JP2518859C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION   The present invention relates to intraocular devices such as contact lenses and intraocular implants, in particular, polio.
(A) high oxygen permeability, (b) good wetting
(C) flexibility, (d) optical clarity, and (e) in the intraocular environment used.
Having specific hybrid properties such as a substantial lack of aqueous swelling of water Related to contact lenses made by Mer.   Optical contact lenses can be used to correct visual impairment or for cosmetic purposes.
It is well known to be used. However, current contact lenses are
For many reasons, many people who might use contact lenses for various reasons
Was found to be unacceptable. For example, early contact lenses
Was made from polymethyl methacrylate (PMMA). PMMA lens is high
A hard lens with excellent optical clarity and good durability, but low oxygen permeability.
You. Therefore, PMMA lenses can irritate the eyes and cause corneal hypoxia.
May cause the wearer to feel foreign and limit the usefulness of such lenses
is there.   With the intention of avoiding these problems, the so-called "
A "soft" lens was developed. Poly (2-hydroxyethyl methacrylate),
Specially manufactured from poly (vinyl alcohol) or poly (vinyl pyrrolidone).
These "soft" or hydrogel lenses feature, in general, almost
Less irritation and foreign body sensation than the PMMA lens. Hid
If large amounts of water are absorbed in the logger, the oxygen permeability will exceed that of the PMMA lens.
The flexibility of such hydrogel lenses is high, and therefore the wearer's
The feeling of wearing is improved. However, the oxygen permeability of such hydrogel lenses
Is generally still low and has low durability. Furthermore, such lenses have a water content
Because of their high, they generally have a tendency to collect and store proteinaceous and other tear materials
Therefore, the lens becomes fogged over a certain period.   In other attempts to solve problems associated with early lenses, silicone or silicone
Roxane rubber lenses were developed. These have high oxygen permeability and when worn
With a fascinating atmosphere. However, obviously silicone rubber in general
Due to low thermal conductivity, silicone rubber lens wearers may feel burning
Have been reported. Also, since silicone lenses have a tendency to be lipophilic,
Such a lens adheres to the cornea and collects foreign material between the lens and the cornea, thereby
Can cause corneal damage. It is also characteristic of such lenses
Due to lipophilicity, silicone rubber is mucophilic and non-wetting. And attract foreign substances in the eye such as proteins, lipids, mucoids, etc.   The object of the present invention is substantially free of siloxane, wettable and oxygen permeable
Is composed of a substantially non-swellable polymer having a polyoxyalkylene skeleton unit.
Providing ophthalmic devices, such as contact lenses and intraocular implants,
It is to overcome these and other disadvantages of the prior art.   It is a further object of the present invention to provide a visual impairment in the form of a refractive index impairment.
By applying such a polymer corrective contact lens to the patient's eye,
It is to provide a method of correcting.   These and other objects of the invention will be apparent from the following specific description of the invention.
Becomes   One embodiment of the present invention is a compound of formula I Optically clear, produced from crosslinked polymer containing segments of
Stable, biologically inert, wettable, flexible and substantially siloxane-containing
No, substantially non-swellable, oxygen permeable, contact lens
Such an intraocular device.   In the above formula, b, d and f are each independently 0 to 4; q is 1 to 1
, 000; x, y and z are each independently 0 to (x + y + z) ×
q is a number from 4 to 1,000;   R¹, R^Two, R^Three~ R⁸, R¹¹~ R¹⁴, R¹⁷And R¹⁸Are each independently hydrogen,
Alternatively, unsubstituted C₁~ C₁₆Alkyl, substituted C₁~ C₁₆Alkyl, unsubstituted C_Two~ C_1
