U.S. patent application number 16/670260 was filed with the patent office on 2020-02-27 for lens solution, contact lens, and production method therefor.
The applicant listed for this patent is JSR CORPORATION. Invention is credited to Satoshi Hyugaji, Kazuhiro ISO.
Application Number | 20200063065 16/670260 |
Document ID | / |
Family ID | 53778053 |
Filed Date | 2020-02-27 |
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United States Patent
Application |
20200063065 |
Kind Code |
A1 |
ISO; Kazuhiro ; et
al. |
February 27, 2020 |
LENS SOLUTION, CONTACT LENS, AND PRODUCTION METHOD THEREFOR
Abstract
Provided is a lens solution which has excellent lipid
detergency, exhibits high hydrophilization performance, and
exhibits an excellent lipid adhesion preventive effect and an
excellent lubricity-imparting effect when the solution is used to
coat a lens. Disclosed is a lens solution containing a polymer
having 2.5% to 95% by mass of the following repeating unit (A) and
2.5% to 95% by mass of the following repeating unit (B): (A) a
hydrophilic repeating unit; and (B) a repeating unit having a
polyoxyalkylene group in a side chain and having the end of the
side chain formed from an alkyl group having 5 to 30 carbon atoms,
an alkanoyl group having 5 to 30 carbon atoms, or an aryl
group.
Inventors: |
ISO; Kazuhiro; (Minato-ku,
JP) ; Hyugaji; Satoshi; (Minato-ku, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JSR CORPORATION |
Minato-ku |
|
JP |
|
|
Family ID: |
53778053 |
Appl. No.: |
16/670260 |
Filed: |
October 31, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15116437 |
Aug 3, 2016 |
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|
PCT/JP2015/053423 |
Feb 6, 2015 |
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16670260 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
G02C 7/049 20130101;
G02C 7/04 20130101; G02B 1/043 20130101; C11D 3/3765 20130101; G02C
2202/16 20130101; C11D 3/3784 20130101; A61F 2/16 20130101; C11D
3/0078 20130101; C11D 3/378 20130101; C11D 3/3773 20130101 |
International
Class: |
C11D 3/00 20060101
C11D003/00; G02C 7/04 20060101 G02C007/04; G02B 1/04 20060101
G02B001/04; C11D 3/37 20060101 C11D003/37 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 6, 2014 |
JP |
2014-021271 |
Claims
1. A polymer comprising 2.5% to 95% by mass of the following
repeating unit (A) and 2.5% to 95% by mass of the following
repeating unit (B): (A) a hydrophilic repeating unit; and (B) a
repeating unit having a polyoxyalkylene group in a side chain and
having the end of the side chain formed from an alkyl group having
5 to 30 carbon atoms, an alkanoyl group having 5 to 30 carbon
atoms, or an aryl group, wherein the repeating unit (A) comprises a
repeating unit (A-3) represented by the following formula (4) and a
betaine-containing repeating unit (A-6) represented by the
following formula (7): ##STR00013## in which in formula (4),
R.sup.12 represents a hydrogen atom or a methyl group; and R.sup.13
and R.sup.14 each independently represent a hydrogen atom, an alkyl
group having 1 to 6 carbon atoms, or a hydroxyalkyl group,
##STR00014## in which in formula (7), Y represents
--(C.dbd.O)O.sup.-, --(O.dbd.S.dbd.O)O.sup.-,
--O(O.dbd.S.dbd.O)O.sup.-, --(S.dbd.O)O.sup.-, --O(S.dbd.O)O.sup.-,
--OP(.dbd.O)(OR.sup.24)O--, --OP(.dbd.O)(R.sup.24)O.sup.-,
--P(.dbd.O)(OR.sup.24)O.sup.-, or --P(.dbd.O)(R.sup.24)O.sup.-,
wherein R.sup.24 represents an alkyl group having 1 to 3 carbon
atoms; R.sup.19 represents a hydrogen atom or a methyl group;
R.sup.20 and R.sup.21 each independently represent a divalent
organic group having 1 to 10 carbon atoms; and R.sup.22 and
R.sup.23 each independently represent a hydrocarbon group having 1
to 10 carbon atoms.
2. The polymer according to claim 1, wherein R.sup.13 and R.sup.14
in formula (4) each independently represent a hydrogen atom or an
alkyl group having 1 to 6 carbon atoms.
3. The polymer according to claim 1, wherein R.sup.20 and R.sup.21
in formula (7) each independently represent a divalent hydrocarbon
group having 1 to 10 carbon atoms.
4. The polymer according to claim 1, wherein the repeating unit (B)
is represented by the following formula (10): ##STR00015## in which
in formula (10), R.sup.32 represent an alkylene group having 2 to 4
carbon atoms; R.sup.33 represents an alkyl group having 5 to 30
carbon atoms, an alkanoyl group having 5 to 30 carbon atoms, or an
aryl group; R.sup.34 represents a hydrogen atom or a methyl group;
R.sup.35 represents --O--, **--(C.dbd.O)--O.sup.-,
**--(C.dbd.O)--NR.sup.36--, **--NR.sup.36--(C.dbd.O)--, wherein
R.sup.36 represents a hydrogen atom or an organic group having 1 to
10 carbon atoms; and the symbol ** represents the position at which
the moiety is bonded to the carbon atom to which R.sup.34 in
formula (10) is bonded, or a phenylene group; and m represents 2 to
100 as an average value.
5. The polymer according to claim 4, wherein R.sup.33 in formula
(10) represents an alkyl group having 5 to 30 carbon atoms.
6. The polymer according to claim 4, wherein R.sup.35 in formula
(10) represents **--(C.dbd.O)--O.sup.-, **--(C.dbd.O)--NR.sup.36--,
**--NR.sup.36--(C.dbd.O)-- or a phenylene group.
7. The polymer according to claim 1, further comprising one or more
of a repeating unit (C) selected from the group consisting of a
repeating unit (C-1) represented by the following formula (11), and
a repeating unit (C-2) having a group represented by the following
formula (12) at the end of a side chain: ##STR00016## in which in
formula (11), R.sup.37 represent a hydrogen atom or a methyl group;
R.sup.38 represents --O--, ***--(C.dbd.O)--O.sup.-,
***--(C.dbd.O)--NR.sup.40--, ***--NR.sup.40--(C.dbd.O)--, wherein
R.sup.40 represents a hydrogen atom or an organic group having 1 to
10 carbon atoms; and the symbol *** represents the position at
which the moiety is bonded to the carbon atom to which R.sup.37 in
formula (11) is bonded), or a phenylene group; and R.sup.39
represents a hydrocarbon group having 4 to 30 carbon atoms,
##STR00017## in which in formula (12), R.sup.41 represents a
divalent organic group having 1 to 10 carbon atoms; R.sup.42 and
R.sup.43 each independently represent an organic group having 1 to
10 carbon atoms; R.sup.44, R.sup.45 and R.sup.46 each independently
represent --OSi(R.sup.49).sub.3, wherein R.sup.49's each
independently represent a hydrogen atom or an organic group having
1 to 8 carbon atoms, or an organic group having 1 to 10 carbon
atoms; and r represents 0 to 200 as an average value.
8. The polymer according to claim 7, wherein the repeating unit (C)
is the repeating unit (C-1).
9. The polymer according to claim 7, wherein a content of the
repeating unit (C) is 0.1% by mass to 40% by mass.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser.
No. 15/116,437, filed on Aug. 3, 2016, which is a national stage
patent application of international patent application
PCT/JP2015/053423, filed on Feb. 6, 2015, the text of which is
incorporated by reference, and claims foreign priority to Japanese
Patent Application No. 2014-021271, filed on Feb. 6, 2014, the
entire content of which is incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a lens solution, a contact
lens, and a production method therefor.
BACKGROUND ART
[0003] Contact lenses are roughly classified into hydrous contact
lenses (including soft contact lenses) and non-hydrous contact
lenses (including hard contact lenses and soft contact lenses), and
hydrous contact lenses generally have an advantage that the lenses
have a more satisfactory feeling of wearing than non-hydrous
contact lenses.
[0004] However, since conventional hydrous contact lenses have high
hydrability, there have been problems, for example, that lenses dry
up quickly, and oxygen permeability is decreased.
[0005] Thus, silicone hydrogel contact lenses, which have high
oxygen permeability while being less hydratable, have been
developed, and in recent years, these constitute the mainstream of
contact lenses. However, silicone hydrogels have a problem that
since the silicone chains contained therein exhibit hydrophobicity,
the feeling of wearing is not satisfactory, and lipids easily
adhere thereto. In a case where the contact lenses are continuously
used in that state while leaving these problems neglected, there is
a risk that, for example, eyestrain, cloudiness, lowering of the
visual acuity correction power, adverse effects on the cornea, may
occur.
[0006] Under such circumstances, various cleaning solutions,
storage solutions and coating solutions for contact lenses have
been suggested for the purpose of eliminating those lipids adhering
to the lens surface, enhancing the hydrophilicity of the lens
surface, preventing the adhesion of lipids, or imparting
lubricity.
[0007] For example, as the cleaning solutions for contact lenses,
poly(oxyethylene)-poly(oxypropylene) block copolymers (poloxamer
and poloxamine), which are nonionic surfactants, have been widely
used heretofore (Patent Literature 1).
CITATION LIST
Patent Literature
[0008] Patent Literature 1: U.S. Pat. No. 6,037,328 A
SUMMARY OF INVENTION
Technical Problem
[0009] However, although the aforementioned nonionic surfactants
have lipid detergency, those surfactants are not satisfactory in
view of the performance for hydrophilizing the contact lens surface
and the performance for imparting lubricity. Furthermore, the
inventors of the present invention conducted an investigation on
the aforementioned nonionic surfactants, and it was found that the
lipid adhesion preventive effect is also insufficient.
[0010] That is, an object of the present invention is to provide a
lens solution which has excellent lipid detergency, exhibits high
hydrophilization performance, and exhibits an excellent lipid
adhesion preventive effect and an excellent lubricity-imparting
effect when used to coat a lens.
Solution to Problem
[0011] Thus, the inventors of the present invention conducted a
thorough investigation. As a result, they found that a lens
solution containing a polymer which has a hydrophilic repeating
unit; and a repeating unit having a polyoxyalkylene group in a side
chain and having a particular hydrophobic group at the end of the
side chain, respectively at particular contents, has excellent
lipid detergency and also exhibits high hydrophilization
performance, and when used to coat a lens, the lens solution
exhibits an excellent lipid adhesion preventive effect and an
excellent lubricity-imparting effect. Thus, the inventors completed
the present invention.
[0012] That is, the present invention provides a lens solution
containing a polymer having 2.5% to 95% by mass of the following
repeating unit (A) and 2.5% to 95% by mass of the following
repeating unit (B):
[0013] (A) a hydrophilic repeating unit; and
[0014] (B) a repeating unit having a polyoxyalkylene group in a
side chain and having the end of the side chain formed from an
alkyl group having 5 to 30 carbon atoms, an alkanoyl group having 5
to 30 carbon atoms, or an aryl group.
[0015] In addition, the present invention provides a method for
producing a surface-modified contact lens, the method including
bringing the solution into contact with at least a part of a
contact lens surface.
[0016] Furthermore, the present invention provides a contact lens
including, in at least a part of the surface, a polymer having 2.5%
to 95% by mass of the following repeating unit (A) and 2.5% to 95%
by mass of the following repeating unit (B):
[0017] (A) a hydrophilic repeating unit; and
[0018] (B) a repeating unit having a polyoxyalkylene group in a
side chain and having the end of the side chain formed from an
alkyl group having 5 to 30 carbon atoms, an alkanoyl group having 5
to 30 carbon atoms, or an aryl group.
[0019] Furthermore, it is another object of the present invention
to provide a method for treating a surface of contact lens, the
method including a step of bringing the solution into contact with
at least a part of a contact lens surface.
Advantageous Effects of Invention
[0020] The lens solution of the present invention has excellent
lipid detergency and also exhibits high hydrophilization
performance, and when used to coat a lens, the lens solution
exhibits an excellent lipid adhesion preventive effect and an
excellent lubricity-imparting effect. Furthermore, the lens
solution exhibits high adsorptiveness to lens surface and is not
easily detachable.
