U.S. patent application number 09/889499 was filed with the patent office on 2003-07-17 for material for plastic lens, production process of the material, composition for plastic lens, plastic lens obtained by curing the composition, and production process of the plastic lens.
Invention is credited to Asai, Yoshifumi, Kai, Kazufumi, Ooga, Kazuhiko, Tajima, Tsuneo, Uchida, Hiroshi.
Application Number | 20030131548 09/889499 |
Document ID | / |
Family ID | 18682410 |
Filed Date | 2003-07-17 |
United States Patent
Application |
20030131548 |
Kind Code |
A1 |
Ooga, Kazuhiko ; et
al. |
July 17, 2003 |
Material for plastic lens, production process of the material,
composition for plastic lens, plastic lens obtained by curing the
composition, and production process of the plastic lens
Abstract
A material for plastic lenses, comprising at least one group
represented by the following formula (1) as a terminal group and a
group represented by the following formula (2) as a repeating unit.
1 wherein each R.sup.1 independently represents an allyl group or a
methallyl group, A.sup.1 and A.sup.2 each independently represents
an organic residue derived from a dicarboxylic acid or a carboxylic
anhydride, and each X independently represents an organic residue
derived from a polyhydric alcohol having from 2 to 3 hydroxyl
groups and containing an alicyclic structure within the molecule,
provided that by the ester bonding, X can have a branched structure
having a group of formula (1) as a terminal group and a group of
formula (2) as a repeating unit.
Inventors: |
Ooga, Kazuhiko; (Oita,
JP) ; Asai, Yoshifumi; (Oita, JP) ; Kai,
Kazufumi; (Oita, JP) ; Tajima, Tsuneo; (Oita,
JP) ; Uchida, Hiroshi; (Oita, JP) |
Correspondence
Address: |
Sughrue Mion Zinn
Macpeak & Seas
Suite 800
2100 Pennsylvania Avenue NW
Washington
DC
20037-3213
US
|
Family ID: |
18682410 |
Appl. No.: |
09/889499 |
Filed: |
July 18, 2001 |
PCT Filed: |
June 8, 2001 |
PCT NO: |
PCT/JP01/04878 |
Current U.S.
Class: |
52/309.1 |
Current CPC
Class: |
C08L 31/06 20130101;
G02B 1/041 20130101; G02B 1/041 20130101 |
Class at
Publication: |
52/309.1 |
International
Class: |
E04C 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 16, 2000 |
JP |
2000-181490 |
Claims
1. A material for plastic lenses, comprising at least one group
represented by the following formula (1) as a terminal group and a
group represented by the following formula (2) as a repeating unit.
15wherein each R.sup.1 independently represents an allyl group or a
methallyl group and each A.sup.1 independently represents an
organic residue derived from a dicarboxylic acid or a carboxylic
anhydride. 16wherein each A.sup.2 independently represents an
organic residue derived from a dicarboxylic acid or a carboxylic
anhydride and each X independently represents an organic residue
derived from a polyhydric alcohol having from 2 to 3 hydroxyl
groups and containing an alicyclic structure within the molecule,
provided that by the ester bonding, X can have a branched structure
having a group of formula (1) as a terminal group and a group of
formula (2) as a repeating unit.
2. The material as claimed in claim 1, wherein the polyhydric
alcohol is at least one selected from the compounds represented by
the following structural formulae (7) to (13) and the following
formula (14). 17wherein each R.sup.2 independently represents at
least one selected from the organic groups represented by the
following structural formulae (15) to (17), each R.sup.3
independently represents at least one selected from the following
structural formulae (18) to (20), a and b each independently
represents 0 or an integer of 1 to 10, and Y represents any one
selected from the organic groups represented by the following
structural formulae (21) and (22)). 18
3. A process for producing a material as set forth in claim 1 or 2,
comprising a step of transesterifying at least one selected from
the compounds represented by the following formula (3) with the
polyhydric alcohol described in claim 1 or 2 in the presence of a
catalyst to obtain a plastic lens material: 19wherein A represents
an organic residue derived from a dicarboxylic acid or a carboxylic
anhydride, and R.sup.4 and R.sup.5 each independently represents an
allyl group or a methallyl group.
4. The process as claimed in claim 3, wherein the catalyst is at
least one member selected from the group consisting of
tetraisopropoxy titanium, tetrabutoxy titanium, dibutyltin oxide,
dioctyltin oxide, hafnium acetylacetonate and zirconium
acetylacetonate.
5. A composition for plastic lenses, comprising at least one
plastic lens material as set forth in claim 1 or 2.
6. A composition for plastic lenses, comprising from 0.1 to 10
parts by mass of at least one radical polymerization initiator per
100 parts by mass of a composition for plastic lenses as set forth
in claim 5.
7. The composition for plastic lenses as claimed in claim 6,
wherein the at least one radical polymerization initiator contains
diisopropylperoxy dicarbonate.
8. The composition for plastic lenses as claimed in any one of
claims 5 to 7, which has a viscosity at 25.degree. C. of 1,000
mPa.s or less.
9. A plastic lens obtained by curing a composition for plastic
lenses as set forth in any one of claims 5 to 8.
10. The plastic lens as claimed in claim 9, wherein a curing
shrinkage in percentage at 23.degree. C. is 10.0% or less.
11. A process for producing a plastic lens as set forth in claim 9
or 10, which comprises curing a plastic lens composition as set
forth in claim 5 or 6.
12. The process as claimed in claim 11, wherein the plastic lens
composition is cast polymerized at a temperature of 30 to
120.degree. C. for 0.5 to 100 hours.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is an application filed under 35 U.S.C.
.sctn.111(a) claiming benefit pursuant to 35 U.S.C. .sctn.119(e)(1)
of the filing date of the Provisional Application 60/218,802 filed
Jul. 18, 2000, pursuant to 35 .sctn.111(b).
TECHNICAL FIELD
[0002] The present invention relates to a material for plastic
lenses, a production process of the material, a plastic lens
composition containing the material, a plastic lens obtained by
curing the composition, and a production process of the plastic
lens.
[0003] More specifically, the present invention relates to a
plastic lens material which can be used for a plastic lens
composition capable of preventing damage to a lens or a mold due to
curing shrinkage arising as a problem during the polymerization of
a polyethylene glycol poly(allyl carbonate)-based plastic lens
material; a production process of the material; a plastic lens
composition containing the material; a plastic lens obtained by
curing the composition; and a production process of the plastic
lens.
BACKGROUND ART
[0004] In recent years, organic glasses are widely used as optical
materials in camera, television, prism, telescope and ophthalmic
lenses. In particular, in the field of ophthalmic lenses, inorganic
glasses are being overtaken by organic glasses, particularly in
plastic lenses. Under these circumstances, the plastic lens is
required to be more lightweight and easier to mold.
[0005] Representative examples of the resin conventionally used as
a raw material for plastic lenses include polystyrene resin,
polycarbonate resin, polymethyl methacrylate resin and
polydiethylene glycol bis(allyl carbonate) resin. The physical
properties and production methods of these resins have been long
known and are described in detail, for example, in Plastic Age,
Vol. 35, pp. 198-202 (1989).
[0006] In this publication, the properties of the plastic lenses
derived from various resins are described as follows. The plastic
lens derived from polystyrene resin has a problem in that a
sufficiently high value cannot be obtained with respect to
birefringence and light scattering, though the refractive index is
high. The plastic lens derived from polycarbonate resin is
disadvantageously inferior in resistance against a solvent or
scratching, though the impact resistance is high. In the plastic
lens derived from polymethyl methacrylate resin, the refractive
index is low and the impact resistance is not at a satisfactory
level.
