U.S. patent application number 15/124873 was filed with the patent office on 2017-01-19 for polymerizable composition for optical material and optical material.
This patent application is currently assigned to MITSUI CHEMICALS, INC.. The applicant listed for this patent is MITSUI CHEMICALS, INC.. Invention is credited to Kenichi GOTO, Masaru KAWAGUCHI, Toshihiko NAKAGAWA, Hidetaka TSUKADA, Satoshi YAMASAKI.
Application Number | 20170015776 15/124873 |
Document ID | / |
Family ID | 54071843 |
Filed Date | 2017-01-19 |
United States Patent
Application |
20170015776 |
Kind Code |
A1 |
TSUKADA; Hidetaka ; et
al. |
January 19, 2017 |
POLYMERIZABLE COMPOSITION FOR OPTICAL MATERIAL AND OPTICAL
MATERIAL
Abstract
A polymerizable composition for an optical material of the
present invention includes polyisocyanate (a) including aliphatic
polyisocyanate (a1) and a modified aliphatic polyisocyanate (a2),
an episulfide (b), and a polythiol (c).
Inventors: |
TSUKADA; Hidetaka;
(Omuta-shi, JP) ; GOTO; Kenichi; (Chiba-shi,
JP) ; NAKAGAWA; Toshihiko; (Ichihara-shi, JP)
; YAMASAKI; Satoshi; (Chiba-shi, JP) ; KAWAGUCHI;
Masaru; (Omuta-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MITSUI CHEMICALS, INC. |
Minato-ku, Tokyo |
|
JP |
|
|
Assignee: |
MITSUI CHEMICALS, INC.
Minato-ku, Tokyo
JP
|
Family ID: |
54071843 |
Appl. No.: |
15/124873 |
Filed: |
March 11, 2015 |
PCT Filed: |
March 11, 2015 |
PCT NO: |
PCT/JP2015/057165 |
371 Date: |
September 9, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 18/022 20130101;
B29K 2075/00 20130101; G02B 1/041 20130101; B29K 2995/0034
20130101; B29D 11/00644 20130101; C08G 18/758 20130101; G02C
2202/16 20130101; C07D 331/02 20130101; B29K 2105/20 20130101; C08G
18/753 20130101; C08G 18/3874 20130101; G02B 1/04 20130101; G02B
1/04 20130101; G02C 7/12 20130101; G02B 1/04 20130101; C08G 18/3876
20130101; C08J 5/00 20130101; B29D 11/00009 20130101; C08L 81/00
20130101; B29D 11/00442 20130101; C08J 2375/04 20130101; C08G
18/792 20130101; C08G 18/73 20130101; C08L 75/04 20130101 |
International
Class: |
C08G 18/38 20060101
C08G018/38; C08G 18/73 20060101 C08G018/73; G02C 7/12 20060101
G02C007/12; B29D 11/00 20060101 B29D011/00; G02B 1/04 20060101
G02B001/04; C08G 18/79 20060101 C08G018/79; C08J 5/00 20060101
C08J005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 11, 2014 |
JP |
2014-047890 |
Sep 12, 2014 |
JP |
2014-185995 |
Claims
1. A polymerizable composition for an optical material including:
polyisocyanate (a) including aliphatic polyisocyanate (a1) and a
modified aliphatic polyisocyanate (a2); an episulfide (b); and a
polythiol (c).
2. The polymerizable composition for an optical material according
to claim 1, wherein the modified aliphatic polyisocyanate (a2) is
an isocyanurate of the aliphatic polyisocyanate.
3. The polymerizable composition for an optical material according
to claim 1, wherein the aliphatic polyisocyanate (a1) and/or the
aliphatic polyisocyanate in the modified aliphatic polyisocyanate
(a2) are obtained from plant-derived materials.
4. The polymerizable composition for an optical material according
to claim 1, wherein the episulfide (b) includes an episulfide
represented by Formula (1): ##STR00006## wherein in the formula
(1), n represents 0 or 1.
5. The polymerizable composition for an optical material according
to claim 1, wherein the episulfide (b) includes an episulfide
obtained from plant-derived materials.
6. The polymerizable composition for an optical material according
to claim 1, wherein the aliphatic polyisocyanate (a1) and/or the
aliphatic polyisocyanate in the modified aliphatic polyisocyanate
(a2) is at least one selected from 1,5-pentamethylene diisocyanate,
1,6-hexamethylene diisocyanate, 1,7-heptamethylene diisocyanate,
lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate,
octamethylene diisocyanate, and decamethylene diisocyanate.
7. The polymerizable composition for an optical material according
to claim 1, wherein the polythiol (c) is at least one selected from
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8 or 4,7 or
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
pentaerythritol tetrakis mercaptoacetate, pentaerythritol tetrakis
mercaptopropionate, 2,5-bis(mercaptomethyl)-1,4-dithiane,
bis(mercaptoethyl)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(mercaptomethylthio) methane, and ethylene glycol
bis(3-mercaptopropionate).
8. The polymerizable composition for an optical material according
to claim 1, wherein the polythiol (c) is a polythiol obtained from
plant-derived materials, and is selected from
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 4,8 or 4,7 or
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.
9. A molding comprising: a resin obtained by polymerizing and
curing the polymerizable composition for an optical material
according to claim 1.
10. The molding according to claim 9, wherein the resin has a
degree of biomass of greater than or equal to 25%.
11. The molding according to claim 9, wherein the molding has a
refractive index of higher than or equal to 1.60.
12. The molding according to claim 9, wherein the molding has a
glass transition temperature (Tg) of higher than or equal to
60.degree. C.
13. An optical material formed of the molding according to claim
9.
14. A plastic spectacle lens formed of the molding according to
claim 9.
15. A plastic polarizing lens, comprising: a polarizing film; and a
layer formed of the molding according to claim 9, wherein the layer
is laminated on at least one surface of the polarizing film.
16. A method for manufacturing a plastic spectacle lens,
comprising: a step of injecting the polymerizable composition for
an optical material according to claim 1 into a mold for lens
casting; and a step of polymerizing and curing the polymerizable
composition for an optical material.
17. A method for manufacturing a plastic polarizing lens,
comprising: a step of fixing a polarizing film into a lens casting
mold in a state in which at least one surface of the polarizing
film is separated from a mold; a step of injecting the
polymerizable composition for an optical material according to
claim 1 into a gap between the polarizing film and the mold; and a
step of laminating a layer formed of a polythiourethane resin on at
least one surface of the polarizing film by polymerization and
curing the polymerizable composition for an optical material.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polymerizable composition
for an optical material, an optical material obtained using the
same, and a plastic lens.
BACKGROUND ART
[0002] Compared with inorganic lenses, plastic lenses have a low
weight, are not easily cracked, and can be dyed, and thus,
recently, have rapidly become widespread in optical elements such
as spectacle lenses and camera lenses.
[0003] For resins for plastic lenses, there has been a demand for
additional improvement in performance, and there has been a demand
for an increase in the refractive index, an increase in the Abbe
number, a decrease in the specific weight, an improvement of the
heat resistance, and the like. Thus far, a variety of resin
materials for lenses have been developed and put into use.
[0004] Among them, optical materials made of sulfide-based resins
have a high refractive index and a high Abbe number and are being
studied as ultrahigh refractive index materials having a refractive
index of higher than or equal to 1.60. Sulfide-based resins are
obtained by polymerizing a polymerizable composition including an
episulfide compound (Patent Documents 1 to 4). In recent years, a
variety of studies also have been carried out in order to improve
the quality of episulfide compounds and resins for optical
materials obtained from the episulfide compounds (Patent Documents
5 and 6).
[0005] Meanwhile, for plastic materials for which fossil resources
are used, there has been a concern regarding the influences on the
global environment such as resource depletion or the emission of
carbon dioxide, and, in the development of materials as well,
studies have been carried out regarding the utilization of biomass
resources such as plant-derived materials.
[0006] Regarding epichlorohydrin as well which is a raw material of
episulfide compounds, a manufacturing route in which
epichlorohydrin is synthesized by means of chlorination or
epoxidation of glycerin originating from natural products has been
developed instead of a manufacturing route in which epichlorohydrin
is synthesized from a fossil raw material (propylene, allyl
alcohol, or the like) of the related art and the application of the
manufacturing route to epoxy resins and the like is being studied
(Patent Document 7). However, no studies are being carried out
regarding optical material use.
[0007] As plastic lens materials obtained using plant-derived
materials, a spectacle lens which includes a polycarbonate resin
having a constituent unit derived from isosorbide as a main
component and is obtained by means of injection molding is proposed
(Patent Document 8). This enables the obtainment of optical lenses
having high heat resistance, high strength, and low distortion
which are manufactured from plant-derived materials, but there is
room for improvement in optical properties such as the refractive
index.
[0008] Furthermore, in Patent Document 9, a resin for which
plant-derived materials are used is proposed, but this resin is not
for use as an ultrahigh refractive index material having a
refractive index of higher than or equal to 1.60, and any optical
properties and the like of the obtained resin are not
exhibited.
RELATED DOCUMENT
Patent Document
[0009] [Patent Document 1] Japanese Unexamined Patent Publication
No. 2002-194083
[0010] [Patent Document 2] Japanese Unexamined Patent Publication
No. 2000-256435
[0011] [Patent Document 3] Japanese Unexamined Patent Publication
No. 2001-163874
[0012] [Patent Document 4] Pamphlet of International Publication
No. WO2013/115212
[0013] [Patent Document 5] Pamphlet of International Publication
No. WO2013/157490
[0014] [Patent Document 6] Japanese Unexamined Patent Publication
No. 2013-142073
[0015] [Patent Document 7] PCT Japanese Translation Patent
Publication No. 2013-541531
[0016] [Patent Document 8] Japanese Unexamined Patent Publication
No. 2010-190919
[0017] [Patent Document 9] Japanese Unexamined Patent Publication
No. 2011-225863
SUMMARY OF THE INVENTION
[0018] An object of the present invention is to provide a
polymerizable composition for an optical material which has an
excellent balance among transparency, heat resistance, and the like
and can be used to obtain ultrahigh refractive index plastic lens
materials having a refractive index of higher than or equal to 1.60
and an optical material that can be obtained from the same.
[0019] As a result of intensive studies, the present inventors
found that a certain composition for which an episulfide compound
is used enables the provision of optical materials such as
ultrahigh refractive index plastic lenses which have an excellent
balance among transparency, refractive index, heat resistance, and
the like and have a refractive index of higher than 1.60 and
completed the present invention.
[0020] That is, the present invention can be described as
below.
[0021] [1] A polymerizable composition for an optical material
including: polyisocyanate (a) including aliphatic polyisocyanate
(a1) and a modified aliphatic polyisocyanate (a2); an episulfide
(b); and a polythiol (c).
[0022] [2] The polymerizable composition for an optical material
according to [1], in which the modified aliphatic polyisocyanate
(a2) is an isocyanurate of the aliphatic polyisocyanate.
[0023] [3] The polymerizable composition for an optical material
according to [1] or [2], in which the aliphatic polyisocyanate (a1)
and/or the aliphatic polyisocyanate in the modified aliphatic
polyisocyanate (a2) are obtained from plant-derived materials.
[0024] [4] The polymerizable composition for an optical material
according to any one of [1] to [3], in which the episulfide (b)
includes an episulfide represented by General Formula (1)
below:
##STR00001##
[0025] in the formula, n represents 0 or 1.
[0026] [5] The polymerizable composition for an optical material
according to any one of [1] to [4], in which the episulfide (b)
includes an episulfide obtained from plant-derived materials.
[0027] [6] The polymerizable composition for an optical material
according to any one of [1] to [5], in which the aliphatic
polyisocyanate (a1) and/or the aliphatic polyisocyanate in the
modified aliphatic polyisocyanate (a2) are at least one selected
from 1,5-pentamethylene diisocyanate, 1,6-hexamethylene
diisocyanate, 1,7-heptamethylene diisocyanate, lysine diisocyanate,
lysine triisocyanate, dimer acid diisocyanate, octamethylene
diisocyanate, and decamethylene diisocyanate.
[0028] [7] The polymerizable composition for an optical material
according to any one of [1] to [6], in which the polythiol (c) is
at least one selected from
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8 or 4,7 or
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
pentaerythritol tetrakis mercaptoacetate, pentaerythritol tetrakis
mercaptopropionate, 2,5-bis(mercaptomethyl)-1,4-dithiane,
bis(mercaptoethyl)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(mercaptomethylthio) methane, and ethylene glycol
bis(3-mercaptopropionate).
[0029] [8] The polymerizable composition for an optical material
according to any one of [1] to [7], in which the polythiol (c) is a
polythiol obtained from plant-derived materials, and is selected
from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 4,8 or
4,7 or
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.
[0030] [9] A molding containing a resin obtained by polymerizing
and curing the polymerizable composition for an optical material
according to any one of [1] to [8].
[0031] [10] The molding according to [9] in which the resin has a
degree of biomass of greater than or equal to 25%.
[0032] [11] The molding according to [9] or [10], in which the
molding has a refractive index of higher than or equal to 1.60.
[0033] [12] The molding according to any one of [9] to [11], in
which the molding has a glass transition temperature (Tg) of higher
than or equal to 60.degree. C.
[0034] [13] An optical material formed of the molding according to
any one of [9] to [12].
[0035] [14] A plastic spectacle lens formed of the molding
according to any one of [9] to [12].
[0036] [15] A plastic polarizing lens, comprising: a polarizing
film; and a layer formed of the molding according to any one of [9]
to [12] in which wherein the layer is laminated on at least one
surface of the polarizing film.
[0037] [16] A method for manufacturing a plastic spectacle lens,
comprising: a step of injecting the polymerizable composition for
an optical material according to any one of [1] to [8] into a mold
for lens casting; and a step of polymerizing and curing the
polymerizable composition for an optical material.
[0038] [17] A method for manufacturing a plastic polarizing lens,
comprising: a step of fixing a polarizing film into a lens casting
mold in a state in which at least one surface of the polarizing
film is separated from a mold; a step of injecting the
polymerizable composition for an optical material according to any
one of [1] to [8] into a gap between the polarizing film and the
mold; and a step of laminating a layer formed of a polythiourethane
resin on at least one surface of the polarizing film by
polymerization and curing the polymerizable composition for an
optical material.
[0039] According to the polymerizable composition for an optical
material of the present invention, it is possible to obtain an
optical material such as an ultrahigh refractive index plastic lens
which has an excellent balance among transparency, refractive
index, heat resistance, dyeing properties, and the like and has a
refractive index of higher than or equal to 1.60.
[0040] Furthermore, when a compound obtained from plant-derived
materials is used, it is possible to provide an optical material
such as a plastic lens having a degree of biomass of higher than or
equal to 25%.
DESCRIPTION OF EMBODIMENTS
[0041] The present invention will be described on the basis of an
embodiment.
[0042] A polymerizable composition for an optical material of the
present embodiment includes polyisocyanate (a) including aliphatic
polyisocyanate (a1) and a modified aliphatic polyisocyanate (a2),
an episulfide (b), and a polythiol (c).
[0043] First, the respective components will be described.
[0044] (Polyisocyanate (a))
[0045] The polyisocyanate (a) includes aliphatic polyisocyanate
(a1) and a modified aliphatic polyisocyanate (a2).
