U.S. patent application number 16/164336 was filed with the patent office on 2019-02-14 for macromonomer mixture, terminal-reactive polymer mixture, intermediate for macromonomer and silicone hydrogel.
The applicant listed for this patent is Johnson & Johnson Vision Care, Inc.. Invention is credited to Kazuhiko Fujisawa, Masataka Nakamura.
Application Number | 20190048117 16/164336 |
Document ID | / |
Family ID | 44188310 |
Filed Date | 2019-02-14 |
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United States Patent
Application |
20190048117 |
Kind Code |
A1 |
Fujisawa; Kazuhiko ; et
al. |
February 14, 2019 |
MACROMONOMER MIXTURE, TERMINAL-REACTIVE POLYMER MIXTURE,
INTERMEDIATE FOR MACROMONOMER AND SILICONE HYDROGEL
Abstract
To obtain a hydrophilic macromonomer mixture which is a highly
polymerized hydrophilic macromonomer, has few components not bonded
to the polymer chain after polymerization, and is less likely to
leaching. Provided is a macromonomer mixture containing
macromonomer A being a macromonomer having a group obtained by
further introducing a polymerizable group into a reactive group
derived from a polymerization initiator at an end thereof; and
macromonomer B being a macromonomer having a group obtained by
further introducing a polymerizable group into a reactive group
derived from a chain transfer agent at an end thereof.
Inventors: |
Fujisawa; Kazuhiko; (Shiga,
JP) ; Nakamura; Masataka; (Shiga, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Johnson & Johnson Vision Care, Inc. |
Jacksonville |
FL |
US |
|
|
Family ID: |
44188310 |
Appl. No.: |
16/164336 |
Filed: |
October 18, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14264465 |
Apr 29, 2014 |
10125209 |
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16164336 |
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12975509 |
Dec 22, 2010 |
8748548 |
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14264465 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 8/46 20130101; C08F
220/26 20130101; C08F 290/046 20130101; C08L 39/06 20130101; C08F
290/042 20130101; C08F 220/36 20130101; C08F 290/02 20130101; C08L
23/26 20130101; C08F 220/38 20130101; C08L 43/04 20130101; C08F
290/044 20130101 |
International
Class: |
C08F 290/02 20060101
C08F290/02; C08F 8/46 20060101 C08F008/46; C08F 220/36 20060101
C08F220/36; C08F 220/38 20060101 C08F220/38; C08L 39/06 20060101
C08L039/06; C08L 43/04 20060101 C08L043/04; C08F 220/26 20060101
C08F220/26; C08L 23/26 20060101 C08L023/26; C08F 290/04 20060101
C08F290/04 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 28, 2009 |
JP |
2009-296803 |
Claims
1. A macromonomer mixture comprising: macromonomer A being a
macromonomer having a macromer backbone derived from a monomer and
having a group obtained by further introducing a polymerizable
group into a reactive group derived from a polymerization initiator
at an end thereof, wherein the polymerization initiator is a
polymerization initiator expressed by any one of the following
formulas (j1) to (j4): ##STR00016## and macromonomer B being a
macromonomer having a group obtained by further introducing a
polymerizable group into a reactive group derived from a chain
transfer agent at an end thereof.
2. (canceled)
3. The macromonomer mixture of claim 1, wherein the reactive group
derived from a polymerization initiator and the reactive group
derived from a chain transfer agent are each independently at least
one kind of functional group selected from the group consisting of
a hydroxy group, an amino group, thiol, ester and carboxylic
anhydride.
4-9. (canceled)
10. A production method of the macromonomer mixture of claim 1,
wherein after radical polymerization of a hydrophilic monomer using
the polymerization initiator of formulas (j1) to (j4), and a chain
transfer agent having at least one functional group selected from
the group consisting of a hydroxy group, an amino group and a
carboxyl group in a molecule, a compound having a radically
polymerizable functional group is reacted with the resulting
polymer mixture.
11. (canceled)
12. The production method of the macromonomer mixture of claim 10,
wherein the chain transfer agent is a chain transfer agent
expressed by any one of the following general formulas (d1) to
(d5): ##STR00017## wherein L.sup.3 represents a divalent group
having 1 to 10 carbon atoms; and R.sup.10 and R.sup.11 represent
alkyl having 1 to 20 carbon atoms.
13-17. (canceled)
18. A silicone hydrogel obtained by copolymerizing at least one
kind of silicone monomer with at least one kind of monomer mixture
containing the macromonomer mixture of claim 1.
19. The macromonomer mixture of claim 1 wherein the monomer of
macromonomer A comprises N-vinylpyrrolidone,
N,N-dimethylacrylamide, N-vinylacetamide, or mixtures thereof.
Description
RELATED APPLICATIONS
[0001] This application claims priority to JP2009-296803 filed on
Dec. 28, 2009.
BACKGROUND
[0002] The present invention relates to a highly functionalized
macromonomer mixture, a terminal-reactive polymer mixture, an
intermediate for macromonomer and a silicone hydrogel. The
macromonomer mixture shows good wettability, has few components not
bonded to the polymer chain, and is less likely to leaching, so
that it is suitably used in medical devices such as ophthalmic
lenses, endoscopes, catheters, transfusion tubes, gas transfer
tubes, stents, sheaths, cuffs, tube connecters, access ports,
drainage bags, blood circuits, wound covering materials and various
types of medicine carriers, above all, contact lenses, intraocular
lenses, and artificial corneas.
[0003] As a material used for continuous wear, a contact lens using
a silicone hydrogel material has been known recently. Since
silicone is hydrophobic, in order to give wettability to the
surface, many ideas have been proposed so far. As one of those,
there is known a method in which a hydrophilic macromonomer is
added to a monomer mixture to copolymerize it with other monomers
(Patent document 1). As a synthetic method of the hydrophilic
macromonomer, there is known a method in which after polymerization
of a hydrophilic monomer containing a chain transfer agent with a
functional group, a compound having a polymerizable functional
group is reacted with the functional group to give a hydrophilic
macromonomer. However, the hydrophilic macromonomer obtained by
this method contains a hydrophilic polymer having a polymerization
initiator fragment with no functional group. Thus, when a
polymerizable group is tried to be introduced, such a polymer chain
with no functional group and into which no polymerizable group can
be introduced is contained, and in the case of use in
copolymerization with a monomer mixture, there has been a problem
that leaching of the hydrophilic polymer occurs. There has also
been a problem that the wettability of the resulting copolymer is
insufficient.
PRIOR ART DOCUMENT
Patent Document
[0004] Patent Document 1: US Patent Publication No.
2008/0003252
SUMMARY
[0005] The present invention aims to provide a highly polymerized
hydrophilic macromonomer obtained by polymerizing a hydrophilic
polymer using a polymerization initiator with a functional group in
a molecule and a chain transfer agent with a functional group in a
molecule concomitantly, then by introducing a polymerizable group
into the functional groups. A polymer obtained by copolymerization
of the hydrophilic macromonomer of the present invention shows good
wettability, has few components not bonded to the polymer chain and
is less likely to leaching, so that it is suitable as a raw
material of ophthalmic lenses such as a contact lens, an
intraocular lens and artificial corneas.