[0021] Therefore, the lens solution of the present invention is
useful as a contact lens cleaning or storage solution, and as a
contact lens coating solution.
[0022] Furthermore, the contact lens of the present invention has
its surface hydrophilically modified, so that lipids are unlikely
adsorbed thereto, and the contact lens has excellent lubricity and
excellent sustainability of those effects.
[0023] Furthermore, according to the method for producing a contact
lens of the present invention, a contact lens to which lipids are
unlikely to be adsorbed thereto, and which has excellent lubricity
and excellent sustainability of those effects, can be produced
conveniently.
DESCRIPTION OF EMBODIMENTS
[0024] [Lens Solution]
[0025] The lens solution of the present invention includes a
polymer having 2.5% to 95% by mass of the above-described repeating
unit (A) and 2.5% to 95% by mass of the above-described repeating
unit (B). First, the polymer used in the present invention will be
explained in detail.
[0026] (Repeating Unit (A))
[0027] A repeating unit (A) may be any hydrophilic repeating unit.
The repeating unit (A) is preferably one or more selected from the
group consisting of a repeating unit having a polyoxyalkylene group
in a side chain and having the end of the side chain formed from a
hydrogen atom or an alkyl group having 1 to 4 carbon atoms (A-1); a
repeating unit represented by the following formula (3) (A-2); a
repeating unit represented by the following formula (4) (A-3); a
repeating unit represented by the following formula (5) (A-4); a
repeating unit represented by the following formula (6) (A-5); a
betaine-like repeating unit represented by the following formula
(7) (A-6); an anionic repeating unit (A-7): and a cationic
repeating unit represented by the following formula (8) (A-8).
[0028] Note that according to the present specification,
hydrophilicity means to exhibit a property of having strong
affinity to water. Specifically, in the case of a homopolymer
composed only of one repeating unit (a homopolymer having a number
average molecular weight of about 10,000 as measured by the
measurement method of Examples), when 1 g or more of the
homopolymer dissolves in 100 g of pure water at normal temperature
(25.degree. C.), the repeating unit is hydrophilic.
##STR00001##
[0029] in which in formula (3),
[0030] R.sup.6 represents a hydrogen atom or a methyl group;
[0031] R.sup.7 represents an alkylene group having 2 to 4 carbon
atoms;
[0032] R.sup.8 represents an alkylene group having 1 to 10 carbon
atoms;
[0033] R.sup.9, R.sup.10 and R.sup.11 each independently represent
a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms;
and
[0034] q represents 1 to 10 as an average value.
##STR00002##
in which in formula (4),
[0035] R.sup.12 represents a hydrogen atom or a methyl group;
and
[0036] R.sup.13 and R.sup.14 each independently represent a
hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a
hydroxyalkyl group.
##STR00003##
in which in formula (5),
[0037] R.sup.15 represents a hydrogen atom or a methyl group;
and
[0038] R.sup.16 and R.sup.17 each independently represent an
alkylene group having 1 to 3 carbon atoms.
##STR00004##
in which in formula (6),
[0039] R.sup.18 represents an alkylene group having 1 to 5 carbon
atoms.
##STR00005##
in which in formula (7),
[0040] Y represents --(C.dbd.O)O.sup.-, --(O.dbd.S.dbd.O)O.sup.-,
--O(O.dbd.S.dbd.O)O.sup.-, --(S.dbd.O)O.sup.-, --O(S.dbd.O)O.sup.-,
--OP(.dbd.O)(OR.sup.24)O.sup.-, --OP(.dbd.O)(R.sup.24)O.sup.-,
--P(.dbd.O)(OR.sup.24)O.sup.-, or --P(.dbd.O)(R.sup.24)O.sup.- (in
which R.sup.24 represents an alkyl group having 1 to 3 carbon
atoms);
[0041] R.sup.19 represents a hydrogen atom or a methyl group;
[0042] R.sup.20 and R.sup.21 each independently represent a
divalent organic group having 1 to 10 carbon atoms; and
[0043] R.sup.22 and R.sup.23 each independently represent a
hydrocarbon group having 1 to 10 carbon atoms.
##STR00006##
in which in formula (8),
[0044] R.sup.25 represents a hydrogen atom or a methyl group;
[0045] R.sup.26 represents --O--, *--(C.dbd.O)--O.sup.-,
*--(C.dbd.O)--NR.sup.31--, *--NR.sup.31--(C.dbd.O)-- (in which
R.sup.31 represents a hydrogen atom or an organic group having 1 to
10 carbon atoms; and the symbol * represents the position at which
the moiety is bonded to the carbon atom to which R.sup.25 in
formula (8) is bonded), or a phenylene group;
[0046] R.sup.27 represents a divalent organic group having 1 to 10
carbon atoms; and
[0047] R.sup.28, R.sup.29 and R.sup.30 each independently represent
a hydrocarbon group having 1 to 10 carbon atoms.
[0048] (Repeating Unit (A-1))
[0049] The repeating unit (A-1) has a polyoxyalkylene group in a
side chain, and has the end of the side chain formed from a
hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
[0050] An example of the repeating unit (A-1) is a repeating unit
containing a structure represented by the following formula (1) in
a side chain. Regarding a polymer species that constitutes a
repeating unit having the structure represented by formula (1) in a
side chain, any known polymer can be used, and above all, for
example, a (meth)acrylate-based polymer species, a
(meth)acrylamide-based polymer species, or a styrene-based polymer
species is preferred. Among these, a repeating unit represented by
the following formula (2) is preferred.
R.sup.1O .sub.nR.sup.2 (1)
in which in formula (1),
[0051] R.sup.1 represents an alkylene group having 2 to 4 carbon
atoms;
[0052] R.sup.2 represents a hydrogen atom or an alkyl group having
1 to 4 carbon atoms; and
[0053] n represents 2 to 100 as an average value.
##STR00007##
in which in formula (2),
[0054] R.sup.3 represents a hydrogen atom or a methyl group;
[0055] R.sup.4 represents --O--, *--(C.dbd.O)--O.sup.-,
*--(C.dbd.O)--NR.sup.5--, *--NR.sup.5--(C.dbd.O)-- (in which
R.sup.5 represents a hydrogen atom or an organic group having 1 to
10 carbon atoms; and the symbol * represents the position at which
the moiety is bonded to the carbon atom to which R.sup.3 in formula
(2) is bonded), or a phenylene group; and
[0056] other variables have the same meanings as those of formula
(1), respectively.
[0057] Here, the respective variables in formulae (1) and (2) will
be explained.
[0058] R.sup.1 represents an alkylene group having 2 to 4 carbon
atoms, and n R.sup.1s may be identical or different.
[0059] The number of carbon atoms of the alkylene group represented
by R.sup.1 is preferably 2 or 3, and more preferably 2.
[0060] Furthermore, the alkylene group represented by R.sup.1 may
be linear or branched, and specific examples thereof include an
ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl
group, a propane-2,2-diyl group, a butane-1,2-diyl group, a
butane-1,3-diyl group, and a butane-1,4-diyl group. Among these,
from the viewpoints of, for example, easy availability and
impartation of hydrophilicity, an ethane-1,2-diyl group is
preferred.
[0061] Furthermore, R.sup.2 represents a hydrogen atom or an alkyl
group having 1 to 4 carbon atoms. The number of carbon atoms of the
alkyl group represented by R.sup.2 is preferably 1 to 3, more
preferably 1 or 2, and even more preferably 1, from the viewpoints
of, for example, easy availability and impartation of
hydrophilicity. Furthermore, the alkyl group represented by R.sup.2
may be linear or branched, and specific examples thereof include a
methyl group, an ethyl group, an n-propyl group, an isopropyl
group, an n-butyl group, an isobutyl group, a sec-butyl group, and
a tert-butyl group.
[0062] Among the groups for R.sup.2 as such, from the viewpoints
of, for example, easy availability and impartation of
hydrophilicity, a hydrogen atom or an alkyl group having 1 to 3
carbon atoms is preferred; a hydrogen atom or an alkyl group having
1 or 2 carbon atoms is more preferred; a hydrogen atom or a methyl
group is even more preferred; and a methyl group is particularly
preferred.
[0063] R.sup.4 represents --O--, *--(C.dbd.O)--O.sup.-,
*--(C.dbd.O)--NR.sup.5--, *--NR.sup.5--(C.dbd.O)--, or a phenylene
group. Examples of such a phenylene group include a 1,2-phenylene
group, a 1,3-phenylene group, and a 1,4-phenylene group.
[0064] Furthermore, the number of carbon atoms of the organic group
represented by R.sup.5 is 1 to 10, and is preferably 1 to 6. The
aforementioned organic group may be a hydrocarbon group. Such a
hydrocarbon group is a concept including an aliphatic hydrocarbon
group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon
group.
[0065] The aliphatic hydrocarbon group for R.sup.5 may be linear or
branched, and specific examples thereof include an alkyl group such
as a methyl group, an ethyl group, an n-propyl group, an isopropyl
group, an n-butyl group, an isobutyl group, a sec-butyl group, a
tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an
octyl group, a nonyl group, and a decyl group.
[0066] Furthermore, the alicyclic hydrocarbon group is roughly
classified into a monocyclic alicyclic hydrocarbon group and a
bridged cyclic hydrocarbon group. Examples of the monocyclic
alicyclic hydrocarbon group include a cycloalkyl group such as a
cyclopropyl group and a cyclohexyl group. Furthermore, examples of
the bridged cyclic hydrocarbon group include an isobornyl
group.
[0067] Furthermore, examples of the aromatic hydrocarbon group
include an aryl group such as a phenyl group.
[0068] Among the groups for R.sup.4 such as described above, from
the viewpoint of, for example, impartation of hydrophilicity,
*--(C.dbd.O)--O-- or a phenylene group is preferred, and
*--(C.dbd.O)--O-- is particularly preferred.
[0069] n represents 2 to 100 as an average value, and is preferably
4 to 90 as an average value, more preferably 8 to 90 as an average
value, even more preferably 8 to 60 as an average value, still more
preferably 8 to 40 as an average value, and particularly preferably
9 to 25 as an average value. Meanwhile, the various "average
values" in the present specification can be analyzed by NMR. For
example, the average value of n can be calculated by analyzing the
structure of the formula (2) described above by .sup.1H-NMR, and
comparing the integrated values of the respective proton peaks of
the alkylene group having 2 to 4 carbon atoms for R.sup.1 and the
terminal methyl group of the alkyl group having 1 to 4 carbon atoms
for R.sup.2.
[0070] Examples of the monomer from which such a repeating unit
(A-1) is derived include polyethylene glycol (meth)acrylate,
polypropylene glycol (meth)acrylate, polyethylene glycol
polypropylene glycol (meth)acrylate, polyethylene glycol
polytetramethylene glycol (meth)acrylate, polypropylene glycol
polytetramethylene glycol (meth)acrylate, methoxypolyethylene
glycol (meth)acrylate, and ethoxypolyethylene glycol
(meth)acrylate. The repeating unit (A-1) may be used singly or as a
combination of two or more thereof. Among these, polyethylene
glycol (meth)acrylate or methoxypolyethylene glycol (meth)acrylate
is preferred.
[0071] (Repeating Unit (A-2)
[0072] The repeating unit (A-2) is represented by the formula (3)
described above.
[0073] In formula (3), R.sup.7 represents an alkylene group having
2 to 4 carbon atoms. Note that when there are plural R.sup.7s, each
of R.sup.7 may be identical or different.
[0074] Furthermore, the number of carbon atoms of the alkylene
group represented by R.sup.7 is preferably 2 or 3, and more
preferably 2.
[0075] The alkylene group represented by R.sup.7 may be linear or
branched, and specific examples thereof include an ethane-1,2-diyl
group, a propane-1,2-diyl group, a propane-1,3-diyl group, a
propane-2,2-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl
group, and a butane-1,4-diyl group. Among these, from the
viewpoints of, for example, easy availability and impartation of
hydrophilicity, an ethane-1,2-diyl group is preferred.
[0076] Furthermore, R.sup.8 represents an alkylene group having 1
to 10 carbon atoms.