[0046] Examples of the aliphatic polyisocyanate (a1) and the
aliphatic polyisocyanate in the modified aliphatic polyisocyanate
(a2) include trimethylene diisocyanate, tetramethylene
diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene
diisocyanate, 1,7-heptamethylene diisocyanate,
2,2,4-trimethylhexamethylene diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate,
lysine diisocyanatomethyl ester, lysine triisocyanate, m-xylylene
diisocyanate, .alpha.,.alpha.,.alpha.',.alpha.'-tetramethylxylylene
diisocyanate, bis(isocyanatomethyl) naphthalene, mesitylene
triisocyanate, bis(isocyanatomethyl)sulfide,
bis(isocyanatoethyl)sulfide, bis(isocyanatomethyl)disulfide,
bis(isocyanatoethyl)disulfide, bis(isocyanatomethylthio) methane,
bis(isocyanatoethylthio) methane, bis(isocyanatoethylthio) ethane,
bis(isocyanatomethylthio) ethane, dimer acid diisocyanate,
octamethylene diisocyanate, decamethylene diisocyanate, and the
like. From the viewpoint of the improvement of transparency, the
adjustment of the refractive index, and the handling properties
(viscosity) of compositions to be obtained, preferred examples
thereof include 1,5-pentamethylene diisocyanate, 1,6-hexamethylene
diisocyanate, 1,7-heptamethylene diisocyanate, lysine diisocyanate,
lysine triisocyanate, dimer acid diisocyanate, octamethylene
diisocyanate, decamethylene diisocyanate, and the like, and the
aliphatic polyisocyanates may be used alone, or two or more may be
used in combination.
[0047] Examples of the modified aliphatic polyisocyanate (a2)
include a multimeric, a biuret modified, an allophanate modified,
an oxadiazinetrione modified, a polyol modified aliphatic
polyisocyanate, and the like.
[0048] Examples of the multimers of the aliphatic polyisocyanate
include multimers such as dimers such as uretdione, urethoimine,
and carbodiimide, and trimers and higher such as an isocyanurate
and iminooxadiazinedione.
[0049] An isocyanurate as the aliphatic polyisocyanate can be
obtained by performing a reaction of aliphatic polyisocyanate in
the presence of a well-known isocyanurate-forming catalyst.
[0050] The biuret modified aliphatic polyisocyanate can be obtained
by reacting aliphatic polyisocyanate and, for example, water, a
tertiary alcohol (for example, t-butyl alcohol), a secondary amine
(for example, dimethylamine or diethylamine), or the like, and then
performing an additional reaction in the presence of a well-known
biuret-forming catalyst.
[0051] The allophanate modified aliphatic polyisocyanate can be
obtained by reacting aliphatic polyisocyanate and a monoalcohol (a
monovalent alcohol, for example, C1 to C10 alcohol), and then
performing an additional reaction in the presence of a well-known
allophanate-forming catalyst.
[0052] The oxadiazinetrione modified aliphatic polyisocyanate can
be obtained from a reaction between aliphatic polyisocyanate and
carbon dioxide.
[0053] The iminooxadiazinedione modified aliphatic polyisocyanate
can be obtained by further reacting aliphatic polyisocyanate in the
presence of a well-known catalyst for forming
imino-oxadiazinedione.
[0054] The polyol modified aliphatic polyisocyanate can be obtained
from a reaction between aliphatic polyisocyanate and an alcohol.
Alcohols that are used to obtain the modified aliphatic
polyisocyanate are tertiary alcohols, monoalcohols, and polyvalent
alcohols, preferred examples thereof include trivalent alcohols
such as glycerin and trimethylolpropane, and the alcohols are more
preferably plant-derived compounds.
[0055] The modified aliphatic polyisocyanate (a2) may be used
alone, or two or more may be used in combination.
[0056] Among the modified aliphatic polyisocyanate (a2), multimers
of the aliphatic polyisocyanate are preferred, an isocyanurate of
the aliphatic polyisocyanate is more preferred, and a mononuclear
isocyanurate (trimer) of the aliphatic polyisocyanate is
particularly preferred.
[0057] In the present embodiment, the aliphatic polyisocyanate (a1)
in the polyisocyanate (a) may be identical or different from
aliphatic polyisocyanate used to obtain the modified aliphatic
polyisocyanate (a2), and at least one kind of aliphatic
polyisocyanate can be included.
[0058] As the polyisocyanate (a), it is possible to use a reaction
mixture obtained when the modified aliphatic polyisocyanate (a2) is
prepared. In this case, the reaction mixture includes the aliphatic
polyisocyanate (a1) and the modified aliphatic polyisocyanate (a2).
That is, in the present embodiment, the polyisocyanate (a) can also
be represented as the polyisocyanate composition (a). In addition,
the polyisocyanate (a) can also be obtained by adding at least one
kind of the aliphatic polyisocyanate (a1) that is identical to or
different from the aliphatic polyisocyanate used to prepare the
modified aliphatic polyisocyanate to the prepared modified
aliphatic polyisocyanate.
[0059] When the polyisocyanate (a) includes the modified aliphatic
polyisocyanate (a2) in the form of a mononuclear aliphatic
polyisocyanate (trimer) within a range of 0% by weight to 80% by
weight, preferably within a range of 5% by weight to 75% by weight,
and more preferably within a range of 10% by weight to 70% by
weight of the polyisocyanate (a), it is possible to provide a
molding formed of an optical material resin having superior
properties such as transparency, refractive index, and heat
resistance.
[0060] In the present embodiment, from the viewpoint of obtaining
optical resins having a high degree of biomass, the aliphatic
polyisocyanate (a1) or the aliphatic polyisocyanate in the modified
aliphatic polyisocyanate (a2) is preferably aliphatic
polyisocyanate obtained from plant-derived materials, and the
aliphatic polyisocyanate (a1) and the aliphatic polyisocyanate in
the modified aliphatic polyisocyanate (a2) are more preferably
aliphatic polyisocyanate obtained from plant-derived materials.
[0061] As the plant-derived aliphatic polyisocyanate, it is
possible to use aliphatic polyisocyanate having 5 to 18 carbon
atoms, and specific examples thereof include 1,5-pentamethylene
diisocyanate, 1,6-hexamethylene diisocyanate, 1,7-heptamethylene
diisocyanate, lysine diisocyanate, lysine triisocyanate, dimer acid
diisocyanate, octamethylene diisocyanate, decamethylene
diisocyanate, and the like, and the plant-derived aliphatic
polyisocyanates may be used alone, or two or more may be used in
combination.
[0062] In the present embodiment, 1,5-pentamethylene diisocyanate
is preferably used.
[0063] The plant-derived aliphatic polyisocyanate can be obtained
by, for example, converting plant-derived divalent carboxylic acid
to a terminal amino group by means of the formation of an acid
amide and reduction and, furthermore, reacting the terminal amino
group with phosgene so as to convert the amino group to an
isocyanate group.
[0064] In addition, the plant-derived aliphatic polyisocyanate can
also be obtained by using an amino acid as a plant-derived material
and converting an amino group thereof to an isocyanate group.
[0065] For example, pentamethylene diisocyanate can be obtained by
decarboxylating a carboxyl group of lysine and then converting an
amino group to an isocyanate group. Examples of the pentamethylene
diisocyanate include 1,5-pentamethylene diisocyanate.
[0066] When aliphatic polyisocyanate obtained from plant-derived
materials is used as the aliphatic polyisocyanate (a1) and/or the
aliphatic polyisocyanate in the modified aliphatic polyisocyanate
(a2), it is possible to provide a molding formed of a resin for an
optical material having a high degree of biomass of higher than or
equal to 25% and having excellent properties such as transparency,
refractive index, and heat resistance.
[0067] In the polymerizable composition for an optical material of
the present embodiment, it is also possible to further use at least
one selected from alicyclic polyisocyanate, aromatic
polyisocyanate, and heterocyclic polyisocyanate in addition to the
polyisocyanate (a).
[0068] Examples of the alicyclic polyisocyanate include
3-isocyanatomethyl-3,5,5-trimethyl cyclohexyl isocyanate,
isophorone diisocyanate, 4,4'-, 2,4'-, or 2,2'-dicyclohexylmethane
diisocyanate and mixtures thereof, 1,4- or 1,
3-bis(isocyanatomethyl) cyclohexane and mixtures thereof, 1,4- or
1,3-bis(isocyanatoethyl) cyclohexane and mixtures thereof,
bis(isocyanatomethyl)-bicyclo[2.2.1] heptane, 1,3-cyclopentane
diisocyanate, 1,4- or 1,3-cyclohexane diisocyanate and mixtures
thereof, methyl-2,4-cyclohexane diisocyanate,
methyl-2,6-cyclohexane diisocyanate, 3,8-bis(isocyanatomethyl)
tricyclodecane, 3,9-bis(isocyanatomethyl) tricyclodecane,
4,8-bis(isocyanatomethyl) tricyclodecane, 4,9-bis(isocyanatomethyl)
tricyclodecane, and the like.
[0069] Meanwhile, bis(isocyanatomethyl)-bicyclo[2.2.1] heptane is a
mixture of isomers of 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]
heptane and 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1] heptane. In
the present embodiment, the compound formed of a mixture of these
isomers can be used as a single kind of compound. The alicyclic
polyisocyanates may be used alone, or two or more may be used in
combination.
[0070] Examples of the aromatic polyisocyanate include tolylene
diisocyanate, 4,4'-diphenylmethane diisocyanate,
2,4'-diphenylmethane diisocyanate, phenylene diisocyanate, and the
like. The aromatic polyisocyanates may be used alone, or two or
more may be used in combination.
[0071] Examples of tolylene diisocyanate include 2,4-tolylene
diisocyanate, 2,6-tolylene diisocyanate, and mixtures of 2,
4-tolylene diisocyanate and 2, 6-tolylene diisocyanate, and, in the
present embodiment, 2, 4-tolylene diisocyanate is preferably
included. Specifically, 2,4-tolylene diisocyanate can be used
singly, or 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate
can be used in the form of mixture, and in a case in which the
mixture is used, the mixing ratio between 2,4-tolylene diisocyanate
and 2,6-tolylene diisocyanate is more preferably within a range of
75:25 to 85:15.
[0072] Examples of the heterocyclic polyisocyanate include
2,5-diisocyanato thiophene, 2,5-bis(isocyanatomethyl) thiophene,
2,5-diisocyanato tetrahydrothiophene, 2,5-bis(isocyanatomethyl)
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,
4,5-bis(isocyanatomethyl)-1,3-dithiolane, and the like. The
heterocyclic polyisocyanates may be used alone, or two or more may
be used in combination.
[0073] It is preferable that the alicyclic polyisocyanate, the
aromatic polyisocyanate, the heterocyclic polyisocyanate, or the
aliphatic polyisocyanate which may be used in combination is the
plant-derived material, and a compound which is not obtained from
the plant-derived material can be used. As it is used, the compound
is may be used such that the degree of biomass of the
polythiourethane resin is in a predetermined range (greater than or
equal to 25%).
