene diisocyanate.
1251 The method of producing a urethane-based resincoated
polarized film according to [24], wherein the coat
layer further contains a silane coupling agent.
[26] The method of producing a urethane-based resincoated
polarized film according to [231, wherein, the
compound having hydroxyl group is a polybutadiene having a
hydroxyl group on the terminal and the aromatic
diisocyanate is a diphenylmethane diisocyanate.
[0018]
The plastic polarized lens of the present invention
has excellent processability and exhibits excellent
adhesion between a polarized film and a plastic lens.
Accordingly, the plastic polarized lens of the present
invention has excellent productivity and is suitable for
mass production. The plastic polarized lens having such
characteristics is particularly useful as a polarized lens
for eyeglasses.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019]
Fig. 1 shows a cross-sectional view schematically
showing a plastic polarized lens according to an embodiment.
Fig. 2 shows a cross-sectional view schematically
showing a lens casting mold according to an embodiment.
DESCRIPTION OF EMBODIMENTS
[0020]
A plastic polarized lens of the present invention is
comprised of a polarized film containing thermoplastic
polyester, a coat layer containing a urethane-based resin
comprised of a structural unit derived from compound having
hydroxyl group and a structural unit derived from aromatic
diisocyanate, which is formed over at least one surface of
the polarized film, and a substrate layer containing a
thiourethane-based resin, which is formed over at least the
coat layer of the coat layer-attached polarized film.
[0021]
Hereinafter, a first embodiment and a second
embodiment of a plastic polarized lens in the present
invention will be described using drawings. Moreover, in
all drawings, the same constituent elements will be marked
with the same reference numerals so as not to repeat the
description thereof.
[0022]

[Plastic polarized lens]
As shown in FIG. 1, a plastic polarized lens 10 of
the present embodiment is comprised a polarized film 12
containing thermoplastic polyester; coat layers 13a and 13b
containing urethane-based resin which are formed over both
surfaces of the polarized film 12; and substrate layers 14a
and 14b containing a thiourethane-based resin which are
formed over both surfaces of the coat layer-attached
polarized film.
In the present embodiment, "a urethane-based resin
comprised of a structural unit derived from
trimethylolpropane and a structural unit derived from
tolylene diisocyanate" is used as 'a urethane-based resin
comprised of a structural unit derived from compound having
hydroxyl group and a structural unit derived from aromatic
diisocyanate" .
[0023]
A urethane-based resin containing a structural unit
derived from compound having three hydroxyl groups or more
has a cross-linked structure. Accordingly, in general, it
is considered that a coat layer containing this urethanebased
resin is not preferable from the view of adhesion
between it and a material to be coated.
However, the present inventors have seriously studied
and found that the urethane-based resin containing a
structural unit derived from compound having three hydroxyl
groups or more has excellent adhesion property, and found
that processing characteristics and adhesion property are
improved by using a structural unit derived from tolylene
diisocyanate in combination. As the result, the present
inventors have completed the plastic polarized lens of the
present embodiment.
[0024]
In the plastic polarized lens of the present
embodiment, a coat layer containing a urethane-based resin
and a substrate layer containing a thiourethane-based resin
are stacked in order over at least one surface of the
polarized film 12 containing thermoplastic polyester.
Accordingly, water resistance becomes excellent,
uncomfortable feeling is inhibited on wearing, the
thickness thereof becomes thin, and peeling of the
polarized film caused in a periphery grinding process as a
post-process is inhibited. That is, these properties are
balanced well.
In addition, as the polarized film 12, a film
containing thermoplastic polyester that is shaped under a
condition of a temperature T represented by the following
formula can be used.
(Formula) glass transition temperature of
thermoplastic polyester +5'C 2 T 5 melting point of
thermoplastic polyester
[0025]
When the polarized film 12 is shaped (curved) into a
shape having a desired curvature under such a temperature
condition, adhesion between the film and the substrate
layer is further improved. Accordingly, the plastic
polarized lens of the present embodiment has superior
productivity and is suitable for mass production.
[0026]
[Method of producing plastic polarized lens]
Hereinafter, the method of producing a plastic
polarized lens will be described with reference to drawings.
The method of producing a plastic polarized lens of
the present embodiment includes the following steps.
[0027]
(a) A step of forming the coat layers 13a and 13b
containing a urethane-based resin comprised of a structural
unit derived from a trimethylolpropane and a structural
unit derived from tolylene diisocyanate, over both surfaces
of the polarized film 12 containing thermoplastic polyester
(b) A step of fixing the coat layer-attached
polarized film 12 into a lens casting mold, in a state
separated from an inner surface of the mold
(c) A step of injecting a monomer mixture into a gap
between both surfaces of the coat layer-attached polarized
film 12 and the inner surface of the mold
(d) A step of stacking the substrate layers 14a and
14b containing a thiourethane-based resin over both
surfaces of the coat layer-attached polarized film 12 by
polymerizing and curing the monomer mixture
Hereinafter, the respective steps will be described
in order.
[0028]
(Step (a))
The polarized film containing a thermoplastic
polyester of the present embodiment is disclosed, for
example, in Japanese Laid-open patent publication No. 2002-
267841. Specifically, it is a polarized film having a
matrix of a thermoplastic polyester. The polarized film
may be obtained by blending a dye in the thermoplastic
polyester, molding it to a film, followed by uniaxial
extension of the film obtained by molding, and subsequent
heat treatment at a prescribed temperature. The thickness
is normally in the range of 10 to 500 pm.
[00291
Specifically, as the thermoplastic polyester
constituting the polarized film 12, polyethylene
terephthalate, polyethylene naphthalate, polybutylene
terephthalate, and the like can be used. In view of water
resistance, heat resistance, and molding processability,
polyethylene terephthalate is preferable. The polyethylene
terephthalate also includes those modified by a technique
of adding copolymerizable components.
[0030]
It is preferable to use a dichroic dye as the dye
used in the present embodiment, and known dyes are used as
the dichroic dye. The dyes are disclosed in, for example,
Japanese Unexarnined Patent Application Publication No. S61-
087757, Japanese Unexamined Patent Application Publication
No. 561-285259, Japanese Unexamined Patent Application
Publication No. 562-270664, Japanese Unexamined Patent
Application Publication No. S62-275163, Japanese Unexamined
Patent Application Publication No. H01-103667, and the like.
Specific examples of the dye include anthraquinone-based
dye, quinophthalone-based dye, azo-based dye, and the like.
Among these, dyes having heat resistance that tolerate
molding of thermoplastic polyester are preferable.
[0031]
In addition, before the step (a) of forming the coat
layers 13a and 13b, a step of shaping the polarized film 12
under a condition of a temperature equal to or higher than
a glass transition temperature of thermoplastic polyester
+5'C and equal to or lower than a melting point of
thermoplastic polyester may be performed. Alternatively,
the shaping step may be performed after the coat layers are
formed (after the step (a) ) .
[0032]
The thermoplastic polyester film can be shaped
preferably in a condition of a temperature equal to or
higher than a glass transition temperature of thermoplastic
polyester +5'C and equal to or lower than a glass
transition temperature of thermoplastic polyester +lOO°C,
more preferably in a condition of a temperature equal to or
higher than a glass transition temperature of thermoplastic
polyester f5'C and equal to or lower than a glass
transition temperature of thermoplastic polyester +80°C,
and particularly preferably in a condition of a temperature
equal to or higher than a glass transition temperature of
thermoplastic polyester +5'C and equal to or lower than a
glass transition temperature of thermoplastic polyester
+70°C. As a method of shaping the thermoplastic polyester
film, a common method can be used as long as the method
makes it possible to shape the film into a shape having a
desired curvature while heating the film at the above
temperature.
At the above shaping temperature, adhesion between
the polarized film 12 containing thermoplastic polyester
and the substrate layers 14a and 14b containing a
thiourethane-based resin is further improved.
[0033]
When the thermoplastic polyester is, for example,
polyethylene terephthalate, a glass transition temperature
thereof is 74"C, and a melting point thereof is 259°C.
Accordingly, shaping can be performed under a condition of
a temperature from 79°C to 25goC, preferably from 79'C to
174"C, more preferably from 7g°C to 154'C, and particularly
preferably from 79'C to 144'C.
The glass transition temperature of the thermoplastic
polyester can be measured using DSC (Differential Scanning
Calorimetry) in general.
[0034]
As the forming method, there are vacuum forming,
pressure forming, vacuum-pressure forming, press forming
and the like. In these forming methods, by adjusting the
temperature of the thermoplastic polyester film to enter
the above-mentioned temperature range, and by forming it
into a desired curvature shape, the adhesiveness between
the polarized film comprised of the thermoplastic polyester
film and the plastic lens can be improved.
[0035]
In the method of shaping the thermoplastic polyester
film, conditions such as a molding pressure and molding
time are appropriately adjusted according to the shaping
method, the temperature at the time of shaping, a
production instrument, and the like. Moreover, before
being shaped in a mold or the like, the thermoplastic
polyester film may be heated such that the temperature
thereof falls within the above temperature range.
In the step (a), urethane coating is performed on the
surface of the polarized film 12 so as to form a urethane
resin-containing coat layer.
100361
In the present embodiment, when urethane coating is
performed on the polarized film 12, a solvent-free
urethane-based coating agent may be coated as is. However,
generally, it is preferable to coat a coating solution
prepared by dissolving or dispersing the coating agent in
an appropriate solvent selected.
[0037]
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. One kind of the
solvent can be used alone, or two or more kinds thereof can
be used concurrently.
[0038]
The concentration of the above coating solution
expressed in terms of a urethane-based resin is 0.1 wt% to
50 !it%, preferably 1 wt% to 50 wt%, and even more
preferably 3 wt% to 30 wt%. If the concentration exceeds
50 wt%, stability of the coating solution over time becomes
poor, the presence of a coating layer becomes noticeable
since the amount of a urethane resin coated increases and
the coating layer becomes too thick, and the adhesion
deteriorates due to peeling caused inside the coating layer,
in some cases. Inversely, if the concentration is lower
than 0.1 wt%, the effect of improving adhesion between the
film and the urethane resin as a substrate is not obtained
sufficiently in some cases.
The thickness of the coating layer is 0.001 pm to 30
pm, preferably 0.01 pm to 10 pm, and more preferably 0.05
pm to 5 pm.
[00391
After the coating solution is optionally coated onto
both surfaces of the polarized film 12 of the present
embodiment, a part of the coating solution having fluidity
is optionally removed from the film, followed by drying.
The drying temperature is not particularly limited, but an
appropriate temperature range is generally 5'C to 100°C,
preferably 20°C to 100°C, more preferably 20°C to 80°C, and
particularly preferably 20°C to 60°C. It is also possible
to apply heat stepwise by combining the above temperature.
[0040]
The drying time is set appropriately according to the
solvent used or the environment such as drying time or air
blowing state and is not particularly limited. Generally,
the drying time is 1 minute or longer.