[0077] The number of carbon atoms of the alkylene group represented
by R.sup.8 is preferably 1 to 6, more preferably 1 to 4, even more
preferably 2 or 3, and particularly preferably 2.
[0078] Furthermore, the alkylene group represented by R.sup.8 may
be linear or branched, and specific suitable examples thereof
include the same groups as the alkylene groups represented by
R.sup.7.
[0079] Furthermore, R.sup.9, R.sup.10 and R.sup.11 each
independently represent a hydrogen atom or a hydrocarbon group
having 1 to 8 carbon atoms; and a hydrocarbon group having 1 to 8
carbon atoms is preferred. The number of carbon atoms of such a
hydrocarbon group is preferably 1 to 4, more preferably 1 or 2, and
particularly preferably 1.
[0080] Examples of the hydrocarbon group include an alkyl group, an
aryl group such as a phenyl group; and an aralkyl group such as a
benzyl group. An alkyl group is preferred.
[0081] The alkyl group may be linear or branched, and specific
suitable examples thereof include a methyl group, an ethyl group,
an n-propyl group, an isopropyl group, an n-butyl group, an
isobutyl group, a sec-butyl group, and a tert-butyl group.
[0082] Furthermore, q represents 1 to 10 as an average value, and
is preferably 1 to 7 as an average value, more preferably 1 to 4 as
an average value, and even more preferably 1.
[0083] Examples of the monomer from which such a repeating unit
(A-2) is derived include
2-(meth)acryloyloxyethyl-2'-(trimethylammonio)ethyl phosphate
(2-(meth)acryloyloxyethyl phosphorylcholine),
3-(meth)acryloyloxypropyl-2'-(trimethylammonio)ethyl phosphate,
4-(meth)acryloyloxybutyl-2'-(trimethylammonio)ethyl phosphate,
2-(meth)acryloyloxyethoxyethyl-2'-(trimethylammonio)ethyl
phosphate,
2-(meth)acryloyloxydiethoxyethyl-2'-(trimethylammonio)ethyl
phosphate, 2-(meth)acryloyloxyethyl-2'-(triethylammonio)ethyl
phosphate, and 2-(meth)acryloyloxyethyl-2'-(tributylammonio)ethyl
phosphate. The repeating unit (A-2) may be used singly or in
combination of two or more thereof.
[0084] (Repeating Unit (A-3))
[0085] The repeating unit (A-3) is represented by the formula (4)
described above.
[0086] In formula (4), R.sup.13 and R.sup.14 each independently
represent a hydrogen atom, an alkyl group having 1 to 6 carbon
atoms, or a hydroxyalkyl group.
[0087] The number of carbon atoms of the alkyl group represented by
R.sup.13 and R.sup.14 is preferably 1 to 3.
[0088] Furthermore, the alkyl group represented by R.sup.13 or
R.sup.14 may be linear or branched, and specific suitable examples
thereof include a methyl group, an ethyl group, an n-propyl group,
and an isopropyl group.
[0089] Furthermore, the number of carbon atoms of the hydroxyalkyl
group represented by R.sup.13 and R.sup.14 is preferably 1 to 6,
and more preferably 1 to 3. The alkyl group contained in the
hydroxyalkyl group may be linear or branched, and specific suitable
examples of the hydroxyalkyl group include a hydroxymethyl group, a
hydroxyethyl group, a hydroxypropyl group, and a hydroxyisopropyl
group. Note that the position of substitution of the hydroxyl group
in the hydroxyalkyl group is arbitrary.
[0090] Examples of the monomer from which such a repeating unit
(A-3) is derived include dimethyl (meth)acrylamide, diethyl
(meth)acrylamide, N-isopropyl (meth)acrylamide,
N-(hydroxymethyl)(meth)acrylamide, and N-(2-hydroxyethyl)
(meth)acrylamide. The repeating unit (A-3) may be used singly or in
combination of two or more thereof.
[0091] (Repeating Unit (A-4))
[0092] The repeating unit (A-4) is represented by the formula (5)
described above.
[0093] In formula (5), R.sup.16 and R.sup.17 each independently
represent an alkylene group having 1 to 3 carbon atoms. The number
of carbon atoms of such an alkylene group is preferably 1 or 2.
[0094] Furthermore, the alkylene group may be linear or branched;
and the alkylene group is preferably linear. Specific suitable
examples thereof include a methane-1,1-diyl group and an
ethane-1,2-diyl group.
[0095] Examples of the monomer from which such a repeating unit
(A-4) is derived include 4-(meth)acryloylmorpholine.
[0096] (Repeating Unit (A-5))
[0097] The repeating unit (A-5) is represented by the formula (6)
described above.
[0098] In formula (6), R.sup.18 represents an alkylene group having
1 to 5 carbon atoms. The number of carbon atoms of such an alkylene
group is preferably 3 to 5.
[0099] Furthermore, the alkylene group may be linear or branched;
and the alkylene group is preferably linear. Specific suitable
examples thereof include a propane-1,3-diyl group, a
butane-1,4-diyl group, and a pentane-1,5-diyl group.
[0100] Examples of the monomer from which such a repeating unit
(A-5) is derived include 1-vinyl-2-pyrrolidone and
N-vinyl-.epsilon.-caprolactam, and the repeating unit (A-5) may
used singly or in combination of two or more thereof.
[0101] (Repeating Unit (A-6))
[0102] The repeating unit (A-6) is a betaine-like repeating unit
represented by the formula (7) described above.
[0103] In formula (7), Y is preferably --(C.dbd.O)O.sup.-. Note
that examples of the alkyl group represented by R.sup.24 include a
methyl group, an ethyl group, an n-propyl group, and an isopropyl
group.
[0104] Furthermore, in formula (7), R.sup.20 and R.sup.21 each
independently represent a divalent organic group having 1 to 10
carbon atoms. The number of carbon atoms of such a divalent organic
group is preferably 1 to 8, and more preferably 1 to 6.
[0105] Furthermore, the divalent organic group is preferably a
divalent hydrocarbon group, and more preferably a divalent
aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon
group may be linear or branched. Also, the divalent aliphatic
hydrocarbon group is preferably an alkylene group. Examples of the
divalent aliphatic hydrocarbon group include a methane-1,1-diyl
group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a
propane-1,2-diyl group, a propane-1,3-diyl group, a
propane-2,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl
group, and a hexane-1,6-diyl group.
[0106] Furthermore, in formula (7), R.sup.22 and R.sup.23 each
independently represent a hydrocarbon group having 1 to 10 carbon
atoms. The number of carbon atoms of the hydrocarbon group is
preferably 1 to 6, and more preferably 1 to 4.
[0107] Examples of the hydrocarbon group represented by R.sup.22
and R.sup.23 include an alkyl group; an aryl group such as a phenyl
group; and an aralkyl group such as a benzyl group; and an alkyl
group is preferred. The alkyl group may be linear or branched, and
examples thereof include a methyl group, an ethyl group, an
n-propyl group, an isopropyl group, an n-butyl group, an isobutyl
group, a sec-butyl group, and a tert-butyl group.
[0108] Examples of the monomer from which such a repeating unit
(A-6) is derived include a (meth)acrylate-based monomer such as
N-(meth)acryloyloxyethyl-N,N-dimethylammonium-.alpha.-N-methylcarboxybeta-
ine and
N-(meth)acryloyloxyethyl-N,N-dimethylammonium-.alpha.-N-propylsulf-
obetaine. The repeating unit (A-6) may be used singly or in
combination of two or more thereof.
[0109] (Repeating Unit (A-7))
[0110] The repeating unit (A-7) is an anionic repeating unit.
Examples of the repeating unit (A-7) include a repeating unit
having an acidic group.
[0111] Furthermore, regarding the repeating unit (A-7), from the
viewpoint of easy availability and safety, a unit derived from a
monomer containing an ethylenically unsaturated bond is
preferred.
[0112] Examples of the acidic group include a carboxyl group, a
sulfo group, a phosphoric acid group, or a salt thereof, and a
repeating unit may have one of these acidic groups, or may have two
or more thereof. Note that examples of the salts include alkali
metal salts such as a sodium salt and a potassium salt; alkaline
earth metal salts such as a magnesium salt and a calcium salt; an
ammonium salt; and an organic ammonium salt.
[0113] Examples of the monomer from which the repeating unit (A-7)
is derived include an unsaturated dicarboxylic acid such as fumaric
acid, maleic acid and itaconic acid, or a salt thereof; an
unsaturated carboxylic acid such as (meth)acrylic acid, or a salt
thereof; a sulfo group-containing polymerizable unsaturated monomer
such as ethylenesulfonic acid, allylsulfonic acid, methallyl
sulfonic acid, 2-sulfoethyl (meth)acrylate, and
2-acrylamido-2-methylpropanesulfonic acid, or a salt thereof; and a
phosphoric acid group-containing polymerizable unsaturated monomer
such as 2-(meth)acryloyloxyethyl acid phosphate and
2-(meth)acryloyloxypropyl acid phosphate, or a salt thereof.
Furthermore, the monomer from which the repeating unit (A-7) is
derived may also be obtained using, for example, a hydrolysate of
an acrylic acid ester; a hydrolysate of an acid anhydride of an
unsaturated dicarboxylic acid such as maleic anhydride or itaconic
anhydride; or an adduct of an acidic group-containing thiol to an
epoxy group of glycidyl methacrylate or (4-vinylbenzyl) glycidyl
ether or the like. The repeating unit (A-7) may be used singly or
in combination of two or more thereof.
[0114] Among these, from the viewpoints of easy availability and
reactivity, acrylic acid, or methacrylic acid is preferred.
[0115] (Repeating Unit (A-8))
[0116] The repeating unit (A-8) is a cationic repeating unit
represented by the formula (8) described above.
[0117] In formula (8), R.sup.26 represents --O--,
*--(C.dbd.O)--O.sup.-, *--(C.dbd.O)--NR.sup.31--,
*--NR.sup.31--(C.dbd.O)--, or a phenylene group. Examples of such a
phenylene group include a 1,2-phenylene group, a 1,3-phenylene
group, and a 1,4-phenylene group.
[0118] The number of carbon atoms of the organic group represented
by R.sup.31 is 1 to 10, and is preferably 1 to 6. Examples of the
organic group include a hydrocarbon group. Such a hydrocarbon group
is a concept including an aliphatic hydrocarbon group, an alicyclic
hydrocarbon group, and an aromatic hydrocarbon group.
[0119] The aliphatic hydrocarbon group for R.sup.31 may be linear
or branched, and specific examples thereof include an alkyl group
such as a methyl group, an ethyl group, an n-propyl group, an
isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl
group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl
group, an octyl group, a nonyl group, and a decyl group.
[0120] Furthermore, the alicyclic hydrocarbon group is roughly
classified into a monocyclic alicyclic hydrocarbon group and a
bridged cyclic hydrocarbon group. Examples of the monocyclic
alicyclic hydrocarbon group include a cycloalkyl group such as a
cyclopropyl group and a cyclohexyl group. Furthermore, examples of
the bridged cyclic hydrocarbon group include an isobornyl
group.
[0121] Furthermore, examples of the aromatic hydrocarbon group
include an aryl group such as a phenyl group.
[0122] In formula (8), R.sup.27 represents a divalent organic group
having 1 to 10 carbon atoms. The number of carbon atoms of such a
divalent organic group is preferably 1 to 8, and more preferably 1
to 6.
[0123] Furthermore, regarding the divalent organic group, a
divalent hydrocarbon group is preferred, and a divalent aliphatic
hydrocarbon group is more preferred. The divalent aliphatic
hydrocarbon group may be linear or branched. The divalent aliphatic
hydrocarbon group is preferably an alkylene group. Examples thereof
include a methane-1,1-diyl group, an ethane-1,2-diyl group, a
propane-1,1-diyl group, a propane-1,2-diyl group, a
propane-1,3-diyl group, a propane-2,2-diyl group, a butane-1,4-diyl
group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.
[0124] In formula (8), R.sup.28, R.sup.29 and R.sup.30
independently represent a hydrocarbon group having 1 to 10 carbon
atoms. The number of carbon atoms of the hydrocarbon group is
preferably 1 to 6, and more preferably 1 to 4.
