POLYMERIZABLE COMPOSITION FOR OPTICAL MATERIAL, OPTICAL MATERIAL
OBTAINED FROM POLYMERIZABLE COMPOSITION, AND MANUFACTURING METHOD
5 OF OPTICAL MATERIAL
TECHNICAL FIELD
[OOOl]
The present invention relates to a polyrnerizable composition
10 for an optical material that provides a urethane-molded product, an
optical material obtained from the polymerizable composition, and
a manufacturing method of the optical material.
BACKGROUND ART
15 [0002]
A p l a s t i c lens is l i g h t e r than an inorganic lens, is not e a s i l y
broken, and is dyeable. Therefore, p l a s t i c lenses have become
rapidly widespread as an o p t i c a l element such as a spectacle lens
or a camera lens. Hitherto, various resins for"spectac1e lenses have
20 beendevelopedandused. Typicalexamplesoftheresinsincludeallyl
resin obtained from diethylene g l y c o l b i s a l l y l carbonate or d i a l l y l
isophthalate, (meth)acryl resin obtained from (meth)acrylate, and
thiopolyurethane r e s i n obtained from isocyanate and t h i o l .
[00031
25 In recent years, urethane resins, which have a r e f r a c t i v e index
lower than t h a t of thiourethane resins and are formed of isocyanate
and an alcohol, have been developed (Patent documents 1 to 5 ) .
Although the refractive index of urethane resins is lower than the
refractive indexofthiourethane resins, theurethane resins are less
expensive. Therefore, urethane resins are expected to be used as
alensmaterial. Forexample, PatentDocument4describesanurethane
5 resin obtained from 4,4'-methylene-bis(cyclohexylisocyanate) as
isocyanate and trimethylolpropane propoxylate and
trimethylolpropane as alcohols.
As the isocyanate, there are tolylene diisocyanate and
diphenylmethane diisocyanate which have a high refractive index and
10 are available at low cost, and functional lenses or high-refractive
index lenses using these polyisocyanate compounds arebeing studied.
[0004]
In Patent Document 6, anexample ofmanufacturingurethane resin
by using tolylene diisocyanate, which is available at low cost, as
15 the isocyanate is described in Comparative example 5. Examples of
commercially available isocyanate include m-xylylene diisocyanate,
2,5-bis(isocyanatomethy1)-bicyclo[2.2.1]heptaner
2,6-bis(isocyanatomethyl)-bicyclo-[2.2.1]heptane,
1,3-bis(isocyanatomethyl)cyclohexane, hexamethylene diisocyanate,
20 isophorone diisocyanate, 4,4'-methylene-bis(cyclohexylisocyanate),
and the like. The market price of tolylene diisocyanate is the
cheapest among, these commercially available products. Therefore,
if tolylene diisocyanate is used, cheaper spectacle lenses can be
suppliedtothemarket, anditcanmakeagreatindustrialcontribution.
25 However, Comparativeexample 5, inwhich theexample ofmanufacturing
urethane resin by using tolylene diisocyanate is described, also
describes that a cured substance is not obtained in some cases due
t o molding defect.
[0005]
Patent Document 7 describes a p l a s t i c lens comprised of
thiourethane resin t h a t is obtained from a composition containing
5 a polyisocyanate compound having an aromatic r i n g , a polythiol
compound, abenzotriazole-basedcompound, andphenols. Thedocument
describes t h a t a p l a s t i c lens having excellent weather resistance
is obtained.
10 RELATED DOCUMENT
PATENT DOCUMENT
[0006]
[Patent Document 11 Pamphlet of International Publication No.
W02008/92597
15 [Patent Document 21 PCT Japanese Translation Patent
Publication No. 2009-520057
[Patent Document 31 Pamphlet of International Publication No.
W02010/43392
[Patent Document41 Japanese UnexaminedPatent PublicationNo.
20 2011-012141
[Patent Document 51 PCT Japanese Translation Patent
Publication No. 2012-521478
[PatentDocument6] JapaneseUnexaminedPatent PublicationNo.
2008-144154
25 [Patent Document 71 Japanese Unexamined Patent Publication No.
2012-181268
DISCLOSURE OF THE INVENTION
[0007]
In a lens comprised of urethane resin using aromatic
polyisocyanate such as tolylene diisocyanate, the occurrence of
5 yellowing is noticed. Therefore, the quality of the lens needs to
be improved.
[00081
Comparative example 5 of Patent Document 6 describes that
because a reaction occurs too fast during the polymerization of
10 tolylenediisocyanateas aromatic isocyanate andanalcohol, amolded
product is not obtained in some cases, because the reactivity of a
urethane composition is higher than that of a thiourethane
composition. Particularly, when aromatic isocyanate is used, the
reactivity of the urethane composition is further increased.
15 Accordingly, during blending, in a state in which heat is being
produced, theviscosityoftheurethanecompositionrapidlyincreases.
Consequentially, it is difficult to cast the urethane composition
into a mold, and the composition has a problem with workability at
the time of blending or casting.
20 [0009]
Regarding a plastic lens comprised of urethane resin, Patent
Document 7 does not describe the improvement of light resistance.
[OOlO]
Considering the problems of the related art, the present
25 inventors conducted intensive examination so as to obtain a
polymerizable composition for an optical material which makes it
possible to obtain a polyurethane-molded product that exhibits
excellent workability at the time of blending or casting and has an
excellent refractive index, heat resistance, transparency, andlight
resistance.
[0011]
5 As a result of conducting intensive examination, the present
inventors found that when specific additives are contained in a
transparent resin, which is polymerized under specific conditions
by using aromatic isocyanate and a polyfunctional alcohol, a
polyurethane-molded product having an excellent refractive index,
10 heat resistance, transparency, and light resistance is obtained.
Furthermore, they also found a manufacturing method of the
polyurethane-molded product. Based on these findings, the present
inventors accomplished the present invention.
[0012]
15 That is, the present invention is as follows.
[I] A polymerizable composition for an optical material,
including (A) at least one kind of isocyanate having two or more
isocyanato groups, which contains aromatic isocyanate, (B) at least
one kind of alcohol having two or more hydroxyl groups, (C) an acidic
20 phosphoric acid ester represented by the following Formula (I), and
(D) a benzotriazole-based compound, in which a ratio of secondary
hydroxyl groups to the total molar number of primary and secondary
hydroxyl groups contained in the alcohol (B) is equal to or greater
than 50%, and the benzotriazole-based compound (D) is contained in
25 an amount of 1 part by weight to 11 parts by weight with respect to
a total of 100 parts by weight of the.isocyanate (A) and the alcohol
(B),
wherein, in the formula, m represents an integer of 1 or 2, n
represents an integer of 0 to 18, R1 represents an alkyl group having
1 to 20 carbon atoms, and each of R2 and R3 independently represents
5 a hydrogen atom, a methyl group, or an ethyl group.
[2] The polymerizable composition for an optical material
described in [I], in which the alcohol (B) contains at least one kind
of compounds selected from among glycerol, diglycerol,
trimethylolpropane, pentaerythritol, di(trimethylolpropane), an
10 ethylene oxide adduct of glycerol, an ethylene oxide adduct of
trimethylolpropane, an ethylene oxide adduct of pentaerythritol, a
propylene oxide adduct of glycerol, a propylene oxide adduct of
trimethylolpropane, andapropylene oxide adductofpentaerythritol.
[3] The polymerizable composition for an optical material
15 described in [I] or [2], in which the alcohol (B) contains at least
one kind of compounds selected from among a propylene oxide adduct
of glycerol, a propylene oxide adduct of trimethylolpropane, and a
propylene oxide adduct of pentaerythritol.
[4] The polymerizable composition for an optical material
20 described in any one of [I] to [3], in which the aromatic isocyanate
is 2,4-tolylene diisocyanate or a mixture of 2,4-tolylene
diisocyanate and 2,Gtolylene diisocyanate.
[5] The polymerizable composition for an optical material
described in any one of [I] to [4], in which a molar ratio of the
isocyanate groups of the isocyanate (A) to the hydroxyl groups of
the alcohol (B) is 0.8 to 1.2.