[0006] In order to achieve the above-described object, the present
invention has the following constitution. That is,
(1) A macromonomer mixture containing macromonomer A being a
macromonomer having a group obtained by further introducing a
polymerizable group into a reactive group derived from a
polymerization initiator at an end thereof; and macromonomer B
being a macromonomer having a group obtained by further introducing
a polymerizable group into a reactive group derived from a chain
transfer agent at an end thereof; (2) The macromonomer mixture of
(1), containing at least one kind of macromonomer A expressed by
the following general formula (I):
[Chemical Structure 1]
[0007] and at least one kind of macromonomer B expressed by the
following general formula (II):
[Chemical Structure 2]
[0008] wherein ------ represents a macromonomer backbone; I-RG
represents a group derived from a polymerization initiator; CTA-RG
represents a group derived from a chain transfer agent; RG
represents a reactive group derived from a polymerization initiator
and a reactive group derived from a chain transfer agent; and PG
represents a group having at least one polymerizable group;
(3) The macromonomer mixture of (1) or (2), wherein the reactive
group derived from a polymerization initiator and the reactive
group derived from a chain transfer agent are each independently at
least one kind of functional group selected from the group
consisting of a hydroxy group, an amino group, thiol, ester and
carboxylic anhydride; (4) A macromonomer mixture containing at
least one kind of macromonomer A having a structure selected from
the group consisting of the following general formulas (i1) to
(i5):
[Chemical Structure 3]
[0009] and at least one kind of macromonomer B having a structure
selected from the group consisting of the following general
formulas (c1), (c2) and (c3):
[Chemical Structure 4]
[0010] wherein R.sup.1 to R.sup.4 represent a group capable of
becoming such a monomer that a monomer expressed by the following
general formula (m) has polymerizability:
[Chemical Structure 5]
[0011] wherein R.sup.5 and R.sup.6 represent alkyl having 1 to 20
carbon atoms, or A.sup.I; R.sup.7 to R.sup.9 represent a hydrogen
atom, alkyl having 1 to 20 carbon atoms, or A.sup.I, provided that
(i1) to (i5) each have at least one A.sup.I; R.sup.5 to R.sup.9 may
form a ring together; R.sup.10 and R.sup.11 represent a hydrogen
atom, or alkyl having 1 to 20 carbon atoms, and may form a ring
together; and A.sup.I and A.sup.c are each independently a group
having 1 to 20 carbon atoms having a radically polymerizable
functional group;
(5) The macromonomer mixture of (4), wherein A.sup.I and A.sup.c
each are a group having a radically polymerizable functional group
selected from the group consisting of acryloyl, methacryloyl,
styryl and vinyl; (6) The macromonomer mixture of (4), wherein AI
and Ac each are a polymerizable group selected from structures
expressed by the following formulas (a1) to (a5):
[Chemical Structure 6]
[0012] wherein R.sup.H represents H or methyl; X represents O or
NH; and L.sup.1 and L.sup.2 represent a divalent group having 1 to
10 carbon atoms;
(7) The macromonomer mixture of (4), wherein the polymerizable
group that a monomer expressed by the general formula (m) has is at
least one kind selected from acryloyl, methacryloyl, styryl and
vinyl; (8) The macromonomer mixture of (4), wherein a monomer
expressed by the general formula (m) is a hydrophilic monomer; (9)
The macromonomer mixture of any one of (4) to (6), wherein a
monomer expressed by the general formula (m) is a monomer selected
from the group consisting of N-vinylpyrrolidone,
N,N-dimethylacrylamide, vinyl alcohol, (meth)acrylic acid, and
2-hydroxyethyl (meth)acrylate; (10) A production method of the
macromonomer mixture of any one of (1) to (9), wherein after
radical polymerization of a hydrophilic monomer using a
polymerization initiator having at least one functional group
selected from the group consisting of a hydroxy group, an amino
group and a carboxyl group in a molecule, and a chain transfer
agent having at least one functional group selected from the group
consisting of a hydroxy group, an amino group and a carboxyl group
in a molecule, a compound having a radically polymerizable
functional group is reacted with the resulting polymer mixture;
(11) The production method of the macromonomer mixture of (10),
wherein the polymerization initiator is a polymerization initiator
expressed by any one of the following formulas (j1) to (j4):
[Chemical Structure 7];
[0013] (12) The production method of the macromonomer mixture of
(10), wherein the chain transfer agent is a chain transfer agent
expressed by any one of the following general formulas (d1) to
(d5):
[Chemical Structure 8]
[0014] wherein L.sup.3 represents a divalent group having 1 to 10
carbon atoms; and R.sup.10 and R.sup.11 represent alkyl having 1 to
20 carbon atoms;
(13) A terminal-reactive polymer mixture containing polymer x with
a reactive group derived from a polymerization initiator, and
polymer y with a reactive group derived from a chain transfer
agent; (14) The terminal-reactive polymer mixture of (13),
containing at least one kind of polymer x expressed by the
following general formula (III):
[Chemical Structure 9]
[0015] and at least one kind of polymer y expressed by the
following general formula (IV):
[Chemical Structure 10]
[0016] wherein ------ represents a macromonomer backbone; I-RG
represents a group derived from a polymerization initiator; CTA-RG
represents a group derived from a chain transfer agent; and RG
represents a reactive group derived from a polymerization initiator
and a reactive group derived from a chain transfer agent;
(15) The terminal-reactive polymer mixture of (13) or (14), wherein
the reactive group derived from a polymerization initiator and the
reactive group derived from a chain transfer agent are each
independently at least one kind of functional group selected from
the group consisting of a hydroxy group, an amino group, thiol,
ester and carboxylic anhydride; (16) A terminal-reactive polymer
mixture containing at least one kind of polymer x having a
structure selected from the group consisting of the following
general formulas (x1) to (x5):
[Chemical Structure 11]
[0017] and at least one kind of polymer y having a structure
expressed by the following general formulas (y1) to (y3):
[Chemical Structure 12]
[0018] wherein R.sup.1 to R.sup.4 represent a group capable of
becoming such a monomer that a monomer expressed by the following
general formula (m) has polymerizability:
[Chemical Structure 13]
[0019] wherein R.sup.12 and R.sup.13 represent alkyl having 1 to 20
carbon atoms, or B.sup.I: R.sup.14 to R.sup.16 represent a hydrogen
atom, alkyl having 1 to 20 carbon atoms, or B.sup.I, provided that
(x1) to (x5) each have at least one B.sup.I; R.sup.12 to R.sup.16
may form a ring together; R.sup.10 and R.sup.11 represent a
hydrogen atom, or alkyl having 1 to 20 carbon atoms, and may form a
ring together; and B.sup.I and B.sup.c are each independently a
group having 1 to 20 carbon atoms having a reactive group;
(17) An intermediate for macromonomer consisting of the
terminal-reactive polymer mixture of any one of (13) to (16); and
(18) A silicone hydrogel obtained by copolymerizing at least one
kind of silicone monomer with at least one kind of monomer mixture
containing the macromonomer mixture of any one of (1) to (9).
[0020] According to the present invention, it is possible to obtain
a macromonomer mixture which is highly functionalized and has few
components not bonded to the main chain, hardly leading to
occurrence of deterioration of wettability and leaching. The
macromonomer mixture is used suitably in various types of medical
devices, particularly contact lenses, intraocular lenses, and
artificial corneas.
BRIEF DESCRIPTION OF THE FIGURES
[0021] FIG. 1 is a MALDI-MS chart of a polymer before introduction
of a polymerizable functional group in Example 4.
[0022] FIG. 2 is a MALDI-MS chart of a polymer in Comparative
Example 1.
[0023] FIG. 3 is a MALDI-MS chart of a polymer in Example 14.
DETAILED DESCRIPTION
[0024] The macromonomer mixture of the present invention is
characterized by containing macromonomer A being a macromonomer
having a group obtained by further introducing a polymerizable
group into a reactive group derived from a polymerization initiator
at an end thereof; and macromonomer B being a macromonomer having a
group obtained by further introducing a polymerizable group into a
reactive group derived from a chain transfer agent at an end
thereof.
[0025] As suitable examples of the reactive group derived from a
polymerization initiator and the reactive group derived from a
chain transfer agent, a hydroxy group, an amino group, thiol, ester
and carboxylic anhydride are mentioned. Among these, from the
viewpoints that reactivity is high and introduction of a
polymerizable group can be enhanced, a hydroxy group and an amino
group are preferable.
[0026] As another preferable aspect of the macromonomer mixture of
the present invention, there is mentioned a macromonomer mixture
characterized by containing at least one kind of macromonomer A
expressed by the following general formula (I):
[Chemical Structure 14]
[0027] and at least one kind of macromonomer B expressed by the
following general formula (II):
[Chemical Structure 15]
[0028] In the general formula (I) or (II), ------ represents a
macromonomer backbone. The macromonomer backbone is composed of a
polymer obtained by polymerization of a radically polymerizable
monomer. As a polymerizable group of such a monomer, a substituent
having a radically polymerizable functional group selected from the
group consisting of acryloyl, methacryloyl, styryl and vinyl is
preferable. Among these, from the viewpoint of physical properties
of a polymer obtained, acryloyl and vinyl are more preferable, and
acryloyl is most preferable.
[0029] As a monomer used in the macromonomer backbone,
(meth)acrylic acids, (meth)acrylates, (meth)acrylamides, styrenes,
N-vinylcarboxylic acid amides, cyclic N-vinylpyridines and
N-vinylimidazoles are preferable. Additionally, in the present
invention, (meth)acryl represents acryl and methacryl.
[0030] As suitable examples in the case that a monomer used in the
macromonomer backbone is a silicone monomer, there are mentioned
3-tris(trimethylsiloxy)silylpropyl (meth)acrylate,
3-bis(trimethylsiloxy)methylsilylpropyl (meth) acrylate,
mono-methacryloyloxypropyl terminated polydimethylsiloxane and a
silicone monomer expressed by the following formulas (s1) to
(s3):
[Chemical Structure 16]
[0031] The monomer used in the macromonomer backbone is preferably
a hydrophilic monomer, and in this case, as suitable examples,
there are mentioned N-vinylpyrrolidone, N,N-dimethylacrylamide,
2-hydroxyethyl (meth)acrylate, N-vinylformamide, N-vinylacetamide,
(meth)acrylic acid, N-vinyl-2-piperidone, N-vinyl-2-caprolactam,
N-vinyl-3-methyl-2-caprolactam, N-vinyl-3-methyl-2-piperidone,
N-vinyl-4-methyl-2-piperidone, N-vinyl-4-methyl-2-caprolactam,
N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone,
N-vinylimidazole, vinyl acetate (after polymerization, it becomes
polyvinyl alcohol by hydrolysis), acryloyl morpholine,
N,N-diethylacrylamide, N-isopropylacrylamide and the like. Among
these, from the viewpoint of balance between hydrophilicity and
solubility of a macromonomer mixture obtained, preferable are
N-vinylpyrrolidone, N,N-dimethylacrylamide, (meth)acrylic acid,
2-hydroxyethyl (meth)acrylate and vinyl acetate (after
polymerization, it becomes polyvinyl alcohol by hydrolysis).
