TECHNICAL FIELD
[0001]
The present invention relates to a polymerizable composition
for an optical material, an optical material, and a use thereof.
10 BACKGROUND ART
[0002]
In the related art, adverse effects due to an exposure of eyes
to ultraviolet rays are regarded as a problem. Furthermore, in recent
years, a blue light included in natural light or a light emitted from
15 liquid crystal displays of office equipment and displays of portable
equipment such as smartphones or mobile phones has had an influence
on the eyes, causing problems such as feelings of fatigue and pain
in the eyes and there is a demand to reduce an amount of exposure
of the eyes to a blue light having a relatively short wavelength of
20 approximately 420 rum from ultraviolet rays.
[0003]
Non-Patent Document 1 describes an influence of the short
wavelength blue light of approximately 420 nm on the eyes. In
Non-Patent Document 1, damage to retinal nerve cells (cultured
25 retinal nerve R28 cells of rats) caused by an irradiation with blue
light emitting diode (LED) light having different peak wavelengths
at 411 nmand 4 70 nm is verified. The results show that the irradiation
.. ,-_
2
with blue light having a peak wavelength at 411 nm (4.5 W/m2
) causes
a cell death of retinal nerve cells within 24 hours, whereas, for
the blue light having a peak wavelength at 470 nm, changes do not
occur in cells even when irradiated with the same amount, and show
5 that suppression of an exposure of a light having a wavelength of
400 to 420 nm is important for an eye disorder prevention.
[0004]
In addition, there is a concern that the exposure of the eyes
to blue light for a long time will result in eyestrain and stress
10 and this is considered to be a factor causing age-related macular
degeneration.
15
Techniques aimed at suppressing a transmission of the blue light
include the following.
IOD05J
Patent Document 1 discloses a plastic lens including an
ultraviolet absorber and having an average light transmittance of
0.5% or less in a wavelength range of equal to or more than 300 nm
and equal to or less than 400 nm.
Patent Document 2 discloses a plastic lens obtained from a
20 composition for a plastic lens which contains a resin material which
25
includes a urethane resin material and at least two types of
ultraviolet absorbers having different maximum absorption
wavelengths.
[ 0006]
Patent Document 3 discloses a plastic lens obtainable from a
composition for a plastic lens which contains a resin material which
includes a urethane resin material and an ultraviolet absorber having
3
a maximum absorption wavelength of 345 nrn or more in a chloroform
solution. Patent Document 3 describes that, with this plastic lens,
there is no yellowing of the lens, changes in a refractive index,
or the like due to the influence of the ultraviolet absorber, and
5 furthermore, a mechanical strength of the lens is not lowered.
[0007]
Patent Document 4 discloses a plastic spectacle lens using a
specific benzotriazole compound. Patent Document 4 describes that
the plastic spectacle lens has a light transmittance in a
10 predetermined range at a wavelength of 395 nrn, a wavelength of 400
nm, and a wavelength of 405 nrn.
15
20
25
RELATED DOCUMENT
PATENT DOCUMENT
[0008]
[Patent Document 1]
H10-186291
[Patent Document 2]
Hll-218 602
[Patent Document 3]
Hll-2 95502
[Patent Document 4]
2005-292240
NON-PATENT DOCUMENT
[0009]
Japanese Laid-open Patent Publication No.
Japanese Laid-open Patent Publication No.
Japanese Laid-open Patent Publication No.
Japanese Laid-open Patent Publication No.
[Non-patent Document 1] The European journal of neuroscience,
vol. 34, Iss. 4, 548-58, (2011)
SUMMARY OF INVENTION
TECHNICAL PROBLEM
[0010]
4
However, in the related art as described above, since the
5 solubility and the like of the ultraviolet absorber in the composition
are not sufficient, a productivity of a product may decrease such
that dissolving an appropriate amount takes time.
On the other hand, in order to improve the productivity, it is
necessary to reduce the amount of ultraviolet absorber, it is
10 difficult to control an effect of blocking a blue light of .
approximately 420 run from harmful ultraviol<:et rays, and there is still
room for improvement in the effect.
In other words, in the related art, there is a trade-off
relationship between the productivity of the products and the effect
15 of blocking the blue light of approximately 420 nm from harmful
ultraviolet rays.
SOLUTION TO PROBLEM
[DOll]
20 It is possible to illustrate the present invention as follows.
[1] A polymerizable composition for an optical material including
(A) an isocyanate compound, (B) an active hydrogen compound, and (C)
one or more types of ultraviolet absorber represented by General
Formula (1) and having a maximum absorption peak in a range of equal
25 to or more than 350 nm and equal to or less than 370 nm,
[Chern. 1]
Cl
N c:;::;.---N
:::::::-.._/
N
5
HO
( 1 )
(in General Formula ( 1) above, R1 and R2 represent an alkyl group having
1 to 8 carbon atoms and may be same or different from each other,
a plurality of R1 present or a plurality of R2 present may be same
5 or different, m represents an integer of 0 to 3, n represents an integer
of 0 to 3, and R3 represents a functional group having 2 to 15 carbon
atoms which includes an ester bond) .
[2] The po1ymerizable composition for an optical material according
to [1], in which the ultraviolet absorber (C) is represented by General
10 Formula (2) below and is one or more types of ultraviolet absorber
having a maximum absorption peak in a range of equal to or more than
350 nm and equal to or less than 370 nm;
[Chern. 2]
Cl
N c:;::;.---N
:::::::-.._/
N
HO
( 2)
15 (in General Formula (2) above, R1 , R2 , m, and n have the same meanings
as in General Formula (1), R4 and R5 independently represent a
hydrocarbon group having 1 to 10 carbon atoms which may be branched) .
[ 3] The polymerizable composition for an optical material according
to [2], inwhichtheultravioletabsorber (C) isrepresentedbyGeneral
6
Formula (3) below and is one or more types of ultraviolet absorber
having a maximum absorption peak in a range of equal to or more than
350 nm and equal to or less than 370 nm;
[Chern. 3]
HO
N
~\ f N--{
~I
Cl
N
R4-C--0--R5
II
5
0 ( 3)
(in General Formula (3) above, R2 , R4 , and R5 have the same meanings
as in General Formula (1) or (2)).
[ 4] The polymerizable composition for an optical material according
to any one of [1] to [3], in which the isocyanate compound (A) includes
10 an alicyclic isocyanate compound.
[5] The polymerizable composition for an optical material according
to any one of [1] to [4], in which the isocyanate compound (A) is
at least one type selected from the group consisting of hexamethylene
diisocyanate, pentamethylene diisocyanate, xylylene diisocyanate,
15 isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, bis
(isocyanatocyclohexyl) methane, 2,5-bis (isocyanatomethyl)
bicyclo-[2.2.1]-heptane, 2,6-bis (isocyanatomethyl)
bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene
diisocyanate, and 4,4'-dipheny1methane diisocyanate.
2 0 [ 6] The polymerizable composition for an optical material according
to any one of [1] to [5], in which the active hydrogen compound (B)
7
is at least one type selected from the group consisting of a polythiol
compound having two or more mercapto groups, a hydroxy thiol compound
having one or more mercapto groups and one or more hydroxyl groups,
a po~yol compound having two or more hydroxyl groups, and an amine
5 compound.
[ 7] The polymerizable composition for an optical material according
to [6], in which the polythiol compound is at least one type selected
from the group consisting of
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
10 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol
tetrakis (2-mercaptoacetate), pentaerythritol tetrakis
(3-mercaptopropionate) , 2, 5-bis (mercaptomethyl) -1, 4-dithiane, bis
15 (mercaptoethy1) sulfide, 1,1,3,3-tetrakis (mercaptomethylthio)
propane, 4,6-bis (mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis
(mercaptomethylthio) ethyl)-1,3-dithietane, 1,1,2,2-tetrakis
(mercaptomethylthio) ethane,
3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris
20 (mercaptomethylthio) methane, and ethylene glycol bis
(3-mercaptopropionate).
[8] The polymerizable composition for an optical material according
to any one of [1] to [7], further including an ultraviolet absorber
having a structure other than the structure of General Formula (1)
25 and having a maximum absorption peak in a range of equal to or more
than 350 nm and equal to or less than 370 nm.
[ 9] The polymerizable composition for an optical material according
8
to any one of [1] to [8], in which the ultraviolet absorber (C) is
included in an amount of 0.1 to 10.0% by weight in 100% by weight
of the polymerizable composition for an optical material.
[10] A molded article obtainable by curing the polymerizable
5 composition for an optical material according to any one of [1] to
[ 9 J .
[11] The molded article according to [10] including 0.1 to 10.0%
by weight of the ultraviolet absorber (C) .
[12] An optical material constituted of the molded article according
10 to [10] or [11].
[ 13] A plastic lens formed of the optical material according to [ 12] .
[14] A method for manufacturing an optical material, the method
including a step of cast polymerizing the polymerizable composition
for an optical material according to any one of [1] to [9].
15 [15] Use of a molded article obtainable by heating and curing the
polymerizable composition for an optical material according to any
one of [1] to [9] as an optical material.
ADVANTAGEOUS EFFECTS OF INVENTION
20 [0012]
According to the present invention, using a specific ultraviolet
absorber makes it possible to provide an optical material having a
high effect of blocking the blue light of approximately 420 nm from
harmful ultraviolet rays, and to provide a polymerizable composition
25 for an optical material which is also excellent in the productivity
of the optical material.
Furthermore, according to the polymerizable compositi·on for an
9
optical material of the present invention, it is possible to provide
an optical material which is colorless and transparent, excellent
in an appearance,, and excellent in optical characteristics such as
a high refractive index and a high Abbe number and various physical
5 properties such as a heat resistance, specifically to provide a
plastic spectacle lens.
DESCRIPTION OF EMBODIMENTS
[ 0013]
10 Detailed description will be given of the present invention.
The polymerizable composition for an optical material of a
present embodiment includes (A) an isocyanate compound, (B) an active
hydrogen compound, and (C) one or more types of ultraviolet absorber
represented by General Formula (1) and having a maximum absorption
15 peak in the range of equal to or more than 350 nm and equal to or
less than 370 nm.