[0007] Other than these, a plastic lens derived from polydiethylene
glycol bis(allyl carbonate) resin is known (see, for example,
European Patent Publication No. 0473163A). This plastic lens is
favored with excellent properties particularly as a plastic lens
for eyeglasses, such as superior impact resistance and high Abbe
number, therefore, is most frequently used despite its low
refractive index of 1.498.
[0008] The polydiethylene glycol bis(allyl carbonate) resin is also
advantageous in that the polymerization reaction proceeds at a low
speed as compared with acrylic resin, therefore, the polymerization
reaction is easy to control and a uniform polymerization reaction
can be attained and, as a result, the plastic lens derived from the
polydiethylene glycol bis(allyl carbonate) resin is advantageously
reduced in optical strain.
[0009] Furthermore, the plastic lens derived from polydiethylene
glycol bis(allyl carbonate) resin is known to have dyeability such
that when the lens is dyed according to a general technique of
dipping a plastic lens obtained by cast-molding in a dye bath at a
high temperature, the dyeing density is higher than those of
plastic lenses derived from other resins.
[0010] In general, a plastic lens is manufactured by so-called cast
polymerization where a monomer is polymerized using two glass
molds. The molds must be cleaned after the cast-molding and the
cleaning is usually performed using a strong alkaline solution or a
strong acid. Unlike metal, glass is scarcely changed in quality by
cleaning, therefore, glass is preferably used. Furthermore, glass
can be easily polished and thereby extremely reduced in surface
roughness.
[0011] The polymerization process generally incurs curing
shrinkage. On the other hand, the lens must perfectly take after
the curve on the glass surface and to this purpose, the monomer is
required to exhibit good adhesion to the glass during the
polymerization.
[0012] If the curing shrinkage in percentage is excessively large,
cracks may be generated on the lens when the curing speed is
increased, or the lens or the mold may be damaged at the release of
lens from the mold. This phenomenon randomly occurs in the
production of lenses. In the case of plastic lenses derived from
polyethylene glycol bis(allyl carbonate) resin, the loss ascribable
to this phenomenon usually reaches several % of the production of
plastic lenses.
DISCLOSURE OF INVENTION
[0013] It is an object of the present invention to provide a
compound useful as a plastic lens material capable of providing a
cured product having a high Abbe number and a relatively small
curing shrinkage, a production process of the compound, a plastic
lens composition containing the compound, a plastic lens obtained
by curing the composition, and a production process of the plastic
lens.
[0014] As a result of extensive investigation to solve the
above-described problems, the present inventors have found that by
using a (meth)ally ester-based compound containing an alicyclic
structure, a plastic lens material capable of providing a cured
product having a high Abbe number and a relatively small curing
shrinkage can be obtained. The present invention has been
accomplished based on this finding.
[0015] More specifically, the present invention (I) is a material
for plastic lenses, comprising at least one group represented by
the following formula (1) as a terminal group and a group
represented by the following formula (2) as a repeating unit: 2
[0016] wherein each R.sup.1 independently represents an allyl group
or a methallyl group and each A.sup.1 independently represents an
organic residue derived from a dicarboxylic acid or a carboxylic
anhydride. 3
[0017] wherein each A.sup.2 independently represents an organic
residue derived from a dicarboxylic acid or a carboxylic anhydride
and each X independently represents an organic residue derived from
a polyhydric alcohol having from 2 to 3 hydroxyl groups and
containing an alicyclic structure within the molecule, provided
that by the ester bonding, X can have a branched structure having a
group of the above formula (1) as a terminal group and a group of
the above formula (2) as a repeating unit.
[0018] The present invention (II) is a process for producing the
material of the present invention (I), comprising a step of
transesterifying at least one member selected from the group
consisting of compounds represented by the following formula (3)
with the polyhydric alcohol described above with respect to the
present invention (I) in the presence of a catalyst to obtain a
plastic lens material. 4
[0019] wherein A represents an organic residue derived from a
dicarboxylic acid or a carboxylic anhydride, and R.sup.4 and
R.sup.5 each independently represents an allyl group or a methallyl
group.
[0020] The present invention (III) relates to a composition for
plastic lenses, comprising at least one material of the present
invention (I).
[0021] The present invention (IV) is a composition for plastic
lenses, comprising from 0.1 to 10 parts by mass of at least one
radical polymerization initiator and 100 parts by mass of the
composition for plastic lenses of the present invention (III).
[0022] The present invention (V) is a plastic lens obtained by
curing the composition for plastic lenses of the present invention
(III) or the present invention (IV).
[0023] The present invention (VI) is a process for producing the
plastic lens of the present invention (V).
BRIEF DESCRIPTION OF DRAWINGS
[0024] The figures attached hereto are a 400 MHz .sup.1H-NMR
spectrum chart and an FT-IR spectrum chart of each compound for
plastic lens materials described in Examples.
[0025] FIG. 1 is a 400 MHz .sup.1H-NMR spectrum chart of the allyl
ester compound produced in Production Example 1.
[0026] FIG. 2 is a FT-IR spectrum chart of the allyl ester compound
produced in Production Example 1.
[0027] FIG. 3 is a 400 MHz .sup.1H-NMR spectrum chart of the allyl
ester compound produced in Production Example 2.
[0028] FIG. 4 is an FT-IR spectrum chart of the allyl ester
compound produced in Production Example 2.
[0029] FIG. 5 is a 400 MHz .sup.1H-NMR spectrum chart of the allyl
ester compound produced in Production Example 3.
[0030] FIG. 6 is an FT-IR spectrum chart of the allyl ester
compound produced in Production Example 3.
[0031] FIG. 7 is a 400 MHz .sup.1H-NMR spectrum chart of the allyl
ester compound produced in Production Example 4.
[0032] FIG. 8 is an FT-IR spectrum chart of the allyl ester
compound produced in Production Example 4.
BEST MODE FOR CARRYING OUT THE INVENTION
[0033] The present invention is described in detail below.
[0034] First, the material of the present invention (I) is
described. The present invention (I) is a material for plastic
lenses, comprising at least one group represented by the following
formula (1) as a terminal group and a group represented by the
following formula (2) as a repeating unit: 5
[0035] wherein each R.sup.1 independently represents an allyl group
or a methallyl group and each A.sup.1 independently represents an
organic residue derived from a dicarboxylic acid or a carboxylic
anhydride. 6
[0036] wherein each A.sup.2 independently represents an organic
residue derived from a dicarboxylic acid or a carboxylic anhydride
and each X independently represents an organic residue derived from
a polyhydric alcohol having from 2 to 3 hydroxyl groups and
containing an alicyclic structure within the molecule, provided
that, by the ester bonding, X can have a branched structure having
a group of the above formula (1) as a terminal group and a group of
the above formula (2) as a repeating unit.
[0037] In formula (1), each R.sup.1 independently represents an
allyl group or a methallyl group. Also, in formula (1), each
A.sup.1 independently represents an organic residue derived from a
dicarboxylic acid or a carboxylic anhydride. In formula (2), each
A.sup.2 independently represents an organic residue derived from a
dicarboxylic acid or a carboxylic anhydride. Also, in formula (2),
each X independently represents an organic residue derived from a
polyhydric alcohol having from 2 to 3 hydroxyl groups and
containing an alicyclic structure within the molecule.
[0038] The term "each R.sup.1 independently represents an allyl
group or a methallyl group" as used herein means that the moiety
represented by R.sup.1 of the terminal group represented by formula
(1) in the material of the present invention (I) all may be
occupied by an allyl group or a methallyl group or may be partially
occupied by an allyl group with the remaining by a methallyl
group.