[0032] The macromonomer contained in the macromonomer mixture of
the present invention may be a polymer copolymerized using a
plurality of kinds of monomers used in the macromonomer
backbone.
[0033] In the general formula (I), I-RG represents a group derived
from a polymerization initiator. Here, a group derived from a
polymerization initiator denotes a group composed of at least a
part of the structure of a polymerization initiator.
[0034] In the general formula (II), CTA-RG represents a group
derived from a chain transfer agent. Here, a group derived from a
chain transfer agent denotes a group composed of at least a part of
the structure of a chain transfer agent.
[0035] In the general formula (I) or (II), RG represents a reactive
group derived from a polymerization initiator, and a reactive group
derived from a chain transfer agent. As suitable examples of RG,
there are mentioned a hydroxy group, an amino group, thiol, ester
and carboxylic anhydride. Among these, from the viewpoints that
reactivity is high and introduction of a polymerizable group can be
enhanced, a hydroxy group and an amino group are preferable.
[0036] In the general formula (I) or (II), PG represents a
polymerizable group. Here, a polymerizable group represents a group
having 1 to 20 carbon atoms having a radically polymerizable
functional group. As suitable examples of the radically
polymerizable functional group, (meth)acryloyl, styryl, vinyl and
the like are mentioned. Among these, from the viewpoint of
polymerizability of a macromonomer mixture obtained, (meth)acryloyl
is most preferable. Further, as the specific structure, a
substituent expressed by the following general formulas (b1) to
(b6) is mentioned:
[Chemical Structure 17]
[0037] In the general formulas (b1) to (b6), R.sup.H represents H
or methyl.
[0038] In the general formulas (b1) to (b6), X represents O or
NH.
[0039] In the general formulas (b1) to (b6), L.sup.1 represents a
divalent group having 1 to 10 carbon atoms. It is more preferably
alkylene and arylene having 1 to 10 carbon atoms. As the suitable
examples, there are mentioned methylene, ethylene, propylene,
butylene, pentylene, octylene, decylene, phenylene and the like.
The alkylene and arylene may be branched or linear. Among these,
more preferable are methylene, ethylene, propylene and butylene,
and ethylene is most preferable.
[0040] In the general formula (b6), R.sup.N represents hydrogen or
a substituent with 1 to 20 carbon atoms. It is more preferably
hydrogen, or alkyl or aryl having 1 to 10 carbon atoms. As the
suitable examples, there are mentioned hydrogen, methyl, ethyl,
n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl,
s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl,
tolyl, xylyl, naphtyl and the like. The alkyl may be branched or
linear. Among these, more preferable are hydrogen, methyl, ethyl,
n-propyl, i-propyl, n-butyl, s-butyl and t-butyl, and hydrogen and
methyl are most preferable.
[0041] As another preferable aspect of the macromonomer mixture of
the present invention, there is mentioned a macromonomer mixture
characterized by containing macromonomer A having a structure
selected from the group consisting of the following general
formulas (i1) to (i5):
[Chemical Structure 18]
[0042] and macromonomer B having a structure selected from the
group consisting of the following general formulas (c1) to
(c3):
[Chemical Structure 19]
[0043] In the general formulas (i1) to (i5) and (c1) to (c3),
R.sup.1 to R.sup.4 and a monomer expressed by the following general
formula (m) are the same as in the case of (x1) to (X5) and (y1) to
(y3):
[Chemical Structure 20]
[0044] In the general formulas (i1) to (i5), R.sup.5 and R.sup.6
represent alkyl having 1 to 20 carbon atoms, or A.sup.I. As
suitable examples in the case that R.sup.5 and R.sup.6 are alkyl
having 1 to 20 carbon atoms, there are mentioned methyl, ethyl,
n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl,
s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl,
icosyl, and the like. The alkyl may be branched or linear. Among
these, more preferable are methyl, ethyl, n-propyl, i-propyl,
n-butyl, s-butyl and t-butyl, and methyl is most preferable.
[0045] In the general formulas (i1) to (i5), A.sup.I is a
substituent having 1 to 20 carbon atoms being a substituent having
a radically polymerizable functional group. As suitable examples of
the radically polymerizable functional group, (meth)acryloyl,
styryl, vinyl and the like are mentioned, and among these, from the
viewpoint of polymerizability of a macromonomer mixture obtained,
(meth)acryloyl is most preferable. Further, as the specific
structure, a substituent expressed by the following general
formulas (a1) to (a5) is mentioned:
[Chemical Structure 21]
[0046] In the general formulas (a1) to (a5), R.sup.H represents H
or methyl.
[0047] In the general formulas (a1) to (a5), X represents O or
NH.
[0048] In the general formulas (a1) to (a5), L.sup.1 and L.sup.2
represent a divalent group having 1 to 10 carbon atoms. It is more
preferably alkylene and arylene having 1 to 10 carbon atoms. As the
suitable examples, there are mentioned methylene, ethylene,
propylene, butylene, pentylene, octylene, decylene, phenylene and
the like. The alkylene and arylene may be branched or linear. Among
these, preferable are methylene, ethylene, propylene and butylene,
and ethylene is most preferable.
[0049] In the general formulas (i2) to (i5), R.sup.7 to R.sup.9
represent H or alkyl having 1 to 20 carbon atoms, or A.sup.I. In
this regard, (i1) to (i5) each are a monomer having at least one
A.sup.I. As suitable examples in the case that R.sup.7 to R.sup.9
are H or alkyl having 1 to 20 carbon atoms, there are mentioned H,
methyl, ethyl, propyl. n-propyl, i-propyl, n-butyl, s-butyl,
t-butyl, n-pentyl, i-pentyl, s-pentyl, neopentyl, hexyl, heptyl,
octyl, nonyl, decyl, dodecyl, icosyl and the like. The alkyl may be
branched or linear. Among these, more preferable are methyl, ethyl,
propyl, n-propyl, i-propyl, n-butyl, s-butyl and t-butyl, and H,
methyl and n-butyl are most preferable.
[0050] In the general formulas (i2) to (i5), R.sup.5 to R.sup.9 may
form a ring together. As a suitable example, the case that
--R.sup.8--R.sup.9-- is ethylene, propylene or butylene is
mentioned. Among these, from the viewpoint of stability of a ring
formed, the case that --R.sup.8--R.sup.9-- is ethylene is most
preferable.
[0051] In the general formula (c2), R.sup.10 and R.sup.11 are the
same as in the case of the general formula (y2).
[0052] In the general formulas (c1) to (c3), A.sup.c represents a
substituent having 1 to 20 carbon atoms being a substituent having
a radically polymerizable functional group. As suitable examples of
the radically polymerizable functional group in A.sup.c,
(meth)acryloyl, styryl and vinyl are mentioned, and among these,
from the viewpoint of polymerizability of a macromonomer mixture
obtained, (meth)acryloyl is most preferable. As a more specific
example, a structure expressed by the following general formulas
(a1) to (a5) is mentioned:
[Chemical Structure 22]
[0053] In the general formulas (a1) to (a5), R.sup.H represents H
or methyl.
[0054] In the general formulas (a1) to (a5), X represents O or
NH.
[0055] In the general formulas (a1) to (a5), L.sup.1 and L.sup.2
represent a divalent group having 1 to 10 carbon atoms. It is more
preferably alkylene and arylene having 1 to 20 carbon atoms. As the
suitable examples, there are mentioned methylene, ethylene,
propylene, butylene, pentylene, octylene, decylene, phenylene and
the like. The alkylene and arylene may be branched or linear.
[0056] As a more specific example of the macromonomer A of the
present invention, a structure expressed by the following general
formulas (e1) to (e6) is mentioned:
[Chemical Structure 23]
[0057] Among these, from the viewpoints that there is no need to
use a condensation reagent hard to remove completely in introducing
a polymerizable functional group, and synthesis is possible by the
combination of a highly reactive amino group, a hydroxy group with
isocyanate and (meth)acrylic acid halide, preferable one in the
point of being capable of introducing a polymerizable functional
group highly is a structure expressed by the general formulas (e1)
to (e5), further from the viewpoint of high reactivity, more
preferable one is the formulas (e1) to (e3), and a structure
obtainable by an initiator having an amino group, and from the
viewpoint of producing no salt in reaction, the most preferable one
is a structure expressed by the formula (e1), and a structure
expressed by the formula (e2) created due to its hydrolysis. The
structure expressed by the formula (e1) is sometimes hydrolyzed,
and for example, in the case of using the macromonomer mixture of
the present invention in an ophthalmic lens, it may be changed to a
structure expressed by the formula (e2) due to heating in boiling
sterilization. The structure of the formula (e2) is preferable
because it is more stable to hydrolysis.