[0014]
[Chern. 4]
Cl
20 [0015]
N
~N
~I
N
HO
f O.(R2)n
-- R3
(1)
(In General Formula (1) above, R1 and R2 represent an alkyl group
having J to 8 carbon atoms and may be same or different from each
other, a plurality of R1 present or a plurality of R2 present may be
10
same or different, m represents an integer of 0 to 3, n represents
an integer of 0 to 3, and R3 represents a functional group having
2 to 15 carbon atoms which includes an ester bond.)
Each component will be described in detail below.
5 [ 0016]
[(A) Isocyanate Compound]
In the present embodiment, the polymerizable composition for
an optical material includes an isocyanate compound having two or
more isocyanate groups.
10 [0017]
Examples of the isocyanate compound (A) include an aliphatic
isocyanate, an alicyclic isocyanate, an aromatic isocyanate, a
heterocyclic isocyanate, and the like., which may be used as one type
or two or more types in a mixture. These isocyanate compounds may
15 include dimers, trimers, and prepolymers.
[0018]
Examples of aliphatic isocyanates include hexamethylene
diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate, pentamethylene
20 diisocyanate, lysine diisocyanatomethyl ester, lysine triisocyanate,
xylylene diisocyanate, a, a, a', a' -tetra methyl xylylene diisocyanate,
bis ( isocyanatomethyl) naphthalene, mesi tylylene triisocyanate, bis
(isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis
(isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis
25 (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane,
bis (isocyanatoethyl thio) ethane, bis (isocyanatomethyl thio) ethane,
and the like and it is possible to use at least one type thereof.
11
[0019]
Examples of alicyclic isocyanates include isophorone
diisocyanate, bis (isocyanatomethyl) cyclohexane, bis
(isocyanatocyclohexyl) methane, cyclohexane diisocyanate,
5 methylcyclohexane diisocyanate, dicyclohexyl-dimethyl methane
isocyanate, 2,5-bis (isocyanatomethyl) bicyclo-[2.2.1]-heptane,
2,6-bis (isocyanatomethyl) bicyclo-[2.2.1]-heptane, 3,8-bis
(isocyanatomethyl) tricyclodecane, 3,9-bis (isocyanatomethyl)
tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis
10 (isocyanatomethyl) tricyclodecane, and the like, and it is possible
to use at least one type thereof.
[0020]
Examples of aromatic isocyanates include tolylene diisocyanate,
4,4'-diphenylmethane diisocyanate, phenylene diisocyanate, and the
15 like and the tolylene diisocyanate is one type or more of isocyanates
selected from 2,4-tolylene diisocyanate and 2,6-tolylene
diisocyanate. Examples of tolylene diisocyanates include
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of
2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and the
20 like, and it is possible to use at least one type thereof.
[0021]
Examples of heterocyclic lsocyanates include
2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene,
2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl)
25 tetrahydrothiophene, 3,4-bis (isocyanatomethyl)
tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis
(isocyanatomethyl)-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane,
12
4,5-bis (isocyanatomethyl)-1,3-dithiolane, and the like, and it is
possible to use at least one type thereof.
[0022]
In the present embodiment, from the viewpoint of improving a
5 transparency of the optical material obtainable using the
polymerizable composition for an optical material, the isocyanate
compound (A) preferably includes at least one type selected from the
group consisting of an aliphatic isocyanate compound and an alicyclic
isocyanate compound, more preferably includes at least one type
10 selected from the group consisting of alicyclic isocyanate compounds,
and even more preferably includes at least one type selected from
the group consisting of isophorone diisocyanate, bis
(isocyanatocyclohexyl) methane, 2,5-bis (isocyanatomethyl)
bicyclo-[2.2.1]-heptane, and 2,6-bis (isocyanatomethyl)
15 bicyclo-[2.2.1]-heptane.
[0023]
In addition, from the viewpoint of improving the transparency
of the optical material obtainable using the polymerizable
composition for an optical material, the total content of the aromatic
20 isocyanate and heterocyclic isocyanate with respect to the whole
isocyanate compound (A) is preferably 50% by weight or less, more
preferably 30% by weight or less, even more preferably 10% by weight
or less, and even more preferably substantially 0% by weight.
25
[0024]
In addition, as the isocyanate compound (A), it is possible to
use at least one type selected from hexamethylene diisocyanate,
pentamethylene diisocyanate, xylylene diisocyanate, isophorone
13
diisocyanate, bis (isocyanatomethyl) cyclohexane, bis
(isocyanatocyclohexyl) methane, 2,5-bis (isocyanatomethyl)
bicyclo-[2.2.1]-heptane, 2,6-bis (isocyanatomethyl)
bicyclo-[2.2.1]-hBptane, tolylene diisocyanate, phenylene
5 diisocyanate, and 4,4'-diphenylmethane diisocyanate.
[0025]
From the viewpoint of improving the optical characteristics of
the optical material obtainable using the polymerizable composition
for an optical material, the content of the isocyanate compound (A)
10 in the polymerizable composition for an optical material is
preferably 30% by weight or more in 100% by wBight of the polymerizable
composition for an optical material, and more preferably 40% by weight
or more, and preferably 70% by weight or less, and more preferably
60% by weight or less.
15 [0026]
[(B) Active Hydrogen Compound]
In the present embodiment, the polymerizable composition for
an optical material includes an active hydrogen compound.
Examples of active hydrogen compounds include a polythiol
20 compound having two or more mercapto groups, a hydroxy thiol compound
having one or more mercapto groups and one or more hydroxyl groups,
a polyol compound having two or more hydroxyl groups, an amine compound,
and the like, and it is possible to use one type or two or more types
in a mixture.
25 [0027]
Examples of polythiol compounds include aliphatic polythiol
compounds such as methanedithiol, 1,2-ethanedithiol,
14
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 glycolbis (2-mercaptoacetate),
5 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
10 (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis
(mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis
(mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis
(mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane,
bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio)
15 ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,2-bis
(3-mercaptopropythio) ethane, 1,2,3-tris (mercaptomethy1thio)
propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris
(3-mercaptopropylthio) propane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
20 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
tetrakis (mercaptomethylthiomethyl) methane, tetrakis
(2-mercaptoethylthiomethyl) methane, tetrakis
25 (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl)
sulfide, 2,5-bis (mercaptomethyl)-1,4-dithiane,
2,5-dimercapto-1,4-dithiane,
15
2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and their esters
of thioglycolic acid and mercaptopropionic acid, hydroxymethyl
sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis
(3-mercaptopropionate), hydroxyethyl sulfide bis
5 (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
10 (3-mercaptopropinate), 2-mercaptoethyl ether bis
(2-mercaptoacetate), 2-mercaptoethyl ether bis
(3-mercaptpropionate), thiodiglycolic acid bis (2-mercaptoethyl
ester), thiodipropionic acid bis (2-mercaptoethyl ester),
dithiodiglycolic acid bis (2-mercaptoethyl ester),
15 dithiodipropionate bis (2-mercaptoethyl ester), 1,1,3,3-tetrakis
(mercaptomethylthio) propane, 1,1,2,2-tetrakis
(mercaptomethylthio) ethane, 4,6-bis
(mercaptomethylthio)-1,3-dithiane, tris (mercaptomethylthio)
methane, tris (mercaptoethylthio) methane, and
20 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane;
aromatic polythiol compounds such as 1,2-dimercaptobenzene,
1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis
(mercaptomethyl) benzene, 1, 3-bis (mercaptomethyl) benzene, 1, 4-bis
(mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis
2 5 (mercaptoethy1) benzene, 1, 4-bis (mercaptoethy1) benzene,
1,3,5-trirnercaptobenzene, 1,3,5-tris (mercaptomethyl) benzene,
1,3,5-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris
16
(mercaptoethy1eneoxy) benzene, 2,5-to1uenedithio1,
3,4-toluenedithiol, 1,5-naphtha1enedithio1, and
2,6-naphthalenedithiol;
heterocyclic polythiol compounds such as
5 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithio1,
bismuthiol, 4,6-bis (mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis
(mercaptomethylthio) ethyl) -1, 3-dithietane, and the like, and it is
possible to use one type or two or more types in a mixture.
10
[0028]
As the polythiol compounds, it is possible to preferably use
at least one type selected from
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9 trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
15 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol
tetrakis (2-mercaptoacetate), pentaerythritol tetrakis
( 3-mercaptopropionate) , 2, 5-bis (mercaptomethy1) -1, 4-di thiane, bis
(mercaptoethyl) sulfide, 1,1,3,3-tetrakis (mercaptomethylthio)
propane, 4,6-bis (mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis
20 (mercaptomethylthio) ethyl)-1,3-dithietane, 1,1,2,2 tetrakis
(mercaptomethylthio) ethane,
3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris
(mercaptomethylthio) methane, and ethylene glycol bis
(3-mercaptopropionate).
25 [0029]
Examples of hydroxy thiol compounds include 2-mercaptoethanol,
3-mercapto-1,2-propanediol, glycerin di(mercaptoacetate),
17
1-hydroxy-4-mercaptocyc1ohexane, 2,4-dimercaptophenol,
2-mercaptohydroquinone, 4-mercaptophenol,
3,4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol,
2,3-dimercapto-l-propano1, 1,2-dimercapto-1,3-butanediol,
5 pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono
(3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate),
pentaerythritol tris (thioglycolate), pentaerythritol pentakis
(3-mercaptopropionate), hydroxymethyl-tris
(mercaptoethylthiomethyl) methane,
10 1-hydroxyethylthio-3-mercaptoethylthiobenzene,
4-hydroxy-4'-mercaptodiphenyl sulfone, 2-(2-mercaptoethylthio)
ethanol, dihydroxyethylsulfide mono (3-mercaptopropionate),
dimercaptoethanemono(salicylate), hydroxyethylthiomethyl-tris
(mercaptoethylthio) methane, and the like.
15 [ 0030]
The polyol compound is one type or more of aliphatic or alicyclic
alcohols and specific examples thereof include linear or branched
aliphatic alcohols, alicyclic alcohols, alcohols to which ethylene
oxide, propylene oxide, and ~;-caprolactone are added to these alcohols,
20 and the like.
