1
SJW: IV I CAT ION
POLYTH.IOL COMPOSITION, POLYMERlttAK^: COMPOSITION FOR OPTICAL
MATERIAL AND USE THEREOF
TECHNICAL FIELD
[Q001J
The present invention relates to a polythiol compos "i ti nn, a
polymer-! zabl e composj t J on for an optica J materi al and use thereof.
10
BACKGROUND ART
[0002]
SlEice a plastic: lens is lighter, hardly brokGii and capable
oi being dyed, compared to an inorganic len^, the plastic lens lias
1!J recently become widely used rapidly in an optical element such as
a spectacJ e J ens or a camera lens.
\nmri]
Higher performance has been demanded for a resin for the
p l a s t i c lens and high r e f r a c t i v e -index, high Abbe number, low
20 density, high heat--resistance, or t h e ] .i ke has been required, Ho
far yari ous kinds of r e s i n materi al s for the 1 ens have been rievel oped
and vised,
[0004]
Among those, an optical material comprised of a
25 polythiourothane-based r e s i n has high r e f r a c t i v e index and high
Abbe number, and is excellent in the impact r e s i s t a n c e , the
d y e a b i l i t y , the processabi1ity, or the l i k e . The
2
pol y t h i o u r e t h a n e - b a s e d r e s i n can be o b t a i n e d by r e a c t i n g a
p o l y t h i o l w i t h a p o l y i s o ( t h i o ) c y a n a t e compound, or t h e l i k e*
[0005]
I n a cajse oi u a i ng in Lhc p l a s t i c l e n s , t he
5 p o l y L h i o u x e t h a n e - b a s e d r e ^ i n i a r e q u i r e d t o Cciu^e l o a ^ c o l o r a L i o n ,
have exoeJ J ent. r e s i n col or and be trLiEiaparezice. In a c a s e where
t h e q u a l i t y o f p o l y t h i o l was d e t e r i o r a t e d , t h e r e were c a s e s where
t h e q u a ] i t y of t h e o b t a i n e d r e s i n was a l s o d e t e r i o r a t e d.
P a t e n t documents which r e l a t e to a p r o c e s s of p r o d u c i ng
1 0 p o l y t h i o l i n c l u d e t h e f o l l o w i n g p a t e n t d o c u m e n t s.
[0006]
I n P a t e n t Document 1 or P a t e n t Document 2, a method In which
2 - m e r e a p t . o e t h a n o ] r e a c t s w i t h c p i c h l o r o h y d r i n , the o b t a i n ed
compound r e a c t s w i t h t h i o u r e a t o o b t a i n HEI i ^ o t h i u r o n i u i n s a l t , and
1 f j next t h e i s o t h i u r o n i v;m sa I t is h y d r e l y z e d to o b t a i n t h e a p e e l l i e
p o l y t h i ol compound i s d e s c r i b e d.
[0007]
i n P a t e n t Document 3, a p r o c e s s of p r o d u c i n g a p o l y t h i ol
compound i n which Lhc amount of t h e s p e c i f i c i m p u r i t i e s i n c l u d ed
2 0 in 2 - m e r c a p t o e L h a r s e l i s a c t t o t h e p r e d e t e r m i n e d r a n g e i s d e s c r i b e d .
I n P a t e n t Document 4, a p r o c e s s of p r o d u c i n g a p o l y t h i ol
compound i n which c a l c i um c o n t e n t i n c l u d e d i n t h i o u r e a i s s e t to
t h e p r e d e t e r m i n e d r a n g e i s d e s c r i b e d.
25 RELATED DOCUMENT
PATENT DOCUMENT
[0008]
3
[Patent Document 1] Japanese Unexamined Patent Publication
No, 2-270859
[Patent Document 2] Japanese Unexam-j ned I'atent Publ j cati on
No. 7-252207
h [Patent Document 3] PCT International Publication No.
2007/129449
[Patent Document 4] PCT InternaLiorial Publication No..
7(107/179450
10 DJ3CLOSURE OF THE INVENTION
[0009]
However, in a case where the plastic lens comprised of the
polyLhiourethane-based resin is produced by using Lhc pclythiol
compound obtained in the methods described in Lhe document, there
15 was loom for improvement of optical proper Lies, such as color,
transparency, stri at i on.
The present inventors ascertained that a trace of the specific
component is included in the pol ythiol compound, as a result, oi
extensive studios in order to improve the opt.ical properties, and
20 found that the specific component included at the predetermined
amount affects the reaction (po] ymeH zati on) aoti vi ty i n a reaction
{polymerization reaction) of the pol ythiol compound ^r\d a
polyisocyanatc compound.
[0010]
25 The present invention can be given as below*
fl] A polyLhiol composition includes a polythiol compound benzene,
15 I,- 3, 5 - t r i s [mercap Lome t h y leneoxy) besi^ene,
1, 3, 5 - L r i s (mercaptooLhylencoxy) benzene.
Ilowevor, the p o l y t h i o l compound {A} is not l i m i t e d to only
t h e exemplary compounds.
[01)22]
20 1 n t h e p r e s e n t embodiment, na a p o i y L h i o l compound {A), a p o l y t h J ol
compound whj oh .1 s p r i m a r i l y comprised of at l e a s t one kind se] e o t ed
f rons t h e groiip con si s t i n q of
^-meroapt.omethyl -1 , 8 - d i m e r e a p t o - 3 , 6-diLhiaocLune r e p r e s e n t e d by
t h e f ol 1 owi ng f orrnvil a (5) ,
25 A , ft-rtimercaptometbyl - \ , \\ - d i mereLspLo-3f 6, 9-Lr ithiLiundecane
r e p r e s e n t e d by t h e fol 1 ow.inq formula ( b] ,
4, 7-d:meroaptoTuet hyl -J , l I - d i m e r c a p L o - 3 , G, 9-LriLhiaiindccane
r e p r e s e n t e d by t h e following formula (7), and
b, V-dimeroaptonsetbyl - 1 , 1 1 -dimcrcapLo-3, 6, 9-LriLhiaundocaiie
r e p r e s e n t e d by t h e fol lowing lorsitultt (8) can be p r e f e r a b l y used
[00731
(5)
[0024J
S
HS-
^ S
i—S—
SH
(6)
(7)
HS- , SI!
—S—
(8)
(Ndtrogen-contai ninq compound (B))
10 The ni t r o g e n - o o n t ^ i ni nq compound (B) has a s t i u c t u r c in which
at 1 e a s t one of a mercapto group of t h e p o l y L h i o l compound (A) having
t h r e e or more mercapto groups is r e p l a c e d with a qroup r e p r e s e n t ed
by t h e f o l l o w i n g formula {a) and at l e a s t one other mercapto group
of t h e p o l y t b i o l compound iA) is r e p l a c e d wiLh a liydroxyl group,
10
002G
NHz
*
\S'
N^ MH2
N.N. ,NH
(a)
%S
NH2
[0027]
In the formula, * represents an atomic bonding.
5 Moreover, the nitrogen-cont.aininq compound {B) can include
a salt oi the compound having the structure described above. The
salt iy nuL particularly limited, however, for example, includes
carboxylic acid such ay acetic acid, an organic acid such as
methanesul foni c acid, a compound having a more^pLo (SH) group, an
10 3 norgani c acid such as hydrochloric acid, suliuric acid or
phosphori c aci d,
[0028]
In the polythiol composi tion of the piesent embodiment, the
peak area of the nitrogen-contain: ng compound [ft) to the peak areu
lb of 100 o£ Lho polyLhiol compound [A} {hereinafter^ also referred.
Lo simply ay "the ratio oi the peak ar^.^ of the ni trogen-oontai ninq
compound (B)") is equal Lo or less than 3.{]r preferably equal Lo
or ltitsa than 1.5, and more preferably equal to or less than 0. bO
in a high performance liquid chromatography measurement, 'I'he 1 ower
20 limit ei Lhe ratio oi Lhe peak ares, of the ni trogen-contai ni nq
compound (B) doe^ not particularly exist, however, ts preferably
equal Lo or more Lhun 0.01, considering the number of step in
purificaLion in an industrial producti on seale.
11
In the usual e a s e , the n i t r o g e n - c o n t a i n i n g compound {B) is a m i x t u re
of a p l u r a l i t y oi isomers, and appears as a peak at t h e predeterrnii ned
r e t e n t i o n time in high performance "liquid chromatography,
Mnraover, the peaks of t h e n i t r o g e n - c o n t a i n i n g compound 029]
The r a t i o of t h e peak a r e a oi t h e n i t r o g e n - c o n t a i n i n g compound
(B) can be c a l c u l a t e d from t h e i o l l o w i n g e x p r e s s i o n based on t he
peak area of high performance l i q u i d chromatography.
15 Expression: f[peak area oi n i t r o g e n - e o n L a i n i n g compound
{B)]/[peak area of p o l y t h i o l compound (A)J}*10Q
Moreover, the c o n d i t i o n s of high periormance l i q u id
chromatography a i e a p p r o p r i a t e ] y se.l eoteri accordi ng to s t r u c t u r e s ,
p r o p e r t i e s , oi the l i k e ol the p o l y t h i o l compound {A) and the
?0 n i t r o g e n - c o n t a i n i n g compound (B) .
ID030J
The r a t i o oi t h e peak a r e a of t h e ni t r o q e n - c o n t a i ni ng compound
(U) in t h e p r e s e n t embodiment, for example, can be d e s c r i b e d , in
a case where t he p o l y t h i o l compound (A) is
?Fi ^-meronptomethy] - 1 . , H-dintereapto-"3, G-di t h i a o c t a n e " and t he
n i t r o g e n - c o n t a i n i n g compound (B) is "a compound in which one of
a mercapto group ot the p o l y t h i o l compound (A) is replaced with
12
a group represented by the formula [a} described above and other
one of a mercapLo group is replaced with a hydroxyl group.
[0031]
In a caue oi measuring by high performance liquid
5 chromatography under the conditions described below and calculaling
the ratio of the peak area of the nitrogen-containing compound (B)
baaed on the expressi o'n described above, the peak area of the
nitrogen-containing compound (tif wbi r.h appears at the retenti on
time from 4.3 minutes to 5.6 minutes is equal to or less than 3.(1,
10 preferably equal Lo or less than 1-0, and more preferably equal
Lo or loss LhEiii O.bO, with respect to the peak area of 100 of the
polyLhiol compound (A) which appears at the reLerttion Lime from
12.0 minutes to ]3-f> minutes. The lower limit of the ratio oi Lite
peak Brf:B of the ni t rogen-containing compound (R) does not
J 5 particularly exi st, however, iu prelexably equal to or more than
0.01, consi dering the number of step in puri fi oation i n an
industrial production seale.
Moreover, in a case of measviri ng under the conditions descri bed
below, any peak of Lhe nitrogen-containing compound (B} which is
20 a mixture of a pluraliLy of isomers appears within the retention
time described above and each peak may be overlapped.
[0032]
MeasureiiienL condiLions of high performance liquid
chromatography
25 Column: YMC-Puck ODS-J\ A-312 {£15*6 mm*150 inift)
Mobile phu^e : aceLoEiiLr ile/0 . 01 moi-po Labium dihydrogen
phosphaLe aqueous J5olution-60/40 (vol /vol }
13
Column temper a t u x e : •iO^C
Flow r a t e : ] . D ml /rnin
D e t e c t o r : ITV d e t e c t o r , wavelength 230 nm
l J r e p a r a t i on of measurement s o l u t i o n : J 60 rnq of a sampl e IK
5 dissolved and mixed in 10 ml of aceton-i t r i 1 e ,
I n j e c t i o n volume: 2uL
[0033]
Furthermore, the r a t i o oi the peak, area ol the
niLrogcn-coiiLLiining compound (B) in t h e p r e s e n t embodiment, for
1 0 example, can a l s o be d e s c r i b e d in a e a s e where Lhe p o l y t h i o l compound
(A} : s '"a pol y t h i ol compound which is p r i m a r i l y comprised ol uL
l e a s t one kind s e l e c t e d from t h e group c o n s i s t i n g of
5, 7 - d i m e r c a p t o m e t h y l - l , 1 1 - d i m e r e a p t o - 3 , 6, ^ - t r i t h i aundeeane,
4 , 7-dimercaptomcLhyl-l, l l - d i n i e r c a p t o - 3 f 6r 9 - t r i t h i a u n d e e a n e , and
15 4 , 8-dimercaptomcLhyl-l, l l - d i r a e r c a p t o - 3 , 6, 9 - t r i t h i a u n d e e a n e " and
Lhe n i t r o g e n - c o n L a i n i n g compound (B) is "a compound in which one
ol a mereapto qxoup oi t h e p o l y t h i o l compound (A) is x-eplaced with
D. group r e p r e s e n t e d by t h e iormula (a) d e s c r i b e d above rj.[t.d o t h er
one oi mereapto qroup i s r e p l a c e d wiLh a hydroxy 1 group".
20 [0034j
In a r.xs& of measuring by high periuriiiunce l i q u id
chromatography under t h e c o n d i t i o n s d e s c r i b e d below and c a l c u l a t i ng
t h e r a t i o of t h e oeak area of t h e n i L r o g e i i - c o i i t a i r i i n q compound {B)
based on the e x p r e s s i on d e s c r i b e d above, the peak area ol the
?T> n i t r o q e n - c o n t a j ni nq compound (B) which appears at t h e r e t on Lion
time from 6-5 minutes to 8.0 minutes is equal to or ler.s t h a n 3.0,
preferab.l y equal to or 1 e s s than 2,0, and more pre i o r a b l y equal
14
to or l e s s than 1.5, with r e s p e c t Lo the peak. ctrea of 100 of the
pol y t h i o} compound [&} whi ch appears at the r e t e n t i o n time from
3?,D mi n u t e s to 2£l. Q m"i n u t e s . The lower l i m i t of t h e r a t i o of t he
peak area of the n i t r o g e n - c o n t a i n.i ng compound (h) does not
S p a r t i c u l a r l y e x i s t . , however, is p r e f e r a b l y equal to or more than
0 . 0 1 , c o n s i d e r i n g Lhe number of s t e p In p u r i f i c a t i o n in an
in.du.til_ r i a l product i on s c a l e -
Moreover, in a case of measuring under t h e c o n d i t i o n s d e s c r i b ed
below, any peak of t h e n i t r o g e n - c o n t a i n i n g compound (B) which is
10 a mixture of a pi v.ral i ty of isomers appears w i t h i n t h e r e t e n t i on
tiree d e s c r i b e d above and each peak may be overlapped.
[0035]
Measurement c o n d i t i o n s of high performance 1 i qui d
oil r oiti rj. t o g r a ph y
lb Column: YMC-Pack ODS-Z_ A-312 (S50>6 mm*.150 mm)
Mobile phase: a c e t o n i L r i l e / 0 . 0 1 mol-potassium dihydrogen
phosphate aqueous s o l u t i on-60/40 (vol/vol)
Col uirm t e m p e r a t u r e : ^O^C
Kl ow r a t e : .1.0 ml/min
20 l>et.ector: UV d e t e c t o r , wavelength 2'30 rim
P r e p a r a t i on of measurement s o l u t i o n : 160 my oi a sample, is
d i s s o l v e d and mixed in 10 ml of a c e t o n i i r i l e.