[6] The polymerizable composition for an optical material
described in any one of [l] to 151, in which the phosphoric acid ester
5 (C) is contained in an amount of 0.1 parts by weight to 3 parts by
weight with respect to the total of 100 parts by weight of the
isocyanate (A) and the alcohol (B) .
171 The polymerizable composition for an optical material
described in any one of [I] to [6], further including a hindered
10 amine-based compound, in which the hindered amine-based compound is
contained in an amount of 0.1 parts by weight to 2 parts by weight
with respect to the total of 100 parts by weight of the isocyanate
(A) and the alcohol (B) .
[8] The polymerizable composition for an optical material
15 described in any one of [I] to [71, in which the benzotriazole-based
compound (D) is contained in an amount of 2.1 parts by weight to 10
parts by weight with respect to the total of 100 parts by mass of
the isocyanate (A) and the alcohol (B) .
191 The polymerizable composition for an optical material
20 described in any one of [I] to [8], further including (E) a
phenol-based compound, in which the phenol-based compound (E) is
contained in an amount of 0.5 parts by weight to 5 parts by weight
with respect to the total of 100 parts by weight of the isocyanate
(A) and the alcohol (B) .
25 [lo] A manufacturing method of a polyurethane-molded product,
including a step of obtaining the polymerizable composition for an
optical material described in any one of [I] to [8] by mixing the
alcohol (B), the acidic phosphoric acid ester (C), and the
benzotriazole-based compound (D) together and then mixing the
resultant withat least one kindofthe isocyanate (A), whichcontains
aromatic isocyanate and has two or more isocyanato groups, at a
5 temperature of equal to or less than 30°C, a step of casting the
polymerizable composition into a casting mold, and a step of
polymerizing the polymerizable composition by starting the
polymerization of the composition at a temperature of equal to or
less than 30°C.
10 [ll] The manufacturing method of a polyurethane-molded product
described in [lo], in which the step of obtaining the polymerizable
composition for an optical material includes a step of obtaining the
polymerizable composition for an optical material described in [9]
by mixing the alcohol (B) , the acidic phosphoric acid ester (C) , the
15 benzotriazole-based compound (D) , and the phenol-based compound (E)
together and then mixing the resultant with at least one kind of the
isocyanate (A), which contains aromatic isocyanate and has two or
more isocyanato groups, at a temperature of equal to or less than
3O0C.
20 [12] A manufacturing method of a plastic polarizing lens,
including a step of obtaining the polymerizable composition for an
optical material described in any one of [I] to [ 8 ] by mixing the
alcohol (B), the acidic phosphoric acid ester (C), and the
benzotriazole-based compound (D) together and then mixing the
25 resultant withat least one kindofthe isocyanate (A), whichcontains
aromatic isocyanate and has two or more isocyanato groups, at a
temperatureofequa1toorlessthan30"C, astepoffixingapolarizing
film in a casting mold for lens casting in a state in which at least
one surface of the polarizing film is separated from the mold, a step
of injecting the polymerizable composition into a space between the
polarizing film and the mold, and a step of laminating a layer
5 comprised of polyurethane resin over at least one surface of the
polarizing film by polymerizing and curing the polymerizable
composition by starting the polymerization of the composition at a
temperature of equal to or less than 30°C.
[I31 The manufacturing method of a plastic polarizing lens
10 described in [12], in which the step of obtaining the polymerizable
composition for an optical material includes a step of obtaining the
polymerizable composition for an optical material described in [9]
by mixing the alcohol (B) , the acidic phosphoric acid ester ( C ) , the
benzotriazole-based compound (D), and the phenol-based compound (E)
15 together and then mixing the resultant with at least one kind of the
isocyanate (A) whichcontains aromatic isocyanate andhas two ormore
isocyanato groups at a temperature of equal to or less than 30°C.
[14] A manufacturing method of a polyurethane-molded product,
including a step (i) of obtaining a prepolymer by adding the alcohol
20 (B) to the isocyanate (A) such that a ratio of the hydroxyl groups
- to the isocyanato groups of the isocyanate (A) falls into a range
of 10 mol% to 20 mol% and reacting the isocyanate (A) with the alcohol
(B) in the presence of the acidic phosphoric acid ester (C), the
benzotriazole-based compound (D), and the hindered amine-based
25 compound, a step (ii) of obtaining the polymerizable composition for
an optical material described in any one of [I] to [8] by further
adding the alcohol (B) to the prepolymer and mixing the alcohol (B)
and the prepolymer together at a temperature of equal to or less than
30°C, and a step (iii) ofpolymerizingthe prepolymer and the alcohol
(B) contained in the polymerizable composition.
[15] The manufacturing method described in [14], in which the
5 step (i) includes a step of obtaining a prepolymer by adding the
alcohol (B) to the isocyanate (A) such that the ratio of the hydroxyl
groups to the isocyanato groups of the isocyanate (A) falls into a
range of 10 mol% to 20 mol% and reacting the isocyanate (A) with the
alcohol (B) in the presence of the acidic phosphoric acid ester (C) ,
10 thebenzotriazole-basedcompound (D), thephenol-basedcompound ( E ) ,
and the hindered amine-based compound.
[16] Themanufacturingmethoddescribedin [I41 or [15], inwhich
in the step (i), the reaction temperature is equal to or less than
30°C.
15 [17] The manufacturing method described in any one of [14] to
[16], in which in the step (iii) , heating is started at a temperature
of equal to or less than 30°C when the prepolymer and the alcohol
(B) are polymerized.
[18] The manufacturing method described in any one of 1141 to
20 [17], in which the viscosity of the prepolymer and the polymerizable
composition is equal to or less than 1,000 Pa.s at 20'~.
[19] The manufacturing method described in any one of 1141 to
[18], in which the step (ii) is performed by a mixing apparatus
including a cylindrical container, a shaft that has been inserted
25 into the container from the upper portion of the container along the
central axis direction of the container, a stirring blade that is
wound in the form of a screw along the outer circumferential surface
of the shaft, a first supply portion that is disposed in the upper
portion of the container and supplies a solution of the prepolymer
into the container, a second supply portion that is disposed in the
upper portion ofthe container and supplies a solutionofthe alcohol
5 (B) into the container, and an ejection portion that is disposed at
the bottom of the container, and the step (ii) includes a step of
supplying the prepolymer and the alcohol (B) into the container from
the first supply portion and the second supply portion respectively
and a step of preparing the polymerizable composition by rotating
10 the shaft such that the prepolymer and the alcohol (B) are moved down
while being mixed together at a temperature of equal to or less than
30°C by the stirring blade, which is wound in the form of a screw
along the outer circumferential surface of the shaft, and ejecting
the obtained polymerizable composition from the ejection portion.
15 [20] The manufacturing method described in [19], in which a
rotation frequency of the shaft is within a range of 1,000 rpm to
4,000 rpm, anda rateatwhichthepolymerizablecompositionisejected
from the ejection portion is within a range of 0.5 g/s to 4.0 g/s.
[21] The manufacturing method described in [I91 or [20], in which
20 in the step (ii), the viscosity of the obtained polymerizable
composition is equal to or.less than 500 mPa.s at 20°C.
[22] Themanufacturingmethoddescribedin [I91 or [21], inwhich
the step (iii) includes a step of injecting the polymerizable
composition into a mold and a step of polymerizing the prepolymer
25 and the alcohol (B) contained in the polymerizable composition in
the mold. .
[23] A manufacturing method of a plastic polarizing lens,
including a step of fixing a polarizing film in a casting mold for
lens castingina state inwhichat least one surfaceofthepolarizing
film is separated from the mold, before the step (iii) in the
manufacturing method of a polyurethane-molded product described in
5 any one of [14] to [22], in which the step (iii) includes a step of
injecting the polymerizable composition obtained in the step (ii)
into a space between the polarizing film and the mold and a step of
laminating a layer comprised of polyurethane resin over at least one
surface of the polarizing film by polymerizing and curing the
10 polymerizable composition.
[24] A polyurethane-molded product obtained by the
manufacturing method described in any one of [lo], [Ill, and [14]
to [22].
[25] An optical material comprised of the polyurethane-molded
15 product described in [24].