[0125] Examples of the hydrocarbon group represented by R.sup.28,
R.sup.29 and R.sup.30 include an alkyl group; an aryl group such as
a phenyl group; and an aralkyl group such as benzyl group; and an
alkyl group is preferred. The alkyl group may be linear or
branched, and examples thereof include a methyl group, an ethyl
group, an n-propyl group, an isopropyl group, an n-butyl group, an
isobutyl group, a sec-butyl group, and a tert-butyl group.
[0126] Note that the repeating unit (A-8) may have a counterion.
Examples of the counterion include a halogeno ion such as chlorine
ion, bromine ion, and iodine ion; a hydrogen sulfide ion; an
alkylsulfuric acid ion such as methylsulfuric acid ion and
ethylsulfuric acid ion; an alkylsulfonic acid ion; an arylsulfonic
acid ion such as dodecylbenzenesulfonic acid ion and
para-toluenesulfonic acid ion; an alkenylsulfonic acid ion such as
sodium 2-methyl-2-propene-1-sulfonate; and a carboxylic acid ion
such as acetic acid ion.
[0127] Specific suitable examples of the monomer species of the
monomer from which the repeating unit (A-8) is derived, include a
(meth)acrylate and a (meth)acrylamide.
[0128] Examples of the monomer species of (meth)acrylate include a
((meth)acryloyloxy-C.sub.1-10 alkyl)-tri-C.sub.1-10 alkylammonium
chloride such as ((meth)acryloyloxyethyl)trimethylammonium
chloride; and a ((meth)acryloyloxy-C.sub.1-10 alkyl)-di-C.sub.1-10
alkyl-C.sub.6-10 aralkylammonium chloride such as
((meth)acryloyloxyethyl)dimethylbenzylammonium chloride. Examples
of the monomer species of (meth)acrylamide include
(3-(meth)acrylamido-C.sub.110 alkyl)-tri-C.sub.110 alkylammonium
chloride such as (3-(meth)acrylamidopropyl)trimethylammonium
chloride; and (3-(meth)acrylamido-C.sub.1-10 alkyl)-di-C.sub.1-10
alkyl-C.sub.6-10 aralkylammonium chloride such as
(3-(meth)acrylamidopropyl)dimethylbenzylammonium chloride. The
repeating unit (A-8) may be used singly or in combination of two or
more thereof.
[0129] Among these, from the viewpoints of easy availability and
reactivity, (3-(meth)acrylamidopropyl)trimethylammonium chloride is
preferred.
[0130] Among these repeating units (A-1) to (A-8), from the
viewpoints of lipid detergency, hydrophilization performance,
peeling resistance, a lipid adhesion preventive effect, and a
lubricity-imparting effect, the repeating unit (A-1), repeating
unit (A-3), repeating unit (A-4), repeating unit (A-6), and
repeating unit (A-7) are preferred, and the repeating unit (A-1),
repeating unit (A-3), repeating unit (A-6) and repeating unit (A-7)
are more preferred.
[0131] Also, in a case where these repeating units are used in
combination, regarding the combination, from the viewpoints of
hydrophilization performance, peeling resistance, and a
lubricity-imparting effect, a combination of one or more selected
from the group consisting of the repeating units (A-1) and (A-3),
and one or more selected from the group consisting of the repeating
units (A-6) and (A-7) is preferred, and a combination of the
repeating unit (A-3) and one or more selected from the group
consisting of the repeating units (A-6) and (A-7) is more
preferred, and a combination of the repeating unit (A-3) and the
repeating unit (A-6) is particularly preferred.
[0132] Furthermore, a total content of the repeating unit (A) is
2.5% to 95% by mass in the polymer; and from the viewpoints of
lipid detergency, hydrophilization performance, peeling resistance,
a lipid adhesion preventive effect and a lubricity-imparting
effect, and from the viewpoint of enhancing the water-solubility of
the polymer, the total content is preferably 5% to 95% by mass,
more preferably 20% to 95% by mass, even more preferably 30% to 95%
by mass, and still more preferably 40% to 90% by mass.
[0133] Furthermore, in a case where the lens solution of the
present invention is intended for contact lens cleaning or for
storage, the total content is particularly preferably 50% to 90% by
mass from the viewpoints of lipid detergency and impartation of
hydrophilicity. On the other hand, in a case where the lens
solution of the present invention is used as a contact lens coating
agent, from the viewpoints of impartation of hydrophilicity,
peeling resistance and a lubricity impartation effect, the total
content is more preferably 30% to 95% by mass, and particularly
preferably 40% to 90% by mass.
[0134] Furthermore, in a case where one or more selected from the
group consisting of the repeating units (A-1) and (A-3) and one or
more selected from the group consisting of the repeating units
(A-6) and (A-7) are used in combination, the content ratio thereof
is, in terms of a mass ratio, preferably 60:40 to 99.9:0.1, more
preferably 75:25 to 99:1, even more preferably 80:20 to 99:1, and
particularly preferably 85:15 to 99:1.
[0135] Note that the content of the repeating unit (A) can be
analyzed by, for example, .sup.1H-NMR or .sup.13C-NMR.
[0136] (Repeating Unit (B))
[0137] The repeating unit (B) is a repeating unit having a
polyoxyalkylene group in a side chain, and has the end of the side
chain formed from an alkyl group having 5 to 30 carbon atoms, an
alkanoyl group having 5 to 30 carbon atoms, or an aryl group. A
polymer may have one or two or more of repeating units
corresponding to the repeating unit (B).
[0138] An example of such a repeating unit (B) is a repeating unit
containing a structure represented by the following formula (9) in
a side chain. Regarding a polymer species that constitutes a
repeating unit having a structure represented by formula (9) in a
side chain, any known polymer species can be used, and above all,
for example, a (meth)acrylate-based polymer species, a
(meth)acrylamide-based polymer species, or a styrene-based polymer
species is preferred. Among them, a repeating unit represented by
the following formula (10) is preferred.
R.sup.32O .sub.mR.sup.33 (9)
in which in formula (9),
[0139] R.sup.32 represents an alkylene group having 2 to 4 carbon
atoms;
[0140] R.sup.33 represents an alkyl group having 5 to 30 carbon
atoms, an alkanoyl group having 5 to 30 carbon atoms, or an aryl
group; and m represents 2 to 100 as an average value.
##STR00008##
in which in formula (10),
[0141] R.sup.34 represents a hydrogen atom or a methyl group;
[0142] R.sup.35 represents --O--, **--(C.dbd.O)--O.sup.-,
**--(C.dbd.O)--NR.sup.36, **--NR.sup.36--(C.dbd.O)-- (in which
R.sup.36 represents a hydrogen atom or an organic group having 1 to
10 carbon atoms; and the symbol ** represents the position at which
the moiety is bonded to the carbon atom to which R.sup.34 in
formula (10) is bonded), or a phenylene group; and
[0143] other variables have the same meanings as those of formula
(9).
[0144] Here, the various symbols in formulae (9) and (10) will be
explained.
[0145] R.sup.32 represents an alkylene group having 2 to 4 carbon
atoms. The number of carbon atoms of the alkylene group represented
by R.sup.32 is preferably 2 or 3, and more preferably 2.
[0146] Furthermore, the alkylene group represented by R.sup.32 may
be linear or branched, and specific examples thereof include an
ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl
group, a propane-2,2-diyl group, a butane-1,2-diyl group, a
butane-1,3-diyl group, and a butane-1,4-diyl group. Among these,
from the viewpoints of, for example, easy availability and lipid
detergency, an ethane-1,2-diyl group is preferred.
[0147] Note that m R.sup.32s may be identical or different.
[0148] Furthermore, R.sup.33 represents an alkyl group having 5 to
30 carbon atoms, an alkanoyl group having 5 to 30 carbon atoms, or
an aryl group.
[0149] The number of carbon atoms of the alkyl group or alkanoyl
group represented by R.sup.33 is preferably 6 to 25, more
preferably 7 to 20, even more preferably 8 to 18, still more
preferably 9 to 16, and particularly preferably 10 to 14, from the
viewpoints of, for example, easy availability and lipid
detergency.
[0150] Furthermore, the alkyl group represented by R.sup.33 may be
linear or branched, and specific examples thereof include a
2-ethylhexyl group, an octyl group, a decyl group, a lauryl group,
a palmityl group, and a stearyl group. Among these, a 2-ethylhexyl
group, a lauryl group or a stearyl group is preferred, and a lauryl
group or a stearyl group is more preferred.
[0151] Furthermore, examples of the alkanoyl group represented by
R.sup.33 include a 2-ethylhexanoyl group, a lauroyl group, and a
stearoyl group.
[0152] The number of carbon atoms of the aryl group represented by
R.sup.33 is 6 to 12. A specific example thereof is a phenyl
group.
[0153] Furthermore, the aryl group may have an alkyl group having 1
to 30 carbon atoms as a substituent. The number of carbon atoms of
such an alkyl group is preferably 3 to 24, and more preferably 5 to
16. Note that the position of substitution and the number of
substitutions of such a substituted alkyl group are arbitrary; and
a suitable number of substitutions is 1 or 2.
[0154] Furthermore, examples of an aryl group having such an alkyl
group having 1 to 30 carbon atoms as a substituent include a
nonylphenyl group.
[0155] Among the groups for R.sup.33 as described above, from the
viewpoints of, for example, easy availability and lipid detergency,
an alkyl group having 5 to 30 carbon atoms or an aryl group is
preferred, and an alkyl group having 5 to 30 carbon atoms is more
preferred.
[0156] Furthermore, R.sup.35 represents --O--,
**--(C.dbd.O)--O.sup.-, **--(C.dbd.O)--NR.sup.36--,
**--NR.sup.36--(C.dbd.O)--, or a phenylene group. Examples of such
a phenylene group include a 1,2-phenylene group, a 1,3-phenylene
group, and a 1,4-phenylene group.
[0157] The number of carbon atoms of the organic group represented
by R.sup.36 is 1 to 10, and is preferably 1 to 6. Examples of the
organic group include a hydrocarbon group. Such a hydrocarbon group
is a concept including an aliphatic hydrocarbon group, an alicyclic
hydrocarbon group, and an aromatic hydrocarbon group.
[0158] The aliphatic hydrocarbon group for R.sup.36 may be linear
or branched, and specific examples thereof include alkyl groups
such as a methyl group, an ethyl group, an n-propyl group, an
isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl
group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl
group, an octyl group, a nonyl group, and a decyl group.
[0159] Furthermore, the alicyclic hydrocarbon group is roughly
classified into a monocyclic alicyclic hydrocarbon group and a
bridged cyclic hydrocarbon group. Examples of the monocyclic
alicyclic hydrocarbon group include cycloalkyl groups such as a
cyclopropyl group and a cyclohexyl group. Also, examples of the
bridged cyclic hydrocarbon group include an isobornyl group.
[0160] Examples of the aromatic hydrocarbon group include an aryl
group such as a phenyl group.
[0161] Among the groups for R.sup.35 as described above,
**--(C.dbd.O)--O-- or a phenylene group is preferred, and
**--(C.dbd.O)--O-- is particularly preferred.
[0162] m represents 2 to 100 as an average value, and is preferably
2 to 90 as an average value, more preferably 4 to 90 as an average
value, even more preferably 9 to 60 as an average value, and
particularly preferably 10 to 40 as an average value.
[0163] Examples of the monomer from which such a repeating unit (B)
is derived include 2-ethylhexyl polyethylene glycol (meth)acrylate,
lauroxypolyethylene glycol (meth)acrylate, stearoxypolyethylene
glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate,
phenoxypolypropylene glycol (meth)acrylate,
nonylphenoxypolypropylene glycol (meth)acrylate, 2-ethylhexyl
polyethylene glycol polypropylene glycol (meth)acrylate, and
nonylphenoxypolyethylene glycol polypropylene glycol
(meth)acrylate. The repeating unit (B) may be used singly or in
combination of two or more thereof. Among these,
lauroxypolyethylene glycol (meth)acrylate or stearoxypolyethylene
glycol (meth)acrylate is preferred.