Examples of linear or branched aliphatic alcohols include
ethylene glycol, diethylene glycol, triethylEme glycol, propylene
glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol,
2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,
25 1,2-butanediol, 1,3-butanediol, 1,4-butanediol,
3-methyl-1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol,
1,5-pentanediol~ 2,4-pentanediol, 2-methyl-2,4-pentanediol,
18
3-methy1-1,5-pentanedio1, 1,6-hexanedio1, 2,5-hexanediol, glycerol,
diglycerol, polyglycerol, trimethylolpropane, pentaerythritol,
di(trimethylolpropane), and the like.
Examples of alicyclic alcohols include 1,2-cyc1opentanediol,
5 1,3-cyclopentanediol, 3-methyl-1,2-cyclopentanediol,
1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanedio1,
4,4'-bicyclohexanol, 1,4-cyclohexanedimethanol, and the like.
The polyol compound may be a compound obtained by adding ethylene
oxide, propylene oxide, or E-caprolactone to these alcohols.
10 Examples thereof include an ethylene oxide adduct of glycerol, an
ethylene oxide adduct of trimethylolpropane, an ethylene oxide adduct
of pentaerythritol, a propylene oxide adduct of glycerol, a propylene
oxide adduct of trimethylolpropane, a propylene oxide adduct of
pentaerythritol, caprolactone-modified glycerol,
15 caprolactone-modified trimethylolpropane, caprolactone-modified
pentaerythritol, and the like.
[0031]
The amine compound may have at least two primary and/or secondary
amine groups (polyamines). Non-limiting examples of suitable
20 polyamines include primary or secondary diamines or polyamines, in
which case the groups attached to the nitrogen atom may be saturated
or unsaturated, aliphatic groups, alicyclic groups, aromatic groups,
aromatically substituted aliphatic groups, aliphatically
substituted aromatic groups, or heterocyclic. Non-limiting
25 examples of suitable aliphatic and alicyclic diamines include
1,2-ethylenediamine, 1,2-propylenediamine, 1,8-octanediamine,
isophoronediamine, propane-2,2-cyclohexylamine, and the like.
19
Non-limiting examples of suitable aromatic diamines include
phenylenediamine and toluenediamine, for example,
a-phenylenediamine and p-tolylenediamine. Also suitable are
polynuclear aromatic diamines, for example, monochloro derivatives
5 and dichloro derivatives of 4,4'-biphenyldiamine,
4,4'-methylenedianiline, and 4,4'-methylenedianiline.
[0032]
It is possible for the polyamines suitable for use in the present
invention to include substances having General Formula (4) below;
10 however, the polyamines are not limited thereto.
[0033]
[Chern. 5]
[0034]
Re
(4)
15 (In the formula, it is possible for R8 and R9 to be each
independently selected from groups of methyl, ethyl, propyl, and
isopropyl, and R10 to be selected from hydrogen and chlorine.)
Non-limiting examples of polyamines for use in the present
invention include the following compounds produced by Lonza Ltd
20 (Basel, Switzerland).
LONZACURE (registered trademark) M-DIPA: Rs=C3H7; Rs=C3H7; R10=H
LONZACURE (registered trademark) MM-DMA: R8=CH3 ; R9=CH3 ; R10=H
5
20
LONZACURE (registered trademark) MM-MEA: Rs=CH3; Rg=CzHs; R10=H
LONZACURE (registered trademark) MM-DEA: Rs=C2Hs; Rg=CzHs; R1 0=H
LONZACURE (registered trademark) MM-MIPA: Rs=CH3; Rg=C3H7; R1o=H
LONZACURE (registered trademark) MM-CDEA: Rs=CzHs; R9=C2Hs; R1o=Cl
Among the above, Rs, Rg and R1o correspond to the chemical formula
described above.
[0035]
Polyamines include diamine reactive compounds and possible
examples thereof include 4,4'-methylenebis
10 ( 3-chloro-2, 6-diethylaniline), (Lonzacure (registered trademark)
M-CDEA), 2,4-diamino-3,5-diethyl-toluene, and
2,6-diamino-3,5-diethyl-toluene commercially available from Air
Products and Chemical, Inc. (Allentown, Pa.) in the United States,
mixtures thereof ( collectively "diethy 1 tol uenediarnine" or "DETDA")
15 commercially available under the trade name Ethacure 100 from
Albemarle Corp., dimethylthiotoluenediamine (DMTDA) commercially
available from Albemarle Corp. under the trade name Ethacure 300,
and 4,4'-methylene-bis-(2-chloroaniline) commercially available as
MOCA from Kingyorker Chemicals. DETDA has a viscosity of 156 cPs
20 at 25°C and is able to a liquid at room temperature. DETDA may be
isomeric, the 2,4-isomer range may be 75 to 81 percent, while the
2, 6-isomer range may be 18 to 24 percent. A color stabilized version
of Ethacure 100 (that is, a formulation containing yellowing reducing
additives) commercially available under the trade name Ethacure 1003
25 may be used in the present invention.
[0036]
Other examples of polyamines can include ethylene amines.
21
Possible suitable ethylene amines include ethylenediamine (EDA),
diethylenetriamine (DETA), triethylenetetramine (TETA),
tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA),
piperazine, morpholine, substituted morpholine, piperidine,
5 substituted piperidine, diethylenediamine (DEDA), and
2-amino-1-ethylpiperazine; however, the ethylene amines are not
limited thereto. In a specific embodiment, the polyamine is one or
a plurality of isomers of a dialkyl toluenediamine with 1 to 3 carbon
atoms, for example, but without being limited thereto, it is possible
10 to select from 3,5-dimethyl-2,4-toluenediamine,
3,5-dimethyl-2,6-toluenediamine, 3,5-diethyl-2,4-toluenediamine,
3,5-diethyl-2,6-toluenediamine,
3,5-diisopropyl-2,4-toluenediamine,
3,5-diisopropyl-2,6-toluenediamine, and mixtures thereof.
15 Methylene dianiline and trimethylene glycol di(para-aminobenzoic
acid) are also suitable.
[0037]
Additional examples of suitable polyamines include
methylenebisaniline, sulfurized aniline, and bianiline, any of which
20 may be hetero-substituted, in which case the substituent may be any
substituent which does not disturb the reaction which occurs between
the reactants. Specific examples thereof include
4,4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis
(2,6-diethylaniline), 4,4'-methylene-bis
25 (2-ethyl-6-methylaniline), 4,4'-methylene-bis
(2,6-diisopropylaniline), 4,4'-methylene-bis
(2-isopropyl-6-methylaniline), and 4,4'-methylene-bis
(2,6-diethyl-3-chloroaniline).
[0038]
22
Diaminotoluenes such as diethyltoluenediamine (DETDA) are also
suitable.
5 [0039]
From the viewpoint of improving the optical characteristics of
the optical material obtainable using the polymerizable composition
for an optical material, the active hydrogen compound (B) is
preferably at least one type selected from the group consisting of
10 a polythiol compound having two or more mercapto groups and
hydroxythiol compounds having one or more mercapto groups and one
or more hydroxyl groups, more preferably at least one type selected
from polythiol compounds having two or more mercapto groups, even
more preferably at least one type selected from the group consisting
15 of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and
pentaerythritol tetrakis (3-mercaptopropionate) .
20 [0040]
From the viewpoint of improving the optical characteristics of
the optical material obtainable using the polymerizable composition
for an optical material, the content of the active hydrogen compound
(B) in the polymerizable composition for an optical material is
25 preferably 30% by weight or more in 100% by weight of the polymerizable
composition for an optical material, and more preferably 40% by weight
or more, and preferably 70% by weight ·or less, and more preferably
23
60% by weight or less.
[0041]
[Ultraviolet Absorber (C)]
The ultraviolet absorber (C) used in the present embodiment is
5 represented by General Formula (l) below and is one type or more of
ultraviolet absorber having a maximum absorption peak in the range
of equal to or more than 350 nrn and equal to or less than 370 nrn when
dissolved in a chloroform solution.
[0042]
10 [Chern. 6]
Cl
[0043]
N
-:::::------N
::::::-..../
N
HO
f ~(R2)n
-- R3
( 1 )
In General Formula (1), R1 and R2 represent an alkyl group with
1 to 8 carbon atoms, preferably an alkyl group with 2 to 6 carbon
15 atoms, which may be same or different. A plurality of R1s present
or a plurality of R2s present may be same or different.
rn represents an integer of 0 to 3, preferably 0 or 1.
n represents an integer of 0 to 3, preferably 1 or 2.
R3 represents a functional group with 2 to 15 carbon atoms
20 including an ester bond, preferably -R.-C (=0) OR5 or -R4-0C (=0) -R5 , and
more preferably -R.-C (=0) OR5 • R4 and R5 independently represent a
hydrocarbon group with 1 to 10 carbon atoms which may be branched.
More specifically, R4 represents a divalent hydrocarbon group with
24
1 to 10 carbon atoms which may be branched, and R5 represents a
monovalent hydrocarbon group with 1 to 10 carbon atoms which may be
branched.
Using such an ultraviolet absorber (C) makes it possible to
5 provide an optical material having a high effect of blocking the blue
light of approximately 420 nm from harmful ultraviolet rays, and also
excellent in an optical material productivity.
[0044]
From the viewpoint of the effect of the present invention, it
10 is possible to preferably use one type or more of ultraviolet absorbers
selected from compounds represented by General Formula (2) below as
the ultraviolet absorber (C) . More preferably, the ultraviolet
absorber (C) is one type or more of ultraviolet absorber which is
a compound represented by General Formula (2) and has a maximum
15 absorption peak in the range of equal to or more than 350 nm and equal
to or less than 370 nm.
[0045]
[Chern. 7]
Cl
20 [0046]
N ::::;.--N
::-.._ I .,N
HO
f O_(R2)n
-- R4-c --o --Rs
II
0 ( 2)
In General Formula (2), R1 , R2 , m, and n have the same meanings
as in General Formula (1) .
R4 represents a hydrocarbon group with l to 10 carbon atoms which
25
may be branched, preferably an alkylene group with 1 to 5 carbon atoms
which may be branched.
R5 represents a hydrocarbon group with 1 to 10 carbon atoms which
may be branched, preferably an alkyl group with 3 to 10 carbon atoms
5 which may be branched.