6Alkenyl and substituted C_Two~ C₁₆Alkenyl, (Where the alkyl and alkenyl substituents are independently C₁~ C₁₆Alkoxy
Carbonyl, C_Two~ C₁₆Alkenyloxycarbonyl, fluoro, 1 carbon atom
Aryl up to 0, C₁~ C₈Alkoxy, C₁~ C₆Alkanoyloxy, Aryloxy having 10 or less carbon atoms, C_Three~ C₆Alkenoyloxy, carbon atom
Aroyloxy of number 11 or less, C_Three~ C₈Cycloalkyl, C_Three~ C₈Cycloalco
Kissi, C_Three~ C₈Cycloalkylcarbonyloxy, C_Three~ C₈Cycloalkoxyka
Rubonyl, oxacycloalkyl having 7 or less carbon atoms, oxo having 7 or less carbon atoms
Sacycloalkoxy, oxacycloalkoxy (C7 or less) -carboni
Oxacycloalkyl (C 7 or less) -carbonyloxy and aryl
(C 10 or less) -oxycarbonyl;
The alkenyl substituent may further optionally be a C₁~ C₆Alkyl, fluoro or
, C₁~ C₆Alkoxy (however, this alkoxy is already single-bonded to another oxygen atom)
Not attached to a carbon atom that is Selected from the group consisting of aliphatic, aromatic or heterocyclic containing groups such as:   R¹, R^Two, R^Five~ R⁸, R¹¹~ R¹⁴, R¹⁷And R¹⁸Is, independently,
Unsubstituted or further substituted with a substituent selected from the above alkyl substituents
Aryl having 10 or less carbon atoms, C_Three~ C₈Cycloalkyl and
Selected from oxacycloalkyls having 7 or less carbon atoms;   R^Three, R^Four, R⁹, R^Ten, R^FifteenAnd R¹⁶Is R¹The same group as above with respect to
Selected from;   Or R^Three, R^Four, R⁹, R^Ten, R^FifteenAnd R¹⁶Are more independent, each further
Fluoro, aryl having 10 or less carbon atoms or C₁~ C₁₆Substituted with alkoxy
May be, C₁~ C₁₆Alkoxycarbonyl, C_Three~ C₁₆Alkenoyloxy,
C_Two~ C₁₆Alkenyloxycarbonyl and C₁~ C₁₆Choose from alkanoyloxy
Selected;   Further, R^Three, R^Four, R⁹, R^Ten, R^FifteenAnd R¹⁶Are independent, each further
Substituents having an oxygen atom or a carbonyl group as a bond to the remainder of the
If not all are substituents on the same carbon atom bonded to another oxygen atom,
Fluoro, C₁~ C₆Alkyl or C₁~ C₆May be substituted with alkoxy
Aryloxy having 10 or less carbon atoms, cycloalkoxy having 8 or less carbon atoms
, Cycloalkyl (having 8 or less carbon atoms) -carbonyloxy, cycloa Lucoxy (8 or less carbon atoms) -carbonyl, aroyloxy with 11 or less carbon atoms
Xy, oxacycloalkoxy having 7 or less carbon atoms, oxa having 7 or less carbon atoms
Cycloalkenyloxy, oxacycloalkoxy (7 or less carbon atoms) -cal
Bonyl, oxacycloalkyl (C7 or less) -carbonyloxy, oxo
Sacycloalkenyloxy (C 7 or less) -carbonyl and aryloxy
It is selected from cis (having 10 or less carbon atoms) -carbonyl. Furthermore, two adjacent
The R groups may be a 5- to 8-membered cycloalkyl ring, a 5- to 8-membered
An oxacycloalkyl ring or a bicycloalkyl ring may be formed. b, d
And f is 0, the R in at least a portion of the segment having the structure of Formula I
¹, R^Two, R^Five~ R⁸, R¹¹~ R¹⁴, R¹⁷And R¹⁸At least one of which is other than hydrogen
R¹, R^Two, R^Five~ R⁸, R¹¹~ R¹⁴, R¹⁷And R¹⁸Can be individually or
Overall, sufficient sparseness such that the resulting polymer is substantially non-swellable in water
Water-soluble and the polymer is less than 60 °, preferably less than 40 °, more preferably
Is less than 25 °, more preferably less than 15 °, most preferably less than 10 °,
It has sufficient hydrophilicity to show a receding contact angle with distilled water at ° C.   All alkyl groups described above, alone or as part of another group,
Preferably, methyl, ethyl, propyl and butyl, especially adjacent on the aryl ring
C, such as t-butyl, except that each group is not t-butyl.₁~ C_FourAl
Kill. These alkyl groups may be straight or branched. Alkyl
Is preferably bonded to the para-position when it is a substituent on the phenyl ring.
Suitable alkenyl groups, alone or as part of another group, are ethenyl, prope
C such as nil and butenyl_Two~ C_FourAlkenyl. (Single or other groups
Suitable aryl groups (as part of) are phenyl and naphthyl, more preferably
Phenyl. Suitable aryl groups further include C₁~ C_FourAlkyl, more preferably
It is most preferably substituted in the para position by t-butyl.   Preferably, b, d and f are independently 0-3, most preferably 1 or 2.