[26] A plastic lens comprised of the optical material described
in [25].
[27] A plastic polarizing lens obtained by the manufacturing
method described in 1121, [13], or [23].
20 [00131
According to the- polymerizable composition for an optical
material of the present invention, it is possible to obtain a
urethane-moldedproduct which exhibits excellent workability at the
time of blending or casting and has an excellent refractive index,
25 heat resistance, transparency, and light resistance. That is, it
is possible to obtain a polyurethane-molded product in which the
aforementioned properties are balanced well. Such a
polyurethane-molded product can be suitably used in various optical
materials that are required to have a high degree of transparency.
BRIEF DESCRIPTION OF THE DRAWINGS
5 [0014]
FIG. 1 is a schematic cross-sectional viewof a mixing apparatus
in the present embodiment.
FIG. 2 is a 'H-NMR measurement chart of a propylene oxide adduct
of trimethylolpropane.
10
DESCRIPTION OF EMBODIMENTS
[00151
Hereinafter, embodiments of the polymerizable composition for
an optical material of the present invention will be described by
15 using specific examples.
The polyrnerizable composition for an optical material of the
present embodiment contains (A) at least one kindofisocyanatehaving
two or more isocyanato groups, which contains aromatic isocyanate,
(B) at least one kind of alcohol having two or more hydroxyl groups,
20 (C) an acidic phosphoric acid ester represented by the following
Formula (I), and (.D) a benzotriazole-based compound. A ratio of
secondary hydroxyl groups to the total molar number of primary and
secondary hydroxyl groups contained in the alcohol (B) is equal to
or greater than 50%, and the benzotriazole-based compound (D) is
25 contained in the polyrnerizable composition, in an amount of 1 part
by weight to 11 parts by weight with respect to a total of 100 parts
by weight of the isocyanate (A) and the alcohol (B) .
Hereinafter, each of the components will be described.
[0016]
[Isocyanate (A) 1
The isocyanate (A) is at least one kind of isocyanate having
5 two or more isocyanato groups, which contains aromatic isocyanate.
The aromatic isocyanate is the isocyanate, in which two or more
isocyanato groups have directly bound to an aromatic ring, and may
contain a dimer, a trimer, or a prepolymer. Specific examples of
the aromatic isocyanate include tolylene diisocyanate,
10 4,4'-diphenylmethane diisocyanate, phenylene diisocyanate, and the
like. One kind of the aromatic isocyanate can be used singly, or
two ormore kindsthereof canbe usedin combination. The isocyanate
(A) contains the aromatic isocyanate in an amount of 80% by weight
to 100% by weight.
15 [0017]
The aromatic isocyanate in the present embodiment preferably
contains tolylene diisocyanate and is more preferably formed of
tolylene diisocyanate. The tolylene diisocyanate is at least one
kind of isocyanate selected fromamong 2,4-tolylene diisocyanate and
20 2,6-tolylene diisocyanate. Examples of the tolylene diisocyanate
-include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and
a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene
diisocyanate.
[0018]
2 5 Inthepresent embodiment, thetolylene diisocyanatepreferably
contains 2,4-tolylene diisocyanate. Specifically, 2,4-tolylene
diisocyanate can be used singly, or alternatively, a mixture of
2,4-tolylene diisocyanateand2,6-tolylene diisocyanate canbe used.
When such a mixture is used, a mixing ratio between 2,4-tolylene
diisocyanate and 2,6-tolylene diisocyanate is preferably within a
range of 75:25 to 85:15.
5 [00191
In the present embodiment, the isocyanate (A) can contain
isocyanate having two or more isocyanato groups, in addition to the
aromatic isocyanate. Examples of such isocyanate include aliphatic
isocyanate, alicyclic isocyanate, heterocyclic isocyanate, and the
10 like.
[0020]
Examples of the aliphatic isocyanate include hexamethylene
diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate
15 methyl ester, lysine triisocyanate, m-xylylene diisocyanate,
a, a,a' , a' -tetramethylxylylene diisocyanate,
bis(isocyanatomethyl)naphthaline, mesitylene triisocyanate,
bis(isocyanatomethyl)sulfide, bis(isocyanatoethyl)sulfide,
bis(isocyanatomethyl)disulfide, bis(isocyanatoethyl)disulfide,
20 bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane,
bis(isocyanatoethylthio)ethane, bis(isocyanatomethylthio)ethane,
and the like.
[00211
Examples of the alicyclic isocyanate include isophorone
25 diisocyanate, bis(isocyanatomethyl)cyclohexane,
dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methyl
cyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate,
2,5-bis(isocyanatomethyl)bicyclo-[2.2.l]-heptane,
2,6-bis (isocyanatomethyl)b icyclo- [2.2.1]- heptane,
3,8-bis(isocyanatomethyl)tricyclodecane,
3,9-bis(isocyanatomethyl)tricyclodecane,
5 4,8-bis(isocyanatomethyl)tricyclodecane,
4,9-bis(isocyanatomethyl)tricyclodecane, and the like.
[0022]
Examples of the heterocyclic isocyanate include
2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene,
10 2,5-diisocyanatotetrahydrothiophene,
2,5-bis(isocyanatomethyl)tetrahydrothiophene,
3,4-bis(isocyanatomethyl)tetrahydrothiophene,
2,5-diisocyanato-1,4-dithiane,
2,5-bis (isocyanatomethyl)- 1,4-dithiane,
15 4,5-diisocyanato-l,3-dithiolane,
4,5-bis (isocyanatomethyl)- 1,3-dithiolane, and the like.
[00231
Inthepresent embodiment, amolarratiooftheisocyanatogroups
ofthe isocyanate (A) tothehydroxylgroups ofthe alcohol (B), which
20 will be described later, is within a range of 0.8 to 1.2, preferably
within a range of 0.85 to 1.2, and even more preferably within a range
of 0.9 to 1.2. Within the above range, it is possible to obtain an
optical material which has excellent optical characteristics such
as refractive index and in which physical properties are balanced
25 well. Particularly, it is possible to obtain a resin that can be
suitably used as a spectacle lens.
[00241
[Alcohol (B) 1
In the alcohol (B) , a r a t i o of secondary hydroxyl groups t o the
t o t a l molar number of primary and secondary hydroxylgroups is equal
t o or greater than 50%. The alcohol (B) may be constituted with one
5 kind of alcohol i n which the r a t i o of the secondary hydroxyl groups
is equal t o or greater than 50%, or may be constituted with two or
more kinds of compounds i n which the r a t i o of the secondary hydroxyl
groupsis equal to or g r e a t e r t h a n 50%. Considering the workability,
the r a t i o of the secondary hydroxyl groups t o the t o t a l molar number
10 of the primary and secondary hydroxyl groups is preferably equal t o
or greater than 60% and more preferably equal t o or greater than 70%.
The r a t i o of the secondary hydroxyl groups can be calculated
by proton nuclear magnetic resonance spectroscopy, 'H-NMR. In a
methylene group (-CH2- (OH) ) and a methine group (-CH ( R ) - (OH) ) i n which
15 hydroxyl groups are adjacent t o each other, the chemical s h i f t s of
protons are overlappedwitheach other in a b r o a d a r e a . Accordingly,
the chemical s h i f t s cannotbeindividuallydifferentiated. However,
when the hydroxyl groups a r e e s t e r i f i e d by carboxylic acid having
an e l e c t r o n - a t t r a c t i n g group such as t r i f l u o r o a c e t i c acid, the
20 chemical s h i f t occurs inalowmagneticfield, a n d a s a r e s u l t , protons
uf the methylene group and the methine group can be d i f f e r e n t i a t e d .
For example, b~hen the hydroxyl groups are e s t e r i f i e d by
t r i f l u o r o a c e t i c anhydride, generally, the protons of the methine
group undergo a chemical s h i f t of 5.3 ppm t o 5.6 ppm, and the protons
25 of the methylene group undergo a chemical s h i f t of 4.2 ppm t o 4.5
ppm. Consequentially, from the r a t i o of an i n t e g r a l value of the
peak thereof, the r a t i o of the secondary hydroxyl groups can be
calculated. Provided that the integral value of the chemical shift
of 5.3 ppm to 5.6 pprn is A, and the integral value of the chemical
shift of 4.2 ppm to 4.5 ppm is B, a ratio X of the secondary hydroxyl
groups can be calculated by the following equation.