[0074] [Episulfide (b)]
[0075] In the present embodiment, examples of the episulfide (b)
include epithioethylthio compounds such as
bis(1,2-epithioethyl)sulfide, bis(1,2-epithioethyl)disulfide,
bis(epithioethylthio) methane, bis(epithioethylthio) benzene,
bis[4-(epithioethylthio) phenyl] sulfide, and
bis[4-(epithioethylthio) phenyl] methane;
[0076] chain aliphatic 2,3-epithiopropylthio compounds such as
compounds having two episulfide groups in the molecule represented
by General Formula (1) below:
##STR00002##
[0077] wherein in the formula (1), n represents 0 or 1;
bis(2,3-epithiopropylthio) methane, 1,2-bis(2,3-epithiopropylthio)
ethane, 1,2-bis(2,3-epithiopropylthio) propane,
1,3-bis(2,3-epithiopropylthio) propane,
1,3-bis(2,3-epithiopropylthio)-2-methylpropane,
1,4-bis(2,3-epithiopropylthio) butane,
1,4-bis(2,3-epithiopropylthio)-2-methylbutane,
1,3-bis(2,3-epithiopropylthio) butane,
1,5-bis(2,3-epithiopropylthio) pentane,
1,5-bis(2,3-epithiopropylthio)-2-methylpentane,
1,5-bis(2,3-epithiopropylthio)-3-thiapentane,
1,6-bis(2,3-epithiopropylthio) hexane,
1,6-bis(2,3-epithiopropylthio)-2-methylhexane,
3,8-bis(2,3-epithiopropylthio)-3,6-dithiaoctane,
1,2,3-tris(2,3-epithiopropylthio) propane,
2,2-bis(2,3-epithiopropylthio)-1,3-bis(2,3-epithiopropylthiometh
yl) propane,
2,2-bis(2,3-epithiopropylthiomethyl)-1-(2,3-epithiopropylthio)
butane,
1,5-bis(2,3-epithiopropylthio)-2-(2,3-epithiopropylthiomethyl)-3--
thiapentane,
1,5-bis(2,3-epithiopropylthio)-2,4-bis(2,3-epithiopropylthiometh
yl)-3-thiapentane,
1-(2,3-epithiopropylthio)-2,2-bis(2,3-epithiopropylthiomethyl)-4-thiahexa-
ne,
1,5,6-tris(2,3-epithiopropylthio)-4-(2,3-epithiopropylthiomethyl-3-thi-
ahexane,
1,8-bis(2,3-epithiopropylthio)-4-(2,3-epithiopropylthiomethyl)-3,-
6-dithiaoctane,
1,8-bis(2,3-epithiopropylthio)-4,5-bis(2,3-epithiopropylthiometh
yl)-3,6-dithiaoctane,
1,8-bis(2,3-epithiopropylthio)-4,4-bis(2,3-epithiopropylthiometh
yl)-3,6-dithiaoctane,
1,8-bis(2,3-epithiopropylthio)-2,5-bis(2,3-epithiopropylthiometh
yl)-3,6-dithiaoctane,
1,8-bis(2,3-epithiopropylthio)-2,4,5-tris(2,3-epithiopropylthiom
ethyl)-3,6-dithiaoctane, 1,1,1-tris[[2-(2,3-epithiopropylthio)
ethyl]thiomethyl]-2-(2,3-epithiopropylthio) ethane,
1,1,2,2-tetrakis[[2-(2,3-epithiopropylthio) ethyl]thiomethyl]
ethane, 1,11-bis(2,3
epithiopropylthio)-4,8-bis(2,3-epithiopropylthiomethyl)-3,6,9-tr
ithiaundecane,
1,11-bis(2,3-epithiopropylthio)-4,7-bis(2,3-epithiopropylthiomet
hyl)-3,6,9-trithiaundecane, and
1,11-bis(2,3-epithiopropylthio)-5,7-bis(2,3-epithiopropylthiomet
hyl)-3,6,9-trithiaundecane;
[0078] cyclic aliphatic 2,3-epithiopropylthio compounds such as
1,3-bis(2,3-epithiopropylthio) cyclohexane,
1,4-bis(2,3-epithiopropylthio) cyclohexane,
1,3-bis(2,3-epithiopropylthiomethyl) cyclohexane,
1,4-bis(2,3-epithiopropylthiomethyl) cyclohexane,
2,5-bis(2,3-epithiopropylthiomethyl)-1,4-dithiane,
2,5-bis[[2-(2,3-epithiopropylthio) ethyl] thiomethyl]-1,4-dithiane,
and 2,5-bis(2,3-epithiopropylthiomethyl)-2,5-dimethyl-1,4-dithiane;
aromatic 2,3-epithiopropylthio compounds such as
1,2-bis(2,3-epithiopropylthio) benzene,
1,3-bis(2,3-epithiopropylthio) benzene,
1,4-bis(2,3-epithiopropylthio) benzene,
1,2-bis(2,3-epithiopropylthiomethyl) benzene,
1,3-bis(2,3-epithiopropylthiomethyl) benzene,
1,4-bis(2,3-epithiopropyl thiomethyl) benzene,
bis[4-(2,3-epithiopropylthio) phenyl] methane,
2,2-bis[4-(2,3-epithiopropylthio) phenyl] propane,
bis[4-(2,3-epithiopropylthio) phenyl] sulfide,
bis[4-(2,3-epithiopropylthio) phenyl] sulfone, and
4,4'-bis(2,3-epithiopropylthio) biphenyl; compounds having one
epithio group such as ethylene sulfide, propylene sulfide,
mercaptopropylene sulfide, mercaptobutene sulfide, and
epithiochlorohydrin;
[0079] chain aliphatic 2,3-epithiopropyloxy compounds such as
bis(2,3-epithiopropyl) ether, bis(2,3-epithiopropyloxy) methane,
1,2-bis(2,3-epithiopropyloxy) ethane, 1,2-bis(2,3-epithiopropyloxy)
propane, 1,3-bis(2,3-epithiopropyloxy) propane,
1,3-bis(2,3-epithiopropyloxy)-2-methyl propane,
1,4-bis(2,3-epithiopropyloxy) butane,
1,4-bis(2,3-epithiopropyloxy)-2-methylbutane,
1,3-bis(2,3-epithiopropyloxy) butane, 1,5-bis(2,3-epithiopropyloxy)
pentane, 1,5-bis(2,3-epithiopropyloxy)-2-methylpentane,
1,5-bis(2,3-epithiopropyloxy)-3-thiahexane,
1,6-bis(2,3-epithiopropyloxy) hexane,
1,6-bis(2,3-epithiopropyloxy)-2-methylhexane,
3,8-bis(2,3-epithiopropyloxy)-3,6-dithiaoctane,
1,2,3-tris(2,3-epithiopropyloxy) propane,
2,2-bis(2,3-epithiopropyloxy)-1,3-bis(2,3-epithiopropyloxymethyl)
propane,
2,2-bis(2,3-epithiopropyloxymethyl)-1-(2,3-epithiopropyloxy)
butane,
1,5-bis(2,3-epithiopropyloxy)-2-(2,3-epithiopropyloxymethyl)-3-t
hiapentane,
1,5-bis(2,3-epithiopropyloxy)-2,4-bis(2,3-epithiopropyloxymethyl-3-thiape-
ntane,
1-(2,3-epithiopropyloxy)-2,2-bis(2,3-epithiopropyloxymethyl)-4-t
hiapentane,
1,5,6-tris(2,3-epithiopropyloxy)-4-(2,3-epithiopropyloxymethyl)-3-thiahex-
ane,
1,8-bis(2,3-epithiopropyloxy)-4-(2,3-epithiopropyloxymethyl)-3,6-dith-
iaoctane,
1,8-bis(2,3-epithiopropyloxy)-4,5-bis(2,3-epithiopropyloxymethyl-
)-3,6-dithiaoctane,
1,8-bis(2,3-epithiopropyloxy)-4,4-bis(2,3-epithiopropyloxymethyl)-3,6-dit-
hiaoctane,
1,8-bis(2,3-epithiopropyloxy)-2,5-bis(2,3-epithiopropyloxymethy-
l)-3,6-dithiaoctane,
1,8-bis(2,3-epithiopropyloxy)-2,4,5-tris(2,3-epithiopropyloxymethyl)-3,6--
dithiaoctane, 1,1,1-tris[[2-(2,3-epithiopropyloxy) ethyl]
thiomethyl]-2-(2,3-epithiopropyloxy) ethane,
1,1,2,2-tetrakis[[2-(2,3-epithiopropyloxy) ethyl]thiomethyl]
ethane,
1,11-bis(2,3-epithiopropyloxy)-4,8-bis(2,3-epithiopropyloxymethyl)-3,6,9--
trithiaundecane,
1,11-bis(2,3-epithiopropyloxy)-4,7-bis(2,3-epithiopropyloxymethyl)-3,
6, 9-trithiaundecane, and
1,11-bis(2,3-epithiopropyloxy)-5,7-bis(2,3-epithiopropyloxymethyl)-3,6,9--
trithiaundecane;
[0080] cyclic aliphatic 2,3-epithiopropyloxy compounds such as
1,3-bis(2,3-epithiopropyloxy) cyclohexane,
1,4-bis(2,3-epithiopropyloxy) cyclohexane,
1,3-bis(2,3-epithiopropyloxymethyl) cyclohexane,
1,4-bis(2,3-epithiopropyloxymethyl) cyclohexane,
2,5-bis(2,3-epithiopropyloxymethyl)-1,4-dithiane,
2,5-bis[[2-(2,3-epithiopropyloxy) ethyl] thiomethyl]-1,4-dithiane,
and 2,5-bis(2,3-epithiopropyloxymethyl)-2,5-dimethyl-1,4-dithiane;
aromatic 2,3-epithiopropyloxy compounds such as
1,2-bis(2,3-epithiopropyloxy) benzene,
1,3-bis(2,3-epithiopropyloxy) benzene,
1,4-bis(2,3-epithiopropyloxy) benzene,
1,2-bis(2,3-epithiopropyloxymethyl) benzene,
1,3-bis(2,3-epithiopropyloxymethyl) benzene,
1,4-bis(2,3-epithiopropyloxymethyl) benzene,
bis[4-(2,3-epithiopropyloxy) phenyl] methane,
2,2-bis[4-(2,3-epithiopropyloxy) phenyl] propane,
bis[4-(2,3-epithiopropyloxy) phenyl] sulfide,
bis[4-(2,3-epithiopropyloxy) phenyl] sulfone, and
4,4'-bis(2,3-epithiopropyloxy) biphenyl. These episulfides may be
used alone, or two or more may be used in combination.
[0081] The episulfide (b) preferably includes a compound having two
episulfide groups in the molecule and more preferably includes a
compound represented by General Formula (1).
[0082] The compound represented by General Formula (1) is
specifically bis(2,3-epithiopropyl)sulfide or
bis(2,3-epithiopropyl)disulfide. This compound can be used singly,
or two or more compounds can also be used in a mixture form.
[0083] The episulfide represented by General Formula (1) can be
synthesized using a well-known method. Specifically, the episulfide
can be synthesized using the following synthesis route I (reaction
scheme (2)) or synthesis route II (reaction scheme (3)).
[0084] (Synthesis Route I)
[0085] The synthesis route I is made up of the following steps.
Meanwhile, in the respective steps, well-known raw materials,
well-known reaction conditions, and the like can be employed as raw
materials used, reaction conditions, and the like, and there are no
particular limitations.
[0086] (i) A step in which epichlorohydrin is reacted with a
sulfating agent, thereby obtaining bischlorohydrin and then a
bis(chlorohydrin)sulfide compound (a) in the following reaction
scheme (2))
[0087] (ii) A step in which the bis(chlorohydrin)sulfide compound
is epoxidized under base conditions, thereby obtaining an epoxy
compound (b) in the following reaction scheme (2))
[0088] (iii) A step in which the epoxy compound is reacted with a
sulfating agent, thereby obtaining bis(2,3-epithiopropyl)sulfide
(c) in the following reaction scheme (2))
##STR00003##
[0089] (Synthesis Route II)
[0090] The synthesis route II is made up of the following steps.
Meanwhile, in the respective steps, well-known raw materials,
well-known reaction conditions, and the like can be employed as raw
materials used, reaction conditions, and the like, and there are no
particular limitations.
[0091] (i) A step in which epichlorohydrin is reacted with a
sulfating agent and then is oxidized, thereby obtaining a
bis(chlorohydrin)disulfide compound (a) in the following reaction
scheme (3))
[0092] (ii) A step in which the bis(chlorohydrin)disulfide compound
is epoxidized under base conditions, thereby obtaining an epoxy
compound (b) in the following reaction scheme (3))
[0093] (iii) A step in which the epoxy compound is reacted with a
sulfating agent, thereby obtaining bis(2, 3-epithiopropyl)
disulfide (c) in the following reaction scheme (3))
##STR00004##
[0094] In the above-described reactions, when the raw material of
epichlorohydrin is changed to a raw material obtained from glycerin
which is a plant-derived material, it is possible to obtain the
episulfide (b) having high degree of biomass.
[0095] Examples of a manufacturing method for obtaining
epichlorohydrin from glycerin include a manufacturing method in
which glycerin is chlorinated so as to obtain dichloropropanol, and
the dichloropropanol is epoxidized, thereby obtaining
epichlorohydrin.
[0096] Examples of epichlorohydrin manufactured from plant-derived
glycerin include EPICHLOROHYDRIN (ECH) (manufactured by Solvay) and
the like.
[0097] [Polythiol (c)]
[0098] In the present embodiment, examples of the polythiol having
a di- or higher-functional thiol group (c) (hereinafter, simply
referred to as the polythiol (c)) include aliphatic polythiol
compounds such as methanedithiol, 1,2-ethanedithiol,
1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl)
thioether, 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
mercaptoacetate, pentaerythritol tetrakis(2-mercaptoacetate),
pentaerythritol tetrakis mercaptopropionate, pentaerythritol
tetrakis(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)
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,
3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane,
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(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, esters of
thioglycolic acids and mercaptopropionic acids thereof,
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-mercaptoethyl ether
bis(2-mercaptoacetate), 2-mercaptoethyl ether
bis(3-mercaptopropionate), bis(2-mercaptoethyl ester)
thiodiglycolate, bis(2-mercaptoethyl ester) thiodipropionate,
bis(2-mercaptoethyl ester) dithiodiglycolate, bis(2-mercaptoethyl
ester) dithiodipropionate,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
1,1,2,2-tetrakis(mercaptomethylthio) ethane,
tris(mercaptomethylthio) methane, and tris(mercaptoethylthio)
methane;
[0099] aromatic polythiol compounds such as 1,2-dimercapto benzene,
1,3-dimercapto benzene, 1,4-dimercapto benzene,
1,2-bis(mercaptomethyl) benzene, 1,3-bis(mercaptomethyl) benzene,
1,4-bis(mercaptomethyl) benzene, 1,2-bis(mercaptoethyl) benzene,
1,3-bis(mercaptoethyl) benzene, 1,4-bis(mercaptoethyl) benzene,
1,3,5-trimercapto benzene, 1,3,5-tris(mercaptomethyl) benzene,
1,3,5-tris(mercaptomethyleneoxy) benzene,
1,3,5-tris(mercaptoethyleneoxy) benzene, 2,5-toluene dithiol,
3,4-toluene dithiol, 1,5-naphthalene dithiol, and 2,6-naphthalene
dithiol;
[0100] heterocyclic polythiol compounds such as
2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophene dithiol,
bismuthiol, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and
2-(2,2-bis(mercaptomethylthio) ethyl)-1,3-dithietane, and at least
one polythiol compound can be used.
[0101] Furthermore, it is also possible to use an oligomer of the
polythiol compound or a halogen-substituted body such as a
chlorine-substituted body or a bromine-substituted body.
[0102] As the polythiol (c), it is possible to preferably use at
least one selected from 4-mercaptomethyl-1,8-dimercapto-3,
6-dithiaoctane, 4,8 or 4,7 or
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
pentaerythritol tetrakis mercaptoacetate, pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol tetrakis
mercaptopropionate, pentaerythritol tetrakis(3-mercaptopropionate),
2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl)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(mercaptomethyl) ethane,
3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane,
tris(mercaptomethylthio) methane, and ethylene glycol
bis(3-mercaptopropionate).
[0103] Furthermore, among these, a polythiol obtained from
plant-derived materials is more preferably used.
[0104] Examples of the polythiol obtained from plant-derived
materials include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
and 4,8 or 4,7 or
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane which
are synthesized using epichlorohydrin manufactured by chlorinating
and epoxidizing glycerin obtained from plant-derived materials as a
raw material, and one or more polythiols among the above-described
polythiols can be used. Meanwhile, the glycerin can be obtained by
extracting glycerin from an aliphatic acid ester of glycerin
included in vegetable oil and fat such as canola oil, palm oil,
castor oil, or olive oil by means of hydrolysis or ester
exchange.
[0105] For example, in a case of the
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, it can be
manufactured through a) a step of adding two molecules of
2-mercaptoethanol into epichlorohydrin manufactured from naturally
originated glycerin, preferably plant-derived glycerin, through
chlorination and epoxidation, and b) a step of synthesizing
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane through a
decomposition step of a base which is continuous to a reaction with
respect to a sulfurizing agent such as thiourea.
[0106] By using the polythiol obtained from plant-derived material
in the polymerizable composition, it is possible to provide a
molding formed of a polythiourethane resin having a high degree of
biomass of greater than or equal to 25% and excellent properties of
transparency, a refractive index, heat resistance, strength, and
the like.
[0107] It is preferable that the polythiol (b) to be used is
obtained from the plant-derived material, and a compound which is
not obtained from the plant-derived material is also may be used.
As it is used, the compound is may be used such that the degree of
biomass of the polythiourethane resin is in a predetermined range
(greater than or equal to 25%).
[0108] (Polymerization Catalyst)
[0109] When the polymerizable composition of the present embodiment
is heated or left to stand at normal temperature in the presence or
absence of a curing catalyst so as to be polymerized, it is
possible to manufacture resins.
[0110] As the kinds of the present polymerization catalyst, amines,
phosphines, organic acids and salts thereof, esters, anhydrides,
inorganic acids, quaternary ammonium salts, quaternary phosphonium
salts, tertiary sulfonium salts, secondary iodonium salts, Lewis
acids, radical polymerization catalysts, cationic polymerization
catalysts, and the like are generally used.
[0111] The polymerization catalyst may be used singly, or two or
more polymerization catalysts may be used in a mixture form, and,
when two or more polymerization catalysts having different reactive
properties are jointly used out of the above-described
polymerization catalysts, there are cases in which the handling
properties of monomers and the optical properties, hue,
transparency, and optical strain (striae) of resins being obtained
improve, and thus there are preferable cases.
[0112] Specific examples of preferred curing catalysts include
quaternary ammonium salts such as tetramethylammonium bromide,
tetraethylammonium bromide, tetrapropylammonium bromide,
tetrabutylammonium bromide, tetrahexylammonium bromide, and
tetraethyl ammonium hydroxide, for example, imidazoles such as
imidazole, 1,2-dimethyl imidazole, benzyl methyl imidazole, and
2-ethyl-4-imidazole, for example, pyrazoles such as pyrazole,
3,5-dimethylpyrazole, for example, hindered amines such as
1,2,2,6,6-pentamethyl-4-piperidinol,
1,2,2,6,6-pentamethyl-4-hydroxyethyl-4-piperidinol,
methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, mixtures of
methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate and
bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,
bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethy
1)-4-hydroxyphenyl]methyl] butylmalonate, and
tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)
butane-1,2,3,4-tetracarboxylate. Additionally, examples thereof
include phosphines such as trimethylphosphine, triethylphosphine,
tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine,
triphenylphosphine, tribenzylphosphine, 1,2-bis(diphenylphosphino)
ethane, and 1,2-bis(dimethylphosphino) ethane, Lewis acids such as
dimethyl tin dichloride, dibutyl tin dichloride, dibutyl tin
dilaurate, tetrachloro tin, dibutyl tin oxide, zinc chloride, zinc
acetylacetone, aluminum chloride, aluminum fluoride, triphenyl
aluminum, tetrachlorotitanium, and calcium acetate, and cationic
polymerization catalysts such as diphenyliodonium
hexafluorophosphate, diphenyliodonium hexafluoroarsenate,
diphenyliodonium hexafluoroantimonate, triphenylsulfonium
tetrafluoroborate, triphenylsulfonium hexafluorophosphate, and
triphenylsulfonium hexafluoroarsenate, but the curing catalyst is
not limited to these exemplary compounds.