[0039] A.sup.1 in Formula (1) and A.sup.2 in formula (2) each
represents an organic residue derived from a dicarboxylic acid or a
carboxylic anhydride.
[0040] Examples of the dicarboxylic acid or carboxylic anhydride
include aliphatic dicarboxylic acids and anhydrides thereof, such
as succinic acid and succinic anhydride, glutaric acid and glutaric
anhydride, adipic acid, malonic acid and malonic anhydride, and
2-methylsuccinic acid and 2-methylsuccinic anhydride dicarboxylic
acids having an alicyclic structure and anhydrides thereof, such as
1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
1,2-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic
anhydride, and 4-methylcyclohexane-1,2-di- carboxylic acid and
4-methylcyclohexane-1,2-dicarboxylic anhydride and aromatic
dicarboxylic acids and anhydrides thereof, such as terephthalic
acid, isophthalic acid, and phthalic acid and phthalic anhydride.
Needles to say, the present invention is not limited to these
specific examples.
[0041] Among those, in view of the fluidity of the compound,
preferred are glutaric acid, succinic acid, adipic acid,
2-methylsuccinic acid and 1,3-cyclohexanedicarboxylic acid, and
more preferred are glutaric acid, 2-methylsuccinic acid, adipic
acid and succinic acid.
[0042] The term "each A.sup.1 independently represents an organic
residue derived from a dicarboxylic acid or a carboxylic anhydride"
or "each A.sup.2 independently represents an organic residue
derived from a dicarboxylic acid or a carboxylic anhydride" as used
herein means that the moiety represented by A.sup.1 of the terminal
group represented by formula (1) in the material of the present
invention (I) and the moiety represented by A.sup.2 of the
repeating unit represented by formula (2) in the material of the
present invention (I) (hereinafter "A.sup.1" and "A.sup.2" are
collectively referred to as "A") each may be entirely occupied by
organic residues derived from dicarboxylic acids or carboxylic
anhydrides having the same structure, may be occupied by organic
residues derived from dicarboxylic acids or carboxylic anhydrides
having different structures, or may be partially occupied by
organic residues derived from dicarboxylic acids having the same
structure with the remaining by organic residues derived from
dicarboxylic acids having different structures.
[0043] More specifically, in the following structural formula (4)
which is one example of the material of the present invention (I),
As in the number of k contained in the repeating structure are
independent of each other. 7
[0044] wherein each A independently represents an organic residue
derived from a dicarboxylic acid, k represents an integer of 2 to
3, and X represents an organic residue derived from a polyhydric
alcohol having from 2 to 3 hydroxyl groups and containing an
alicyclic structure within the molecule.
[0045] In structural formula (4), the As, in the number k, all may
be organic residues derived from dicarboxylic acids having
different structures (that is, organic residues are derived one by
one from dicarboxylic acids having k kinds of structure) or all may
be organic residues derived from dicarboxylic acid having the same
structure (that is, organic residues in the number of k are derived
from dicarboxylic acids having one kind of structure). A mixed
structure where some of As, in the number k, are organic residues
derived from dicarboxylic acids having the same structure and some
others are organic residues derived from dicarboxylic acids having
different kinds of structure may also be used.
[0046] The term "each X independently represents" as used herein
means that in the following structural formula (5) as one example
of the repeating unit represented by formula (2), the Xs, in the
number m, contained in the repeating structure are independent of
each other. 8
[0047] wherein each X independently represents an organic residue
derived from a polyhydric alcohol having from 2 to 3 hydroxyl
groups and containing an alicyclic structure within the molecule, m
represents 0 or an integer of 1 or more, and when m is an integer
of 1 or more, n represents 0 or an integer of 1 or more and each A
independently represents an organic residue derived from a
dicarboxylic acid.
[0048] For example, in structural formula (5), the Xs, in the
number m, all may be organic residues derived from different
polyhydric alcohols (that is, organic residues are derived one by
one from m kinds of polyhydric alcohol) or all may be organic
residues derived from the same kind of polyhydric alcohol (that is,
organic residues in the number of m are derived from one kind of
polyhydric alcohol). A mixed structure where some of the Xs, in the
number m, are organic residues derived from the same kind of
polyhydric alcohol and some others are organic residues derived
from different kinds of polyhydric alcohol may also be used.
Moreover, in this mixed structure, all may be completely random or
a part may be repeated.
[0049] By the ester bonding, X can have a branched structure
containing the formula (1) as a terminal group and the formula (2)
as a repeating unit. More specifically, for example, when an
organic residue derived from cyclohexane-1,2,4-trimethanol, which
is one example of the trihydric saturated alcohol, is present in X,
the material of the present invention (I) can have a partial
structure represented by the following structural formula (6).
9
[0050] Each X is of course independently an organic residue derived
from a polyhydric alcohol having from 2 to 3 hydroxyl groups and
containing an alicyclic structure within the molecule. Also, each A
is independently an organic residue derived from a dicarboxylic
acid.
[0051] In formula (2), each X independently represents an organic
residue derived from a polyhydric alcohol having from 2 to 3
hydroxyl groups and containing an alicyclic structure within the
molecule. Examples of the polyhydric alcohol having from 2 to 3
hydroxyl groups and containing an alicyclic structure within the
molecule include the following compounds. Needless to say, however,
the present invention is not limited to these specific examples.
10
[0052] A dihydric alcohol represented by the following formula (14)
may also be used. 11
[0053] wherein each R.sup.2 independently represents at least one
member selected from the organic groups represented by the
following structural formulae (15) to (17), each R.sup.3
independently represents at least one member selected from the
organic residues represented by the following structural formulae
(18) to (20), a and b each independently represents 0 or an integer
of 1 to 10, and Y represents an organic group selected from the
following structural formulae (21) and (22). 12
[0054] In formula (14), the term "each R.sup.2 independently
represents at least one member selected from the organic groups"
means that R.sup.2s in the number of a all may be organic groups
having the same structure, all may be organic groups having
different structures, or may be partially organic groups having the
same structure with the remaining being organic groups having
different structures, where, however, R.sup.2 must be selected from
the organic groups represented by structural formulae (15) to
(17).
[0055] In formula (14), the term "each R.sup.3 independently
represents at least one member selected from the organic residues"
means that R.sup.3s in the number of b all may be organic groups
having the same structure, all may be organic groups having
different structures or may be partially organic groups having the
same structure with the remaining being organic groups having
different structures, where, however, R.sup.3 must be selected from
the organic groups represented by structural formulae (18) to
(20).
[0056] In formula (14), a and b each independently represents 0 or
an integer of 1 to 10. Y represents an organic group selected from
the following structural formulae (21) and (22).
[0057] Specific examples of the dihydric alcohol represented by
formula (14) include 2,2-bis[4-(2-hydroxyethoxy)cyclohexyl]propane,
2,2-bis[4-(2-hydroxypropoxy)cyclohexyl]propane, 3 mol ethylene
oxide adducts of 2,2-bis(4-hydroxycyclohexyl)propane, 4 mol
propylene oxide adducts of (4-hydroxycyclohexyl)propane,
bis[4-(2-hydroxyethoxy)cyclohexy- l]methane,
bis[4-(2-hydroxypropoxy)cyclohexyl]methane, 3 mol ethylene oxide
adducts of bis(4-hydroxycyclohexyl)methane, and 4 mol propylene
oxide adducts of bis(4-hydroxycyclohexyl)methane. Needless to say,
however, the present invention is not limited to these specific
examples.