[0041]
Although, in the present embodiment, there is no
particular limit on the method of coating of the coating
solution on both surfaces of the polarized film 12
containing thermoplastic polyester, it is largely
classified into a method of treating the polarized film
with a coating agent containing urethane-based resin and
then forming a curvature, a method of treating with a
coating agent containing urethane-based resin after forming
a curvature, or a method of employing both of above methods
in combination. Any of the above methods may be employed,
and depending on each condition, conventionally known
methods such as a roll-coating method, a spin-coating
method, a spray-coating method, a bar-coating method, a
dipping method and the like may be used. After drying, the
coating can be performed once or more, and the coating
solution used for each time may be the same or of different
kinds. Typically, the object of the present embodiment can
be achieved by one-time coating and drying without repeated
coating.
[0042]
After coating the polarized film with the urethanebased
resin used for the above-mentioned primer coating
treatment, drying and/or heat treatment are performed as
necessary. As long as the applied temperature of the
drying and/or heat treatment does not actually deteriorate
the function of the polarized film, there is no particular
limit. After coating the resin on the polarized film, an
active energy line may be irradiated on it. As the active
energy line, there is an ultraviolet ray or an electron
beam.
[0043]
The urethane-based resin used for the coating
treatment is a polymer comprised of a structural unit
derived from trimethylolpropane and a structural unit
derived from tolylene diisocyanate. The coating solution
may further contain a silane coupling agent.
[0044]
Examples of the silane coupling agent include silane
coupling agents having one or more substituents among an
epoxy group, an amino group, a (meth)acryloyl group, a
vinyl group, a mercapto group, a halogen group, an imino
group, an isocyanate group, and a ureido group. Examples
of a hydrolysable group binding to a silicon atom of the
silane coupling agent include an alkoxy group which may
have two or more oxygen atoms, an alkyl carboxyl group, a
halogen group, and the like. Among these, an alkoxysilane
cornbound having an alkoxy group which may have two or more
oxygen atoms is more preferable.
[0045]
Specific examples thereof include silane coupling
agents having an epoxy group, such as y-glycidoxypropyl
trimethoxysilane, y-glycidoxypropyl methyl diethoxysilane,
P-(3,4-epoxycyc1ohexyl)ethyl trimethoxysilane, and yglycidoxypropyl
methyl diethoxysilane; silane coupling
agents having an amino group, such as y-aminopropyl
trimethoxysilane, y-aminopropyl triethoxysilane, N-P-
(aminoethy1)-y-aminopropyl trimethoxysilane, N-P-
(aminoethy1)-y-aminopropyl methyl dimethoxysilane, Nphenyl-
y-aminopropyl trimethoxysilane, bis[3-
(trimethoxysilyl)p ropyl] amine, and bis [3-
(trimethoxysilyl)propyl]ethylene diamine, or silane
coupling agents including hydrochloride thereof; silane
coupling agents having a (meth)acryloxy group, such as ymethacryloxypropyl
trirnethoxysilane, y-methacryloxypropyl
methyl dimethoxysilane, y-methacryloxypropyl
triethoxysilane, y-methacryloxypropyl methyl diethoxysilane,
y-methacryloxypropyl tris(methoxyethoxy)silane, and yacryloxypropyl
trimethoxysilane; silane coupling agents
having a vinyl group, such as vinyl trimethoxysilane, vinyl
triethoxysilane, vinyl trichlorosilane, vinyl tris(Pmethoxyethoxy)
silane, styryl ethyl trimethoxysilane, ally1
triethoxysilane, and 3-(trimethoxysily1)propyl
methacrylate; silane coupling agents having a mercapto
group, such as y-mercaptopropyl trimethoxysilane, ymercaptopropyl
methyl dimethoxysilane, and y-mercaptopropyl
triethoxysilane; silane coupling agents having a halogen
group, such as y-chloropropyl trimethoxysilane and ychloropropyl
triethoxysilane; silane coupling agents having
an isocyanate group, such as y-isocyanatepropyl
trimethoxysilane and y-isocyanatepropyl triethoxysilane;
silane coupling agents having a ureido group, such as y-
(ureidopropyl)trimethoxysilane and y-
(ureidopropyl)triethoxysilane; and the like.
[0046]
Among these, examples of preferable silane coupling
agents include y-glycidoxypropyl trimethoxysilane, yaminopropyl
trimethoxysilane, N-P-(aminoethy1)-yaminopropyl
methyl dimethoxysilane, N-phenyl-y-aminopropyl
trirnethoxysilane, y-methacryloxypropyl trimethoxysilane, ymethacryloxypropyl
methyl dimethoxysilane, ymethacryloxypropyl
triethoxysilane, y-methacryloxypropyl
methyl diethoxysilane, y-methacryloxypropyl
tris(methoxyethoxy)silane, y-acryloxypropyltrimethoxysilane,
vinyl trimethoxysilane, vinyl triethoxysilane, vinyl
tris(P-methoxyethoxy)silane, y-mercaptopropyl
trimethoxysilane, y-isocyanatepropyl trimethoxysilane, and
the like. Particularly, (meth)acryloxyalkyl alkoxysilane
such as y-methacryloxypropyl trimethoxysilane, yrnethacryloxypropyl
methyl dimethoxysilane, ymethacryloxypropyl
triethoxysilane, y-methacryloxypropyl
methyl diethoxysilane, y-methacryloxypropyl
tris(methoxyethoxy)silane, y-acryloxypropyl
trirnethoxysilane, vinyl trichlorosilane are preferable.
These may be used alone, or two or more kinds thereof
may be used concurrently. In addition, a case where a
chemical reaction is caused between different types of
silane coupling agents is also included.
to0471
Before coating treatment with the urethane-based
resin on the polarized film 12 surface, at least one kind
of pretreatments selected from those such as treatment with
chemicals such as gas or chemical solution, treatment with
corona discharge, treatment with plasma, treatment with
ultra violet irradiation, treatment with electron beam
irradiation, treatment with surface roughening, and
treatment with burning may be performed on the polarized
film 12 in advance.
[ 0 0 4 8 ]
Specific examples of the chemical treatment include
gas treatment using gas such as ozone, halogen gas, and
chlorine dioxide, and a chemical solution treatment using
an oxidant or a reductant such as sodium hypochlorite,
alkali metal hydroxide, alkali earth metal hydroxide, metal
sodium, sulfuric acid or nitric acid ,or using an acid or a
base. In the chemical solution treatment, an oxidant, a
reductant, an acid or a base, or the like is generally
dissolved in water, alcohol, aqueous ammonia, or the like
so as to be used in the form of a solution.
[ 0 0 4 9 ]
When the chemical used for the treatment is alkali
metal hydroxide and/or alkali earth metal hydroxide,
examples of the alkali metal hydroxide include lithium
hydroxide, sodium hydroxide, potassium hydroxide and the
like, and examples of the alkali earth metal hydroxide
include magnesium hydroxide, calcium hydroxide, barium
hydroxide, and the like. One or two or more kinds of these
can be selected and used. Among these, sodium hydroxide
and potassium hydroxide are preferable, and sodium
hydroxide is particularly preferable.
[ 0 0 5 0 ]
The alkali metal hydroxide and/or alkali earth metal
hydroxide are (is) preferably used in the form of a
solution. Examples of solvents of the solution include
water and/or organic solvents, and examples of the organic
solvent include methanol, ethanol, isopropanol, and the
like.
The concentration of the solution is in a range of 5%
by weight to 55% by weight, and preferably in a range of
10% by weight to 45% by weight. The temperature of the
solution is in a range of 0°C to 95'C, preferably in a
range of 20°C to 90°C, and more preferably in a range of
30°C to 80°C.
[0051]
The pretreatment by alkaline metal hydroxides and/or
alkaline earth metal hydroxides with respect to the present
embodiment can be performed by bringing into contact the
solution, which is within the above-mentioned solution
concentration and temperature range, 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 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, methods such as stirring,
convection current flowing, and jet flowing can be adopted.
Although there is no particular limit on the time period of
contact, it should be within a time period range of 1
minute to 24 hours, preferably 5 minutes to 10 hours, and
more preferably 5 minutes to 5 hours.
[0052]
When the solution of the alkali metal hydroxide
and/or alkali earth metal hydroxide is brought into contact
with the polarized film, physical stimulation such as
ultrasonic irradiation or vibration can be used
concurrently.
[0053]
In order to improve the wetting of the polarized film
with the solution, the alkaline metal hydroxides and/or
alkaline earth metal hydroxides may contain anionic,
nonionic surfactants and the like.
[0054]
During the contact between the alkaline metal
hydroxides and/or alkaline earth metal hydroxides with the
polarized film, the solution concentration, the solution
temperature and the contact time period can be selected
suitably within a range that the optical characteristics of
the polarized film does not actually deteriorate.
[0055]
After a solution of alkaline metal hydroxides and/or
alkaline earth metal hydroxides is brought in contact with
the polarized film, the polarized film is pulled out of the
solution, and when necessary, the cleaning and drying of
the polarized film may be performed with water and/or
organic solvents such as methanol, ethanol, isopropanol,
acetone, methylethyl ketone.
[0056]
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 ions, which is a surface
treatment technique employed widely. As the gas of
discharge treatment, there is air, but the gas may be
nitrogen gas, carbon dioxide gas, ammonia gas and the like.
The corona discharge treatment can be achieved, for example,
by a method of treating the polarized film surface using
the corona generated by supplying voltage to electrodes of
a known high frequency generation apparatus. The corona
discharge treatment strength should be preferably 1 to 500
w.min/m2, and more preferably 5 to 400 wmin/rn2.
Examples of the plasma treatment mentioned above are
a normal pressure plasma treatment and a vacuum plasma
treatment (low temperature plasma treatment).
In the normal pressure plasma treatment, discharge
treatment is performed within a single or mixed gas
atmosphere of gas such as air, water vapor, argon, nitrogen,
helium, carbon dioxide, carbon monoxide and the like.
[0057]
The vacuum plasma treatment can be performed within a
reduced pressure, for example, by placing the polarized
film inside a discharge treatment apparatus of an internal
electrode type which 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 0.02 to 1
Torr, a high voltage of direct current or alternating
current is supplied between the electrodes and discharged,
generating plasma of the treatment gas, exposing the
polarized film surface thereto. Although the treatment
conditions of the vacuum plasma treatment depends 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. As the
treatment gas, for example, argon, nitrogen, helium, carbon
dioxide, carbon monoxide, air, water vapor and the like may
be used singularly or in mixture.
By the above step (a), a urethane-based resin-coated
polarized film can be obtained.
[0058]
(Step (b))
As shown in FIG. 2, the plastic polarized lens of the
present embodiment is obtained by injecting a polymerizable
composition containing a specific isocyanate compound and a
specific active hydrogen compound into a lens casting mold
20 into which the polarized film 12 containing
thermoplastic polyester and provided with the urethanebased
coat layers 13a and 13b is fixed, followed by
polymerizing and curing.
Generally, the lens casting mold 20 is constituted
with two molds 22a and 22b held by a gasket 22c.
[0059]
Examples of the material of the gasket 22c include
polyvinyl chloride, an ethylene-vinyl acetate copolymer, an
ethylene-ethyl acrylate copolymer, an ethylene-propylene
copolymer, an ethylene-propylene-diene copolymer, a
polyurethane elastomer, fluororubber, or soft elastic
resins obtained by blending these with polypropylene.
Among these, materials that do not swell or are not eluted
for the polymerizable composition containing a specific
isocyanate compound and a specific active hydrogen compound
that is used in the present embodiment are preferable.