[0164] A total content of the repeating unit (B) is 2.5% to 95% by
mass in the polymer; and from the viewpoints of lipid detergency,
hydrophilization performance, peeling resistance, and a lipid
adhesion preventive effect, and from the viewpoint of enhancing the
water-solubility of the polymer, the total content is preferably 5%
to 95% by mass, more preferably 5 to 80% by mass, even more
preferably 10 to 70% by mass, and still more preferably 10% to 60%
by mass.
[0165] Furthermore, in a case where the lens solution of the
present invention is intended for contact lens cleaning or for
storage, from the viewpoints of lipid detergency and impartation of
hydrophilicity, the total content is particularly preferably 10% to
50% by mass. On the other hand, in a case where the lens solution
of the present invention is used as a contact lens coating agent,
from the viewpoints of impartation of hydrophilicity and peeling
resistance, the total content is particularly preferably 10% to 60%
by mass.
[0166] Note that the content of the repeating unit (B) may be
analyzed in the same manner as in the case of the content of the
repeating unit (A).
[0167] (Repeating Unit (C))
[0168] It is preferable that the polymer used in the present
invention has one or more repeating unit (C) selected from the
group consisting of a repeating unit (C-1) represented by the
following formula (11) and a repeating unit (C-2) having a group
represented by the following formula (12) at the end of a side
chain. When the polymer includes such repeating units (C), the
hydrophilization performance is enhanced, and the polymer is
unlikely peeled off from the lens surface.
##STR00009##
in which in formula (11),
[0169] R.sup.37 represent a hydrogen atom or a methyl group;
[0170] R.sup.38 represents --O--, ***--(C.dbd.O)--O.sup.-,
***--(C.dbd.O)--NR.sup.4--, ***--NR.sup.40--(C.dbd.O)-- (in which
R.sup.40 represents a hydrogen atom or an organic group having 1 to
10 carbon atoms; and the symbol *** represents the position at
which the moiety is bonded to the carbon atom to which R.sup.37 in
formula (11) is bonded), or a phenylene group; and
[0171] R.sup.39 represents a hydrocarbon group having 4 to 30
carbon atoms.
##STR00010##
in which in formula (12),
[0172] R.sup.41 represents a divalent organic group having 1 to 10
carbon atoms;
[0173] R.sup.42 and R.sup.43 each independently represent an
organic group having 1 to 10 carbon atoms;
[0174] R.sup.44, R.sup.45 and R.sup.46 independently represent
--OSi(R.sup.49).sub.3 (in which R.sup.49 independently represent a
hydrogen atom or an organic group having 1 to 8 carbon atoms), or
an organic group having 1 to 10 carbon atoms; and r represents 0 to
200 as an average value.
[0175] (Repeating Unit (C-1))
[0176] The repeating unit (C-1) is represented by the formula (11)
described above.
[0177] R.sup.38 represents --O--, ***--(C.dbd.O)--O.sup.-,
***--(C.dbd.O)--NR.sup.40--, ***--NR.sup.40--(C.dbd.O)--, or a
phenylene group. Examples of such a phenylene group include a
1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene
group.
[0178] The number of carbon atoms of the organic group represented
by R.sup.40 is 1 to 10, and is preferably 1 to 6. Examples of the
aforementioned organic group include a hydrocarbon group. Such a
hydrocarbon group is a concept including an aliphatic hydrocarbon
group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon
group.
[0179] The aliphatic hydrocarbon group for R.sup.40 may be linear
or branched, and specific examples thereof include an alkyl group
such as a methyl group, an ethyl group, an n-propyl group, an
isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl
group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl
group, an octyl group, a nonyl group, and a decyl group.
[0180] Furthermore, the alicyclic hydrocarbon group is roughly
classified into a monocyclic alicyclic hydrocarbon group and a
bridged cyclic hydrocarbon group. Examples of the monocyclic
alicyclic hydrocarbon group include a cycloalkyl group such as a
cyclopropyl group and a cyclohexyl group. Furthermore, examples of
the bridged cyclic hydrocarbon group include an isobornyl
group.
[0181] Furthermore, examples of the aromatic hydrocarbon group
include an aryl group such as a phenyl group.
[0182] Among the groups for R.sup.38 as described above, from the
viewpoint of enhancing lipid detergency and hydrophilization
performance, as well as from the viewpoint of unlikely making the
polymer peeling from the lens surface, ***--(C.dbd.O)--O.sup.-,
***--(C.dbd.O)--NR.sup.40--, or a phenylene group is preferred,
***--(C.dbd.O)--O-- or ***--(C.dbd.O)--NR.sup.40-- is more
preferred, and ***--(C.dbd.O)--O-- or ***--(C.dbd.O)--NH-- is
particularly preferred.
[0183] Furthermore, R.sup.39 represents a hydrocarbon group having
4 to 30 carbon atoms, and may be linear or branched, or may contain
a cyclic structure. R.sup.39 is preferably an alkyl group.
[0184] Furthermore, the number of carbon atoms of the hydrocarbon
group is preferably 6 to 24, more preferably 8 to 18, and even more
preferably 8 to 14.
[0185] Examples of the alkyl group include a 2-ethylhexyl group, an
octyl group, a decyl group, a lauryl group, a palmityl group, and a
stearyl group. Among these, from the viewpoints of, for example,
easy availability and lipid detergency, a 2-ethylhexyl group, a
lauryl group and a stearyl group are preferred, and a 2-ethylhexyl
group and a lauryl group are more preferred.
[0186] Examples of the monomer from which such a repeating unit
(C-1) is derived include 2-ethylhexyl (meth)acrylate, lauryl
(meth)acrylate, and stearyl (meth)acrylate. The repeating unit
(C-1) may be used singly or in combination of two or more
thereof.
[0187] (Repeating Unit (C-2))
[0188] Regarding a polymer species that constitutes a repeating
unit having a group represented by the formula (12) described above
at the end of a side chain, any known polymer species can be used,
and above all, for example, a (meth)acrylate-based polymer species,
a (meth)acrylamide-based polymer species, or a styrene-based
polymer species is preferred. Among these, a repeating unit
represented by the following formula (13) is preferred.
##STR00011##
in which in formula (13),
[0189] R.sup.47 represents a hydrogen atom or a methyl group;
[0190] R.sup.48 represents --O--, *--(C.dbd.O)--O--,
*--(C.dbd.O)--NR.sup.50, *--NR.sup.50--(C.dbd.O)-- (in which
R.sup.50 represents a hydrogen atom or an organic group having 1 to
10 carbon atoms; and the symbol * represents the position at which
the moiety is bonded to the carbon atom to which R.sup.47 in
formula (13) is bonded), or a phenylene group; and other variables
have the same meanings as those of formula (12).
[0191] Here, the respective variables in formulae (12) and (13)
will be explained.
[0192] R.sup.41 represents a divalent organic group having 1 to 10
carbon atoms. The number of carbon atoms of such a divalent organic
group is preferably 2 to 8, more preferably 2 to 6, and even more
preferably 2 to 4.
[0193] Examples of the divalent organic group include a divalent
hydrocarbon group. The divalent hydrocarbon group is preferably a
divalent aliphatic hydrocarbon group, and may be linear or
branched; and the divalent hydrocarbon group is more preferably an
alkylene group. Specific suitable examples of such an alkylene
group include an ethane-1,2-diyl group, a propane-1,2-diyl group, a
propane-1,3-diyl group, a propane-2,2-diyl group, a butane-1,2-diyl
group, a butane-1,3-diyl group, and a butane-1,4-diyl group.
[0194] Furthermore, R.sup.42 and R.sup.43 independently represent
an organic group having 1 to 10 carbon atoms. Note that when there
are plural R.sup.42's and plural R.sup.43's, each of R.sup.42 may
be identical or different, and each of R.sup.43 may also be
identical or different.
[0195] Furthermore, the number of carbon atoms of the organic group
is preferably 1 to 6, more preferably 1 to 4, and even more
preferably 1 or 2.
[0196] Examples of the organic group include a hydrocarbon group.
The hydrocarbon group may be linear or branched, and is preferably
an alkyl group. Specific examples of such an alkyl group include a
methyl group, an ethyl group, an n-propyl group, an isopropyl
group, an n-butyl group, an isobutyl group, a sec-butyl group, and
a tert-butyl group.
[0197] R.sup.44, R.sup.45 and R.sup.46 independently represent
--OSi(R.sup.49).sub.3 or an organic group having 1 to 10 carbon
atoms, and R.sup.49 independently represent a hydrogen atom or an
organic group having 1 to 8 carbon atoms.
[0198] The number of carbon atoms of the organic group represented
by R.sup.44, R.sup.45 and R.sup.46 or the organic group represented
by R.sup.49 is preferably 1 to 6, more preferably 1 to 4, and even
more preferably 1 or 2. Furthermore, examples of the organic group
represented by R.sup.44, R.sup.45 and R.sup.46 or the organic group
represented by R.sup.49 include the same groups as the organic
groups represented by R.sup.42.
[0199] Furthermore, among the groups for R.sup.44, R.sup.45 and
R.sup.46, from the viewpoints of lipid detergency and impartation
of hydrophilicity, --OSi(R.sup.49).sub.3 is preferred. Furthermore,
among the groups for R.sup.49, from the viewpoints of lipid
detergency and impartation of hydrophilicity, an organic group
having 1 to 8 carbon atoms is preferred.
[0200] r represents 0 to 200 as an average value; and from the
viewpoints of lipid detergency and impartation of hydrophilicity, r
is preferably 0 to 100, more preferably 0 to 50, even more
preferably 0 to 25, and particularly preferably 0 to 10.
[0201] Note that R.sup.48 is similar to R.sup.38, and R.sup.50 is
similar to R.sup.4
[0202] Examples of the monomer from which such a repeating unit
(C-2) is derived include 3-[tris(trimethylsiloxy)silyl]propyl
(meth)acrylate, 3-[bis(trimethylsiloxy)(methyl)silyl]propyl
(meth)acrylate, and silicone (meth)acrylate (for example, X-22-2475
(manufactured by Shin-Etsu Silicones, Inc.) and FM-0711
(manufactured by JNC Corp.)). The repeating unit (C-2) may be used
singly or in combination of two or more thereof.
[0203] Furthermore, from the viewpoints of lipid detergency,
hydrophilization performance, peeling resistance and a lipid
adhesion preventive effect, a total content of the repeating unit
(C) is preferably 40% by mass or less, more preferably 0.1% to 40%
by mass, even more preferably 0.5% to 35% by mass, still more
preferably 0.5% to 30% by mass, even more preferably 0.5% 25% by
mass, still more preferably 0.5% to 20% by mass, even more
preferably 1% to 20% by mass, still more preferably 1% to 15% by
mass, still more preferably 1.5% to 15% by mass, and particularly
preferably 1.5% to 10% by mass, in the polymer.
[0204] Note that the content of the repeating unit (C) may be
measured in the same manner as in the case of the content of the
repeating unit (A).
[0205] Furthermore, a mass ratio between the repeating unit (A) and
the repeating unit (B) included in the polymer used for the present
invention, [(A):(B)], is, from the viewpoints of lipid detergency,
hydrophilization performance, peeling resistance and a lipid
adhesion preventive effect and from the viewpoint of enhancing the
water-solubility of the polymer, preferably 20:80 to 95:5, more
preferably 30:70 to 95:5, even more preferably 40:60 to 90:10,
still more preferably 50:50 to 90:10, and particularly preferably
55:45 to 90:10.
[0206] Furthermore, in a case where the polymer used for the
present invention has a repeating unit (C), from the viewpoints of
lipid detergency, hydrophilization performance, peeling resistance
and a lipid adhesion preventive effect, the mass ratio,
[((A)+(B)):(C)], is preferably 60:40 to 99:1, more preferably 70:30
to 99:1, even more preferably 75:25 to 99:1, still more preferably
80:20 to 98.5:1.5, and particularly preferably 85:15 to
98.5:1.5.
[0207] Furthermore, it is particularly preferable that the mass
ratio [(A):(B)] is in the range of the mass ratio [(A):(B)]
mentioned above, and the mass ratio [((A)+(B)):(C)] is in the range
of the mass ratio [((A)+(B)):(C)] mentioned above.
[0208] The polymer used for the present invention may be a
copolymer, and may be any of a block copolymer, a random copolymer
and an alternating copolymer.