I n j e c t i o n volume: 2uii
By s e t t i n g the r a t i o of t h e peak area of the
25 n i t r o g e n - c o n t a i n i n g compound {H} to t h e range d e s c r i b e d above, it
i s p o s s i b l e to o b t a i n the pi ast.i c 1 ens cornpri serf of the
p o l y t h i o u r e t h a n e - b a s e d r e s i n which is e x c e l l e n t in q u a l i t y such
l b
as odor, transparency and atriation .
L0G36]
As described above, in the present, embodiment., by giving two
typea of the pelythi ol compound described above as a polythiol
5 compound (A) , as an example, a case where the nitrogen-containing
compound (BJ is "a compound in which one of a roercapto group o±
two typos oi the polyLhiol compound described above is replaced
with a group represented by the formula (a) described above and
oLher one oi a ntereapto group is replaced with a hydroxyl group"
10 has been descri bed, however, aspects including Lhe
nitrogen-containing compound {!!>) as El) or {2) described below may
also be included,
(1) The nitrogen-centaining compound {H] in which at least
one of a mcrcapLo group of two types of the polythiol coinponnd
15 described above is replaced witb a group represented by the formula
(a) described above Luid est least t.wo mercapto groups are replaced
with a hydroxyl group.
(2) The nitrogen-containing compound (B> in which at least
two oi a mercapto group oi Lwo types of Lhe polyLhiol compound
?{) described above Eire- repl aced with a group represented by the iormula
{&.) described above and at leasL one of a mcrcapLo group is replaced
with a hydroxyl group.
KJOHV |
In addifi on, i n the present embodiment, a ease where Lhe
?T> DOI ythi ol compound (A) ^r
The polyLhiol composition of the present embodiment, can be
!j produced by Lho following steps.
Step A: The polyaleohol compound is obtained,
Step H: The polyaleohol compound obtained in the step A reacts
with thiourea in the presence of hydrogen chloride Lo obLain an
i sothi uronium salt*
10 Step C: while a reaction solution including the ii^oLhiuronium
salt obtained in the step H is maintained at the temperature Iron*
20"C Lo GG"C, aqueous ammonia is added i nt.o the reaction solution
within 80 minutes and Lhe iscthiuronium sa]t is hydrolyzed at the
temperature from 2flnC to 60"C to obtain the polythiol composition.
lb Step D: The polythiol composition obtained in the step O is
purified.
[00391
I n the present embodiment, Lhe cases where the polyLhiol
compositions includi no two types el Lhe polythiol compound
20 described below are obtained are described.
As a joolythi ol compound, a ease oi producing "a polyLhiol
compound which is primarily comprised oi
4-mercaptomethyl-l,8-dimercapto-3, 6-dithiaoctan" is set Lo an
embodiment, I and a case of producinq '"a polythiol compound which
25 is primarily comprised of at least one kind selected from the group
consisting of
4 , fl-dimercaptomethyl- 1,11 -dimercapLo-3, 6, 9-Lr iihiaurideeuiie,
17
4, 7 - d i m c r c a p t o m e t h y l - I , 1"J - d i r n e r c a p t o - 3 , 6, 9 - t r i t t i i aundecane, imd
b, 7-dlraojLCcEptosiioLhyl-l, l l - d i m e r c a p t o - 3 , f>, 9 - t r i t h i a v m d e c a n e " i a
s e t to an ombodliisonL II to be d e s c r i b e d.
[QQ'IQJ
[Embodiment T |
Hereinafter, each step w i l l bo d e s c r i b e d in order.
[0041]
(Step AJ
In t h e s t e p A, a 2-mercaptoethanol r e a c t s wi th an epi ha"] o h y d r in
compound repiCseriLcd by the f o l l o w i n g f orjnu] a (1) , t h e r e b y it is
p o s s i b l e to o b t a i n a Lxiol compound r e p r e s e n t e d by Lhe following
formula (2) as a po.l y a l c o h o l compound,
[0047]
o
X
0)
0043]
L0044]
In t h e formula (1), X is a halogen atom which is a f l u o r i ne
atom, a c h l o r i n e atom, a bromine atom, or an i o d i n e atom, anri
p r e i e r a b i y a c h l o r i n e atoiii,
| 004bJ
I n the p r e s e n t embodiment, the r e a c t i o n can be performed in
18
a range from 10&C to EjG°(I, preferably from ]fj°c to 50&CJ, and more
preferably from 25°C to 45°C. 'I'he reaction temperature is lower
than 30°C, since the reaction does not progress in the iirsL half
of the reaction, unrcactcd materials are stagnated in the reaction
b system, arid thus there are cases where Lhe reaction rapidly progress.
When higher than '">0°C, there are eases where color of the lens
deqenerat.es. That is, when in a ranqe of the temperature described
above, the control 1 abi 1 i ty of the react.! on i s excel] ent, further
col or of the obtaj ned piasti c J ens is aJ so excel 1ent-
10 The reaction can be performed for 2 hours to 12 hours, and
preferably for 3 hours to 10 hours.
[0046]
The reaction described above, lor example, can be performed
as iollows. Firstly, aftei 2-meieaptoethanol and a base are added
lb inLo water or 1 nwer alcohol solvent such as methanol, or ethanol
as necessary, epi hal ohydrin is added dropwise to perforin the
reaction. It is preferahle to adjust so that the reacti on
temperature and the react J on time are in the ranges described above.
Moreover, the reaction time includes the time of adding dropwise
20 of epi hal ohydrin, and the temperature of the reaction sol Lit ion needs
to be adjusted to the reaction temperature described above when
adding dropwise. The used amount of ?-mercaptoethanol is more
preferably equal to or more than .1 .9 mol and equal to or loss than
2-1 mol, with respect to 1 mol of epihalohydrin.
25 [0047]
As a base, a metal hydroxide such as sodium bydruxide,
p o t a s s i um h y d r o x i d e , a metal carbonate such as sodium c a r b o n a t e,
19
pnt.i1ssiurn carbonate, and a tor Liary amine such as triethylamiiio,
tri butyl ami ne are i nclnrleri, however , sodium hydros! de .is most
preferable, in the light of the reactivity and the economy- In a
case of a monovalent base, the used amount of the base is equal
5 to or more than 0, 5 moi and equal to or 1 ess than 2 moi, and preferabl y
equal Lo or more than 0.3 moi and equal to or less Lhan 1.1 moi,
wiLh respect Lo 1 moi oi epihnlohydrin. In a case ol a bivalent
base, the half amount of the used amount. oi a monovalent base is
preierable. The base can be used as an aqueous solution, an alcohol
3 solution, or the 1i ke, and in a case or. usinq as a solution, the
concentration of the base can be appropriately selected.
[0048]
In addition, except the method described above, by the
two-stage reaction in which once diol is produced represented by
5 the following loriiiula (3), thereafter 2-mercaptoothanol is added
dropwise, it is also possible to obtain the Lriol compound
reprosecuted by the formula (2) .
In the method, fi rstiyr 2 mereaptoethanol reao£ s with an
epihalohydri r\ compound represented by the formula {1) described
0 above to obtai n a compound represented by the foilowi nq for inula
(3) .
[coayi
S ^^
-—Oi]
(3)
1 CI
00 M M
Trie reaction temperature is from 10°C to 2Q"C. The reaction
time is from approximately ? hours to 10 hours.
[0051]
Next, the compound described above: represented by the formula
5 (3} reads with 2-mercaptocthanol to obtain the triol compound
represented by the formula (2) . The reaction temperature i.s from
10°C to r>[}°C, preferably lbnC to 50UC, and more preferably. 20°c:
to 45°C The reaction time is from. approximately 2 hours to 12
hours.
10 By performing the steps i si a range oi the temperature described
above, the controllability of the reaction is excellent,
L0052]
Specifically, the method can be performed &3 follows.
Firstly, epihalohydrin is added dropwise into a solution
15 comprised of 2-mercaptoethanol, and water or lower alcohol so! ution
such as methanol or ethanol as necessary, and an aqueous solution
of the base of the catalyst quantity or lower alcohol such 3^
methanol or ethanol solution of the base oi the catalyst quantity,
It is preferable to adjust so that the reaction temperature and
20 the reaction time are in the ranges described above. In the solution
to which epihalohydrin is added dropwise, the used amount of
2-mercaptoethanol is equal to or moce than 1 moi and equal to or
loss than 3 moi, and preferably equal to or more than 1 moi and
equal to or lesc than 2 moi, with respect to 1 mo! of epihalohydrin.
2b In addition, the base described above of the catalyst quantity is
used, and in a case ol a monovalent base, the used amount oi the
base described above is equal to or maie than 0.001 rnol and equal
21
to or less thFjn 0.1 moi, with respect to epi bal ohydrin. in a case
of a b.i val ent base, the halt amount of the used amount of a monoval ent.
base .is preferable. The base can be used as an aqueous solution,
an al cobol soluti on, or the like, and In a case of using as a soiuLion,
5 the concentration of the base can be appropriately selected. By
epihalohydrin being added dropwise into the solution described
above, diol represented by the formula {.!) is obtained.
[0Qb3j
Subsequently, by iurLher addj ng 2-mercaptoethanol so that
10 2-mercaptoetbanol is equal Lo or more than 1.5 mol and equal to
or less than 3-0 mol, with respect to 1 mol ol epihalohydrin jf
there is any shortage, and by further adding thti shortage oi the
base so that the base is equal to or moio than 1.0 mol and equal
to or less Lhun 2.0 mol, with respect to epihalohydrin, the
lb polyalcohol ceeftpeund represented by the formula {?) can be obtained.
IL is preferable lo adjust so that the reaction temperaf.ure and
the reaction time are in the ranges described above-
|00MJ
In a synthesis of diol represented by the formula (3), in a
20 case where a strong base such sodium hydroxide is used, it is
appropriate for the reaction temperature to be set to equal to or
more than 10°C and equal to or less than 50"C. The reaction
temperature is too high, since Lhe base added with Lhe catalyst
quanti ty i s consumed i n a producing reaction oi Lhe polyalcohol
2 5 compound from diol, there is some possibi11Ly oi decreasing the
yi eld of a di o] .
Tl
(Step B)
Next, the polyal cohol compound rcprcsenLod by the formula (2 }
obtaj ned in the step A reacts wiLh Lhiourou in the presence oi
hydrogen chloride to obtai n the isoLhiuzorn urn salt.
5 [005G]
Specilieally, thiourea wbich i s equal to or more than 2. 7 mol,
preferably equal Lo or more than 2-7 mol and equal to or less-than
tl. D mol, and more preferably equal to or more than 2.9 mol and equal
to or less than '3/1 mol, with respect to 1 mol of the polyalcohol
10 compound, is added to the polyalcohol compound reproseiiLed by the
formul a (2) to react , The re Lie Lion is periormed in the presence
of hydrogen chloride which i s equal to or more than 3 mol, preferably
equal Lo or more Lhan 3 mo] and equal to or less than 1? mol , and
more preferably equal Lo or more than 3 mol and equal to or less
15 Lhan 5 mol, wiLh rcspceL to 1 mol of the polyalcohol compound, in
a range from room temperature to the reflux temperature, and
preferably at the temperature from 90°Ctol2 0°C, for approximat el y
i hour to HI hours. By the reacLion of the polyalcohol compound
and th.iourea, the "i soth: irroniusu ESUIL compound is formed. By using
?D hydrogen chl orj de, it is possible Lo obLain Lbe suit icieitt reaction
speed, furthermore, control the eoloraLion oi Lhe Lhiol compound
and col or of the obtai ned plasLic lens. Rn hydrogen chloride, a
hydroohl orj c acid aqueous solution and hydrogeri chloride gas can
be used- Jn a case of usinq a hydrochloric acid aqueous soluLion,
25 the concent rat 1 on thereof can be appropriately sefeeLed.
[0057]
(Htfip C)
23
Aqueous ammonia Is added i n t o t h e r e a c t i o n s o l u t i o n i n c l u d i ng
Lhe IsoLhiuronium s a l t o b t a i ned i n t h e s t e p K, and t h e i s o t h i u r o n i urn
s a l t is hydroxy zed to o b t a i n t h e pol y t h i ol compound. As a polyth.i ol
compound, It is p o s s i b l e t o o b t a i n t h e p o l y t h i o l composition which
5 in p r i m a r i l y comprised ol
4-TFiercaptoTrcethyl -1 , R-dimereapLo-3, 6 - d l L h i a o e t a n e r e p r e s e n t e d by
t h e f ol 1 owl ng formul a (f>) .
[0058]
1 SH (5)
1 0 1C)C>1J9!
Speci f i cal 1 y, wbi 1 e the reaction solution including Lhe
i sothi uroni urn salt "is maintained in a range ol the temperature from
15°C to 60°C, preferebly from 3l"C to bb"C, more preferably Irom
31°C to 45°C, aqueous ammonia in added into the reaction solution
15 for equal to or shorter than GO minutes, preferably for equal to
or shorter Lhan 70 minutes, and more preferably from 20 minutes
to 60 minuter. The Lime of adding aqueous ammonia is preferably
shorter, however, the time is set to wi thi n the ti me described above,
considering Lhe equipment capaci ty such as cool ability, or the 1 i ke .
20 [0060]
Beiore adding aqueous ammonia, an organic solvent Is
prelerably added. By adding Lhe organic solvent, the quality such
as color ol Lhe obtained plastic lens is improved. The additive
amount oL Lhe organic solvent is appropriately selected according
to the classiiication oL Lhe solvent, or Lhe like, howcvoi, it is
possibl e to add w.i th the amount which is Irom 0 . 1 t"imes to .-!•. 0 times,
and preferabl y from 0. 2 times to 1,0 time, with respect, to the
thinroni urn sail t rea ot~i on sol uti on. As an organi o solvent, tol uene,
5 xylene, chlorobenzene, dj chlorobenzene, and the like are incl uiied.
Toluene is preferable from the viewpoint of the offeet described
above.
[0061]
Aqueous ammonia can bo added within the addition Linte described
1 0 above so that ammonia (NIJ3} is. equal Lo or more than 1 rnol, preferably
equal to or more than 1 rnol and equal to or less than 3 moi, and
more preferably equal to or more than 1 . 1 rnol and equal to or less
than 2 rnol, with 1 rnol of the used amount of hydrogen chloride
described above. The concentration of aqueous ammonia can be set
15 to from 10ft Lo 25%. In addition, ammonia gas can be used inst.ead
of aqueous ammonia. In a case where ammonia ga.s is added in place
of all or part of aqueous Lntimonia, it is possible to perform .in
tho same oonditi oris {the used amount, Lhe addition time, the
addition temperature) as aqueous ammonia.