[0058] As a more specific example of the macromonomer B of the
present invention, a structure expressed by the following general
formulas (f1) to (f5) is mentioned:
[Chemical Structure 24]
[0059] Among these, from the viewpoints that there is no need to
use a condensation reagent hard to remove completely in introducing
a polymerizable functional group, and synthesis is possible by the
combination of highly reactive amino group, a hydroxy group with
isocyanate and (meth)acrylic acid halide, preferable one in the
point of being capable of introducing a polymerizable functional
group highly is a structure of (f1) to (f4), and from the viewpoint
of producing no salt in reaction, the most preferable one is a
structure expressed by the formulas (f1) and (f2).
[0060] The molecular weight of the macromonomer mixture of the
present invention is preferably 1000 to 2000000, more preferably
10000 to 1000000, and most preferably 200000 to 800000 since there
arises a problem that when it is too small, physical properties of
the macromonomer mixture is not sufficiently exhibited and when it
is too large, viscosity of the polymerization mixture becomes high
and solubility becomes low.
[0061] In obtaining the macromonomer mixture of the present
invention, as a functionalization agent for introducing a
polymerizable functional group of the macromonomer, it is possible
to use a compound having a polymerizable group and further having a
functional group capable of reacting with a functional group of the
polymerization initiator and the chain transfer agent. As the
suitable examples, (meth)acrylic acid chloride, 2-isocyanatoethyl
methacrylate, (meth)acrylic anhydride and 2-hydroxyethyl
(meth)acrylate are mentioned. Among these, (meth)acrylic acid
chloride, 2-isocyanatoethyl (meth)acrylate, and (meth)acrylic
anhydride are preferable because of high reactivity, and further,
2-isocyanatoethyl (meth)acrylate is most preferable because it has
no leaving group.
[0062] The silicone hydrogel of the present invention is obtained
by copolymerization of at least one kind of silicone monomer with
the macromonomer mixture of the present invention.
[0063] As examples of a silicone monomer used in the silicone
hydrogel of the present invention, there are mentioned
3-tris(trimethylsiloxy)silylpropyl (meth)acrylate,
3-bis(trimethylsiloxy)methylsilylpropyl (meth) acrylate,
mono-methacryloyloxypropyl terminated polydimethylsiloxane, and a
silicone monomer expressed by the following formulas (s1) to
(s3);
[Chemical Structure 25]
[0064] The terminal-reactive polymer mixture of the present
invention is characterized by containing polymer x having a
reactive group derived from a polymerization initiator, and a
polymer y having a reactive group derived from a chain transfer
agent.
[0065] As suitable examples of the reactive group derived from a
polymerization initiator and the reactive group derived from a
chain transfer agent, a hydroxy group, an amino group, thiol, ester
and carboxylic anhydride are mentioned. Among these, from the
viewpoints that reactivity is high and introduction of a
polymerizable group can be enhanced, a hydroxy group and an amino
group are preferable.
[0066] As another preferable aspect of the terminal-reactive
polymer mixture of the present invention, there is mentioned a
terminal-reactive polymer mixture characterized by containing at
least one kind of polymer x expressed by the following general
formula (III):
[Chemical Structure 26]
[0067] and at least one kind of polymer y expressed by the
following general formula (IV):
[Chemical Structure 27]
[0068] In the general formula (III) or (IV), ------ represents a
terminal-reactive polymer backbone. The terminal-reactive polymer
backbone is composed of a polymer obtained by polymerization of a
radically polymerizable monomer. As a polymerizable group of such a
monomer, a substituent having a radically polymerizable functional
group selected from the group consisting of acryloyl, methacryloyl,
styryl and vinyl is preferable. Among these, from the viewpoint of
physical properties of a polymer obtained, acryloyl and vinyl are
more preferable, and acryloyl is most preferable.
[0069] As a monomer used in the terminal-reactive polymer backbone,
(meth)acrylic acids, (meth)acrylates, (meth)acrylamides, styrenes,
N-vinylcarboxylic acid amides, cyclic N-vinylpyridines and
N-vinylimidazoles are preferable.
[0070] As suitable examples in the case that a monomer used in the
terminal-reactive polymer backbone is a silicone monomer, there are
mentioned 3-tris(trimethylsiloxy)silylpropyl (meth) acrylate,
3-bis(trimethylsiloxy)methylsilylpropyl (meth)acrylate,
mono-methacryloyloxypropyl terminated polydimethylsiloxane and a
silicone monomer expressed by the following formulas (s1) to
(s3):
[Chemical Structure 28]
[0071] The monomer used in the terminal-reactive polymer backbone
is preferably a hydrophilic monomer, and in this case, as suitable
examples, there are mentioned N-vinylpyrrolidone,
N,N-dimethylacrylamide, 2-hydroxyethyl (meth) acrylate,
N-vinylformamide, N-vinylacetamide, (meth)acrylic acid,
N-vinyl-2-piperidone, N-vinyl-2-caprolactam,
N-vinyl-3-methyl-2-caprolactam, N-vinyl-3-methyl-2-piperidone,
N-vinyl-4-methyl-2-piperidone, N-vinyl-4-methyl-2-caprolactam,
N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone,
N-vinylimidazole, vinyl acetate (after polymerization, it becomes
polyvinyl alcohol by hydrolysis), acryloyl morpholine,
N,N-diethylacrylamide, N-isopropylacrylamide and the like. Among
these, from the viewpoint of balance between hydrophilicity and
solubility of a macromonomer mixture obtained, preferable are
N-vinylpyrrolidone, N,N-dimethylacrylamide, (meth)acrylic acid,
2-hydroxyethyl (meth)acrylate and vinyl acetate (after
polymerization, it becomes polyvinyl alcohol by hydrolysis).
[0072] The macromonomer contained in a polymer contained in the
terminal-reactive polymer mixture of the present invention may be a
polymer copolymerized using a plurality of kinds of monomers used
in the macromonomer backbone.
[0073] In the general formula (III), I-RG represents a group
derived from a polymerization initiator. Here, a group derived from
a polymerization initiator denotes a group composed of at least a
part of the structure of a polymerization initiator.
[0074] In the general formula (IV), CTA-RG represents a group
derived from a chain transfer agent. Here, a group derived from a
chain transfer agent denotes a group composed of at least a part of
the structure of a chain transfer agent.
[0075] In the general formula (III) or (IV), RG represents a
reactive group derived from a polymerization initiator, and a
reactive group derived from a chain transfer agent. As suitable
examples of RG, there are mentioned a hydroxy group, an amino
group, thiol, ester and carboxylic anhydride. Among these, from the
viewpoints that reactivity is high and introduction of a
polymerizable group can be enhanced, a hydroxy group and an amino
group are preferable.
[0076] As another preferable aspect of the terminal-reactive
polymer mixture of the present invention, there is mentioned a
terminal-reactive polymer mixture composed of polymer x having a
structure selected from the group consisting of the following
general formulas (x1) to (x5):
[Chemical Structure 29]
[0077] and polymer y having a structure selected from the group
consisting of the following general formulas (y1) to (y3);
[Chemical Structure 30]
[0078] In the general formulas (x1) to (x5) and (y1) to (y3),
R.sup.1 to R.sup.4 represent a group in which a monomer expressed
by the following general formula (m) can become a monomer having
polymerizability:
[Chemical Structure 31]
[0079] As a polymerizable group of a monomer expressed by the
general formula (m), a substituent having a radically polymerizable
functional group selected from the group consisting of acryloyl,
methacryloyl, styryl and vinyl is preferable. Among these, from the
viewpoint of physical properties of a polymer obtained, acryloyl
and vinyl are more preferable, and acryloyl is most preferable.
[0080] As a monomer expressed by the general formula (m),
(meth)acrylic acids, (meth)acrylates, (meth)acrylamides, styrenes,
N-vinylcarboxylic acid amides, cyclic N-vinylpyridines and
N-vinylimidazoles are preferable.
[0081] As suitable examples in the case that a monomer expressed by
the general formula (m) is a silicone monomer, there are mentioned
3-tris(trimethylsiloxy)silylpropyl (meth)acrylate,
3-bis(trimethylsiloxy)methylsilylpropyl (meth) acrylate,
mono-methacryloyloxypropyl terminated polydimethylsiloxane and a
silicone monomer expressed by the following formulas (s1) to
(s3):
[Chemical Structure 32]
[0082] The monomer expressed by the general formula (m) is
preferably a hydrophilic monomer, and in this case, as suitable
examples, there are mentioned N-vinylpyrrolidone,
N,N-dimethylacrylamide, 2-hydroxyethyl (meth)acrylate,
N-vinylformamide, N-vinylacetamide, (meth)acrylic acid,
N-vinyl-2-piperidone, N-vinyl-2-caprolactam,
N-vinyl-3-methyl-2-caprolactam, N-vinyl-3-methyl-2-piperidone,
N-vinyl-4-methyl-2-piperidone, N-vinyl-4-methyl-2-caprolactam,
N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone,
N-vinylimidazole, vinyl acetate (after polymerization, it becomes
polyvinyl alcohol by hydrolysis), acryloyl morpholine,
N,N-diethylacrylamide, N-isopropylacrylamide and the like. Among
these, from the viewpoint of balance between hydrophilicity and
solubility of a macromonomer mixture obtained, preferable are
N-vinylpyrrolidone, N,N-dimethylacrylamide, (meth)acrylic acid,
2-hydroxyethyl (meth)acrylate and vinyl acetate (after
polymerization, it becomes polyvinyl alcohol by hydrolysis).