[0113] The curing catalysts may be used alone, or two or more may
be used in combination.
[0114] The amount of the curing catalyst added is within a range of
0.001 wt % to 10 wt % and preferably within a range of 0.01 wt % to
1 wt % of the total weight of the polymerizable compound.
[0115] (Sulfur)
[0116] To the polymerizable composition of the present embodiment,
it is possible to add sulfur in order to improve the refractive
index of moldings to be obtained. For sulfur that is used for
optical resins, the purity thereof is preferably higher than or
equal to 98%, more preferably higher than or equal to 99%, and
still more preferably higher than or equal to 99.5%. In order to
increase the purity, there are cases in which a method for removing
a volatile component is also preferred.
[0117] Regarding the properties, sulfur may have any forms as long
as the sulfur can be dissolved in the polymerizable composition,
but a powder form is preferred, and a fine powder form is more
preferred.
[0118] In a case in which the total weight of the episulfide
compound and sulfur is set to 100 parts by weight, the amount of
sulfur added is in a range of 10 parts by weight to 50 parts by
weight, preferably in a range of 10 parts by weight to 40 parts by
weight, and more preferably in a range of 10 parts by weight to 30
parts by weight. During addition, a well-known vulcanization
catalyst such as an imidazole or an amine can be jointly used.
[0119] (Resin Modifier)
[0120] Examples of a resin modifier include epoxy compounds,
olefins including (meth)acrylates, amino compounds, thiol
compounds, polyphenols, amino acid and mercaptoamines, organic
acids, anhydride, and mercapto organic acids.
[0121] (Other Additives)
[0122] In addition to the resin modifier, a variety of well-known
additives such as an internal mold release agent, a light
stabilizer, a bluing agent, an ultraviolet absorber, an
antioxidant, a dye, and a filler may be used depending on the
purpose as long as no problems are caused. As the internal mold
release agent, an acidic phosphoric acid ester represented by
Formula (4) can be used.
##STR00005##
[0123] In formula (4), m represents an integer of 1 or 2, n
represents an integer of 0 to 18, R1 represents an alkyl group
having 1 to 20 carbon atoms, and each of R2 and R3 independently
represents a hydrogen atom, a methyl group, or an ethyl group. The
number of carbon atoms in [ ].sub.m is preferably 4 to 20.
[0124] Examples of R1 in General Formula (4) include organic
residues derived from a linear aliphatic compound such as methane,
ethane, propane, butane, pentane, hexane, heptane, octane, nonane,
decane, undecane, dodecane, tetradecane, and hexadecane;
[0125] organic residues derived from a branched aliphatic compound
such as 2-methylpropane, 2-methylbutane, 2-methylpentane,
3-methylpentane, 3-ethylpentane, 2-methylhexane, 3-methylhexane,
3-ethylhexane, 2-methylheptane, 3-methylheptane 4-methylheptane,
3-ethylheptane, 4-ethylheptane, 4-propylheptane, 2-methyloctane,
3-methyloctane, 4-methyloctane, 3-ethyloctane, 4-ethyloctane, and
4-propyloctane;
[0126] organic residues derived from alicyclic compounds such as
cyclopentane, cyclohexane, 1,2-dimethylcyclohexane,
1,3-dimethylcyclohexane, and 1, 4-dimethylcyclohexane; and the
like, but R1 is not limited to these exemplary compounds.
[0127] Examples of commercially available products of the acidic
phosphoric acid ester include ZelecUN manufactured by Stepan
Company, JP series manufactured by Johoku Chemical Co., Ltd.,
PHOSPHANOL series manufactured by Toho Chemical Industry Co., Ltd.,
AP and DP series manufactured by Daihachi Chemical Industry Co.,
Ltd., and the like.
[0128] As the light stabilizer, hindered amine-based compounds can
be used.
[0129] Examples of the hindered amine-based compounds include
Lowilite 76 and Lowilite 92 manufactured by Chemtura Corporation,
Tinuvin 123, Tinuvin 144, Tinuvin 292, Tinuvin 765, and Tinuvin
770DF manufactured by BASF, ADEKASTAB LA-52 and LA-72 manufactured
by ADEKA Corporation, JF-90 and JF-95 manufactured by Johoku
Chemical Co., Ltd., and the like.
[0130] Examples of the bluing agent include bluing agents which
have an absorption band in a wavelength range from orange color to
yellow color in the visible light range and have a function of
adjusting the hues of optical materials formed of a resin. More
specific examples of the bluing agent include substances exhibiting
blue color through violet color.
[0131] Examples of the ultraviolet absorber include
benzophenone-based ultraviolet absorbers such as
2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-acryloyloxy
benzophenone, 2-hydroxy-4-acryloyloxy-5-tert-butyl benzophenone,
and 2-hydroxy-4-acryloyloxy-2',4'-dichlorobenzophenone,
[0132] triazine-based ultraviolet absorbers such as
2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]4,6-bis
(2,4-dimethylphenyl)-1,3,5-triazine,
2-[4-(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dim-
ethylphenyl)-1,3,5-triazine,
2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis
(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-tria-
zine, and
2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-pheny-
lphenyl)-1,3,5-triazine; and
[0133] benzotriazole-based ultraviolet absorbers such as
2-(2H-benzotriazol-2-yl)-4-methylphenol,
2-(2H-benzotriazol-2-yl)-4-tert-octylphenol,
2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) phenol,
2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol,
2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol,
2-(5-chloro-2H-benzotriazol-2-yl)-2,4-tert-butylphenol, and
2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)ph-
enol]; and the like, and preferred examples thereof include
benzotriazole-based ultraviolet absorbers such as
2-(2H-benzotriazol-2-yl)-4-tert-octylphenol and
2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol.
These ultraviolet absorbers may be used alone, or two or more may
be used in combination.
[0134] The amount of these additives is preferably within a range
of 0.05 parts by weight to 2.0 parts by weight and more preferably
within a range of 0.05 parts by weight to 1.5 parts by weight of a
total of 100 parts by mass of the constituent components (a) to
(c).
[0135] The polymerizable composition for an optical material of the
present embodiment can be obtained by mixing the above-described
components. Regarding the method for mixing, a well-known method in
the related art can be used for mixing the components.
[0136] In the polymerizable composition for an optical material of
the present embodiment, the molar ratio of all mercapto groups in
the polythiol (c) to all isocyanate groups in the polyisocyanate
(a) is within the range between 0.7 and 1.5, preferably the range
between 0.80 and 1.3, and more preferably the range between 0.85
and 1.2.
[0137] In the above-described range, it is possible to obtain a
polymerizable composition for an optical material that is
preferably used as an optical material, particularly, a spectacle
lens.
[0138] Effects in a preferred aspect of the present invention will
be described below.
[0139] As described above, in recent years, there has been a demand
for the development of biomass products produced in consideration
of influences on the global environment. In order to improve the
degree of biomass, there is a need for utilizing aliphatic
polyisocyanate that can be manufactured from plant-derived
materials. However, aliphatic polyisocyanate obtained from
plant-derived materials has a chain portion that is long enough to
have 5 to 18 carbon atoms, and for resin moldings obtained using
the above-described aliphatic polyisocyanate, there has been room
for improvement in heat resistance.
[0140] In the present invention, when the polyisocyanate (a)
including aliphatic polyisocyanate (a1) having 5 to 18 carbon
atoms, which is obtained from plant-derived materials, and the
modified aliphatic polyisocyanate (a2), the episulfide (b), and the
polythiol (c) are included, it is possible to improve heat
resistance while maintaining a high level of the degree of biomass,
and furthermore, it is possible to obtain a polymerizable
composition for an optical material which can be used to provide
moldings being excellent in terms of other properties such as
transparency, refractive index, and dyeing properties.
[0141] [Molding]
[0142] When the polymerizable composition for an optical material
of the present embodiment is polymerization-cured, it is possible
to obtain moldings having excellent properties such as
transparency, refractive index, and heat resistance.
[0143] Furthermore, when a plant-derived material is used, it is
possible to obtain moldings including a resin for an optical
material which are in harmony with the global environment. The
degree of biomass of the resin for an optical material can be set
to higher than or equal to 25%, preferably set to higher than or
equal to 30%, and more preferably set to higher than or equal to
50%.
[0144] From the viewpoint of utilizing non-fossil resources, it is
preferable to use a material for which a plant-derived material is
used and which has high degree of biomass. However, as the degree
of biomass of a resin is improved, there have been cases in which
properties and the like degrade.
[0145] As a result of intensive studies, the present inventors
found that, when a compound obtained from at least one
plant-derived material selected from the polyisocyanate (a), the
episulfide (b), and the polythiol (c) which are obtained from
plant-derived materials is used, a resin for an optical material
having a degree of biomass of higher than or equal to 25% and a
molding including the resin can be obtained, and a resin for an
optical material being excellent in terms of transparency and heat
resistance and also having an excellent balance among properties
such as refractive index, Abbe number, mold release properties, and
the like and a molding including the resin can be obtained and the
present inventors completed the present invention.
[0146] The glass transition temperature (Tg) of the molding is
higher than or equal to 60.degree. C., preferably higher than or
equal to 70.degree. C., and more preferably higher than or equal to
80.degree. C. The refractive index is higher than or equal to 1.60,
preferably higher than or equal to 1.63, and more preferably higher
than or equal to 1.67.
[0147] [Use]
[0148] Optical materials formed of the molding of the present
embodiment can be provided with a variety of shapes by changing
molds during casting polymerization. Specifically, the optical
materials can be used in a variety of uses such as plastic lenses,
camera lenses, light-emitting diodes (LEDs), prisms, optical
fibers, information-recording substrates, filters, light-emitting
diodes, optical lenses for vehicles, and optical lenses for robots.
Particularly, the optical materials are preferred as optical
materials and optical elements such as plastic lenses, camera
lenses, and light-emitting diodes.
[0149] Examples of plastic lenses include plastic spectacle lenses
formed of a resin molding for an optical material and plastic
polarizing lenses in which a layer formed of the resin molding is
laminated on at least one surface of a polarizing film.
[0150] [Method for Manufacturing Plastic Spectacle Lens]
[0151] A method for manufacturing a plastic spectacle lens of the
present embodiment includes the following steps.
[0152] Step (1): Injecting the polymerizable composition for an
optical material of the embodiment into a lens casting mold.
[0153] Step (2): Polymerizing and curing the polymerizable
composition for an optical material in the lens casting mold.
[0154] Hereinafter, the respective steps will be sequentially
described.
[0155] Step (1)
[0156] In this step, the polymerizable composition of the
embodiment is injected into a molding mold (the lens casting mold)
held by a gasket, tape, or the like. At this time, it is preferable
that, as necessary, a defoaming treatment under reduced pressure, a
filtration treatment such as pressurization and depressurization,
or the like, is performed according to the properties required to a
molding to be obtained.
[0157] Step (2)
[0158] In this step, polymerization of the polymerizable
composition casted in the casting mold at a predetermined
temperature is initiated, and the composition is polymerized. The
polymerization conditions are considerably different based on the
kinds of polyisocyanate or polythiols to be used, the shape of the
mold, and the like, and thus, the conditions are not limited, and
the polymerization is performed at a temperature of 0.degree. C. to
140.degree. C. for 1 hour to 48 hours.
[0159] The obtained plastic spectacle lens may be used after being
provided with a coating layer (s) on one or both surface (s) as
necessary. Examples of the coating layer include a primer layer, a
hard coat layer, an antireflection layer, an antifogging coating
layer, an antifouling layer, and a water-repellent layer. Each of
these coating layers may be used singly, or a plurality of the
coating layers may be used in a multilayer form. In a case in which
the coating layers are provided on both surfaces, the same coating
layers or different coating layers may be provided on the
respective layers.
[0160] With these coating layers, an ultraviolet absorber for the
purpose of protecting the lens or eyes from ultraviolet rays, an
infrared absorber for the purpose of protecting eyes from infrared
rays, a light stabilizer or an antioxidant for the purpose of
improving the weather resistance of the lens, dyes or pigments and,
furthermore, photochromic dyes or photochromic pigments for the
purpose of enhancing the fashion properties of the lens, an
antistatic agent, and, additionally, well-known additives for
enhancing the performance of the lens may be jointly used. For
layers coated by means of coating, a variety of levelling agents
intended to improve coating properties may be used.
[0161] The primer layer is generally formed between a hard coat
layer described below and an optical lens. The primer layer is a
coating layer intended to improve adhesiveness to the hard coat
layer and the lens which are formed on the primer layer and, in
some cases, is also capable of improving impact resistance. Any
material can be used for the primer layer as long as the material
is highly adhesive to the obtained optical lens; however,
generally, primer compositions including a urethane-based resin, an
epoxy-based resin, a polyester-based resin, a melamine-based resin,
and polyvinyl acetal as main components and the like are used. In
the primer composition, an appropriate solvent having no influences
on the lens may be used in order to adjust the viscosity of the
composition. It is needless to say that no solvents may be
used.
[0162] The primer composition can also be formed using any one of a
coating method and a dry method. In a case in which a coating
method is used, the primer layer is formed by applying the primer
composition onto a lens using a well-known coating method such as
spin coating or dip coating and then solidifying the primer
composition. In a case in which a dry method is used, the primer
layer is formed using a well-known dry method such as a CVD method
or a vacuum deposition method. During the formation of the primer
layer, the surface of the lens may be subjected to a pretreatment
such as an alkali treatment, a plasma treatment, or an ultraviolet
treatment as necessary in order to improve adhesiveness.
[0163] The hard coat layer is a coating layer intended to impart
functions such as abrasion resistance, wear resistance, moisture
resistance, hot water resistance, heat resistance, and weather
resistance to the lens surface.
[0164] For the hard coat layer, generally, a hard coat composition
including one or more kinds of fine particles constituted of a
complex oxide of a curable organic silicon compound and one or more
kinds of oxide fine particles of an element selected from an
element group of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and
Ti and/or two or more kinds of elements selected from the
above-described element group is used.
[0165] The hard coat composition preferably includes, in addition
to the above-described components, at least any of amines, amino
acids, metallic acetylacetonate complexes, organic acid metallic
salts, perchloric acids, salts of perchloric acids, acids, metal
chlorides, and polyfunctional epoxy compounds. In the hard coat
composition, an appropriate solvent having no influences on the
lens may be used. It is needless to say that the hard coat
composition may include no solvents.
[0166] The hard coat layer is generally formed by applying the hard
coat composition using a well-known coating method such as spin
coating or dip coating and then curing the hard coat composition.