[0047]
From the viewpoint of the effects of the present invention, it
is possible to even more preferably use one type or more of ultraviolet
absorbers selected from the compounds represented by General Formula
10 (3) below as the ultraviolet absorber (C) . Even more preferably,
the ultraviolet absorber (C) is one type or more of an ultraviolet
absorber which is a compound represented by General Formula ( 3) and
has a maximum absorption peak in the range of equal to or more than
350 nm and equal to or less than 370 nm.
15 [0048]
[Chern. 8]
HO
N
~\ f N---(
~I
Cl
N
R4-C--0--R5
11· ·
0 ( 3)
[0049]
In General Formula (3), R2 , R4 , and R5 have the same meanings
2 0 as in General Formula ( 1) or ( 2) .
[0050]
26
In the present embodiment, it is possible to further preferably
use one type or more selected from isomers of the compounds represented
by the following chemical formula as the ultraviolet absorber (C).
[0051]
5 [Chem. 9]
HO tBu
Cl
[0052]
Examples of the ultraviolet absorber (C) include a mixture of
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
10 1] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] propionate 2-ethyl hexyl, and the like, and it is possible to use
EVERSORB 109 (produced by EVER LIGHT) artd the like.
[0053]
15 From the viewpoint of the effects of the present invention, it
is possible to include the ultraviolet absorber (C) in an amount of
0.1 to 10.0% by weight in 100% by weight of the polymerizable
composition for an optical material, and preferably 0.5 to 7.5% by
weight. In addition, from the same viewpoint, the content of the
20 ultraviolet absorber (C) in 100% by weight of the polymerizable
composition for an optical material is preferably 0.1% by weight or
27
more, more preferably 0.5% by weight or more, and, preferably 10.0%
by weight or less, and more preferably 7.5% by weight or less. The
ultraviolet absorber (C) is excellent in solubility and
dispersibility in the isocyanate compound (A) and the active hydrogen
5 compound (B), and is able to be easily added by mixing and stirring
with the above.
[0054]
Since the ultraviolet absorber (C) is excellent in solubility
and dispersibility in the isocyanate compound (A) and the active
10 hydrogen compound (B), it is possible to obtain a homogeneous
polymerizable composition in a short time, and the productivity is
excellent.
Furthermore, since the solubility and dispersibility are
excellent, it is possible to add a large amount of the ultraviolet
15 absorber (C) and, even if added in a large amount, the ultraviolet
absorber (C) does not bleed out from the optical material, thus white
turbidity and the like are unlikely to occur. Accordingly, using
the ultraviolet absorber (C) makes it possible to easily control the
wavelength cut according to the addition amount, and to provide an
20 optical material having high effect of blocking the blue light of
approximately 420 nm from harmful ultraviolet rays.
[ 0055]
In the present embodiment, from the viewpoint of improving the
balance between the effect of improving the productivity of the
25 product and the effect of blocking the blue light of approximately
420 nm from harmful ultraviolet rays, specific examples of
combinations of the isocyanate compound (A), the active hydrogen
28
compound (B), and the ultraviolet absorber (C) are as follows.
Preferable examples of the isocyanate compound (A) include at least
one type selected from the group consisting of an aliphatic isocyanate
compound and an alicyclic isocyanate compound, more preferably
5 include at least one type selected from the group consisting of
alicyclic isocyanate compounds, and even more preferably include at
least one type selected from the group consisting of isophorone
diisocyanate, bis (isocyanatocyclohexyl) methane, 2,5-bis
(isocyanatomethyl) bicyclo-[2.2.1]-heptane, and 2,6-bis
10 ,(isocyanatomethyl) bicyclo-[2.2.1]-heptane;
preferable examples of the active hydrogen compound (B) include at
least one type selected from the group consisting of a polythiol
compound having two or more mercapto groups and a hydroxy thiol
compound having one or more mercapto groups and one or more hydroxyl
15 groups, more preferably at least one type selected from the group
consisting of a polythiol compound having two or more mercapto groups,
and even more preferably at least one type selected from the group
consisting of
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
20 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3~6,9-trithiaundecane,
'4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and
pentaerythritol tetrakis (3-mercaptopropionate);
the ultraviolet absorber (C) is preferably at least one type selected
25 from the compounds represented by General Formula (2) above, more
preferably at least one type selected from the compounds represented
by General Formula (3) above, and even more preferably at least one
29
type selected from
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] octyl propionate, and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
5 1] propionate 2-ethyl hexyl.
[0056]
In the present embodiment, other ultraviolet absorbers may be
included in addition to the ultraviolet absorber (C). Examples
thereof include benzophenone-based compounds, triazine compounds,
10 benzotriazole-based compounds, and the like.
Examples of benzophenone-based compounds include
2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2'-4,4'-tetrahydroxybenzophenone, and the like.
Examples of triazine compounds include ADK STAB LA-F70 produced
15 by ADEKA Corp., TINUVIN 400 produced by BASF Corp., and the like.
In addition, the other ultraviolet absorber is preferably an
ultraviolet absorber having a structure other than General Formula
(1) and having a maximum absorption peak in a range of equal to or
more than 350 nm and equal to or less than 370 nm.
20 [0057]
In the present embodiment, a benzotriazole-based compound is
preferably used, and examples of benzotriazole-based compounds
include a linear alkyl ester-substituted benzotriazole-based
compound, a chloro-substi tuted benzotriazole-based compound, and the
25 like.
Among these, chloro-substituted benzotriazole-based compounds
represent"ed by General Formula ( 5) below are preferable.
30
[0058]
[Chern. 10]
HO
(Q1)~~ N :::::---"\ f x(Q2)q
N ~/ ~
Cl N Q3
(5)
[0059]
5 In General Formula (5), Q1 and Q2 , may be the same or different
and represent an alkyl group having 1 to 8 carbon atoms, and preferably
an alkyl group having 2 to 6 carbon atoms. A plurality of Q1s present
or a plurality of Q2s present may be the same or different. p is an
integer o£ 0 to 3, and q is an integer o£ 0 to 3. Q3 represents an
10 alkyl group having 1 to 5 carbon atoms.
[0060]
Among the compounds represented by General Formula (5), it is
preferable to use an ultraviolet absorber having a maximum absorption
peak in a range of equal to or more than 350 nm and equal to or less
15 than 370 nm, and examples thereof include
2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole. As
commercially available products, it is possible to use TINUVIN 326
produced by BASF Corp., SEESEORB 703 produced by SHIPRO KASEI KAISHA,
LTD., Viosorb 550 produced by KYODO CHEMICAL CO., LTD., KEMISORB 73
20 produced by CHEMIPRO KASEI, and the like.
From the viewpoint of the e£fect of the present invention, the
mixing ratio of the ultraviolet absorber (C) and the other ultraviolet
absorber is 99/1 to 1/99, preferably 95/5 to S/95, more preferably
31
90/10 to 10/90, and even more preferably 80/20 to 20/80.
[0061]
In addition, in the present embodiment, from the viewpoint of
improving the effect of blocking the blue light of approximately 420
5 nm from harmful ultraviolet rays, specific examples of combinations
of the ultraviolet absorber (C) and other ultraviolet absorbers are
as follows. The ultraviolet absorber (C) is preferably at least one
type selected from the compounds represented by General Formula (2)
above, more preferably one type or more of compound selected from
10 the compounds represented by General Formula (3) above, and even more
preferably at least one type selected from
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
15 1] propionate 2-ethylhexyl;
while preferable examples of other ultraviolet absorbers include
benzotriazole-based compounds, more preferably at least one type
selected from the group consisting of a linear alkyl
ester-substituted benzotriazole-based compound and a
20 chloro-substituted benzotriazole-based compound, even more
preferably at least one type selected from chloro-substituted
benzotriazole-based compounds represented by General Formula (5)
above, and still more preferably
2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole.
25 [0062]
In the present embodiment, using the ultraviolet absorber (C)
represented by General Formula (1) in combination with another
5
32
ultraviolet absorber further improves the effect of blocking the blue
light of approximately 420 nm from harmful ultraviolet rays and makes
it possible to obtain a synergistic effect.
[0063]
In the present embodiment, the molar ratio of the active hydrogen
group in the active hydrogen compound (B) to the isocyanato group
in the isocyanate compound (A) is in the range of 0. 8 to 1. 2, preferably
in the range of 0.85 to 1.15, and more preferably in the range of
0.9 to 1.1. Within the ranges described above, it is possible to
10 obtain a resin suitably used as an optical material, specifically
as a plastic lens material for spectacles.
[0064]
(Other Components)
The polymerizable composition for an optical material of the
15 present embodiment may further include a polymerization catalyst,
an internal release agent, a resin modifier, a photostabilizer, a
bluing agent, and the like as other components.
20
[0065]
(Catalyst)
Examples of catalysts include Lewis acid, amines, organic acids,
amine organic acid salts, and the like, preferably Lewis acid, amines,
and amine organic acld salts, and more preferably dimethyl.tin
chloride, dibutyl tin chloride, and dibutyl tin laurate.
[0066]
25 (Internal Release Agent)
As the internal release agent, it is possible to use an acidic
phosphate ester. Possible examples of acidic phosphate esters
33
include phosphate monoesters and phosphate diesters, which are able
to be used alone or in a combination of two or more types. For example,
it is possible to use ZelecUN produced by STEPAN Company, an internal
mold release agent for MR produced by Mitsui Chemicals, Inc. , JP series
5 produced by Johoku Chemical Co., Ltd., Phosphanol series produced
by Toho Chemical Industry Co. , Ltd. , AP, DP Series produced by Daihachi
Chemical Industry Co., Ltd., and the like.
10
[0067]
(Resin Modifier)
In the polymerizable composition for an optical material of the
present embodiment, it is possible to add the resin modifier within
a range not impairing the effect of the present invention for the
purpose of controlling various physical properties such as optical
characteristics, impact resistance, and specific gravity of the
15 obtainable resin and adjusting the handleability of the polymerizable
composition.
[0068]
Examples of resin modifiers include episulfide compounds,
alcohol compounds, amine compounds, epoxy compounds, organic acids
20 and anhydrides thereof, olefin compounds including (meth)acrylate
compounds or the like, and the like.
