U.S. patent application number 10/644776 was filed with the patent office on 2004-03-18 for ocular lens material and process for producing the same.
This patent application is currently assigned to Menicon Co., Ltd.. Invention is credited to Ito, Eri, Kawai, Tetsuji, Nakada, Kazuhiko, Nishibayashi, Misako, Oono, Sadanori.
Application Number | 20040054106 10/644776 |
Document ID | / |
Family ID | 15063674 |
Filed Date | 2004-03-18 |
United States Patent
Application |
20040054106 |
Kind Code |
A1 |
Ito, Eri ; et al. |
March 18, 2004 |
Ocular lens material and process for producing the same
Abstract
An ocular lens material comprising a siloxane-containing polymer
obtained by polymerizing a monomer mixture containing (A) a
siloxane macromonomer having at least two active unsaturated groups
and a number average molecular weight of 2,000 to 100,000; and (B)
a vinyl ester of lower fatty acid as essential components. An
ocular lens material comprising a polymer obtained by
saponification of the siloxane-containing polymer. Processes for
producing the ocular lens materials. The ocular lens materials are
excellent not only in lipid-stain resistance, wettability and
oxygen permeability, but also in flexibility, particularly, shape
recovery at the same time.
Inventors: |
Ito, Eri; (Kasugai-shi,
JP) ; Kawai, Tetsuji; (Kasugai-shi, JP) ;
Oono, Sadanori; (Kasugai-shi, JP) ; Nakada,
Kazuhiko; (Kasugai-shi, JP) ; Nishibayashi,
Misako; (Kasugai-shi, JP) |
Correspondence
Address: |
ARMSTRONG, KRATZ, QUINTOS, HANSON & BROOKS, LLP
1725 K STREET, NW
SUITE 1000
WASHINGTON
DC
20006
US
|
Assignee: |
Menicon Co., Ltd.
Nagoya-shi
JP
|
Family ID: |
15063674 |
Appl. No.: |
10/644776 |
Filed: |
August 21, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10644776 |
Aug 21, 2003 |
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09926459 |
Nov 7, 2001 |
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09926459 |
Nov 7, 2001 |
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PCT/JP00/02939 |
May 9, 2000 |
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Current U.S.
Class: |
526/279 |
Current CPC
Class: |
C08F 218/04 20130101;
C08L 51/085 20130101; C08F 290/06 20130101; C08F 8/12 20130101;
A61L 27/18 20130101; C08F 290/068 20130101; C08F 218/08 20130101;
G02B 1/043 20130101; C08F 230/08 20130101; C08F 283/12 20130101;
G02B 1/043 20130101; C08L 51/085 20130101; A61L 27/18 20130101;
C08L 83/10 20130101; C08L 51/085 20130101; C08L 2666/02 20130101;
C08F 8/12 20130101; C08F 230/08 20130101; C08F 230/08 20130101;
C08F 220/281 20200201; C08F 230/08 20130101; C08F 218/08 20130101;
C08F 8/12 20130101; C08F 290/068 20130101; C08F 290/068 20130101;
C08F 230/08 20130101; C08F 290/068 20130101; C08F 218/08 20130101;
C08F 218/08 20130101; C08F 220/20 20130101; C08F 230/08 20130101;
C08F 230/08 20130101; C08F 218/08 20130101 |
Class at
Publication: |
526/279 |
International
Class: |
C08F 230/08; C08F
130/08; C08F 030/08 |
Foreign Application Data
Date |
Code |
Application Number |
May 12, 1999 |
JP |
131678/1999 |
Claims
1. An ocular lens material comprising a siloxane-containing polymer
obtained by polymerizing a monomer mixture containing (A) a
siloxane macromonomer having at least two active unsaturated groups
and a number average molecular weight of 2,000 to 100,000; and (B)
a vinyl ester of lower fatty acid as essential components.
2. The ocular lens material of claim 1, wherein said monomer
mixture further contains (C) a silicon-containing monomer.
3. The ocular lens material of claim 1, wherein said monomer
mixture further contains (D) a fluorine-containing monomer.
4. The ocular lens material of claim 2, wherein the weight ratio of
the total of said siloxane macromonomer (A) and said
silicon-containing monomer (C) to said vinyl ester of lower fatty
acid (B), the total weight of (A) and (C)/the weight of (B), is
30/70 to 90/10.
5. The ocular lens material of claim 3, wherein the weight ratio of
the total of said siloxane macromonomer (A), said vinyl ester of
lower fatty acid (B) and said silicon-containing monomer (C) to
said fluorine-containing monomer (D), the total weight of (A), (B)
and (C)/the weight of (D), is at least 20/80.
6. The ocular lens material of claim 2, wherein the weight ratio of
said siloxane macromonomer (A) to said silicon-containing monomer
(C), the weight of (A)/the weight of (C), is at least 20/80.
7. The ocular lens material of claim 1, wherein said siloxane
macromonomer (A) is a macromonomer represented by the formula
(I-1):
A.sup.1-(-U.sup.1--S.sup.1--).sub.n--U.sup.2--S.sup.2--U.sup.3-A.sup.2
(I-1) wherein each of A.sup.1 and A.sup.2 is independently an
active unsaturated group, an active unsaturated group having an
alkylene group having 1 to 20 carbon atoms or an active unsaturated
group having an alkylene glycol group having 1 to 20 carbon atoms;
U.sup.1 is a diurethane type group which contains urethane bonds
formed with adjacent A.sup.1 and adjacent S.sup.1 on both sides or
which contains urethane bonds with adjacent two S.sup.1 on both
sides; U.sup.2 is a diurethane type group which contains urethane
bonds formed with adjacent A.sup.1 and adjacent S.sub.2 on both
sides or which contains urethane bonds with adjacent S.sup.1 and
adjacent S.sub.2 on both sides; U.sup.3 is a diurethane type group
which contains urethane bonds formed with adjacent S.sup.2 and
adjacent A.sup.2 on both sides; each of S.sup.1 and S.sub.2 is
independently a group represented by the formula: 19in which each
of R.sup.1 and R.sup.2 is independently an alkylene group having 1
to 20 carbon atoms, each of R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 is independently a linear, branched or cyclic
alkyl group having 1 to 20 carbon atoms which may be substituted
with a fluorine atom, or a group represented by the formula:
A.sup.3-U.sup.4--R--O--R.sup.2- in which A.sup.3 is an active
unsaturated group, an active unsaturated group having an alkylene
group having 1 to 20 carbon atoms or an active unsaturated group
having an alkylene glycol group having 1 to 20 carbon atoms,
U.sup.4 is a urethane type group which contains urethane bonds
formed with adjacent A.sup.3 and adjacent R.sup.1 on both sides,
each of R.sup.1 and R.sup.2 is the same as the above, x is an
integer of 1 to 1500, y is 0 or an integer of 1 to 1499, and x+y is
an integer of 1 to 1500; and n is 0 or an integer of 1 to 10; or a
macromonomer represented by the formula (I-2):
B.sup.1--S.sup.3--B.sup.1 (I-2) wherein B.sup.1 is an active
unsaturated group having urethane bond, and S.sup.3 is a group
represented by the formula: 20in which each of R.sup.1 and R.sup.2
is independently an alkylene group having 1 to 20 carbon atoms,
each of R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is
independently a linear, branched or cyclic alkyl group having 1 to
20 carbon atoms which may be substituted with a fluorine atom, or a
group represented by the formula: A.sup.3--U.sup.4--R.sup.1
--O--R.sup.2- in which A.sup.3 is an active unsaturated group, an
active unsaturated group having an alkylene group having 1 to 20
carbon atoms or an active unsaturated group having an alkylene
glycol group having 1 to 20 carbon atoms, U.sup.4 is a urethane
type group which contains urethane bonds formed with adjacent
A.sup.3 and adjacent R.sup.1 on both sides, each of R.sup.1 and
R.sup.2 is the same as the above, x is an integer of 1 to 1500, y
is 0 or an integer of 1 to 1499, and x+y is an integer of 1 to
1500.
8. The ocular lens material of claim 1, wherein said vinyl ester of
lower fatty acid (B) is a compound represented by the formula (II):
21wherein R is hydrogen atom or an alkyl group having 1 to 15
carbon atoms which may be substituted with a halogen atom.
9. The ocular lens material of claim 1, wherein said vinyl ester of
lower fatty acid (B) is vinyl acetate, vinyl propionate or vinyl
pivalate.
10. The ocular lens material of claim 2, wherein said
silicon-containing monomer (C) is a silicon-containing
(meth)acrylate.