[0209] A weight average molecular weight (M.sub.w) of the polymer
used for the present invention is preferably 10,000 to 10,000,000,
more preferably 10,000 to 5,000,000, even more preferably 10,000 to
3,000,000, and particularly preferably 10,000 to 2,000,000. When
the weight average molecular weight is adjusted to such a range,
peeling resistance and handleability are enhanced together.
[0210] Furthermore, a number average molecular weight (M.sub.n) of
the polymer used for the present invention is preferably 10,000 to
10,000,000, more preferably 10,000 to 5,000,000, even more
preferably 10,000 to 3,000,000, still more preferably 10,000 to
2,000,000, and particularly preferably 10,000 to 500,000.
[0211] Also, a molecular weight distribution (M.sub.w/M.sub.n) is
preferably 1 to 10, more preferably 1 to 7, and particularly
preferably 1 to 5.
[0212] Note that the weight average molecular weight, the number
average molecular weight, and the molecular weight distribution may
be measured by the method described in the following Examples.
[0213] The polymer used for the present invention is preferably a
polymer which dissolves in a lower alcohol having about 1 to 4
carbon atoms or in water. Furthermore, in a case where the lens
solution of the present invention is used for cleaning and storage
of contact lenses, the polymer is particularly preferably a polymer
which is dissolved in water (water-soluble polymer). Here, in the
present specification, the dissolution means that when the polymer
is added and mixed into a solvent (25.degree. C.) so as to obtain a
polymer solid content of 0.5% by mass, the mixture visually becomes
transparent.
[0214] Furthermore, the polymer used for the present invention can
be obtained by, for example, mixing the monomers from which the
respective repeating units are derived, optionally dissolving the
resulting mixture in a solvent such as water, acetonitrile, or
ECUAMIDE B-100 (manufactured by Idemitsu Kosan Co., Ltd.), and
performing radical polymerization by adding a polymerization
initiator thereto.
[0215] The polymerization initiator used when the radical
polymerization is performed is not particularly limited as long as
the polymerization initiator is a conventional radical
polymerization initiator; and examples thereof include benzoyl
peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, t-butyl
peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl
peroxydiisobutyrate, azobis(isobutyronitrile),
azobis(isodimethylvaleronitrile), persulfuric acid salts, and
persulfuric acid salt-hydrogensulfite salt systems.
[0216] Furthermore, an input amount of the polymerization initiator
is preferably 0.001 to 10 parts by mass, and more preferably 0.01
to 5 parts by mass, relative to 100 parts by mass of the monomer
components. Furthermore, a polymerization temperature is preferably
20.degree. C. to 100.degree. C., and a polymerization time is
preferably 0.5 to 48 hours.
[0217] The lens solution of the present invention can be produced
according to a conventional method, except that a polymer
obtainable as described above is used.
[0218] As will be disclosed in the following Examples, the lens
solution of the present invention has excellent lipid detergency,
exhibits high hydrophilization performance, and exhibits an
excellent lipid adhesion preventive effect and an excellent
lubricity-imparting effect when the lens solution is used to coat a
lens. Also, the lens solution exhibits high adsorptiveness to lens
surfaces, and unlikely peels.
[0219] Therefore, the lens solution of the present invention is
useful as a solution for an ophthalmic lens.
[0220] The ophthalmic lens is a concept including contact lenses
such as a soft contact lens and a hard contact lens, as well as
spectacles and an intraocular lens, and the contact lenses may be
any of non-hydrous, less hydrous and highly hydrous contact
lenses.
[0221] Since the lens solution of the present invention has
excellent lipid detergency and high hydrophilization performance,
the lens solution is especially suitable to be used for cleaning
and storage of contact lenses. Also, since the lens solution has
high hydrophilization performance, lubricity-imparting performance
and peeling resistance, the lens solution is also suitable to be
used for coating a contact lens. Furthermore, through a surface
treatment method of bringing the lens solution of the present
invention into contact with at least a part of a contact lens
surface, the surface is hydrophilically modified, so that a contact
lens to which lipids are unlikely adsorbed, and lubricity is
imparted, and which has excellent sustainability of those effects,
can be obtained.
[0222] Next, specific embodiments of a solution for contact lens
cleaning or storage and a solution for contact lens coating will be
explained.
[0223] [Contact Lens Cleaning Solution and Contact Lens Storage
Solution]
[0224] In a case where the lens solution of the present invention
is used as a solution for contact lens cleaning or storage, from
the viewpoints of lipid detergency, hydrophilization performance
and cost, a concentration of the polymer is preferably 0.001% to
10% by mass, more preferably 0.001% to 5% by mass, and even more
preferably 0.05% to 3% by mass.
[0225] The solution for contact lens cleaning or storage of the
present invention may also include, in addition to the polymer
described above, a solvent, a surfactant other than the polymer, an
isotonic agent, a chelating agent, a pH adjusting agent, a
buffering agent, a thickening agent, a stabilizer, a proteolytic
enzyme, a pharmacologically active component, a physiologically
active component, and the various additives described in
Encyclopedia of Pharmaceutical Excipients 2007 (edited by the
International Pharmaceutical Excipients Council Japan).
Furthermore, one kind among these may be used singly, or two or
more thereof may be used in combination.
[0226] Examples of the solvent include water; various buffer
solutions such as a phosphate buffer solution, a glycine buffer
solution, Good's buffer solution, a Tris buffer solution, and an
ammonia buffer solution; and an alcohol-based solvent such as
methanol, ethanol, and isopropyl alcohol.
[0227] Examples of the surfactant include an amphoteric surfactant
such as alkyldiaminoethylglycine or a salt thereof (for example,
hydrogen chloride salt); a cationic surfactant such as benzalkonium
chloride and benzethonium chloride; and an anionic surfactant such
as an alkyl benzenesulfonate, an alkyl sulfate, a polyoxyethylene
alkyl sulfate, an aliphatic .alpha.-sulfomethyl ester, and an
.alpha.-olefin sulfonate.
[0228] Furthermore, examples of the isotonic agent include disodium
hydrogen phosphate, sodium dihydrogen phosphate, potassium
dihydrogen phosphate, sodium hydrogen sulfite, sodium sulfite,
potassium chloride, calcium chloride, sodium chloride, magnesium
chloride, potassium acetate, sodium acetate, sodium hydrogen
carbonate, sodium carbonate, sodium thiosulfate, magnesium sulfate,
glycerin, and propylene glycol.
[0229] Examples of the chelating agent include
ethylenediaminetetraacetic acid (EDTA), salts of
ethylenediaminetetraacetic acid such as disodium
ethylenediaminetetraacetate (EDTA.2Na) and trisodium
ethylenediaminetetraacetate (EDTA.3Na), citric acid, gluconic acid,
tartaric acid, and salts thereof (for example, sodium salts).
[0230] Furthermore, examples of the pH adjusting agent include
hydrochloric acid, boric acid, .epsilon.-aminocaproic acid, citric
acid, acetic acid, sodium hydroxide, potassium hydroxide, calcium
hydroxide, magnesium hydroxide, sodium hydrogen carbonate, sodium
carbonate, borax, triethanolamine, monoethanolamine,
diisopropanolamine, sulfuric acid, phosphoric acid, polyphosphoric
acid, propionic acid, oxalic acid, gluconic acid, fumaric acid,
lactic acid, tartaric acid, malic acid, succinic acid,
gluconolactone, and ammonium acetate.
[0231] The pH adjusting agent may be used such that the pH value is
adjusted to be about 4.0 to 9.0, preferably about 6.0 to 8.0, and
more preferably near 7.0.
[0232] Examples of the buffering agent include an acid such as
citric acid, malic acid, lactic acid, ascorbic acid, maleic acid,
gluconic acid, phosphoric acid, boric acid, oxycarboxylic acid, an
amino acid such as glycine and glutamic acid, and
tris(hydroxymethyl)aminomethane (Tris), or salts thereof (for
example, sodium salts); Good Buffer containing taurine or
derivatives thereof; and hydroxyalkylamine such as
bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane (Bis-Tris).
[0233] Furthermore, examples of the thickening agent and the
stabilizer include a synthetic organic polymer compound such as
polyvinyl alcohol, poly-N-vinylpyrrolidone, polyethylene glycol,
polypropylene glycol, and polyacrylamide; a cellulose derivative
such as hydroxyethyl cellulose, hydroxypropyl cellulose, and
hydroxypropyl methyl cellulose; a starch derivative such as sodium
carboxymethyl starch and hydroxyethyl starch; chondroitin sulfate,
and a hyaluronic acid salt.
[0234] Furthermore, examples of the proteolytic enzyme include
biologically derived proteases such as papain, bromelain, glazyme,
ficin, trypsin, chymotrypsin, and pancreatin.
[0235] Furthermore, examples of the pharmacologically active
component and the physiologically active component include the
active ingredients in the ophthalmic medicines described in
Approval Standards for Manufacturing (Import) of Non-Prescription
Drugs, Edition of 2000 (reviewed by Pharmaceutical Affairs Study
Group). Specific examples thereof include an antihistamine such as
iproheptine, diphenhydramine hydrochloride, chlorpheniramine
maleate, ketotifen fumarate, and pemirolast potassium;
decongestants such as tetrahydrozoline hydrochloride, naphazoline
hydrochloride, naphazoline sulfate, epinephrine hydrochloride,
ephedrine hydrochloride, and methylephedrine hydrochloride;
disinfectants such as cetylpyridinium, benzalkonium chloride,
benzethonium chloride, chlorhexidine hydrochloride, and
chlorhexidine gluconate; vitamins such as flavin adenine
dinucleotide sodium, cyanocobalamin, retinol acetate, retinol
palmitate, pyridoxine hydrochloride, panthenol, calcium
pantothenate, and tocopherol acetate; amino acids such as potassium
aspartate and magnesium aspartate; and anti-inflammatory agents
such as dipotassium glycyrrhizate, pranoprofen, allantoin, azulene,
sodium azulene sulfonate, guaiazulene, .epsilon.-aminocaproic acid,
berberine chloride, berberine sulfate, lysozyme chloride, and
licorice; as well as sodium cromoglycate, sodium chondroitin
sulfate, sodium hyaluronate, sulfamethoxazole, and sulfamethoxole
sodium.
[0236] The solution for contact lens cleaning or storage is
appropriate for the cleaning or storage of soft contact lenses, and
is especially suitable for the cleaning or storage of silicone
hydrogel contact lenses.
[0237] [Contact Lens Coating Solution]
[0238] In a case where the lens solution of the present invention
is used as a contact lens coating solution, the concentration of
the polymer is preferably 0.001% to 20% by mass, more preferably
0.01% to 15% by mass, and even more preferably 0.1% to 10% by mass,
from the viewpoints of hydrophilization performance,
lubricity-imparting performance, peeling resistance, and cost.
[0239] The contact lens coating agent of the present invention may
include, for example, a solvent, a disinfectant, and an antiseptic,
in addition to the polymer described above. Examples of the solvent
include the same solvents as those used in the solution for contact
lens cleaning or storage. The total content of the solvent is
preferably 50% to 99.9% by mass, and more preferably 80% to 99.9%
by mass.
[0240] Furthermore, the contact lens coating solution is
appropriate for the coating of soft contact lenses, and is
especially suitable for the coating of silicone hydrogel contact
lenses.
[0241] [Contact Lens]
[0242] The contact lens of the present invention has the
aforementioned polymer used for the present invention on at least a
part of the surface. Specifically, at least a part of the contact
lens is coated with the polymer used for the present invention.
Furthermore, the surface of the contact lens has been
hydrophilically modified as a hydrophilic layer is formed on the
contact lens surface.
[0243] The contact lens is preferably a soft contact lens, and more
preferably a silicone hydrogel contact lens. Furthermore, the
contact lens may have been subjected to, for example, a plasma
treatment, a UV-ozone treatment, or an internal wetting agent
treatment.
[0244] [Method for Producing Contact Lens and Method for
Surface-Treating Contact Lens]
[0245] The method for producing a surface-modified contact lens of
the present invention is characterized by including a step of
bringing the solution described above into contact with at least a
part (preferably, a concave surface) of a contact lens surface.