5 X = A/(A + B/2) x 100
[0025]
The alcohol (B) is at least one kind of aliphatic or alicyclic
alcohol. Specific examples thereof include linear or branched
aliphatic alcohols, alicyclic alcohols, alcohols obtained by adding
10 ethylene oxide, propylene oxide, or E-caprolactone to the
aforementioned alcohols, and the like.
[0026]
Examples of the linear or branched aliphatic alcohols include
ethylene glycol, diethylene glycol, triethylene glycol, propylene
15 glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol,
2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,
1,2-butanediol, 1,3-butanediol, 1,4-butanediol,
3-methyl-1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol,
1,5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol,
20 3-methyl-l,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, glycerol,
. . diglycerol, polyglycerol, trimethylolpropane, pentaerythritol,
di (trimethylolpropane) , and the like.
[0027]
Examplesofthealicyclicalcoholsinclude1,2-cyclopentanediol,
25 1,3-cyclopentanediol, 3-methyl-1,2-cyclopentanediol,
1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol,
4,4'-bicyclohexanol, 1,4-cyclohexanedimethanol, and the like.
[0028]
The alcohol (B) may be a compound obtained by adding ethylene
oxide, propylene oxide, or E-caprolactone to the above alcohols.
Examples ofthecompoundincludeanethyleneoxideadductofglycerol,
5 an ethylene oxide adduct of trimethylolpropane, an ethylene oxide
adduct of pentaerythritol, a propylene oxide adduct of glycerol, a
propylene oxide adduct of trirnethylolpropane, a propylene oxide
adduct of pentaerythritol, caprolactone-modified glycerol,
caprolactone-modified trimethylolpropane, caprolactone-modified
10 pentaerythritol, and the like.
The molar number of ethylene oxide, propylene oxide, or
c-caprolactone added to the alcohols is preferably 0.7 moles to 3.0
moles and more preferably 0.7 moles to 2.0 moles with respect to 1
mole of hydroxyl groups in the alcohols.
15 [0029]
In the present embodiment, as the alcohol (B) , at least one kind
selected from among ethylene glycol, diethylene glycol, triethylene
glycol, propylene glycol, dipropylene glycol, tripropylene glycol,
glycerol, diglycerol, polyglycerol, trimethylolpropane,
20 pentaerythritol, di(trimethylolpropane), an ethylene oxide adduct
of glycerol, an ethylene oxide,adduct of trimethylolpropane, an
ethylene oxide adduct of pentaerythritol, a propylene oxide adduct
of glycerol, a propylene oxide adduct of trimethylolpropane, and a
propylene oxide adduct of pentaerythritol are preferably used; and
25 at least one kind selected from among glycerol, diqlycerol,
trimethylolpropane, pentaerythritol, di(trimethylolpropane), an
ethylene oxide adduct of glycerol, an ethylene oxide adduct of
trimethylolpropane, an ethylene oxide adduct of p e n t a e r y t h r i t o l , a
propylene oxide adduct of glycerol, a propylene oxide adduct of
trimethylolpropane, and a propylene oxide adduct of p e n t a e r y t h r i t o l
are more preferably used.
5 In the present embodiment, it is p a r t i c u l a r l y preferable for
the alcohol (B) to contain a t l e a s t one kind selected from among a
propylene oxide adduct of glycerol, a propylene oxide adduct of
trimethylolpropane, andapropylene oxide adductofpentaerythritol.
[00301
10 As the propylene oxide adduct of glycerol, an adduct is
preferable in which the amount of propylene oxide added t o glycerol
is 0.7 moles t o 1.3 moles with respect t o 1 mole of hydroxyl groups
in the glycerol. A hydroxyl value of the adduct is preferably from
520 mg K O H / ~ t o 810 mg KOH/g, and more preferably from 580 mg KOH/g
15 to680mgKOH/g. Asthepropyleneoxideadductoftrimethylolpropane,
an adduct is preferable in which the amount of propylene oxide added
t o trimethylolpropane is 0.8 moles t o 1.3 moles with respect t o 1
mole of hydroxylgroups in the trimethylolpropane. Ahydroxylvalue
of the adduction is preferably from 460 mg KOH/g to 600 mg KOH/g,
20 and more preferably from 520 mg KOH/g t o 580 mg KOH/g. The hydroxyl
value can be measured by a known method.
[0031]
[Acidic phosphoric acid e s t e r ( C ) ]
The acidic phosphoric acid e s t e r (C) is represented by Formula
25 (1) and has been used as a release agent i n t h e r e l a t e d a r t . However,
i n the present embodiment, t h e a c i d i c phosphoric acid e s t e r (C) is
also used as urethanation c a t a l y s t .
[0033]
In the~formula,m represents an integer of 1 or 2, n represents
5 an integer of 0 to 18, R1 represents an alkyl group having 1 to 20
carbon atoms, and each of R* and R3 independently represents a hydrogen
atom, a methyl group, or an ethyl group. The unit in the "[I,"
preferably has 4 to 20 carbon atoms.
[0034]
10 Examples of R' in Formula (1) include organic residues derived
from linear aliphatic compounds such as methane, ethane, propane,
butane, pentane, hexane, heptane, octane, nonane, decane, undecane,
dodecane, tetradecane, andhexadecane; organic residues derived from
branchedaliphaticcompounds suchas 2-methylpropane, 2-methylbutane,
15 2-methylpentane, 3-methylpentane, 3-ethylpentane, 2-methylhexane,
3-methylhexane, 3-ethylhexane, 2-methylheptane, 3-methylheptane,
4-methylheptane, 3-ethylheptane, 4-ethylheptane, 4-propylheptane,
2-methyloctane, 3-methyloctane, 4-methyloctane, 3-ethyloctane,
4-ethyloctane, and 4-propyloctane; organic residues derived from
20 alicyclic compounds such as cyclopentane, cyclohexane,
1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, and
1,4-dimethylcyclohexane; and the like. However, R1 is not limited
to these examplecompoundsandmaybe inthe forrnofamixturethereof.
Furthermore, in Formula (I), n is preferably 0, and the compound
can be represented by Formula (2)
[00351
[00361
5 In Formula (2), x represents an integer of 1 or 2, and R4
represents an alkyl group having 8 to 16 carbon atoms.
Examples of R4 in Formula (2) include organic residues derived
from linear aliphatic compounds such as octane, nonane, decane,
undecane, dodecane, tetradecane, and hexadecane; organic residues
10 derived from branched aliphatic compounds such as 2-ethylhexane,
3-ethylhexane, 2-methylheptane, 3-methylheptane, 4-methylheptane,
3-ethylheptane, 4-ethylheptane, 4-propylheptane, 2-methyloctane,
3-methyloctane, 4-methyloctane, 3-ethyloctane, 4-ethyloctane, and
4-propyloctane; organic residues derived from alicyclic compounds
15 such as 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, and
1,4-dimethylcyclohexane; and the like. However, R~ is not limited
tothese examplecompounds andmaybe inthe formof amixturethereof.
[00371
As the acidic phosphoric acid ester (C) , Zelec UN manufactured
20 by Stepan Company, internal release agents for MR manufactured by
Mitsui Chemicals, Inc., a JP series manufactured by JOHOKU CHEMICAL
CO., LTD., a PhosphanolseriesmanufacturedbyTOHOChemicalIndustry
Co., Ltd., an AP or DP series manufactured by DAIHACHI CHEMICAL
INDUSTRY CO., LTD., and the like can be used. Among these, Zelec
25 UN manufactured by Stepan Company and internal release agents for
MR manufactured by Mitsui Chemicals, Inc. are more preferable.
100381
The amount o f t h e acidicphosphoric a c i d e s t e r (C) is preferably
0 . 1 p a r t s byweight t o 3 part byweight, andmore preferably 0.2 p a r t s
5 by weight to 2 p a r t s by weight with respect t o a t o t a l of 100 p a r t s
by weight of the isocyanate (A) and the alcohol (B).