[0060]
Examples of the material of the molds 22a and 22b
include glass, metals, and the like, and glass is generally
used. In order to improve releasing properties of the
obtained lens, the molds 22a and 22b may be coated with a
release agent in advance. Moreover, in order to impart
hard coat performance to the lens material, the mold may be
coated with a coat liquid in advance.
[0061]
In the space of the lens casting mold 20, the
polarized film 12 containing thermoplastic polyester 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, gaps 24a
and 24b are formed respectively. A distance "a" that
indicates the narrowest space of the gaps 24a and 24b is
about 0.2 rnrn to 2.0 mm.
[0062]
(Step (c))
Next, in the space of the lens casting mold 20, a
monomer mixture (polymerizable composition) is injected
into the two gaps 24a and 24b between the molds 22a and 22b
and the polarized film 12, by a predetermined injection
unit. In the present embodiment, a polymerizable
composition containing the (A) isocyanate compound and the
(B) active hydrogen compound having a thiol group can be
used. In the present embodiment, a polymerizable
composition containing the (A) isocyanate compound and the
(B) active hydrogen compound having a thiol group can be
used. Accordingly, viscosity at the time of injection is
low, and the composition can be easily injected even into
the gaps having the space described above.
[0063]
The (A) isocyanate compound used in the present
embodiment includes compounds having an isothiocyanate
group, and is specifically one or two or more kinds of
compounds selected from a polyisocyanate compound, an
isocyanate compound having an isothiocyanate group, and a
polyisothiocyanate compound.
[0064]
Examples of the polyisocyanate compound include
aliphatic polyisocyanate compounds such as hexamethylene
diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4,4-
trimethyl hexamethylene diisocyanate, lysine
diisocyanatomethyl ester, lysine triisocyanate, m-xylylene
diisocyanate, a, a, a' ,a' -tetramethyl xylylene diisocyanate,
bis(isocyanatomethyl)naphthalene, mesitylene triisocyanate,
bis(isocyanatomethyl)sulfide, bis(isocyanatoethyl)sulfide,
bis (isocyanatomethyl)d isulfide,
bis(isocyanatoethyl)disulfide,
bis(isocyanatomethylthio)methane,
bis(isocyanatoethylthio)methane,
bis(isocyanatoethylthio)ethane, and
bis(isocyanatomethy1thio)ethane; alicyclic polyisocyanate
compounds such as isophorone diisocyanate,
bis(isocyanatomethyl)cyclohexane, dicyclohexyl methane
diisocyanate, cyclohexane diisocyanate, methyl cyclohexane
diisocyanate, dicyclohexyldimethyl methane isocyanate, 2,5-
bis (isocyanatomethyl) -bicycle l2.2.11 -hepane, 2,6-
bis (isocyanatomethyl) -bicycle [2.2.1] -hepane, 3,8-
bis(isocyanatomethyl)tricyclodecane, 3,9-
bis(isocyanatomethyl)tricyclodecane, 4,8-
bis(isocyanatomethyl)tricyclodecane, 4,9-
bis(isocyanatomethyl)tricyclodecane, bis(4-
isocyanatocyclohexyl)methane, 1,3-
bis(isocyanatomethyl)cyclohexane, and 1,4-
bis(isocyanatomethyl)cyclohexane; aromatic polyisocyanate
compounds such as 2,4-tolylene diisocyanate, 2,6-tolylene
diisocyanate, 4,4'-diphenylmethane diisocyanate, and
diphenyl sulfide-4,4-diisocyanate; heterocyclic
polyisocyanate compounds such as 2,5-diisocyanatothiophene,
2,5-bis (isocyanatomethyl)t hiophene, 2,5-
diisocyanatotetrahydrothiophene, 2,5-
bis(isocyanatomethy1)tetrahydrothiophene 3,4-
bis(isocyanatomethy1)tetrahydrothiophene 2,5-diisocyanato-
1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-
diisocyanato-1,3-dithiolane, and 4,5-bis(isocyanatomethy1)-
1,3-dithiolane; and the like, but the present embodiment is
not limited to these example compounds.
[0065]
Examples of the isocyanate compound having an
isothiocyanate group include compounds obtained by changing
a portion of the isocyanate groups of the polyisocyanate
compounds exemplified above into an isothiocyanate group,
but the present embodiment is not limited to these.
[0066]
Examples of the polyisothiocyanate compound include
aliphatic polyisothiocyanate compounds such as
hexamethylene diisothiocyanate, lysine
diisothiocyanatomethyl ester, lysine triisothiocyanate, mxylylene
diisothiocyanate, bis(isothiocyanatomethyl)sulfide,
bis(isothiocyanatoethyl)sulfide, and
bis(isothiocyanatoethyl)disulfide; alicyclic
polyisothiocyanate compounds such as isophorone
diisothiocyanate, bis(isothiocyanatomethyl)cyclohexane,
dicyclohexyl methane diisothiocyanate, cyclohexane
diisothiocyanate, methyl cyclohexane diisothiocyanate, 2,5-
bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-
bis (isothiocyanatomethyl)b icyclo- [2.2.1]- heptne, 3,8-
bis(isothiocyanatomethyl)tricyclodecane, 3,9-
bis(isothiocyanatomethyl)tricyclodecane, 4,8-
bis(isothiocyanatomethyl)tricyclodecane, and 4,9-
bis(isothiocyanatomethyl)tricyclodecane; aromatic
polyisothiocyanate compounds such as diphenyl disulfide-
4,4-diisothiocyanate; sulfur-containing heterocyclic
polyisothiocyanate compounds such as 2,5-
diisothiocyanatothiophene, 2,5-
bis(isothiocyanatomethyl)thiophene, 2,5-
diisocyanatotetrahydrothiophene, 2,5-
bis(isothiocyanatomethyl)tetrahydrothiophene, 3,4-
bis(isothiocyanatomethyl)tetrahydrothiophene, 2,5-
diisothiocyanato-1,4-dithiane, 2,sbis(
isothiocyanatomethyl)-1,4-dithiane, 4,5-
diisothiocyanato-1,3-dithiolane, and 4,5-
bis(isothiocyanatomethy1)-1,3- dithiolane; and the like,
but the present embodiment is not limited to these example
compounds.
[0067]
In addition, it is possible to use these isocyanate
compounds substituted with halogen, such as chlorinesubstituted
isocyanate compounds and bromine-substituted
isocyanate compounds, alkyl-substituted isocyanate
compounds, alkoxy-substituted isocyanate compounds, nitrosubstituted
isocyanate compounds, prepolymer type modified
isocyanate compounds combined with polyol, carbodiimidemodified
isocyanate compounds, urea-modified isocyanate
compounds, biuret-modified isocyanate compounds, products
of a dimerization or trimerization reaction, and the like.
These isocyanate compounds can be used alone, or two or
more kinds thereof can be used by being mixed with each
other.
[00681
As the isocyanate compound (A), diisocyanate
compounds are preferably used, in view of easy availability,
price, and the performance of the obtained resin. For
example, m-xylylene diisocyanate, 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, 4,4'-diphenyl methane
diisocyanate, 2,5-bis(isocyanatomethy1)-bicyclo[2.2.1]-
heptane, 2,6-bis (isocyanatomethyl) -bicycle [2.2.1] -heptane,
bis(4-isocyanatocyclohexyl)methane, 1,3-
bis (isocyanatomethyl) cyclohexane, 1,4-
bis(isocyanatomethyl)cyclohexane, and hexamethylene
diisocyanate are preferably used, and 2,5-
bis(isocyanatomethy1)-bicyclo[2.2.1]-heptane, 2,6-
bis(isocyanatomethy1)-bicyclo[2.2.1]-heptane, and mxylylene
diisocyanate are particularly preferably used.
One kind of these can be used, or two or more kinds of
these can be used in combination.
[0069]
The (B) active hydrogen compound used in the present
embodiment is one or two or more kinds of active hydrogen
compounds selected from a thiol compound having a hydroxy
group and a polythiol compound.
[0070]
Examples of the thiol compound having a hydroxy group
include 2-mercaptoethanol, 3-mercapto-1,2-propanediol,
glycerin bis(mercaptoacetate), 4-mercaptophenol, 2,3-
dimercapto-1-propanol, pentaerythritol tris(3-
mercaptopropionate), and pentaerythritol
tris(thioglycolate), and the like, but the present
embodiment is not limited to these example compounds.
[00711
Examples of the polythiol compound include aliphatic
polythiol compounds such as methanedithiol, 1,2-
ethanedithiol, 1,2,3-propanetrithiol, 1,2-
cyclohexanedithiol, 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 tris(2-mercaptoacetate),
trimethylolpropane tris(3-mercaptopropionate),
trimethylolethane tris(2-mercaptoacetate),
trimethylolethane tris(3-mercaptopropionate),
pentaerythritol tetrakis(2-mercaptoacetate),
pentaerythritol tetrakis(3-mercaptopropionate),
bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide,
bis(mercaptoethyl)suIfide, bis(mercaptoethyl)disulfide,
bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane,
bis(2-mercaptoethylthio)methane, bis(3-
mercaptopropylthio)methane, 1,2-
bis(mercaptomethylthio)ethane, 1,2-bis(2-
mercaptoethylthio) ethane, 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-1,8-
dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,lldimercapto-
3,6,9-trithiaundecane, 4,7-dimercaptomethyl-
1,ll-dimercapto-3,6,9-trithiaundecane, 4,8-
dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-
mercaptoethylthiomethyl)methane, tetrakis(3-
mercaptopropylthiomethyl)methane, bis(2,3-
dimercaptopropyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane,
2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-
dimethyl-1,4-dithiane, thioglycolic acid of these and ester
of mercaptopropionic acid, hydroxymethyl sulfide bis(2-
mercaptoacetate), hydroxymethyl sulfide bis(3-
mercaptopropionate), hydroxyethyl sulfide bis(2-
mercaptoacetate), hydroxyethyl sulfide bis(3-
mercaptopropionate), hydroxymethyl disulfide bis(2-
mercaptoacetate), hydroxymethyl disulfide bis(3-
mercaptopropionate), hydroxyethyl disulfide bis(2-
mercaptoacetate), hydroxyethyl disulfide bis(3-
mercaptopropionate), 2-mercaptoethylether bis(2-
mercaptoacetate), 2-mercaptoethylether bis(3-
mercaptopropionate), thiodiglycolic acid bis(2-
mercaptoethylester), thiodipropionic acid bis(2-
mercaptoethylester), dithiodiglycolic acid bis(2-
mercaptoethylester), dithiodipropionic acid bis(2-
mercaptoethylester) , 1,1,3,3-
tetrakis (mercaptomethylthio)p ropane, 1,1,2,2-
tetrakis (mercaptomethylthio)e thane, 4,6-
bis (mercaptomethylthio) -1,3-dithiane,
tris(mercaptomethylthio)methane, and
tris(mercaptoethy1thio)methane; aromatic polythiol
compounds such as 1,2-dimercaptobenzene, 1,3-
dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-
bis (mercaptomethyl)b enzene, 1,3-bis (mercaptomethyl)b enzene,
1,4-bis (mercaptomethyl)b enzene, 1,2-
bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene,
1,4-bis (mercaptoethyl)b enzene, 1,3,5-trimercaptobenzene,
1,3,5-tris (mercaptomethyl) benzene, 1,3,5-
tris (mercaptomethylenoxy)b enzene, 1,3,5-
tris(mercaptoethylenoxy)benzene, 2,5-toluenedithiol, 3,4-
toluenedithiol, 1,5-naphthaleneditihol, and 2,6-
naphthalenedithiol; heterocyclic polythiol compounds such
as 2-methylamino-4,6-dithiol-sym-triazine, 3,4-
thiophenedithiol, bismuththiol, 4,6-
bis (mercaptomethylthio)- 1,3-dithiane, and 2- (2,2-
bis (mercaptomethylthio)e thyl)- 1,3-dithiane; and the like,
but the present embodiment is not limited to these example
compounds.