11. The ocular lens material of claim 2, wherein said
silicon-containing monomer (C) is tris(trimethylsiloxy)silylpropyl
acrylate.
12. The ocular lens material of claim 3, wherein said
fluorine-containing monomer (D) is a fluoroalkyl
(meth)acrylate.
13. An ocular lens material comprising a polymer prepared by
saponifying a siloxane-containing polymer obtained by polymerizing
a monomer mixture containing (A) a siloxane macromonomer having at
least two active unsaturated groups and a number average molecular
weight of 2,000 to 100,000; and (B) a vinyl ester of lower fatty
acid as essential components.
14. A process for producing an ocular lens material, characterized
by preparing a siloxane-containing polymer by polymerization of a
monomer mixture containing (A) a siloxane macromonomer having at
least two active unsaturated groups and a number average molecular
weight of 2,000 to 100,000; and (B) a vinyl ester of lower fatty
acid as essential components; and then subjecting said
siloxane-containing polymer to saponification.
15. The process of claim 14, wherein said saponification is carried
out by alkali treatment.
16. The process of claim 15, wherein a methanol aqueous solution
containing sodium hydroxide in a concentration of 0.01 to 1 mol/L
is used for said alkali treatment as a treatment solution.
17. The process of claim 16, wherein the volume ratio of methanol
to water in said methanol aqueous solution, methanol/water, is
30/70 to 90/10.
18. The process of claim 15, wherein after preparing said
siloxane-containing polymer, a dye is dispersed in the
siloxane-containing polymer and then, said dye is fixed to the
siloxane-containing polymer during said saponification by said
alkali treatment.
19. The process of claim 14, wherein after preparing said
siloxane-containing polymer, photo-irradiation is conducted and
saponification is carried out subsequently.
20. The process of claim 19, wherein said photo-irradiation is
conducted by using ultraviolet ray whose wavelength is at most 380
nm.
21. The process of claim 19, wherein said photo-irradiation is
conducted out by using ultraviolet ray whose wavelength is at most
300 nm.
22. The process of claim 19, wherein said photo-irradiation is
conducted out for 0.1 to 600 minutes.
Description
TECHNICAL FIELD
[0001] The present invention relates to an ocular lens material and
a process for producing the same. More particularly, the present
invention relates to an ocular lens material suitably used for, for
example, soft contact lens and soft intraocular lens, which is
excellent not only in lipid-stain resistance, wettability and
oxygen permeability, but also in flexibility, particularly, shape
recovery at the same time, and a process for producing the ocular
lens material.
BACKGROUND ART
[0002] Recently, consumer's demands for contact lenses, for
example, are directed to a soft contact lens with high oxygen
permeability, and for intraocular lenses, for example, a foldable
intraocular lens. For these reasons, various materials having
properties such as high oxygen permeability and excellent
flexibility in particular are suggested.
[0003] For instance, a contact lens comprising a copolymer obtained
by polymerizing siloxanyl (meth)acrylate and vinyl ester is
disclosed in Japanese Unexamined Patent Publication No.
163811/1988, and a contact lens comprising a copolymer obtained by
polymerizing siloxanyl (meth)acrylate, a vinyl ester, and vinyl
(meth)acrylate and/or allyl (meth)acrylate is disclosed in Japanese
Unexamined Patent Publication No. 301919/1988.
[0004] However, it cannot be said that these contact lenses are
excellent in flexibility taking the monomer mixture into account
though all of them have high oxygen permeability and excellent
stain resistance.
[0005] In addition to the above, a water-containing contact lens
obtained by saponifying a polymer comprising a (meth)acrylate
polymer, which has at least one polymerizable group on average, a
vinyl monomer, a vinyl ester of fatty acid and a crosslinkable
monomer, is disclosed in Japanese Unexamined Patent Publication No.
102471/1994, and a silicone-containing hydrogel material formed
from a polymer prepared by using a monomer mixture comprising a
polysiloxane pre-polymer, a bulk polysiloxanylalkyl (meth)acrylate
monomer and a hydrophilic monomer is disclosed in Japanese
Unexamined Patent Publication No. 508063/1995. Also, in
International Publication No. WO 97/09169, an ocular lens material
obtained by hydrating, by using a water-soluble organic solvent, a
polymer prepared by solution polymerization of a polymerizable
silicon-containing compound and/or a polymerizable
fluorine-containing compound, hydroxyalkyl (meth)acrylate, and a
cross-linked compound is disclosed.
[0006] However, though these contact lenses and materials have
properties such as high oxygen permeability, lipid-stain resistance
and wettability, they only have one or a plurality of such
properties, and do not show flexibility, particularly shape
recovery, which is one of the important properties required for an
ocular lens material, in particular, a soft ocular lens
material.
[0007] As mentioned above, ocular lens materials having not only
high oxygen permeability, excellent lipid-stain resistance and
superior wettability but also shape recovery at the same time have
not been provided yet. Accordingly, development of such materials
as the above has been expected.
[0008] The present invention has been carried out from the
viewpoint of the above prior arts. An object of the present
invention is to provide an ocular lens material which has not only
high oxygen permeability, excellent wettability and superior
lipid-stain resistance, but also flexibility, particularly shape
recovery at the same time, and an easy process for producing the
ocular lens material.
DISCLOSURE OF INVENTION
[0009] The present invention relates to
[0010] (1) an ocular lens material comprising a siloxane-containing
polymer obtained by polymerizing a monomer mixture containing
[0011] (A) a siloxane macromonomer having at least two active
unsaturated groups and a number average molecular weight of 2,000
to 100,000; and
[0012] (B) a vinyl ester of lower fatty acid as essential
components;
[0013] (2) an ocular lens material comprising a polymer prepared by
saponifying a siloxane-containing polymer obtained by polymerizing
a monomer mixture containing
[0014] (A) a siloxane macromonomer having at least two active
unsaturated groups and a number average molecular weight of 2,000
to 100,000; and
[0015] (B) a vinyl ester of lower fatty acid as essential
components; and
[0016] (3) a process for producing the above ocular lens material,
characterized by preparing a siloxane-containing polymer by
polymerization of a monomer mixture containing
[0017] (A) a siloxane macromonomer having at least two active
unsaturated groups and a number average molecular weight of 2,000
to 100,000; and
[0018] (B) a vinyl ester of lower fatty acid as essential
components; and then subjecting said siloxane-containing polymer to
saponification.
BEST MODE FOR CARRYING OUT THE INVENTION
[0019] The ocular lens material of the present invention,
hereinafter referred to as an ocular lens material I, comprises a
siloxane-containing polymer obtained by polymerizing a monomer
mixture containing (A) a siloxane macromonomer having at least two
active unsaturated groups and a number average molecular weight of
2,000 to 100,000; and (B) a vinyl ester of lower fatty acid as
essential components.
[0020] The siloxane macromonomer (A) is a component which mainly
imparts flexibility as typified by shape recovery and mechanical
strength to the ocular lens material I.
[0021] The active unsaturated group in the siloxane macromonomer
(A) is an active unsaturated group which can be subjected to
radical polymerization. Examples of the active unsaturated group
are (meth)acryloyl group, vinyl group, allyl group,
(meth)acryloyloxy group, vinyl carbamate group and the like. Among
these, acryloyloxy group and vinyl group are preferable from the
viewpoint that they can impart excellent flexibility to the ocular
lens material I and copolymerizability with other monomers is
excellent.
[0022] In the instant specification, "(meth)acryl - - -" means
"acryl - - - and/or methacryl - - - ".
[0023] It is desired that a number average molecular weight of the
siloxane macromonomer (A) is at least 2,000, preferably at least
2,500 and more preferably at least 3,000 in order to impart
excellent flexibility to the ocular lens material I without
increasing hardness extremely. Also, it is desired that a number
average molecular weight of the siloxane macromonomer (A) is at
most 100,000, preferably at most 50,000, more preferably at most
10,000 not to make shape recovery inferior though the ocular lens
material I becomes softened.
[0024] As the siloxane macromonomer (A), for example, the
macromonomer of dialkyl siloxane having an active unsaturated group
described in U.S. Pat. No. 4,189,546 specification can be used to
obtain the aimed ocular lens material I.
[0025] Usually, many siloxane macromonomers are bad in wettability
and relatively lack mechanical strength when each of the
macromonomers is homopolymerized. Accordingly, as the siloxane
macromonomer (A) used in the present invention, a siloxane
macromonomer having a urethane group represented by the formula:
1
[0026] in the macromonomer structure is preferable in order to
improve wettability.