Examples of a curing method include curing methods in which the
hard coat composition is cured by means of thermal curing or
irradiation with energy rays such as ultraviolet rays or visible
light rays. In order to suppress the generation of interference
stripes, the refractive index of the hard coat layer is preferably
in a range of .+-.0.1 from the refractive index of the lens.
[0167] Generally, the antireflection layer is formed on the hard
coat layer as necessary. Antireflection layers are classified into
inorganic antireflection layers and organic antireflection layers,
and, in a case in which the antireflection layer is an inorganic
antireflection layer, the antireflection layer is formed using an
inorganic oxide such as SiO.sub.2 or TiO.sub.2 and a dry method
such as a vacuum deposition method, a sputtering method, an ion
plating method, an ion beam assist method, or a CVD method. In a
case in which the antireflection layer is an organic antireflection
layer, the antireflection layer is formed using a composition
including an organic silicon compound and silica-based fine
particles having internal voids and a wet method.
[0168] The antireflection layer may have a single layer structure
or a multilayer structure, and, in a case in which a single
layer-structured antireflection layer is used, the refractive index
of the antireflection layer is preferably lower than the refractive
index of the hard coat layer by at least greater than or equal to
0.1. In order to effectively develop an antireflection function, a
multilayered antireflection film is preferably formed, and, in this
case, low-refractive index films and high-refractive index films
are alternately laminated. In this case as well, the difference in
the refractive index between the low-refractive index film and the
high-refractive index film is preferably greater than or equal to
0.1. Examples of the high-refractive index films include films of
ZnO, TiO.sub.2, CeO.sub.2, Sb.sub.2O.sub.5, SnO.sub.2, ZrO.sub.2,
and Ta.sub.2O.sub.5, and examples of the low-refractive index films
include SiO.sub.2 films and the like.
[0169] On the antireflection layer, an antifogging coating layer,
an antifouling layer, and a water-repellent layer may be formed as
necessary. Regarding methods for forming the antifogging coating
layer, the antifouling layer, and the water-repellent layer,
treatment methods, treatment materials, and the like are not
particularly limited as long as there are no adverse effects on the
antireflection function, and well-known antifogging coating
treatment methods, antifouling treatment methods, and
water-repellent treatment methods, and materials can be used.
Examples of antifogging coating and antifouling treatment methods
include a method in which the surface is covered with a surfactant,
a method in which a hydrophilic film is attached to the surface so
as to impart water-absorbing properties, a method in which the
surface is covered with fine protrusion and recesses so as to
enhance water-absorbing properties, a method in which
water-absorbing properties are imparted using a photocatalytic
activity, a method in which a superhydrophobic treatment is carried
out so as to prevent the attachment of water droplets, and the
like. In addition, examples of the water-repellent treatment
include a method in which a water-repellent treatment layer is
formed by depositing or sputtering a fluorine-containing silane
compound or the like, a method in which a fluorine-containing
silane compound is dissolved in a solvent and then is applied,
thereby forming a water-repellent treatment layer, and the
like.
[0170] The plastic spectacle lens of the present embodiment may be
dyed using appropriate colorants in order to impart fashion
properties or photochromic properties. The lens can be dyed using a
well-known dyeing method and is dyed using, for example, the
following method.
[0171] Generally, a lens raw material finished to a predetermined
optical surface is immersed in a dyeing fluid in which a colorant
being used is dissolved or uniformly dispersed (dyeing step), and
then the colorant is fixed by heating the lens as necessary
(post-dyeing annealing step). Colorants that are used in the dyeing
step are not particularly limited as long as the colorants are
well-known colorants; however, generally, oil-soluble dyes or
dispersive dyes are used. The solvent that is used in the dyeing
step is not particularly limited as long as the solvent is capable
of dissolving or uniformly dispersing colorants being used. In this
dyeing step, a surfactant for dispersing the colorants in the
dyeing fluid or a carrier for accelerating dyeing may be added as
necessary. In the dyeing step, colorants and a surfactant, which is
added as necessary, are dispersed in water or a mixture of water
and an organic solvent so as to prepare a dyeing bath, an optical
lens is immersed in this dyeing bath, and dyeing is carried out at
a predetermined temperature for a predetermined time. The dyeing
temperature and the dyeing time vary depending on desire coloration
densities; however, generally, the dyeing temperature and the
dyeing time are preferably lower than or equal to 120.degree. C.
and approximately several minutes to several tens of hours, and the
dyeing density of the dyeing bath is within a range of 0.01% by
weight to 10% by weight. In addition, in a case in which dyeing is
difficult, the lens may be dyed under pressurization. The
post-dyeing annealing step which is carried out as necessary is a
step in which a heating treatment is carried out on the dyed lens
material. In the heating treatment, water remaining on the surface
of the lens material dyed in the dyeing step is removed using a
solvent or the like or the solvent is dried with wind, and then the
lens material is retained in, for example, a furnace such as an
infrared heating furnace in the atmosphere or a resistance heating
furnace for a predetermined time. The post-dyeing annealing step
prevents the discoloration of the dyed lens material (discoloration
prevention step) and removes moisture that has intruded into the
lens material during dyeing.
[0172] [Method for Manufacturing Plastic Polarizing Lens]
[0173] A method for manufacturing a plastic polarizing lens of the
present embodiment includes the following steps.
[0174] Step (a): Fixing a polarizing film into a lens casting mold
in a state where at least one surface of the polarizing film is
separated from a mold.
[0175] Step (b): Injecting the polymerizable composition for an
optical material of the embodiment into a gap between the
polarizing film and the mold.
[0176] Step (c): Laminating a layer formed of a polythiourethane
resin on at least one surface of the polarizing film by
polymerizing and curing the polymerizable composition for an
optical material.
[0177] Hereinafter, the respective steps will be sequentially
described.
[0178] Step (a)
[0179] The polarizing film is disposed in a space of the lens
casting mold such that at least one surface of the film is parallel
to the facing inner surface of the mold. A gap portion is formed
between the polarizing film and the mold. The polarizing film may
be formed in advance.
[0180] Various films such as a polyvinyl alcohol polarizing film
and a thermoplastic polyester polarizing film can be used in the
polarizing film. Examples of the thermoplastic polyester may
include polyethylene terephthalate, polyethylene naphthalate,
polybutylene terephthalate, and the like.
[0181] Specifically, examples of the polarizing film include a
dichromic dye-containing thermoplastic polyester polarizing film,
an iodine-containing polyvinyl alcohol polarizing film, a dichromic
dye-containing polyvinyl alcohol polarizing film, and the like.
[0182] Step (b)
[0183] Next, in the space of the lens casting mold, the
polymerizable composition for an optical material of the embodiment
is injected into the gap portion between the mold and the
polarizing film by a predetermined injection unit.
[0184] Step (c)
[0185] Next, the lens casting mold into which the polymerizable
composition for an optical material is injected and into which the
polarizing film is fixed is heated in a device in which heating is
may be performed, such as an oven or water according to a
predetermined temperature program for several hours to several tens
of hours, and thus, the molding is performed by polymerizing and
curing the polymerizable composition for an optical material.
[0186] The polymerizing and curing temperature is not limited since
conditions are different according to the composition of the
polymerizable composition, the kinds of catalyst, the shape of the
mold, and the like, but the polymerizing and curing is performed at
a temperature of 0.degree. C. to 140.degree. C. for 1 hour to 48
hours.
[0187] When the polymerizable composition for an optical material
is removed from the mold for lens casting after the end of the
curing and molding, it is possible to obtain the plastic polarizing
lens of the present embodiment in which a layer formed of a
polythiourethane resin is laminated on at least one surface of the
polarizing film.
[0188] For the plastic polarizing lens of the present embodiment,
for the purpose of alleviating strain caused by the polymerization,
it is desirable to carry out an annealing treatment by heating the
released lens.
[0189] The plastic polarizing lens of the present embodiment may be
used after being provided with a coating layer(s) on one or both
surface(s) as necessary. Examples of the coating layer, similar to
the coating layer for the plastic spectacle lens, include a primer
layer, a hard coat layer, an antireflection layer, an antifogging
coating layer, an antifouling layer, and a water-repellent
layer.
[0190] The embodiment of the present invention has been described
above, but the embodiment is an example of the present invention,
and a variety of other constitutions can be employed as long as the
effects of the present invention are not impaired.
EXAMPLES
[0191] Hereafter, the present invention will be described in more
detail using examples, but the present invention is not limited
thereto. In the following description, unless otherwise
particularly stated, "parts" and % are based on a weight.
[0192] (Method for Measuring the Concentration (%) of Unreacted
1,5-Pentamethylene Diisocyanate in Polyisocyanate (1) which is a
Composition Including a Modified 1,5-Pentamethylene
Diisocyanate)
[0193] The concentration of unreacted 1, 5-pentamethylene
diisocyanate in polyisocyanate (1) including a modified product was
obtained from standard curves produced using 1,5-pentamethylene
diisocyanate obtained in Preparation Example 4 described below as a
standard product and the following device.
[0194] Device: Prominence (manufactured by Shimadzu
Corporation)
[0195] Column: SHISEIDO SILICA SG-120
[0196] Column temperature: 40.degree. C.
[0197] Eluent: n-Hexane/methanol/1,2-dichloroethane=90/5/5 (volume
ratio)
[0198] Flow rate: 0.2 ml/min
[0199] Detector: UV 225 nm
[0200] R. Time: 16.9 min
[0201] Preparation of measurement solution: A sample (0.1 g) and
dibenzyl amine amounting to approximately 20 times the mole of the
sample were added to a 50 ml measuring flask, and the mass was
increased using 1,2-dichloroethane, thereby preparing a measurement
solution.
[0202] Measurement: The measurement solution (1 .mu.L) was
injected, and the concentration was measured.
[0203] (Method for Measuring the Concentration (%) of Isocyanate
Groups in Polyisocyanate (1))
[0204] The concentration of an isocyanate group of the
polyisocyanate was obtained by being measured by an n-dibutyl amine
method using a potential difference titration device on the basis
of JIS K-1556.
[0205] (Method for Measuring the Concentration (%) of Mononuclear
Isocyanurate in Polyisocyanate (1))
[0206] The area ratio of a peak corresponding to a molecular weight
three times the molecular weight of 1,5-pentamethylene diisocyanate
to the entire peak area was obtained as the concentration (%) of
mononuclear isocyanurates in polyisocyanate (1) from chromatograms
obtained by means of gel permeation chromatography using the
following device.
[0207] Device: HLC-8020 (manufactured by Tosoh Corporation)
[0208] Column: Direct connection of G1000HXL, G2000HXL, and
G3000HXL (manufactured by Tosoh Corporation)
[0209] Column temperature: 40.degree. C.
[0210] Eluent: Tetrahydrofuran
[0211] Flow rate: 0.8 ml/min
[0212] Detector: Differential Refractometer
[0213] R. Time: Mononuclear Isocyanurate, 27.2 min
[0214] Standard substance: Polyethylene oxide (manufactured by
Tosoh
[0215] Corporation, TSK standard polyethylene oxide)
[0216] Measurement: The specimen (30 mg) was dissolved in
tetrahydrofuran (10 ml), the obtained solution (100 .mu.L) was
injected, and the concentration was measured.
[0217] (Method for Calculating the Average Number of Functional
Groups in Polyisocyanate (1))
[0218] The average number of functional groups in polyisocyanate
(1) was calculated by the following expression using a number
average molecular weight obtained by the same measurement as that
of the concentration of the mononuclear isocyanurate in the
polyisocyanate (1), and the concentration of isocyanate groups in
polyisocyanate (1).
(The average number of functional groups in polyisocyanate
(1))=(the number-average molecular weight of polyisocyanate
(1)).times.(the concentration (%) of isocyanate groups in
polyisocyanate (1))/4202
[0219] (Degree of Biomass (%))
[0220] The degree of biomass is obtained by a calculation method on
a carbon basis, that is, is defined as follows.
Degree of Biomass (%)={(Number of Plant-derived Carbon
Atoms)/(Number of Plant-derived Carbon Atoms+Number of
Petroleum-Derived Carbon Atoms)}.times.100
[0221] (Method for Calculating Degree of Biomass (%) of
Polyisocyanate (1))
[0222] The degree of biomass of the polyisocyanate (a-II) was
calculated on a carbon basis according to the degree of biomass of
the 1,5-pentamethylene diisocyanate.
(Degree of biomass (%) of polyisocyanate (1))={Number of carbon
atoms in 1,5-pentamethylene diisocyanate).times.(Degree of biomass
(%) of 1,5-pentamethylene diisocyanate)}/{(Number of carbon atoms
in 1,5-pentamethylene diisocyanate)+(Number of carbon atoms in a
compound added during the reaction)}
[0223] (Method for Calculating Degree of Biomass (%) of Episulfide
Compound (2))
[0224] The carbon-based degree of biomass of epichlorohydrin which
was a plant-derived material was considered as 100%, and the degree
of biomass of the synthesized episulfide compound was calculated in
terms of carbon on the basis of the above-described degree of
biomass.
Degree of biomass (%) of the episulfide compound={(Number of carbon
atoms derived from epichlorohydrin in the episulfide
compound).times.(Degree of biomass (%) of
epichlorohydrin)}/{(Number of carbon atoms in the episulfide
compound)}
[0225] (Method for Calculating Degree of Biomass (%) of Polythiol
Compound (3))
[0226] The degree of biomass of the synthesized polythiol was
calculated on a carbon basis by using epichlorohydrin which was
obtained from a plant-derived material and had a degree of biomass
of 100% on a carbon basis.
Degree of biomass of polythiol={(Number of epichlorohydrin-derived
carbon atoms in molecules of polythiol).times.(Degree of biomass
(%) of epichlorohydrin)}/{(Number of carbon atoms in molecules of
polythiol)}
[0227] (Method for Calculating Degree of Biomass (%) of Resin for
Optical Material)
[0228] The degree of biomass of the resin for an optical material
was calculated on a carbon basis according to the degree of biomass
of the polyisocyanate (1), the episulfide compound (2), and the
polythiol compound (3).
(Degree of biomass (%) of the resin for an optical
material)={(Number of carbon atoms in the polyisocyanate (1)
used).times.(Degree of biomass (%) of the polyisocyanate
(1))+(Number of carbon atoms in the episulfide compound (2)
used).times.(Degree of biomass (%) of the episulfide compound
(2))+(Number of carbon atoms in the polythiol compound (3)
used).times.(Degree of biomass (%) of the polythiol compound
(3))}/{(Number of carbon atoms in the polyisocyanate (1)
used)+(Number of all carbon atoms in other polyisocyanates)+(Number
of carbon atoms in the episulfide compound (2) used)+(Number of
carbon atoms in the polythiol compound (3) used)}
[0229] (Method for Evaluating Performance of Lens)
[0230] The lens obtained by means of polymerization was evaluated
by carrying out a performance test. The performance test was
carried out in terms of the refractive index, the Abbe number, the
heat resistance, and the dyeing properties, and these were
evaluated using the following test methods. [0231] Refractive index
(ne) and Abbe number (.nu.e): The refractive index and the Abbe
number were measured at 20.degree. C. using a Pulfrich
refractometer KPR-30 manufactured by Shimadzu Corporation. [0232]
Heat resistance: The glass transition temperature (Tg) in a TMA
penetration method (with a load of 50 g and a pin tip diameter of
0.5 mm.phi.) was set as heat resistance by using TMA-60
manufactured by Shimadzu Corporation. [0233] Dyeing properties:
"FSP Red E-A" (manufactured by Futaba Corporation) (1.0 g), "FSP
Yellow P-E" (manufactured by Futaba Corporation) (1.0 g), "FSP Blue
AUL-S" (manufactured by Futaba Corporation) (2.0 g), "NICCA SUNSOLT
#7000" (manufactured by Nicca Chemical Co., Ltd.) (4.0 g), and
"DK-CN" (manufactured by Daiwa Chemical Industries Co., Ltd.) (4.0
g) were added to pure water (2,986 g), thereby preparing a dye
dispersed liquid. This liquid was heated to 90.degree. C., and then
a 9 mm-thick molding piece was dyed by being immersed therein for
five minutes at 90.degree. C. The transmittance (% T) of the dyed
molding piece at a wavelength of 565 nm was measured. Molding
pieces having a transmittance of lower than or equal to 40% after
dyeing were evaluated as "having favorable dyeing properties" and
molding pieces having a transmittance of higher than or equal to
60% were evaluated as "having poor dyeing properties".