[0069]
(Photostabilizer)
As the photostabilizer, it is possible to use a hindered
25 amine-base compound. Examples of hindered amine-based compounds
include Lowilite 76 and Lowilite 92 produced by Chemtura Corp.,
Tinuvin 144, Tinuvin 292, Tinuvin 765 produced by BASF Corp., ADK
5
34
STAB LA-52 and LA-72 produced by ADEKA Corp., JF-95 produced by Johoku
Chemical Co., Ltd., and the like.
[0070]
(Bluing Agent)
Examples of bluing agents include bluing agents having an
absorption band in the orange to yellow wavelength range of the visible
light region and having a function of adjusting a hue of an optical
material formed of a resin. More specifically, the bluing agent
includes a substance exhibiting a blue to purple color.
10 [0071]
It is possible to obtain the polymerizable composition for an
optical material by mixing the isocyanate compound (A), the active
hydrogen compound (B), the ultraviolet absorber (C) by a
predetermined method with other thiol compounds, catalysts, internal
15 release agents, and other additives as necessary.
The temperature during mixing is usually 25°C or less. From the
viewpoint of the pot life of the polymerizable composition for an
optical material, it may be preferable to further lower the
temperature. However, in a case where the solubility of the catalyst,
20 the internal mold release agent and the additive ln the isocyanate
compound (A) or the active hydrogen compound (B) is not favorable,
it is also possible to dissolve the above by warming in advance.
A mixing order and a mixing method of each component in the
composition are not limited as long as it is possible to uniformly
25 mix each component and to carry out the mixing by a known method.
As a known method, there is, for example, a method of preparing a
master batch including predetermined amounts of additives and
35
dispersing and dissolving the master batch in a solvent.
[0072]

In the present embodiment, the method for manufacturing the
5 molded article is not limited; however, preferable examples of a
manufacturing method include casting polymerization. First, a
polymerizable composition for an optical material is injected between
molded molds held by a gasket, a tape, or the like. At this time,
depending on the physical properties required for the plastic lens
10 to be obtained, as necessary, it is often preferable to carry out
a defoaming treatment under reduced pressure, filtration treatment
such as pressurization, depressurization, or the like.
(0073]
The polymerization conditions are not limited because the
15 conditions are largely different depending on the polymerizable
composition for an optical material, the type and amount of catalyst
used, the shape of the mold, and the like; however, the conditions
are approximately 1 to 50 hours at a temperature of -50 to 150°C.
In some cases, it is preferable to hold or gradually raise the
20 temperature in a range of 10 to 150°C so as to carry out curing over
1 to 25 hours.
[0074]
The molded article of the present embodiment may be subjected
to a treatment such as annealing as necessary. The treatment
25 temperature is usually in the range of 50 to 150°C, but the treatment
is preferably carried out at 90 to 140°C, and more preferably 100
to 130°C.
5
36
[0075]
It is possible to obtain the molded article of the present
embodiment as molded articles of various shapes by changing the mold
during casting polymerization.
In addition, the molded article of the present embodiment is
obtainable by curing, for example, the polymerizable composition for
an optical material.
In addition, in the present embodiment, it is possible to use
a molded article obtainable by heat curing the polymerizable
10 composition for an optical material as, for example, an optical
material.
The molded article of the present embodiment is colorless and
transparent, excellent in appearance, excellent in optical
characteristics such as a high refractive index and a high Abbe number
15 and various physical properties such as heat resistance, and the
molded article is able to be used as various optical materials by
being formed into a desired shape and provided with a coat layer to
be formed as necessary, other members, and the like.
20
[0076]
From the viewpoint of improving the effect of blocking the blue
light of approximately 420 nm from harmful ultraviolet rays, the
content of the ultraviolet absorber (C) included in the molded article
is preferably 0.1% by weight or more, and more preferably 0.5% by
weight or more and preferably 10.0% by weight or less, and more
25 preferably 7.5% by weight or less.
In addition, it is possible for the molded article of the present
embodiment to include the ultraviolet absorber (C) as 0.1 to 10.0%
37
by weight, and preferably 0.5 to 7.5% by weight. Due to this, the
effect of blocking the blue light of approximately 420 nm from harmful
ultraviolet rays is excellent.
[0077]
5
Examples of the optical material of the present embodiment
include a plastic lens, a camera lens, a light emitting diode (LED),
a prism, an optical fiber, an information recording substrate, a
filter, a light emitting diode, and the like. Specifically, the
10 optical material of the present embodiment is suitable as an optical
material or an optical element such as a plastic lens, a camera lens,
a light emitting diode, and the like.
I0078J
The plastic lens using the molded article of the present
15 embodiment may be used by applying a coating layer on one side or
both sides as necessary. Examples of coating layers include a primer
layer, a hard coat layer, an anti-reflection film layer, an anti-fog
coating film layer, an anti-fouling layer, a water-repellent layer,
and the like. It is also possible for each of these coating layers
20 to be used alone, or a plurality of coating layers are able to be
used in multiple layers. In a case of applying coating layers on
both sides, the same coating layer may be applied to each side or
different coating layers may be applied to each side.
25
[0079]
These coating layers may each contain a combination of an
infrared absorber for the purpose of protecting eyes from infrared
rays, a photostabilizer and an anti-oxidant for the purpose of
38
improving the weather resistance of the lens, a dye and a pigment
for the purpose of increasing the fashionability of the lens, a
photochromic dye or a photochromic pigment, an anti-static agent,
and other known additives for enhancing the performance of the lens.
5 A coating layer or a primer layer such as a hard coat or an
anti-reflection coat may be provided.
[0080]
The plastic lens using the molded article of the present
embodiment may be used after being dyed for the purpose of imparting
10 fashionability, a photochromic property, or the like using a coloring
material according to the purpose. ·It is possible to carry out the
dyeing of the lens by a known dyeing method.
In addition, the method for manufacturing the optical material
of the present embodiment includes, for example, a step of cast
15 polymerizing the polymerizable composition for an optical material
of the present embodiment.
[0081]
Although the present invention has been described based on the
present embodiment, it is possible to adopt various configurations
20 within a range not impairing the effects of the present invention.
[0082]
The present invention includes the following aspects.
1. A polymerizable composition for an optical material including
(A) an isocyanate compound, (B) an active hydrogen compound, and (C)
25 one or more types of ultraviolet absorber represented by General
Formula (1) and having a maximum absorption peak in a range of equal
to or more than 350 nm and equal to or less than 370 nm,
39
HO
Cl (1)
(R1 and R2 represent an alkyl group having 1 to 8 carbon atoms and
may be same or different from each other, a plurality of R1 present
or a plurality of R2 present may be same or different, m represents
5 an integer of 0 to 3, n represents an integer of 0 to 3, and R3 represents
a functional group having 2 to 15 carbon atoms which includes an ester
bond.)
2. The polymerizable composition for an optical material according
to the above it€I!l 1., in which the ultraviolet absorber (C) is
10 represented by General Formula (2) below and is one or more types
of ultraviolet absorber having a maximum absorption peak in the range
of equal to or more than 350 nm and equal to or less than 370 nm,
HO
Cl
(2)
(R1 , R2 , m, and n have the same meanings as in General Formula (1),
15 R4 and R5 independently represent a hydrocarbon group having 1 to 10
carbon atoms which may be branched) .
3. The polymerizable composition for an optical material according
to the above item 2., in which the ultraviolet absorber (C) is
represented by General Formula (3) below and is one or more types
40
of ultraviolet absorber having a maximum absorption peak in the range
of equal to or more than 350 nm and equal to or less than 370 nm,
Cl
N :;:;:---N
~I
N
HO
R4-c--o--R5
II
0 ( 3)
(R2 , R4 , and R5 have the same meanings as in General Formula (1) or
5 (2) ) .
4. The polymerizable composition for an optical material according
to any one of the above i terns 1. to 3., in which the isocyanate compound
(A) includes at least one type selected from hexamethylene
diisocyanate, pentamethylene diisocyanate, xyly1ene diisocyanate,
10 isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, bis
(isocyanatocyclohexyl) methane, 2,5-bis (isocyanatomethyl)
bicyclo-[2.2.1]-heptane, 2,6-bis (isocyanatomethyl)
bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene
diisocyanate, and 4,4'-diphenylmethane diisocyanate.
15 5. The polymerizable composition for an optical material according
to any one of the above i terns 1. to 4. , in which the active hydrogen
compound (B) is at least one type selected from a polythiol compound
having two or more mercapto groups, a hydroxy thiol compound having
one or more mercapto groups and one or more hydroxyl groups, a polyol
20 compound having two or more hydroxyl groups, and an amine compound.
6; The polymerizable composition for an optical material according
41
to the above item 5., in which the polythiol compound is at least
one type selected from
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
5 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol
tetrakis (2-mercaptoacetate), pentaerythritol tetrakis
(3-mercaptopropionate), 2,5-bis (mercaptomethyl)-1,4-dithiane, bis
(mercaptoethy1) sulfide, 1,1,3,3-tetrakis (mercaptomethylthio)
10 propane, 4,6-bis (mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis
(mercaptomethylthio) ethyl)-1,3-dithietane, 1,1,2,2-tetrakis
(mercaptomethylthio) ethane,
3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris
(mercaptomethylthio) methane, and ethylene glycol bis
15 (3-mercaptopropionate) .
7. The polymerizable composition for an optical material according
to the above i terns 1. to 6. , further including an ultraviolet absorber
having a structure other than General Formula (1) and having a maximum
absorption peak in a range of equal to or more than 350 nm and equal
20 to or less than 370 nm.
8. The polymerizable composition for an optical material according
to any one of the above items 1. to 7., in which the ultraviolet
absorber (C) is included in an amount of 0.1 to 10.0% by weight in
100% by weight of the polymerizable composition for an optical
25 material.
9. A molded article obtainable by heating and curing the
polymerizable composition for an optical material according to any
42
one of the above items 1. to 8.
10. The molded article according to the above item 9. including 0.1
to 10.0% by weight of the ultraviolet absorber (C).
11. An optical material constituted of the molded article according
5 to the above item 9. or 10.
12. A plastic lens formed of the optical material according to the
above i tern 11.
13. A method for manufacturing an optical material, the method
including a step of cast polymerizing the polymerizable composition
10 for an optical material according to any one of the above items 1.
to 8.