[0027] When the siloxane macromonomer (A) contains the above
urethane group, suitable mechanical strength and excellent
wettability can be imparted to the ocular lens material I. It is
desired that the number of the urethane group in the siloxane
macromonomer (A) is at least 2, preferably at least 4 on average in
order to impart sufficient mechanical strength and wettability. On
the other hand, when too many urethane groups are introduced,
flexibility of the ocular lens material I decreases. Therefore, it
is desired that the average number of the urethane group in the
siloxane macromonomer (A) is at most 20, preferably at most 14.
[0028] In the present invention, the macromonomer to which
hydrophilic parts are introduced at the both ends of the siloxane
structure described in U.S. Pat. No. 4,495,361 specification or
U.S. Pat. No. 5,807,944 specification can also be used as the
siloxane macromonomer (A) in order to obtain the ocular lens
material I whose flexibility, particularly shape recovery, is
improved.
[0029] In the present invention, as the siloxane macromonomer (A),
a macromonomer represented by the formula (I-1) is preferably
used:
A.sup.1-(-U.sup.1--S.sup.1--).sub.n--U.sup.2--S.sup.2--U.sup.3-A.sup.2
(I-1)
[0030] wherein each of A.sup.1 and A.sup.2 is independently an
active unsaturated group, an active unsaturated group having an
alkylene group having 1 to 20 carbon atoms or an active unsaturated
group having an alkylene glycol group having 1 to 20 carbon
atoms;
[0031] U.sup.1 is a diurethane type group which contains urethane
bonds formed with adjacent A.sup.1 and adjacent S.sup.1 on both
sides or which contains urethane bonds with adjacent two S.sup.1 on
both sides;
[0032] U.sup.2 is a diurethane type group which contains urethane
bonds formed with adjacent A.sup.1 and adjacent S.sup.2 on both
sides or which contains urethane bonds with adjacent S.sup.1 and
adjacent S.sup.2 on both sides;
[0033] U.sup.3 is a diurethane type group which contains urethane
bonds formed with adjacent S.sup.2 and adjacent A.sup.2 on both
side;
[0034] each of S.sup.1 and S.sub.2 is independently a group
represented by the formula: 2
[0035] wherein each of R.sup.1 and R.sup.2 is independently an
alkylene group having 1 to 20 carbon atoms, each of R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is independently a
linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
which may be substituted with a fluorine atom, or a group
represented by the formula:
A.sup.3-U.sup.4--R.sup.1--O--R.sup.2-
[0036] in which A.sup.3 is an active unsaturated group, an active
unsaturated group having an alkylene group having 1 to 20 carbon
atoms or an active unsaturated group having an alkylene glycol
group having 1 to 20 carbon atoms, U.sup.4 is a urethane type group
which contains urethane bonds formed with adjacent A.sup.3 and
adjacent R.sup.1 on both sides, and each of R.sup.1 and R.sup.2 is
the same as above, x is an integer of 1 to 1500, y is 0 or an
integer of 1 to 1499, and x+y is an integer of 1 to 1500;
[0037] n is 0 or an integer of 1 to 10;
[0038] or a macromonomer represented by the following formula (I-2)
is preferably used:
B.sup.1--S.sup.3--B.sup.1 (I-2)
[0039] wherein B.sup.1 is an active unsaturated group having
urethane bond; and
[0040] S.sup.3 is a group represented by the formula: 3
[0041] wherein each of R.sup.1 and R.sup.2 is independently an
alkylene group having 1 to 20 carbon atoms, each of R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is independently a
linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
which may be substituted with fluorine atom, or a group represented
by the formula:
A.sup.3-U.sup.4--R.sup.1--O--R.sup.2-
[0042] in which A.sup.3 is an active unsaturated group, an active
unsaturated group having an alkylene group having 1 to 20 carbon
atoms or an active unsaturated group having an alkylene glycol
group having 1 to 20 carbon atoms, U.sup.4 is a urethane type group
which contains urethane bonds formed with adjacent A.sup.3 and
adjacent R.sup.1 on both sides, and each of R.sup.1 and R.sup.2 is
the same as above, x is an integer of 1 to 1500, y is 0 or an
integer of 1 to 1499, and x+y is an integer of 1 to 1500.
[0043] In the formula (I-1), examples of the active unsaturated
group represented by A.sup.1 and A.sup.2 are (meth)acryloyl group,
vinyl group, allyl group, (meth)acryloyloxy group, vinyl carbamate
group and the like as mentioned above. Among them, acryloyloxy
group and vinyl group are preferable and acryloyloxy group is
particularly preferable, since more excellent flexibility can be
imparted to the ocular lens material I and copolymerizability with
other monomers is excellent.
[0044] When the above active unsaturated group has an alkylene
group or an alkylene glycol group, it is desired that the number of
carbon atoms of the alkylene group or the alkylene glycol group is
1 to 20, preferably 1 to 10.
[0045] In the formula (I-1), as to the group S.sup.1 or S.sub.2
represented by the formula: 4
[0046] wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, x and y is the same as above, each of
R.sup.1 and R.sup.2 is preferably an alkylene group having 1 to 5
carbon atoms, and each of R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 is preferably an alkyl group having 1 to 5
carbon atoms. A.sup.3 in the formula:
A.sup.3-U.sup.4--R.sup.1--O--R.sup.2-, which represents R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7 or R.sup.8, is the same active
unsaturated group as the above-exemplified one. When the active
unsaturated group has an alkylene group or an alkylene glycol
group, it is desired that the number of carbon atoms of the
alkylene group or the alkylene glycol group is 1 to 20, preferably
1 to 10 carbon atoms. In addition, it is desired that x is an
integer of 1 to 500, y is 0 or an integer of 1 to 499, and x+y is
an integer of 1 to 500.
[0047] In the formula (I-1), it is desired that n is 0 or an
integer of 1 to 5.
[0048] In the formula (I-2), examples of the active unsaturated
group having urethane bond, represented by B.sup.1 are
(meth)acryloylisocyanate group, (meth)acryloyloxyisocyanate group,
allylisocyanate group, vinylbenzylisocyanate group and the like.
The group represented by S.sup.3 in the formula (I-2) is the same
as the group represented by S.sup.1 or S.sup.2 in the above formula
(I-1).
[0049] Among the above macromonomers, because flexibility such as
shape recovery and mechanical strength can be greatly imparted to
the lens material, a macromonomer represented by the formula:
A.sup.1-U.sup.2--S.sup.2--U.sup.3-A.sup.2
[0050] wherein each of A.sup.1, A.sup.2, U.sup.2, U.sup.3 and
S.sup.2 is the same as above; and a macromonomer represented by the
formula:
A.sup.1-(-U.sup.1--S.sup.1--).sub.n.--U.sup.2--S.sup.2--U.sup.3-A.sup.2
[0051] wherein each of A.sup.1, A.sup.2, U.sup.1, U.sup.2, U.sup.3,
S.sup.1 and S.sup.2 is the same as above, and n' is an integer of 1
to 4, are preferable. In particular, a macromonomer represented by
the formula: 5
[0052] wherein A is a group represented by the formula: 6
[0053] and a is an integer of 20 to 50, is preferable.
[0054] The above vinyl ester of lower fatty acid (B) is a component
which mainly imparts shape recovery to the ocular lens material I
and hydrophilic property to the ocular lens material II according
to the saponification mentioned below.
[0055] Typical examples of the vinyl ester of lower fatty acid (B)
is a compound represented by the formula (II): 7
[0056] wherein R is hydrogen atom or an alkyl group having 1 to 15
carbon atoms, which may be substituted with a halogen atom.
Concrete examples of the compound are vinyl formate, vinyl acetate,
vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate,
vinyl laurate, vinyl stearate, vinyl monochloroacetate, vinyl
monofluoroacetate, vinyl trichloroacetate, vinyl trifluoroacetate
and the like. These can be used alone or in admixture thereof.
[0057] Among the above vinyl esters of lower fatty acid (B),
because shape recovery and hydrophilic property can be greatly
imparted to the lens material, vinyl acetate, vinyl propionate and
vinyl pivalate are preferable. In particular, vinyl acetate is
preferable.
[0058] The siloxane-containing polymer which constitutes the ocular
lens material I of the present invention is prepared by
polymerizing the monomer mixture containing the siloxane
macromonomer (A) and the vinyl ester of lower fatty acid (B) as
essential components. The monomer mixture can also contain, for
instance, a silicon-containing monomer (C).