[00721
In addition, oligomers of these active hydrogen
compounds and the active hydrogen compounds substituted
with halogen, such as chlorine-substituted active hydrogen
compounds or bromine-substituted active hydrogen compounds
may be used. These active hydrogen compounds can be used
alone, or two or more kinds thereof can be used be being
mixed with each other.
[00731
Among these active hydrogen compounds, polythiol
compounds are preferably used, in view of easy availability,
price, and the performance the obtained resin. For example,
pentaerythritol tetrakis(3-mercaptopropionate), 5,7-
dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-
dimercaptomethyl-1,4-dithiane, 1,1,3,3-
tetrakis(mercaptomethylthio)propane, 4,6-
bis (mercaptomethylthio) -1,3-dithiane, and 2- (2,2-
bis(mercaptomethylthio)ethyl)-1,3-dithiane are preferably
used, and pentaerythritol tetrakis(3-mercaptopropionate),
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-
dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
and 4,8-dimercaptomethyl-1,ll-dimercapto-3,6,9-
trithiaundecane are particularly preferably used. One
kinds of these can be used, or two or more kinds thereof
can be used in combination.
[0074]
Moreover, the (A) isocyanate compound used in the
present embodiment may be preliminarily reacted with a
portion of the (B) active hydrogen compound. Furthermore,
the (B) active hydrogen compound used in the present
embodiment may be preliminarily reacted with a portion of
the (A) isocyanate compound.
[0075]
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, an olefin compound including (meth) acrylate
compound or the like may be added. Herein, the resin
modifier is a compound which adjusts or improves physical
properties such as refractive index, Abbe's number, heat
resistance, specific gravity, and mechanical strength such
as impact strength of thiourethane-based resin.
[0076]
Examples of the hydroxy compound used as the resin
modifier include diethylene glycol, triethylene glycol,
dipropylene glycol, tripropylene glycol, 1,4-butanediol,
thiodiethanol, dithiodiethanol, glycerin,
trimethylolpropane, pentaerythritol, and oligomers of these,
but the present embodiment is not limited to these example
compounds.
Examples of the epoxy compound that can be added as
the resin modifier include phenol-based epoxy compounds
obtained by a condensation reaction between a polyphenol
compound such as bisphenol A glycidyl ether and an
epihalohydrin compound; alcohol-based epoxy compounds
obtained by the condensation between a polyol compound such
as hydrogenated bisphenol A glycidyl ether and an
epihalohydrin compound; glycidyl ester-based epoxy
compounds obtained by the condensation between a polyvalent
organic acid compound such as 3,4-epoxycyclohexylmethyl-
3',4'-epoxycyclohexane carboxylate and an epihalohydrin
compound; amino-based epoxy compounds obtained by the
condensation between primary and secondary diamine
compounds and an epihalohydrin compound; aliphatic
polyvalent epoxy compounds such as vinylcyclohexene
diepoxide; and the like, but the present embodiment is not
limited to these example compounds.
[00771
Examples of the episulfide compound that can be added
as the resin modifier include chain-like aliphatic 2,3-
epithiopropylthio compounds such as bis(2,3-
epithiopropylthio) sulfide, bis (2,3-
epithiopropylthio) disulf ide, bis (2,3-
epithiopropylthio)methane, 1,2-bis(2,3-
epithiopropylthio) ethane, and 1,5-bis (2,3-
epithiopropy1thio)-3-thiapentane; cyclic aliphatic 2,3-
epithiopropylthio compounds having a heterocycle, such as
1,3-bis (2,3-epithiopropylthio)c yclohexane and 2,5-bis (2,3-
epithiopropylthiomethy1)-1,4-dithiane; aromatic 2,3-
epithiopropylthio compounds such as 1,3-bis(2,3-
epithiopropylthio) benzene and 1,4-bis (2,3-
epithiopropy1thio)benzene; and the like, but the present
embodiment is not limited to these example compounds.
[0078]
Examples of the organic acid and anhydride thereof
that can be added as the resin modifier include
thiodiglycolic acid, thiodipropionic acid,
dithiodipropionic acid, phthalic anhydride,
hexahydrophthalic anhydride, methyl hexahydrophthalic
anhydride, methyl tetrahydrophthalic anhydride, maleic
anhydride, trimellitic anhydride, pyromellitic anhydride,
and the like, but the present embodiment is not limited to
these example compounds.
[0079]
Examples of the olefin compound that can be added as
the resin modifier include (meth)acrylate compounds such as
benzyl acrylate, benzyl 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 diacrylate, diethylene glycol dimethacrylate,
triethylene glycol diacrylate, triethylene glycol
dirnethacrylate, neopentyl glycol diacrylate, neopentyl
glycol dimethacryalte, ethylene glycol bisglycidyl acrylate,
ethylene glycol bisglycidyl methacrylate, bisphenol A
diacrylate, bisphenol A dimethacrylate, bisphenol F
diacrylate, bisphenol F dimethacryalte, trimethylopropane
triacrylate, trimethylolpropane trimethacrylate, glycerol
diacrylate, glycerol dimethacrylate, pentaerythritol
triacrylate, pentaerythritol tetraacrylate, pentaerythritol 1
tetramethacrylate, xylylene dithiol diacrylate, xylylene
dithiol dimethacrylate, mercaptoethyl sulfide diacrylate,
and mercaptoethyl sulfide dimethacrylate; allyl compounds
such as allyl glycidyl ether, diallyl phthalate, diallyl
terephthalate, diallyl isophthalate, and diethylene glycol
bisallyl carbonate; vinyl compounds such as styrene,
chlorostyrene, methyl styrene, bromostyrene, dibromostyrene,
divinyl benzene, and 3,9-divinylspiro-bi(m-dioxane); and
the like, but the present embodiment is not limited to
these example compounds.
These resin modifiers can be used alone, or two or
more kinds thereof can be used by being mixed with each
other.
[0080]
The ratio between the (A) isocyanate compound and (B)
active hydrogen compound (also including the hydroxy
compound as a modifier) used in the present embodiment is
generally in a range of 0.8 to 1.5 and preferably in a
range of 0.9 to 1.2, in terms of the molar ratio between
functional groups of (NCO+NCS) / (SH+OH) .
[0081]
The (A) isocyanate compound and the (B) active
hydrogen compound employed in the present embodiment are
selected after considering the availability, cost,
handleability, performance of the obtainable resin and the
like.
The important factor in the convenience of handling
is the viscosity of the polymerizable composition during
injection. The viscosity during injection is decided 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 modifier.
Furthermore, when employing a catalyst, this includes the
type and amount of the catalyst.), but when the viscosity
is too high, the production of the polarized lens becomes
very difficult since it is very difficult to inject into
the narrow spaces 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
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 polymerizable composition is measured
by using a B type viscometer at a solution temperature of
20°C.
[0082]
A refractive index is considered to be an important
performance of the resin, and a resin having a high
refractive index can be preferably used. For example, a
combination (including the type and amount of a resin
modifier when the resin modifier is used) of the (A)
isocyanate compound and (B) active hydrogen compound that
can produce a resin having a refractive index generally in
a range of 1.50 to 1.70, preferably in a range of 1.57 to
1.70, more preferably in a range of 1.59 to 1.70, and even
more preferably in a range of 1.65 to 1.68 is preferable.
If the refractive index is too low, the film put in the
polarized lens is clearly noticeable, so the exterior of
the lens becomes poor.
100831
The same type of the polymerizalble composition of
the (A) isocyanate compound and (B) active hydrogen
compound used in the present embodiment is applied to both
surfaces of the polarized film in general. H o P J ~ v ~ ~ ,
different types of the compositions may also be used.
[0084]
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 and the like, ultraviolet
ray absorbing agents such as benzotriazole-based agents,
internal mold releasing agents such as acidic phosphate
ester and the like, photostabilizers, antioxidants,
reaction initiators such as radical reaction initiator and
the like, chain elongators, cross-linking agents,
anticoloring agents, oil-soluble dyes, fillers and the like
may be added as necessary.
[OOSS]
When producing an injection solution by mixing a
reaction catalyst, mold releasing agents or other additives
to the (A) isocyanate compound and the (B) active hydrogen
compound, the adding of the catalyst, the mold releasing
agents and other additives are 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 dissolved
in the (B) active hydrogen compound in advance, or added
and dissolved in the polymerizable composition containing
the (A) isocyanate compound and the (B) active hydrogen
compound. In addition, there is no problem in dissolving
it in a part of the (A) isocyanate compound or the (B)
active hydrogen compound to produce a master solution and
then adding it to the mixture. The adding order is not
limited by the exemplary methods, and is suitably selected
on the basis of operability, safety and convenience.
[00861
Mixing is generally performed at a temperature not
higher than 30°C. In view of pot life of the polymerizable
composition, it is preferable to further reduce the
temperature in some cases. Moreover, when the solubility
of the additive such as a catalyst or a release agent is
not excellent in the (A) isocyanate compound or (B) active
hydrogen compound, sometimes the additive is warmed in
advance and then dissolved in the (A) isocyanate compound,
(B) active hydrogen compound, or a mixture of these.
[0087]
Further, depending on the physical properties
required for the plastic lens to be obtained, it is
preferable to optionally perform degassing treatment under
reduced pressure or filtering treatment under increased or
reduced pressure in many cases.
100881
(Step (d))
Subsequently, the lens casting mold, into which the
polymerizable composition of the (A) isocyanate compound
and (B) active hydrogen compound has been injected and the
polarized film has been fixed, is heated for several hours
or several tens of hours by a predetermined temperature
program in a device that can perform heating, such as an
oven, or in water, thereby performing curing molding.
[0089]
The temperature of polymerization curing is not
limited since the condition varies with the makeup of the
polymerizable composition, the type of catalyst, the mold
shape, and the like. However, the polymerization curing is
performed for 1 hour to 100 hours at about -50°C to 200°C.
[00901
Generally, the curing starts from a temperature in a
range of 5°C to 40°C, then the temperature is slowly raised
to a range of 80°C to 130°C, and heating is performed for 1
hour to 4 hours at this temperature.
[0091]
After the curing molding ends, the resultant is taken
out of the lens casting mold hereby the plastic polarized
lens of the present embodiment as shown in FIG. 1 can be
obtained. In this plastic polarized lens 10, the coat
layer 13a and the substrate layer 14a are stacked in order
over one surface of the polarized film 12, and the coat
layer 13b and the substrate layer 14b are stacked in order
over the other surface thereof. With this constitution, it
is possible to prevent the polarized film 12 from being
peeled from the lens material during the periphery grinding
process, whereby a large amount of polarized lens can be
produced industrially.