[00391
Generally, as a c a t a l y s t for urethane resins, t e r t i a r y amine,
an aminocarboxylic acid s a l t , a metal c a t a l y s t , or the l i k e is used.
10 I f such a c a t a l y s t is used for the polymerizable composition for an
o p t i c a l m a t e r i a l o f t h e p r e s e n t embodiment, the r e a c t i v i t y i n c r e a s e s .
Therefore, the viscosity of the polymerizable composition f o r an
o p t i c a l material of the present embodiment increases too much a t the
time of injecting the composition i n t o a mold, workability
15 d e t e r i o r a t e s , and as a r e s u l t , s t r i a e occurs in the obtained molded
product in some cases. In the present embodiment, when s p e c i f i c
cyclicamines are usedconcurrentlywith a specificacidicphosphoric
a c i d e s t e r , it is preferable sinceworkabilityatthetime ofblending
and casting becomes b e t t e r , the occurrence of s t r i a e is e f f e c t i v e l y
20 inhibited, andthemoldedproduct formedofisocyanate andanalcohol
of the present embodiment t h a t i s applicable to spectacles can be
manufactured with high quality and excellent workability.
[0040]
Examples of t h e s p e c i f i c cyclic amines include imidazoles such
25 as imidazole, 1,2-dimethylimidazole, benzylmethyl imidazole,
2-ethyl-4-imidazole; and hindered amines as 1,2,2,6,6-piperidine
compounds such as 1,2,2,6,6-pentamethyl-4-piperidinol,
1,2,2,6,6-pentamethyl-4-hydroxyethyl-4-piperidinol,
methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, a mixture of
methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate and
bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
5 bis (1,2,2,6,6-pentamethyl-4-piperidyl)s ebacate,
bis (2,2,6,6-tetramethyl-1-( octyloxy)- 4-piperidyl)s ebacate,
bis (1,2,2,6,6-pentamethyl-4-piperidyl) [ [3,5-bis (1,l-dimethylethy
1) -4-hydroxyphenyl]methyl] butyl malonate, and
tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)b utane-1,2,3,4-tetrac
10 arboxylate.
[00411
As the cyclic amines, imidazoles, hindered amines, and the like
are preferable, and hindered amines are more preferable.
The acidic phosphoric acid ester (C) can be concurrently used
15 the hindered amines. The hindered amines can be contained in an
amount of 0.1 parts by weight to 2 parts by weight and preferably
inanamount of 0.2 parts byweightto1.5 parts byweight with respect
to atotalof 100 parts byweight ofthe isocyanate (A) andthe alcohol
(B). Withintheaboverange, itispossibletoobtainamoldedproduct
20 which has excellent color and in which the occurrence of striae is
inhibited. -
[0042]
Hindered amine is used as a light stabilizer. Examples of
commercially available products thereof include Lowilite 76 and
25 Lowilite 92 manufactured by Chemtura Corporation, Tinuvin 144,
Tinuvin 292, andTinuvin 765manufacturedbyBASFCorporation, Adeka
Stab LA-52 and LA-72 manufactured by ADEKA CORPORATION, JF-95
manufactured by JOHOKU CHEMICAL CO., LTD., and the like.
[0043]
In the present embodiment, from the viewpoint of the
aforementionedeffects, itispreferabletousetolylenediisocyanate
5 as the isocyanate (A) i n c o m b i n a t i o n r i i t h a t l e a s t o n e kindof compound
selected fromamong apropylene oxide adduct of glycerol, apropylene
oxide adduct of trimethylolpropane, and a propylene oxide adduct of
pentaerythritol as the alcohol (B).
[0044]
10 [Benzotriazole-based compound (D)]
The benzotriazole-based compound (D) may be a compound having
a benzotriazole skeleton. Examples thereof include
2- (2' -hydroxy-5'-methylphenyl) benzotriazole,
2-(2'-hydroxy-4'-ethoxyphenyl)benzotriazole,
15 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole,
2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole,
2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,
20 2- (2' -hydroxy-3', 5' -bis (dimethylbenzyl)p henyl)b enzotriazole,
2-(2~-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazo
le,
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3'-dodecyl-5'-methylphenyl)benz0triaz01e,
25 2-{2' -hydroxy-3' -dimethylbenzyl-5' - (1,1,3,3-tetramethy1)phenyl)b
enzotriazole, and the like.
These benzotriazole-based compounds may be used singly, or two
or more kinds thereof may be used in combination.
[0045 j
Among these, from the viewpoint of solubility in the components
(A) and (B) in the composition, the composition preferably contains
5 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, and
particularly preferably contains only
2-(2-hydroxy-5-tert-octylphenyl)-2H-benz0triaz01e.
[0046]
The amount of the benzotriazole-based compound (D) contained
10 inthecompositionis lpartbyweighttollpartsbyweight, preferably
1 part by weight to 10 parts by weight, more preferably 2.1 parts
b y w e i g h t t o l o p a r t s b y w e i g h t , andparticularlypreferably2.5 parts
by weight to 10 parts by weight, with respect to a total of 100 parts
by weight of the isocyanate (A) and the alcohol (B) . When the amount
15 ofthe benzotriazole-basedcompound (D) containedinthe composition
is within the above range, it is possible to obtain a urethane-molded
product which exhibits excellent workability at the time of mixing
or casting and has an excellent refractive index, heat resistance,
transparency, andlight resistance. That is, itispossibletoobtain
20 a urethane-moldedproduct in which the aforementionedproperties are
-.balanced well. Such a urethane-molded'product is suitably used
particularly as a spectacle lens.
[0047 j
[Phenol-based compound (E) j
25 In the present embodiment, the polymerizable composition can
further contain a phenol-based compound (E).
Examples of the phenol-based compound (E) include phenol,
substituted phenols such as cresol, ethyl phenol, isopropyl phenol,
tert-butylphenol, hexylphenol, cyclohexylphenol, 2-methoxyphenol,
4-methoxyphenol, 2,6-dimethyl-p-cresol, 2,6-diethyl-p-cresol,
2,6-di-n-propyl-p-cresol, 2,6-diisopropyl-p-cresol,
5 2,6-di-n-butyl-p-cresol, 2,6-diisobutyl-p-cresol, and
4-allyl-2-methoxyphenol, 2,4-bis[(octylthio)methyl]-o-cresol,
hindered phenols, polyphenols such as catechol, resorcin,
hydroquinone, tert-butyl catechol, and pyrogallol, biphenols such
as biphenol and dimethyl biphenol, bisphenols such as bisphenol A,
10 bisphenol F, bisphenol S, methylene-bis(methy1-tert-butylphenol),
and thio-bis(methy1-tert-butylphenol), naphthols such as naphthol
and dihydroxynaphthalene, compounds obtained when these phenols are
substituted with halogen, and the like.
Among the above, from the viewpoint of the external appearance
15 of a plastic lens to be obtained, the phenol-based compound (E) is
preferablythe hinderedphenols, andmore preferablyan alkyl group,
a methyl group, or a tert-butyl group having a
(3-tert-butyl-4-hydroxy-5-alky1)phenyl group.
[00481
2 0 Examples of the hindered phenol-based compound having the
- % (3-tert-butyl-4-hydroxy-5-alky1)phenyl group include
2,6-di-tert-butyl-p-cresol,
1,6-hexamethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propi
onatel,
25 2,4-bis (octylthio)- 6- (4-hydroxy-3,5-di-tert-butylamino-)l ,3,5-tr
iazine, pentaerythritol
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
triethylene
glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxypheyl)propionate],
2,2-thio-diethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)pro
pionate],
5 octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
de), 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate diethyl ester,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)ben
zene, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurater
10 isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the
like.
Among these, from the viewpoint of solubility in the components
(A) and (B) in the composition, it is preferable to use
2,6-di-tert-butyl-p-cresol.
These phenol-based compounds can be used singly, or two or more
kinds thereof may be used in combination.
[00491
The content of the phenol-based compound (E) is 0.5 parts by
weight to 5 parts by weight, preferably 0.5 parts by weight to 4 parts
20 byweight, andparticularlypreferably 0.5 parts by weight to 2 parts
by weight, with respect to a total of 100 parts by weight of the
isocyanate (A) and the alcohol (B) .