[0058] Among these polyhydric alcohols, since raw materials are
easily available, the compounds of structural formula (7),
structural formula (8) and structural formula (9), and
2,2-bis[4-(2-hydroxyethoxy)cyclohexyl- ]propane,
2,2-bis[4-(2-hydroxypropoxy)cyclohexyl]propane and 3 mol ethylene
oxide adducts of 2,2-bis(4-hydroxycyclohexyl)propane are preferred,
and the compound of structural formula (7),
2,2-bis[4-(2-hydroxyethoxy)cyclohexyl]propane,
2,2-bis[4-(2-hydroxypropox- y)cyclohexyl]propane and 3 mol ethylene
oxide adducts of 2,2-bis(4-hydroxycyclohexyl)propane are more
preferred.
[0059] The repeating number of the group represented by formula (2)
which is a repeating unit of the material of the present invention
(I) is not particularly limited. A mixture of materials having
various repeating numbers may also be used. Furthermore, a material
where the repeating number is 0 and a material where the repeating
number is an integer of 1 or more may be used in combination.
However, use of only a compound where the repeating number is 0 is
disadvantageous in achieving the object of the present
invention.
[0060] Usually, the repeating number of the group represented by
formula (2) as a repeating unit of the material of the present
invention (I) is preferably an integer of from 0 to 50. If a
plastic lens material comprising only compounds where the repeating
number exceeds 50 is used for a plastic lens composition, the allyl
group concentration decreases and this may cause adverse effects,
for example, at the time of curing, the curing may be retarded or a
part of the compound may remain uncured to reduce the physical
properties of the cured product such as mechanical properties. In
all compounds contained in the plastic lens material, the repeating
number is preferably an integer of 0 to 50, more preferably from 0
to 30, still more preferably from 0 to 10.
[0061] Depending of the production conditions, the compound
represented by formula (3) as a raw material may remain in the
material of the present invention (I) but the material may be used
as it is as a plastic lens material. However, when the present
invention (I) is used as a plastic lens material, it is
disadvantageous for reducing the curing shrinkage in percentage
that the compound represented by formula (3) is present in a
proportion of 90% by mass or more based on the entire curable
component.
[0062] Incidentally, the term "entire curable component" as used in
the present invention means the total amount of the material of the
present invention (I) and a monomer copolymerizable with at least
one material of the present (I).
[0063] The present invention (II) is described below. The present
invention (II) is a process for producing the material of the
present invention (I), comprising a step of transesterifying at
least one member selected from the group consisting of compounds
represented by formula (3) with a polyhydric alcohol in the
presence of a catalyst to obtain a compound for the plastic lens
material.
[0064] In formula (3), R.sup.4 and R.sup.5 each independently
represents an allyl group or a methallyl group.
[0065] Furthermore, in formula (3), A represents an organic residue
derived from a dicarboxylic acid or a carboxylic anhydride. The
dicarboxylic acid and carboxylic anhydride include aliphatic
dicarboxylic acids and anhydrides thereof, such as succinic acid
and succinic anhydride, glutaric acid and glutaric anhydride,
adipic acid, malonic acid and malonic anhydride, and
2-methylsuccinic acid and 2-methylsuccinic anhydride; dicarboxylic
acids having an alicyclic structure and anhydrides thereof, such as
1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
1,2-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic
anhydride, and 4-methylcyclohexane-1,2-di- carboxylic acid and
4-methylcyclohexane-1,2-dicarboxylic anhydride; and aromatic
dicarboxylic acids and anhydrides thereof, such as terephthalic
acid, isophthalic acid, and phthalic acid and phthalic anhydride.
Needles to say, however, the present invention is not limited to
these specific examples.
[0066] The compound of the material of the present invention (I)
can be produced, for example, by the following process.
[0067] The objective compound can be obtained using at least one
compound represented by formula (3) in a constant ratio through a
step of transesterifying these compounds with at least one
polyhydric alcohol having from 2 to 3 hydroxyl groups and
containing an alicyclic structure within the molecule in the
presence of a catalyst. Of course, the present invention is not
limited thereto and a step such as purification may be included, if
desired.
[0068] The catalyst for use in the above-described step is not
particularly limited as long as it is a catalyst capable of being
used for transesterification in general. An organic metal compound
is particularly preferred and specific examples thereof include
tetraisopropoxy titanium, tetrabutoxy titanium, dibutyltin oxide,
dioctyltin oxide, hafnium acetylacetonate and zirconium
acetylacetonate, however, the present invention is not limited
thereto. Among these, dibutyltin oxide and dioctyltin oxide are
preferred.
[0069] The reaction temperature in this step is not particularly
limited but is preferably from 100 to 230.degree. C., more
preferably 120 to 200.degree. C. In the case where a solvent is
used, the reaction temperature is sometimes limited by the boiling
point of the solvent.
[0070] In this step, a solvent is usually not used, however a
solvent may be used, if desired. The solvent which can be used is
not particularly limited as long as it does not inhibit the
transesterification. Specific examples thereof include benzene,
toluene, xylene and cyclohexane, however, the present invention is
not limited thereto. Among these, benzene and toluene are
preferred. However, as described above, the step may be performed
without using a solvent.
[0071] The composition for plastic lenses of the present invention
(III) or the present invention (IV) is described below.
[0072] The present invention (III) is a composition for plastic
lenses, comprising at least one compound of the material of the
present invention (I).
[0073] The amount of the compound of the material of the present
invention (I) blended is preferably from 5 to 80% by mass, more
preferably from 15 to 70% by mass, based on the entire curable
component contained in the composition for plastic lenses of the
present invention (III). If the amount of the material blended is
less than 5% by mass, the two requirements of high Abbe number and
low curing shrinkage can seldom be satisfied at the same time and
this is not preferred.
[0074] For the purpose, mainly, of adjusting the viscosity of the
composition, one or more compounds copolymerizable with the
compound of the material of the present invention (I) may be added
to the present invention (III).
[0075] Examples of the compound include monomers having an acryl
group, a vinyl group or an allyl group. Specific examples of the
monomer having an acryl group include methyl (meth)acrylate and
isobornyl (meth)acrylate, and specific examples of the monomer
having a vinyl group include vinyl acetate and vinyl benzoate, and
specific examples of the monomer having an allyl group include the
compounds having a structural formulae (23) to (29) shown below. In
addition, polyethylene glycol bis(allyl carbonate) resin
represented by CR-39 (trade name, produced by PPG) may also be
used. Of course, the present invention is not limited to these
specific examples and diallyl phthalate, diallyl terephthalate,
diallyl isophthalate, allyl benzoate and the like may also be used
within the range of not impairing the physical properties of the
plastic lens obtained by curing.
[0076] Specific examples of the compound which is preferably used
include the compounds represented by the following structural
formulae (23) to (29) and polyethylene glycol bis(allyl carbonate)
resin. 13
[0077] The amount of the compound added greatly varies depending on
the monomer used, however, the amount added is usually 90% by mass
or less, preferably 80% by mass or less, more preferably 75% by
mass or less, based on the entire curable component contained in
the plastic lens composition of the present invention. If the
compound is added in excess of 90% by mass, the two requirements
for the plastic lens of the present invention, namely, high Abbe
number and low curing shrinkage, are difficult to attain at the
same time and this is not preferred.
[0078] With respect to other effects, when the plastic lens
material of the present invention is added in an amount of 0.5% by
mass or more to polyethylene glycol bis(allyl carbonate) resin, the
uneven dyeing which appears at the dyeing of polyethylene glycol
bis(allyl carbonate) resin can be reduced.
[0079] An optimal monomer is selected by taking account of the
kinds and the mixing ratios of the above-described compound and the
allyl ester oligomer contained in the resin composition for plastic
lenses and the physical property values such as optical property
required for the plastic lens obtained by curing the
composition.