[Examples]
[0083]
Description will be given below of the present invention in more
15 detail with reference to examples, but the present invention is not
limited thereto. The evaluation methods in the examples of the
present invention are as follows.
[0084]

20 e Dissolution Completion Time of Ultraviolet Absorber
25
In the Examples, the time of complete dissolution after adding
the isocyanate solution to various additives including the
ultraviolet absorber was visually confirmed.
• Light Transmittance
The UV-visible light spectrum was measured using a 2 mm thick
plano lens and as a measuring device using Shimadzu spectrophotometer
UV-1600 produced by Shimadzu Corp., and the transmittance at specific
43
wavelengths (410 nm, 420 nm, and 440 nm) was measured.
• Measurement of Refractive Index and Abbe Number
Measurement was carried out at 20°C using a Pulfrich
refractometer KPR-30 produced by Shimadzu Corp.
5 • Heat Resistance (Measurement of Glass Transition Temperature (Tg))
Measurement was carried out with a thermal mechanical analyzer
TMA-60 produced by Shimadzu Corp. according to the TMA penetration
method (with a load of 50 g, a pin tip of 0. 5 mm~, a temperature increase
rate of l0°C/min) .
10 [0085]

The maximum absorption peak of the ultraviolet absorber used
in the Examples was as follows.
Measurement method: The ultraviolet-visible light spectrum was
15 measured using a 2 mm thick plano lens and using a Shimadzu
spectrophotometer UV-1600 produced by Shimadzu Corp. as a measuring
device.
EVERSORB 109: The maximum absorption peak was present in the
range of equal to or more than 350 nm and equal to or less than 370
20 nm.
25
TINUVIN 326: The maximum absorption peak was present in the range
of equal to or more than 350 nm and equal to or less than 370 nm.
[0086]
[Example 1]
A homogeneous solution was obtained by stirring and mixing 0.1
parts by weight of ZelecUN (produced by STEPAN), 1. 5 parts by weight
of a mixture (EVERSORB 109 produced by EVER LIGHT) of
44
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] propionate 2-ethyl hexyl and 58.9 parts by weight of
5 bis(4-isocyanatocyclohexyl) methane at 20°C. A mixed solution was
obtained by adding 41.1 parts by weight of a mixture of
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and
10 0.15 parts by weight of dibutyltin (II) dichloride to the above
homogeneous solution and stirring and mixing at'20°C. After this
mixed solution was defoamed at 600 Pa for 1 hour and filtrated with
a 1 ~ PTFE filter, the mixed solution was introduced into a mold
formed of a 2C (curve, the same applies below) plano glass mold with
15 a center thickness of 2 mm and a diameter of 80 mm and a flat glass
mold with a center thickness of 2 mm and a diameter of 7 8 mm. This
mold was placed in a polymerization oven and polymerization was
carried out by gradually raising the temperature from 20°C to 130°C
over 21 hours. After completion of the polymerization, the mold was
2 0 removed from the oven. The obtained plano lens was further annealed
at 130°C for 2 hours. The obtained 2 mm thick plano lens had a
transparency and had a refractive index (ne) of 1: 60, an Abbe number
(ve) of 39, and a heat resistance of 125°C, which was suitable as a
transparent resin for an optical material. The ultraviolet-visible
25 light spectrum of the obtained plano lens was measured using a
spectrophotometer UV-1600 (produced by Shimadzu Corp.). The
evaluation results are shown in Table 1.
[0087]
[Example 2]
45
A 2 rrnn thick plano lens was obtained by the same method as Example
1 except that 1.50 parts by weight of the mixture (EVERSORB 109
5 produced by EVER LIGHT) of
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] propionate 2-ethyl hexyl was changed to 3. 00 parts by weight. The
10 obtained plano lens had a transparency and had a refractive index
(ne) of 1.60, an Abbe number (ve) of 39, and a heat resistance of
122°C, and was sui table as a transparent resin for optical materials.
The ultraviolet-visible light spectrum of the obtained plano lens
was measured using a spectrophotometer UV-1600 (produced by Shimadzu
15 Corp.). The evaluation results are shown in Table 1.
[0088]
[Example 3]
A 2 rrnn thick plano lens was obtained by the same method as Example
1 except that 1.50 parts by weight of the mixture (EVERSORB 109
20 produced by EVER LIGHT) of
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] propionate 2-ethyl hexyl was changed to 5. 00 parts by weight. The
25 obtained plano lens had a transparency and had a refractive index
(ne) of 1.60, an Abbe number (ve) of 39, and a heat resistance of
11 7"C, and was sui table as a transparent resin for optical materials.
46
The ultraviolet-visible light spectrum of the obtained plano lens
was measured using a spectrophotometer UV-1600 (produced by Shimadzu
Corp.). The evaluation results are shown in Table 1.
[0089]
5 [Example 4]
A homogeneous solution was obtained by stirring and mixing 0.1
parts by weight of ZelecUN (produced by STEPAN), 0. 6 parts by weight
of 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole
( TINUVIN 32 6 produced by BASF Corp. ) , 1. 5 parts by weight of a mixture
10 (EVERSORB 109 produced by EVER LIGHT) of
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] octyl propionate and
3-I3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] propionate 2-ethyl hexyl and 58.9 parts by weight of
15 bis (4-isocyanatocyclohexyl) methane at 20°C. A mixed solution was
obtained by adding 41.1 parts by weight of a mixture of
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and
20 0.15 parts by weight of dibutyltin (II) dichloride to the above
homogeneous solution and stirring and mixing at 20°C. After this
mixed solution was defoamed at 600 Pa for 1 hour and filtrated with
a 1 pm PTFE filter, the mixed solution was introduced into a mold.
This mold was placed in a polymerization oven and polymerization was
25 carried out by gradually raising the temperature from 20°C to 130°C
over 21 hours. After completion of the polymerization, the mold was
removed from the oven. The obtained plano lens was further annealed
47
at 130°C for 2 hours. The obtained 2 mm thick plano lens had a
transparency and had a refractive index (ne) of 1. 60, an Abbe number
(ve) of 39, and a heat resistance of 123°C, and was,suitable as a
transparent resin for optical materials. The ultraviolet-visible
5 light spectrum of the obtained plano lens was measured using a
spectrophotometer UV-1600 (produced by Shimadzu Corp.). The
evaluation results are shown in Table 1.
[0090]
[Example 5]
10 A 2 mm thick plano lens was obtained by the same method as Example
4 except that 1.50 parts by weight of the mixture (EVERSORB 109
produced by EVER LIGHT) of
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] octyl propionate and
15 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxypheny
1] propionate 2-ethyl hexyl was changed to 2. 00 parts by weight. The
obtained plano lens had a transparency and had a refractive index
(ne) of 1.60, an Abbe number (ve) of 39, and a heat resistance of
122°C, and was sui table as a transparent resin for optical materials.
20 The ultraviolet-visible light spectrum of the obtained plano lens
was measured using a spectrophotometer UV-1600 (produced by Shimadzu
Corp.). The evaluation results are shown in Table 1.
[0091]
[Example 6]
25 A 2 mm thick plano lens was obtained by the same method as Example
4 except that 1.50 parts by weight of the mixture (EVERSORB 109
produced by EVER LIGHT) of
48
3-[3-tert-butyl-5-(5-chloro-28-benzotriazol-2-yl)-4-hydroxypheny
1] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-28-benzotriazol-2-yl)-4-hydroxypheny
l] propionate 2-ethyl hexyl was changed to 5. 00 parts by weight. The
5 obtained plano lens had a transparency and had a refractive index
(ne) of L 60, an Abbe number (ve) of 39, and a heat resistance of
117°C, and was sui table as a transparent resin for optical materials.
The ultraviolet-visible light spectrum of the obtained plano lens
was measured using a spectrophotometer UV-1600 (produced by Shimadzu
10 Corp.). The evaluation results are shown in Table 1.
[0092]
[Example 7]
A homogeneous solution was obtained by stirring and mixing 0. 1
parts by weight of ZelecUN (produced by STEPAN) , 1. 5 parts by weight
15 of a mixture (EVERSORB 109 produced by EVER LIGHT) of
3-[3-tert-butyl-5-(5-chloro-28-benzotriazol-2-yl)-4-hydroxypheny
l] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazo1-2-yl)-4-hydroxypheny
1] octyl propionate 2-ethyl hexyl and 56.1 parts by weight of
20 isophorone diisocyanate at 20°C. A mixed solution was obtained by
adding 43.9 parts by weight of
4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 0. 20 parts by
weight of dimethyltin (II) dichloride to the above homogeneous
solution and stirring and mixing at 20°C. After this mixed solution
25 was defoamed at 600 Fa for 1 hour and filtrated with a 1pm PTFE filter,
the mixed solution was introduced into a mold formed of a 2C plano
glass mold with a center thickness of 2 mm and a diameter of 80 mm
49
and a flat glass mold with a center thickness of 2 mm and a diameter
of 78 mm. This mold was placed in a polymerization oven and
polymerization was carried out by gradually raising the temperature
from 20°C to 130°C over 21 hours. After completion of the
5 polymerization, the mold was removed from the oven. The obtained
plano lens was further annealed at 130°C for 2 hours. The obtained
plano lens had a transparency and had a refractive index (ne) of 1. 60,
an Abbe number (ve) of 39, and a heat resistance of 129°C, and was
suitable as a transparent resin for optical materials. The
10 ultraviolet-visible light spectrum of the obtained plano lens was
measured using a spectrophotometer UV-1600 (produced by Shimadzu
Corp.). The evaluation results are shown in Table 2.
[0093]
[Example 8]
15 A 2 mm thick plano lens was obtained by the same method as Example
7 except that 1. 5 parts by weight of the mixture (EVERSORB 109 produced
by EVER LIGHT) of
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] octyl propionate and
20 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] propionate 2-ethyl hexyl was changed to 3. 0 parts by weight. The
obtained plano lens had a transparency and had a refractive index
(ne) of 1.60, an Abbe number (ve) of 38, and a heat resistance of
124°C, and was suitable as a transparent resin for optical materials.
25 The ultraviolet-visible light spectrum of the obtained plano lens
was measured using a spectrophotometer UV-1600 (produced by Shimadzu
Corp.). The evaluation results are shown in Table 2.