[00501
[Components other than components (A) to (E) 1
25 According to the purpose, the polymerizable composition for an
opticalmaterial ofthe present embodiment can containadditives such
as a light stabilizer, an ultraviolet absorber, an antioxidant, a
coloring inhibitor, a dye, and a resin modifier.
[00511
As the light stabilizer, hindered amine-based compounds can be
used. Examples of commercially available products of the hindered
5 amine-based compounds include Lowilite 76 and Lowilite 92
manufactured by Chemtura Corporation, Tinuvin 144, Tinuvin 292, and
Tinuvin 765 manufactured by BASF Corporation, Adeka Stab LA-52 and
LA-72manufacturedbyADEKACORPORATION, JF-95manufacturedbyJOHOKU
CHEMICAL CO., LTD., and the like.
10 [0052]
The ultraviolet absorber cancontain atriazine-basedcompound,
a benzophenone-based compound, or a benzoate-based compound. The
amount of the ultraviolet absorber added is preferably 0.05 parts
by weight to 2.0 parts by weight and more preferably 0.05 parts by
15 weight to 1.5 parts by weight, with respect to a total of 100 parts
by weight of the components (A) and (B) .
[0053]
When thiol is added as an additive to the polymerizable
composition of for an optical material the present embodiment, light
20 resistance of the product markedly deteriorates. When a primary
amine and a secondary amine are added as amines to the composition,
a reaction between the amines and the isocyanate of the present
embodiment proceeds rapidly, and consequentially, the viscosity of
the polymerizable composition for an optical material increases too
25 much at the time of casting. As a result, workability deteriorates,
or striae occur in the obtained molded product. The problems caused
by the addition of a metal catalyst are as described above. In many
cases, an organic tin compound is used as a metal catalyst in a
thiourethane resin. The polymerizable composition for an optical
material of the present embodiment does not contain the organic tin
compound, which has become an issue due to its harmfulness to the
5 humanbody resulting fromhightoxicityandendocrine disruptor, and
makes it possible to manufacture a resin used for spectacles.
Accordingly, the safety of the manufacturing process thereof or the
safety of the obtained molded product is much higher.
[0054]
10 In the present embodiment, from the viewpoint of further
improving the workability at the time of blending or casting and
effectively inhibiting the occurrence of striae, it is preferable
to use tolylene diisocyanate as the isocyanate (A) in combination
with at least one kind of compound selected from among a propylene
15 oxide adduct of glycerol, a propylene oxide adduct of
trimethylolpropane, and a propylene oxide adduct of pentaerythritol
as the alcohol (B) .
[0055]
According to the polymerizable composition for an optical
20 material of the present embodiment, it is possible to obtain a
urethane-moldedproductwhich exhibits excellent workability'at the
time of blending or casting and has an excellent refractive index,
heat resistance, transparency, and light resistance. That is,
according to the present embodiment, it is possible to obtain a
25 urethane-molded product in which the above properties are balanced
well.
[0056]
[usel
By varying the mold used at the time of cast polymerization,
the urethane-moldedproductofthepresentembodimentcanbeobtained
in various forms. Having a high degree of transparency, the
5 urethane-molded product of the present embodiment can be used for
various purposes such as a plastic lens, a camera lens, a Light
Emitting Diode (LED), a prism, optical fiber, an information
recording substrate, a filter, and optical resin for a light emitting
diode or the like. Particularly, the urethane-molded product is
10 suitable as an optical material and an optical element such as a
plastic lens, a camera lens, and a light emitting diode.
[0057]
Examples of the plastic lens include a plastic spectacle lens
comprisedofpolyurethaneresinandaplasticpolarizinglensinwhich
15 alayer formed of polyurethane resinhas been laminated over at least
one surface of a polarizing film.
Hereinafter, a manufacturing method of a urethane-molded
product and a manufacturing method of a plastic polarizing lens will
be described based on a first embodiment and a second embodiment
20 respectively by appropriately using drawings. Herein, the same
constituents are marked with the same reference numerals, and the
description thereof will not be repeated.
[0058]

25 [Manufacturing method of urethane-molded product]
The manufacturing method of a urethane-molded product of the
present embodiment includes a step (1) of obtaining the
aforementioned polymerizable composition for an optical material by
mixing the alcohol ( B ) , the acidic phosphoric acid ester (C), and
the benzotriazole-based compound (D) together and then mixing the
resultant with the isocyanate (A) at a temperature of equal to or
5 less than 30°C, a step (2) of casting the polymerizable composition
into a casting mold, and a step (3) of polymerizing the composition
by starting polymerization of the polymerizable composition.
[0059]
[Step (I)]
10 When the isocyanate (A) is mixed with the acidic phosphoric acid
ester (C), white solids having low solubility are precipitated in
some cases. Therefore, if the polymerizable composition is
polymerizedinthis state, thetransparencyoftheresintobeobtained
deteriorates, and thus the resin becomes unsuitable for being used
15 for spectacles in some cases. Accordingly, it is preferable to mix
the alcohol (B) and the acidic phosphoric acid ester (C) together
first and then mix the resultant with the isocyanate (A). When the
components are mixed in this way, the occurrence of the white solids
having low solubility is inhibited, and a molded product having
20 excellent transparency is obtained.
The temperature at the time of mixing the isocyanate (A) is
preferably equal to or less than 30°C, because the viscosity of the
polymerizable composition for an optical material is kept low, and
thus a molded product can be manufactured without deteriorating the
25 workability. When tolylene diisocyanate is used as the isocyanate
(A), it is particularly preferable to control the temperature to be
equal to or less than 30°C.
When the polymerizable composition contains the alcohol ( B ) ,
the acidic phosphoric acid ester (C), the benzotriazole-based
compound (D), and a phenol-based compound, the step (1) can include
a step of mixing components (B) , (C) , and (D) with the phenol-based
5 compound (E) and then mixing the resultant with the isocyanate (A)
at a temperature of equal to or less than 30°C.
The mixing apparatus is not particularly limited, and it is
possible to use the apparatus which will be described later.
[OOfiO]
10 [Step (2)l
In this step, the polymerizable composition for an optical
material of the present embodiment is injected into a mold (casting
mold) held by a gasket, a tape, or the like. At this time, depending
on the physical properties required for the molded product to be
15 obtained, if necessary, it is preferable to perform degassing
processing under reduced pressure or filtration processing such as
pressurization or pressure reduction.
[0061]
[Step (3) 1
20 In this step, the polymerization of the polymerizable
composition for an optical material that has been cast into the mold
is started so as to polymerize the composition. The temperature at
which the polymerization is started is preferably equal to or less
than 30°C, because at this temperature, release properties of the
25 molded product obtained after the polymerization become excellent,
and striae does not occur in the obtained molded product. The
polymerization conditions are not limited, because the conditions
greatly vary with the type of the isocyanate or the alcohol used,
the shape of the mold, and the like. However, the polymerization
is performed at a temperature of about O"C to 140'~ for 1 hour to
48 hours.
5 [00621
Because the procedure for preparing the polymerizable
composition greatly varies with the type of the isocyanate (A), the
alcohol (B) and the additives used and the amount thereof used, the
method of adding the additives is not particularly limited and is
10 appropriately selected in consideration of the solubility of the
additives, operability, safety, convenience, and the like.
[0063]
If necessary, the urethane-molded product of the present
embodiment may be subjected to processing such as annealing. The
15 processingtemperature is generally with ina range of 50°Cto 150°C.
However, the processing is preferably performed at a temperature of
90°Cto140"C, andmorepreferablyperformedatatemperatureoflOO°C
to 130°C.
[0064]
2 0 If necessary, a plastic lens comprised of the urethane-molded
product of the present embodiment may be used after a coating layeris
provided over one or both surfaces of the lens. Examples of the
coating layer include a primer layer, a hard coat layer, an
antireflection layer, an antifogging coating layer, an antifouling
25 layer, a water repellent layer, and the like. Each of these coating
layers may be used singly, or a plurality of the coating layers may
be used in the form of a multi-layer. When the coating layer is
provided over both surfaces of the p l a s t i c lens, the same coating
l a y e r o r differentcoatinglayersmaybeprovidedoverthe respective
surfaces.