[0080] On taking account of operability in the casting, the
viscosity of the plastic lens composition of the present invention
(III) is generally 3,000 mPa.s or less at 25.degree. C., preferably
1,000 mPa.s or less, more preferably 500 mPa.s or less.
[0081] The term "viscosity" as used herein is a viscosity measured
by a rotational viscometer. The rotational viscometer is described
in detail in Iwanami Rikagaku Jiten (Iwanami Physics and Chemistry
Encyclopedia), 3rd ed., 8th imp. (Jun. 1, 1977).
[0082] The present invention (IV) is a composition for plastic
lenses, comprising from 0.1 to 10 parts by mass of at least one
radical polymerization initiator per 100 parts by mass of the
composition for plastic lenses of the present invention (III).
[0083] The plastic lens composition of the present invention (IV)
may contain a radical polymerization initiator as a curing agent
and this is preferred.
[0084] The radical polymerization initiator which can be added to
the plastic lens composition of the present invention (IV) is not
particularly limited and a known radical polymerization initiator
may be added as long as it does not adversely affect the physical
property values such as optical property of the plastic lens
obtained by curing the composition.
[0085] The radical polymerization initiator for use in the present
invention is, however, preferably a radical polymerization
initiator which is soluble in other components present in the
composition to be cured and which generates free radicals at 30 to
120.degree. C. Specific examples of the radical polymerization
initiator which can be added include diisopropylperoxy dicarbonate,
dicyclohexylperoxy dicarbonate, di-n-propylperoxy dicarbonate,
di-sec-butylperoxy dicarbonate and tert-butyl perbenzoate, but the
present invention is not limited thereto. In view of the
curability, diisopropylperoxy dicarbonate is preferred.
[0086] The amount of the radical polymerization initiator added is
in the range from 0.1 to 10 parts by mass, preferably from 1 to 5
parts by mass, per 100 parts by mass of the entire curable
component contained in the plastic lens composition of the present
invention (III). If the amount added is less than 0.1 part by mass,
curing of the composition may proceed insufficiently, whereas if it
exceeds 10 parts by mass, the profitability decreases and this is
not preferred.
[0087] The plastic lens composition of the present invention (III)
or the present invention (IV) may contain additives commonly used
for the purpose of improving the performance of the plastic lens,
such as a coloring agent including dye and pigment, an ultraviolet
absorbent, a mold-releasing agent and an antioxidant.
[0088] Examples of the coloring agent include organic pigments such
as anthraquinone type, azo type, carbonium type, quinoline type,
quinoneimine type, indigoid type and phthalocyanine type; organic
dyes such as azoic dye and sulfur dye; and inorganic pigments such
as titanium yellow, yellow iron oxide, zinc yellow, chrome orange,
molybdenum red, cobalt violet, cobalt blue, cobalt green, chromic
oxide, titanium oxide, zinc sulfide and carbon black.
[0089] Examples of the mold-releasing agent include stearic acid,
butyl stearate, zinc stearate, stearic acid amide,
fluorine-containing compounds and silicone compounds.
[0090] Examples of the ultraviolet absorbent include triazoles such
as 2-(2'-hydroxy-tert-butylphenyl)benzotriazole, benzophenones such
as 2,4-dihydroxybenzophenone, salicylates such as
4-tert-butylphenyl salicylate, and hindered amines such as
bis-(2,2,6,6-tetramethyl-4-piperi- dinyl)sebacate.
[0091] Examples of the antioxidant include phenols such as
2,6-di-tert-butyl-4-methylphenol and
tetrakis[methylene-3-(3',5'-di-tert--
butyl-4-hydroxyphenyl)propionate]methane; sulfurs such as
dilauryl-3,3'-thiodipropionate; and phosphorus-containing
antioxidants such as trisnonylphenylphosphite.
[0092] The total amount of the additives added, such as a coloring
agent including dye and pigment, an ultraviolet absorbent, a
mold-releasing agent and an antioxidant, is preferably 1% by mass
or less based on the entire curable resin component contained in
the resin composition for plastic lenses of the present
invention.
[0093] The present invention (V) is described below. The present
invention (V) is a plastic lens obtained by curing the plastic lens
composition of the present invention (III) or the present invention
(IV).
[0094] The curing shrinkage in percentage of the plastic lens in
the present invention is preferably 10.0% or less at 23.degree. C.
The reason therefor is that if the curing shrinkage in percentage
on curing is excessively large, cracks are readily generated during
the curing and, as a result, the yield at the molding
decreases.
[0095] Finally, the present invention (VI) is described. The
present invention (VI) is a process for producing the plastic lens
of the present invention (V), comprising curing the plastic lens
composition of the present invention (III) or the present invention
(IV).
[0096] In the present invention, the mold-working of the plastic
lens composition is suitably performed by cast-molding.
Specifically, a method of adding a radical polymerization initiator
to the composition, injecting the mixture through a line into a
mold fixed by an elastomer gasket or a spacer, and curing it under
heating in an oven may be used.
[0097] The constructive material of the mold used here is a metal
or glass. In general, the mold for plastic lenses must be cleaned
after the cast-molding and such cleaning is usually performed using
a strong alkali solution or a strong acid. Unlike metal, glass is
scarcely changed in the quality by the cleaning and furthermore,
glass can be easily polished and thereby extremely reduced in the
surface roughness, therefore, glass is preferably used.
[0098] The plastic lens composition of the present invention (III)
or the present invention (IV) has an alicyclic structure,
accordingly, depending on the molecular design, the refractive
index can be easily approximated to the refractive index 1.498 of
the plastic lens starting from polydiethylene glycol bis(allyl
carbonate) which is used for plastic lenses in many cases. This is
advantageous in that the mold or the like conventionally used in
the molding need not be changed but can be used as it is.
[0099] The curing temperature at the molding is from about 30 to
120.degree. C., preferably from 40 to 100.degree. C. With respect
to the operation of curing temperature, on taking account of
shrinkage or strain at the curing, a method of allowing the curing
to gradually proceed while elevating the temperature is preferably
used. The curing time is generally from 0.5 to 100 hours,
preferably from 3 to 50 hours, more preferably from 10 to 30
hours.
[0100] The method for dyeing the plastic lens of the present
invention is not particularly limited. Any method may be used as
long as it is a known dyeing method for plastic lenses. Among
these, a dip dyeing method conventionally known as a general method
is preferred. The "dip dyeing method" as used herein means a method
of dispersing a disperse dye together with a surfactant in water to
prepare a dye bath and dipping a plastic lens in this dyeing
solution under heating, thereby dyeing the plastic lens.
[0101] The method for dyeing the plastic lens is not limited to
this dip dyeing method but other known methods may be used, for
example, a method of sublimating an organic pigment and thereby
dyeing a plastic lens (see, Japanese Examined Patent Publication
No. 35-1384, JP-B-35-1384) or a method of sublimating a sublimable
dye and thereby dyeing a plastic lens (see, Japanese Examined
Patent Publication Nos. 56-159376 and 1-277814, JP-B-56-159376 and
JP-B-1-277814) may be used. In view of simple operation, the dip
dyeing method is most preferred.
[0102] The present invention is further illustrated below by
referring to the following examples, however, the present invention
should not be construed as being limited thereto.
[0103] Various physical properties were measured as follows.
[0104] 1. Refractive Index (n.sub.D) and Abbe Number
(.nu..sub.D)
[0105] A test piece of 9 mm.times.16 mm.times.4 mm was prepared and
measured on the refractive index (n.sub.D) and Abbe number
(.nu..sub.D) at 25.degree. C. using "Abbe Refractometer 1T"
manufactured by Atago. The contact solvent used was
.alpha.-bromonaphthalene.