2 0 I 00£2 I
In t h e p r e s e n t embodiment, ammonia (NII3} Is cidd^d. so t h a i the
a d d i t i o n r a t e is equal t.o or more than 1.2b mol%/minute, p r e f e r a b ly
equal to or more than 1 . 2!J mol^/minute and equal t.o or l e s s than
3.'fb rnol %/mi n u t e , and more p r e f e r a b l y equal to or more t.han 1.38
75 moi&/mi n u t e and equal to or l e s s t h a n 2 . !> rnol^/mi nut.e, with 1 mol
of hydrogen c h l o r i d e . I n the s t e p , it is not n e c e s s a r y to
eonLinuousi y add wi t.h the r ^ t o d e s c r i b e d above, imci t h e average
25
a d d i t i o n r a t e in t.be a d d i t i o n time d e s c r i b e d above only hay Lo be
i n c l u d e d in the range.
And, a f t e r aqueous ammonia is added, a h y d r o l y s i s r e a c t i on
i s continued to be performed in a range from room t e m p e r a t u r e to
5 the r e f l u x LcfflpcidLurc, and p r e f e r a b l y from 30"C to B0"C, for
a p p r o x i m a t e l y 1 hour to B h o u r s.
[0C)6:-il
(.Step D]
1 n the present embed i merit, the poly thiol composH Lon obLainod
10 in the step C is purjfied by washing.
[00G^]
Specifically, acid washing and then plural times of aqueous
washing can bo performed. Aqueous washing before acid washing and
alkaline washing after acid washing c^n be performed. It is
15 possible to decrease the number of times of aqueous washing by
alkaline washi ng. Hy a washing s top, it is possible to effectively
remove .impuriti es, or the like. Dy purl lying by means oi washing,
it. is possible to produce the plastic lens oi high mialLty in which
color of the plastic lens obtained from the polythio.l composition
20 is improved, further the occurrence of cloud i ng and str.i at ion is
decreased, in a satisfactory yield, and the efficiency percentage
is also improved. As an example of the preferred aspect., alter
hydrolyzing, a method of performing aqueous washi nq, aci d washing,
aqueous washing, alkaline washing ^nd aqueous washing in order,
25 a method of performing acid washing, aqueous washing, alkaJine
washing and aqueous washing in order, a method of performing acid
washing and aqueous washing in order, and the like can be included.
26
Each washing may be repeated plural times.
[Q065J
Acid washing can be performed by adding hydrochloric acid to
the solution including the obtained polyLhiol composition. The
5 concentration of hydrochloric ncid can be scL Lo lroiti 2b% Lo 36%,
and preferably 30% to 36%- When the concentration o± hydrochloric
acid is lower than 25%, there are cases where c.J ondinq occurs in
the plasLie lens by impurities or the like. "In addition, the
temperature of. E^eid washing can be set to from 10*C ho 5(lnC,
10 preferably iroiu lbnC Lo 5G°C, more preferably from ?Q°C to 50°Cr
and even more preferably from 30 C to 45 C-
[0066]
Kor aqueous wasbi ng, deqFisscd w^Ler in which the eoiicenLreition
of oxygen is equal to or 1 ess than 7 ing/L can be used.
15 As a process of producing degassed water, a method oi blowing
nitrogen to remove dissolved oxygen, a method of driving ouL
dissolved oxygen by lhe heat treatment, a method of driving ouL
dissolved oxygon by Lhe vacuum degassi ng, and the 1 i ke are i ncl uded,
however, the method is noL particularly 1imi ted, i f the method can
2u make Lhe concentration oi oKygen be equal to or less than 5 ing/Ji.
In Lhis manner, iL is possible to effectively suppress color
or Lurbidity which becomes a problem in the optical material such
as Lhe plastic lens.
L0067J
?.!> In addition, alkaline washing can be performed by adding an
alkaline aqueous solution and stirring in a range from 20°C to riO°C
lor 10 minutes to 3 hours. As an alkaline aqueous soluti on, aqueous
27
ammonia 1H preferable. In addition, the concenLraLion of aqueous
ammoni a can be set to f rom 0.1s! Lo 10%, pro I or ably 0. 1& to 1&, more
preferably 0-1% to 0.5%.
[006E]
5 Moreover, also in acid washi nq and al kal i ne washing, by using
water in which Lhe concent rati on of oxygen i s equal to or less than
7 mg/L, it is possible Lo oifectively suppress color or turbidity
which becomes a problem in Lhe optical material such as Lhe plastic
lens.
JO [QQ691
After the step \~>, by performing a step o± removing a solvent,
a step of removing a low boi1inq point compound as necessary, a
step of fillering, and a step of di st"i 1 1i ng, it is posslbl e t c obtain
Lhe polyLhioi composition including
15 4-mercapLoitieLhyl-l, S-dimercapto-3, 6-di t.hi a octane as a polytbi ol
compound.
The step of removing a solvent is a step of removing an organi c
solvent under normal pressures or reduced pressure, and Lhe
deoompressi on degree and the tempera Luxe Eire appropriately selected
?Q ar.r.orc)i ng to the vised sol vent or the like, however , it is preiexable
that the step be performed at 100"C or less, and preiexably 85UC
or 1 ess, under reduced pressure.
The step of removi ng a low boiling point compound is a sLep
of removing t.he low boi 1 ing point compound contained in the target
25 compound under normal pressures ot reduced pressure after the stop
of removing a solvent, and the decompression degree and the
temperature are appronH ately selected according to the used
solvent or the 1J ke, however, iL i^j preferable that the sLep be
performed at equal to or lower than l(]t}nCr and preferably equal
to or lower than 85DC, under reduced pressure. I rj doing so, the
sLep may be performed while ventilating inert gas such as nitrogen
]) (JLIS .
The step of filtering is a step of removing by filtering a
solid material such as a sail, and a method oi filLering and the
1 i ke ctrB appropri atel y selected, however, a filtration under
reduced pressure or a pressure liltraLion using a membrane iilter
10 or a cartridge filter and the like tz-cin be used. It is preferable
that the slop bo performed with a filter which the pore size of
a filler is equal Lo or less than 5 um, and preferably equal to
or less than 2 pin.
The step of distilling is a step of purifying the polythiol
l'.i compound by distilling, and Lhe decompression degree and the
temperature arn appropriately selected according Lo Lhe used
sol vent or the 1 i ke, however, iL is preferable tiiuL the step be
performed at equal t.o or 1 ower than 2bCi"C, and preferably equal
to or lower than 2 00 "C, under reduced pressure.
20 In addition, in order to adiustinq the ratio of the peak area
of the nitrogen-contaJnjng compound (B), a step of reducing Lhe
nitrogen-containing compound (B) by purifyinq by means oi acid
washing is sometimes employed. In this oa.se, it .is neoessaiy Lo
confirm Lhe amount of the ni trogen-contai ni nq compound (H) i ncluded
25 in the polyLhiol composition and appropriately set the conditions
of acid washing so that the amount of the nitrogen-containing
compound (B) is in the predetermined range.
29
It is considered that the ratio of the peak, area of the
nitrogen-containing compound (B) is multiply determined by a
combination oi the conditions over a plurality of steps dining
synthesi zi ng or purifying . On Lhe oLhor hand, the prodiici ng
5 conditions disclosed in the present invention have extremely good
repeatability and can provide the polythiol composition including
the nitrogen-containing compound oi less than 12 mol, with respect to 1 mol of the LeLraol compound
-in a range from room temperature to the reflux Lemper a Lure, and
preferabl y at the temperature irom 90"C Lo 120"C, ior approximately
1 hour to 10 hours, By the reaction oi Lhc Letraol compound and
thi ourea, the tsothi uroni urn salt compound i^ formed. By using
10 hydrogen chloride, it is possi hie to obtain the suf f i ci ent reaction
speed, furthermore, control the coloration of a product. As
hydrogen chloride, a hydrochloric acid aqueous solution ar-6
hydrogen chloride qas can bo used,
10083 |
lb (Step D}
Aqueous ammonia 'is added inLo Lhe r e a c t i o n s o l u L i o n i n c l u d i ng
t h e i sot hi uronium sa.l t o b t a i n e d in Lhe sLep C to hydrolyze Lhe
i s c t b i u r o n i um s a l t and the p o i y t h i o l composition is o b t a i n e d.
In t h e p r e s e n t embodiment, as a p o i y t h i o l compound, it in
20 possible Lo o b t a i n Lhe p o J y t h i o l composition i n c l u d i n g t he
p o i y t h i o l compound which is p r i m a r i l y comprised of at ]easL one
kind s e l e c t e d from Lhe group c o n s i s t i n g of
4, 8-dimerc.apLomeLhyl-l, l l - d i m e r o a p t o - . i , S, 9 - t r i t h i aundecane
r e p r e s e n t e d by Lhe following formula !6)f
2 5 4 , 7-dimcrcapLomeLhyl-l, l l - d i m e r o a p t o - 3 , 6, 9 - t r i t h i a u n d e o a r ie
represenLed by Lhe following formula (7), and
5, 7-dimcrcapLomeLhyl-l, l l - r l i m e r c a p t o - 3 , f t , 9 - t r i t h i aundecane
34
represented by the following formula [#}.
"s-
HSs
•
•SH
(6)
(7)
-3—
-SH
(8)
|008 6j
5) Speci f i cal 1 y, wbi 1 e the reaction seluLlon including Lhe
i sot hi urort J urn salt is Tfiai ntained in a range oi the temperature Iroin
?Q"{\ to 60°C, preferably from 2bflC to bb"Cr and more preierably
front 25"C to 50UC, aqueous ammonia is added into the reaction
solution for equal to or shorter than BO minutes, preferably equal
10 Lo or shorLer Lhan 70 minutes, more preferably from ZQ minutes to
60 minute;;, and even more preferafo] y from ?0 mj nutes to 30 rr>i niites .
The Lime oi adding aqueous ammonia is preferably shorter, however,
the Lime Its ueL Lo wiLhin the time described above, considering
Lhe equipment eapaeiLy alien as coolability, or the likelb
[0087]
Deioro adding aqueous ammonia, an organic solvent is
preierably added. By adding the organic solvent, iL is possible
to suppress to produce a by-product. The additive amount of the
oiyanie :HJ1VQIIL is appropri atel y selected according to the
ol assi f"i cati on of the solvent, ox Lhe 11 ko, however, it is possible
to add with the amount which is from 0,1 times to 3.0 times, and
preferably from 0.2 times to 2.0 times, with respect to the
thiuronium salt reaction so] uti on , As an organic solvent, to! uene,
b xylene, chlorobenzenc, dichlorobenTiene, and the like are Inc] uded.
Toluene is preferable, Irem the viewpoint of the elfect described
above.
[DORR]
Aqueous amnion i a can be added within Lite additioEs L LIELO described
10 above so that amnioni a (NH^) i a equal to ci more than 1 mol, pref eeably
equal to or more than 1 mol and equal to or less than 3 mol, and
more preferably'equal te or more than 1 .1 mol and equal to or less
than 2 mol, with 1 mol ef Lhe used amount of hydrogen chloride
deseribed above. The eoneentration of aqueous ammonia can be set
lb to Ixeiii 10% to 2b% . In addiLion, ammonia gas can ctlso be used instead
of aqueous ammonia. In a case where ammonia gas is added in place
of all or part of aqueous ammonia, il_ iti possible to perform in
the same condi ti ons (the used amount, the addition time, the
addi ti on temperature) as aqueous ammonia.
20 [00S9]
J n the present embodiment, ammonia (Nh^) is added so that Lhe
addition rate is equal to or more than 1.2!i mol %/mi nute, preferably
equal to or more than 1.25 mol£/minute and equal to or less than
3.75 mol%/minule, and more preferably equal to or more than l.iB
25 mol %/minute and equal to or less than ? . 5 mol %/mi nute, wi th respect
to 1 mol of hydrogen chloride. In the step, it is not necessary
to continuously add with the rate described above, and the average
3h
addition rate in Lhe addition time described above has only to be
i nelijded in the range,
And, after aqueous ijmmonia is added, a hydrolysis reaction
is continued to be performed in a range iroin room temperature to
5 the reflux tempers tin re, and preferably at the temperature from 30 "C
to 80°C, for approximate]y 1 hour to ft hours,
[0090]
(Stop E)
In the protonL embodiment, the polythiol compositi on obtai ned
10 iii the stop D is purilied. The stop E in the present embodiment
can be performed "i n the .same way as embodiment I.
In addition, the step after the step E can also be periormed
in the same way as Kmbodiment I.
[0033]
15 tfy such a process of producing, the polythiol coTnposition
including the polythiol compound (A) and the nitrogen-containing
compound (B) in Lhe predetermined range in the present embodiment
can be suitably obtained.
10092]
20 As described above, in Lhe present embodiment, specifically,
description or the process el producing the polythiol composition
including two types of polythiol compound as Lhe polythiol compound
(A) IIEAS been given as an example, however, other method can be
employed if the ratio of the peak, areti ol the iiiLrogen-conLaining
?5 compound (B} c.an be set to the prede Lor mined range.
In addition, for even poiyLhiol compound excepL Lhe Lwo Lypes
seiecLed liom the exemplified poiyLhiol compounds described above,
~.J>~!
by a p p r o p r i a t e l y changing the producing c o n d i t i o n s , the r a t i o of
t h e peak a r e a of t h e n i t r o q o n - c o i s L a i n i n g compound
The p o l y m e r ! z a b l e composi t."i on for t h e opti ca] rnateri al in the
p r e s e n t embodiment. i n c l u d e s the po] y t h i o.l composition for the
o p t i c a l iriLiLoriai which is o b t a i n e d by t h e method d e s c r i b e d above
and p o l y i s o ( t h i o ) c y a n a L c compound,
10 ]0094 J
The pol yi so ( t h i o) c y a n a t e compound i s noL p a r t i c u l a r l y l i m i t ed
as long EIS t h e p o l y i s o ( t h i n> c y a n a t e compound is a compound having
at l e a s t two or more i s o ( t h i o) c y a n a t e gcoups in one jnolecuio.