[0059] The above silicon-containing monomer (C) is preferably used
since it is a component which mainly imparts oxygen permeability
and further, flexibility, particularly shape recovery, to the
ocular lens material I.
[0060] Typical examples of the silicon-containing monomer (C) are a
silicon-containing (meth)acrylate such as
pentamethyldisiloxanylmethyl (meth)acrylate,
trimethylsiloxydimethylsilylpropyl (meth)acrylate,
methylbis(trimethylsiloxy) silylpropyl (meth)acrylate,
tris(trimethylsiloxy)silylpropyl (meth)acrylate, mono[methylbis(tri
methylsiloxy) siloxy]bis(trimethylsiloxy) silylpropyl
(meth)acrylate, tris[methylbis(trimethylsiloxy) siloxy]silylpropyl
(meth) acrylate, trimethylsilylmethyl (meth)acrylate,
trimethylsilylpropyl (meth)acrylate,
methylbis(trimethylsiloxy)silylethyltetramethyldisiloxanylmethyl
(meth) acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl
(meth)acrylate,
tetramethyltriisopropylcyclotetrasiloxybis(trimethylsilox- y)
silylpropyl (meth)acrylate or trimethylsiloxydimethylsilylpropyl
(meth)acrylate; a silicon-containing styrene derivative represented
by the formula: 8
[0061] wherein p is an integer of 1 to 15, q is 0 or 1 and r is an
integer of 1 to 15, such as tris(trimethylsiloxy)silylstyrene,
methylbis(trimethylsiloxy)silylstyrene, dimethylsilylstyrene,
trimethylsilylstyrene, tris(trimethylsiloxy)
siloxanyldimethylsilylstyren- e, [methylbis(trimethylsiloxy)
siloxanyl]dimethylsilylstyrene, pentamethyldisiloxanylstyrene,
heptamethyltrisiloxanylstyrene, nonamethyltetrasiloxanylstyrene,
pentadecamethylheptasiloxanylstyrene,
heneicosamethyldecasiloxanylstyrene,
heptacosamethyltridecasiloxanylstyre- ne,
hentriacontamethylpentadecasiloxanylstyrene,
trimethylsiloxypentamethy- ldisiloxymethylsilylstyrene,
tris(pentamethyldisiloxy) silylstyrene,
[tris(trimethylsiloxy)siloxanyl]bis(trimethylsiloxy)silylstyrene,
methylbis (heptamethyltrisiloxy) silylstyrene,
tris[methylbis(trimethylsi- loxy) siloxy]silylstyrene,
trimethylsiloxybis[tris(trimethylsiloxy) siloxy]silylstylene,
heptakis(trimethylsiloxy) trisiloxanylstyrene,
tris[tris(trimethylsiloxy) siloxy] silylstyrene,
[tris(trimethylsiloxy)he- xamethyltetrasiloxy]
[tris(trimethylsiloxy)-siloxy]trimethylsiloxysilylsty- rene,
nonakis(trimethylsiloxy)tetrasiloxanylstyrene,
methylbis(tridecamethylhexasiloxy) silylstyrene,
heptamethylcyclotetrasil- oxanylstyrene,
heptamethylcyclotetrasiloxybis(trimethylsiloxy)silylstyrene or
tripropyltetramethylcyclotetrasiloxanylstyrene; and the like. These
can be used alone or in admixture thereof.
[0062] Among the above silicon-containing monomers (C), because
high oxygen permeability and flexibility, in particular, shape
recovery can be greatly imparted to the ocular lens material I at
the same time, the silicon-containing (meth)acrylate is preferable.
In particular, tris(trimethylsiloxy)silylpropyl acrylate is
preferable.
[0063] Furthermore, the monomer mixture can also contain, for
instance, a fluorine-containing monomer (D), in addition to the
siloxane macromonomer (A), the vinyl ester of lower fatty acid (B)
and the silicon-containing monomer (C).
[0064] The fluorine-containing monomer (D) is a component which
mainly imparts oxygen permeability and flexibility to the ocular
lens material I, improving lipid-stain resistance at the same
time.
[0065] Typical examples of the fluorine-containing monomer (D) are
2,2, 2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl
(meth)acrylate, 2,2,3,3-tetrafluoro-t-pentyl (meth)acrylate,
2,2,3,4,4,4-hexafluorobutyl (meth)acrylate,
2,2,3,4,4,4-hexafluoro-t-hexy- l (meth)acrylate,
2,3,4,5,5,5-hexafluoro-2,4-bis(trifluoromethyl)pentyl
(meth)acrylate, 2,2,3,3,4,4-hexafluorobutyl (meth)acrylate,
2,2,2,2',2',2'-hexafluoroisopropyl (meth)acrylate,
2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylate, 2,2,3,3,4,4,5,
5-octafluoropentyl (meth)acrylate; a fluoroalkyl (meth)acrylate
represented by the formula: 9
[0066] wherein R.sub.1 is a fluoroalkyl group having 3 to 15 carbon
atoms and R.sub.2 is hydrogen atom or a methyl group, such as
3-perfluorobutyl-2-hydroxypropyl (meth)acrylate,
3-perfluorohexyl-2-hydro- xypropyl (meth)acrylate,
3-perfluorooctyl-2-hydroxypropyl (meth)acrylate,
3-(perfluoro-3-methylbutyl)-2-hydroxypropyl (meth)acrylate,
3-(perfluoro-5-methylhexyl)-2-hydroxypropyl (meth)acrylate or
3-(perfluoro-7-methyloctyl)-2-hydroxypropyl (meth)acrylate; and the
like.
[0067] Among them, fluoroalkyl acrylate is preferable since
flexibility can be greatly imparted to the ocular lens material I
particularly out of oxygen permeability, flexibility and
lipid-stain resistance.
[0068] Usually, many fluorine-containing compounds can impart
oxygen permeability and lipid-stain resistance to a material, but
are bad in wettability. To the contrary, a fluoroalkyl acrylate
having a hydroxyl group represented by the formula: 10
[0069] wherein R'.sub.1 is a perfluoroalkyl group having 3 to 15,
preferably 3 to 8, more preferably 4 to 6 carbon atoms is
particularly preferable from the viewpoint that flexibility and
wettability can be imparted to the ocular lens material I without
lacking oxygen permeability and lipid-stain resistance.
[0070] The proportion of the siloxane macromonomer (A), the vinyl
ester of lower fatty acid (B) and the silicon-containing monomer
(C) used as occasion demands is preferably defined as mentioned
below. That is, in order to impart sufficient flexibility,
mechanical strength and oxygen permeability to the ocular lens
material I, it is desired that the ratio of the total weight of the
siloxane macromonomer (A) and the silicon-containing monomer (C) to
the weight of the vinyl ester of lower fatty acid (B), the total
weight of (A) and (C)/the weight of (B), that is, when the
silicon-containing monomer (C) is not used, the weight of (A)/the
weight of (B), is at least 30/70, preferably at least 50/50. In
order to impart sufficient shape recovery and hydrophilic property
to the ocular lens material I, it is desired that the above ratio
is at most 90/10, preferably at most 80/20.
[0071] When the silicon-containing monomer (C) is used, the ratio
of the weight of the siloxane macromonomer (A) to the weight of the
silicon-containing monomer (C), the weight of (A)/the weight of
(C), is preferably defined as mentioned below. That is, in order to
impart sufficient mechanical strength to the ocular lens material I
without lowering shape recovery, it is desired that the weight of
(A)/the weight of (C) is at least 20/80, preferably at least 25/75.
In order to impart sufficient oxygen permeability to the ocular
lens material I, it is desired that the above ratio is at most
90/10, preferably at most 80/20.
[0072] The proportion of the siloxane macromonomer (A) and the
vinyl ester of lower fatty acid (B), and the silicon-containing
monomer (C) and the fluorine-containing monomer (D) which are used
as occasion demands is preferably defined as mentioned below. That
is, in order to impart effects from the siloxane macromonomer (A),
the vinyl ester of lower fatty acid (B) and the silicon-containing
monomer (C) sufficiently to the ocular lens material 1, it is
desired that the ratio of the total weight of siloxane macromonomer
(A), the vinyl ester of lower fatty acid (B) and the
silicon-containing monomer (C) to the weight of the
fluorine-containing monomer (D), the total weight of (A), (B) and
(C)/the weight of (D), is at least 20/80, preferably at least
40/60. In order to impart sufficient lipid-stain resistance in
particular to the ocular lens material I, it is desired that the
above ratio is at most 90/10, preferably at most 85/15.