Furthermore, the method for surface-treating a contact lens of the
present invention is characterized by including a step of bringing
the solution described above into contact with at least a part
(preferably, a concave surface) of a contact lens surface.
[0246] The contact step in the method for producing a contact lens
of the present invention and the method for surface-treating a
contact lens of the present invention may be carried out in the
same manner as a conventional coating method for a contact lens,
except that the lens solution of the present invention is used.
Furthermore, the steps other than the contacting step in the method
for producing a contact lens of the present invention may be
carried out in the same manner as in a conventional production
method for a contact lens.
[0247] Examples of the coating method include: (1) a method of
bringing the lens solution of the present invention into contact
with a contact lens, and physically adsorbing the polymer to the
resin surface in a solution with the solvent remaining therein; and
(2) a method of bringing the lens solution of the present invention
into contact with a contact lens, subsequently volatilizing the
solvent by drying, and forming a dried film of the polymer on the
contact lens surface. Note that in the method (1), after inducing
the physical adsorption, a contact lens having the polymer adsorbed
thereto can be obtained via a process of removing the remaining
solution, usually by a method of, for example, tilting the contact
lens so that the solution flows out, lifting up the contact lens
from the solution, blowing away the solution on the contact lens,
or pouring in a solvent in a large amount.
EXAMPLES
[0248] Hereinafter, the present invention will be described in
detail by way of Examples, but the present invention is not
intended to be limited to these Examples.
[0249] Each of analysis conditions in the Examples are as
follows.
[0250] <Measurement of Molecular Weight>
[0251] The weight average molecular weight (Mw) and the number
average molecular weight (Mn) were measured by gel permeation
chromatography (GPC) based on polystyrene standards, using a TSKgel
.alpha.-M column manufactured by Tosoh Corp., under the conditions
of flow rate: 0.5 ml/min, elution solvent: NMP solvent
(H.sub.3PO.sub.4: 0.016 M, LiBr: 0.030 M), and column temperature:
40.degree. C.
[0252] <Nmr Spectrum>
[0253] The .sup.1H-NMR spectrum was measured using Model AVANCE 500
(500 MHz) manufactured by Bruker Corp., using d.sub.6-DMSO as a
solvent and an internal reference substance.
Synthesis Example 1 Synthesis of Copolymer (N-1)
[0254] 1.95 g of methoxypolyethylene glycol (9) monomethacrylate
(M-90G (manufactured by Shin Nakamura Chemical Co., Ltd.;
hereinafter, referred to as MPEGM), 0.9 g of lauroxypolyethylene
glycol (30) monomethacrylate (PLE-1300 (manufactured by NOF Corp.);
hereinafter, referred to as LPEGM), 0.03 g of
2,2'-azobis(isobutyronitrile) as a polymerization initiator, and 12
g of ECUAMIDE B-100 (manufactured by Idemitsu Kosan Co., Ltd.) as a
solvent were mixed, and the resulting mixture was introduced into a
flask. Nitrogen was blown into this flask, the temperature was
increased up to 70.degree. C., and polymerization was performed for
8 hours. Thereafter, the resultant was cooled to room temperature.
The solution thus obtained was dialyzed with pure water, and
thereby an aqueous solution of a copolymer (N-1) was obtained.
[0255] In regard to the copolymer (N-1) thus obtained, the content
of a repeating unit derived from MPEGM was 65% by mass, and the
content of a repeating unit derived from LPEGM was 35% by mass.
Note that these contents were measured by .sup.1H-NMR.
[0256] Furthermore, the weight average molecular weight of the
copolymer (N-1) thus obtained was 111,000, the number average
molecular weight was 23,300, and the molecular weight distribution
was 4.8.
Synthesis Example 2 Synthesis of Copolymer (N-2)
[0257] 2.10 g of MPEGM, 0.75 g of LPEGM, 0.15 g of 2-ethylhexyl
acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03
g of 2,2'-azobis(isobutyronitrile) as a polymerization initiator,
and 12 g of ECUAMIDE B-100 (manufactured by Idemitsu Kosan Co.,
Ltd.) as a solvent were mixed, and the resulting mixture was
introduced into a flask. Nitrogen was blown into this flask, the
temperature was increased up to 70.degree. C., and polymerization
was performed for 8 hours. Thereafter, the resultant was cooled to
room temperature. The solution thus obtained was dialyzed with pure
water, and thereby an aqueous solution of a copolymer (N-2) was
obtained.
[0258] In regard to the copolymer (N-2) thus obtained, the content
of a repeating unit derived from MPEGM was 70% by mass, the content
of a repeating unit derived from LPEGM was 25% by mass, and the
content of a repeating unit derived from 2-ethylhexyl acrylate was
5% by mass. Note that these contents were measured by
.sup.1H-NMR.
[0259] Furthermore, the weight average molecular weight of the
copolymer (N-2) thus obtained was 118,000, the number average
molecular weight was 33,800, and the molecular weight distribution
was 3.5.
Synthesis Example 3 Synthesis of Copolymer (N-3)
[0260] 2.10 g of MPEGM, 0.86 g of LPEGM, 0.05 g of a silicone
methacrylate represented by the following formula (X) (manufactured
by Tokyo Chemical Industry Co., Ltd.), 0.03 g of
2,2'-azobis(isobutyronitrile) as a polymerization initiator, and 12
g of ECUAMIDE B-100 (manufactured by Idemitsu Kosan Co., Ltd.) as a
solvent were mixed, and the resulting mixture was introduced into a
flask. Nitrogen was blown into this flask, the temperature was
increased up to 70.degree. C., and polymerization was performed for
8 hours. Thereafter, the resultant was cooled to room temperature.
The solution thus obtained was dialyzed with pure water, and
thereby an aqueous solution of a copolymer (N-3) was obtained.
[0261] In regard to the copolymer (N-3) thus obtained, the content
of a repeating unit derived from MPEGM was 70% by mass, the content
of a repeating unit derived from LPEGM was 28.5% by mass, and the
content of a repeating unit derived from silicone methacrylate (X)
was 1.5% by mass. Note that these contents were measured by
.sup.1H-NMR.
[0262] Furthermore, the weight average molecular weight of the
copolymer (N-3) thus obtained was 133,000, the number average
molecular weight was 39,400, and the molecular weight distribution
was 3.4.
##STR00012##
Synthesis Example 4 Synthesis of Copolymer (N-4)
[0263] 4.25 g of dimethylacrylamide ((manufactured by Kohjin Co.,
Ltd.) hereinafter, referred to as DMAA), 0.125 g of
N-methacryloyloxyethyl-N,N-dimethylammonium-.alpha.-N-methylcarboxybetain-
e (GLBT (manufactured by Osaka Organic Chemical Industry, Ltd.);
hereinafter, referred to as GLBT), 0.50 g of LPEGM, 0.125 g of
N-dodecylacrylamide ((manufactured by Tokyo Chemical Industry Co.,
Ltd.) hereinafter, referred to as DDAA), 0.05 g of
2,2'-azobis(isobutyronitrile) as a polymerization initiator, 31.05
g of acetonitrile (manufactured by Mitsubishi Rayon Co., Ltd.) as a
solvent, and 13.50 g of pure water were mixed, and the resulting
mixture was introduced into a flask. Nitrogen was blown into this
flask, the temperature was increased up to 60.degree. C., and
polymerization was performed for 6 hours. Thereafter, the resultant
was cooled to room temperature. The solution thus obtained was
dialyzed with pure water, and thereby an aqueous solution of a
copolymer (N-4) was obtained.
[0264] In regard to the copolymer (N-4) thus obtained, the content
of a repeating unit derived from DMAA was 85% by mass, the content
of a repeating unit derived from GLBT was 2.5% by mass, the content
of a repeating unit derived from LPEGM was 10% by mass, and the
content of a repeating unit derived from DDAA was 2.5% by mass.
Note that these contents were measured by .sup.1H-NMR.
[0265] Furthermore, the weight average molecular weight of the
copolymer (N-4) thus obtained was 515,000, the number average
molecular weight was 128,000, and the molecular weight distribution
was 4.2.
Synthesis Example 5 Synthesis of Copolymer (N-5)
[0266] 7.5 g of N-(2-hydroxyethyl)acrylamide ((manufactured by
Kohjin Co., Ltd.) hereinafter, referred to as HEAA), 2.00 g of
LPEGM, 0.50 g of DDAA, 0.10 g of 2,2'-azobis(isobutyronitrile) as a
polymerization initiator, and 39.10 g of isopropanol (manufactured
by Tokuyama Corp.) as a solvent were mixed, and the resulting
mixture was introduced into a flask. Nitrogen was blown into this
flask, the temperature was increased up to 60.degree. C., and
polymerization was performed for 6 hours. Thereafter, the resultant
was cooled to room temperature. The solution thus obtained was
dialyzed with pure water, and thereby an aqueous solution of a
copolymer (N-5) was obtained.
[0267] In regard to the copolymer (N-5) thus obtained, the content
of a repeating unit derived from HEAA was 75% by mass, the content
of a repeating unit derived from LPEGM was 20% by mass, and the
content of a repeating unit derived from DDAA was 5% by mass. Note
that these contents were measured by .sup.1H-NMR.
[0268] Furthermore, the weight average molecular weight of the
copolymer (N-5) thus obtained was 32,000, the number average
molecular weight was 16,000, and the molecular weight distribution
was 2.0.
Synthesis Example 6 Synthesis of Copolymer (N-6)
[0269] 4.00 g of DMAA, 0.125 g of acrylic acid ((manufactured by
Toagosei Co., Ltd.) hereinafter, referred to as AA), 0.75 g of
LPEGM, 0.125 g of DDAA, 0.05 g of 2,2'-azobis(isobutyronitrile) as
a polymerization initiator, 31.05 g of acetonitrile (manufactured
by Mitsubishi Rayon Co., Ltd.) as a solvent, and 13.50 g of pure
water were mixed, and the resulting mixture was introduced into a
flask. Nitrogen was blown into this flask, the temperature was
increased up to 60.degree. C., and polymerization was performed for
6 hours. Thereafter, the resultant was cooled to room temperature.
0.153 g of sodium hydrogen carbonate was added to the solution thus
obtained, and then the mixture was dialyzed with pure water.
Thereby, an aqueous solution of a copolymer (N-6) was obtained.
[0270] In regard to the copolymer (N-6) thus obtained, the content
of a repeating unit derived from DMAA was 80% by mass, the content
of a repeating unit derived from AA was 2.5% by mass, the content
of a repeating unit derived from LPEGM was 15% by mass, and the
content of a repeating unit derived from DDAA was 2.5% by mass.
Note that these contents were measured by .sup.1H-NMR.
[0271] Furthermore, the weight average molecular weight of the
copolymer (N-6) thus obtained was 430,000, the number average
molecular weight was 108,000, and the molecular weight distribution
was 4.0.
Reference Example 1 Synthesis of Copolymer (N-7)
[0272] 2.85 g of MPEGM, 0.15 g of 2-ethylhexyl acrylate
(manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of
2,2'-azobis(isobutyronitrile) as a polymerization initiator, and 12
g of ECUAMIDE B-100 (manufactured by Idemitsu Kosan Co., Ltd.) as a
solvent were mixed, and the resulting mixture was introduced into a
flask. Nitrogen was blown into this flask, the temperature was
increased up to 70.degree. C., and polymerization was performed for
8 hours. Thereafter, the resultant was cooled to room temperature.
The solution thus obtained was dialyzed with pure water, and
thereby an aqueous solution of a copolymer (N-7) was obtained.
[0273] In regard to the copolymer (N-7) thus obtained, the content
of a repeating unit derived from MPEGM was 95% by mass, and the
content of a repeating unit derived from 2-ethylhexyl acrylate was
5% by mass. Note that these contents were measured by
.sup.1H-NMR.
[0274] Furthermore, the weight average molecular weight of the
copolymer (N-7) thus obtained was 115,000, the number average
molecular weight was 26,800, and the molecular weight distribution
was 4.3.