However, s p e c i f i c a l l y , the pol yi so ( t h i of c y a n a t e i nclindes an
15 a l i p h a t i c polyisoeytmaLc compound si;cb as hexamethyl ene
diisocyan^Lo, 1, b - p e n i a i i e d i i s o c y a n a t e , ?, ? - d i m e t h y ] p e n t a ne
diisoeyLsnaie, 2, 2, 4-trimeLhylhexane di i s o c y a n a t e , butene
d i i s o c y a i m h e , 1 r 1 - b u t a d i e n e - l , 4 - d i i s o c y a n a t e ,
2, 4, 4-triniet.hyl hexamethylene d i i s o c y a n a t e , 1,6,11-undo cane
?0 t r i i . s o c y a n a t e , 1 , 3, 6-hexamethylene L i i i s o c y a n a t e,
1, B - d i i s o c y a n a t o - 4 - i socyai;aLomcLhyloetane,
b i s ( i s o c y a n a t o e t h y l ) c a r b o n a t o , b i s ( i s o c y a n a L o c L h y l ) c L h e r , l y s i ne
d i i s o c y a n a t o m e t b y l e s t e r , or l y s i n e triisoeyana-Le;
an aJ i oyol i c pol yi sr>cyar\ar.& compound such us isophorone
2 5 di i s o c y a n a t e , bi s ! i s o o y a n a t o m e t h y l } oyolohoxane,
di eye] nbaxyl methane d:- i s o c y a n a t c , oyolohoxane diisocyanaLo,
methyl cyc.l ohexane di i socyanaLc, dicyclohexyldiiiieLhylmeLhdne
38
isocyanaLe, 2, 5 - b i s [ i s o c y a n a t o n i e t h y l) - b i c y c l o [2 , 2 . 1J h e p t a n e ,
2, 6 - h i a (isocyanaLomeLhylf ^bicycl o F? . 2 . 1 | h e p t a n e ,
3, 8 - b i s [ i soeyana L omo Lhyl) tricyc.1 odecane,
.3, '3-bis [i sooyanatornethyl) L r i e y c l o d e c a n e ,
5 4, G-bi a ( i s o o y a n a t o n i e t b y l ) L r i e y c l o d e c a n e ,
4, 9 - b i s (isocyanatomethyl) t r i c y c l o d c c a n e,
b i s { 4 ~ i s o e y a n a t o c y c l o h e x y l ) m e t h a n e ,
1, 3 - b i s {i^ocyctnatomethyl) cycl ohexane, ox
1, 4 - b i s {isoeyLsnatomethyl} cycl ohexarie;
TO a polyisocyLinate compound having an a r o m a t i c r i n g compound such
a a 1, 2-rii .i aocyanatobonzene, 1,3-dii socyanatobenzene,
1,4-di i a o c y a n a t o b e n z e n e , Lolylcne d i 1 s o c y a n a t e,
2, 4-di i s o c y a n a t o t o l uenp, 2, • b - d i i s o e y a n a t o t o l u e n e , ethyl phenylene
d i i s o c y a n a t e , isopropylpbenylone d i i s o c y a n a t e , dimethylphenyiene
15 d i i s o c y a n a t e , d i e t h y l p h e n y i e n c d i i s o c y a n a t e,
d i i s o p r o p y l p h c n y l e n e di J s o c y a n a t e , LriiftcLhylbenzene
LriisocyanaLe, benzene t r i i s o c y a n a t e , biphenyl d i i s o c y a n a t e,
t o l u i d i n e diisocyunaLc, 4,4' -riiethylenobis (phenyl i s o c y a n a t e ) ,
4 , 4 ' - i i i e t h y i e n e b i s (2-iiteLhylphenyl i s o c y a n a t e } r
?{) bibenzyl-4 r 4 ' - d i i i i o c y a n a L c , bi a {i socyanatopbenyl) e t h y l e n e ,
b i s ( i s o e y a n a t e n i e t h y l ) benzene, m-xylyiene diisoeyaziaLe,
b i s ( i s o e y a n a t o e t h y l ) b e n z e n e , bi a ( i s o c y a n a t o p r o p y l ) b e n z e n e ,
n.,<.-x, bi a ( isocyanatomethylpbeEiyl) e t h e r , bi s (i s o c y a n a t o e t b y l ) p h t h a l a L e ,
or 2 , b-di {i socyanatoEnethyl) l u r a n;
a s L i l i u r - c o n t a i n i n g a l i p h a t i c pel yi s o c y a n a t e compound such as
39
b i s (isocyanaLoEiLeLhyl) s u l f i d e , b"i s (i s o c y a n a t o e t h y ] } s u l f i d e ;
b i s (isocyuEiuLopropyl) s u l f i d e , bis ( i socyanatohcxyl} s u l f i d e ,
b i s ( i s ocyusiuLoiiicLhyl) s u l f o n e , bis (isocyanatomcthyl) d i s u l f i d e ,
b i s ( i s o c y a n a t o a t h y l ) d i s u l f i d e , bis (isocyanaLopropyl) d i s u l f i d e ,
5 bi s (i socyanatometbyl t h i o) methane,
bj s (i s o c y a n a t o e t b y ] t h i o)methane,
b i s ( j socyanatonxethylthio) e t h a n e , bis [ i s o c y a n a t o e t b y ] t h i o) e t h a n e ,
1, 5 - d i i s o c y a n a L o - 2 - i s o c y a n a t o m e t h y l -3-thd a pent an e,
1,2, 3 - t r i s {isoeyanatomethylth-i o)propane,
10 1,2, 3 - t r i s {isocyaiiul_ocLhylthio) propane,
3 , 5 - d i t h i a - I , 2 , 6 , V - h e p t a r j c L c t r a i s o c y a n a t e,
2, 6 - d i i s o o y a n a t o m e t h y l - 3 , b - d i l _ h i a - l , 7-hapLane diisocyanaLo,
7, 5-d: "i s o c y a n a t e methyl tbiophtmo, or
4-i s o c . y a n a t o e t h y l t h i o - ? , f j - d i t h i a - l , 8 - o c t a n e t i \ i s o c y a n a t s ;
15 an aromatic s u l f i d e - b a s e d p o l y i s o c y a n a t e compound such as
2-J s o c y a n a t o p h e n y l - 4 - i s o c y a n a t o p h e n y l suit"j tie,
b i s ( 4 - i s o c y a n a t o p h e n y l ) su] f "i d e , or
b i s H-isocyuEiuLoiiicLhyiphenyl) suJ f "i d e ;
an aromaLic d i s u l i i d e - b a s c d p o l y i s o c y a n a t e compound such as
20 bis H-isocyan.-jtophenyll d i s u l f i d e ,
b i s (2-inoLSiyl-b-isocyanaLophenyl} dj sul f i de,
b i s (3-iiieLhyl-b-isocyanaLophenylf d: su] f i d e ,
b i s (3-methyl-6-ii5ocyaEiutophcnylf d i s u l f i d e ,
b i s (4-niethyi-!>-iso(-.ya[iLiLophcnyl) d i s u l f i d e , or
2b bis (•l-methoxy-H-isooyanaLophcayl) d i s u l f i d e ;
a si_U_iur-conta:i ni nq a i i c y c l i c p o l y i s o c y a n a t c cotiipcUEid such as
2, 5 ' - d i i s o c y a n a t o t e i r a h y d r o t h i ophene, 2 , 5 - d i i s o c y a n a t o m e t h y l
40
tetruhydrothiopheriG, 3, 4 - d i i s o c y a n a t o m e t h y l t e l r a h y d r o L h i o p h e n e,
7, 5 - d i i s o c y a n a t o - l , 4 - d i t h i a n c ,
2, b-diisocyanatoTTietbYl-l, d - d i t h i a n e ,
4, 5-rH i s o c y a n a t o - l , 3-di t h i o l a n e ,
5 4, 5 - b i s (isocy3.n5.tomethy 1J - ] , 3 - d i t h i a l a n a , or
4, 5-diisooyanaLomethyI-2-met.hy] -1 , 3-d i t h i ol a n e ;
LIII a l i p h a t i c p o l y i s o L h i o c y a n a t e compound such as
1, 2-diiyothiocyaiiatooLhaisc or 1, 6 - d i i s o t h i o c y a n a t o h e x a n c ;
an a l i e y c i i c p o i y i u o t h i o c y a n a t e compound such as cyclohcxane
G d i i i s o t h i o c y a n a t e;
an aromati c po] yi s o t h i ooynnuLe compound such a:s
1, ?—di i s o t h i o c y a n a t o benzene, 1, 3 - d i i s o t h i o c y a n a t o benzene,
1, 4 - d i i s o t h i o c y a n a t o benzene, ?, 4-di i sot-hi ooyanato t.ol uene,
2, 5-dii£oLhiuoyana.Lo-iri'-xylerief 4,4' -methyl e n e b i s (phenyl
5 isothiocyariai_u) , A, 4 T -methy 1 enebi s {?-methylphenyl
x^oLhioeyanLtLo) , 4, 4 - m e t h y l e n e b i s (3-methylpheiryl i s o t h i o c y a n a t e ) ,
A, A ! - d i i s o t h i o c y a n a L o beiizephenone,
A, A 1 - d i i s o t h i o c y a n a t o - 3 , 3 ' - d i m e t h y l bcnzophcrione, or
b i s ( 4 - i s a t b i ooyanatophenyl)eLhcr;
0 f u r t h e r m o r e , a car bony] polyisoLhiucyariEiLe compound such a.s
1,J-benzene dicarbony1 diisoLhioeyanaLe, 1,4-benzene dicarbony]
d i i s o t b . i o o y a n a t e , or (2, 2 - p y r i d i n e ) -A , 4-dicarbonyi.
di i s o t h i o c y a n a t e ;
a Sinl finr-oontai ni ng a l i p h a t i c p o l y i s o L h i o c y a n a t e compound such as
5 thiobi s f 3 - i s o t h i o c y a n a t o p r o p a n e ) ,
t h i obi s ( ? - i s o t h i o c y a n a t o e t h a n e } , or
d i t h i o b i s ( 2 - i s o t h i ocyanatoeLhane};
41
a sulfur-containing aromatic polyisothiocyanate compound such as
l-isothiocyanaLo-4- [ (2-isothi ocyanato) sul fonyl]benzene*
thiobis (4~isoi:hiocyanatoben7ene) ,
suifonyl(4-isoLhiocyanaLobenzene), or
5 dithiobiu (d-isothiocyanaLobc-nsene) ;
a sulfur-containinq alicyclic polyisoLhiocyunato compound such as
?, r?-di :i sot.hi ooyanatotbi ophena, or 2, b-diisothiocyanato
-],4-di thiane;
a compound having an i s o c y a n a t o qroup and an j s o h h i o c y a n a t o group
10 such as l - i s o c y a n a t o - 6 - i s o t h i ocyanatohexane,
l - i s o c y a n t E L o - 4 - i s o l h i o c y a n a t o c y c l ohexane,
l-iijocyLsiiaLo-4-i^oLhiocyuitaLobenzene,
^-iriuUiyl-^-isocyanato-l-isoLhioeyanaLobcnzcrH:,
2 - i s o c y a n a t o - 4 , 6-nH i s o t h i o c y a n a L o - 1 , 3, 5 - L r i a z i n c ,
\ 5 4-isocyanatophenyl -4-isot.hiocyar3iiiLophonyl t s u l i i d c , or
7-\ s o c y a n a t o e t h y l — ? — i sothiocyasiaLouLhyl d i s u l f i d e , and t h e l i k e .
[0095]
A p o l y i s o ( I h i o ) cyanat.e compound p r e f e r a b l y i n c l u d e s an
a l i p h a t i c - b a s e d p o l y i s o c y a n a t e compound such as bexarnethyl en«
20 diisocyanaLe, 1, 5 - p c n L a n e d i i s o c y a n a t e , i sophorone di i s o c y a n a t e ,
b i s (isocyanatoniethyl) eyeIohexane, di cycl ohexylmethane
diisocyanaLe-, 2, 5 - b i s (isocyanatometbyl > -hi cycl o [2 - ? - i ] h e p t a n e ,
2, ij--bis (IsocyanaLonicLhyl) - b i c y c ] o [? . ? . 1 ] h e p t a n e ,
b i s ( 4 - i ^ o c y a n a L o c y c l o h c x y l ) m e t h a n e ,
25 1, 3 - b i s [i^ooyaiiaLoiiioLhyl) cyclohexane, or
I , 4 - b i s ( i s o c y a n a L o i f t c L h y l ) c y c l o h e x a n e ;
a polyisocyanaLe compound having ^r\ aromatic r i n g compound such
42
as bj s(isocyanatomethy])benzene, m-xylylene dii socyanate,
1, 3-diisocyanatobenzene, to] y.l pne di i socyanate,
2, 4-diisocyanatotoluene, 2, S-di i socyanatotoluene,
4,4'-methylcnebis(phenylisocyanate).
T> i 0096]
In a d d i t i o n , it. is p o s s i b l e Lo use \i halogen sabsLiLutioil
t h e r e o f such as a c h l o r i n e s u b s t i t u t i o n or a bromine s u b s t i t u L i o n,
an a] ky] substi t . u t i on t h e r e o f , an alkoxy substri t u t i o n t h e r e o f , n
ni t.ro s u b s t 1 t u t i on t h e r e o f , a prepolymer t y p e mod: f i e d p r o d u c t w i th
10 polyalcohol, a carbodiimide modified product., a urea modified
p r o d u c t , a b u r e t modified p r o d u c t , a r e a c t i o n product of
dimerizLiLioii ai t r i m e r i z a L i o n , and t h e l i k e . The compounds may be
used Li l o n e or in a combinaLion of two types or more,
T (J 097 |
15 As a p o l y t h i o l compound used in. the p o l y m e r i z a b l e composition
f o r the opt i cal materi a ] , in a d d i t i o n to the p o l y t h i o l compound
f o r t h e o p t i c a l m a t e r i a ] which is o b t a i n e d by t h e method d e s c r i b ed
above, other p o l y t h i o l compound for the opt.ical m a t e r i a l can be
used.
20 Other p o l y t h i o l compound for t h e o p t i c a ] m a t e r i a ] p r e f e r a b ly
i n c l u d e s an a l i p h a t i c p o l y t h i o ] compound such as methane d i t h i o i ,
1 , 2 - e t h a n e d i t h i o l , 1 , 2 , 3 - p r o p a n e t r i t h i o l , p e n t a e r y t h r i t o]
t e t r a k i s ( 2 - m c r e a p L o d C c t a t o ) , p e n t a e r y t h r i t o]
t e t r a k i s (3-mercapLopropionate}, hi s (mercaptoethy]) su] f i d e ,
2b 2, 5'-diiiierc^pLoiiieLhyl-l, 4 - d i t h i a n e , t e t r a k i s (mercaptomet-hyl t h i o
methyl) methane, LcIrakis (2-mercaptoethy] t h i o methyl)methane,
t e t r a k t s ( 3 - m e r c a p L o p r o p y l t n i o methyl J methane,
43
b i s { 2 , 3 - d i m e r c a p t o p r o p y I ) s u l f i de,
2, 5-diiiiereap Lome thy i - 1 , 4 - d i t h i a.ne, ?, 5 - d i m e r c a p t o - l , 4 - d i t h i ane,
2, S-dimereapLomethy1-2, 5-dimethyl -1 , 4-di t h i a n e ,
1 , 1 , 3 , 3-LoLrakis (mercapLomcthylthio) propane,
5 1,1,2, 2 - t e t r a k i s {mencaptomeLhylLhio) cLhane, or
4 F 6-bi s •(mercapf.oKiet.hyl t.hio} - 1 , 3-diLhiarie .
The usage r a t i o of the p o l y t . h i o l conspoijnd and the
pol yj so {thio) c y a n a t e compoiind is not. p a r t i c u l a r ! y .1 irni t e d , however,
10 the molar r a t i o is u s u a l l y w i t h i n a range of a SH groirp/a NCO
group=0. 5 Lo 3,0, w i t h i n a range of p r e f e r a b l y 0.6 to 2 , 0 , and more
p r e f e r a b l y O.H to 1.3. II Lhe usage r a t i o is w i t h i n the range
d e s c r i b e d above, "it. becomes p o s s i b l e Lo s a t i s f y a n i c e b a l a n c e of
v a r i o u s ki nds of performance such as Lhe r e t r a c t i v e index or Lhe
] 5 heat r e s i s t a n c e demanded as t h e o p t i c a l m a t e r i a l such as Lhc p l a s t i c
l e n s and the t r a n s p a r e n t m a t e r i a l.