[0065]
5 For each of the coating layers, an u l t r a v i o l e t absorber for
protecting the lens or the eye from u l t r a v i o l e t rays, an infrared
absorberforprotectingtheeyefrominfraredrays, a l i g h t s t a b i l i z e r
or an antioxidant for improving l i g h t resistance of the lens, a dye
or a pigment for making the lens more fashionable, a photochromic
10 dye, a photochromic pigment, an a n t i s t a t i c agent, and other known
additives for improving the performance of the lens may be
concurrentlyused. Forthe layer t o b e subjectedto coating, various
leveling agents for improving coating properties may be used.
[0066]
15 T h e p r i m e r l a y e r i s g e n e r a l l y f o r m e d b e t r ~ e e n t h e h a r d c o a t l a y e r ,
r ~ h i c h r i i l l b e d e s c r i b e d l a t e r , and the o p t i c a l l e n s . Theprimer layer
is a coating layer for improving the adhesiveness between the hard
coat layer t o be formed over the primer layer and the l e n s . I n some
cases, the primer layer can also improve the impact r e s i s t a n c e . For
20 the primer layer, any material can be used as long as it exhibits
. a high degree of adhesiveness with respect t o the obtained lens.
However, generally, a primer composition or the l i k e t h a t contains
aurethane-basedresin, anepoxy-basedresin, apolyester-basedresin,
amelanin-basedresin, orpolyvinylacetalasamaincomponentisused.
25 In order t o adjust t h e v i s c o s i t y of the primer composition, an
appropriate solvent t h a t does not exert an influence on the lens may
be used for the primer composition. Needless to say, a solvent may
not be used for the primer composition.
100671
The primer composition can be formed by any of a coating method
and a drymethod. When the coatingmethod is used, the lens is coated
5 with the primer composition by a knov~n coating method such as spin
coating or dip coating, andthen the resultant is solidified, whereby
the primer layer is formed. When the dry method is used, the primer
layer is formed by a known dry method such as a CVD method or a vacuum
deposition method. In forming the primer layer, if necessary, in
10 order to improve the adhesiveness, the lens surface may be subjected
to preprocessing such as alkali processing, plasma processing, or
ultraviolet processing.
The hard coat layer is a coating layer for giving functions such
as scratchresistance, abrasionresistance, moisture resistance, hot
15 water resistance, heat resistance, and light resistance to the lens
surface.
[00681
For the hard coat layer, generally, a hard coat composition is
used which contains an organic silicon compound having curability,
20 at least one kind of oxide particles of an element selected from the
., . group of elements including Si, A l , Sn, Sb, Ta, Ce, La, Fe, Zn, W, . .,
Zr, In, and Ti and/or at. least one kind of particles composed of a
composite oxide of two or more kinds of elements selected from the
group of elements.
25 100691
The hard coat composition preferably contains at least any of
amines, amino acids, metal acetylacetonate complexes, organic acid
metal salts, perchloric acids, salts of perchloric acids, acids,
metal chlorides, and polyfunctional epoxy compounds, in addition to
the aforementioned components. For the hard coat composition, an
appropriate solvent that does not exert an influence on the lens may
5 be used. Needless to say, a solvent may not be used for the
composition.
[0070]
Generally, the lens is coated with the hard coat composition
by a known coating method such as spin coating or dip coating, and
10 then the composition is cured, whereby the hard coat layer is formed.
Examples of curing methods include thermal curing, curing methods
performed by irradiation of energy rays such as ultraviolet rays or
visible rays, and the like. In order to inhibit formation of
interference fringes, a difference between the refractive index of
15 the hardcoat layer andthe refractive index ofthe lens is preferably
within a range of fO.l.
[0071]
Generally, the antireflection layer is formed on the hard coat
layer if necessary. The antireflection layer is classified into an
20 inorganic antireflection layer and an organic antireflection layer.
The inorganic antireflection layer is formed of an inorganic oxide'
suchas SiOz or TiOzbyadrymethodsuchas a vacuumdepositionmethod,
a sputtering method, an ion plating method, an ion beam-assisted
method, anda CVDmethod. The organic antireflection layer is formed
25 of a composition, which contains an organic silicon compound and
silica-based particles having internal cavities, by a wet method.
[0072]
The a n t i r e f l e c t i o n layer is composed of a single layer or
multiple layers. When it is used i n the form of a single l a y e r , a
value obtained by subtracting the r e f r a c t i v e index of the
a n t i r e f l e c t i o n layer fromthe r e f r a c t i v e index o f t h e hardcoat layer
5 is preferably a t l e a s t equal to or greater than 0.1. In order t o
cause t h e a n t i r e f l e c t i o n layer t o e f f e c t i v e l y perform an
a n t i r e f l e c t i o n function, it is preferable t o constitute the
a n t i r e f l e c t i o n f i l m with multiple films, and in t h i s case, a film
with a low r e f r a c t i v e index and a film with a high r e f r a c t i v e index
10 a r e a l t e r n a t e l y laminated on each other. Even in t h i s case, a
index and the film with a high r e f r a c t i v e index is preferably equal
t o or greater than 0.1. Examples of t h e f i l m with a high r e f r a c t i v e
index include films of ZnO, Ti02, Ce02, Sb~05, SnOz, Zr02, Ta205, and

1. Apolymerizable composition for an optical material , comprising:
(A) atleastonekindofisocyanatehavingtwoormoreisocyanato
5 groups, which contains aromatic isocyanate;
(B) at least one kind of alcohol having two or more hydroxyl
groups;
(C) anacidicphosphoricacidesterrepresentedbythe following
Formula (1); and
( D ) a benzotriazole-based compound,
wherein aratio of secondary hydroxyl groups to the total molar
number of primary and secondary hydroxyl groups contained in the
alcohol (B) is equal to or greater than 50%, and the
benzotriazole-based compound (D) is contained in an amount of 1 part
15 by weight to 11 parts by weight with respect to a total of 100 parts
by weight of the isocyanate (A) and the alcohol ( B ) ,
- wherein, in the formula, m represents .an integer of 1 or 2, n
representsan integer of 0 to 18, R1 represents an alkyl group having
20 1 to 20 carbon atoms, and each of R2 and R3 independently represents
a hydrogen atom, a methyl group, or an ethyl group.
2. The polymerizable composition for an optical material according
to claim 1,
wherein the alcohol (B) contains at least one kind of compounds
selected from among glycerol, diglycerol, trimethylolpropane,
pentaerythritol, di(trimethylolpropane), an ethylene oxide adduct
of glycerol, an ethylene oxide adduct of trimethylolpropane, an
5 ethylene oxide adduct of pentaerythritol, a propylene oxide adduct
of glycerol, a propylene oxide adduct of trimethylolpropane, and a
propylene oxide adduct of pentaerythritol.
3. The polymerizable composition for an optical material according
10 to claim 1 or 2,
wherein the alcohol (B) contains at least one kind of compounds
selected fromamongapropylene oxide adduct of glycerol, apropylene
oxide adduct of trimethylolpropane, and a propylene oxide adduct of
pentaerythritol.
15
4. The polymerizable composition for an optical material according
to any one of claims 1 to 3,
wherein the aromatic isocyanate is 2,4-tolylene diisocyanate
or a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene
20 diisocyanate.
5. The polymerizable composition for an optical material according
to any one of claims 1 to 4,
vrherein amolar ratio oftheisocyanato groups ofthe isocyanate
25 (A) to the hydroxyl groups of the alcohol (B) is 0.8 to 1.2.
6. The polymerizable composition for an optical material according
to any one of claims 1 to 5,
wherein the acidic phosphoric acid ester (C) is contained in
an amount of 0.1 parts by weight to 3 parts by weight with respect
to the total of 100 parts by weight of the isocyanate (A) and the
5 alcohol (B) .