You. In a more preferred embodiment, the group of formula I is at least 25%, even more preferably
Contains 30%, more preferably 40%, even more preferably almost halogen. And most preferably contains no halogen. Whenever a cyclic group is indicated,
Any of carbocycles and heterocycles preferably has 5 to 6 ring members,
The case preferably has only carbon atoms and one oxygen atom as ring members.   Bicycloalkyl is a group in which two adjacent R groups in a segment of formula I are taken together.
Form a ring, one of which is already a cycloalkyl group
Then it is understood. In other words, two pairs of R groups and the carbon atoms attached to them
A fused ring composed of For example, R¹Is cyclopropyl, R^TwoIs methyl
If R¹And R^TwoIs, together with the carbon atom to which it is attached, (2,1,0) cyclopent-
It can be 2,2-diyl.   When b is greater than 1 in Formula I, multiple R^ThreeAnd R^FourGroups are the same or different
All R^ThreeAre the same and all R^FourAre preferably identical
No. The same goes for d, R⁹And R^TenF, R^FifteenAnd R¹⁶Applies to   Preferably, b, d and f are each independently an integer from 0 to 2, most preferably 0.
Or 1.   In one aspect of the invention, R¹~ R^Five, R⁷~ R¹¹And R¹³~ R¹⁷Each
Hydrogen and b, d and f are each 0,
And some of the R⁶, R¹²And R¹⁸At least one is other than hydrogen. Suitable
Has R in most segments⁶, R¹²And R¹⁸At least one is hydrogen
Other than. More preferably, most (most preferably all) of the segments of formula I
), R⁶, R¹²And R¹⁸At least one is other than hydrogen.   Preferably, the substituent R⁶, R¹²And R¹⁸Is an alkyl having 16 or less carbon atoms;
C16 or less substituted with alkoxy or fluoro having 8 or less atoms
Lower alkyl; unsubstituted or fluoro, alkoxy or C6 or less
Is phenyl substituted with alkyl having 6 or less carbon atoms; phenyl ring is unsubstituted,
Or fluoro, alkoxy having 6 or less carbon atoms or alkyl having 6 or less carbon atoms
Benzyl substituted with a kill; cyclohexyl; or a 4-5 membered ring of carbon atoms.
Oxacycloalkyl.   A very advantageous sub-concept is: [Wherein, b, d, f, q, x, y, z, R⁶, R¹²And R¹⁸Is synonymous with the above
, R (if present)⁶, R¹²And R¹⁸At least one is other than hydrogen] Wet, non-swellable intraocular device made from a polymer comprising
More specifically, it relates to contact lenses.   There are two very advantageous embodiments of formula II, which are of formula III: (Where n is b + 1, m is d + 1, p is f + 1, and n, m and p are respectively
Independently preferably 1 to 3, more preferably 1 or 2, most preferably 1
Yes, R⁶And R¹⁸At least one, and preferably both, are aliphatic, aromatic,
Or a heterocyclic group, preferably an alkyl having 6 or less carbon atoms;
Alkyl having 6 or less carbon atoms, substituted by alkoxy or fluoro;
Substituted or fluoro, alkoxy having 6 or less carbon atoms or 6 or less carbon atoms
Lower alkyl-substituted phenyl; unsubstituted phenyl ring, or fluoro, carbon
Substituted with alkoxy having 6 or less carbon atoms or alkyl having 6 or less carbon atoms
Benzyl; cyclohexyl or oxacyclo having 4 or 5 ring carbon atoms
Alkyl)),   Or the following formula IV: Where n, m, p, x, y, z and q are as defined above for Formula III
The same, R¹²Is preferably R of formula III⁶Selected from the same group as Indicated by either   In the above description, the units x, y and z are random in the block segment.
It is to be understood that they are arranged for each other or alternately.   Other preferred embodiments correspond to Formulas II, III and IV where z is 0.   Desirably, the polymer segment of Formula I or II in the finished polymer is an acid
Having free hydroxyl groups within the polymer which has a tendency to reduce oxygen permeability
Absent.   Free hydroxyl groups on the outer surface of the formed polymer allow water to enter the polymer matrix.