[0099]
For t h e purpose t o improve v a r i ons p r o p e r t i e s , the o p e r a b i l i t y ,
t h e polymcri^aLion r e a c t i v i t y , or the l i k e of the
20 polythioureLhaiie-based r o s i n of the present, i n v e n t i o n , other
s u b s t a n c e s may be added, in a d d i t i o n to t h e p o l y t h i o l compound and
t h e i s o {Lhio) cyanaLe compound which form an viret.bane r e s i n . ^'nr
example, at l e a s t one kind of an a c t i v e hydrogen compound which
i s t y p i l i c d by Lnidne or Lhe l i k e , a c a r b o n a t e compound, 3.]-< e s t er
25 compound, a inetEil, a m e t a l l i c oxide, an o r g a n i c metal compound,
an i n o r g a n i c s u b s t a n c e , or Lhe l i k e may be added, in a d d i t i o n to
a u r e t h a n e tannine, m a t e r i a l.
I0100J
I n a d d i t i o n , in accordance with the purpose, various kinds
of s u b s t a n c e s such as a chain exLender, a c r o i i b l i n k i n g agenL, a
1 i gbt s t a b i 1 i z e r , an u l t r a v i oleL a b s o r b e r , an a n t i o x i d i z i n g agenL,
5 an o i l c o l o r , a f i ] ] . e r , or a mold r e l e a s e agent may be added in
t h e same way as a well-known forming p r o c e s s . In order to adju^L
t h e d e s i r e d reacLion r a t e , a welJ-known r e a c t i o n c a t a l y s t used in
producing a t h i o c a r b a m i e acid s - a l k y l e s t e r or a
polyLhiouroLliane-based r e s i n may be a p p r o p r i a t e l y added.
10 As a r e a c t i o n c a t a l y s t , a well-known r e a c t i o n c a t a l y s t used in
producing a thi ocarbami c a c i d 5 - a l k y l esLcr or a
pol ythi our e t h a n e - b a s e d res? n can be a p p r o p r i a t e l y added.
A r e a c t i o n c a t a l y s t J nnl udes d i a l k y l t i n h a ] : (Jes such aii
d i b u t y l t i n d i c h l o r i d c , or d i m e t h y l t i n di c b l o r i d e , di a l k y l t i n
15 dicarboxylaLes such as d i m e t h y l t i n d i a c e t a t e r di bitty] t i n
d i o c t a n o a L e , or d i b u L y l l i n d i l a u r a t e , di al kyl t i n rji al koxi dei; such
an d i b u t y l t i n d i b u t o x i d e , d i o c t y l t i n d i b u t o x i d e , or d i a l k y l t . in
d i t h i o a l k o x i d e s such as d i b u L y l l i n d i ( t h i o b u t o x i d e ) , d i a l k y l t i n
oxidos such ^F. di ( 2 - e t h y l h o x y l ) Lin oxide, diocLylLin oxide, or
?{'i bis (butoxy di b u t y l t i n ) oxi de, d i a l k y l t i n s u l f i d e s such as
d i b u t y l t i n s u l f i d e are i n c l u d e d . D i a l k y l t i n h a l i d e s such 3s
d i b u t y l t i n d i c h l o r i d e , dimethylLin d i c h l o r i d e , as a p r e f e r r ed
example.
\Q1011
?5 furthermore, as a purpose oi modi l y i n g a r o s i n , a r e s in
modi f ying agent such as a bydroxyl compound, un epoxy compound,
an e p i s n l p h i d e compound, an o i y a n i c a c i d and an anhydride Lhereof,
lb
an olulin compound Including a (metha)aorylate compound or the like
may be added. Here, a reaiii modifying agent i^ a compound which
ad-justs or improves properties of a material comprised of a
th i oureth an e -based resi n such as Lite re tractive i rid ex, the Abbe
5 number, the heat resistance and the specific gravity, and the
mechanical strength thereof such as the impact resistance, or the
like.
[0102]
In addition, the polymerlzable composition for the optical
ID material of the present embodiment can include a blueing agent,
as necessary. 'The bl ueinq agenL has an absorption bund in a
wave! ength range from orange-colored Lo yellow-colored in a visible
light region and has a function of ad-justing color of an optieul
material comprised of a resin- More specifically, the blueing
15 agent includes a substance showing from blue-colored to
purple-colored.
[0103]
The biueinq agent used in the polymerizable composition for
the optical material of the present embodiment Is iioL particularly
20 limited, specifically, a dye, a fluorescent briyhLeiiing Lsgent, a
iiuorescent piqment, an inorganic pigment and the like arc included,
however, from among the substances which can be used us a blueing
aqent, the bluei nq aqent is appropriately selected, according to
physical properties which are required lor the optical eoEitponents,
2!i resin color, or the like. The blueing ugenLs may be respectively
used alone or in a combination two or more kinds.
I 01041
46
Among the blueing agents, a dye is preierabie, from the?
viewpoint of the solubility to the polymer: zabl e composition and
the viewpoint oi" the transparency of the optical material which
Is obtained.
•3 1010b]
Prom the viewpoint oi Lhc absorption wavelength, it is
preferred that a dye i n which Lhc maximum absorption wavelength
is equal to or more than T?^D nm and equal Lo or less than 600 nm
is used- It is more preferred that a dye in which the maximum
0 absorption wavelength is equal to or more than 54 0 nm and equal
Lo or loss Lhan 580 nm is used.
In addition, art anthraquinone-based dye is preferable, from
the viewpoint of the structure of the compound.
[0106]
5 A method of adding the blueing agent is noL particularly
limited, and it is desired to add Lo a monomer system IEE advance-
As method, various ki nds of methods such as a method oi being
dissolved in A monomer or a method in which a master solution
containing the high concentration of the blueing aqent is prepared
0 and the master solution is diluted by a monomer or ot.her additive
agent which is used to be added can be employed.
[0107]
The polymer-izable composi ti on for the opti cal materi a.l of the
pxcscnL err ibo dime nL is obtained ^s a mixed liquid, speci f i caiiy,
b by mixing Lhc polythiol composition obtained by the process oi
producing described above and the polyiso{thio)cyanate compound,
furthermore other components as necessary. The mi xeri 1 i quid is put
i nto a iriol d Fincl is usually, gradually heated irom a low tempera Lure
to a hi gh temperature to he polymer ized after degassi ng by ai;
appropriate method aa necessary.
[0103]
b In Lhis maanor, a molded product comprised of the
polythiourethane-based rosin obtained by curing Lhc polymerizable
composition of the present embodiment has eharue:Loris Lieu which
are the high refractive index, the low dispersion, cxeellenL heat
resistance and durability, lighL weiy-h, and excel ten L impact
10 resistance, furthermore, color is favorable and it is suitable tts
the optical material such as a spectacle lens, a camera lens ntid
the transparent material element,
[0109]
In addition, the plastic lens obtained by using the
lb polythiourethane-bLised resin of the present embodiment may be
subjeeted to a physical or chemical treatment sijch LSS Lhc surface
polishing, the antistatic treatment, the hard eoat treatment, the
anti ref1ection coat treatment, the dyeing treatment, the dimming
treatment a s necessary, i n order to perform an i mproventent oL
20 anti-reflection, imparti nq hi gh hardness, enhancing abrasive
resi stance, enhanoi no; chemical resistance, imparting anti leg
propert.i es, imparting fashi onabi J ity, or the 1 i ke .
[Examples]
[0110]
2 5 Hereinafter, more detai1ed descripti on wi11 be gi ven ot the
present invention according to Kxamples, however, the present
invention is not limited thereto.
48
[01111
Moreover, "in the f ol 1 owing Examples , proper!.: es were measured
by the f ol 1 owi rig methods of measurement.
* Specific gravity: measured in conforrni ty to J I £ K OQfel.
h " APHA: APHA is a method of displaying color and determined
by using a standard solution which was prepared by dissolving a
reaqent oi platinum and cobalt and comparing Lhc standard solution
diluted solution having the concentration equal to the color of
samples, the '"frequency" was sot Lo the measured value.
10 n'l'he amount of water: A monomer was dissolved in toluene,
and the water measurement was conducted by Karl Kischer Moisture
Titrate,
h Viscosity: IL was measured in accordance with JJ3 K 7117.
a Refractive index: It was measured at 20UC by RA-600 digital
lb rcfractometer manuiacLured by KYOTO ELECTRONICS MANUFACTURING CO.,
LTD.
• AmmoniiJTTi content: A monomer was dissolved in chloroform,
extracted by wafer and measured by an ion chrcmatoqraphy.
» Aci d content: A monomer was dissolved in a solvent,
20 calculated ci^ the HCl content, by titrating by a methanol solution
of KOH.
" Loss degree of transparency el resin: A fiat plate ol y mm
was produced w.i th the produci nq conditions of the pi as tic lenses
of Kxamples to measure by a loss degree of transparency measurinq
25 apparatus (manufactured by HAYASI5T WATCH-WORKS: UJM I NAR ACE
n Resi n Y i ; If is a yellow index in the nvaluation of color.
4 9
VI "is measurer] by a c o l o r - d i l l c i c n c c :i!oLer. A l l uL p l a t e oi 9 mm
was produced with t h e producing c o n d i t i o n s of t h e p l a s t i c l e n s es
of Kxamples to measure a YE value u s i n g a col o r - d i f f e r e n o e meter
(CR-400) manufactured by KOtt!CA M1N0NTA, INC,
b • StriaLicio: The l e n s was produced with t h e p r o d u c i ng
c o n d i t i o n s ol the pl«s1_ic l e n s e s of Examples and v i s u a l l y observed
under a h i g h - p r e s s u r e mercury lamp, and t h e le-fiu in which a
s t r i p e - l i k e p a t t e r n was not observed was 0 and Lhc lens in which
a s t r i p e - l i k e p a t t e r n was observed was X.
0 [-dil_hiaoctane)
123.6 p a r t s by weiqbt of 2-mereapLooth.anol and liS . 3 parLs by
wei qht of degassed water {the c o n c e n t r a t i o n of d i s s o l v e d oxygon
0 is ? ppni) were charged i n t o a r e a c t i o n v e s s e l . After 101. b parLs
by wei ght of 32% by wei gb of sodium hydroxide aqueous ^oiuLion VMS
added dropwise and charged from 12nC to 3b°C over 30 m i n u t e s , 73.6
p a r t s by weight of e p i c h l o r o h y d r i n was added dropwise and charged
from 23°V, to 3 6"C over 4 , 5 hours, and c o n t i n u o u s l y, s t i r r i n g was
5 performed for 4 0 m i n u t e s . Krorn an NMR d a t a , the p r o d u c t i on ot
1 r 3 - b i s ( 2 - h y d r o x y e t h y l t h i o ) - ? - p r o p a n o J was confi rmed.
T3^ .5 p a r t s by weight of Jb,b& h y d r o c h l o r i c a c i d was charged,
and subsequently, 183.8 p a r t s by weight of the p u r i t y of 99-90%
of t h i ourea was charged and s L i r r c d at 110UC for 3 houru under r e f l ux
to convert, "i n t o a thiuroriiuin ^ a l t . After c o o l i n g to 45JC, 32 0 ,5
p a r t s by wei ght of t o l nena was added and e o o i e d to 3l"CF 243.1 p a r t s
5 by weight of 25% by weight of ammonia aqueous s o l u t i o n was charged
from 31UC to 41UC over 44 minutes and s t i r r e d from f>4°0 to 62"C
l o r 3 hours, and a t o l u e n e s o l u t i o n of t h e p o l y t h i o l composition
which i s p r i m a r i l y comprised of 4-niercaptOTnethyl-I, 8-dimeroapto-3,
6 - d i L h i a o c t a n e wa^ o b t a i n e d , 162, 8 . p a r t s by weight, of 35-5S
10 hydrochloric a c i d wajo added i n t o the t o l u e n e s o l u t i o n and acid
washing was performed from 3b:'C Lo 43JC for 1 hour. 174.1 p a r ts
by weight of degassed water (the c o n c e n t r a t i o n or d i s s o l v e d oxygen
is 2 ppm) was added and washing which was performed from 3b"C Lo
45^0 for 30 minutes was conducted t w i c e . 167.1 p a r t s by weight oi
15 0,1% aqueous ammonia was added to wash f o r 30 mi n u t e s . 174 .2 p a r ts
by weight oi degassed water was added and washi ng whi ch was performed
irom 3b"C to 4b"C l o r 30 minutes was conducted t w i c e . After t o l uene
and i x ^ c e wpit.er were removed under h e a t i n g and reduced p r e s s u r e,
f i l t r a t i o n under reduced p r e s s u r e was performed by PTFE type
7.0 membrane f i l t e r of 1.2 pn; to obLain 205,0 p a r t s by weight of a
p o l y t h i o l composition which is p r i m a r i l y comprised of
•1-mercaptomethyl -1 , 8-dimercL*pto-3, G - d i t h i a o c t a n c . Physical
p r o p e r t i e s of t h e obtained p o l y t h i o l composition arc shown in
Table-1 .
75 [01 13]
The r e s u l t s of Bn elemenLary amity ^ iu and a NMR a n a l y s i s of
4-jriercaptomethy! -1 , B-dimer c a p t o - 3 , fj-dithiaocLanc are shown -
f)1
Elementary a n a l y s i s {ax C-jHi^SrJ
CHS a n a l y s i s value 3?.12 6.19 61.69 C a l c u l a t e d value 32.27
6.19 61.53 *H NMR (CDClj)
5 ppai=1.74 tc 1.91 (3H, m, SHJ
2.70 to 3.00 {13H, m, CH)
[ o i : r> |
i a C NMR (In CDC 1 a)
a „ „ = 2 4 , 7 -S-GlhClhSB
2 4 . 9 -S-CHaCHa8H
2 8 . 6 -S-CH*CHCEUSH
!
s-
[0116]
35.4 -5CB*CHiSH
36, 0 -SCHaCHaSH
36. 8 -5CHsCHCH2SB
i
s-
48.7 -SCH1CHCH2SH
I
[0117]
[Purification and structure confirmation}
By a silica gel column chromatography (toluene-methanol,
stepwise method) was repeatedly periocined, a nitrogen-containing
compound (xelex'red to as B-1 J was fractionated and purified from
the polyLhiol composition which is primarily comprised ot
4-mercaptomeLhyI-l, 8-dimerc.apto-3, 6 -dithi a octane.
From the results of i nstxijinental analysis, it was idoiiLilied
52
15
20
t h a t t h e n i t r o g e n - c o n t a i n i n g compound (K-1) had a. s t r u c t u r e in whi oh
one of a mcrcapLo group of
4 - m c r c a p t o i i i c t h y l - l , B-dimercapto-3, 6-da t h i a o c t a n c was r e p l a c ed
with EI group r e p r e s e n t e d by t h e f o l l o w i n g IOHIIUILS {a) , i u r t h e r m o re
o t h e r one o± a mercapto group was r e p l a c e d with a hydroxy! qioup.
In t h e f o.l 1 owing f o rims J a (a) , * r e p r e s e n t H an a torn "i o bond"! nq.