[0092]
In the plastic polarized lens of the present
embodiment, it is preferable to heat the released lens for
an annealing treatment in order to lessen the distortion
caused by the polymerization. The annealing temperature is
generally in a range of 80°C to 150°C, preferably in a
range of 100°C to 130°C, and more preferably in a range of
110°C to 130°C. The annealing time is generally in a range
of 0.5 hours to 5 hours and preferably in a range of 1 hour
to 4 hours.
[0093]
The plastic polarized lens of the present embodiment
is used having coated layer(s) formed on one surface or
both surfaces as necessary. As the coated layers, there
are primer layers, hard coated layers, antireflection film
layers, antifog coated layers, antipollutant layers, waterrepellent
layers and the like. These coated layers can be
each employed singularly, or they may be employed as multilayers
with plural coated layers. When forming the coated
layers on both surfaces, the same coated layer may be
formed on each surface, or different coated layers may be
formed thereon.
[0094]
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, photostabilizers or
antioxidants for improving the weathering resistance of the
lens, dye or pigment for 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
leveling agents may be employed for improving the coating
characteristic.
[0095]
The primer layer is generally formed between the
polarized lens substrate (thiourethane-based resin) and the
hard coat layer so as to improve the adhesion of the hard
coat layer or the impact resistance of the polarized lens,
and the film thickness thereof is generally about 0.1 pm to
10 pm.
[0096]
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 coating method such as spin
coating, dip 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 or a
vacuum plating method. When forming the primer layer, a
preprocessing of the lens surface such as alkali treatment,
plasma treatment, ultraviolet ray treatment and the like in
order to improve the adhesiveness may be performed as
necessary.
[0097]
As the primer composition, materials which enable
high adhesiveness between the solidified primer layer and
the lens material (thiourethane-based resin) are preferred,
and typically, primer compositions having urethane-based
resins, epoxy-based resins, polyester-based resins,
melanin-based resins, and polyvinylacetals as main
ingredients are employed. The primer composition can be
employed without a solvent, but it may employ appropriate
solvents which do not affect the lens in order to adjust
the viscosity of the composition and the like.
[0098]
The hard coated layer is a coated layer which aims to
provide functions such as abrasion resistance, wear
resistance, moisture resistance, hot water resistance, heat
resistance, weathering resistance and the like, and its
layer thickness is typically 0.3 to 30 pm.
[0099]
The hard coated layer is typically formed by curing
after coating the hard coating composition by the known
coating methods such as a spin coating method, dip coating
method and the like. As the 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, a preprocessing of the
coating surface (the lens material or the primer layer)
such as alkali treatment, plasma treatment, ultraviolet ray
treatment and the like in order to improve the adhesiveness
may be performed as necessary.
[OlOO]
As hard coating compositions, the mixture of organic
silicone compounds having curability and fine oxide
particles (including complex fine oxide particles) of Si,
Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In , Ti and the like
are frequently employed. Besides these, amines, amino
acids, metal acetylacetonate complexes, organic acid metal
salts, perchloric acids, salts of perchloric acids, acids,
metal chlorides, multifunctional epoxy compounds and the
like may be employed. The hard coating composition can be
employed without a solvent, but it may be employed with
appropriate solvents which do not affect the lens.
[OlOl]
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 antireflection layer is frequently formed
by dry methods such as vacuum plating method, sputtering
method, ion plating method, ion beam assisting method, CVD
method and the like, which employ inorganic oxides such as
SiO2, Ti02 and the like. Generally, the organic-based
antireflection layer is frequently formed by a wet method
which employs organic silicone compounds and compositions
including silica-based fine particles having internal
cavities.
[0102]
The antireflection layer may be a single layered or
multi-layered, but when employed as a single layer, it is
preferable for its refractive index to be lower than the
refractive index of the hard coated layer by 0.1 or more.
The multi-layered antirefractive layer is preferable in
order to effectively realize the antireflection function,
and in this case, a low refractive index layer and a high
refractive index layer are typically stacked 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. As the
high refractive index layer, there are, for example, ZnO,
Ti02, CeOz, Sb205, Sn02, Zr02, Ta205 and the like, and as for
the low refractive index layer, there is Si02 and the like.
The thickness of the layer is typically 50 to 150 nm.
Furthermore, in the plastic polarized lens of the
present embodiment, rear side polishing, antistatic
treatment, dye treatment, light modulation treatment and
the like may be performed as necessary.
This plastic polarized lens is useful as polarized
lenses of eyeglasses, and in particular, as the lens for
correcting visual acuity due to the fact that thin-shaping
is possible.
[0103]
The plastic polarized lens and the method of
producing the same of the present embodiment have been
described as above, but the present embodiment also
includes the following embodiment.
[0104]
The plastic polarized lens of the present embodiment
also includes an embodiment in which the coat layer 13a (or
13b) and the substrate layer 14a (or 14b) are stacked only
over one surface of the polarized film 12. In this case,
the substrate layer may be formed over the other surface
(without the coat layer) of the polarized film 12.
[0105]
The method of producing a plastic polarized lens of
the present embodiment also employs an embodiment including
the following steps.
(a) A step of forming a coat layer containing a
urethane-based resin comprised of a structural unit derived
from trimethylolpropane and a structural unit derived from
tolylene diisocyanate, over one surface of a polarized film
containing thermoplastic polyester
(b)A step of fixing the coat layer-attached polarized
film into a lens casting mold, in a state separated from an
inner surface of the mold
(c) A step of injecting a monomer mixture into a gap
between the coat layer of the coat layer-attached polarized
film and the inner surface of the mold
(d) A step of stacking a substrate layer containing a
thiourethane-based resin over the coat layer of the coat
layer-attached polarized film by polymerizing and curing
the monomer mixture.
[0106]
(a) A step of forming a coat layer containing a
urethane-based resin comprised of a structural unit derived
from trimethylolpropane and a structural unit derived from
tolylene diisocyanate, over one surface of a polarized film
containing thermoplastic polyester
(b) A step of fixing the coat layer-attached
polarized film into a lens casting mold, in a state
separated from an inner surface of the mold
(c) A step of injecting a monomer mixture into a gap
between the coat layer of the coat layer-attached polarized
film and the inner surface of the mold and a gap between
the polarized film and the inner surface of the mold
(d) A step of stacking a substrate layer containing a
thiourethane-based resin over both surfaces of the coat
layer-attached polarized film by polymerizing and curing
the monomer mixture
[0107]
Moreover, in the present embodiment, after the coat
layer-attached polarized film is formed, a substrate film
containing a thiourethane-based resin that is prepared in
advance is stacked over the surface of the coat layer,
whereby a plastic polarized lens can be produced.
[0108]

[Plastic polarized lens]
A plastic polarized lens of the present embodiment
has the constitutions of the first embodiment except for a
composition of a coat layer.
In the present embodiment, 'a urethane-based resin
comprised of a structural unit derived from polybutadiene
having a hydroxyl group on the terminal and a structural
unit derived from diphenylmethane diisocyanate" is used as
'a urethane-based resin comprised of a structural unit
derived from compound having hydroxyl group and a
structural unit derived from aromatic diisocyanate".
[0109]
[Method of producing plastic polarized lens]
Hereinafter, the method of producing a plastic
polarized lens will be described with reference to drawings.
The method of producing a plastic polarized lens of
the present embodiment includes the following steps.
[OllO]
(a) A step of forming the coat layers 13a and 13b
containing a urethane-based resin comprised of a structural
unit derived from polybutadiene having a hydroxyl group on
the terminal and a structural unit derived from
diphenylmethane diisocyanate, over both surfaces of the
polarized film 12 containing thermoplastic polyester
(b) A step of fixing the coat layer-attached
polarized film 12 into a lens casting mold, in a state
separated from an inner surface of the mold
(c) A step of injecting a monomer mixture into a gap
between both surfaces of the coat layer-attached polarized
film 12 and the inner surface of the mold
(d) A step of stacking the substrate layers 14a and
14b containing a thiourethane-based resin over both
surfaces of the coat layer-attached polarized film 12 by
polymerizing and curing the monomer mixture.
Hereinafter, the respective steps will be described
in order.
[Olll]
(Step (a))
The step (a) is carried out in the same manner as the
first embodiment except for following conditions.
In the present embodiment, before the step of shaping
the polarized film 12 under a condition of a temperature
equal to or higher than a glass transition temperature of
thermoplastic polyester f5'C and equal to or lower than a
melting point of thermoplastic polyester, heating treatment
may be performed on the polarized film. The conditions of
the heating treatment are selected appropriately.
[0112]
In the present embodiment, when urethane coating is
performed on the polarized film 12, a solvent-free
urethane-based coating agent may be coated as is. However,
generally, it is preferable to coat a coating solution
prepared by dissolving or dispersing the coating agent in
an appropriate solvent selected.
The solvent can be used one described in the first
embodiment.
[0113]
The concentration of the above coating liquid
expressed in terms of a urethane-based resin is 0.1 wt% to
50 wt%, preferably 0.3 wt% to 50 wt%, and even more
preferably 0.5 wt% to 30 wt%. If the concentration exceeds
50 wt%, stability of the coating liquid over time becomes
poor, the presence of a coating layer becomes noticeable
since the amount of a urethane resin coated increases and
the coating layer becomes too thick, and the adhesion
deteriorates due to peeling caused inside the coating layer,
in some cases. Inversely, if the concentration is lower
than 0.1 wt%, the effect of improving adhesion between the
film and the urethane resin as a substrate is not obtained
sufficiently in some cases.
The thickness of the coating layer is 0.0001 pm to 30
pm, preferably 0.0005 pm to 10 pm, and more preferably
0.0005 pm to 1 pm.
[0114]
The urethane-based resin used for the coating
treatment is a polymer comprised of a structural unit
derived from polybutadiene having a hydroxyl group on the
terminal and a structural unit derived from diphenylmethane
diisocyanate.
The "structural unit derived from diphenylmethane
diisocyanate" may include a structural unit derived from
modified diphenylmethane diisocyanate. Examples of the
modified diphenylmethane diisocyanate include urethanemodified
diphenylmethane diisocyanate, carbodiimidemodified
diphenylmethane diisocyanate, and the like. Among
these, urethane-modified diphenylmethane diisocyanate is
preferable.
[0115]
The urethane-modified diphenylmethane diisocyanate
refers to a reaction product of a diphenylmethane
diisocyanate and an alcohol having two or more hydroxyl
groups. Examples of the alcohol having two or more
hydroxyl groups include ethylene glycol, diethylene glycol,
triethylene glycol, and the like, and among these, alcohols
including diethylene glycol are preferable. A proportion
of the modified diphenylmethane diisocyanate included in
the structural unit derived from diphenylmethane
diisocyanate is less than 30%, preferably less than 20%,
and more preferably less than 10%.
The polybutadiene having a hydroxyl group on the
terminal is a polymer having a structural unit derived from
polybutadiene which has one or more hydroxyl groups on the
molecular terminal thereof. The number of hydroxyl group
is preferably 2 or greater and more preferably 2. The
polybutadiene is a polymer of 1,3-butadiene, and may
include 1,2-conjugate or l,4-conjugate in any proportion.