[0083] A polymer contained in the terminal-reactive polymer mixture
and a macromonomer contained in the macromonomer mixture of the
present invention may each be a polymer copolymerized using a
plurality of kinds of monomers expressed by the formula (m).
[0084] In the general formulas (x1) to (x5), R.sup.12 and R.sup.13
represent alkyl having 1 to 20 carbon atoms, or B.sup.I. As
suitable examples in the case that R.sup.12 and R.sup.13 are alkyl
having 1 to 20 carbon atoms, there are mentioned methyl, ethyl,
n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl,
s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl,
icosyl, and the like. The alkyl may be branched or linear. Among
these, more preferable are methyl, ethyl, n-propyl, i-propyl,
n-butyl, s-butyl and t-butyl, and methyl is most preferable.
[0085] In the general formulas (x1) to (x5), B.sup.I is a
substituent having 1 to 20 carbon atoms having a reactive group. As
suitable examples of the reactive group, a hydoxy group, an amino
group and a carboxyl group are mentioned. Among these, from the
viewpoint of reactivity, a hydoxy group and an amino group are more
preferable, and an amino group is most preferable.
[0086] In the general formulas (x2) to (x5), R.sup.14 to R.sup.16
represent H or alkyl having 1 to 20 carbon atoms, or B.sup.I. In
this regard, (x1) to (x5) each are monomer having at least one
B.sup.I. As suitable examples in the case that R.sup.14 to R.sup.16
are H or alkyl having 1 to 20 carbon atoms, there are mentioned H,
methyl, ethyl, propyl, n-propyl, i-propyl, n-butyl, s-butyl,
t-butyl, n-pentyl, i-pentyl, s-pentyl, neopentyl, hexyl, heptyl,
octyl, nonyl, decyl, dodecyl, icosyl, and the like. The alkyl may
be branched or linear. Among these, more preferable are methyl,
ethyl, propyl, n-propyl, i-propyl, n-butyl, s-butyl and t-butyl,
and H, methyl and n-butyl are most preferable.
[0087] In the general formulas (x2) to (x5), R.sup.12 to R.sup.16
may form a ring together. As a suitable example, the case that
--R.sup.15--R.sup.16-- is ethylene, propylene and butylene is
mentioned. Among these, from the viewpoint of stability of a ring
formed, the case that --R.sup.15--R.sup.16-- is ethylene is most
preferable.
[0088] In the general formula (y2), R.sup.10 and R.sup.11 represent
a hydrogen atom or alkyl having 1 to 20 carbon atoms, and may form
a ring together. As suitable examples, there are mentioned, methyl,
ethyl, propyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl,
n-pentyl, i-pentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl,
nonyl, decyl, dodecyl, icosyl, and the like. The alkyl may be
branched or linear. Among these, from the viewpoints of being less
sterically hindered and easy occurrence of chain transfer, methyl,
ethyl and propyl are preferable. As suitable examples in the case
of forming a ring together, the case that --R.sup.10--R.sup.11-- is
ethylene, propylene, butylene, pentylene, hexylene and the like is
mentioned. Among these, from the viewpoint of stability in a ring
formed, butylene and pentylene are preferable.
[0089] In the general formulas (y1) to (y3), B.sup.c is a
substituent having 1 to 20 carbon atoms having a reactive group. As
suitable examples of the reactive functional group, a hydroxy
group, an amino group and a carboxyl group are mentioned. Among
these, from the viewpoint of reactivity, a hydoxy group and an
amino group are more preferable, and a hydroxy group is most
preferable.
[0090] The terminal-reactive polymer mixture of the present
invention is a mixture of a plurality of kinds of polymers having a
reactive group at one end, and has a feature that it is capable of
lowering the content of the polymer not having a functional group
in the mixture.
[0091] The terminal-reactive polymer mixture of the present
invention is suitable for intermediates in various types of polymer
products by utilizing reactivity of the end, and for modifying
agents of various products (for example, surface treatment agents
and coating materials). Above all, it is suitable for an
intermediate for macromonomer.
[0092] A polymerization initiator, which is used to obtain the
terminal-reactive polymer mixture and the macromonomer mixture of
the present invention by radical polymerization, has at least one
functional group selected from the group consisting of a hydroxy
group, an amino group and a carboxyl group in a molecule.
[0093] As a suitable example, a polymerization initiator expressed
by the following general formulas (j1) to (j4):
[Chemical Structure 33]
[0094] can be mentioned. Of the above, from the viewpoint of high
reactivity in the initiator-end of a polymer obtained, a
polymerization initiator expressed by the formulas (j1) to (j3)
having a hydroxy group or an amino group in a molecule is more
preferable, and a polymerization initiator expressed by the formula
(j1) having an amino group in a molecule is most preferable. The
use amount should be suitably adjusted according to a target
molecular weight of the terminal-reactive polymer mixture and the
macromonomer mixture to be obtained. When the amount is too small,
polymerization does not start, whereas when it is too large, the
molecular weight becomes too low, or because recombination
termination tend to occur, a polymer or a macromonomer having
functional groups at both ends tends to be produced. Thus, the
amount is preferably 0.001 to 5 mol %, more preferably 0.005 to 3
mol %, and most preferably 0.01 to 1 mol % relative to the
monomer.
[0095] A chain transfer agent, which is used to obtain the
terminal-reactive polymer mixture and the macromonomer mixture of
the present invention by radical polymerization, preferably has at
least one functional group selected from the group consisting of a
hydroxy group, an amino group and a carboxyl group in a molecule.
As a suitable example, a chain transfer agent expressed by the
following general formulas (d1) to (d5) is mentioned:
[Chemical Structure 34]
[0096] Among these, since it has an amino group or a hydroxy group
that easily causes chain transfer and has high reactivity, from the
viewpoint that a polymerizable functional group can be introduced
highly, a chain transfer agent expressed by (d1) or (d2) is
preferable.
[0097] In the formulas (d1) to (d5), L.sup.3 represents a divalent
group having 1 to 10 carbon atoms. It is more preferably alkylene
and arylene having 1 to 20 carbon atoms. As the examples, there are
mentioned methylene, ethylene, propylene, butylene, pentylene,
octylene, decylene, phenylene and the like. The alkylene and
arylene may be branched or linear. Among these, from the viewpoints
of being less sterically hindered and easy occurrence of chain
transfer, ethylene and propylene are most preferable.
[0098] In the general formulas (d1) to (d5), R.sup.10 and R.sup.11
represent alkyl having 1 to 20 carbon atoms. As the examples, there
are mentioned methyl, ethyl, propyl, n-propyl, i-propyl, n-butyl,
s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, neopentyl, hexyl,
heptyl, octyl, nonyl, decyl, dodecyl, icosyl, and the like. The
alkyl may be branched or linear. Among these, from the viewpoints
of being less sterically hindered and easy occurrence of chain
transfer, methyl, ethyl and propyl are preferable. As suitable
examples of --R.sup.10--R.sup.11-- in the case that R.sup.10 and
R.sup.11 form a ring together, there are mentioned ethylene,
propylene, butylene, pentylene, hexylene, heptylne, octylene,
nonylene, decylene, docecylene and icosylene. Among these, from the
viewpoint of stability of a ring formed, butylene and pentylene are
preferable.
[0099] As suitable examples of a chain transfer agent used in
obtaining the terminal-reactive polymer mixture and the
macromonomer mixture of the present invention, there are mentioned
2-mercaptoethanol, 2-aminoethanethiol, 2-aminoethanethiol
hydrochloride, 2-thiopropionic acid and the like. Among these, from
the viewpoint of high reactivity at an end of a chain transfer
agent obtained, 2-mercaptoethanol, 2-aminoethanethiol and
2-aminoethanethiol hydrochloride are most preferable. The use
amount should be suitably adjusted according to a target molecular
weight of the macromonomer mixture to be obtained. When the amount
is too large, since the unreacted chain transfer agent tends to
remain in the system, it is preferably 0.01 to 50 mol %, more
preferably 0.05 to 40 mol %, and most preferably 0.1 to 25 mol %
relative to the monomer.