[0073] As occasion demands, the monomer mixture can also contain a
crosslinkable compound (E) having at least two polymerizable
groups.
[0074] The above crosslinkable compound (E) is a component which
mainly imparts optical properties such as transparency to the
ocular lens material I and further improves mechanical strength
thereof so that the ocular lens material I can be used as a lens
material.
[0075] Typical examples of the crosslinkable compound (E) are
ethylene glycol di(meth)acrylate, diethylene glycol
di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene
glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, allyl
(meth)acrylate, vinyl (meth) acrylate; trimethylolpropane tri(meth)
acrylate, methacryloyloxydiethyl acrylate, divinylbenzene, diallyl
phthalate, diallyl adipate, diethylene glycol diallyl ether,
triallylisocyanurate, .alpha.-methylene-N-vinylpyrrolidone- ,
4-vinylbenzyl (meth)acrylate, 3-vinylbenzyl (meth)acrylate,
2,2-bis(p-(meth)acryloyloxyphenyl) hexafluoropropane,
2,2-bis(m-(meth)acryloyloxyphenyl)hexafluoropropane,
2,2-bis(o-(meth) acryloyloxyphenyl)hexafluoropropane,
1,4-bis(2-(meth)acryloyloxyhexafluor- oisopropyl)benzene,
1,3-bis(2-(meth)acryloyloxyhexafluoroisopropyl)benzene- , 1,2-bis
(2-(meth) acryloyloxyhexafluoroisopropyl) benzene,
1,4-bis(2-(meth)acryloyloxyisopropyl)benzene,
1,3-bis(2-(meth)acryloyloxy- isopropyl)benzene,
1,2-bis(2-(meth)acryloyloxyisopropyl)benzene and the like. These
can be used alone or in admixture thereof.
[0076] Among the above crosslinkable compounds (E), because optical
property and mechanical strength can be greatly imparted to the
ocular lens material I and handling is easy, ethylene glycol
di(meth)acrylate, diethylene glycol di(meth)acrylate, diallyl
adipate and diethylene glycol diallyl ether are preferable. In
particular, ethylene glycol di(meth)acrylate and diethylene glycol
diallyl ether are preferable.
[0077] In order to impart sufficient optical property and
mechanical strength to the ocular lens material I, it is desired
that the amount of the crosslinkable compound (E) in the monomer
mixture is at least 0.01% by weight, preferably at least 0.05% by
weight. In order to remove fear that flexibility of the ocular lens
material I is lowered although mechanical strength is imparted to
the ocular lens material I, it is desired that the amount of the
crosslinkable compound (E) in the monomer mixture is at most 15% by
weight, preferably at most 10% by weight.
[0078] The above monomer mixture may further contain an
ultraviolet-ray absorbing agent in order to improve ultraviolet-ray
absorbability of the ocular lens material I.
[0079] Examples of the ultraviolet-ray absorbing agent are a
benzotriazole ultraviolet-ray absorbing agent such as
2-(2'-hydroxy-5'-methacryloxyethy-
leneoxy-t-butylphenyl)-5-methylbenzotriazole or a compound
represented by the formula (III): 11
[0080] wherein Z.sup.1 is hydrogen atom, a halogen atom such as
chlorine atom, bromine atom or iodine atom, an alkyl group having 1
to 6 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms,
and each of Z.sup.2 and Z.sup.3 is independently hydrogen atom or
an alkyl group having 1 to 6 carbon atoms, such as
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
5-chloro-2-(3'-t-butyl-2'-hydroxy-5'-methylphenyl)benzotriazole or
2-(5-chloro-2H-benzotriazole-2-yl)-6-(1,1-dimethyl)-4-methylphenol;
a benzophenone ultraviolet-ray absorbing agent such as
2-hydroxy-4-methoxybenzophenone or 2-hydroxy-4-octoxybenzophenone;
a salicylic acid derivative ultraviolet-ray absorbing agent; a
hydroxyacetophenone derivative ultraviolet-ray absorbing agent; and
the like. Among them, the benzotriazole ultraviolet-ray absorbing
agent is preferable from the viewpoint of ultraviolet-ray
absorbability. In particular, the compound represented by the
formula (III), such as
2-(5-chloro-2H-benzotriazole-2-yl)-6-(1,1-dimethyl)-4-methylphenol
is preferable.
[0081] The above ultraviolet-ray absorbing agent may or may not
have a polymerizable group, and is not particularly limited.
[0082] It is desired that the amount of the above ultraviolet-ray
absorbing agent in the monomer mixture is at least 0.01% by weight,
preferably at least 0.05% by weight in order to impart sufficient
ultraviolet-ray absorbability to the ocular lens material I. Also,
it is desired that the amount is at most 5% by weight, more
preferably at most 3% by weight in order to prevent relative
decrease in other properties and induction of polymerization
inhibition caused by excessive addition.
[0083] In order to produce the ocular lens material I of the
present invention, a siloxane-containing polymer can be prepared by
polymerizing the above monomer mixture.
[0084] In preparing the above siloxane-containing polymer, a
radical polymerization initiator, a photo sensitizer and the like
are usually added first to the monomer mixture obtained by
adjusting kind and amount of monomers. They are added in accordance
with a radical polymerization method such as a thermal
polymerization method or a photo polymerization method mentioned
below, wherein radical generated in an active unsaturated group is
subjected to polymerization reaction.
[0085] Typical examples of the radical polymerization initiator are
a thermal polymerization initiator such as azobisisobutyronitrile,
azobisdimethylvaleronitrile, benzoyl peroxide, t-butyl
hydroperoxide, cumene peroxide; a benzoin photo polymerization
initiator such as methylorthobenzoyl benzoate, methylbenzoyl
formate, benzoin methyl ether, benzoin ethyl ether, benzoin
isopropyl ether, benzoin isobutyl ether or benzoin-n-butyl ether; a
phenone photo polymerization initiator such as
2-hydroxy-2-methyl-1-phenylpropane-1-one,
p-isopropyl-.alpha.-hydroxyisob- utylphenone,
p-t-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetoph-
enone, .alpha.,.alpha.-dichloro-4-phenoxyacetophenone or
N,N-tetraethyl-4,4-diaminobenzophenone; 1-hydroxycyclohexyl phenyl
ketone; 1-phenyl-1,2-propanedione-2-(o -ethoxycarbonyl)oxime; a
thioxanthone photo polymerization initiator such as
2-chlorothioxanthone or 2-methylthioxanthone; dibenzosvarron;
2-ethylanthraquinone; benzophenone acrylate; benzophenone; benzyl;
and the like.
[0086] The photo sensitizer is not activated independently by
irradiation of ultraviolet-ray. However, when used together with a
photo initiator, the photo sensitizer effects as a promotor and
show more excellent effects than the photo initiator alone.
Examples of the photo sensitizer are 1,2-benzoanthraquinone; an
amine compound such as n-butylamine, di-n-butylamine or
triethylamine; tri-n-butylphosphine; allylthiourea;
s-benzylisothiuronium-p-toluenesulfinate; diethylaminoethyl
methacrylate; and the like.
[0087] The radical polymerization initiator and the photo
sensitizer can be suitably selected and used alone or in admixture
thereof. It is desired that the amount thereof is about 0.002 to 2
parts by weight (hereinafter referred to as "part(s)"), preferably
about 0.01 to 1 part, based on 100 parts of the total amount of the
monomer mixture.
[0088] In the radical polymerization method, only a radical
polymerization initiator and a photo sensitizer may be used for
polymerization of the monomer mixture. However, a diluent can be
also used, for instance, to improve compatibility of each
monomer.
[0089] Typical examples of the diluent are an alcohol such as
methanol, ethanol, propanol, butanol, pentanol or hexanol; a ketone
such as acetone or methyl ethyl ketone; an ether such as diethyl
ether or tetrahydrofuran; and the like. These can be used alone or
in admixture thereof.
[0090] Among the diluents, an alcohol having 1 to 6 carbon atoms is
preferable since the monomer mixture gains excellent solubility. In
particular, n-propanol, n-butanol and n-pentanol are
preferable.
[0091] The monomer mixture is admixed with the diluent according to
the following proportion. That is, in order to dissolve the monomer
mixture in the diluent sufficiently, it is desired that the weight
ratio of the monomer mixture to the diluent, the monomer
mixture/the diluent, is at most 90/10, preferably at most 80/20. In
order to remove fear that the aimed polymer becomes cloud in white
to lower optical property and the polymer lacks mechanical
strength, it is desired that the above weight ratio is at least
30/70, preferably at least 50/50.