[0110]
NH2
*
N. .NH2
(a)
NH2
I 01191
(1 } Mass spectrum
KAH-MS: TO./7.310 (M1) (Matrix m-NBA)
{?.} .IK (Universal A'i'K method}:
3300 cm"1: NH s t r e t c h i n g , ?541 cm"1: SH s t r e t c h i n g , J 606 cm *:
C~N s t r e t c h i n g , [520 cm-1: MH vending.
(3) 1H-MMR (DMSO^ds) :
5 ppm 2 . 3 - 2 . 9 (llfl {-CHZ-, SH) ) , 3 . 1 - 3 . 4 5 (3H {-CH-, CB2OU) ) ,
6 . 6 - 6 . 8 <6H (NH2) ) .
{4)1:JC-KMR (DMSO-ds) :
5 ppm 24-4 0 {CIIZ) , 46-48 (CH) , 70.3 (C-OH (C a d j a c e n t to OJ ) ,
166.5, 178.1 (-C-N- {iiielaiiiine s k e l e t o n } }.
[0120]
The r a t i o or t h e peak urett ol the n i t r o g e n - c o n t a i n i n g compound
(B-l) to 4-Liiercaptomethyl"!, 8-dimercapt r>-3, 6 - d i t h i a o c t a ne
53
(referred to as a VJOI ythi ol oosupound {A-I) ) was determined in the
following manner.
1, Measurement conditions of high performance ]iguid
chromatography
Column: YMC-Pack ODS-A A-312 <35<1>6 mm*150 mm}
Mobile phase : acetoniLrile/Q , 01 mol-po Labium dihydrogen
phosphate aqueous so.l ut ion—£10/40 { vol/vol)
Colnnm temperature: ^O^C
h'l ow rate : 1,0 ml /rnin
Detector: UV detector, wave] enqth 2 3D rirn
Preparation o£ measurement solution; 160 mg of a sample is
dissolved and mixed in 10 ml of acetonitri le,
IuJGction volumG: 2uL
[<1121|
2 . Rati o of the peak area oi niLrogen-contfining compound (B-l)
1 n the pol ythi ol c.omposiLion which wat; produced in Example
A-1 , the rati o o f the peak area of the nitrogtm-containing compound
(hi-.l } to the po I ythiol compound {A-1) was ca3 oulated using Lhc
foil owing expression,
Expression: {[peak area of nitrogen-containing compound
(B-l>]/[peak area of polyfhiol compound [A-1 > ] ] * 1 0(1
The result calculated usi ng the expressi on for computation
described above was 0.21.
Moreover, Lhc ±-e Lent ion times of the pol ythi ol compound (A-1 )
and Lhe nitrogen-conLuining compound (H-J) were as follows. A
chart el high periormance liquid chromatography is shown in S''iq.
1.
54
P o l y t h l o l compound {A-I) : EXOIII 12.0 minutes to 13.!J m i n u t e s.
N i t r o g e n - c o n t a i n i n g compound {B-l): From A,3 minutes to h.fe
m i n u t e s .
[0122]
b {Manufacturing of p l a s t i c lens}
b'2 p a r t s by weight oi m-xylylene diisocyariijLc, 0.015 p a r ts
by wei qht of di b u t y l t i n d i c h l o r i d c as a c u r i n g eaLalysL, 0 .10 p a r ts
by wei g h t of Y.V.hKC UN {trade name, a prodijcL manufactured by SLopan
Company; aci di o phosphor i c e : i i c i ) , 0.05 parLs by weight oi Viosorb
10 583 ( t r a d e name, manufactured by CHEMICAL CO., LTD.; u l t r a v i o l e t
a b s o r b i n g agent) wore mixed and d i s s o l v e d at ?0CC. 4R p a r t s by
weighL oi the obLaiiscd p o l y t h i o] composition which is p r i m a r i ly
comprised oi the polyLhiol compound (A-l) was charged and mixed
t o s e t t o a mixed homogeneous l i q u i d . After t h e homogeneous l i q u id
1 ]"j was deqassed at 600 Pa i o r 1 hour, the homogeneous l i q u i d was put
i n t o a mol d di e con s i s t i n q oi a g l a s s mold and a t a p e a i l or l i l t r a t i n g
usi ng a 'I'ef 1 on (regi s f e r e d trademark) i l l t o r oi 1 pin. The mold d ie
was put i n t o an oven, g r a d u a l l y healed up iroin 10"C to 120"C, and
polymerized for 20 hours- After t h e p o l y m e r i z a t i o n was f i n i s h e d,
20 the mold d i e was t a k e n out from t h e oven to o b t a i n a r e s i n by r e l e a s i ng
from t h e mold d i e . The o b t a i ned r e s i n was l u r t b e r a n n e a l e d at 120"C
f o r 3 h o u r s . Physical p r o p e r t i e s of t h e o b t a i n e d p l a s t i c l e n s a rc
shown in T a b l e - 1.
[0123]
25 [Examples A-2 to A-10J
The polyLhiol composition whi ob is p r i m a r i l y cornpri sed of t he
p o l y t h i o l compound {A—.1 } in t h e same way as Kxample A--1 except
55
c u t t i n g to Lhe producing c o n d i t i o n s d e s c r i b e d in Table-1 was
produced and Lho p l a s t i c lens was manvifactured, The r e s u l t s are
shown in T n b l e - 1.
I0124J
5 [RxampJa Ft-1 |
{Synthesis of polyt.hio] composition which is p r i m a r i l y comprised
of 4-mereaptomethyl-l, 8-rHmerc:apto-3r fc-ditbiaor.tane)
124,6 p a r t s by weight of 7-niercaptoeth.anol and 18.3 p a r t s by
weight of degassed water (the c o n c e n t r a t i o n of d i s s o l v e d oxygen
10 is 2 ppnt) wore charged i n t o a r e a c t i o n v e s s e l . After 101-5 p a r ts
by weigh! oi 32% by weigh of sodium hydroxide aqueous s o l u t i o n was
added dropwise? and charged irum 12°C to 35°C over 40 m i n u t e s , 73,6
p a r t s by weight of epi ch.lorohydrin waa added dropwiso and charged
from ?G °C to 36°C over A . 5 hours, and c o n t i n u o u s l y , s t i r r i n g was
1 5 performed for 4 0 mi n n t . e s . From NMR d a t a , Lhe producLion el 1,
3-bi s ( 2 - h y d r o x y e t h y l t h i o ) - ? - p r o p a n o l was confirmed.
Next, 183,7 p a r t s by weight of t h e p u r i t y of 99.90% of t h i o u r ea
was charged, 10U.6 p a r t s by weight of the p u r i t y of 90*7$ of
h y d r o c h l o r i c a c i d gas was blown and s t i r r e d at JJ0°C for 3 hours
20 under r a i l u x lo cenvcrL i n t o a t h i u r o n i um s a l t . After o o o l i n q to
45UC, 320. 5 p u r l s by weight of t o ! uene was added and cool ed to 31°C,
216.7 p a r t s by weiyhL ol 25% by weight of aqueous ammonia s o l u t i on
was charged i r em 31°C Lo d0uC over 29 minutes and matured from FiA*C
lo 63"C i o i 3 hours, and ix Loluene s o l u t i o n of t h e p o l y t h i ol
2b composition which is p r i m a r i l y comprised of 4-niercaptomethy"*-1r
y - d i m e r c a p t o - 3 , fa-dithiaocLane was o b t a i n e d . 162.9 p a r t s by
weighL oi 35.b^ h y d r o c h l o r i c acid was added i n t o the t o l u e ne
soiution and acid washing was performed from 34°C to 43°C for 1
hour. MA,? parts by weight of degassed water (Lhe concentration
of cii ssol vpd oxyqen is 2 ppin) WLIS added and washing which wus
performed from 35°C to 4f?°C tor 30 minutes was conduct ad twice.
5 162 . 8 parts by weight of Q, 1 £ aqueous amnion: a was added to wash
lor 30 minutes. 174,2 parts by weight of degassed water (the
eoneenLrution oL dissolved oxygen is 2 ppm} was added and washing
which was performed Irom 34"C to 43°C for 30 minutes was conducted
twice. Aiter toluene tind trace water were removed under heating
10 and reduced pressure, filtration under reduced pressure was
performed by PI'KK type membrane iilter ei 1.2 put Le obtain 20 5.0
parts by weight of pol ythi ol composition which is primarily
comprised oi 4-mereaptomethy'i -1 , n-diinercapto-B, fr-di thiaocLane (a
pelythiol compound (A-l)). Physical properties of the obtained
15 pelythiol composition are shown jn 'I'able-t.
The identilieaLiun of
4-iuercaptomethyl-l, 8-dimereaptO"3, 6-dithiaoctarte was performed
in the same way as Example A-l and Lhe same results were obtained.
[Purification and structure coolirmaLion)
?Q Hy a sill ca gel co.l umn chromatography (Lolucnc-methano.l,
stepwise method) was repeatedly performed* the nitrogen-contaj ni ng
compound (H-l) was fractionated and purified irom Lhe pelythiol
cornposi ti on whi ch i s primarily comprised el polyLhiol compound
( A - l )•
25 h'roTn the results of instrumental analysis, 1L was identified
that the ni trogen-contai ni nq compound (B-1) had a struct uEG in which
one of a meroapto group ot
57
•1-mer cap Lome Lhy 1-1, 8-dimcrcapto-3, 6-d"i tiii a octane was repl aced
with a qroup repre^onLcd by Lhc following formula (a) , furthermore
other one ot a morcapLo group was replaced wiLh a hydroxyl group,
In the f ol] nwi nq formula (a) , * represents an atomic bonding.
[01?5]
3 N . .AH (a)
NH?
L012G]
(1) Mans spectrum
t^AW-MH: jn/y.'M{) {M1} (Matrix m-NBA)
0 <2) IR (Universal ATR method}:
3300 cm"1: NH s t r e t c h i n g , 2541 cm ': Si] s t r e t c h i n g , ] 6(3 6 cm"1:
C~N s t r e t c h i n g , 1520 cm"'; NH vending.
J3) ^-NHR (D^SO-dt) :
5 p p m 2 . 3 - 2 . 9 (11R <-CH2-, SH) ) , 3.1-3."45 (3H (-CH-, C^OJO) ,
5 6.6-6,8 [611 (EII?) ) .
U) "C-NMR (DH30-dft) :
b ppm 21-40 {CII?) , 16-48 ) WLIS determined by
pertoriD.i ng in the same way as Example A^l.
101271
{Mamifactuminq p l a s L i c lens)
58
52 parLs by weight of m-xylylene di i socyanate, Q.QlTi parts.
by weight of dibutyltin dichloride as a coring catalyst, 0.10 parts
by weight oi ZELEC UK (trade name, a product manufactured by Stepan
Company; acidic phosphoric esLor) , 0.05 parLs by weight oi Viosorb
5 583 [trade, name, manufactured by KYODO CHEMICAL CO., LTD. ;
ultraviolet absorbing agent) were mixed and dissolved at 20"C. 48
parts by weight of the po]ythi oJ composition which is primarily
comprised of the obtained polythi oJ compound [A-}) was charged and
mixed to set to a mixed homogeneous liquid. After the homoqeneoii:;
10 liquid was degassed at 600 Pa for 1 hour, the homogeneous liquid
was put into a mold die consisting of a glass mold and a tape after
fiItrating using a Teflon (rogisLered trademark) filter of 1 u.m.
The mold die was put into an oven, gradually heated up irom 10 C
to 1?Q°C, and polymeri?ed for AD hours. After the polymerization.
15 was finished, the mold die was taken out from the oven to obtain
a resin by releasing from the mold die. The obtained resin was
further annealed at 12Q°C for 3 hours. I:hysi cal properties oi the
obtained lens are shown in Table-1-
[0128]
20 [Examples B-2 to B-10]
The polythiol composition which is primarily comprised of the
polythiol coEupouiid (A-l) in the same way as Example B-l except
setting to the producing eonditions described in Table-1 was
produced and the plastic lens was manufactured. The results are
2b shown in Tabl e-1.
[0130]
[Examples I-J to 1-4, Comparative Example J —11
( P r e p a r a t i o n of t.bi ol composition added the predetermined
amount of n i t r o g e n - c o n t a i n i n g compound fB-1))
b The predeLermined amount of the n i t r o g e n - c o n t a i n i n g compound
(B-l> which way irLicLionated in advance was added to t h e p o l y t h i ol
composition t h a t is p r i m a r i l y comprised of the p o l y t h i o l compound
(A-l) , t h e r a t i o of t h e peak Liroa ol Lhc n i t r o g e n - c o n t a i n i n g compound
(H-l) to t h e pol y t h i ol compound (2V-1) was analyzed by high performance
10 1i qui d chromatography in accordance with Lhe condiLions d e s c r i b ed
above. The r e s u l t s a r e shown in Table-2.
(VisccsiLy measurement of polyrcierizable composition)
The producing Lime of the polymeri ?abl e composition was set. to
0 hour and the v i s c o s i L y afLcr 7 hours was e v a l u a t e d ds an index.
lb b2 p a r t s by weight el m-xylylene d.i i s o c y a n a t e , 0,015 p a r t s byweight
of d i b u t y l t i n dichlo±-ide as a c u r i n g c a t a l y s t , 0,10 p a r t s by
weight of tfKI.KC UN (trade name, a product manufactured by iltepan
Company; a c i d i c phosphoric e s t e r } , 0.05 parLs by weigiiL ol Viosorb
r}83 (trade name, manufactured by KYODO CHEMICAL CO., LTD.;
£0 u l t r a v i o l e t absorbing agent) were mixed and d i s s o l v e d at 20"C. 48
p a r t s by weight of the p o l y t h i o i composiLion which is p r i m a r i ly
comprised of t h e obtained p o i y t h i o l compound (A-l) was charged and
mixed to s e t to a mixed homogeneous l i q u i d . Tin?, producing Lime ei
t h e mixed homogeneous s o l u t i o n was s e t to 0 hour and t h e visce^iLy
25 after 7 hours was e v a l u a t e d by a Hrookfield tiypfi v i s c o m e t e r . The
r e s u l t s arc shown in Table-?,
[0111]
63
(Manufacturing plastic lens)
52 parts by weight of m-xyl yl enp di i socyanate, 0-015 parts by
weight ol dibutyllin dichloride as a curing catalyst, 0.10 parts by
weight of EELEC UU {Lradc name, a product manufactured by frtepan
5 Company; acidic phosphoric ester), 0,05 parts by weight of Viosorb
583 (trade name, rnanufpictured by KYODO CHEMICAL CO., LTD.;
ultraviolet absorbing agent) were mixed and dissolved at 20"C. 43
parts by weight of the po] ythi ol composition wbi ch is primarily
comprised of the obtained po] ythiol compound [A-]} was charged and
10 mixed Lo set Lo a mixed homogeneous liquid. Then, the homogeneous
liquid was degassed at GOO Pa for J hour, the homogeneous 1 i qui d was
put into a mold die consisting of a glass mold and a tape after
fi ] trati nq usi ng a Teflon (registered trademark) iiltcroflum. The
mol d di e was put into an oven, gradually healed up irom 10 "C Lo 120 C,
L5 and pol ymeri zed for 70 hours. AiLcr Lhe polymerization was finished,
the mold die was taken out from the even Lo obtain a resin by releasing
from the mold die. The obtained resin was iurther annealed at 12Q"C
for 3 hours. Physical properties of the obtained plastic lens are
shown in Tuble-2.