[0106] 2. Viscosity
[0107] In Example 1, Examples 3 to 6, Examples 8 to 15, and
Comparative Examples 1 to 5, 300 g of the specimen was charged into
a 300-ml tall beaker. The viscosity of them was measured at
25.degree. C. and at 20 rpm using No. 1 rotor by B-Type Viscometer
(Model BH) manufactured by Tokyo Keiki Co., Ltd.
[0108] In Example 2 and Example 7, 5.2 ml of the specimen was
charged into a designated sample adapter. The viscosity of them was
measured at 25.degree. C. at 100 rpm using an HH-1 rotor by B-Type
Viscometer (Model B8U) manufactured by Tokyo Keiki Co., Ltd.
[0109] 3. Barcol Hardness
[0110] The Barcol hardness was measured using Model 934-1 according
to JIS K 6911.
[0111] 4. Measurement of Curing Shrinkage in Percentage
[0112] The value of curing shrinkage in percentage (%) was
calculated using the following formula from the specific gravity of
the composition before curing and the specific gravity of the cured
product.
[0113] Curing Shinkage in Percentage (%)=(1-(specific gravity of
composition before curing/specific gravity of cured
product)).times.100
[0114] At this time, the specific gravity of the composition before
curing was measured by a specific gravity bottle at a measuring
temperature of 23.degree. C. according to the measuring method for
specific gravity (see, JIS Z 8804). The specific gravity after
curing was measured by a sink-float method (at 23.degree. C.) (see,
JIS K 7112).
[0115] 5. Dyeing Method and Evaluation of Uneven Dyeing
[0116] To a 1 l beaker, 0.8 g of Sumikaron Blue E-FBL (produced by
Sumitomo Chemical Co., Ltd.) and 0.5 L of water were added and
dissolved with stirring. The resulting solution was heated in a
water bath at 80.degree. C. and into this disperse dye solution,
cured plastic lens samples each fixed to a holder so as not to
overlap one on another were dipped at 80.degree. C. for 10 minutes.
Thereafter, the samples were taken out, thoroughly washed with
water and then hot-air dried in an oven at 30.degree. C.
[0117] The thus-obtained dyed plastic lens samples were observed
with an eye and those failed in having a uniformly dyed appearance
and revealed to have uneven dyeing were rated "defective". By
evaluating 30 cured samples in total, the number of "defective"
samples was counted.
PRODUCTION EXAMPLE 1
[0118] Into a 500 ml three-neck flask with a distillation unit,
160.2 g of dimethyl glutarate, 232.3 g of allyl alcohol, 0.27 g of
potassium acetate and 1.33 g (1% by mass based on dimethyl
glutarate) of calcium hydroxide were charged. The system was heated
at a bath temperature of 110 to 120.degree. C. in a nitrogen
stream, and methanol generated was distilled off. The reaction was
continued until a theoretical amount of methanol was distilled off,
and when 64 g (100% based on the theoretical distillation amount of
methanol) was distilled off, the reactor was cooled. The resulting
reaction solution was purified by distillation under reduced
pressure, as a result, 200 g of diallyl glutarate was obtained as a
colorless transparent liquid (isolation yield: 95%, raw material: 1
mol).
[0119] Into a 300 ml three-neck flask with a distillation unit, 101
g (0.48 mol) of diallyl glutarate, 53.8 g (0.373 mol) of
1,4-cyclohexane dimethanol and 0.1 g (1% by mass based on diallyl
glutarate) of dibutyltin oxide were charged. The system was heated
at 180.degree. C. in a nitrogen stream, and the allyl alcohol
generated was distilled off. When about 26 g of allyl alcohol was
distilled off, the pressure within the reaction system was reduced
to 1.33 kPa to increase the distillation rate of allyl alcohol.
After a theoretical amount (43.6 g) of allyl alcohol was distilled
off, the system was heated for another one hour and then kept at
190.degree. C. and 0.13 kPa for one hour. Thereafter, the reactor
was cooled, as a result, 110 g of an allyl ester compound was
obtained (hereinafter referred to as "Sample A"). FIG. 1 and FIG. 2
show 400 MHz .sup.1H-NMR spectrum (solvent: CDCl.sub.3) and FT-IR
spectrum of Sample A, respectively.
[0120] In FIG. 1, the peak in the vicinity of 0.9 to 2.0 ppm is
attributable to a proton derived from cyclohexane ring, the peak in
the vicinity of 2.3 to 2.5 ppm is attributable to a proton derived
from glutaric acid skeleton, the peak in the vicinity of 3.7 to 4.1
ppm is attributable to a proton of methylene derived from
cyclohexanedimethanol which is ester-bonded, the peak in the
vicinity of 4.6 ppm is attributable to a proton of methylene at the
allyl position, the peak in the vicinity of 5.3 ppm is attributable
to a proton in the terminal of the double bond at the allyl
position, and the peak in the vicinity of 5.8 ppm is attributable
to a proton in the inner side of the double bond at the allyl
position.
[0121] In FIG. 2, the peak at 1738 cm.sup.-1 is absorption by the
carbonyl stretching vibration of the carboxyl group.
[0122] Sample A was analyzed by gas chromatography (GC-14B
manufactured by Shimadzu Corp., hydrogen flame ionization detector,
column used: OV-17 of 0.5 m, the temperature condition: 160.degree.
C. and constant) and found to contain 3.88% by mass of diallyl
glutarate.
PRODUCTION EXAMPLE 2
[0123] Into a 3 l three-neck flask with a distillation unit, 660.6
g of succinic anhydride, 1,056 g of allyl alcohol, 1,000 ml of
benzene and 6.61 g (1% by mass based on succinic anhydride) of
concentrated sulfuric acid were charged. The system was heated at
100.degree. C. in a nitrogen stream, and H.sub.2O generated was
distilled off. The reaction was continued until a theoretical
amount of H.sub.2O was distilled off and when 109 g (100% based on
the theoretical distillation amount of H.sub.2O) of H.sub.2O was
distilled off, the reactor was cooled. The resulting reaction
solution was neutralized with an aqueous NaOH solution and washed
with water. After benzene and excess allyl alcohol were distilled
off, the reaction solution was purified by distillation under
reduced pressure, as a result, 1,130 g of diallyl succinate was
obtained as a colorless transparent liquid.
[0124] Into a 3 l three-neck flask with a distillation unit, 1,784
g of diallyl succinate, 829 g of 1,4-cyclohexanedimethanol and
1.784 g (1% by mass based on diallyl succinate) of dibutyltin oxide
were charged. The system was heated at 180.degree. C. in a nitrogen
stream and the allyl alcohol generated was distilled off. When
about 418 g of allyl alcohol was distilled off, the pressure within
the reaction system was reduced to 1.33 kPa to increase the
distillation rate of allyl alcohol. After a theoretical amount (618
g) of allyl alcohol was distilled off, the system was heated for
another one hour and then kept at 190.degree. C. and 0.13 kPa for
one hour. Thereafter, the reactor was cooled, as a result, 1,897 g
of an allyl ester compound was obtained (hereinafter referred to as
"Sample B"). FIG. 3 and FIG. 4 show 400 MHz .sup.1H-NMR spectrum
(solvent: CDCl.sub.3) and FT-IR spectrum of Sample B,
respectively.