Reference Preparation Example
Synthesis of 1,5-Pentamethylene Diisocyanate Using Plant-Derived
Material
Preparation Example 1
Preparation of Bacteria-Disintegrated Liquid
[0234] (Cloning of Lysine Decarboxylase Gene (cadA)) A genome DNA
prepared from an Escherichia coli W3110 strain (ATCC27325)
according to an ordinary method was used as a mold for PCR.
[0235] Oligonucleotides (synthesized by Invitrogen in trust) having
base sequences shown in sequence numbers 1 and 2 which were
designed on the basis of the base sequence of lysine decarboxylase
gene (cadA) (GenBank Accession No. AP009048) were used as primers
for PCR. These primers respectively have restriction enzyme
recognition sequences of KpnI and XbaI near a 5' terminal.
[0236] A reaction cycle made up of denaturation at 94.degree. C.
for 30 seconds, annealing at 55.degree. C. for 30 seconds, and an
elongation reaction at 68.degree. C. for two minutes was carried
out 30 times using a PCR reaction liquid (25 .mu.L) including the
genome DNA (1 ng/.mu.L) and the respective primers (0.5
pmol/.mu.L), thereby performing PCR.
[0237] The PCR reaction product and plasmid pUC18 (manufactured by
Takara Shuzo Co., Ltd.) were digested using KpnI and XbaI, were
coupled together using LIGATION HIGH (manufactured by Toyobo Co.,
Ltd.), and the genetic transformation of Eschrichia coli DH5.alpha.
(manufactured by Toyobo Co., Ltd.) was carried out using the
obtained recombined plasmid. The genetic-transformed body was
cultured in an LB agar medium including ampicillin (Am) (100
.mu.g/mL) and X-Gal
(5-bromo-4-chloro-3-indolyl-.beta.-D-galactoside), thereby
obtaining a genetic-transformed body which was resistant to Am and
was formed of white colonies. Plasmids were extracted from the
genetic-transformed body obtained in the above-described
manner.
[0238] According to an ordinary method for determining base
sequences, it was confirmed that the base sequence of a DNA
fragment introduced into the plasmid was the base sequence shown in
the sequence number 3.
[0239] A plasmid having a DNA that coded the obtained lysine
decarboxylase was named as pCADA. Bacillus coli that had been
genetic-transformed using pCADA was cultured, whereby lysine
decarboxylase having the amino acid sequence shown in the sequence
number 4 could be produced.
[0240] (Production of Genetic-Transformed Body)
[0241] An Escherichia coli W3110 strain was genetic-transformed
according to an ordinary method using pCADA, and the obtained
genetic-transformed body was named as W/pCADA.
[0242] This genetic-transformed body was inoculated to an LB agar
medium (500 ml) including Am (100 .mu.g/mL) in a three-neck flask
equipped with a baffle and was shaken and cultured until OD (660
nm) reached 0.5 at 30.degree. C., then,
isopropyl-.beta.-thiogalactopyranoside(IPTG) was added thereto so
as to reach 0.1 mmol/L, and furthermore, the mixture was shaken and
cultured for 14 hours. The culture solution was centrifugally
separated at 8,000 rpm for 20 minutes, thereby obtaining
bacteria.
[0243] These bacteria were suspended in a sodium phosphate buffer
solution (pH 6.0) (20 mmol/L), and then ultrasonic disintegration
was carried out, thereby preparing a bacteria-disintegrated
liquid.
Preparation Example 2
Preparation of Aqueous Solution of 1,5-Pentamethylene Diamine
[0244] To a flask, a substrate solution (120 parts by weight)
prepared by adding L-lysine monohydrochloride (manufactured by Wako
Pure Chemical Industries, Ltd.) so that the final concentration
reached 45% by weight and pyridoxal phosphate (manufactured by Wako
Pure Chemical Industries, Ltd.) so that the final concentration
reached 0.15 mmol/L was added. Next, the W/pCADA
bacteria-disintegrated liquid (finishing dried bacteria-equivalent
weight: 0.3 g) was added thereto, and a reaction was initiated. The
reaction conditions were set to 37.degree. C. and 200 rpm. The pH
of a reaction liquid was adjusted to 6 using hydrochloric acid (6
mol/L). After 24 hours, the reaction yield of 1,5-pentamethylene
diamine reached 99%. The pH of the reaction liquid after 24 hours
from the reaction was adjusted to 2 using hydrochloric acid (6
mol/L), activated carbon (manufactured by Mitsukura Chemical Co.,
Ltd., powdered activated carbon PM-SX) (0.6 parts by weight) was
added thereto, and the components were stirred at 25.degree. C. for
one hour, and then filtration was carried out using filter paper
(5C manufactured by ADVANTEC Co., Ltd.). Next, the pH of this
filtrate was adjusted to 12 using sodium hydroxide, thereby
obtaining an aqueous solution of 1,5-pentamethylene diamine (17.0%
by weight aqueous solution).
Preparation Example 3
Preparation of 1,5-Pentamethylene Diamine
[0245] An aqueous solution of 1,5-pentamethylene diamine (100 parts
by weight) and n-butanol (100 parts by weight) were prepared at
23.degree. C. in a separating funnel, were mixed together for 10
minutes, and then were left to stand for 30 minutes. The lower
layer which was a water layer was removed, and then the upper layer
which was an organic layer (n-butanol including 1,5-pentamethylene
diamine) was removed. The extraction rate was measured and was
found to be 91.6%. Next, the extraction liquid (80 parts by weight)
of the organic layer was prepared in a four-neck flask equipped
with a thermometer, a distillation tower, a cooling tube, and a
nitrogen introduction tube, the oil bath temperature was set to
120.degree. C., and n-butanol was distilled away at a reduced
pressure of 10 kPa. Next, the oil bath temperature was set to
140.degree. C., and 1,5-pentamethylene diamine was distilled away
at a reduced pressure of 10 kPa, thereby obtaining 1,
5-pentamethylene diamine having a purity of 99.9% by weight.
Preparation Example 4
Manufacturing of 1,5-Pentamethylene Diisocyanate
[0246] o-Dichlorobenzene (2,000 parts by weight) was prepared in a
pressurization reactor equipped with a jacket provided with an
electromagnetic induction stirrer, an automatic pressure adjustment
valve, a thermometer, a nitrogen introduction line, a phosgene
introduction line, condenser, and a raw material-feeding pump.
Next, phosgene (2,300 parts by weight) was added from the phosgene
introduction line, and stirring was initiated. Cooling water was
made to flow through the gasket in the reactor, and the inside
temperature was held at approximately 10.degree. C. A solution
obtained by dissolving o-dichlorobenzene (2,600 parts by weight) in
1,5-pentamethylene diamine (400 parts by weight) obtained in
Preparation Example 1 was fed thereto using a feeding pump over 60
minutes, and cold phosgenation was initiated at lower than or equal
to 30.degree. C. at normal pressure. After the end of the feeding,
a light brown and white slurry-form liquid was formed in the
pressurization reactor.
[0247] Next, the liquid in the reactor was pressurized to 0.25 MPa
while being slowly heated to 160.degree. C., and furthermore, hot
phosgenation was carried out at a pressure of 0.25 MPa and a
reaction temperature of 160.degree. C. for 90 minutes. Meanwhile,
in the middle of the hot phosgenation, phosgene (1,100 parts by
weight) was further added thereto. In the process of hot
phosgenation, the liquid in the pressurization reactor turned into
a light brown clear solution. After the end of the hot
phosgenation, nitrogen gas was made to flow through at 100 L/hour
at 100.degree. C. to 140.degree. C. and was degassed.
[0248] Next, o-dichlorobenzene was distilled away at reduced
pressure, and then, similarly, 1,5-pentamethylene diisocyanate was
distilled under reduced pressure, thereby obtaining
1,5-pentamethylene diisocyanate (558 parts by weight) having a
purity of 98.7%.
[0249] Next, 1,5-pentamethylene diisocyanate (558 parts by mass)
and tris(tridecyl)phosphate (manufactured by Johoku Chemical Co.,
Ltd, trade name: JP-333E) (0.02 parts by weight of 100 parts by
weight of 1,5-pentamethylene diisocyanate) were loaded into a
four-neck flask equipped with a stirrer, a thermometer, a reflux
tube, and a nitrogen introduction tube and were heated at normal
pressure at 210.degree. C. for two hours while introducing nitrogen
into the flask, thereby obtaining 1,5-pentamethylene diisocyanate
(553 parts by weight) having a purity of 98.3%. The yield of
1,5-pentamethylene diisocyanate in the thermal treatment was
99.6%.
[0250] Next, the heated 1,5-pentamethylene diisocyanate was loaded
into a glass flask and was further purified while being refluxed
under conditions of 127.degree. C. to 132.degree. C. and 2.7 KPa
using a purification device equipped with a distillation tube
loaded with four elements of the filled substance (manufactured by
Sumitomo Heavy Industries, Ltd., trade name: Sumitomo/Sulzer
Laboratory Packing EX-type), a distillation tower equipped with a
reflux ratio adjustment timer (manufactured by Sibata Scientific
Technology Ltd., trade name: distillation head K-type), and a
cooler, thereby obtaining 1,5-pentamethylene diisocyanate having a
purity of 99.9% by weight. The degree of biomass of this
1,5-pentamethylene diisocyanate was measured using the following
method.
[0251] (Method for Measuring Degree of Biomass (%) of
1,5-Pentamethylene Diisocyanate)
[0252] The degree of biomass (%) of 1,5-pentamethylene diisocyanate
was calculated by measuring the basic value difference in the
content of radioactive carbon (C14) from CO.sub.2 generated by
combusting a sample by means of accelerator mass spectrometry (AMS)
according to the test method of American Society for Testing and
Materials (ASTM) D6866 (Standard Test Method for Determining the
Biobased Content of Natural Range Materials Using Radiocarbon and
Isotope Ratio Mass Spectrometry Analysis).
[0253] 1,5-Pentamethylene diisocyanate was made into methyl
carbamate (urethane) using methanol, and the degree of biomass of
the methyl carbamate substance was obtained by means of measurement
according to the test method of ASTM D6866. As a result, the degree
of biomass of the methyl carbamate body was 55.5%. The degree of
biomass of 1,5-pentamethylene diisocyanate was obtained from the
above-described value using the following equation and was found to
be 71%.
Degree of biomass (%) of 1,5-pentamethylene diisocyanate=(Degree of
biomass (%) of the methyl carbamate body).times.(Number of carbon
atoms in the methyl carbamate)/(Number of carbon atoms in the
1,5-pentamethylene diisocyanate)
Synthesis Example 1
Synthesis of Modified 1,5-Pentamethylene Diisocyanate (Preparation
of Polyisocyanate (1))
[0254] 1,5-Pentamethylene diisocyanate obtained in Preparation
Example 4 (hereinafter, in some cases, abbreviated as PDI) (500
parts), isobutyl alcohol (hereinafter, in some cases, abbreviated
as IBA) (1 part), 2,6-di(tert-butyl)-4-methyl phenol (hereinafter,
in some cases, abbreviated as BHT) (0.3 parts), and
tris(tridecyl)phosphite (manufactured by Johoku chemical Co., Ltd.,
trade name: JP-333E) (0.3 parts) were loaded into a four-neck flask
equipped with a stirrer, a thermometer, a reflux tube, and a
nitrogen introduction tube and were reacted together at 80.degree.
C. for two hours. Next,
N-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethylhexanoate
(manufactured by Air Products Japan, Inc. trade name:
DABCO.RTM.TMR) (0.05 parts) were added thereto as a trimerization
catalyst. After a 50-minute, o-toluenesulphoneamide (hereinafter,
in some cases, abbreviated as OTS) (0.12 parts) was added thereto.
The obtained reaction liquid was distilled at a degree of vacuum of
0.09 kPa and a temperature of 150.degree. C. by being passed
through a thin film distillation device, thereby obtaining
unreacted pentamethylene diisocyanate (401 parts). Furthermore,
o-toluenesulphoneamide (0.02 parts) was added to the obtained
composition (100 parts), thereby obtaining polyisocyanate (1) (100
parts) which is a composition including a modified
1,5-pentamethylene diisocyanate. The amount derived from
1,5-pentamethylene diisocyanate constituting this modified product
was 98% by weight.
[0255] The polyisocyanate (1) has a concentration of unreacted
1,5-pentamethylene diisocyanate of lower than 1% by weight, a
concentration of mononuclear isocyanurate of 65% by weight, a
number-average molecular weight of 554.7, a concentration of
isocyanate groups of 25%, the average number of functional groups
of 3.3, and a degree of biomass of 71%.
[0256] The degree of biomass of the polyisocyanate (1) is
calculated using the following equation in terms of carbon on the
basis of the degree of biomass of 1,5-pentamethylene diisocyanate
of 71%. DABCO.RTM. TMR which was the catalyst used to form an
isocyanurate was a mixture of N-(2-hydroxypropyl)-N,N,N-trimethyl
ammonium-2-ethyl hexanoate (33.8% by weight), 2-ethylhexanoic acid
(41.2% by weight), and ethylene glycol (25% by weight).
[0257] Degree of biomass of the polyisocyanate (1)={500 (parts by
weight of PDI)/154.2 (the molecular weight of PDI).times.7 (the
total number of carbon atoms in one PDI molecule).times.71 (degree
of biomass (%) of PDI)}/{500 (parts by weight of PDI)/154.2 (the
molecular weight of PDI).times.7 (the total number of carbon atoms
in one PDI molecule)+1 (part by weight of IBA)/74.1 (the molecular
weight of IBA).times.4 (the number of carbon atoms in one IBA
molecule)+0.3 (parts by weight of BHT)/220.4 (the molecular weight
of BHT).times.15 (the number of carbon atoms in one BHT
molecule)+0.3 (parts by weight of JP-333E)/628 (the molecular
weight of JP-333E).times.39 (the number of carbon atoms in one
JP-333E molecule)+0.02 (parts by mass of
N-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethyl
hexanoate)/118.2 (the molecular weight of
N-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethyl
hexanoate).times.6 (the number of carbon atoms in one
N-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethylhexanoate
molecule)+0.02 (parts by weight of 2-ethylhexanoic acid)/144.2 (the
molecular weight of 2-ethylhexanoic acid).times.8 (the number of
carbon atoms in one 2-ethylhexanoic acid molecule)+0.01 (parts by
weight of ethylene glycol)/62.1 (the molecular weight of ethylene
glycol).times.2 (the number of carbon atoms in one ethylene glycol
molecule)+0.12 (parts by mass of OTS)/171.2 (the molecular weight
of OTS).times.7 (the number of carbon atoms in one OTS
molecule)}=71%
Synthesis Example 2
Synthesis of Episulfide Compound (2)
[0258] Epichlorohydrin manufactured from plant-derived glycerin
(EPICHLOROHYDRIN (ECH) manufactured by Solvay) (190 g (2 mol)),
methanol (500 ml), and calcium hydroxide (1.0 g) were prepared in a
reaction flask equipped with a stirring rod, a thermometer, a gas
sealing tube, and a condenser, the inside temperature was held in a
range of 0.degree. C. to 5.degree. C. under stirring, hydrogen
sulfide gas (75 g, 2.2 mol) was blown into the reaction system
through the gas sealing tube over two hours, and the components
were aged at 5.degree. C. for three hours.