[0100] In obtaining the terminal-reactive polymer mixture and the
macromonomer mixture of the present invention by polymerization, a
polymerization solvent can be used. As the solvent, various types
of organic or inorganic solvents can be adopted. For example, there
are various kinds of alcohol solvents such as water, methanol,
ethanol, propanol, 2-propanol, butanol, tert-butanol, tert-amyl
alcohol, 3-methyl-3-pentanol, 3,7-dimethyl-3-octanol and
tetrahydrolinalool; various kinds of aromatic hydrocarbon solvents
such as benzene, toluene and xylene; various kinds of aliphatic
hydrocarbon solvents such as hexane, heptane, octane, decane,
petroleum ether, kerosene, ligroin and paraffin; various kinds of
ketone solvents such as acetone, methyl ethyl ketone and methyl
isobutyl ketone; various kinds of ester solvents such as ethyl
acetate, butyl acetate, methyl benzoate, dioctyl phthalate and
ethylene glycol diacetate; various kinds of glycol ether solvents
such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol
dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol
dialkyl ether, tetraethylene glycol dialkyl ether, polyethylene
glycol dialkyl ether, polyethylene glycol-polypropylene glycol
block copolymer, and polyethylene glycol-polypropylene glycol
random copolymer; various kinds of amide solvents such as
N,N-dimethylformamide, N,N-dimethylacetamide and
N-methylpyrrolidone; and dimethylsulfoxide, and these can be used
alone or in combination. Among these, from the viewpoint of hard to
inhibit radical polymerization, more preferable are water,
tert-butanol, tert-amyl alcohol, 3-methyl-3-pentanol and
3,7-dimethyl-3-octanol.
[0101] In obtaining the terminal-reactive polymer mixture and the
macromonomer mixture of the present invention, the concentration of
monomer in the case of using a polymerization solvent is preferably
10% by weight to 80% by weight, more preferably 15% by weight to
65% by weight, and most preferably 20% by weight to 50% by weight,
since when it is too low, a sufficient molecular weight cannot be
obtained, whereas when it is too high, there is a danger of
overdrive due to polymerization heat.
[0102] When the content of a silicone component in the silicone
hydrogel is too small, oxygen permeability necessary to wear an
ophthalmic lens continuously is not obtained, whereas when it is
too large, compatibility with a hydrophilic component tends to be
hardly obtained. Thus, given that the total weight of various
monomers is 100 parts by weight, the content of a silicone monomer
is preferably 20 to 80 parts by weight, more preferably 30 to 80
parts by weight, and most preferably 50 to 80 parts by weight.
[0103] The silicone hydrogel of the present invention may contain a
hydrophilic monomer as a copolymerization component. As a
hydrophilic monomer to be copolymerized, it is not particularly
restricted as long as it is polymerizable, and there can be used a
monomer having (meth)acryloyl, styryl, allyl, vinyl, and other
polymerizable carbon-carbon unsaturated bonds.
[0104] Hereinafter, several examples of the monomer are mentioned,
but the present invention is not limited thereto: carboxylic acids
such as (meth)acrylic acid, itaconic acid, crotonic acid and
vinylbenzoic acid, (meth)acrylates having a hydroxy group such as
2-hydorxyethyl (meth)acrylate, (meth)acrylamides such as
N,N-dimethylacrylamide, and N-vinylpyrrolidone, N-vinylimidazole
and the like.
[0105] In obtaining the silicone hydrogel of the present invention
by polymerization, from the viewpoints of obtaining good mechanical
properties and good resistance to a disinfectant and a washing
liquid, it is preferable to use a monomer having at least two
copolymerizable carbon-carbon unsaturated bonds in a molecule as a
copolymerization component. The copolymerization ratio of a monomer
having at least two copolymerizable carbon-carbon unsaturated bonds
in a molecule is preferably 0.1 to 20% by weight, more preferably
0.3 to 15% by weight, and further preferably 0.5 to 10% by
weight.
[0106] The silicone hydrogel of the present invention may contain a
UV absorber, a dye, a colorant and the like. They may be contained
in a form that the UV absorber, the dye and the colorant having a
polymerizable group are copolymerized.
[0107] In obtaining the silicone hydrogel of the present invention
by polymerization, for making polymerization easy, it is preferable
to add a thermal polymerization initiator typified by a peroxide
and an azo compound, and a photopolymerization initiator. In the
case of carrying out thermal polymerization, a thermal
polymerization initiator with optimal decomposition characteristics
to a desired reaction temperature is selected and used. In general,
an azo initiator and a peroxide initiator with a 10-hour half-life
period temperature of 40.degree. C. to 120.degree. C. are suitable.
As a photopolymerization initiator, there can be mentioned a
carbonyl compound, a peroxide, an azo compound, a sulfur compound,
a halide, a metal salt and the like. These polymerization
initiators are used alone or in combination, and used up to about 1
part by weight relative to 100 parts by weight of the monomer
component.
[0108] In obtaining the silicone hydrogel of the present invention
by polymerization, a polymerization solvent can be used. As the
solvent, various types of organic or inorganic solvents can be
adopted. For example, there are water, various kinds of alcohol
solvents such as methanol, ethanol, propanol, 2-propanol, butanol,
tert-butanol, tert-amyl alcohol, 3,7-dimethyl-3-octanol and
tetrahydrolinalool; various kinds of aromatic hydrocarbon solvents
such as benzene, toluene and xylene; various kinds of aliphatic
hydrocarbon solvents such as hexane, heptane, octane, decane,
petroleum ether, kerosene, ligroin and paraffin; various kinds of
ketone solvents such as acetone, methyl ethyl ketone and methyl
isobutyl ketone; various kinds of ester solvents such as ethyl
acetate, butyl acetate, methyl benzoate, dioctyl phthalate and
ethylene glycol diacetate; various kinds of glycol ether solvents
such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol
dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol
dialkyl ether, tetraethylene glycol dialkyl ether, polyethylene
glycol dialkyl ether, polyethylene glycol-polypropylene glycol
block copolymer and polyethylene glycol-polypropylene glycol random
copolymer; various kinds of amide solvents such as
N,N-dimethylformamide, N,N-dimethylacetamide and
N-methylpyrrolidone; and dimethylsulfoxide and these can be used
alone or in combination. Among these, alcohol solvents and glycol
ether solvents are preferable from the viewpoint that they can be
easily removed by washing with water from the medial materials
obtained.
[0109] The silicone hydrogel of the present invention can be molded
independently into a desired shape and used, and it can also be
molded after being mixed with other materials. It is also suitable
to apply coating to the surface of a molded product.
[0110] In the case of molding the silicone hydrogel of the present
invention to use as an ophthalmic lens, the following methods can
be usually used as the polymerization method and the forming
method. For example, there can be mentioned a method where the
silicone hydrogel is once formed into a round bar or a plate and
this is processed into a desired shape by cutting work or the like,
a mold polymerization method, spin casting method and the like.
[0111] As one example, a case where an ophthalmic lens made from
the silicone hydrogel of the present invention is obtained by a
mold polymerization method will be explained below.
[0112] A monomer composition is filled in a space between two molds
having a lens shape. Photopolymerization or thermal polymerization
is carried out to form a lens shape. The mold is made from a resin,
glass, ceramic, a metal or the like. In the case of
photopolymerization, an optically transparent material is used, and
usually, a resin or glass is used. When an ophthalmic lens is
produced from a silicone hydrogel, in many cases, a space is formed
by two facing molds, and a monomer composition is filled in the
space. Subsequently, the molds with the monomer composition filled
in the space are irradiated with an active ray such as UV, or
heated in an oven or a liquid tank to polymerize the monomer. It is
also possible to use a method concomitantly using both, where heat
polymerization is carried out after photopolymerization, or
photopolymerization is carried out after heat polymerization. In
the case of photopolymerization, generally, for example, light
including much UV from a mercury lamp or an insect trapping lamp as
a light source is irradiated for a short time (usually hour or
less). In the case of carrying out thermal polymerization, a
condition that the temperature is raised gradually from around room
temperature to a temperature of 60.degree. C. to 200.degree. C.
over several hours to several tens of hours is preferred for
maintaining optical homogeneity and quality of the polymer and
increasing reproducibility.
[0113] The silicone hydrogel of the present invention can undergo
modifying treatment by various methods. As a specific modifying
method, there can be mentioned electromagnetic wave (including
light) irradiation, plasma irradiation, chemical vapor deposition
treatment such as evaporation coating and sputtering, heating, base
treatment, acid treatment, use of other suitable surface treatment
agents and the combination of these.
[0114] Oxygen permeability of the silicone hydrogel of the present
invention is preferably 70.times.10.sup.-11 (cm.sup.2/sec)
mLO.sub.2/(mLhPa) or more in terms of oxygen permeability
coefficient.
[0115] The dynamic contact angle (advancing contact angle) of the
silicone hydrogel of the present invention is preferably 90.degree.
or less, more preferably 75.degree. or less, and most preferably
60.degree. or less.
[0116] The silicone hydrogel of the present invention is suitable
for medical devices such as ophthalmic lenses, endoscopes,
catheters, transfusion tubes, gas transfer tubes, stents, sheaths,
cuffs, tube connecters, access ports, drainage bags, blood
circuits, wound covering materials and various types of medicine
carriers, above all, contact lenses, intraocular lenses, and
artificial corneas.