[0092] The ocular lens material I can be prepared by means of every
conventional method. However, from the viewpoint of achieving
maximum benefit from the properties of the ocular lens material I,
it is particularly preferable to produce a lens by preparing a
siloxane-containing polymer according to polymerization reaction
after injecting the above monomer mixture and, if necessary, the
above diluent into a mold composed of two parts, one part
corresponding to the front shape of a lens, such as, a contact lens
or an intraocular lens, and the other part corresponding to the
back shape of the lens, and sealing the mold. In case of producing
an intraocular lens, a mold having a shape corresponding to a
one-piece intraocular lens in which an optic and haptics are united
with each other may be used. Also, a mold having a shape
corresponding to the optic and a mold having a shape corresponding
to the haptics may be used.
[0093] After a monomer mixture and, if necessary, a diluent are
injected into the mold, polymerization reaction is carried out to
give a siloxane-containing polymer. Any usual method can be
employed for the polymerization without particular limitation.
[0094] The methods for the polymerization are, for instance, a
thermal polymerization method, wherein a mixture of a monomer
mixture containing the above radical polymerization initiator and,
if necessary, a diluent, is heated at about 30.degree. C. to
60.degree. C. for several hours to several 10 hours to polymerize
the mixture, and then the temperature of reaction system is
gradually increased to about 120.degree. C. to 140.degree. C. over
several hours to ten and several hours to complete the
polymerization; a photo polymerization method, wherein the above
mixture is irradiated with light ray such as ultraviolet-ray, which
has wavelength corresponding to absorption band of activation of
the radical polymerization initiator and then, the monomer mixture
is polymerized; and a combination method of thermal polymerization
and photo polymerization.
[0095] When the thermal polymerization method is carried out, the
above mixture can be heated in a thermostat container or a
thermostat room, and can be irradiated with electromagnetic wave
such as microwave. The temperature of the mixture may be increased
stepwise. When the photo polymerization method is carried out, the
photo sensitizer may be further added to the mixture.
[0096] The thus-obtained siloxane-containing polymer is put out
from the mold to give the ocular lens material I of the present
invention.
[0097] The above ocular lens material I can be subjected to
mechanical process such as cutting process or polishing process as
occasion demands.
[0098] The above ocular lens material I has excellent properties
sufficient and suitable for an ocular lens material. However, the
above siloxane-containing polymer is subjected to saponification to
obtain a material whose wettability is further improved.
[0099] That is, the ocular lens material of the present invention,
hereinafter referred to as ocular lens material II, comprises a
polymer prepared by saponifying a siloxane-containing polymer
obtained by polymerizing a monomer mixture containing (A) a
siloxane macromonomer having at least two active unsaturated groups
and a number average molecular weight of 2,000 to 100,000; and (B)
a vinyl ester of lower fatty acid as essential components. The
process of the present invention is characterized by the above
saponification.
[0100] The saponification in the present invention is to form vinyl
alcohol as mentioned below by subjecting units derived from the
vinyl ester of lower fatty acid (B) in the polymer, which can
decompose by saponification, to alkali treatment with an alkaline
compound or to acid treatment with, for instance, sulfuric acid
according to the conventionally known saponification method of
polyvinyl ester. In saponification by the acid treatment, however,
there are defects that saponification speed is late, uniform
saponification is difficult and that side reaction occurs. For
these reasons, saponification by the alkali treatment is preferred.
By saponification, hydrophilic property, in other words surface
wettability, can be imparted to the ocular lens material II without
much increase of water content. 12
[0101] wherein R is the same as the above.
[0102] Examples of the alkaline compound used for the alkali
treatment are ammonia, an alkaline metal hydroxide, an alkaline
earth metal hydroxide and the like. Concrete examples of the
alkaline compound are ammonium hydroxide, sodium hydroxide,
potassium hydroxide, calcium hydroxide and the like. Because most
alkaline compounds are solids, it is preferred that these alkaline
compounds are dissolved in water, an alcohol, an ether or the like
to give an alkaline solution and the alkaline solution is used for
saponification.
[0103] Examples of the alcohol are methanol, ethanol, propanol,
butanol and the like. Examples of the ether are diethyl ether,
tetrahydrofuran and the like.
[0104] Among the alkaline solutions of alkaline compound used for
saponification, those obtained from an alcohol are preferable. In
order to carry out saponification efficiently, a methanol aqueous
solution of sodium hydroxide having a concentration of 0.01 to 1
mol/L is more preferable. In particular, a methanol aqueous
solution of sodium hydroxide, in which the volume ratio of methanol
to water, methanol/water, is 30/70 to 90/10, is preferable.
[0105] An ocular lens material can be subjected to dyeing in case
where saponification is carried out by alkali treatment in the
present invention.
[0106] Specifically, a siloxane-containing polymer is prepared as
mentioned above, then immersed and swollen in a mixture obtained by
dispersing, or dissolving a dye in an organic solvent such as
methanol, ethanol or 2-propanol, and non-reacted residual monomers
in the siloxane-containing polymer are eluted while the dye is
dispersed in the polymer at the same time. The dye can be fixed to
the siloxane-containing polymer in subsequent saponification by
alkali treatment.
[0107] There is no particular limitation for the above dye.
Preferable examples thereof are, for example, reactive dyes such as
C. I. Reactive Black 5, C. I.: standing for "Color Index",
hereinafter referred to as the same, C. I. Reactive Blue 21, C. I.
Reactive Orange 78, C. I. Reactive Yellow 15, C. I. Reactive Blue
4, C. I. Reactive Red 11, C. I. Reactive Yellow 86, C. I. Reactive
Blue 163, C. I. Reactive Red 180, and the like. The amount of the
dye is not particularly limited as long as it is used in such an
amount that sufficient dyeing of the ocular lens material II can be
achieved.
[0108] The siloxane-containing polymer is subjected to
saponification by immersing the polymer in the above alkaline
solution or the above solution of acidic compound.
[0109] The temperature in saponification is not particularly
limited. In general, it is desired that the temperature is about
0.degree. C. to about 100.degree. C., preferably about 10.degree.
C. to about 70.degree. C.
[0110] The treatment time for saponification, which is not
determined as a whole, can be changed depending on kind of alkaline
compound and acidic compound, concentration of alkaline compound
and acidic compound, or temperature of saponification. However, it
is desired that the treatment time is at least 0.1 hour, preferably
at least 0.5 hour in order to improve hydrophilic property of the
ocular lens material II effectively. Also, it is desired that the
treatment time is at most 30 hours, preferably at most 15 hours, in
order to remove fears that an inappropriate material for an ocular
lens is produced because the material becomes cloud in white to
lower transparency, or because mechanical strength thereof is
lowered, and that working efficiency is lowered due to extended
treatment time.
[0111] The saponified polymer can be boiled in physiological saline
(0.9% sodium chloride aqueous solution) for several hours.
[0112] Further, it is also possible to carry out the above
saponification after photo-irradiation to the prepared
siloxane-containing polymer in the present invention.
[0113] The ocular lens material II obtained by the saponification
of alkali treatment after photo-irradiation to the
siloxane-containing polymer has further increased surface
wettability.
[0114] It is preferable to carry out photo-irradiation before the
saponification to a siloxane-containing polymer as mentioned above,
but there is no particular limitation for the condition of the
siloxane-containing polymer as long as the polymer is dried or
swollen by an extraction solution employed for removing residual
monomers during extraction process.
[0115] It is desired that light to be irradiated is ultraviolet ray
having a wavelength of preferably at most 380 nm, more preferably
at most 300 nm from the viewpoint of efficient improvement of
wettability. It is particularly preferable to irradiate ultraviolet
ray having a wavelength near 185 nm and ultraviolet ray having a
wavelength near 250 nm simultaneously.
[0116] It is desired that the photo-irradiation time is 0.1 to 600
minutes, preferably 1 to 60 minutes from the viewpoint of efficient
improvement of wettability without affecting productivity to
produce a desired ocular lens from the ocular lens material II.
[0117] Either of the above steps may precede when both of the steps
are employed together, one step being such that a
siloxane-containing polymer is immersed and swollen in a mixture
obtained by dispersing, or dissolving, a dye in an organic solvent
to elute residual monomers in the siloxane-containing polymer which
did not react while the dye is dispersed in the polymer at the same
time, and the other step being such that the siloxane-containing
polymer is irradiated with photo. When the photo-irradiation step
is carried out after the elution step, light may be irradiated
after a sample is dried for increased efficiency of
photo-irradiation.