The proportion of the l,4-conjugate is preferably 50% or
higher, more preferably 70% or higher, and even more
preferably 80% or higher.
The coating liquid may further contain a silane
coupling agent.
[0116]
(Steps (b) to (d))
In the present embodiment, steps (b) to (d) can be
carried out in the same manner as the first embodiment.
[0117]
The method of producing a plastic polarized lens of
the present invention also employs an embodiment including
the following steps.
(a) A step of forming a coat layer containing a
urethane-based resin comprised of a structural unit derived
from polybutadiene having a hydroxyl group on the terminal
and a structural unit derived from diphenylmethane
diisocyanate, over one surface of a polarized film
containing thermoplastic polyester
(b)A step of fixing the coat layer-attached polarized
film into a lens casting mold, in a state separated from an
inner surface of the mold
(c) A step of injecting a monomer mixture into a gap
between the coat layer of the coat layer-attached polarized
film and the inner surface of the mold
(d) A step of stacking a substrate layer containing a
thiourethane-based resin over the coat layer of the coat
layer-attached polarized film by polymerizing and curing
the monomer mixture.
[0118]
(a) A step of forming a coat layer containing a
urethane-based resin comprised of a structural unit derived
from polybutadiene having a hydroxyl group on the terminal
and a structural unit derived from diphenylmethane
diisocyanate, over one surface of a polarized film
containing thermoplastic polyester
(b) A step of fixing the coat layer-attached
polarized film into a lens casting mold, in a state
separated from an inner surface of the mold
(c) A step of injecting a monomer mixture into a gap
between the coat layer of the coat layer-attached polarized
film and the inner surface of the mold and a gap between
the polarized film and the inner surface of the mold
(d) A step of stacking a substrate layer containing a
thiourethane-based resin over both surfaces of the coat
layer-attached polarized film by polymerizing and curing
the monomer mixture
101191
Moreover, in the present embodiment, after the coat
layer-attached polarized film is formed, a substrate film
containing a thiourethane-based resin that is prepared in
advance is stacked over the surface of the coat layer,
whereby a plastic polarized lens can be produced.
[Examples]
101201
Hereinafter, the present invention will be described
in more detail based on examples, but the present invention
is not limited thereto.
[0121]

[Example All
A polarized film [glass transition temperature
70.7"CI (thickness 140 pm) made of polyethylene
terephthalte was preheated for 15 minutes in an oven at
140°C and then shaped into a curved shape of 6 C (curve) by
heat press at a shaping temperature of 160°C. The
polarized film was cut according to the size of a mold, and
then the front and back surfaces of the polarized film were
irradiated with plasma for 20 seconds by using a plasma
irradiation surface modifying apparatus (PS-601SW model:
manufactured by WEDGE co., ltd.), folloried by washing with
methanol and then air drying, thereby preparing a polarized
film. Both surfaces of this polarized film made of
polyethylene terephthalate were coated with Foundation
#123LLR-2 coating agent (SOTECH Corporation) and dried at
about 50°C to 60°C. This film was inserted into a mold
(front surface 6 C/back surface 6 C glass mold set, a
central thickness 12 rnm) for molding a polarized lens.
Subsequently, 44.3 parts by weight of m-xylylene
diisocyanate, 55.7 parts by weight of a mixture of 1,1,3,3-
tetrakis(mercaptomethy1thio)propane and 4,6-
bis(mercaptomethy1thio)-1,3-dithiacyclohexane, 0.02 parts
by weight of dibutyl tin dichloride as a curing accelerator,
0.12 parts by weight of Zelec UN (registered trademark,
manufactured by Stepan Co., Ltd.) as a release agent, and
0.05 parts by weight of Seesorb 709 (manufactured by SHIPRO
KASEI KAISHA, LTD.) as an ultraviolet absorber were stirred
and dissolved, and then degassing treatment was performed
on the mixture under reduced pressure. Immediately after
being prepared, the resultant was provided as a monomer
mixture to be injected. The monomer mixture to be injected
was injected into the mold for molding a polarized lens
that was prepared as above, and the temperature thereof was
raised to 100°C from 25'C over 16 hours in an oven and then
kept at 100°C for 10 hours. After being slowly cooled, the
lens casting mold was taken out of the oven. The lens was
released from the lens casting mold, followed by annealing
for 2 hours at llS°C, thereby obtaining a polarized lens
having a shape of semi-finished lens. Subsequently, the
back surface of the lens was cut and polished, thereby
obtaining a lens having a 6 C shape.
The obtained 5 lenses having a 6 C shape were
subjected to a lens edging process by using a lens edger
(ALE-100DX) manufactured by TOPCON CORPORATION so as to be
lenses having a width of 49 mm and a height of 28 mm, and
then evaluated in terms of the adhesion between the
polarized film made of polyethylene terephthalate and the
thiourethane resin. As a result, in all of the 5 lenses,
peeling was not caused, and this showed excellent adhesion.
[0122]
Moreover, the composition of the Foundation #123LLR-2
was analyzed to be as below.
Isocyanate component: tolylene diisocyanate
Polyol component: trimethylolpropane and ethanol
Compositional ratio (molar ratio): tolylene
3-(trimethoxysily1)propyl methacrylate in a small
content (about 0.25%)
Solvent: ethyl acetate (EA) , butyl acetate (BA) ,
EA/BA=45/55
Solid content: 32%
[0123]
[Comparative example All
A finished lens having a 6 C shape was obtained in
the same manner as in Example Al, except thatboth sides of
the polarized film made of polyethylene terephthalate were
not coated with anything. The obtained lens was subjected
to the lens edging process and evaluated in terms of the
adhesion between the polarized film made of polyethylene
terephthalate and the thiourethane resin as a substrate.
As a result, in all of five lenses, peeling of the
polarized film made of polyethylene terephthalate was
caused.
[0124]
[Comparative example A21
A finished lens having a 6 C shape was obtained in
the same manner as in Example Al, except that SANPRENE IB-
422 (polyester-based polyurethane coating agent
manufactured by Sanyo Chemical Industries, Ltd.) was used
for both sides of the polarized film made of polyethylene
terephthalate. The obtained lens was subjected to the lens
edging process and evaluated in terms of the adhesion
between the polarized film made of polyethylene
terephthalate and the thiourethane resin as a substrate.
As a result, in 3 lenses among 5 lenses, peeling of the
polarized film made of polyethylene terephthalate was
caused. The evaluation results are summarized in Table-1.
Moreover, the composition of the SANPRENE IB-422 was
analyzed to be as below.
Isocyanate component: isophorone diisocyanate
Polyester component: polyester polyol containing
adipic acid, 1,4-butanediol, and 3-methyl-1,5-pentanediol
as components.
Compositional ratio (molar ratio): isophorone
diisocyanate//polyester polyol=1.0//4.3
Solvent: methyl ethyl ketone (MEK), isopropyl alcohol
(IPA), MEK/IPA=60/40
Solid content: 30%
LO1251
[Comparative example A31
A finished lens having a 6 C shape was obtained in
the same manner as in Example Al, except that SK Dyne 2094
(acrylic coating agent manufactured by Soken Chemical &
Engineering Co., Ltd.) was used for both sides of the
polarized film made of polyethylene terephthalate. The
obtained lens was subjected to the lens edging process and
evaluated in terms of the adhesion between the polarized
film made of polyethylene terephthalate and the
thiourethane resin as a substrate. As a result, in 4
lenses among 5 lenses, peeling of the polarized film made
of polyethylene terephthalate was caused. The evaluation
results are summarized in Table-1.
[0126]
[Comparative example A41
A finished lens having a 6 C shape was obtained in
the same manner as in Example Al, except that SHC900
(silicon-based coating agent manufactured by Momentive
Performance Materials Inc.) was used for both sides of the
polarized film made of polyethylene terephthalate. The
obtained lens was subjected to the lens edging process and
evaluated in terms of the adhesion between the polarized
film made of polyethylene terephthalate and the
thiourethane resin as a substrate. As a result, in all 5
lenses, peeling of the polarized film made of polyethylene
terephthalate was caused. The evaluation results are
summarized in Table-1.
[0127]
[Comparative example A53
A finished lens having a 6 C shape was obtained in
the same manner as in Example Al, except that STYCAST1266J
(epoxy-based coating agent manufactured by Henkel AG & CO.)
was used for both sides of the polarized film made of
polyethylene terephthalate. The obtained lens was
subjected to the lens edging process and evaluated in terms
of the adhesion between the polarized film made of
polyethylene terephthalate and the thiourethane resin as a
substrate. As a result, in all 5 lenses, peeling of the
polarized film made of polyethylene terephthalate was
caused. The evaluation results are summarized in Table-1.
*Adhesion evaluation
0: no peeling in all 5 lenses
X: peeling was caused in one or more lenses among 5 lenses.
[0129]
[Example B l ]
A polarized film (thickness 140 pm) made of
polyethylene terephthalte was shaped into a curved shape of
6 C (curve) by heat press at a shaping temperature of 160°C.
The polarized film was cut according to the size of a mold,
and then the front and back surfaces of the polarized film
were irradiated with plasma for 20 seconds by using a
plasma irradiation surface modifying apparatus (PS-601SW
model: manufactured by WEDGE co., ltd.), followed by
washing with methanol and then air drying.
In order to prepare a coat liquid, 7.69 parts by
weight of Assist 7M (manufactured by SOTECH Corporation) as
a main agent and 2.31 parts by weight of a curing agent
were weighed and taken, and diluted with a toluene solvent,
such that the 1.0 part by weight of the main agent and
curing agent in total yielded a concentration of 0.5% by
weight. Both surfaces of the polarized film made of
polyethylene terephthalate treated as above were coated
with the prepared Assist 7M coating agent at a
concentration of 0.5% by weight by dip coating and dried at
about 50°C to 60°C. This film was inserted into a mold
(front surface 6 C/back surface 6 C glass mold set, a
central thickness 12 mm) for molding a lens.
Subsequently, 44.3 parts by weight of m-xylylene
diisocyanate, 55.7 parts by weight of a mixture of 1,1,3,3-
tetrakis(mercaptomethylthio)propane and 4,6-
bis(mercaptomethy1thio)-1,3-dithiacyclohexane, 0.02 parts
by weight of dibutyl tin dichloride as a curing accelerator,
0.12 parts by weight of Zelec UN (registered trademark,
manufactured by Stepan Co., Ltd.) as a release agent, and
0.05 parts by weight of Seesorb 709 (manufactured by SHIPRO
KASEI KAISHA, LTD.) as an ultraviolet absorber were stirred
and dissolved, and then degassing treatment was performed
on the mixture under reduced pressure, thereby preparing a
monomer mixture to be injected.