[0094]
[Example 9]
50
A 2 mm thick plano lens was obtained by the same method as Example
7 except that 1. 5 parts by weight of the mixture (EVERSORB 109 produced
5 by EVER LIGHT) of
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] propionate 2-ethyl hexyl was changed to 5. 0 parts by weight. The
10 obtained plano lens had a transparency and had a refractive index
(ne) of 1.60, an Abbe number (ve) of 38, and a heat resistance of
120°C, and was suitable as a transparent resin for optical materials.
The ultraviolet-visible light spectrum of the obtained plano lens
was measured using a spectrophotometer UV-1600 (produced by Shimadzu
15 Corp.). The evaluation results are shown in Table 2.
[0095]
[Example 10]
A homogeneous solution was obtained by stirring and mixing 0.1
parts by weight of ZelecUN (produced by STEPAN), 1. 5 parts by weight
20 of a mixture (EVERSORB 109 produced by _EVER LIGHT) of
3-[3-tert-butyl-5-(5-ch1oro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] propionate 2-ethyl hexyl and 50.6 parts by weight of a mixture
25 of 2,5-bis (isocyanatomethyl) bicyclo-[2.2.1]-heptane and 2,6-bis
(isocyanatomethyl) bicyclo-[2.2.1]-heptane at 20°C. A mixed
solution was obtained by adding 25.5· parts by weight of
51
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 23.9 parts by
weight of pentaerythritol tetrakis (3-mercaptopropionate), 0.035
parts by weight of dibutyl tin (II) dichloride to the above homogeneous
solution, and mixing and stirring at 20°C. After this mixed solution
5 was defoamed at 600 Pa for 1 hour and filtrated with a 1 J.lill PTFE filter,
the mixed solution was introduced into a mold formed of a 2C plano
glass mold with a center thickness of 2 mm and a diameter of 80 mm
and a flat glass mold with a cent€r thickness of 2 mm and a diamet€r
of 78 mm. This mold was plac€d in a polymerization oven and
10 polymerization was carried out by gradually raising the temperature
from 20°C to 130°C over 21 hours. After completion of the
polymerization, the mold was removed from the oven. The obtained
plano lens was further annealed at 130°C for 2 hours. The obtained
plano lens had a transparency and had a refractive index (n€) of 1. 60,
15 an Abbe number (ve) of 39, and a heat resistance of 114°C, and was
suitable as a transparent resin for optical matBrials. Th€
ultraviolet-visible light spectrum of the obtained plano lens was
measured using a spectrophotometer UV-1600 (produced by Shimadzu
Corp.). The evaluation results are shown in Table 2.
20 [0096]
[Example 11]
A 2 mm thick plano lens was obtained by the same method as Example
10 except that 1.5 parts by weight of the mixture (EVERSORB 109
produced by EVER LIGHT) of
25 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
52
l] propionate 2-ethyl hexyl was changed to 3. 0 parts by weight. The
obtained plano lens had a transparency and had a refractive index
(ne) of 1.60, an Abbe number (ve) of 39, and a heat resistance of
ll2°C, and was suitable as a transparent resin for optical materials.
5 The ultraviolet-visible light spectrum of the obtained plano lens
was measured using a spectrophotometer UV-1600 (produced by Shimadzu
Corp.). The evaluation results are shown in Table 2.
10
[0097]
[Example 12]
A homogeneous solution was obtained by stirring and mixing 0. 1
part by weight of ZelecUN (produced by STEPAN) , 1. 5 parts by weight
of a mixture (EVERSORB 109 produced by EVER LIGHT) of
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
1] octyl propionate and
15 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] propionate 2-ethyl hexyl, 29.19 parts by weight of a mixture of
2,5-bis (isocyanatomethyl) bicyclo-[2.2.1]-heptane and 2,6-bis
(isocyanatomethyl) bicyclo-[2.2.1]-heptane, and 19.48 parts by
weight of 1,6-hexamethylene diisocyanate at 20°C. A mixed solution
20 was obtained by adding 27.85 parts by weight of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 23.48 parts by
weight of pentaerythritol tetrakis (3-mercaptopropionate), and 0. 04
parts by weight of dimethyltin (II) dichloride to the above
homogeneous solution, and mixing and stirring at 20°C. After this
25 mixed solution was defoamed at 600 Pa for 1 hour and filtrated with
a 1 ~m PTFE filter, the mixed solution was introduced into a mold
formed of a 2C plano glass mold with a center thickness of 2 mm and
53
a diameter of 80 mm and a flat glass mold with a center thickness
of 2 mm and a diameter of 78 mm. This mold was placed in a
polymerization oven and polymerization was carried out by gradually
raising the temperature from 20°C to l30°C over 21 hours. After
5 completion of the polymerization, the mold was removed from the oven.
The obtained plano lens was further annealed at 130°C for 2 hours.
The obtained plano lens had a transparency and had a refractive index
(ne) of 1.60, an Abbe number (ve) of 39, and a heat resistance of
92°C, and was sui table as a transparent resin for optical materials.
10 The ultraviolet-visible light spectrum of the obtained plano lens
was measured using a spectrophotometer UV-1600 (produced by Shimadzu
Corp.). The evaluation results are shown in Table 2.
15
[0098]
[Example 13]
A homogeneous solution was obtained by stirring and mixing 0.1
parts by weight of ZelecUN (produced by STEPAN) , 1. 5 parts by weight
of a mixture (EVERSORB 109 produced by EVER LIGHT) of
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] octyl propionate and
20 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] propionate 2-ethyl hexyl, 24.15 parts by weight of
1,5-pentamethylene diisocyanate, and 28.15 parts by weight of a
polyisocyanate which includes isocyanurate of 1,5-pentamethylene
diisocyanate at 20°C. A mixed solution was obtained by adding 33.1
25 parts by weight of a mixture of
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
54
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 14.65
parts by weight of pentaerythritol tetrakis (3-mercaptopropionate),
0.03 parts by weight of 1-benzyl-2-methylimidazole to the above
homogeneous solution and mixing and stirring at 20°C. P"fter this
5 mixed solution was defoamed at 600 Pa for 1 hour and filtrated with
a 1 ~ PTFE filter, the mixed solution was introduced into a mold
formed of a 2C plano glass mold with a center thickness of 2 mm and
a diameter of 80 mm and a flat glass mold with a center thickness
of 2 mm and a diameter of 78 mm. This mold was placed in a
10 polymerization oven and polymerization was carried out by gradually
raising the temperature from 20°C to 130°C over 21 hours. After
completion of the polymerization, the mold was removed from the oven.
The obtained plano lens was further annealed at 130°C for 2 hours.
The obtained plano lens had a transparency and had a refractive index
15 (ne) of 1.60, an Abbe number (ve) of 39, and a heat resistance of
85°C, and was suitable as a transparent resin for optical materials.
The ultraviolet-visible light spectrum of the obtained plano lens
was measured using a spectrophotometer UV-1600 (produced qy Shimadzu
Corp.). The evaluation results are shown in Table 2.
20 [0099]
[Comparative Example 1]
A homogeneous solution was obtained by stirring and mixing 0. 1
parts by weight of ZelecUN (produced by STEPAN) , 0. 6 parts by weight
of 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole
25 (TINUVIN 326 produced by BASF Corp.), and 58.9 parts by weight of
bis (4-isocyanatocyclohexyl) methane at 20°C. A mixed solution was
obtained by adding 41.1 parts by weight of a mixture of
55
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and
0.15 parts by weight of dibutyltin (II) dichloride to the above
5 homogeneous solution and stirring and mixing at 20°C. After this
mixed solution was defoamed at 600 Pa for 1 hour and filtrated with
a 1 pm PTFE filter, the mixed solution was introduced into a mold.
This mold was placed in a polymerization oven and polymerization was
carried out by gradually raising the temperature from 20°C to 130°C
10 over 21 hours. After completion of the polymerization, the mold was
removed from the oven. The obtained plano lens was further annealed
at 130°C for 2 hours. The obtained 2 mm plano lens had a transparency
and had a refractive index (ne) of 1.60, an Abbe number (ve) of 40,
and a heat resistance of 134°C. The ultraviolet-visible light
15 spectrum of the obtained plano lens was measured using a
spectrophotometer UV-1600 (produced by Shimadzu Corp.). The
evaluation results are shown in Table 1.
20
[0100]
[Comparative Example 2]
A 2 rnm thick plano lens was obtained by the same method as
Comparative Example 1 except that 0.6 parts by weight of
2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole
( TINUVIN 32 6 produced by BASF Corp. ) was changed to 1. 1 parts by weight.
Here, when the dissolution completion time of the ultraviolet
25 absorber was confirmed, the ultraviolet absorber took 100 minutes
to completely dissolve. The obtained plano lens had a transparency,
and had a refractive index (ne) of 1.60, an Abbe's number (ve) of
56
39, and a heat resistance of 134°C. The ultraviolet-visible light
spectrum of the obtained plano lens was measured using a
spectrophotometer UV-1600 (produced by Shimadzu Corp.). The
evaluation results are shown in Table 1.
5 [0101]
[Comparative Example 3]
The experiment was carried out by the same method a.s Comparative
Example l except that 0.6 parts by weight of
2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole
10 (TINUVIN 326 produced by BASF Corp.) was changed to 1.2 parts by weight
but the dissolution was not completed and the mixed solution was
suspended. After defoaming and filtering in accordance with
Comparative Example 1, the mixed solution was transparent. After
this mixed solution was defoamed at 600 Pa for 1 hour and filtrated
15 with a 1 pm PTFE filter, the mixed solution was introduced into a
mold. At this time, the viscosity of the polymerizable composition
increased and it was difficult to introduce the composition into the
mold. This mold was placed in a polymerization oven and
polymerization was carried out by gradually raising the temperature
20 from 20°C to 130°C over 21 hours. After completion of the
polymerization, the mold was removed from the oven. The obtained
plano lens was further annealed at 130°C for 2 hours. The obtained
2 mm thick plano lens was cloudy and unsuitable as a transparent resin
for optical materials.