[0259] The reaction liquid was filtered, methanol was desolvated,
and then the residue was distilled away, thereby obtaining
chloromercaptopropanol. The obtained chloromercaptopropanol, pure
water (1,000 ml), and sodium hydrogen carbonate (168 g, 2 mol) were
prepared, solid iodine (254 g, 1 mol) was loaded in a split manner
over one hour while holding the inside temperature in a range of
5.degree. C. to 10.degree. C., and the components were aged at
10.degree. C. for 12 hours. The reaction liquid that had been aged
was filtered, and the obtained white crystals were dried at reduced
pressure.
[0260] The dried white crystals, methanol (250 ml), and toluene
(500 ml) were again loaded into the reactor, 47 wt % caustic soda
(240 g, 2.8 mol) was added dropwise for one hour while holding the
inside temperature in a range of 3.degree. C. to 5.degree. C., and
the components were aged for 30 minutes. After the end of the
reaction, toluene (100 ml) was added thereto, and the organic layer
was washed with pure water three times. The filtrate obtained by
dehydrating the obtained organic layer with anhydrous magnesium
sulfate and filtering the organic layer was desolvated. After the
desolvation, the residual was filtered, and bis(2, 3-epoxypropyl)
disulfide was obtained (yield: 92%).
[0261] Bis(2,3-epoxypropyl) disulfide) (100 g, 0.54 mol), thiourea
(100 g, 1.3 mol), acetic acid (2 g), toluene (250 ml), and methanol
(200 ml) were prepared in a reaction flask equipped with a stirrer,
a thermometer, and a condenser, the inside temperature was held at
15.degree. C., and the components were stirred for 16 hours. After
the end of the reaction, toluene (150 ml) was added thereto, and
the mixture was washed with saline solution, 1% sulfuric acid
water, and, again, saline solution.
[0262] The filtrate obtained by dehydrating the obtained organic
layer with anhydrous magnesium sulfate and filtering the organic
layer was desolvated. Acetonitrile (600 ml) was added to and
dissolved in the desolvated residue, and the supernatant solution
was filtered.
[0263] The residue of the obtained filtrate after the desolvation
was filtered, thereby obtaining a composition (77.5 g) (the
purity-equivalent yield was 58%) of a thioepoxy compound containing
85 wt % of bis(2,3-epithiopropyl)disulfide. This composition (50 g)
of a thioepoxy compound having a purity of 85 wt % was sorted by
means of silica gel column chromatography, thereby obtaining an
episulfide compound (2) (38 g).
[0264] The degree of biomass of the episulfide compound (2) is
calculated using the following equation in terms of carbon on the
basis of the degree of biomass of epichlorohydrin of 100%.
Degree of biomass of the episulfide compound (2)={(Number of carbon
atoms derived from epichlorohydrin in the episulfide compound
(2)).times.(Degree of biomass (%) of epichlorohydrin)}/{(Number of
carbon atoms in the episulfide compound (2))}=1000
Synthesis Example 3
Synthesis of Polythiol Compound (3)
Synthesis of Polythiol Including 4,8 and 4,7 and
5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane as Main
Component
[0265] 2-Mercaptoethanol (51.2 parts by weight), degassed water
(dissolved oxygen level: 2 ppm) (26.5 parts by weight), and an
aqueous solution of 49% by weight of sodium hydroxide (0.16 parts
by weight) were loaded into a reactor. Epichlorohydrin manufactured
from plant-derived glycerin (EPICHLOROHYDRIN (ECH) manufactured by
Solvay) (61.99 parts by weight) was added dropwise and loaded over
6.5 hours at 9.degree. C. to 11.degree. C. and, subsequently, was
stirred for 60 minutes.
[0266] Next, an aqueous solution of 17.3% soda sulfide (150.0 parts
by weight) was added dropwise and loaded over 5.5 hours at
7.degree. C. to 37.degree. C. and, subsequently, was stirred for
120 minutes.
[0267] In addition, 35.5% hydrochloric acid (279.0 parts by weight)
was loaded thereinto, then, thiourea having a purity of 99.90%
(125.8 parts by weight) was loaded thereinto, and the components
were stirred for three hours under a reflux at 110.degree. C.,
thereby causing a thiuronium chlorination reaction. After the
cooling of the mixture to 45.degree. C., toluene (214.0 parts by
weight) was added thereto, the mixture was cooled to 26.degree. C.,
an aqueous solution of 25% by weight of ammonia (206.2 parts by
weight) was loaded thereinto at 26.degree. C. to 50.degree. C. over
30 minutes, and the components were stirred at 50.degree. C. to
65.degree. C. for one hour so as to cause a hydrolysis reaction,
thereby obtaining a toluene solution of the target polythiol
compound. 36% Hydrochloric acid (59.4 parts by weight) was added to
the toluene solution, and the mixture was washed with an acid at
34.degree. C. to 39.degree. C. for 30 minutes twice. Degassed water
(dissolved oxygen level: 2 ppm) (118.7 parts by weight) was added
thereto and was washed at 35.degree. C. to 45.degree. C. for 30
minutes five times. After the toluene and a small amount of
moisture were removed under heating and depressurization, the
mixture was filtered at reduced pressures using a 1.2 .mu.m
PTFE-type membrane filter, thereby obtaining a polythiol compound
(115.9 parts by weight) including [0268] 4, 8-dimercaptomethyl-1,
11-dimercapto-3, 6, 9-trithiaundecane (Compound A), [0269] 4,
7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane
(Compound B), and [0270] 5, 7-dimercaptomethyl-1, 11-dimercapto-3,
6, 9-trithiaundecane (Compound C) as main components (an isomer
mixture of Compounds A/B/C=85/5/10 (molar ratio)).
[0271] The degree of biomass of the polythiol compound (3) is
calculated using the following equation in terms of carbon on the
basis of the degree of biomass of epichlorohydrin of 100%.
Degree of biomass of the polythiol compound (3)={(Number of carbon
atoms derived from epichlorohydrin in the polythiol compound
(3)).times.(Degree of biomass (%) of epichlorohydrin)}/{(Number of
carbon atoms in the polythiol compound (3))}=60%
Example 1
[0272] Bis(2, 3-epithiopropyl) disulfide (the episulfide compound
(2); 6.0 g) and (the polythiol compound (3); 4.4 g) including 4,
8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4,
7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, and 5,
7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane as main
components were sequentially added to a mixture of
tetrabutylammonium bromide (17.4 mg) and acidic phosphoric acid
ester (ZelecUN; 8.7 mg) and were stirred at room temperature for 15
minutes. After confirming that the solid substance was dissolved,
the polyisocyanate (1) (7 g) was sequentially added thereto and was
stirred and degassed at reduced pressure for 30 minutes, thereby
preparing a liquid mixture. The liquid mixture was filtered using a
1 .mu.m PTFE filter and then was injected into a glass mold for 2C
plano having a central thickness of 2 mm and a diameter of 80 mm.
This glass mold was heated to 30.degree. C. to 120.degree. C. for
15 hours and then was cooled to 25.degree. C. for one hour, and the
liquid mixture was removed from the glass mold, thereby obtaining a
lens. The obtained lens was further annealed at 120.degree. C. for
three hours. The obtained lens had a refractive index (ne) of 1.64,
an Abbe number of 37, a glass transition temperature (Tg) of
78.degree. C., and a degree of biomass of 78%. The dyeing
properties were also favorable.
[0273] Degree of biomass (%) of the resin=[{6 (parts by weight of
the episulfide compound (2))/210.4 (the molecular weight of the
episulfide compound (2)).times.6 (the number of carbon atoms in one
episulfide compound (2) molecule).times.100 (degree of biomass % of
the episulfide compound (2))}+{7 (parts by weight of the
polyisocyanate (1))/554.7 (the number-average molecular weight of
the polyisocyanate (1)).times.23 (the number of carbon atoms in an
average molecule of the polyisocyanate (1)).times.71 (degree of
biomass % of the polyisocyanate (1))}+{4.4 (parts by weight of the
polythiol compound (3))/366.7 (the molecular weight of the
polythiol compound (3)).times.10 (the number of carbon atoms in one
polythiol compound (3) molecule).times.60 (degree of biomass % of
the polythiol compound (3))}]/[6 (parts by weight of the episulfide
compound (2))/210.4 (the molecular weight of the episulfide
compound (2).times.6 (the number of carbon atoms in one episulfide
compound (2) molecule))+{7 (parts by weight of the polyisocyanate
(1))/554.7 (the number-average molecular weight of the
polyisocyanate (1)).times.23 (the number of carbon atoms in an
average molecule of the polyisocyanate (1)}+{4.4 (parts by weight
of the polythiol compound (3))/366.7 (the molecular weight of the
polythiol compound (3)).times.10 (the number of carbon atoms in one
polythiol compound (3) molecule)}]=78%
Example 2
[0274] Bis(2,3-epithiopropyl) disulfide (the episulfide compound
(2); 6.0 g) and (the polythiol compound (3); 4.4 g) including 4,
8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4,
7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, and 5,
7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane as main
components were sequentially added to a mixture of
tetrabutylammonium bromide (16.0 mg) and acidic phosphoric acid
ester (ZelecUN; 8.1 mg) and were stirred at room temperature for 15
minutes. After confirming that the solid substance was dissolved,
the polyisocyanate (1) (2.70 g) and m-xylylene diisocyanate (3.0 g)
were sequentially added thereto and was stirred and degassed at
reduced pressure for 30 minutes, thereby preparing a liquid
mixture. The liquid mixture was filtered using a 1 .mu.m PTFE
filter and then was injected into a glass mold for 2C plano having
a central thickness of 2 mm and a diameter of 80 mm. This glass
mold was heated to 30.degree. C. to 120.degree. C. for 15 hours and
then was cooled to 25.degree. C. for one hour, and the liquid
mixture was removed from the glass mold, thereby obtaining a lens.
The obtained lens was further annealed at 120.degree. C. for three
hours. The obtained lens had a refractive index (ne) of 1.67, an
Abbe number of 32, and a degree of biomass of 57%. The dyeing
properties were also favorable.
[0275] Degree of biomass (%) of the resin=[{6 (parts by weight of
the episulfide compound (2))/210.4 (the molecular weight of the
episulfide compound (2)).times.6 (the number of carbon atoms in one
episulfide compound (2) molecule).times.100 (degree of biomass % of
the episulfide compound (2))}+{2.7 (parts by weight of the
polyisocyanate (1))/554.7 (the number-average molecular weight of
the polyisocyanate (1)).times.23 (the number of carbon atoms in an
average molecule of the polyisocyanate (1)).times.71 (degree of
biomass % of the polyisocyanate (1))}+{4.4 (parts by weight of the
polythiol compound (3))/366.7 (the molecular weight of the
polythiol compound (3)).times.10 (the number of carbon atoms in one
polythiol compound (3) molecule).times.60 (degree of biomass % of
the polythiol compound (3))}]/[6 (parts by weight of the episulfide
compound (2))/210.4 (the molecular weight of the episulfide
compound (2).times.6 (the number of carbon atoms in one episulfide
compound (2) molecule))+{2.7 (parts by weight of the polyisocyanate
(1))/554.7 (the number-average molecular weight of the
polyisocyanate (1)).times.23 (the number of carbon atoms in an
average molecule of the polyisocyanate (1)}+{4.4 (parts by weight
of the polythiol compound (3))/366.7 (the molecular weight of the
polythiol compound (3)).times.10 (the number of carbon atoms in one
polythiol compound (3) molecule)}]+{3 (parts by weight of
m-xylylene diisocyanate)/188.2 (the molecular weight of m-xylylene
diisocyanate).times.10 (the number of carbon atoms in one
m-xylylene diisocyanate molecule)}]=57%
[0276] As described above, in Examples 1 and 2, it was possible to
obtain sulfide-based resins for optical materials which had a
degree of biomass of higher than or equal to 25% and satisfied
properties such as transparency, refractive index, and heat
resistance from a polymerizable composition including an episulfide
compound obtained using a plant-derived material. In addition, in
Example 1, both the polythiol compound and the aliphatic
polyisocyanate compound were combined only with a compound
manufactured from plant-derived materials, and it was possible to
obtain a resin for an optical material which had a high degree of
biomass of higher than or equal to 70% and satisfied properties
such as transparency, refractive index, and heat resistance. In
Example 2, m-xylylene diisocyanate was added thereto, and thus it
was possible to obtain a resin for an optical material which had a
high degree of biomass of higher than or equal to 25%, satisfied
transparency, refractive index, and the like, and, simultaneously,
had excellent dyeing properties.
[0277] The present application claims priority on the basis of
Japanese Patent Application No. 2014-047890 filed on Mar. 11, 2014
and Japanese Patent Application No. 2014-185995 filed on Sep. 12,
2014, the contents of which are incorporated herein.