[0125] In FIG. 3, the peak in the vicinity 0.9 to 2.0 ppm is
attributable to a proton derived from a cyclohexane ring, the peak
in the vicinity 2.6 to 2.7 ppm is attributable to a proton derived
from a succinic acid skeleton, the peak in the vicinity 3.9 to 4.2
ppm is attributable to a proton of methylene derived from
cyclohexanedimethanol which is ester-bonded, the peak in the
vicinity 4.5 ppm is attributable to a proton of methylene at the
allyl position, the peak in the vicinity 5.3 ppm is attributable to
a proton in the terminal of the double bond at the allyl position,
and the peak in the vicinity 5.9 ppm is attributable to a proton in
the inner side of the double bond at the allyl position.
[0126] In FIG. 4, the peak of 1736 cm.sup.-1 is absorption by the
carbonyl stretching vibration of the carboxyl group.
[0127] Sample B was analyzed by gas chromatography (GC-14B:
manufactured by Shimadzu Corp., hydrogen flame ionization detector,
column used: OV-17 of 0.5 m, temperature condition: 160.degree. C.
and constant) and found to contain 11.8% by mass of diallyl
succinate.
PRODUCTION EXAMPLE 3
[0128] Into a 1 l three-neck flask with a distillation unit, 1,000
g of dimethyl 2-methylsuccinate, 1,441 g of allyl alcohol, 25 g of
potassium acetate and 5 g of calcium hydroxide were charged. The
system was heated at 110.degree. C. in a nitrogen stream, and
methanol generated was distilled off. The reaction was continued
until a theoretical amount of methanol was distilled off and when
385.7 g (97%) was distilled off, the reactor was cooled. The
resulting reaction solution was filtered by suction using a No. 5C
Kiriyama funnel to separate the solid matters in the reaction
solution. Thereafter, the solution was purified by distillation
under reduced pressure, as a result, 1,200 g of diallyl
2-methylsuccinate was obtained as a colorless transparent
liquid.
[0129] Into a 1 l three-neck flask with a distillation unit, 640 g
of diallyl 2-methylsuccinate, 336 g of 1,4-cyclohexanedimethanol
and 0.639 g of dibutyltin oxide were charged. The system was heated
at 180.degree. C. in a nitrogen stream and allyl alcohol generated
was distilled off. When about 190 g of allyl alcohol was distilled
off, the pressure within the reaction system was reduced to 1.33
kPa to increase the distillation rate of allyl alcohol. After a
theoretical amount (270.7 g) of allyl alcohol was distilled off,
the system was heated for another one hour and then kept at
190.degree. C. and 0.13 kPa for one hour. Thereafter, the reactor
was cooled and, as a result, 705 g of an allyl ester compound was
obtained (hereinafter referred to as "Sample C"). FIG. 5 and FIG. 6
show 400 MHz .sup.1H-NMR spectrum (solvent: CDCl.sub.3) and FT-IR
spectrum of Sample C, respectively.
[0130] In FIG. 5, the peak in the vicinity of 0.9 to 2.0 ppm is
attributable to a proton derived from a cyclohexane ring, with the
peak in the vicinity of 1.2 ppm being a peak derived from the
branched methyl group in succinic acid, the peak in the vicinity of
2.4 to 3.0 ppm is attributable to a proton derived from
2-methylsuccinic acid skeleton, the peak in the vicinity of 3.9 to
4.2 ppm is attributable to a proton of methylene derived from
cyclohexanedimethanol which is ester-bonded, the peak in the
vicinity of 4.6 ppm is attributable to a proton of methylene at the
allyl position, the peak in the vicinity of 5.3 ppm is attributable
to a proton in the terminal of the double bond at the allyl
position, and the peak in the vicinity of 5.8 to 6.0 ppm is
attributable to a proton in the inner side of the double bond at
the allyl position.
[0131] In FIG. 6, the peak of 1738 cm.sup.-1 is absorption by the
carbonyl stretching vibration of the carboxyl group.
[0132] Sample C was analyzed by gas chromatography (GC-14B:
manufactured by Shimadzu Corp., hydrogen flame ionization detector,
column used: OV-17 of 0.5 m, temperature condition: 160.degree. C.
and constant) and found to contain 3.8% by mass of diallyl
2-methylsuccinate.
PRODUCTION EXAMPLE 4
[0133] Into a 3 l three-neck flask with a distillation unit, 660.6
g of succinic anhydride, 1,056 g of allyl alcohol, 1,000 ml of
benzene and 6.61 g (1% by mass based on succinic anhydride) of
concentrated sulfuric acid were charged. The system was heated at
100.degree. C. in a nitrogen stream and H.sub.2O generated was
distilled off. The reaction was continued until a theoretical
amount of H.sub.2O was distilled off and when 109 g (100% based on
the theoretical distillation amount of H.sub.2O) of H.sub.2O was
distilled off, the reactor was cooled. The resulting reaction
solution was neutralized with an aqueous NaOH solution and washed
with water. After benzene and excess allyl alcohol were distilled
off, the reaction solution was purified by distillation under
reduced pressure and, as a result, 1,130 g of diallyl succinate was
obtained as a colorless transparent liquid.
[0134] Into a 1 l three-neck flask with a distillation unit, 396.4
g of diallyl succinate, 328.5 g of
2,2-bis[4-(2-hydroxyethoxy)cyclohexyl]propa- ne (HBA-2, trade name,
produced by Nippon Nyukazai K.K.) and 0.4 g of dibutyltin oxide
were charged. The system was heated at 180.degree. C. in a nitrogen
stream and the allyl alcohol generated was distilled off. When
about 81.3 g of allyl alcohol was distilled off, the pressure
within the reaction system was reduced to 1.33 kPa to increase the
distillation rate of allyl alcohol. After a theoretical amount
(116.2 g) of allyl alcohol was distilled off, the system was heated
for another one hour and then kept at 190.degree. C. and 0.13 kPa
for one hour. Thereafter, the reactor was cooled and, as a result,
256 g of an allyl ester compound was obtained (hereinafter referred
to as "Sample D"). FIG. 7 and FIG. 8 show 400 MHz .sup.1H-NMR
spectrum (solvent: CDCl.sub.3) and FT-IR spectrum of Sample D,
respectively.
[0135] In FIG. 7, the peak in the vicinity 0.6 to 0.8 ppm is
attributable to a proton derived from a propane skeleton, the peak
in the vicinity 0.9 to 2.2 ppm is attributable to a proton derived
from a cyclohexane ring, the peak in the vicinity 2.6 ppm is
attributable to a proton derived from a succinic acid skeleton, the
peak in the vicinity 3.6 is attributable to a proton of methylene
derived from cyclohexanedimethanol which is ester-bonded, the peak
in the vicinity 4.6 ppm is attributable to a proton of methylene at
the allyl position, the peak in the vicinity 5.3 ppm is
attributable to a proton in the terminal of the double bond at the
allyl position, and the peak in the vicinity 5.8 to 6.0 ppm is
attributable to a proton in the inner side of the double bond at
the allyl position.
[0136] In FIG. 8, the peak of 1737 cm.sup.-1 is absorption by the
carbonyl stretching vibration of the carboxyl group.
[0137] Sample D was analyzed by gas chromatography (GC-14B:
manufactured by Shimadzu Corp., hydrogen flame ionization detector,
column used: OV-17 of 0.5 m, temperature condition: 160.degree. C.
and constant) and found to contain 12.3% by mass of diallyl
succinate.
[0138] In the following examples, Samples A to D were diluted so as
to decrease the viscosity, using the compound of the following
structural formula (23) or the following structural formula (28).
14
[0139] The kind and composition of each diluted compound are shown
in Table 1.