25
57
[ 0102]
Table 1
Parts by
Campa rat Comparat Comparat
weight
Example 1 J:'_;xample 2 Example 3 Example 4 Example 5 Example 6 ive ive ive
Example 1 xample2 Example 3
Isocyanat
e
compound
a-1 58.9 58.9 58.9 58.9 58.9 58.9 58.9 58.9 58.9
Active
hydrogen
compound
b-1 41.1 41.1 41.1 41.1 41.1 41.1 41.1 41.1 41.1
Ultraviol
et
absorber
c-1
1.5 3.0 5.0 1.5 2.0 5.0
- - -
(15000) (30000) (50000) (15000) (20000) (50000)
c-2
- - - 0.6 0.6 0.6 0.6 1.1 1.2
(6000) ( 6000) (6000) I 60001 (11000) (12000)
ZelecUN 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Dibutylti I
n (II)
0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 dichlorid
!
e
Dissoluti
on
Completio lOrain 10min 30min 30min 30min 30min 30min 100rnin
Uncomple
n Tline ed
(20"C)
Light
transmiss
ion
rate~ %
410nm 1.3 0.1 0.1 0.1 0.1 0.1 0.3 0.1 -
420nm 42.0 22.6 10.6 11.7 9.6 6.5 27.0 15.9 -
440ma 87.7 86.4 84.8 83.9 83.5 82.8 86.4 85.9 -
Transpare Transpar Transpar Transpar Transpar Transpar Transpar Transpar Transpar ~ot
pcy ent ent ent ent ent ent ent ent
transpar
ent
Refractiv
e index 1. 60 1. 60 1. 60 1. 60 1. 60 1. 60 1. 60 1. 60 -
(ne)
fAbbe
number 39 39 39 39 39 39 40 39 -
(ve)
Heat
resistanc 125 122 1]7 123 122 117 134 134 -
e: Tg
In parentheses is the amount (ppm) of the ultraviolet absorber with
respect to the total amount of the isocyanate compound and the active
5 hydrogen compound.
58
[0103]
Table 2
Parts by Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 weight Example 13
Isocyanate
compound
a-1
a-2 56.1 56.1 56.1
a-3 50.6 50.6 29.19
a-4 19.48
a-5 24.15
a-6 28.15
Active
hydrogen
compound
b-1 33.1
b-2 43.9 43.9 43.9 25.5 25.5 27.85
b-3 23.9 23.9 23.48 14.65
Ultraviolet
absorber
c-1
1.5 3.0 5.0 1.5 3.0 1.5 1.5
(15000) (30000) (50000) 115000 I (30000) (15000) (15000)
Dissolution
Completion 10min 10min 30min 10min _lQmin 10min lOmin
Time (20"C)
Light
transmissio
n rate: %
410nm 0.1 0.1 0.1 0.3 0.1 0.1 0.3
420nm 40.9 22.7 10.0 41.5 20.4 39.1 40.8
440nm . 87.3 85.5 84.9 87.3 85.4 82.9 84.2
Transparenc Transparen Transparen Transparen Transparen Transparen Transparen Transparen
y t t t ~- t t t
RefrB..Ctive -~
1.60
index (ne)
1. 60 1. 60 1. 60 1. 60 1. 60 1. 60
Abbe number
(ve)
39 38 38 39 39 39 39
Heat
resistance: 129 124 120 114 112 92 85
Tg
In parentheses is the amount (ppm) of the ultraviolet absorber with
respect to the total amount o:' the isocyanate compound and the active
5 hydrogen compound.
5
10
59
[0104]
The isocyanate compound, active hydrogen compound, and
ultraviolet absorber described in Table 1 and Table 2 are as follows.
a-1: bis (4-isocyanatocyclohexyl) methane
a-2: isophorone diisocyanate
a-3: a mixture of 2,5-bis (isocyanatomethyl)
bicyclo-[2.2.1]-heptane and 2,6-bis (isocyanatornethyl)
bicyclo-[2.2.1]-heptane
a-4: 1,6-hexamethylene diisocyanate
a-5: 1,5-pentarnethylene diisocyanate
a-6: polyisocyanate which includes isocyanurate of
1,5-pentamethylene diisocyanate
b-1: a mixture of
5,7-dimercaptornethyl-1,11-dirnercapto-3,6,9-trithiaundecane,
15 4,7-dirnercaptomethyl-1,11-dirnercapto-3,6,9-trithiaundecane, and
4,8-dimercaptornethyl-1,11-dimercapto-3,6,9-trithiaundecane
b-2: 4-mercaptomethyl-1,8-dirnercapto-3,6-dithiaoctane
b-3: pentaerythritol tetrakis (3-mercaptopropionate)
c-1: a mixture of
20 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxypheny
l] octyl propionate and
3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4~hydroxypheny
l] propionate 2-ethyl hexyl
c-2:
25 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-chlorobenzotriazole
[0105]
From Table 1 and Table 2, in each example, it is possible to
5
60
quickly dissolve the ultraviolet absorber while the concentration
of the ultraviolet absorber in the polymerizable composition was
higher than the concentration in each comparative example, and each
example was superior in product productivity.
In addition, the lenses obtained in each example have a
transparent and excellent appearance, and are excellent in the
balance between each characteristic .of the characteristic of
suppressing the transmission of light having a wavelength of 410 to
440 nm, the optical characteristics of a high refractive index and
10 a high Abbe number, and heat resistance.
[0106]
This application claims priority based on Japanese Patent
Application No. 2015-018141 filed on February 2, 2015, the disclosure
of which is incorporated herein in its entirety.

CLAIMS
1. A polymerizable composition for an optical material comprising:
(A) an isocyanate compound;
5 (B) an active hydrogen compound; and
(C) one or more types of ultraviolet absorber represented by
General Formula (1) below and having a maximum absorption peak in
a range of equal to or more than 350 nm and equal to or less than
370 nm;
10 [Chern. 1]
HO
Cl (1)
(in General Formula (1) above, R1 and R2 represent an alkyl group having
1 to 8 carbon atoms and.may be same or different from each other,
a plurality of R1 present or a plurality of R2 present may be same
15 or different, m represents an integer of 0 to 3, n represents an integer
of 0 to 3, and R3 represents a functional group having 2 to 15 carbon
atoms which includes an ester bond) .
2. The polymerizable composition for an optical material according
20 to claim 1,
wherein the ultraviolet absorber (C) is represented by General
Formula (2) below and is one or more types of ultraviolet absorber
having a maximum absorption peak in a range of equal to or more than
62
350 nrn and equal to or less than 370 nrn;
[Chern. 2]
HO
Cl
(2)
(in General Formula (2) above, R1 , R2 , rn, and n have the same meanings
5 as in General Formula (1), R4 and R5 independently represent a
hydrocarbon group having 1 to 10 carbon atoms which may be branched) .
3. The polyrnerizable composition for an optical material according
to claim 2,
10 wherein the ultraviolet absorber (C) is represented by General
Formula (3) below and is one or more types of ultraviolet absorber
having a maximum absorption peak in a range of equal to or more than
350 nrn and equal to or less than 370 nrn;
[Chern. 3]
HO
N
~\ f N--...
~I
Cl
N
R4-c--o--R5
II
15
0 ( 3)
(in General Formula (3) above, R2 , R4 , and R5 have the same meanings
as in General Formula (1) or (2)).
63
4. The polymerizable composition for an optical material according
to any one of claims 1 to 3,
wherein the isocyanate compound (A) includes an alicyclic
5 isocyanate compound.
5. The polymerizable composition for an optical material according
to any one of claims 1 to 4,
wherein the isocyanate compound (A) is at least one type selected
10 from the group consisting of hexamethylene diisocyanate,
pentamethylene diisocyanate, xylylene diisocyanate, isophorone
diisocyanate, bis (isocyanatomethyl) cyclohexane, bis
(isocyanatocyclohexyl) methane, 2,5-bis (isocyanatomethyl)
bicyclo-[2.2.1]-heptane, 2,6-bis (isocyanatomethyl)
15 bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene
diisocyanate, and 4,4'-diphenylmethane diisocyanate.
20
25
6. The polymerizable composition for an optical material according
to any one of claims 1 to 5,
wherein the active hydrogen compound (B) is at least one type
selected from the group consisting of a polythiol compound having
two or more mercapto groups, a hydroxy thiol compound having one or
more mercapto groups and one or more hydroxyl groups, a polyol compound
having two or more hydroxyl groups, and an amine compound.
7. The polymerizable composition for an optical material according
to claim 6,
64
wherein the polythiol compound is at least one selected from
the group consisting of
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
5 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol
tetrakis (2-mercaptoacetate), pentaerythritol tetrakis
(3-mercaptopropionate), 2,5-bis (mercaptomethyl)-1,4-dithiane, bis
(mercaptoethyl) sulfide, 1,1,3,3-tetrakis (mercaptomethylthio)
10 propane, 4, 6-bis (mercaptomethylthio) -1, 3-di thiane, 2- (2, 2-bis
(rnercaptomethylthio) ethyl)-1,3-dithietane, 1,1,2,2-tetrakis
(mercaptomethylthio) ethane,
3-rnercaptomethyl-1,5-dirnercapto-2,4-dithiapentane, tris
(rnercaptomethylthio) methane, and ethylene glycol bis
15 (3-mercaptopropionate) .
8. The polymerizable composition for an optical material according
to any one of claims 1 to 7, further comprising:
an ultraviolet absorber having a structure other than the
2 0 structure of General Formula ( 1) and having a maximum absorption peak
in a range of equal to or more than 350 nm and equal to or less than
370 nm.
9. The po1ymerizable composition for an optical material according
25 to any one of claims 1 to 8,
wherein the ultraviolet absorber (C) is included in an amount
of 0.1 to 10.0% by weight in 100% by weight of the polymerizable
65
composition for an optical material.
10. A molded article obtainable by curing the polymerizable
composition for an optical material according to any one of claims
5 l to 9.
ll. The molded article according to claim 10 comprising 0.1 to 10.0%
by weight of the ultraviolet absorber (C) .
10 12. An optical material constituted of the molded article according
to claim 10 or 11.
13. A plastic lens formed of the optical material according to claim
12.
15
14. A method for manufacturing an optical material, the method
comprising:
a step of cast polymerizing the polymerizable composition for
an optical material according to any one of claims 1 to 9.
20
15. Use of a molded article obtainable by heating and curing the
polymerizable composition for an opt:Ltal material according to any
one of claims 1 to 9 as an optical material.