Sequence CWU 1
1
4147DNAArtificialPrimer 1aaggtaccac aaaaaggata aaacaatgaa
cgttattgca atattga 47230DNAArtificialPrimer 2agtctagatt attttttgct
ttcttctttc 3032177DNAEscherichia coliCDS(24)..(2171) 3ggtaccacaa
aaaggataaa aca atg aac gtt att gca ata ttg aat cac atg 53 Met Asn
Val Ile Ala Ile Leu Asn His Met 1 5 10 ggg gtt tat ttt aaa gaa gaa
ccc atc cgt gaa ctt cat cgc gcg ctt 101Gly Val Tyr Phe Lys Glu Glu
Pro Ile Arg Glu Leu His Arg Ala Leu 15 20 25 gaa cgt ctg aac ttc
cag att gtt tac ccg aac gac cgt gac gac tta 149Glu Arg Leu Asn Phe
Gln Ile Val Tyr Pro Asn Asp Arg Asp Asp Leu 30 35 40 tta aaa ctg
atc gaa aac aat gcg cgt ctg tgc ggc gtt att ttt gac 197Leu Lys Leu
Ile Glu Asn Asn Ala Arg Leu Cys Gly Val Ile Phe Asp 45 50 55 tgg
gat aaa tat aat ctc gag ctg tgc gaa gaa att agc aaa atg aac 245Trp
Asp Lys Tyr Asn Leu Glu Leu Cys Glu Glu Ile Ser Lys Met Asn 60 65
70 gag aac ctg ccg ttg tac gcg ttc gct aat acg tat tcc act ctc gat
293Glu Asn Leu Pro Leu Tyr Ala Phe Ala Asn Thr Tyr Ser Thr Leu Asp
75 80 85 90 gta agc ctg aat gac ctg cgt tta cag att agc ttc ttt gaa
tat gcg 341Val Ser Leu Asn Asp Leu Arg Leu Gln Ile Ser Phe Phe Glu
Tyr Ala 95 100 105 ctg ggt gct gct gaa gat att gct aat aag atc aag
cag acc act gac 389Leu Gly Ala Ala Glu Asp Ile Ala Asn Lys Ile Lys
Gln Thr Thr Asp 110 115 120 gaa tat atc aac act att ctg cct ccg ctg
act aaa gca ctg ttt aaa 437Glu Tyr Ile Asn Thr Ile Leu Pro Pro Leu
Thr Lys Ala Leu Phe Lys 125 130 135 tat gtt cgt gaa ggt aaa tat act
ttc tgt act cct ggt cac atg ggc 485Tyr Val Arg Glu Gly Lys Tyr Thr
Phe Cys Thr Pro Gly His Met Gly 140 145 150 ggt act gca ttc cag aaa
agc ccg gta ggt agc ctg ttc tat gat ttc 533Gly Thr Ala Phe Gln Lys
Ser Pro Val Gly Ser Leu Phe Tyr Asp Phe 155 160 165 170 ttt ggt ccg
aat acc atg aaa tct gat att tcc att tca gta tct gaa 581Phe Gly Pro
Asn Thr Met Lys Ser Asp Ile Ser Ile Ser Val Ser Glu 175 180 185 ctg
ggt tct ctg ctg gat cac agt ggt cca cac aaa gaa gca gaa cag 629Leu
Gly Ser Leu Leu Asp His Ser Gly Pro His Lys Glu Ala Glu Gln 190 195
200 tat atc gct cgc gtc ttt aac gca gac cgc agc tac atg gtg acc aac
677Tyr Ile Ala Arg Val Phe Asn Ala Asp Arg Ser Tyr Met Val Thr Asn
205 210 215 ggt act tcc act gcg aac aaa att gtt ggt atg tac tct gct
cca gca 725Gly Thr Ser Thr Ala Asn Lys Ile Val Gly Met Tyr Ser Ala
Pro Ala 220 225 230 ggc agc acc att ctg att gac cgt aac tgc cac aaa
tcg ctg acc cac 773Gly Ser Thr Ile Leu Ile Asp Arg Asn Cys His Lys
Ser Leu Thr His 235 240 245 250 ctg atg atg atg agc gat gtt acg cca
atc tat ttc cgc ccg acc cgt 821Leu Met Met Met Ser Asp Val Thr Pro
Ile Tyr Phe Arg Pro Thr Arg 255 260 265 aac gct tac ggt att ctt ggt
ggt atc cca cag agt gaa ttc cag cac 869Asn Ala Tyr Gly Ile Leu Gly
Gly Ile Pro Gln Ser Glu Phe Gln His 270 275 280 gct acc att gct aag
cgc gtg aaa gaa aca cca aac gca acc tgg ccg 917Ala Thr Ile Ala Lys
Arg Val Lys Glu Thr Pro Asn Ala Thr Trp Pro 285 290 295 gta cat gct
gta att acc aac tct acc tat gat ggt ctg ctg tac aac 965Val His Ala
Val Ile Thr Asn Ser Thr Tyr Asp Gly Leu Leu Tyr Asn 300 305 310 acc
gac ttc atc aag aaa aca ctg gat gtg aaa tcc atc cac ttt gac 1013Thr
Asp Phe Ile Lys Lys Thr Leu Asp Val Lys Ser Ile His Phe Asp 315 320
325 330 tcc gcg tgg gtg cct tac acc aac ttc tca ccg att tac gaa ggt
aaa 1061Ser Ala Trp Val Pro Tyr Thr Asn Phe Ser Pro Ile Tyr Glu Gly
Lys 335 340 345 tgc ggt atg agc ggt ggc cgt gta gaa ggg aaa gtg att
tac gaa acc 1109Cys Gly Met Ser Gly Gly Arg Val Glu Gly Lys Val Ile
Tyr Glu Thr 350 355 360 cag tcc act cac aaa ctg ctg gcg gcg ttc tct
cag gct tcc atg atc 1157Gln Ser Thr His Lys Leu Leu Ala Ala Phe Ser
Gln Ala Ser Met Ile 365 370 375 cac gtt aaa ggt gac gta aac gaa gaa
acc ttt aac gaa gcc tac atg 1205His Val Lys Gly Asp Val Asn Glu Glu
Thr Phe Asn Glu Ala Tyr Met 380 385 390 atg cac acc acc act tct ccg
cac tac ggt atc gtg gcg tcc act gaa 1253Met His Thr Thr Thr Ser Pro
His Tyr Gly Ile Val Ala Ser Thr Glu 395 400 405 410 acc gct gcg gcg
atg atg aaa ggc aat gca ggt aag cgt ctg atc aac 1301Thr Ala Ala Ala
Met Met Lys Gly Asn Ala Gly Lys Arg Leu Ile Asn 415 420 425 ggt tct
att gaa cgt gcg atc aaa ttc cgt aaa gag atc aaa cgt ctg 1349Gly Ser
Ile Glu Arg Ala Ile Lys Phe Arg Lys Glu Ile Lys Arg Leu 430 435 440
aga acg gaa tct gat ggc tgg ttc ttt gat gta tgg cag ccg gat cat
1397Arg Thr Glu Ser Asp Gly Trp Phe Phe Asp Val Trp Gln Pro Asp His
445 450 455 atc gat acg act gaa tgc tgg ccg ctg cgt tct gac agc acc
tgg cac 1445Ile Asp Thr Thr Glu Cys Trp Pro Leu Arg Ser Asp Ser Thr
Trp His 460 465 470 ggc ttc aaa aac atc gat aac gag cac atg tat ctt
gac ccg atc aaa 1493Gly Phe Lys Asn Ile Asp Asn Glu His Met Tyr Leu
Asp Pro Ile Lys 475 480 485 490 gtc acc ctg ctg act ccg ggg atg gaa
aaa gac ggc acc atg agc gac 1541Val Thr Leu Leu Thr Pro Gly Met Glu
Lys Asp Gly Thr Met Ser Asp 495 500 505 ttt ggt att ccg gcc agc atc
gtg gcg aaa tac ctc gac gaa cat ggc 1589Phe Gly Ile Pro Ala Ser Ile
Val Ala Lys Tyr Leu Asp Glu His Gly 510 515 520 atc gtt gtt gag aaa
acc ggt ccg tat aac ctg ctg ttc ctg ttc agc 1637Ile Val Val Glu Lys
Thr Gly Pro Tyr Asn Leu Leu Phe Leu Phe Ser 525 530 535 atc ggt atc
gat aag acc aaa gca ctg agc ctg ctg cgt gct ctg act 1685Ile Gly Ile
Asp Lys Thr Lys Ala Leu Ser Leu Leu Arg Ala Leu Thr 540 545 550 gac
ttt aaa cgt gcg ttc gac ctg aac ctg cgt gtg aaa aac atg ctg 1733Asp
Phe Lys Arg Ala Phe Asp Leu Asn Leu Arg Val Lys Asn Met Leu 555 560
565 570 ccg tct ctg tat cgt gaa gat cct gaa ttc tat gaa aac atg cgt
att 1781Pro Ser Leu Tyr Arg Glu Asp Pro Glu Phe Tyr Glu Asn Met Arg
Ile 575 580 585 cag gaa ctg gct cag aat atc cac aaa ctg att gtt cac
cac aat ctg 1829Gln Glu Leu Ala Gln Asn Ile His Lys Leu Ile Val His
His Asn Leu 590 595 600 ccg gat ctg atg tat cgc gca ttt gaa gtg ctg
ccg acg atg gta atg 1877Pro Asp Leu Met Tyr Arg Ala Phe Glu Val Leu
Pro Thr Met Val Met 605 610 615 act ccg tat gct gca ttc cag aaa gag
ctg cac ggt atg acc gaa gaa 1925Thr Pro Tyr Ala Ala Phe Gln Lys Glu
Leu His Gly Met Thr Glu Glu 620 625 630 gtt tac ctc gac gaa atg gta
ggt cgt att aac gcc aat atg atc ctt 1973Val Tyr Leu Asp Glu Met Val
Gly Arg Ile Asn Ala Asn Met Ile Leu 635 640 645 650 ccg tac ccg ccg
gga gtt cct ctg gta atg ccg ggt gaa atg atc acc 2021Pro Tyr Pro Pro
Gly Val Pro Leu Val Met Pro Gly Glu Met Ile Thr 655 660 665 gaa gaa
agc cgt ccg gtt ctg gag ttc ctg cag atg ctg tgt gaa atc 2069Glu Glu
Ser Arg Pro Val Leu Glu Phe Leu Gln Met Leu Cys Glu Ile 670 675 680
ggc gct cac tat ccg ggc ttt gaa acc gat att cac ggt gca tac cgt
2117Gly Ala His Tyr Pro Gly Phe Glu Thr Asp Ile His Gly Ala Tyr Arg
685 690 695 cag gct gat ggc cgc tat acc gtt aag gta ttg aaa gaa gaa
agc aaa 2165Gln Ala Asp Gly Arg Tyr Thr Val Lys Val Leu Lys Glu Glu
Ser Lys 700 705 710 aaa taa tctaga 2177Lys 715 4715PRTEscherichia
coli 4Met Asn Val Ile Ala Ile Leu Asn His Met Gly Val Tyr Phe Lys
Glu 1 5 10 15 Glu Pro Ile Arg Glu Leu His Arg Ala Leu Glu Arg Leu
Asn Phe Gln 20 25 30 Ile Val Tyr Pro Asn Asp Arg Asp Asp Leu Leu
Lys Leu Ile Glu Asn 35 40 45 Asn Ala Arg Leu Cys Gly Val Ile Phe
Asp Trp Asp Lys Tyr Asn Leu 50 55 60 Glu Leu Cys Glu Glu Ile Ser
Lys Met Asn Glu Asn Leu Pro Leu Tyr 65 70 75 80 Ala Phe Ala Asn Thr
Tyr Ser Thr Leu Asp Val Ser Leu Asn Asp Leu 85 90 95 Arg Leu Gln
Ile Ser Phe Phe Glu Tyr Ala Leu Gly Ala Ala Glu Asp 100 105 110 Ile
Ala Asn Lys Ile Lys Gln Thr Thr Asp Glu Tyr Ile Asn Thr Ile 115 120
125 Leu Pro Pro Leu Thr Lys Ala Leu Phe Lys Tyr Val Arg Glu Gly Lys
130 135 140 Tyr Thr Phe Cys Thr Pro Gly His Met Gly Gly Thr Ala Phe
Gln Lys 145 150 155 160 Ser Pro Val Gly Ser Leu Phe Tyr Asp Phe Phe
Gly Pro Asn Thr Met 165 170 175 Lys Ser Asp Ile Ser Ile Ser Val Ser
Glu Leu Gly Ser Leu Leu Asp 180 185 190 His Ser Gly Pro His Lys Glu
Ala Glu Gln Tyr Ile Ala Arg Val Phe 195 200 205 Asn Ala Asp Arg Ser
Tyr Met Val Thr Asn Gly Thr Ser Thr Ala Asn 210 215 220 Lys Ile Val
Gly Met Tyr Ser Ala Pro Ala Gly Ser Thr Ile Leu Ile 225 230 235 240
Asp Arg Asn Cys His Lys Ser Leu Thr His Leu Met Met Met Ser Asp 245
250 255 Val Thr Pro Ile Tyr Phe Arg Pro Thr Arg Asn Ala Tyr Gly Ile
Leu 260 265 270 Gly Gly Ile Pro Gln Ser Glu Phe Gln His Ala Thr Ile
Ala Lys Arg 275 280 285 Val Lys Glu Thr Pro Asn Ala Thr Trp Pro Val
His Ala Val Ile Thr 290 295 300 Asn Ser Thr Tyr Asp Gly Leu Leu Tyr
Asn Thr Asp Phe Ile Lys Lys 305 310 315 320 Thr Leu Asp Val Lys Ser
Ile His Phe Asp Ser Ala Trp Val Pro Tyr 325 330 335 Thr Asn Phe Ser
Pro Ile Tyr Glu Gly Lys Cys Gly Met Ser Gly Gly 340 345 350 Arg Val
Glu Gly Lys Val Ile Tyr Glu Thr Gln Ser Thr His Lys Leu 355 360 365
Leu Ala Ala Phe Ser Gln Ala Ser Met Ile His Val Lys Gly Asp Val 370
375 380 Asn Glu Glu Thr Phe Asn Glu Ala Tyr Met Met His Thr Thr Thr
Ser 385 390 395 400 Pro His Tyr Gly Ile Val Ala Ser Thr Glu Thr Ala
Ala Ala Met Met 405 410 415 Lys Gly Asn Ala Gly Lys Arg Leu Ile Asn
Gly Ser Ile Glu Arg Ala 420 425 430 Ile Lys Phe Arg Lys Glu Ile Lys
Arg Leu Arg Thr Glu Ser Asp Gly 435 440 445 Trp Phe Phe Asp Val Trp
Gln Pro Asp His Ile Asp Thr Thr Glu Cys 450 455 460 Trp Pro Leu Arg
Ser Asp Ser Thr Trp His Gly Phe Lys Asn Ile Asp 465 470 475 480 Asn
Glu His Met Tyr Leu Asp Pro Ile Lys Val Thr Leu Leu Thr Pro 485 490
495 Gly Met Glu Lys Asp Gly Thr Met Ser Asp Phe Gly Ile Pro Ala Ser
500 505 510 Ile Val Ala Lys Tyr Leu Asp Glu His Gly Ile Val Val Glu
Lys Thr 515 520 525 Gly Pro Tyr Asn Leu Leu Phe Leu Phe Ser Ile Gly
Ile Asp Lys Thr 530 535 540 Lys Ala Leu Ser Leu Leu Arg Ala Leu Thr
Asp Phe Lys Arg Ala Phe 545 550 555 560 Asp Leu Asn Leu Arg Val Lys
Asn Met Leu Pro Ser Leu Tyr Arg Glu 565 570 575 Asp Pro Glu Phe Tyr
Glu Asn Met Arg Ile Gln Glu Leu Ala Gln Asn 580 585 590 Ile His Lys
Leu Ile Val His His Asn Leu Pro Asp Leu Met Tyr Arg 595 600 605 Ala
Phe Glu Val Leu Pro Thr Met Val Met Thr Pro Tyr Ala Ala Phe 610 615
620 Gln Lys Glu Leu His Gly Met Thr Glu Glu Val Tyr Leu Asp Glu Met
625 630 635 640 Val Gly Arg Ile Asn Ala Asn Met Ile Leu Pro Tyr Pro
Pro Gly Val 645 650 655 Pro Leu Val Met Pro Gly Glu Met Ile Thr Glu
Glu Ser Arg Pro Val 660 665 670 Leu Glu Phe Leu Gln Met Leu Cys Glu
Ile Gly Ala His Tyr Pro Gly 675 680 685 Phe Glu Thr Asp Ile His Gly
Ala Tyr Arg Gln Ala Asp Gly Arg Tyr 690 695 700 Thr Val Lys Val Leu
Lys Glu Glu Ser Lys Lys 705 710 715
* * * * *