[0118] The ocular lens material I of the present invention is most
suitable for a soft ocular lens material in particular. This is
because the ocular lens material I has excellent flexibility,
particularly shape recovery, in addition to advantages of
conventional soft ocular lens materials, such as high oxygen
permeability, superior lipid-stain resistance and excellent
wettability. The reason why a material excellent in shape recovery
is suitable for a soft ocular lens material can be seen when a
material inferior in shape recovery is taken into account. When
used as a contact lens, a material inferior in shape recovery
disturbs stable eyesight immediately after wearing lenses, causes
uncomfortable feeling to patients during wearing lenses, and
further, induces troubles in eyeball. Meanwhile, when an ocular
lens material is used as a soft intraocular lens, the best
advantage of the soft intraocular lens resides in the fact that
incision of eyeball can be extremely small since the lens is
foldable when inserted in the eye. However, when an ocular lens
material is inferior in shape recovery, wide incision is therefore
necessary because the material is difficult to fold. In addition,
when shape recovery is inferior, it is difficult for a lens to
recover its original shape after insertion in the eye and function
as a lens is not achieved, resulting in lowering of eyesight.
Accordingly, the ocular lens material I of the present invention is
very suitable for an ocular lens material for the reason that it
has excellent flexibility, particularly shape recovery, in addition
to high oxygen permeability, superior lipid-stain resistance and
excellent wettability.
[0119] Furthermore, in recent growing development of soft ocular
lens materials with high oxygen permeability, use of a
silicon-containing component is becoming essentially important for
high oxygen permeability. However, though high oxygen permeability
is imparted to the material, the material becomes extremely
vulnerable to stain by lipid and inferior in hydrophilic property
when used for an ocular lens because of high affinity of the
silicon-containing component with a lipid component. Such
characteristics are also inappropriate for an ocular lens material.
On the contrary, the ocular lens material II of the present
invention has not only high oxygen permeability and excellent
flexibility as typified by shape recovery, but also excellent
hydrophilic property, surface wettability in other words, and lipid
stain resistance at the same time due to saponification, showing
most suitable properties for an ocular lens material all
together.
[0120] Next, the ocular lens material and the process for producing
the same of the present invention are explained in detail, but the
present invention is not limited thereto.
EXAMPLES 1 to 11 and COMPARATIVE EXAMPLES 1 to 6
[0121] Each of monomer mixtures shown in Tables 1 and 2 was mixed
with 2-hydroxy-2-methyl-1-phenylpropane-1-one, as a polymerization
initiator, in an amount of 0.2 part based on the monomer mixture.
Then, the obtained mixture was injected into a mold having shape of
a contact lens (made of polypropylene, corresponding to a contact
lens having a diameter of 13.8 mm and a thickness of 0.2 mm).
[0122] Next, the mold was transferred into a constant temperature
condition and photo polymerization was carried out by irradiating
ultraviolet ray having a wavelength of 360 nm in about 1
mW/cm.sup.2 to the content in the mold for an hour by using a
mercury lamp to give a siloxane-containing polymer having shape of
a contact lens.
[0123] The saponification of siloxane-containing polymers shown in
Tables 1 and 2 was carried out by immersing the polymer in a 60%
methanol aqueous solution containing 0.25 mol/L of sodium hydroxide
whose temperature was 25.degree. C. for six hours.
[0124] In Examples 6 and 10, a polymer having shape of a contact
lens was obtained by directly saponifying the obtained
siloxane-containing polymer, and a polymer having shape of a
contact lens was obtained by irradiating ultraviolet ray having
wavelength of 185 nm and ultraviolet ray having a wavelength of 254
nm for 10 minutes and then saponifying the obtained
siloxane-containing polymer. These polymers to which ultraviolet
ray was irradiated were used only for measuring dynamic contact
angle mentioned below.
[0125] Oxygen permeability, shape recovery, flexibility in other
words, surface wettability and lipid-stain resistance of polymers
having shape of a contact lens in Examples 1 to 11 and Comparative
Examples 1 to 6 were examined in accordance with the following
method. The results are shown in Tables 3 to 5.
[0126] (a) Oxygen Permeability
[0127] Dk values defined by ISO which stands for "International
Organization for Standardization" were measured according to Fatt
method.
[0128] (b) Shape Recovery (Flexibility)
[0129] The periphery of a polymer was fixed, while the center
thereof was fixed to an apparatus for loading by using a spherical
tool whose tip diameter was about 3 mm.
[0130] Stress was given to the fixed polymer up to about 20 g. This
stress was removed and loss of repulsive force from the polymer was
measured. The value T.sub.1, the maximum load on the polymer, and
then the value T.sub.2, repulsive force from the polymer after 30
seconds were measured.
[0131] Using the measured values T.sub.1 and T.sub.2, shape
recovery coefficient (%) was calculated on the basis of the
following equation.
[0132] The larger the shape recovery coefficient is, the more
inferior the shape recovery is. Particularly, when shape recovery
coefficient is at least 18%, such material is inappropriate for an
ocular lens, especially for a soft contact lens or a soft
intraocular lens. In case of the soft contact lens, such material
is not suitable because feeling for wearing becomes poor and
unstable eyesight may be caused at wearing the lens immediately
after the lens is handled by fingers. In case of the soft
intraocular lens, such material is not suitable because trouble is
caused for folding in operation and mark is left on the lens after
insertion.
Shape recovery coefficient
(%)={(T.sub.1-T.sub.2)/T.sub.1}.times.100
[0133] (a) Surface wettability
[0134] After immersing the obtained polymer in saline for about 16
hours, the polymer was taken out and the surface thereof was
observed with naked eyes. Evaluation was made according to the
following criteria.
[0135] (Criteria for Evaluation)
[0136] .circleincircle.: Wettability for water is excellent on the
whole. There is no repelling and cloud at all.
[0137] .largecircle.: Repelling is partly observed, whereas there
is no cloud and wettability is good.
[0138] .DELTA.: Wettability for water is not good. Repelling and
cloud is partly observed, or the material is clouded on the
whole.
[0139] x: Wettability for water is poor. Repelling and cloud are
observed.
[0140] In Examples 6 and 10 as well as Comparative Examples 1 and
4, the obtained polymer was cut into strip test pieces having a
size of 5 mm wide, about 12 mm long and about 0.6 mm thick (which
were prepared by using a punching knife to have the same width,
obtained by changing an immersing solution from saline to distilled
water; and whose thickness is measured for each piece). Dynamic
contact angle was measured by using a dynamic contact angle
measuring device DCA-322 made by CAHN Co., Ltd., equipped with
cover glass, wherein distilled water for injection is used as a
test solution. The measuring process is as follows.
[0141] First, the cover glass was used as a test piece to measure
surface tension T of the test solution. Second, dynamic contact
angle of each test piece was measured in accordance with measuring
principle of Wilhelmy method under the following conditions.
[0142] Rate of immersion: 90 .mu.m/s
[0143] Depth of immersion: 10 mm
[0144] Test weight: 500.0 mg
[0145] Test solution: distilled water for injection
[0146] Surface tension of test solution: the above measured value
T
[0147] Cycle: 3 cycles
[0148] As a result of the above measurement, the value at the
second cycle was employed as dynamic contact angle (.degree.)
[0149] Dynamic contact angle is an index for wettability of a
polymer. A polymer whose dynamic contact angle is at least
120.degree. has poor wettability and is inappropriate for an ocular
lens material.
[0150] (b) Lipid-Stain Resistance
[0151] The obtained polymer was put in a glass bottle containing 2
ml of an artificial tear lipid solution, a buffer solution of pH 7,
which comprises 0.3 g of oleic acid, 0.3 g of linoleic acid, 4.0 g
of tripalmitic acid, 1.0 g of cetyl alcohol, 0.3 g of palmitic
acid, 4.0 g of spermaceti, 0.4 g of cholesterol, 0.4 g of
cholesterol palmitate and 14.0 g of yolk lecithin. The glass bottle
was shaken at 37.degree. C. for 5 hours.
[0152] After five hours, the polymer was picked up from the
artificial tear lipid solution and then, lipid components which
adhered to the polymer were extracted by immersing the polymer in 1
ml of a mixed solution of ethanol and ether (ethanol:ether=3:1
(volume ratio)).
[0153] To 500 .mu.l of the obtained lipid extracted solution was
added 1 ml of concentrated sulfuric acid and then, 3 mg of vanillin
and 2 ml of phosphoric acid were added thereto. Adhering lipid
amount (mg/cm.sup.2) of the polymer was quantitated.