To increase wettability without the absorption of However, actually
If you want to manufacture contact lenses with high oxygen permeability,
Is preferably substantially smaller. Broken free hydroxyl groups present
A preferred means of checking is to allow them to interact with the chromophore.   Representative chromophoric groups useful in these embodiments include American Hoechst
Examples include hydroxy-reactive dyes known in the art under the trade name Ramazol manufactured by
However, the present invention is not limited to these. Particularly suitable Ramazol dyes are listed in the table below.
For example.  All of the above substances have at least one of the following formulas: Which reacts with the hydroxyl groups of the polymer or monomer and has the formula:     Dye-SO_Two-CH_Two-CH_Two-O-polymer Or , Preferably the former. In this way, excess free hydroxyl groups At the same time to obtain colored contact lenses. Treat these excess hydroxyl groups
Another way to manage this is to use these entities to exploit various degrees and types of cross-links.
Is to form   In a further embodiment of the present invention, the intraocular device, preferably a contact lens,
In particular, the following equation V: From a polymerized unit of the reactive monomer of   In the above formula, A is each independently a divalent group of the formula I (however, any polymer
In the above, all the A groups are homopolymers of polyethylene glycol.
Preferably, but not limited to, all A groups are polyethylene glycol or polypropylene.
It is not necessarily a homopolymer of lenglycol, and any one or more A groups
Is -N (R¹⁹)-).   L is each independently selected from -BRB'-;   w is 0-8, preferably 0-4, most preferably 0, 1 or 2;   D is each independently oxygen or -N (R¹⁹)-Is;   R¹⁹Is independently hydrogen, C₁~ C_FourSelected from alkyl and phenyl;
Preferably hydrogen;   B and B 'each represent the following formula in which a carbonyl group is bonded to A or D: A group selected from:   R is preferably each   (A) oxy, carbonyloxy, amino, aminocarbonyl, oxycarbo
Interrupted by nil, ureido, oxycarbonylamino or carbonylamino
A divalent aliphatic group having 25 or less carbon atoms, which may be present;   (B) a 5- to 7-membered divalent alicyclic group having 5 to 25 carbon atoms;   (C) a divalent arylene group having 6 to 25, preferably 7 to 15 carbon atoms;
  (D) divalent aralkyl or aralkyl having 7 to 25, preferably 8 to 16 carbon atoms. A rukari group (wherein groups (b) and (d) may optionally be
The same groups as mentioned above may be interrupted; aryl in the groups (c) and (d)
The ring is halogen, preferably fluorine or chlorine, C₁~ C_FourAlkyl, preferably
Is methyl, and C₁~ C₁₂Perhaloalkyl, especially C₁~ C₁₂Perfluoroalkyl
Optionally further substituted by one or more substituents selected from
A divalent linking group;   L 'is hydrogen, P'-BR-B'-, and P'-RB-' (where B, R and
And B 'represent those defined above, except that the carbonyl group of B is bonded to P'
, P ', when co-reacted with hydrogen, amino, hydroxy or a suitable crosslinking agent,
Or a portion containing a crosslinkable group that can be crosslinked when exposed to actinic radiation
Is selected);   L "is hydrogen, L" ", -BR-B'-P ', and -BR as defined below.
-P '(where B, R, B' and P 'are the same as above except that the carbonyl of B' is replaced by P '
As defined above except that it is bonded to   L "" is a monovalent aliphatic, aromatic or alicyclic terminal having 14 or less carbon atoms.
Group.   P 'is a vinyl-containing group, for example: (R^aAnd R^bIs as defined below) In the case of a group containing a moiety represented by the formula:
Cross-linking in the presence or absence of up to about 10% (but the final product
Contains substantially no hydroxyl group).   The vinyl comonomer is most useful without substantially altering the other properties described above.
Often used to increase the degree of hydrophilicity of the end product. Usually vinyl
The comonomer has the formula: Of polyethylene glycol or of the following formula:(Where g is 1 to 25, R^eIs hydrogen or methyl
Yes, R^dIs CH_Two= CH-CH_Two= C (CH_Three)-Or other UV curable groups
), The resulting polymer is more hydrophilic than the conventional polymer,
Is substantially the same as when no comonomer is present.   Typically, the vinyl comonomer, when present, will comprise from about 2 to about 1 of the resulting polymer.