20 [0132]
Table-2
EKasnple
Comparative
Example
1-1
I 2
T-J
T-'i
I 1
R a t i o ot pF?ak av^i •:'-'<
n i t r o g e n containing
compound {E)-l)
0.8
1,2
• ,H
?.a
-5.2
VJ : . l : l . ; . l l _y
Fi 1 1. E?T 7
(ipE'a - a J
&A
SO
B4
117
1 0fto<
C.-ii in
YT
4.(i
4 , 5
4.b
4.3
L11 r 1 01 i n r-i i i 2
1 oHfn i l ^ q i H i 1 t:l"
l . j i i n ^ | : . ] r H n cy
19
19
22
23
25
!o! s l . l L l O fi
u
O
O
0
X
The ratio of the peak area ol the nitrogen-containing compound
Kxpressi on : f [peak a~re-a of nitrogen-containing compound (B-l) ] / [peak
64
area ol polyLhiol compound [A-l}]|xlOQ
f()]:«l
From the results described above, Irt a ca^G where? the ratio oi
the peak ari?a of the nitroqen-containing compoiind •( H—1 ) to the
5 po]ytbiol compound (A-l) was equal to or less than 3,0 as Examples
1-1 to 1-4, color and the loss degree of transparency were excellent
and sLriation also did not occur- Furthermore, the viscosity of the
polynierizable compos!Lion alter 7 hours was lew arid handling
cheEraeLerisLios were excellent.
10 On the other hand, in a ease where the raLio oi Lhe peak area
of the ni troqen-containing compound (B-l) was over '3 . 0 as ComparaLive
Fxainple I-1, si nee the vi scosity of the polymeri ?able composition
after 7 hours was over 1, 000 in Pa - s, -it became cl ear that mannfacturinq
stability of the plastic lens was also affected,
15 [0134]
[Example C-l]
{SynLhesi^ ei polyLhlol composition which is primarily
comprised of
bis (mercaptometbyl}-3f6,y-LrlLhia-1,11-undeeauediLhiol)
2Q !>1.2 parts by we.iqht of ^-mercapLocLbanol, 2fc. b partti by weight
oi degassed water (the concenLxaLion ol dissolved oxygen is 2 ppm) ,
and 0.1k parts by weight of 4 9£ by weighL sodium hydroxide aqueous
solution were charged into a reaction vessel. 61.99 parts by weighL
of epi chl orobyriri n was added dropwise and changed from y^C Lo 11"C
?T> over 6.5 hours, and r.onti nuously, sLirring was performed tor 60
minutes. From an NMR data, the producLion of
l-ehloro-H- (7-hydroxyetliylLhiof -2-propanol was coniiniied.
6 b
Next, IbO.O p a r t s by weight of 17,3D- sodium s u l p h i d e aqueous
so l i l t i on was added dropwi se and changed Irom 7 "C Lo 37 JC over 5. 5
hours and s t i r r e d for 120 m i n u t e s . From Lin IMP. d a t a , the p r o d u c t i on
of a t e t r a o l . compound of t h e formula (4) was confirmed. Then, 279,0
b parts by weight of 35 . 5% hydror.hl o r i c a c i d was charged, arid then 125. 8
p a r t s by weight ol the p u r i t y of 93.903 of t h i o u r e a was charged and
s t i r r e d at 110 "C l o r 3 hours under r e f l u x to con. v e r t i n t o a t h i uroni urn
s a l t . After cooling to 4bIiC, 214.0 p a r t s by weight of toluene was
added and cooled to 2£iclCF 20 6.2 p a r t s by weight of 25% by w i g h t aqueous
10 ammonia s o l u t i o n was charged from 2G"C to 50"C over 30 minutes and
s t i r r e d from 50°C to 65°£1 for 1 hour, and a toluene s o l u t i o n of the
p o l y t h i o l composition which is p r i m a r i l y comprised of
A , 8-dimercapLomethyl-l, Il^diTnercapt.o-3, 6, 9 - t r i t h i aundecane,
A , 7-dimercuptomothyl-l, l l - d i m e r c a p t o - 3 , 6, 9 - t r . i t M a u n d e c a n e and
lb b, 7-dimercuptomethyl-l, l l - d i m e r c a p t o - 3 , 6, 9 - t . r i t b i aundecane was
o b t a i n e d . The t o l u e n e soiuLion was added i n t o 59-4 p a r t s by weight
of 363 h y d r o c h l o r i c a c i d and a c i d washing which was performed from
?A°C to 390C: for 30rninut.es was conducted t w i c e . 113.7 pctrLs by wei ght.
of degassed water (the concenLratieii of d i s s o l v e d oxygen is 2 ppm)
20 was added and washing which was periormed irom 35'1C to 45"C for 30
minutes was conducted f i v e t i m e s . AlLer Loluene and trance water were
removed under h e a t i n g and reduced p r e s s u r e , i i i t r a t i o n under reduced
p r e s s u r e was performed by I'Th'K type membrane i l i t e r of 1. 2 urn Lo o b t a in
115,9 p a r t s by weight cf t h e poly t h i o l composition which i s p r i m a r i ly
25 comprised of
4, 3-dimercapl: o n t e t h y l - l r 1 1 -di rneroapto-3, 6, 9 - t r i . t h i aundecane
( h e r e i n a f t e r , compound A),
hb
10
l b
A, 7-di-mercaptomethyl - 3 , l l - d i m . e r c a p L o - - 3 , 6 , 9 - t r i t h i a u n d c c a n e ( h e r e i
n a f t e r , compound B), arid
5, 7-d Jineroapt-ometby] - 1 , 1 1 -diniercupLo-3,, 6, 9 - L r i t h i a u z i d e c a r K '
( h e r e i n a f t e r , compound C) [an is earner m i x t u r e of compound
A/B/C=85/5/10 (molar r a t i o ) ) , 1'hysica.l p r o p e r t i e s of t h e o b t a i n ed
p o i y L h i o l c o m p o s i t i o n a r c shown in ' l ' a b l e - 3,
| 0 l 3 bJ
P o l y t b : o J comprised oi the i s o m e r s was r e s p e c t i v e l y i s o l a t ed
Tiud i d e n t i f i e d by r e v e r s e d p h a s e c h r o m a t o g r a p h y . F i r s t l y , t.ne
r e s u l t s of e l e m e n t a r y a n a l y s i s , TR, MS and NMR ol t h e compound A a re
shown,
[0136]

Measured v a l u e {%}
\V? .'I
6 . 2
hi .1
C a l c u l a t e d value_(%)_
32."8
6 1 . 2
- i -
0138
[ 0 1 3 7 ]
2 5 ^ 3 {34)
m / z - 3 6 6 (M1")
. ^C-NMR CDCi3>
FTSCII2CII2S -
ag RZ
_ S —
-SH
az ai
SCH2CI-12SII
S ppln
aj ^ 2 4- 9
as - 3 5, I
as - 2 8„ 5
fl.4 = 4 8. 7
20 Next, t h e r e s u l t.s of NMR oi Lhc compound C a r c tihown. The r e s u l ts
of e J e m e n t a r y a n a l y s i s , IR and MS were t l i e same as t h e compound A.
67
[014(1
< 1 3C -NMR CDCb ^
IISCH2CH2S -] C 3 csrSC:H2CH2SH
6 P pm
«4
113 -*cs
..... s c4
Cb SH
c i ^ a 4. 7
c 2 = 3 6 . 5
c 3 = 3 6 . 3
c 4 = 4 9 , 4
[01411
L a s t ! y, t h e r e s u l t s of NMR of t h e compound B a r e shown. The
r e s u j t s of e l e m e n t a r y anal y s i s , IR and MS were t h e sasne a:; t h e compound
A,
[0142]
< l i !U-NMK CDCto>
bi bz
llSnba
b5
bg bjo
HSCK2CH2S - b 4 W SCIi2CHaSH
S b7
bflLHH
5 P p m . _ . . „ . . . „ . . . „ . . „ . „ . . . „ . .
h2 =3 5* 1
b3 ---•?. 8. 5
b^ =--=4 3 , 7
b 5 = 3 5. 9
b(j - ^ 8 . 6
1>7 -A 9. 4
b 8 = 3«_ 8
b 0 = 3 5 . 5
bio 2 4. 7
[Q143]
10 (Fractionation and s t r u c t u r e c o n f i r m a t i o n)
The n i t r o g e n - c o n t a i n i n g compound ( r e f e r r e d t o as B-?} i n c l u d ed
i n t h e p o l y t h i o l c o m p o s i t i o n was f r a c t i o n a t e d from t h e p o l y t h i oJ
c o m p o s i t i o n which i s p r i m a r i l y comprised of t h e p o . l y t h i o ] compound
[ r e f e r r e d to eta A-2} comprised of
15 5, 7 - d i n i e r c a p L o m o l h y l - l , l l - d i m e r o a p t o - 3 , G, 9 - t r i t h i a u n d e c a n e r
4r 7-diiiiercupLosucLhyl-l, l l - d i m e r o a p t o - 3 , G, 9 - t r i t h i a u n d e c a n e , and
4r B - d l v i i e r c a p t o i i i c t h y l - l , J1 - d i r n e r c a p t o - 3 , 6, 9 - t r i t h i a u n d e c a n e by
68
p e r f o r m i n g p r e p a r a t i ve h"i qh paElormaiiee l i q u i d ehiomatocfraohy.
From t h e r e s u l t s of i n s t r u m e n t a l a n a l y s i s , it was p r o v e d t h at
t h e n i t r o g e n - c o n t a i n i n g compound (fi-2) had a s t r u c t u r e "in which one
ol a mcreapLu group of t h e p o l y t h i o l compound
{2} 1R ( U n i v e r s a ] A'J'H m e t h o d ):
3329, 3198 cm- 1 : NH s t r e t c h i n g , 2:">39 cm *: f-JH s t r e t c h i n g , 1606
20 enf1: C=N s t r e L c h i n g , 1525 cm"1: NH v e n d i n g.
(3) ^-NMR (CDClj) :
5 ppm 1 . 6 - 1 . 8 {4H (SH)}, 2 , 5 - 3 - 5 [13H [-C;H2 - , -CH-) ) , : ^ H - J .9
<3H (-CHOK, CH2OH> ) •
(4) 1JC-NMR tCDCl-j) :
69
fippm 25-19 {CM2} , 4H-JJt> [CI1}, 61 (CII?-OII {C a d j a c e n t to OJ , 69-/0
fCH-OH {C adjacent toO) ), 166, H80 {-C-N- [C of a t r i azi ne s k e l e t o n } ) ,
[0146]
The r a t i o of t h e peak area of t h e ni t r o g e n - o o n t a i n i n g compound
5 (B-2) to t h e p o l y l h l o l compound (A-2) was determined in t h e following
manner.
1. Measurement c o n d i t i o n s of high performance l i q u id
oh romatograph y
Column: YMC-Pack ODS-A A-312 (SbE6 miu*lb0 mm)
10 Mobile phase: a c e t o n i t r i l e / 0 . 01 mo J -potassium; dihydrogen
phosphate aqueous solution-6Q/40 {vol/vol}
Column LumperaLurc: 40UC
Flow r a t e : 1.0 ml/min
D e t e c t o r : UV d e t e c t o r , wavelength 230 mti
lb Preparation oi measurement s o l u t i o n : 160 mg of a sample is
d i s s o l v e d Find mixed in 10 mi oi nee Lon.it r i l e .
Inject"! ori volume: 2uL
[01471
?- Ratio of peak area of n i t r o q e n - c o n t a i n i n g compound (B-2)
20 The composition r a t J o of t h e p o l y t h i o ! composition which was
produced in Example C-1 was c a l c u l a t e d using t h e following
e x p r e s s i o n .
Expression: {[peak area of n i t r o g e n - c o n t a i n i n g compound
( B - 2 ) ] / [ p e a k area of p o l y t h i o ! compound (A-2) ] 1 *.l 00
25 The r e s u l t c a l c u l a t e d using the expression for computation
d e s c r i b e d above was 1.16.
Moreover, the r e t e n t i o n times of the p o l y t h i o l compound (A-2)
70
and the nitrogen-containing compound (tf-?) were as fol 1 ows . A chart
of high pertormance liquid chromatography is shown in Fig. 2.
Polythiol compound (A-2): From 22,0 minutes to 28,0 minutes
Mitroqen-oontai nirsq compound (B-2J ; From 6.5 minules Lo 8,0 minutes
5 [0148]
(Manufacturing plastic lens)
50.7 parts by weight of m-xyly.lene ri.i .i socyanate, 0.01 parts by
weight ol dibutyltin dichloride 3.3 a curing catalyst, 0-10 parts by
weight ol ZELEC UN (trade name, a product manufactured by Shepan
10 Company; acidic phosphoric ester), 0-05 parts by weight of Vi o.sorb
50 3 (trade name, manufactured by KYODO CHEMICAL CO., LTD.;
u] travi ol et absorb"i nq aqent) wore mixed ttiid dissolved at 20°C. 49.3
parts by weight of the pol ythiol composition which is primuriiy
comprised of the obtained polythiol compound (A-2) was charged and
15 mixed to set to a mixed bomoqeneou.s liquid. After the homogeneous
liquid was degassed at 600 i?a for 1 hour, the homogeneous liquid was
puL inLc Li mold die consisting of a glass mold and a tape after
iiltiLiLinq using a Tellon (registered trademark) filter of 1 pm. The
mold die was put into an oven, gradually heated up from 10°C to \?Q"C.I
70 and polymerized for 20 hours . Alter the polymerization was f J ni shed,
the mold die WFJS taken ouL Ixcm the oven to obtain a resin by rel easing
from the mold die. The obLained resin was further annealed at 1 3(1 °C
for 4 hours. Physical properLies of Lhe obtained lens are shown in
Tab]e -3.
?5 [01491
[Samples C-? to C-lt)|
The polythiol composition which is primarily comprised of the
71
p o l y L h l o l compound (A-2) in t h e same way as Kxampl e C- J e x c e p t s e t t i n g
t o t h e p r o d u c i n g c o n d i t i o n s d e s c r i b e d i n T a b l c ^ 3 was produced and
t h e p l a s t i c : l e n s wna iiinnuiacLured. The r e s u l t s a r e shown i n T a b l e - 3 .
F 01 r.Q 1
5 [Kxample l)-1 ]
( S y n t h e s i s of pol y t b i ol c o m p o s i t i o n wbi oh i s p r i m a r i ly
c o m p r i s e d of
b i s (mercapLomeLhyl) - 3 , 6, 9 - t r i t h i a - l , ) 1 - u n d e c a n e d i t h i o l )
5 1 . 2 p a r l s by w e i g h t of 2 - i T i e r c a p t o e t h a n o I , 2 6 . 5 p a r t s by weight.