[0154] When adhering lipid amount is more than 0.3 mg/cm.sup.2,
lipid easily adheres to the polymer. Thus, the polymer has poor
lipid-stain resistance, and is not suitable for an ocular lens such
as a contact lens or an intraocular lens.
[0155] Abbreviations in Tables 1 and 2 indicate the following
compounds.
[0156] SiMa1: a macromonomer represented by the formula: 13
[0157] wherein A is a group represented by the formula: 14
[0158] in which a is an integer of 20 to 50;
[0159] whose number average molecular weight is 6,000; and having
four urethane groups on average.
[0160] SiMa2: a macromonomer represented by the formula: 15
[0161] wherein A' is a group represented by the formula: 16
[0162] in which a' is an integer of 10 to 20 and a" is an integer
of 20 to 40;
[0163] whose number average molecular weight is 7,500; and having
four urethane groups on average.
[0164] SiMa3: a macromonomer represented by the formula: 17
[0165] wherein A" is a group represented by the formula: 18
[0166] in which a'" is an integer of 5 to 25 and b is an integer of
1 to 5;
[0167] whose number average molecular weight is 9,000; and having
eight urethane groups on average.
[0168] V1: vinyl acetate
[0169] V2: vinyl propionate
[0170] V3: vinyl pivalate
[0171] SiMo1: tris(trimethylsiloxy)silylpropyl acrylate
[0172] SiMo2: tris(trimethylsiloxy)silylpropyl methacrylate
[0173] F1: 2-hydroxy-3-perfluorohexylpropyl acrylate
[0174] F2: 2-hydroxy-3-perfluorooctylpropyl acrylate
[0175] C 1: ethylene glycol dimethacrylate
[0176] C2: diethylene glycol diallyl ether
[0177] 2HEMA: 2-hydroxyethyl methacrylate
[0178] 2HEA: 2-hydroxyethyl acrylate
[0179] DMAA: N,N-dimethylacrylamide
[0180] NVP: N-vinylpyrrolidone
[0181] Number average molecular weights of the above SiMa 1, SiMa2
and SiMa3 were converted to polystylene basis according to size
exclusion chromatography.
1 TABLE 1 Monomer mixture (part) (E) Ex. (A) (B) (C) (D) C1/C2 =
1/2 No. SiMa1 SiMa2 SiMa3 V1 V2 V3 SiMo1 SiMo2 F1 F2 (weight ratio)
Saponification 1 40 -- -- 30 -- -- 30 -- -- -- 1 not saponified 2
40 -- -- 30 -- -- 30 -- -- -- 1 saponified 3 20 -- -- 40 -- -- 40
-- -- -- 1 not saponified 4 50 -- -- 35 -- -- 15 -- -- -- 1
saponified 5 -- 50 -- 35 -- -- 15 -- -- -- 1 saponified 6 -- -- 40
30 -- -- 30 -- -- -- 1 saponified 7 50 -- -- 35 -- -- -- 15 -- -- 1
saponified 8 50 -- -- -- 35 -- 15 -- -- -- 1 saponified 9 50 -- --
-- -- 35 15 -- -- -- 1 saponified 10 40 -- -- 28 -- -- 12 -- 20 --
1 saponified 11 40 -- -- 28 -- -- 12 -- -- 20 1 saponified
[0182]
2 TABLE 2 Monomer mixture (part) (E) (A) (C) C1/C2 = 1/2 Others
Com. Ex. No. SiMa1 SiMa3 SiMo1 (weight ratio) 2HEMA 2HEA DMAA NVP
Saponification 1 40 -- 30 1 30 -- -- -- not saponified 2 40 -- 30 1
30 -- -- -- saponified 3 -- 40 30 1 30 -- -- -- not saponified 4 40
-- 30 1 -- 30 -- -- not saponified 5 40 -- 30 1 -- -- 30 -- not
saponified 6 40 -- 30 1 -- -- -- 30 not saponified
[0183]
3 TABLE 3 Properties of polymer (ocular lens material) Lipid-stain
resistance Oxygen permeability Shape recovery Surface wettability
(Adhering lipid amount Ex. No. (DK value) (Shape recovery
coefficient (%)) for water (mg/cm.sup.2)) 1 115 5 .largecircle.
0.2.gtoreq. 2 110 5 .circleincircle. 0.2.gtoreq. 3 105 11
.largecircle. 0.2.gtoreq. 4 130 9 .circleincircle. 0.2.gtoreq. 5
130 11 .circleincircle. 0.2.gtoreq. 6 110 10 .circleincircle.
0.2.gtoreq. 7 130 11 .circleincircle. 0.2.gtoreq. 8 130 10
.circleincircle. 0.2.gtoreq. 9 130 10 .circleincircle. 0.2.gtoreq.
10 130 10 .circleincircle. 0.1.gtoreq. 11 130 10 .circleincircle.
0.1.gtoreq.
[0184]
4 TABLE 4 Surface wettability for water of polymer (ocular lens
material) Ultraviolet-ray (dynamic contact angle (.degree.))
irradiation Ex. No. 6 98 not irradiated 60 irradiated 10 95 not
irradiated 60 irradiated Com. Ex. No. 1 130 not irradiated 4 140
not irradiated
[0185]
5 TABLE 5 Properties of polymer (ocular lens material) Com. Lipid
stain resistance Ex. Oxygen permeability Shape recovery Surface
wettability (Adhering lipid amount No. (DK value) (Shape recovery
coefficient (%)) for water (mg/cm.sup.2)) 1 110 25 .DELTA. 0.5 2 80
25 .largecircle. 0.5 3 110 25 .DELTA. 0.5 4 110 9 .DELTA. 0.6 5 110
9 .DELTA. 0.6 6 110 6 .DELTA. 0.5
[0186] The results in Table 3 prove that a polymer which has high
oxygen permeability, superior lipid-stain resistance, excellent
surface wettability, and excellent shape recovery at the same time
can be obtained when a siloxane macromonomer (A) and a vinyl ester
of lower fatty acid (B) are used together as in Examples 1 to 11.
The results also show that a polymer which has further improved
surface wettability can be obtained when saponification is carried
out as in Examples 2 and 4 to 11. It is also proved that a polymer
which has particularly excellent lipid-stain resistance in addition
to the above advantages can be obtained when a fluorine-containing
monomer (D) is used as in Examples 10 and 11. The results in Table
4 indicate that when short wavelength ultraviolet ray is irradiated
before saponification as in Examples 6 and 10, a polymer has
smaller dynamic contact angle and more excellent surface
wettability than those in Comparative Examples 1 and 4 and cases in
Examples 6 and 10 where ultraviolet ray was not irradiated.
[0187] On the contrary, the results in Table 5 shows that when a
hydrophilic monomer of 2-hydroxyethyl (meth)acrylate,
N,N-dimethylacrylamide or N-vinylpyrrolidone is used instead of the
vinyl ester of lower fatty acid (B) as in Comparative Examples 1 to
6, surface wettability is inferior as in Comparative Examples 1 and
3 to 6, shape recovery is poor as in Comparative Examples 1 to 3,
and lipid-stain resistance is particularly low.
EXAMPLES 12 and 13
[0188] C.I. Reactive Blue 4 available from Mitsui BASF Dye Co.,
Ltd. was dissolved in 20 ml of distilled water in an amount of
0.0511 g to obtain a solution. To 20 ml of 2-propanol was added 1
ml of the above solution at 25.degree. C. A siloxane-containing
polymer obtained in the same manner as in Example 2 (Example 12),
and a siloxane-containing polymer obtained in the same manner as in
Example 10 without ultraviolet-ray irradiation before
saponification (Example 13) were immersed in the mixture for 16
hours, respectively. Next, these polymers were immersed in the same
methanol aqueous solution containing sodium hydroxide as used in
Example 2 for 6 hours at 25.degree. C., and then each polymer was
taken out therefrom, transferred to distilled water, and taken out
therefrom after 120 minutes.
[0189] All polymers assumed uniform and transparent blue color, and
was equal to polymers obtained in Examples 2 or 10 in high oxygen
permeability, and excellent lipid-stain resistance, surface
wettability and shape recovery.
INDUSTRIAL APPLICABILITY
[0190] The ocular lens material of the present invention is
excellent not only in lipid-stain resistance, wettability and
oxygen permeability, but also in flexibility, particularly, shape
recovery at the same time, and can be suitably used for ocular
lenses such as soft contact lens and soft intraocular lens.
According to the process of the present invention, the above ocular
lens material is easily produced.
* * * * *