EXAMPLES
[0117] Hereinafter, the present invention is specifically explained
by means of examples, but the present invention is not limited
thereto.
[0118] Analysis Method
[0119] (1) Gel Permeation Chromatography (GPC) measurement (Tables
1, 3 and 5)
[0120] GPC measurement of Tables 1, 3 and 5 was conducted under the
following conditions.
Apparatus: Tosoh Corporation HLC-8220 GPC
[0121] Column: TSKgel SUPER HM-H, two pieces (particle diameter: 5
.mu.m, 6.0 mm ID.times.15 cm) Moving phase: N-methylpyrrolidone (10
mM LiBr) Column temperature: 40.degree. C. Measuring time: 40
minutes Injection amount: 10 .mu.L Detector: RI detector Flow rate:
0.2 mL/min Sample concentration: 0.4% by weight Standard sample:
Polystyrene (molecular weight 500 to 1090000)
[0122] (2) MALDI-MS Measurement
[0123] The vicinity of the top of peak in a macromonomer mixture in
GPC was fractionated, and MALDI-MS measurement (positive) was
carried out by a reflector mode using dithranol as a matrix and
trifluoroacetic acid as a cationizing agent.
[0124] (3) Dynamic Contact Angle Measurement
[0125] As a sample for dynamic contact angle, a film of about 5
mm.times.10 mm.times.0.1 mm in size cut out from a film-like sample
was used, and a dynamic contact angle in advancing to a borate
buffer solution (pH 7.1 to 7.3) was measured. The immersion speed
was set to 0.1 mm/sec, and the immersion depth was set to 7 mm.
[0126] (4) GPC Measurement (Table 7)
[0127] GPC measurement of Table 7 was carried out under the
following conditions.
Apparatus: Shimadzu Corporation LC-20AD (pump), RID-20A (RI
detector), CTO-20A (column oven) Column: TSKgel GMPW.sub.XL
(particle diameter: 13 .mu.m, 7.8 mm ID.times.30 cm) Moving phase:
Water/Methanol=50/50 (0.1 N LiNO.sub.3) Column temperature:
40.degree. C. Measuring time: 30 minutes Injection amount: 100
.mu.L Detector: RI detector Flow rate: 0.5 mL/min Sample
concentration: 0.1% by weight Standard sample: Polyethylene glycol
(molecular weight 106 to 1258000)
Example 1
[0128] To a three-neck flask of 500 mL were added
N-vinylpyrrolidone (NVP, 77.80 g, 0.70 mol %), a polymerization
initiator expressed by the following formula (j1) (VA-061, Wako
Pure Chemical Industries, Ltd., 0.44 g, 1.76 mmol),
2-mercaptoethanol (2-ME, 10.00 g, 128 mmol) and t-amyl alcohol
(TAA, 205.89 g), and a three way stopcock, a thermometer and a
mechanical stirrer were equipped. The inside of the three-neck
flask was deaerated by a vacuum pump, and after argon substitution
was repeated three times, the temperature was raised to 75.degree.
C., and the mixture was stirred for 7 hours.
[Chemical Structure 35]
[0129] After completion of polymerization, the temperature was
decreased to room temperature and the polymerization reaction
liquid was poured in 900 mL of n-hexane, allowed to stand still,
and then the supernatant was removed by decantation. The residue
was washed twice with n-hexane/ethanol=450 mL/20 mL. The solid
content was dried by a vacuum dryer at 40.degree. C. for 16 hours.
After putting liquid nitrogen, it was pulverized with a spatula and
transferred to a bag with a chuck. Drying was conducted by a vacuum
dryer at 40.degree. C. for 3 hours, thereby to obtain a
terminal-reactive polymer mixture. The molecular weight of the
terminal-reactive polymer mixture obtained is as shown in Table
1.
Examples 2 to 4
[0130] The same polymerization as in Example 1 was carried out at a
charging ratio shown in Table 1. The molecular weight of the
terminal-reactive polymer mixture obtained is as shown in Table
1.
Example 5
[0131] 50 g of the terminal-reactive polymer mixture obtained in
Example 1, 15.0 mg of BHT (300 ppm to polymer) and 330 g of
1,4-dioxane were added to a four-neck round-bottom flask of 500 mL.
To the four-neck round-bottom flask, a mechanical stirrer, a glass
stopper, a connecting tube connected to a nitrogen line and a
Claisen tube were equipped, and to the forepart, a Liebig
condenser, a distillation adaptor and a recovery flask were
connected. While stirring under nitrogen stream, the temperature
was raised to 126.degree. C. (bath temperature), and the mixture
was maintained at 126.degree. C. till the remaining amount of
1,4-dioxane became about 110 to 120 g, removing water from the
reaction system. The temperature was decreased to 90.degree. C. 30
.mu.L of Dibutyltin (IV) dilaurate and 1.581 g of 2-isocyanatoethyl
methacrylate (MOI) were added thereto under nitrogen stream, and
reacted at 90.degree. C. for 3 hours.
[0132] After completion of reaction, the temperature was decreased
to 70.degree. C., and 20 g of ethanol was added and the mixture was
stirred for 60 minutes. After cooling to room temperature, the
polymerization reaction liquid was poured in 600 mL/10 mL of
n-hexane/methanol. The supernatant was removed by decantation. The
residue was washed twice with n-hexane/methanol=400 mL/20 mL. The
solid content was dried by a vacuum dryer at 40.degree. C. for 16
hours. After putting liquid nitrogen, it was pulverized with a
spatula and transferred to a bag with a chuck. Drying was conducted
by a vacuum dryer at 40.degree. C. for 3 hours, thereby to obtain a
macromonomer mixture.
Examples 6 to 8
[0133] Using the terminal-reactive polymer mixtures obtained in
Examples 2 to 4, the same functionalization as in Example 5 was
carried out by a MOT amount of Table 2.
Comparative Example 1
[0134] The same polymerization as in Example 1 was carried out
except that the polymerization initiator VA-061 was replaced with a
polymerization initiator (ADVN Wako Pure Chemical Industries, Ltd.)
expressed by the following formula (j0) and the charging ratio was
changed to one shown in Table 1.
[Chemical Structure 36]
[Table 1]
[Table 2]
Example 9
[0135] In regard to the terminal-reactive polymer mixture of
Example 4, a fraction obtained by fractionating the vicinity of the
top of main peak in GPC was concentrated and MALDI-MS measurement
was carried out. The MALDI-MS chart of the terminal-reactive
polymer mixture of Example 4 is shown in FIG. 1. As a result, the
terminal-reactive polymer mixture of Example 4 had reactive groups
in both the polymer with a chain transfer agent-end and polymer
with an initiator-end, and it was confirmed that a target
macromonomer mixture was obtained by introducing a polymerizable
group.
Comparative Example 2
[0136] The same MALDI-MS measurement as in Example 6 was carried
out except for using the terminal-reactive polymer mixture of
Comparative Example 1. The MALDI-MS chart of the terminal-reactive
polymer mixture of Comparative Example 1 is shown in FIG. 2. As a
result, it was confirmed that the terminal-reactive polymer mixture
of Comparative Example 1 contained a polymer having an initiator
(ADVN) end and unable to introduce a polymerizable functional
group.
Examples 10 to 12
[0137] Using N,N-dimethylacrylamide in place of N-vinylpyrrolidone,
the same polymerization as in Example 1 was carried out at a
charging ratio shown in Table 3, thereby to obtain a
terminal-reactive polymer mixture.
[Table 3]
Examples 13 to 15
[0138] Using the terminal-reactive polymer mixtures obtained in
Examples 10 to 12, the same functionalization as in Example 5 was
carried out by a MOI amount of Table 4.
[Table 4]
Example 16
[0139] The MALDI-MS measurement of the macromonomer mixture of
Example 14 to which the polymerizable functional group was
introduced was carried out. The MALDI-MS chart of the macromonomer
mixture of Example 14 is shown in FIG. 3. It can be understood that
no nonfunctional peak is observed and a target macromonomer mixture
is obtained.
Example 17
[0140] A silicone monomer expressed by the following formula (s1)
(30 parts by weight), N,N-dimethylacrylamide (31 parts by weight),
a silicone monomer expressed by the following formula (s2) (23
parts by weight), the macromonomer mixture obtained in Example 5 (6
parts by weight), ethylene glycol dimethacrylate (0.75 parts by
weight), a photo-initiator Irgacure 819 (0.23 parts by weight) and
tert-amyl alcohol (40 parts by weight) were mixed and stirred. A
homogeneous, transparent monomer mixture was obtained. This monomer
mixture was deaerated under argon atmosphere. In a glove box under
nitrogen atmosphere, between two glass plates of 10 cm square and 3
mm thick (to one of them, an aluminum foil was attached for easy
peeling off), two pieces of Parafilm of 100 .mu.m thick whose
center part was cut off were inserted as a spacer, into which a
monomer mixture was cast, and polymerization between plates was
conducted by light irradiation (Toshiba Corporation, FL6D, 8.4 kls,
for 15 minutes) to obtain a film-like sample.