7 . The polyrnerizable composition for an optical material according
to anyone of claims 1to 6, further comprisinga hinderedamine-based
compound,
10 wherein the hindered amine-based compound is contained in an
amount of 0.1 parts by weight to 2 parts by weight with respect to
the total of 100 parts byweight ofthe isocyanate (A) and the alcohol
(B) .
15 8. The polymerizable composition for an optical material according
to any one of claims 1 to 7,
wherein the benzotriazole-based compound (D) is contained in
an amount of 2.1 parts by weight to 10 parts by weight with respect
tothe total of 100 parts bymass ofthe isocyanate (A) andthealcohol
20 (B) .
9. The polymerizable composition for an optical material according
to any one of claims 1 to 8, further comprising (E) a phenol-based
compound;
25 wherein the phenol-based compound (E) is containedin an amount
of 0.5 parts by weight to 5 parts by weight with respect to the total
of 100 parts by weight of the isocyanate (A) and the alcohol (B) .
10. A manufacturing method of a polyurethane-molded product,
comprising:
a step ofobtainingthepolymerizable composition for anoptical
5 material according to any one of claims 1 to 8 by mixing the alcohol
(B) , the acidic phosphoric acid ester (C) , and the
benzotriazole-based compound (D) together and then mixing the
resultant withat least one kindofthe isocyanate (A), whichcontains
aromatic isocyanate and has two or more isocyanato groups, at a
10 temperature of equal to or less than 30°C;
a step of casting the polymerizable composition into a casting
mold; and
a stepofpolymerizingthepolymerizable compositionby starting
the polymerization of the composition at a temperature of equal to
15 or less than 30°C.
11. The manufacturing method of a polyurethane-molded product
according to claim 10,
wherein the step of obtainingthe polymerizable composition for
20 an optical material includes a step of obtaining the polymerizable
composition for an optical material according to claim 9 by mixing
the alcohol ( B ) , the acidic phosphoric acid ester ( C ) , the
benzotriazole-based compound ( D ) , and the phenol-based compound (E)
together and then mixing the resultant with at least one kind of the
25 isocyanate (A), which contains aromatic isocyanate and has two or
more isocyanato groups, at a temperature of equal to or less than
30°C.
12. Amanufacturingmethodofaplasticpolarizing lens, comprising:
a stepofobtainingthepolymerizable composition for anoptical
material according to any one of claims 1 to 8 by mixing the alcohol
5 (B) , the acidic phosphoric acid ester (C) , and the
benzotriazole-based compound (D) together and then mixing the
resultant withat least one kindofthe isocyanate (A), whichcontains
aromatic isocyanate and has two or more isocyanato groups, at a
temperature of equal to or less than 30°C;
10 a step of fixing a polarizing film in a casting mold for lens
casting in a state in which at least one surface of the polarizing
film is separated from the mold;
a step of injecting the polymerizable composition into a space
between the polarizing film and the mold; and
15 a step of laminating a layer comprised of polyurethane resin
over at least one surface of the polarizing film by polymerizing and
curingthe polymerizable composition by starting the polymerization
of the composition at a temperature of equal to or less than 30°C.
20 13. Themanufacturingmethodof a plasticpolarizinglens according
to claim 12,
wherein the step of obtainingthe polymerizable composition for
an optical material includes a step of obtaining the polymerizable
composition for an optical material according to claim 9 by mixing
25 the alcohol (B), the acidic phosphoric acid ester ( C ) , the
benzotriazole-based compound (D), and the phenol-based compound (E)
together and then mixing the resultant with at least one kind of the
isocyanate (A), which contains aromatic isocyanate and has two or
more isocyanato groups, at a temperature of equal to or less than
30°C.
5 14. A manufacturing method of a polyurethane-molded product,
comprising:
a step (i) of obtaining a prepolymer by adding the alcohol (B)
to the isocyanate (A) such that a ratio of the hydroxyl groups to
the isocyanato groups of the isocyanate (A) falls into a range of
10 10 mol% to 20 mol% and reacting the isocyanate (A) with the alcohol
(B) in the presence of the acidic phosphoric acid ester (C), the
benzotriazole-based compound (D), and the hindered amine-based
compound,
a step (ii) of obtaining the polymerizable composition for an
15 optical material described in any one of claims 1 to 8 by further
adding the alcohol (B) to the prepolymer and mixing the alcohol (B)
and the prepolymer together at a temperature of equal to or less than
30°C; and
a step (iii) of polymerizing the prepolymer and the alcohol (B)
20 contained in the polymerizable composition.
15. The manufacturing method according to claim 14,
wherein the step (i) includes a step of obtaining a prepolymer
by adding the alcohol (B) to the isocyanate (A) such that the ratio
25 of the hydroxyl groups to the isocyanato groups of the isocyanate
(A) fallsintoa rangeof10mol%to20mol%andreactingtheisocyanate
(A) with the alcohol (8) in the presence of the acidic phosphoric
acid ester (C), the benzotriazole-based compound (D), the
phenol-based compound (E), and the hindered amine-based compound.
16. The manufacturing method according to claim 14 or 15,
5 wherein in the step (i), the reaction temperature is equal to
or less than 30°C.
17. The manufacturing method according to any one of claims 14 to
16,
10 wherein in the step (iii), heating is started at a temperature
of equal to or less than 30°C when the prepolymer and the alcohol
(B) are polymerized.
18. The manufacturing method according to any one of claims 14 to
15 17,
wherein the viscosity of the prepolyrner and the polymerizable
composition is equal to or less than 1,000 Pa.s at 20°C.
19. The manufacturing method according to any one of claims 14 to
20 18,
wherein the step (ii) is performed by a mixing apparatus
comprising a cylindrical container, a shaft that has been inserted
into the container from the upper portion of the container along the
central axis direction of the container, a stirring blade that is
25 wound in the form of a screw along the outer circumferential surface
of the shaft, a first supply portion that is disposed in the upper
portion of the container and supplies a solution of the prepolymer
into the container, a second supply portion that is disposed in the
upperportion ofthe container andsupplies a solution ofthe alcohol
(B) into the container, and an ejection portion that is disposed at
the bottom of the container,
5 wherein and the step (ii) includes
a step of supplying the prepolymer and the alcohol (B) into the
container fromthe first supplyportion andthe second supplyportion
respectively and
a step of preparing the polymerizable composition by rotating
10 the shaft such that the prepolymer and the alcohol (B) are moved down
while being mixed together at a temperature of equal to or less than
30°C by the stirring blade, which is wound in the form of a screw
along the outer circumferential surface of the shaft, and ejecting
the obtained polymerizable composition from the ejection portion.
15
20. The manufacturing method according to claim 19,
wherein a rotation frequency of the shaft is within a range of
1,000 rpm to 4,000 rpm, and a rate at which the polymerizable
composition is ejected from the ejection portion is within a range
20 of 0.5 g/s to 4.0 g/s.
21. The manufacturing method according to claim 19 or 20,
wherein in the step (ii), the viscosity of the obtained
polymerizable composition is equal to or less than 500 mPa.s at 20°C.
25
22. The manufacturing method according to claim 19 or 21,
wherein the step (iii) includes
a step of injecting the polymerizable composition into a mold,
and
a step of polymerizing the prepolymer and the alcohol (B)
contained in the polymerizable composition in the mold.
5
23. Amanufacturingmethodofaplasticpolarizinglens, comprising:
a step of fixing a polarizing film in a casting mold for lens
casting in a state in which at least one surface of the polarizing
film is separated from the mold, before the step (iii) in the
10 manufacturing method of a polyurethane-molded product according to
any one of claims 14 to 22,
wherein the step (iii) includes
a step of injecting the polymerizable composition obtained in
the step (ii) into a space between the polarizing film and the mold,
15 and
a step of laminating a layer comprised of polyurethane resin
over at least one surface of the polarizing film by polymerizing and
curing the polymerizable composition.
20 24. A polyurethane-molded product obtained by the manufacturing
method according to any one of claims 10, 11, and 14 to 22.
25. Anopticalmaterialcomprisedofthepolyurethane-moldedproduct
according to claim 24.
25
26. A plastic lens comprised of the optical material according to
claim 25.
27. A plastic polarizing lens obtained by the manufacturing method
according to claim 12, 13, or 23.