The monomer mixture to be injected was injected into
the mold for molding a lens in which the polarized film was
disposed, and the temperature thereof was raised to 10O0C
from 25°C over 16 hours in an oven and then kept at 100°C
for 10 hours. After being slowly cooled, the mold for
casting a lens was taken out of the oven. The lens was
released from the mold for casting a lens, followed by
annealing for 2 hours at 115'C, thereby obtaining a
polarized lens blank. Subsequently, the back surface of
the lens was cut and polished, thereby obtaining a lens of
S: -2.50 D. The obtained lens was excellent lens not
showing cloudiness. The obtained 5 lenses of S: -2.50 D
were subjected to a lens edging process by using a lens
edger (ALE-100DX) manufactured by TOPCON CORPORATION so as
to be matched with a frame of eyeglasses, and then
evaluated in terms of the adhesion between the polarized
film and the substrate (thiourethane resin). As a result,
in all of the 5 lenses, peeling was not caused, and this
showed excellent adhesion. The evaluation results are
summarized in Table-2.
[0130]
Moreover, the composition of Assist 7M was analyzed
to be as below.
Curing agent component: diphenylmethane diisocyanate
partially modified with urethane
Main agent component: polybutadiene having a hydroxyl
group on the terminal
[01311
[Example B2]
A polarized lens blank showing no cloudiness was
obtained in the same manner as in Example B1, except that
the concentration of Assist 7M coating agent diluted with
toluene was adjusted to 1.5% by weight. The obtained lens
was subjected to lens edging process and evaluated in terms
of the adhesion between the polarized film and the
substrate. As a result, in all 5 lenses, peeling was not
caused, which showed excellent adhesion. The evaluation
results are summarized in Table-2.
[0132]
[Comparative example Bl]
A finished lens of S: -2.50 D was obtained in the
same manner as in Example B1, except that both sides of the
polarized film made of polyethylene terephthalate were not
coated with anything. The obtained lens was subjected to
the lens edging process and evaluated in terms of the
adhesion between the polarized film made of polyethylene
terephthalate and the thiourethane resin as a substrate.
As a result, in all of 5 lenses, peeling of the polarized
film made of polyethylene terephthalate was caused. The
evaluation results are summarized in Table-2.
[0133]
[Comparative example B2]
A finished lens of S: -2.50 D was obtained in the
same manner as in Example B1, except that SANPRENE IB-422
(polyester-based polyurethane coating agent manufactured by
Sanyo Chemical Industries, Ltd.) was used for both sides of
the polarized film made of polyethylene terephthalate. The
obtained lens was subjected to the lens edging process and
evaluated in terms of the adhesion between the polarized
film made of polyethylene terephthalate and the
thiourethane resin as a substrate. As a result, in 3
lenses among 5 lenses, peeling of the polarized film made
of polyethylene terephthalate was caused. The evaluation
results are summarized in Table-2.
Moreover, the composition of the SANPRENE IB-422 was
analyzed to be as below.
Isocyanate component: isophorone diisocyanate
Polyester component: polyester polyol containing
adipic acid, 1,4-butanediol, and 3-methyl-1,5-pentanediol
as components.
Compositional ratio (molar ratio): isophorone
diisocyanate//polyester polyol=1.0//4.3
Solvent: methyl ethyl ketone (MEK), isopropyl alcohol
(IPA) , MEK/IPA=60/40
Solid content: 30%
[0134]
[Comparative example B3]
A finished lens of S: -2.50 D was obtained in the
same manner as in Example B1, except that SK Dyne 2094
(acrylic coating agent manufactured by Soken Chemical &
Engineering Co., Ltd.) was used for both sides of the
polarized film made of polyethylene terephthalate. The
obtained lens was subjected to the lens edging process and
evaluated in terms of the adhesion between the polarized
film made of polyethylene terephthalate and the
thiourethane resin as a substrate. As a result, in 4
lenses among 5 lenses, peeling of the polarized film made
of polyethylene terephthalate was caused. The evaluation
results are summarized in Table-2.
[0135]
[Comparative example B4]
A finished lens of S: -2.50 D was obtained in the
same manner as in Example B1, except that SHC900 (siliconbased
coating agent manufactured by Momentive Performance
Materials Inc.) was used for both sides of the polarized
film made of polyethylene terephthalate. The obtained lens
was subjected to the lens edging process and evaluated in
terms of the adhesion between the polarized film made of
polyethylene terephthalate and the thiourethane resin as a
substrate. As a result, in all 5 lenses, peeling of the
polarized film made of polyethylene terephthalate was
caused. The evaluation results are summarized in Table-2.
101361
[Comparative example B5]
A finished lens of S: -2.50 D was obtained in the
same manner as in Example B1, except that STYCAST1266J
(epoxy-based coating agent manufactured by Henkel AG & CO.)
was used for both sides of the polarized film made of
polyethylene terephthalate. The obtained lens was
subjected to the lens edging process and evaluated in terms
of the adhesion between the polarized film made of
polyethylene terephthalate and the thiourethane resin as a
substrate. As a result, in all 5 lenses, peeling of the
polarized film made of polyethylene terephthalate was
caused. The evaluation results are summarized in Table-2.
Table-2
*Adhesion evaluation
0: no peeling in all 5 lenses
X: peeling was caused in one or more lenses among 5 lenses.
This application claims a priority based on Japanese
Patent Application No. 2012-049779, filed March 6, 2012, a
priority based on Japanese Patent Application No. 2012-
160158, filed July 19, 2012, U.S. Provisional Application
No. 61/607,279, filed March 6, 2012 and U.S. Provisional
Application No. 61/673,377, filed July 19, 2012, and all
disclosure of these references are incorporated in the
present application.
[0139]
The present invention includes following embodiments.
[all A plastic polarized lens, comprising:
a polarized film containing thermoplastic polyester,
a coat layer containing a urethane-based resin
comprised of a structural unit derived from
trimethylolpropane and a structural unit derived from
tolylene diisocyanate, which is formed over at least one
surface of the polarized film and
a substrate layer containing a thiourethane-based
resin, which is formed over at least the coat layer of the
coat layer-attached polarized film.
[a21 The plastic polarized lens according to [all, wherein
the coat layer further contains a silane coupling agent.
[a31 The plastic polarized lens according to [all or [a2],
wherein the coat layer and the substrate layer are
stacked in order over both surfaces of the polarized film.
[a41 The plastic polarized lens according to any one of
[all to [a31,
wherein the thiourethane-based resin is obtained by
reacting at least one of isocyanate compound(s) (A)
selected from a group consisting of a polyisocyanate
compound, an isocyanate compound having an isothiocyanate
group, and a polyisothiocyanate with at least one of active
hydrogen compound(s) (B) selected from a group consisting
of a thiol compound having a hydroxyl group and a polythiol
compound.
[0140]
[a51 The plastic polarized lens according to any one of
[all to [a41,
wherein the polarized film is shaped under a
condition of a temperature T represented by the following
formula,
(Formula) glass transition temperature of
thermoplastic polyester +5"C < T < melting point of
thermoplastic polyester.
[a61 The plastic polarized lens according to any one of
[all to Ia51,
wherein the polarized film is a polyethylene
terephthalate film.
[a71 The plastic polarized lens according to any one of
[a41 to [a61,
wherein the isocyanate compound(s) (A) is at least
one of diisocyanate compounds selected from a group
consisting of m-xylylene diisocyanate, 2,4-tolylene
diisocyanate, 2,6-tolylene diisocyanate, 4,4'-
diphenylmethane diisocyanate, 2,5-bis(isocyanatomethy1)-
bicyclo l2.2.11 -heptane, 2,6-bis (isocyanatomethyl) -
bicyclo[2.2.1]-heptane, bis(4-isocyanatocyclohexyl)methane,
1,3-bis (isocyanatomethyl) cyclohexane, 1,4-
bis(isocyanatomethyl)cyclohexane, and hexamethylene
diisocyanate, and
the active hydrogen compound(s) (B) is at least one
of polythiol compounds selected from a group consisting of
pentaerythritol tetrakis(3-mercaptopropionate), 5,7-
dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-
dimercaptomethyl-1,4-dithiane, 1,1,3,3-
tetrakis(mercaptomethylthio)propane, 4,6-
bis (mercaptomethylthio) -1,3-dithiane, and 2- (2,2-
bis(mercaptomethylthio)ethyl)-1,3-dithietane.
[0141]
[a81 The plastic polarized lens according to any one of
[all to [a71,
wherein a refractive index at e-line of the
thiourethane-based resin is in a range of 1.50 to 1.70.
[a91 A method of producing a plastic polarized lens,
comprising:
forming a coat layer containing a urethane-based
resin comprised of a structural unit derived from
trimethylolpropane and a structural unit derived from
tolylene diisocyanate, over at least one surface of a
polarized film containing thermoplastic polyester;
fixing the coat layer-attached polarized film into a
lens casting mold, in a state separated from an inner
surface of the mold;
injecting a monomer mixture into a gap between,at
least the coat layer of the coat layer-attached polarized
film and the inner surface of the mold; and
stacking a substrate layer containing a thiourethanebased
resin over at least the coat layer of the coat layerattached
polarized film by polymerizing and curing the
monomer mixture.
[a101 The method of producing a plastic polarized lens
according to [a91,
wherein the coat layer further contains a silane
coupling agent.
[01421
[all] The method of producing a plastic polarized lens
according to [a91 or [alO],
wherein the forming a coat layer includes forming the
coat layer over both surfaces of the polarized film.
[a121 The method of producing a plastic polarized lens
according to any one of [a91 to [all], further comprising:
shaping the polarized film under a condition of a
temperature equal to or higher than a glass transition
temperature of thermoplastic polyester +5OC and equal to or
lower than a melting point of thermoplastic polyester,
before the forming a coat layer.
[a131 The method of producing a plastic polarized lens
according to any one of [a91 to [all], further comprising:
a step of shaping the polarized film under a
condition of a temperature equal to or higher than a glass
transition temperature of thermoplastic polyester +5'C and
equal to or lower than a melting point of thermoplastic
polyester, after the forming a coat layer.
[a141 The method of producing a plastic polarized lens
according to any one of [a91 to [al3],
wherein, in the injecting a monomer mixture, a
viscosity at 20°C of the monomer mixture is not more than
200 mPaes.
[0143]
[a151 A urethane-based resin-coated polarized film
comprising:
a polarized film containing thermoplastic polyester
and
a coat layer containing a urethane-based resin
comprised of a structural unit derived from
trimethylolpropane and a structural unit derived from
tolylene diisocyanate, which is formed over at least one
surface of the polarized film.
[a161 The urethane-based resin-coated polarized film
according to [a15],
wherein the coat layer further contains a silane
coupling agent.
[a171 A method of producing a urethane-based resin-coated
polarized film, comprising:
forming a coat layer containing a urethane-based
resin comprised of a structural unit derived from
trimethylolpropane and a structural unit derived from
tolylene diisocyanate, over at least one surface of a
polarized film containing thermoplastic polyester.
[a181 The method of producing a urethane-based resincoated
polarized film according to [a17],
wherein the coat layer further contains a silane
coupling agent.
[0144]
[bl] A plastic polarized lens, comprising:
a polarized film containing thermoplastic polyester,
a coat layer containing a urethane-based resin
comprised of a structural unit derived from polybutadiene
having a hydroxyl group on the terminal and a structural
unit derived from diphenylmethane diisocyanate, which is
formed over at least one surface of the polarized film and
a substrate layer containing a thiourethane-based
resin, which is formed over at least the coat layer of the
coat layer-attached polarized film.