EXAMPLE 1
Production of Composition for Plastic Lens
[0140] As shown in Table 1, 40.0 parts by mass of the allyl ester
compound as Sample A, 60.0 parts by mass of the compound
represented by structural formula (24) and 3 parts by mass of
diisopropylperoxy dicarbonate (IPP) were blended and mixed with
stirring to form a completely homogeneous solution composition. The
viscosity at this time was measured. Thereafter, a vessel
containing this solution was placed in a desiccator capable of
depressurization and the pressure was reduced by a vacuum pump for
about 15 minutes to deaerate gases in the solution. The resulting
solution composition was injected by a syringe into a mold
fabricated from a glass-made mold for ophthalmic plastic lenses and
a resin-made gasket, while taking care to prevent intermixing of
gas, and then cured in an oven, according to a temperature rising
program, under heating at 40.degree. C. for 7 hours, heating at
from 40 to 60.degree. C. for 10 hours, heating at from 60 to
80.degree. C. for 3 hours, heating at 80.degree. C. for 1 hour and
heating at 85.degree. C. for 2 hours.
[0141] The lens obtained was measured on the refractive index, Abbe
number, Barcol hardness and curing shrinkage in percentage. The
results are shown in Table 1.
1 TABLE 1 Comparative Comparative Example 1 Example 2 Example 3
Example 4 Example 5 Example 1 Example 2 Blending Compound of
structural 60.0 100 (parts by formula (23) mass) Compound of
structural 60.0 60.0 30.0 40.0 formula (28) Sample A 40.0 Sample B
40.0 Sample C 40.0 Sample D 70.0 60.0 CR-39 100 Viscosity
(25.degree.) (mPa .multidot. s) 144 2160 200 180 136 25 10
Initiator IPP (parts by mass) 3 3 3 3 3 3 3 Physical Refractive
index (n.sub.D) 1.525 1.516 1.525 1.518 1.521 1.503 1.517
properties Abbe number 53.3 59.7 53.6 57.7 54.9 51.6 56.1 of cured
Barcol hardness 25 30 30 13 22 29 47 product Specific gravity 1.210
1.198 1.210 1.189 1.194 1.316 1.188 Curing shrinkage in 7.4 9.0 7.3
6.1 6.2 12.8 11.6 percentage
EXAMPLES 2 TO 5 AND COMPARATIVE EXAMPLES 1 AND 2
Production of Composition for Plastic Lenses
[0142] Compositions were prepared by the blending shown in Table 1
and measured on the viscosity and after the curing, on the
refractive index, Abbe number, Barcol hardness and curing shrinkage
in percentage, in the same manner as in Example 1. The results are
shown in Table 1.
EXAMPLES 6 TO 10 AND COMPARATIVE EXAMPLES 3 AND 4
Production of Plastic Lens
[0143] A vessel containing a solution having each composition shown
in Table 1 (compositions of Examples 1 to 5 and Comparative
Examples 1 and 2) was placed in a desiccator capable of
depressurization and the pressure was reduced by a vacuum pump for
about 15 minutes to deaerate gases in the solution. The resulting
solution composition was injected by a syringe into a mold
(thickness: 3 mm) fabricated from a glass-made mold for ophthalmic
plastic lenses and a resin-made gasket, while taking care to
prevent intermixing of gas, and then cured in an oven, according to
a temperature rising program, under heating at 40.degree. C. for 3
hours, heating at from 40 to 85.degree. C. for 3 hours, and heating
at 85.degree. C. for 2 hours.
[0144] According to the method described above, whether the cured
product was cracked or not at the curing was observed with an eye.
The results are shown in Table 2.
2 TABLE 2 Example Comparative Comparative Example 6 Example 7
Example 8 Example 9 10 Example 3 Example 4 Blending Compound of
structural 60.0 100 (parts formula (23) by mass) Compound of
structural 60.0 60.0 30.0 40.0 formula (28) Sample A 40.0 Sample B
40.0 Sample C 40.0 Sample D 70.0 60.0 CR-39 100 Viscosity
(25.degree.) (mpa .multidot. s) 144 2160 200 180 136 25 10
Initiator IPP (parts by mass) 3 3 3 3 3 3 3 Cracked or not at
curing None None None None None Cracked Cracked
EXAMPLE 11
Production of Plastic Lens
[0145] As shown in Table 3, 95.0 parts by mass of diethylene glycol
bisallyl carbonate (CR-39, trade name, produced by PPG), 5.0 parts
by mass of Sample A and 3 parts by mass of diisopropylperoxy
dicarbonate (IPP) were blended and mixed with stirring to form a
completely homogeneous solution composition. The viscosity at this
time was measured. Thereafter, a vessel containing this solution
was placed in a desiccator capable of depressurization and the
pressure was reduced by a vacuum pump for about 15 minutes to
deaerate gases in the solution. The resulting solution composition
was injected by a syringe into a mold fabricated from a glass-made
mold for ophthalmic plastic lenses and a resin-made gasket, while
taking care to prevent intermixing of gas, and then cured in an
oven, according to a temperature rising program, under heating at
40.degree. C. for 7 hours, heating at from 40 to 60.degree. C. for
10 hours, heating at from 60 to 80.degree. C. for 3 hours, heating
at 80.degree. C. for 1 hour and heating at 85.degree. C. for 2
hours.
[0146] The lens obtained was measured on the refractive index, Abbe
number and Barcol hardness and evaluated on the dyeing speck. The
results are shown in Table 3.
[0147] In Example 11, the viscosity (at 25.degree. C.) of the
compound before curing was less than 100 mPa.s.
EXAMPLES 12 TO 15 AND COMPARATIVE EXAMPLE 5
Production of Plastic Lens
[0148] Compositions were prepared by the blending shown in Table 3
and subjected to measurement on the viscosity and after the curing,
on the refractive index, Abbe number and Barcol hardness and to
evaluation on the dyeing speck, in the same manner as in Example 6.
The results are shown in Table 3.
[0149] In Examples 12 to 15, the viscosity (25.degree. C.) of each
compound before curing was less than 100 mPa.s.
3 TABLE 3 Comparative Example 11 Example 12 Example 13 Example 14
Example 15 Example 5 Blending (parts CR-39 95.0 90.0 95.0 95.0 85.0
100 by mass) Sample A 5.0 10.0 Sample B 5.0 Sample C 5.0 Sample D
15.0 Initiator IPP (parts by mass) 3 3 3 3 3 3 Physical Refractive
index (n.sub.D) 1.503 1.499 1.501 1.503 1.501 1.499 properties Abbe
number (.nu..sub.D) 56.1 60.0 53.6 56.1 64.2 51.6 Barcol hardness
27 23 27 29 25 29 Dyeing failure (number 1 1 1 1 0 8 of
defectives)
[0150] It is apparent from the results in Tables 1 and 2 that,
according to the present invention, a plastic lens having high Abbe
number and small curing shrinkage in percentage can be produced and
at the same time, the curing time can be shortened.
[0151] Furthermore, it is apparent from the result in Table 3 that
the plastic lens material of the present invention has an effect of
improving dyeing of the polyethylene glycol bis(allyl carbonate)
resin.
INDUSTRIAL APPLICABILITY
[0152] As verified in the foregoing pages, it is apparent that the
compound of the present invention is a compound having small curing
shrinkage in percentage as compared with conventional polyethylene
glycol bis(allyl carbonate) resin and a cured product having high
Abbe number can be produced therefrom similarly to the polyethylene
glycol bis(allyl carbonate) resin.
[0153] Accordingly, more efficient production of plastic lenses can
be attained than in conventional methods using polyethylene glycol
bis(allyl carbonate) resin.
[0154] Furthermore, when the compound of the present invention is
used by mixing it with polyethylene glycol bis(allyl carbonate)
resin, dyeing specks generated in the dyeing of polyethylene glycol
bis(allyl carbonate) resin can be improved.
* * * * *