Reference Example 2 Synthesis of Copolymer (N-8)
[0275] 2.40 g of DMAA, 0.60 g of 2-ethylhexyl acrylate
(manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of
2,2'-azobis(isobutyronitrile) as a polymerization initiator, and 12
g of ECUAMIDE B-100 (manufactured by Idemitsu Kosan Co., Ltd.) as a
solvent were mixed, and the resulting mixture was introduced into a
flask. Nitrogen was blown into this flask, the temperature was
increased up to 70.degree. C., and polymerization was performed for
8 hours. Thereafter, the resultant was cooled to room temperature.
The solution thus obtained was dialyzed with pure water, and
thereby an aqueous solution of a copolymer (N-8) was obtained.
[0276] In regard to the copolymer (N-8) thus obtained, the content
of a repeating unit derived from DMAA was 80% by mass, and the
content of a repeating unit derived from 2-ethylhexyl acrylate was
20% by mass. Note that these contents were measured by
.sup.1H-NMR.
[0277] Furthermore, the weight average molecular weight of the
copolymer (N-8) thus obtained was 49,000, the number average
molecular weight was 14,300, and the molecular weight distribution
was 3.4.
[0278] Each of the copolymers (N-1) to (N-8) obtained in the
various Synthesis Examples and Reference Examples was mixed with
purified water at 25.degree. C., and the concentration was adjusted
to 0.5% by mass. The various copolymers were all dissolved in
purified water.
Example 1
[0279] A treatment agent was obtained by mixing 0.5 parts by mass
of the copolymer (N-1) obtained in Synthesis Example 1, with 99.5
parts by mass of a phosphate buffered physiological saline
(hereinafter, referred to as PBS).
Examples 2 to 6
[0280] Treatment agents were obtained in the same manner as in
Example 1, by mixing 0.5 parts by mass of each of the copolymers
(N-2) to (N-6) obtained in Synthesis Examples 2 and 3, with 99.5
parts by mass of PBS.
Comparative Examples 1 and 2
[0281] Treatment agents were obtained in the same manner as in
Example 1, by mixing 0.5 parts by mass of each of the copolymers
(N-7) and (N-8) obtained in Reference Examples 1 and 2, with 99.5
parts by mass of PBS.
Comparative Example 3
[0282] A treatment agent was obtained by mixing 0.5 parts by mass
of POLOXAMER 407 (manufactured by Sigma-Aldrich Co.), which is a
nonionic surfactant used in a general contact lens detergent, with
99.5 parts by mass of PBS.
Test Example 1 Lipid Cleaning Test
[0283] First, prior to the test, 99% by mass of lipid triglycerides
and 1% by mass of Sudan Black B (dye) were thermally fused, and a
lipid solution was prepared. 200 .mu.L of the lipid solution was
dropped into a screw cap bottle such that the liquid surface was
maintained flat, and then the lipid solution was cooled to room
temperature. Thus, a screw cap bottle containing colored pseudo-eye
discharge pellets was prepared.
[0284] Subsequently, 1 mL of each of the treatments of Examples and
Comparative Examples was introduced into this screw cap bottle
containing pellets, and the bottle was shaken for 14 hours at room
temperature. Thereby, the colored pseudo-eye discharge pellets were
dissolved. After completion of shaking, each of the treatment
agents was removed from the screw cap bottle, and the absorbance at
570 nm of each agent was measured using Model 680 Microplate Reader
(manufactured by BIO-RAD Laboratories, Inc).
[0285] Furthermore, the same procedure as described above was
carried out, except that PBS was used instead of the treatments,
and the absorbance at 570 nm was measured. This was used as a
control, and the difference of absorbance was calculated by the
following expression. The test results are presented in Table
2.
(Difference of absorbance)=(Absorbance of each treatment
agent)-(absorbance of control)
[0286] Note that a higher difference of absorbance implies that the
dissolving power for the colored pseudo-eye discharge pellets is
higher, that is, the lipid detergency is superior.
Test Example 2 Hydrophilization Performance Test
[0287] First, as contact lenses, commercially available contact
lenses (manufactured by Johnson & Johnson, Inc., ACUVUE OASYS)
formed from a silicone hydrogel were prepared, and these contact
lenses were washed 3 times with PBS.
[0288] Subsequently, the contact lenses were respectively immersed
in 1 mL of each of the treatment agents of Examples and Comparative
Examples, and the contact lenses were left to stand for 2 hours at
room temperature and then were washed 3 times with PBS. After the
moisture on the contact lens surfaces was wiped out, the contact
angle in accordance with a water drop method was measured using a
contact angle meter DM-701 (manufactured by Kyowa Interface Science
Co., Ltd).
[0289] The test results as the contact angle immediately after
coating are presented in Table 2. Note that the control in the
table represents the results obtained by a test carried out as
described above using PBS instead of the various treatment
agents.
Test Example 3 Coating Durability Test
[0290] The contact lenses treated with the various treatment agents
used for the measurement in Test Example 2 were washed 10 times by
rubbing using a commercially available contact lens cleaning
solution (OPTI-FREE PLUS (manufactured by Alcon, Inc.)), and the
lenses were rinsed and then were washed 3 times with PBS.
Subsequently, after the moisture on the contact lens surfaces was
wiped out, the contact angles in accordance with a water drop
method were measured using a contact angle meter (DM-701
(manufactured by Kyowa Interface Science Co., Ltd.)).
[0291] The test results as the contact angle after washing with
rubbing are presented in Table 2. The control in the table
represents the results obtained by a test carried out as described
above using PBS instead of the various treatment agents.
Test Example 4 Lipid Antifouling Test
[0292] First, prior to the test, a lipid solution was obtained by
homogenizing oleic acid: 1.20% by mass, linolic acid: 1.20% by
mass, tripalmitic acid: 16.23% by mass, cetyl alcohol: 4.01% by
mass, palmitic acid: 1.20% by mass, cetyl palmitate: 16.23% by
mass, cholesterol: 1.60% by mass, cholesterol palmitate: 1.60% by
mass, and lecithin: 56.71% by mass by heating and stirring. 0.5
parts by mass of this lipid solution and 99.5 parts by mass of
water were mixed and emulsified, and thus an artificial lipid
solution was prepared.
[0293] Subsequently, as contact lenses, commercially available
contact lenses (manufactured by Johnson & Johnson, Inc., ACUVUE
OASYS) formed from a silicone hydrogel were prepared, and these
contact lenses were washed 3 times with PBS. Subsequently, each of
the contact lenses were respectively immersed in 1 mL of each of
the treatment agents of Examples and Comparative Examples, and the
contact lenses were left to stand for 2 hours at room temperature
and then were washed 3 times with PBS.
[0294] Subsequently, each of the contact lenses thus treated were
immersed in 1 mL of the artificial lipid solution, and the contact
lenses were shaken for 1 hour. Subsequently, the contact lenses
were removed, and were washed 3 times with PBS and then dried under
reduced pressure. Thereafter, each of these contact lenses was
immersed in 1 mL of an ethanol/diethyl ether (75/25 vol %)
solution, and was left to stand for 30 minutes. Thereby, the lipids
remaining on the lenses were extracted. 0.5 mL of this extract
solution was collected in a test tube, and the solvent was
evaporated at 90.degree. C.
[0295] Subsequently, 0.5 mL of concentrated sulfuric acid was added
to the test, and the mixture was heated for 30 minutes at
90.degree. C. This solution was cooled to room temperature, and
then 2.5 mL of a 0.6 mass % vanillin aqueous solution/phosphoric
acid (20/80 vol %) solution was added thereto. The mixture was
maintained for 15 minutes at 37.degree. C. This solution was cooled
to room temperature, and then the absorbance at 540 nm was
measured. Solutions of known lipid concentrations were previously
analyzed by the same method as described above, and thereby a
calibration curve was prepared. Thus, the amounts of lipids
adsorbed to the contact lenses were determined from the absorbances
of the analysis results.
[0296] The test results are presented as the lipid antifouling
amounts in Table 2. Note that the control in the table represents
the results obtained by a test carried out as described above using
PBS instead of the various treatment agents. Furthermore, the lipid
antifouling amount represents the amount of lipid adhesion that is
decreased compared to the control, and as the value is larger, the
lipid antifouling effect is superior.
Test Example 5 Lubricity Test
[0297] First, a silicone hydrogel was prepared prior to the test.
That is, 50 parts by mass of the silicone methacrylate represented
by formula (X) (manufactured by Tokyo Chemical Industry Co., Ltd.),
45 parts by mass of DMAA (manufactured by Kohjin Co., Ltd.), 5
parts by mass of polyethylene glycol dimethacrylate n a 4
(manufactured by Tokyo Chemical Industry Co., Ltd.), and 1 part by
mass of 2,2-dimethoxy-2-phenylacetophenone were mixed, and the
resulting mixture was poured into a glass Petri dish. The mixture
was irradiated with UV in air such that the amount of UV
irradiation was 1.5 J/cm.sup.2, and thus a transparent
polymerization product was obtained. This polymerization product
was swollen with ion-exchanged water, and then was stored in PBS.
Thus, a silicone hydrogel was obtained.
[0298] Subsequently, the silicone hydrogel thus produced was washed
3 times with PBS, and then was immersed in 1 mL of each of the
treatments of the Examples and Comparative Examples. The hydrogel
was left to stand for 2 hours at room temperature, and then was
washed 3 times with PBS. Subsequently, for the silicone hydrogel
after washing, the lubricity perceived when the silicone hydrogel
was touched with a dry finger was evaluated by five subjects in
accordance with the following criteria based on grades 1 to 4, and
the average value of the lubricity grades was calculated.
[0299] (Evaluation Criteria for Lubricity)
TABLE-US-00001 Grades 1 Equal to base material (control) 2 Having
slight lubricity. 3 Having lubricity generally without squeaking 4
Having high lubricity
[0300] The test results are presented as lubricity in Table 2. Note
that the control in the table represents the results obtained by a
test carried out as described above using PBS instead of the
various treatment agents.
TABLE-US-00002 TABLE 1 Synthesis Synthesis Synthesis Synthesis
Synthesis Synthesis Reference Reference Example 1 Example 2 Example
3 Example 4 Example 5 Example 6 Example 1 Example 2 N-1 N-2 N-3 N-4
N-5 N-6 N-7 N-8 (A) MPEGM 65 mass % 70 mass % 70 mass % -- -- -- 95
mass % -- DMAA -- -- -- 85 mass % -- 80 mass % -- 80 mass % HEAA --
-- -- -- 75 mass % -- -- -- GLBT -- -- -- 2.5 mass % -- -- -- -- AA
-- -- -- -- -- 2.5 mass % -- -- (B) LPEGM 35 mass % 25 mass % 28.5
mass % 10 mass % 20 mass % 15 mass % -- -- (C) 2-EHA (*1) -- 5 mass
% -- -- -- -- 5 mass % 20 mass % DDAA -- -- -- 2.5 mass % 5 mass %
2.5 mass % -- -- Si-MA (*2) -- -- 1.5 mass % -- -- -- -- --
Water-solubility (0.5 mass %) Transparent Transparent Transparent
Transparent Transparent Transparent Transparent Transparent (*1):
2-Ethylhexyl acrylate, (*2): Silicone methacrylate
TABLE-US-00003 TABLE 2 Example Comparative Example Control 1 2 3 4
5 6 1 2 3 Polymer -- N-1 N-2 N-3 N-4 N-5 N-6 N-7 N-8 POLOXAMER 407
Difference of absorbance 0 +0.048 +0.07 +0.064 +0.040 +0.055 +0.042
+0.036 +0.028 +0.05 Contact Immediately 69 35 15 16 12 14 13 60 71
41 angle (.degree.) after coating After washing 76 47 41 37 27 43
35 75 84 83 by rubbing Lipid antifouling amount (.mu.g) 0 9 11 7 8
8 9 0 0 0 Lubricity 1 2.6 2.8 3.2 3.8 3.0 3.4 1.8 2.2 2.4
[0301] As indicated in Table 2, the solutions of Examples 1 to 6
exhibited excellent properties in lipid detergency,
hydrophilization performance, peeling resistance, a lipid adhesion
preventive effect, and a lubricity-imparting effect. Furthermore,
the solutions of Examples 2 to 6 exhibited particularly excellent
hydrophilization performance and peeling resistance.
* * * * *