[b2] The plastic polarized lens according to [bl],
wherein the coat layer and the substrate layer are
stacked in order over both surfaces of the polarized film.
[b3] The plastic polarized lens according to [bl] or [b2],
wherein the thiourethane-based resin is obtained by
reacting at least one kind of isocyanate compound(s) (A)
selected from a group consisting of a polyisocyanate
compound, an isocyanate compound having an isothiocyanate
group, and a polyisothiocyanate with at least one kind of
active hydrogen compound(s) (B) selected from a group
consisting of a thiol compound having a hydroxy group and a
polythiol compound.
[0145]
[b4] The plastic polarized lens according to any one of
[bll to [b3lr
wherein the polarized film is shaped under a
condition of a temperature T represented by the following
formula,
(Formula) glass transition temperature of
thermoplastic polyester +5'C < T < melting point of
thermoplastic polyester.
[b5] The plastic polarized lens according to any one of
[bll to [b41,
wherein the polarized film is a polyethylene
terephthalate film.
[b6] The plastic polarized lens according to any one of
[b31 to [b51,
wherein the isocyanate compound(s) (A) is at least
one of diisocyanate compounds selected from a group
consisting of m-xylylene diisocyanate, 2,4-tolylene
diisocyanate, 2,6-tolylene diisocyanate, 4,4' -
diphenylmethane diisocyanate, 2,5-bis(isocyanatomethy1)-
bicyclo [2.2.1] -heptane, 2,6-bis (isocyanatomethyl)-
bicyclo[2.2.1]-heptane, bis(4-isocyanatocyclohexyl)methane,
1,3-bis(isocyanatomethyl)cyclohexane, 1,4-
bis(isocyanatomethyl)cyclohexane, and hexamethylene
diisocyanate, and
the active hydrogen compound(s) (B) is at least one
of polythiol compounds selected from a group consisting of
pentaerythritol tetrakis(3-mercaptopropionate), 5,7-
dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-
dimercaptomethyl-1,4-dithiane, 1,1,3,3-
tetrakis(mercaptomethylthio)propane, 4,6-
bis (mercaptomethylthio) -1,3-dithiane, and 2- (2,2-
bis(mercaptomethylthio)ethyl)-1,3-dithietane.
[0146]
[b7] A method of producing a plastic polarized lens,
comprising:
forming a coat layer containing a urethane-based
resin comprised of a structural unit derived from
polybutadiene having a hydroxyl group on the terminal and a
structural unit derived from diphenylmethane diisocyanate,
over at least one surface of a polarized film containing
thermoplastic polyester;
fixing the coat layer-attached polarized film into a
mold for casting a lens in a state separated from an inner
surface of the mold;
injecting a monomer mixture into a gap between at
least the coat layer of the coat layer-attached polarized
film and the inner surface of the mold; and
stacking a substrate layer containing a thiourethanebased
resin over at least the coat layer of the coat layerattached
polarized film by polymerizing and curing the
monomer mixture.
[b8] The method of producing a plastic polarized lens
according to [b71,
wherein the forming a coat layer includes forming the
coat layer over both surfaces of the polarized film.
[b9] The method of producing a plastic polarized lens
according to [b8],
wherein, before forming a coat layer, shaping the
polarized film under a condition of a temperature T
represented by the following formula,
(Formula) glass transition temperature of
thermoplastic polyester +5"C < T I melting point of
thermoplastic polyester.
[0147]
[blO] A urethane-based resin-coated polarized film
comprising:
a polarized film containing thermoplastic polyester;
and
a coat layer containing a urethane-based resin
comprised of a structural unit derived from polybutadiene
having a hydroxyl group on the terminal and a structural
unit derived from diphenylmethane diisocyanate, which is
formed over at least one surface of the polarized film.
[bll] A method of producing a urethane-based resin-coated
polarized film, comprising:
forming a coat layer containing a urethane-based
resin comprised of a structural unit derived from
polybutadiene having a hydroxyl group on the terminal and a
structural unit derived from diphenylmethane diisocyanate,
over at least one surface of a polarized film containing
thermoplastic polyester.

CLAIMS
1. A plastic polarized lens, comprising:
a polarizedfilm containing thermoplastic polyester,
a coat layer containing a urethane-based resin
comprised of a structural unit derived from compound having
hydroxyl group and a structural unit derived from aromatic
diisocyanate, which is formed over at least one surface of
the polarized film, and
a substrate layer containing a thiourethane-based
resin, which is formed over at least the coat layer of the
coat layer-attached polarized film.
2. The plastic polarized lens according to claim 1,
wherein, the compound having hydroxyl group is a
trimethylolpropane and the aromatic diisocyanate is a
tolylene diisocyanate.
3. The plastic polarized lens according to claim 2,
wherein the coat layer further contains a silane
coupling agent.
4. The plastic polarized lens according to claim 1,
wherein, the compound having hydroxyl group is a
polybutadiene having a hydroxyl group on the terminal and
the aromatic diisocyanate is a diphenylmethane diisocyanate
5 . The plastic polarized lens according to any one of
claims 1 to 4,
wherein the coat layer and the substrate layer are
stacked in order over both surfaces of the polarized film.
6. The plastic polarized lens according to any one of
claims 1 to 5,
wherein the thiourethane-based resin is obtained by
reacting isocyanate compound(s) (A) with active hydrogen
compound(s) (B) and
wherein the isocyanate compound(s) (A) is at lease
one selected from a group consisting of a polyisocyanate
compound, an isocyanate compound having an isothiocyanate
group and a polyisothiocyanate, and the active hydrogen
compound(s) (B) is at least one selected from a group
consisting of a thiol compound having a hydroxyl group and
a polythiol compound.
7. The plastic polarized lens according to any one of
claims 1 to 6,
wherein the polarized film is shaped under a
condition of a temperature T represented by the following
formula,
(Formula) glass transition temperature of
thermoplastic polyester +5"C 5 T 5 melting point of
thermoplastic polyester.
8. The plastic polarized lens according to any one of
claims 1 to 7,
wherein the polarized film is a polyethylene
terephthalate film.
9. The plastic polarized lens according to any one of
claims 6 to 8,
wherein the isocyanate compound(s) (A) is at least
one of diisocyanate compounds selected from a group
consisting of m-xylylene diisocyanate, 2,4-tolylene
diisocyanate, 2,6-tolylene diisocyanate, 4,4'-
diphenylmethane diisocyanate, 2,5-bis(isocyanatomethy1)-
bicyclo [2.2.1] -heptane, 2,6-bis (isocyanatomethyl)-
bicyclo[2.2.1]-heptane, bis(4-isocyanatocyclohexyl)methane,
1,3-bis (isocyanatomethyl) cyclohexane, 1,4-
bis(isocyanatomethyl)cyclohexane, and hexamethylene
diisocyanate, and
the active hydrogen compound(s) (B) is at least one
of polythiol compounds selected from a group consisting of
pentaerythritol tetrakis(3-mercaptopropionate), 5,7-
dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-
dimercaptomethyl-1,4-dithiane, 1,1,3,3-
tetrakis (mercaptomethylthio)p ropane, 4,6-
bis (mercaptomethylthio) -1,3-dithiane, and 2- ( 2 , 2 -
bis (mercaptomethylthio)e thyl) -1,3-dithietane.
10. The plastic polarized lens according to claim 2 or 3,
wherein a refractive index at e-line of the
thiourethane-based resin is in a range of 1.50 to 1.70.
11. A method of producing a plastic polarized lens,
comprising:
forming a coat layer containing a urethane-based
resin comprised of a structural unit derived from compound
having hydroxyl group and a structural unit derived from
aromatic diisocyanate, over at least one surface of a
polarized film containing thermoplastic polyester;
fixing the coat layer-attached polarized film into a
lens casting mold, in a state separated from an inner
surface of the mold;
injecting a monomer mixture into a gap between at
least the coat layer of the coat layer-attached polarized
film and the inner surface of the mold; and
stacking a substrate layer containing a thiourethanebased
resin over at least the coat layer of the coat layerattached
polarized film by polymerizing and curing the
monomer mixture.
12. The method of producing a plastic polarized lens
according to claim 11,
wherein, the compound having hydroxyl group is a
trimethylolpropane and the aromatic diisocyanate is a
tolylene diisocyanate.
13. The method of producing a plastic polarized lens
according to claim 12 ,
wherein the coat layer further contains a silane
coupling agent.
14 . The method of producing a plastic polarized lens
according to claim 11,
wherein, the compound having hydroxyl group is a
polybutadiene having a hydroxyl group on the terminal and
the aromatic diisocyanate is a diphenylmethane diisocyanate
15. The method of producing a plastic polarized lens
according to any one of claims 11 to 1 4 ,
wherein the forming a coat layer includes forming the
coat layer over both surfaces of the polarized film.
16 . The method of producing a plastic polarized lens
according to any one of claims 11 to 15, further
comprising:
shaping the polarized film under a condition of a
temperature equal to or higher than a glass transition
temperature of thermoplastic polyester +5"C and equal to or
lower than a melting point of thermoplastic polyester,
before the forming a coat layer.
17. The method of producing a plastic polarized lens
according to claim 12 or 13, further comprising:
a step of shaping the polarized film under a
condition of a temperature equal to or higher than a glass
transition temperature of thermoplastic polyester +5'C and
equal to or lower than a melting point of thermoplastic
polyester, after the forming a coat layer.
18. The method of producing a plastic polarized lens
according to any one of claims 12, 13 and 17,
wherein, in the injecting a monomer mixture, a
viscosity at 20°C of the monomer mixture is not more than
200 mPa.s.
19. A urethane-based resin-coated polarized film
comprising:
a polarized film containing thermopiascic polyester
and
a coat layer containing a urethane-based resin
comprised of a structural unit derived from compound having
hydroxyl group and a structural unit derived from aromatic
diisocyanate, which is formed over at least one surface of
the polarized film.
20. The urethane-based resin-coated polarized film
according to claim 19,
wherein, the compound having hydroxyl group is a
trimethylolpropane and the aromatic diisocyanate is a
tolylene diisocyanate.
21. The urethane-based resin-coated polarized film
according to claim 20,
wherein the coat layer further contains a silane
coupling agent.
22. The urethane-based resin-coated polarized film
according to claim 19,
wherein, the compound having hydroxyl group is a
polybutadiene having a hydroxyl group on the terminal and
the aromatic diisocyanate is a diphenylmethane diisocyanate.
23. A method of producing a urethane-based resin-coated
polarized film, comprising:
forming a coat layer containing a urethane-based
resin comprised of a structural unit derived from compound
having hydroxyl group and a structural unit derived from
aromatic diisocyanate, over at least one surface of a
polarized film containing thermoplastic polyester.
24. The method of producing a urethane-based resin-coated
polarized film according to claim 23,
wherein, the compound having hydroxyl group is a
trimethylolpropane and the aromatic diisocyanate is a
tolylene diisocyanate.
25. The method of producing a urethane-based resin-coated
polarized film according to claim 24,
wherein the coat layer further contains a silane
coupling agent.
26. The method of producing a urethane-based resin-coated
polarized film according to claim 23,
wherein, the compound having hydroxyl group is a
polybutadiene having a hydroxyl group on the terminal and
the aromatic diisocyanate is a diphenylmethane diisocyanate.