10 oi d e g a s s e d water (Lhe c o n c e n t r a t i o n of d i s s o l v e d oxygen is 2 ppm) ,
and Q.lf. p a r t s by w e i g h t oi A9% by weight sodium, h y d i o x i d c aqueous
s o l u t i o n were c h a r g e d -into a r e a c t i o n v e s s e l . 61.99 paxLs by weight
of e p i o h l o r o h y d r i n was added d r o p w i s e and c h a r g e d from 9"C io 13"C
o v e r G.5 h o u r s , and c o n t i n u o u s ! y , s t i r r i n g was performed fox •IQ
15 minutes. From an NMR d a t a , t h e p r o d u c t i o n of
l - c h l o r o - 3 - ( 2 - h y d r o x y e t h y l t h i o ) - ? - p r o p a n o l was conf i rmed.
NexL, 150.0 p a r t s by weight of 37,3% sodium s u l p h i d e aqueous
s o l u t i o n waa added d r o p w i s e and c h a r g e d from 5UC to 42°C over 4. fj
h o u r s , and c o n t i n u o u s l y , s t i r r i n g was p e r f o r m e d f o r 40 m i n u t e s - H'roTi
20 an NMR d a t a , t h e p r o d u c t i o n oi a LeLraol compound of t h e formula (4)
was c o n f i r m e d . Next 11 / . A p a r t s by weight of t h e p u r i t y of 99.90%
of t h i o u r e a was c h a r g e d , 84.3 parLc hfj weight of t h e p u r i t y of 30.1%
of hydsroch! o r i c a c i d gas was blown ttnd s L i r r e d aL 110UC f o r 3 h o u rs
u n d e r r e f 1 nx to c o n v e r t i n t o a t h i u r o n i um £>alt. AIL or. c o o l i n g to
25 $1>°C, 214.0 p a r t s by w e i g h t of t o l u e n e was a d d e d and c o o l e d Lo 26°C,
J5H.4 p a r t s by w e i g h t of 2l/"i by weight aqueous aiEiiuoniLi s o l u t i o n was
c h a r g e d from 2(i"C to /lb"C over 25 m i n u t e s and m a t u r e d from 54°C to
72
62"C l o r 1 hour, and a Loluone s o l u t i o n of t h e p o J y t h i o l composition
which is p r i m a r i l y comprised oi the p o l y t h i o l compound , 7-dimercaptomethyi-l, l l - d i n i o r e a p L o - 3 , 6, 9-LriLhiaundecanC:,
5 4,7 -di rnercaptomethyl - 1 , 1 1 - d i m e r c a p t o - 3 , tlr 9 - t r i t h i a u n d e c a n e and
A, 8-di rnercaptomethyl - 1 , J .1 -dimprcapt.o-^, 6F 9-t.H t h i aundecane wa::
o b t a i n e d , 59,4 p a r t s by weight of 36^ h y d r o c h l o r i c a c i d was added
i n t o t h e t o l u e n e s o l u t i o n and acid washing which was performed from
33 "C to 40 UC l o r 3D minuLcs was conducted twi c e , 110-7 p ^ r t s by wei qht
10 oi degassed water (the c o n c e n t r a t i o n of d i s s o l v e d oxygen is 2 ppm>
was added and washing which wd^ performed from 35"C Lo ^"C for 30
minutes was conducted f i v e t i m e s . AiLer Loluene and t r a c e waLor wore
removed under h e a t i n g and reduced p r e s s u r e , f i l t r a t i o n under reduced
p r e s s u r e was performed by EPTKK type membrane f i l t e r of K 2 pm to ohtLiin
15 115-0 p a r t s by weight of t h e pol y t h i o i composite on wbi r.h i s p r i m a r i ly
comprised of t h e p o l y t h i o l compound {A-?}. Physical p r o p e r t i e s oi
t h e obtained polyLhiol composition an?, shown in T a b l e - 3 . The
i d e n L i i i c a L i o n ol Lhe polyLhiol compounds was performed by an HMR,
and Lhe same, r e s u l t s as Example C-l were o b t a i n e d.
20 [OlblJ
(Fractionation and structure confirmation)
The nitroqen-containing compound (referred Lo as B-2)included
in the polythiol composition was fractionaLcd Irom Lhe polythiol.
composition which is primarily comprised oi the polyLhiol compound
2b (A-2} by perform!nq preparaLive high performance liquid
ch r oma t oq r a ph y.
From the results oi instrumental anal ysi,L;, iL wa^ proved that
7 3
t h e n i t r o g e n - c o n t a i n i n g compound (B-2) had a s t r u c t u r e in which one
of a mercapto group of t h e pol y t h i o l compound (A-2) wa^ r e p l a c e d w i th
a group r e p r e s e n t e d by t h e f ol ] owing ± ox inula (a) , tuxthcrmoxc, o t h er
one of a mercapto group was replaced with a hydroxyl group. In Lhe
following formula (a), * r e p r e s e n t s an atomic bonding.
The xcEoult^ ol an a n a l y s i s of the n i t r o g e n - c o n t a i n i n g compound
{B-2) included in t h e p o l y t h i o l composition a r e shown.
f01!>21
NH2
* .
(a)
-1 ."I .
. NyNH2
Nc^NH
NH2
10 L01b3j
(1) Mass ^pectrurit
FAB-MS: m/z'Wh (K1 ) (Matrix ifc-NBA)
{2} IK (Universal ATR method):
33?9f .^1 98 cm"1: NH s t r e t c h i n g , 2539 ciifs: SH s t r e t c h i n g , 1606 cm"':
1 5 C=N s t r e t c h i n g , .1575 cm : Nil vending.
(3) ^-NMR {CDCl-j) :
b ppm 1.6-1*8 (4H (SH)}, 2 . b - 3 . b (llil (-CII?-, -CH-)), 3 , 8 - 3 .9
(3H (-CHOH, CH2OH) ) ,
(4) 1JC-NMR (CDCl-j) :
20 5 ppm 25-39 (CH;,), 48-50 (Cl-E) , 61 (CII?-OII (C adineent LoO]),
69-70 (CH-OH (C adjacent to 0}) , 166, 1H0 (-C-N- ( C o£ a txiazinc
skeleton)),
[0154]
74
The raLio of the peak area of the nitiogen-containi ng compound
IB-2) Lo the polyLhiol compound {A-?) was determined by performing
in Lho same way a^ Example C-1 -
fSUijbl
f> (Manufacturing plastic lens)
FiO.l parts by weight ot m-xylylene diisocyanate, 0.01 pa-rLs by
weight of dibutyltin diobloride as a curing catalyst, 0.10 parly by
weight of. ZELEC UN (trade name, a product manufactured by SLepan
Company; acidic phosphoric ester}, ().0!> parts by weight of Viosorb
10 583 (trade name, manufactured by KV01JO CHKMECAI. 00,, LTD. ;
ultraviolet absorbing agent) were mj xed 3.nd di ssolved at ?0°O. 4 9. ."i
parts by weight of the polyLhiol composition which is primarily
comprised of the obtained polyLhiol compound (A-2) was charged and
mixed to set to a mixed homogeneous liquid. AiLor Lhe homogeneous
15 Diquid was degassed at 60(1 Pa tor 1 hour, Lhe homogeneous liquid was
put into a mold die consisting of a glass mold and a Lape after
filtrating using a Teflon (registered trademark) filter ot 1 UEIL. The
mold die was puL inLo an oven, gradual 1 y heated \ip from i 0nC to 120"C,
and polymerized lor 20 hours . After the pol ymeri zati on was finished,
20 the moid die was taken ouL from the oven to obtai n a resi n by releasing
irom Lhe mold die. The obtained resin was further annealed at 130"C
tor A hours. Physical properties of the obtained lens are shown in
Table-3.
IGlbfcj
7b LExampJes D-2 to D-I0J
The poUyfhiol composiLion which is primarily comprised of the
polyLhiol compound (A-2) in the same way as Kxampl e n-1 except setting
to the producing conditions dcscx'rbod in Table-3 was produced and
Lhu p l a s t i c lens was manufactured. Tlic r e s u l t s are shown in Tublc-3.
19
loibyj
IExamp]es JJ-1 to II-3, Comparative Example II-1J
(Preparation of thiol composition added the predetermined
amount of nitrogen-contai ninq compound (B-2))
5 The predetermi ned amount of the nitxoqen-contai ri"i ng compound
(B-2) which was fractionated J n advance was added to the po.lytbio]
composition that is primarily comprised of the polythiol compound
(A-2) , the ratio oi the peak area of the nitrogen-containing compound
{B-2) was analyzed by high performance liquid chromatography in
10 accordance- with the conditions described above. The results are
shown in Table-4.
[0159]
(Viscosity measurement of pol ymarizable r.ornpos.i txon}
The producing time cf the pol ymeri zabl e composition was set to
15 0 hour and the viscosity after 7 hours was evaluated as an index.
50.7 partti by weight of m-xy]ylene diisooyanate, 0.015 parts
by weight oi dibutyitin dichloride as a curing catalyst, 0,10 parts
by weight of ZELFIC UN (trade name, a product manufactured by Stepan
Company; acidic phosphoric e^ter), 0.05 parts by weight of Viosorb
20 oH3 (trade name, manufactured by KYODO CHEMICAL CO., LTD.;
ultraviolet absorbinq agent) wore mixed and dissolved at 20°C. 49,3
parts by weight of the polythiol composition which its primarily
comprised of the obtained polythiol compound {A-2) was chaxged and
mixed to set to a mixed homoqentiouii liquid. The pxoducinoj time of
/Ti the mixed homogeneous, solution wa^ set to 0 IIOLLL and the viscosity
after 7 hours was evaluated by a Bxookfield type viseometex. The
results are shown i n Table-4,
80
[01GO]
(Manul a c t urine. p l a s t i c lens)
50.7 parts; by weight of m-xy] yl ene d i i s o c y a n a t e , 0-0.1 p a r t s by
weight of d i b u t y i t i r s d i c h l o r i d e as a c u r i n g c a t a l y s t , 0.10 p a r t s by
5 wei qht of 'AFA&T. UNJ (trade name, a product mariuiLscLured by Stepan
Company; a c i d i c phosphoric e s t e r ) , 0.05 pEirLs by weight oi Viusorb
583 (trade name, manufactured by CHEMICAL CO., LTD.; u l t r a v i o i eL
absorbing agent) were mixed arid d i s s o l v e d at ^.O^C. •19.3 p a c t s by
weight of t h e p o l y t h i o l composition which is p r i m a r i l y comprised oi
10 the o b t a i n e d p o l y t h i o l compound (A-?) was charged and mixed to s et
to a mixed homogeneous l i q u i d . After t h e homogeneous l i q u i d was
degassed at fcOO-Pa f o r 1 hour, the homogeneous l i q u i d was put i n to
a mold riie consi s t i n g of a q l n s s mold and a Lape a l t e r f i l t r a t i ng
u s i n g a Teflon ( r e g i s t e r e d trademark) f i l t e r of 1 uiii. The mold d ie
i 5 was put i n t o an overi, g r a d u a l l y hemLed up from 10 "C Lo 120 "C, and
po] ymerized for 20 hours- After t h e polymonizatioi; was f i n i s h e d,
t h e mold d i e was taken out from t h e oven to obtni n a resi n by r e l e a s i ng
from t h e mold d i e . The obtained r e s i n was f u r t h e r annea \ ed at 130"C
for 4 hours. Physical p r o p e r t i e s of t h e obtained p l a s t i c lens a re
20 shown in Table-4.
[0161]
Table-4
Example
Comparative
Example
11-1
11-2
H-1
Ratio d peak area oi
iiitroyen-conlaKiiiig
compound (B-2)
075
1.50
2.80
3 20
Viscosity after
7 hours
(mPa's)
175
"309
569
10QQ<
Evaluatio
Color
VI
l of resin
Loss degree of
Transparency
%
4.1 23
41 I 22
4.3
4.3
30
23
Striata
0
0
0
X
Rati o of peak area of ni troqen-coiiLaininq compound
HI
Kxpressi on : { [peak area of n i t r o g e n - c o n t a i n i n g compound (B~2) ] / [peak
area of p o l y t h i o l compound {A-2}J}*100
[0L62]
From the results described above, in a case where the ratio o£
the peak area ol the nitrogen-containing oompovind (H-?) to the
polythiol compound (A-2) was 3,0 or less as Examples II-1. to 1 l>3,
color and the loss deqrec oi transparency were excellent and striation
al so did not oociir. Fart hern-ore, Lhc viscosity ol Lhc polymerizabl e
composition after 7 hours wa^ low and handling characteristics were
excel 1ent.
On the other hand, in a case where the ratio of the peak area
oi the nitrogen-containing compound (K-2) was over 3 , 0 as Comparative
Example 11-1, since Lhc viscosity of the polymerizable composition
after 7 hours was over 1, 000 mPa- s, it became clear that nianuf actvirinq
stability ot the plastic lens was also affected,
I 0163 J
This application claims a priority based on Japanese Patent
Application No- 2017-179899, filed Aug 14, 2012 and a priority based
on PCT/.JP2013/001201, filed Feb 28, 2013, and all disclosure of" these
references are incorporated in the present application.
CLAIMS
1, A poJythiol composition comprising:
a polythiol compound (A) having three or more mercapto groups;
and
a nitrogen-containing compound (B) in which one of a mercapto
•group of the polythiol compound (A) is replaced wiLh a group
represented hy the fo]lowing iormula (a)
wherein, in the formula, * represents an aLomic bonding,
arid other one o± a mercapLo group of the polythiol compound (A) is
replaced wi th a hydroxy! group,
wherein the peak area of the nlLrogon-corsLainiiig compound (B)
is equal to or less than 3*0, with respect to the peak area oi 100
of the polythiol compound (A) in a high performance liquid
chromatography measurement.
2, The polythiol composition according to claim 1,
wherein the polythiol compound (A) is represented by the
following formula (5)
3. The pol y t h i o l composition Ltccordiny Lo ciaim 1,
wherein the pol y t h i oi compound {A} is p r i m a r i l y comprised ai
at ] e a s t one kind se] ect.ed from the compounds r e p r e s e n t e d by Lhc
following formulae (G) to (ft)
4 , A polymoriiLjblc composition for an opti oal materi al compri si nq:
t h e p o l y l h i o l composition according to any of claims 1 to 3;
u i id
d poiy ^'ilhio/isocyuna^ij coinpouriu'.
5. A method ol mdriulact^ri ng a molded product, oornpri si nq:
mixing Llic- polyt.h.i o.l oompo^i r.i on according to any oi claims 1 Lo 3
Liiid a poly (thi o) i ^ooyanate compound i.o obLain a polymeri zabl e
composition for an opti cal m a t e r i a l ; and.
p n t i n g t h e p o l y m e r i z a b l e compu^iLiori i n t o a mold and c u r i n g t ne
composi tJ on,
6. A molded product which is ofol aiiitid by c u r i n g t h e po.l ymerizab.l e
composition according Lo c l a im 4,
7. An o p t i c a l oioiiiont comprised of t h e molded producL accuidiny Lo
cLiica G.
8. A 1 ens comprised ol t.ho opt.i cal el sment acco-nding Lo claim /.