[Chemical Structure 37]
[Chemical Structure 38]
[0141] The film-like sample obtained was irradiated with ultrasonic
wave in water for 20 minutes, and peeled from the glass plate,
immersed in a 60% aqueous isopropyl alcohol (IPA) solution at
60.degree. C. overnight, further, immersed in a 80% aqueous IPA
solution at 60.degree. C. for 2 hours to extract impurities such as
the residual monomer, and hydrated by immersion in a liquid with
stepwisely lowered IPA concentrations, that is, a 50% aqueous IPA
solution, a 25% aqueous IPA solution and water each for about 30
minutes. This was immersed in a borate buffer solution (pH 7.1 to
7.3) in a 200 mL glass bottle, the glass bottle was placed in an
autoclave, and subjected to boiling treatment at 120.degree. C. for
30 minutes. After standing to cool, the film-like sample was taken
out from the glass bottle, and immersed in a borate buffer solution
(pH 7.1 to 7.3).
Examples 18 to 21
[0142] At a charging ratio shown in Table 5, the same
polymerization as in Example 1, the same functionalization as in
Example 5 and the same polymerization of silicone hydrogel polymer
as in Example 17 were carried out. The molecular weight and dynamic
contact angle (advancing contact angle) of the macromonomer mixture
obtained were as shown in Table 5.
Comparative Examples 3 to 6
[0143] At a charging ratio shown in Table 5, the same
polymerization as in Example 1, the same functionalization as in
Example 5 and the same polymerization of silicone hydrogel polymer
as in Example 17 were carried out. The molecular weight and dynamic
contact angle (advancing contact angle) of the macromonomer mixture
obtained were as shown in Table 5.
[0144] Therefore, in Examples 18 to 21 and Comparative Examples 3
to 6, when dynamic contact angles of silicone hydrogels using the
macromonomer mixtures having the almost same molecular weight are
compared, it was confirmed that the dynamic contact angle of
Examples 18 to 24 was small, and good wettability was shown.
[Table 5]
Example 22
[0145] To a three-neck flask of 1 L were added 144.12 g (2.000 mol
%) of acrylic acid (hereinafter, AA), 640.0 g of water, a
polymerization initiator VA-061 (Wako Pure Chemical Industries,
Ltd., 0.375 g, 1.51 mmol) and 2-aminoethanethiol (hereinafter,
2-AET, 15.43 g, 0.2 mol %), and a three way stopcock, a condenser,
a thermometer and a mechanical stirrer were equipped. The inside of
the three-neck flask was deaerated by a vacuum pump, and after
argon substitution was repeated three times, the temperature was
raised to 50.degree. C., and the mixture was stirred. After about
30 minutes, after confirming start of decrease in polymerization
heat, the temperature was raised to 70.degree. C., and the mixture
was stirred for 3 hours.
[0146] After completion of polymerization, the temperature was
decreased to room temperature and the polymerization reaction
liquid was concentrated by an evaporator to about 380 g, poured in
acetone/n-hexane=1000 mL/200 mL, allowed to stand still overnight,
and then the supernatant was removed by decantation. The residue
was washed five times with acetone/n-hexane=500 mL/50 mL. The solid
content was dried by a vacuum dryer at 40.degree. C. overnight.
After putting liquid nitrogen, it was pulverized with a spatula and
transferred to a bag with a chuck. Drying was conducted by a vacuum
dryer at 40.degree. C. for 3 hours, thereby to obtain a
terminal-reactive polymer mixture.
Example 23
[0147] 90.00 g of the terminal-reactive polymer mixture obtained in
Example 22, 30.0 mg of BHT (300 ppm to the polymer), 266.67 g of
1,4-dioxane and 400.00 g of N,N-dimethylacetamide were added to a
four-neck flask of 1 L. To the four-neck flask, a mechanical
stirrer, a glass stopper, a connecting tube connected to a nitrogen
line and a Claisen tube were equipped, and to the forepart, a
Liebig condenser, a distillation adaptor and a recovery flask were
connected. While stirring under nitrogen stream, the temperature
was raised to 132.degree. C. (bath temperature), 94.59 g of
1,4-dioxane was distilled away, removing water from the reaction
system. The temperature was decreased to 110.degree. C., 60 .mu.L
of dibutyltin (IV) dilaurate and 18.08 g (0.1144 mol %,
MOI/AET=1.02) of 2-isocyanatoethyl methacrylate (MOI) were added
thereto under nitrogen stream, and reacted at 110.degree. C. for 2
hours.
[0148] After completion of reaction, the temperature was decreased
to 70.degree. C., 70 ml of ethanol was added and the mixture was
stirred for 30 minutes. After cooling to room temperature, the
polymerization reaction liquid was poured in
acetone/n-hexane=700/300 mL. After allowing to stand still
overnight, the supernatant was removed by decantation. The
precipitate was washed twice with acetone/n-hexane=600 mL/150 mL,
once with acetone/n-hexane/water=600 mL/150 mL/20 mL, and four
times with acetone/n-hexane=600 mL/150 mL.
[0149] The solid content was dried by a vacuum dryer at 40.degree.
C. overnight. After putting liquid nitrogen, it was pulverized with
a spatula and transferred to a bag with a chuck. Drying was
conducted by a vacuum dryer at 40.degree. C. for 3 hours, thereby
to obtain a target macromonomer mixture. The molecular weight of
the macromonomer mixture obtained is as shown in Table 7.
Example 24
[0150] At a charging ratio shown in Table 6, the same
polymerization as in Example 22 was carried out.
[Table 6]
Example 25
[0151] At a charging ratio shown in Table 7, and using the
terminal-reactive polymer mixture of Example 24, the same
functionalization as in Example 23 was carried out. The molecular
weight of the macromonomer mixture obtained is as shown in Table
7.
[Table 7]
INDUSTRIAL APPLICABILITY
[0152] The present invention relates to a highly functionalized
macromonomer mixture, and the macromonomer mixture is suitably used
particularly in contact lenses, intraocular lenses, artificial
corneas and the like.
SPECIFICATION
##STR00001## ##STR00002## ##STR00003## ##STR00004## ##STR00005##
##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010##
##STR00011## ##STR00012## ##STR00013## ##STR00014##
##STR00015##
TABLE-US-00001 [0153] TABLE 1 NVP Initiator 2-ME TAA Mn Mw (g) (g)
(g) (g) (kD) (kD) Example 1 77.80 VA-061 0.44 10.00 205.89 48 129
Example 2 77.80 VA-061 0.44 0.68 184.16 48 161 Example 3 77.80
VA-061 0.44 2.50 121.11 26 81 Example 4 77.80 VA-061 1.78 5.00
197.28 13 30 Comparative 77.80 ADVN 2.00 5.00 109.70 13 36 Example
1
TABLE-US-00002 TABLE 2 Terminal-reactive polymer MOI mixture (g)
(g) Example 5 Example 1 50.00 1.581 Example 6 Example 2 50.00 1.581
Example 7 Example 3 50.00 1.443 Example 8 Example 4 50.00 2.635
TABLE-US-00003 TABLE 3 DMA VA-061 2-ME TAA Mn Mw (g) (g) (g) (g)
(kD) (kD) Example 10 99.10 0.625 7.81 250.92 7.8 19 Example 11
99.10 0.313 1.95 236.52 21 63 Example 12 99.10 0.156 0.98 233.87 24
81
TABLE-US-00004 TABLE 4 Terminal-reactive polymer MOI mixture (g)
(g) Example 13 Example 10 50.00 2.635 Example 14 Example 11 50.00
1.581 Example 15 Example 12 50.00 1.581
TABLE-US-00005 TABLE 5 Advancing NVP Initiator 2-ME TAA MOI Mn Mw
contact (g) (g) (g) (g) (g) (kD) (kD) angle (.degree.) Example 18
77.80 VA-061 1.75 2.50 2.055 191.45 16 46 88 Example 19 77.80
VA-061 0.44 1.37 2.055 185.75 48 129 63 Example 20 77.80 VA-061
0.44 0.68 2.055 184.16 48 161 59 Example 21 77.80 VA-061 0.25 0.86
1.028 210.12 89 231 61 Comparative 77.80 ADVN 7.78 4.67 4.110
216.53 18 48 107 Example 3 Comparative 77.80 ADVN 1.56 4.67 3.426
201.60 56 117 104 Example 4 Comparative 77.80 ADVN 1.56 1.56 3.425
194.13 72 159 78 Example 5 Comparative 77.80 ADVN 0.78 1.56 1.027
192.27 96 235 73 Example 6
TABLE-US-00006 TABLE 6 AA VA-061 2-AET Water (g) (g) (g) (g)
Example 22 144.12 0.375 15.43 640.00 Example 24 144.12 0.500 15.43
640.20
TABLE-US-00007 TABLE 7 Terminal-reactive polymer MOI Mn Mw mixture
(g) (g) (kD) (kD) Example 23 Example 22 90.00 18.08 45 69 Example
25 Example 24 90.00 18.08 52 87
* * * * *