It is used in an amount of 0% by weight. The compound of formula V has a molecular weight greater than 8,000
In this case, it is advantageous to use 5% or less of a vinyl comonomer. Typically,
If the compound of Formula V has a molecular weight of less than about 4,000, no more than 10% by weight of
Nyl based comonomers can be used. The compound of formula V is a molecule of 4,000-8,000
If present, the upper limit for the vinyl comonomer is from 5 to 10% by weight.   If P 'does not have a vinyl group but participates in cross-linking, P' is, for example, an active hydrogen
It contains. Preferably P 'is OH, NHR^c(R^cIs hydrogen or lower alkyl
), The residue directly attached to the carbonyl of B or B ',
If not, complete with a normal acyl residue, SCN- or OCN-
Can be Next, crosslinking is usually accomplished by condensation with a 2- or multifunctional co-reactive monomer.
Or, by addition. For example, when P 'is OH, the co-reactive monomer
The functional group is -NHR^c, -COOH, OCN-, SCN- and the like;
R^cWhere the reactive comonomer functionality is a normal acyl or a normal residue.
Also linked acyl; and when P 'has OCN- or SCN-,
The reactive comonomer functionality may be OH. Similarly, P 'or co-reactive
Other co-reactive functional groups, described as nomers, are those described as part of (P ').
Are on the co-reactive monomer, those described as part of the co-reactive monomer are P
').   Vinyl comonomer and co-reactive monomer suitable for condensation are shown below. However However, not all of these are listed here, and these modifications, additions and changes are not
It will be appreciated by those skilled in the art that they can also be used.   One or both of L ′ and L ″ is hydrogen, or P ′ is hydrogen and P
′, At least one further crosslinkable moiety is R¹~ R¹⁸
As one of the radicals or R¹~ R¹⁸Must be present as one substituent of a group
No. Such a crosslinkable group has one or both of L 'and L "bridged therein.
Even when the compound has a bridging group, one or more R¹~ R¹⁸As the above substituent,
Can exist instead of these. However, the finished cross-linked polymer
The degree of crosslinking is 10% or less, preferably 5% or less, more preferably 1 to 4%,
Most preferably it should be in the range of 2-3%.   In a preferred embodiment, A is a compound of formula II, most preferably of formula III or IV.
Is a valence group.   L ′ and / or L ″ is the following formula VI: (Where R^aAnd R^bAre each independently hydrogen or methyl, but simultaneously
is not) Particular preference is given to polymers with monomers of the formula V   An important sub- concept of the present invention is substantially the following formula VII: (Where R^a, B, R, B 'and A are as defined above,^aAre each other
Different from Ophthalmic device, preferably a contact lens, made of a polymer comprising polymerized units of
. Particularly preferred are those in which R is a divalent arylene group having 6 to 14 carbon atoms, or a divalent arylene group.
C_Two~ C₆Alkylene-oxycarbonyl-C₆~ C_TenAn arylene group, wherein D is
-NHC, wherein B and B 'each have their nitrogen directly attached to R
Polymers with monomers of formulas VI and VII, which are O-.   In a very preferred embodiment, A is of the formula: (Where R²⁰Is alkyl having 1 to 4 carbon atoms, most preferably methyl, y is
Is about 6 to about 200, preferably about 25 to about 100, and most preferably about 50 to about 7
5) Is a polymer from monomers of formulas V and VII.   A very preferred embodiment is where A is of the formula VIII: (Where x is from about 2 to about 20, y is from about 8 to about 100, and z is from about 4 to about 80) Is a polymer based on the monomers of the formulas V and VII. Other important practices
In some embodiments, the value of y is at least about twice x and R²⁰Has 1 to 4 carbon atoms
Need to be alkyl, preferably methyl.   The reactive vinyl monomer is characteristically polymerized under ordinary polymerization conditions. this
In vinyl-based monomers containing only one vinyl group, a small amount
For example, from about 0.01 to about 5% by weight of a conventional crosslinking agent based on the monomer of Formula V
You may. Suitable crosslinking agents include acrylic acid and allyl methacrylate;
Ethylene glycol acrylate, diethylene glycol dimethacrylate and dimethacrylate
Di-acrylic acid and -methacrylic acid such as propylene glycol acrylate
Cylene glycol and polyalkylene glycol; trimethylo triacrylate
Lupropane; Pentaerythritol tetraacrylate; Divinylbenzene;
Nyl ether; Divinyl sulfone; Diacrylic acid or bisph-methacrylate
Enol A; methylenebisacrylamide; diallyl phthalate; triallylamella
Mineo and diolefins such as di-acrylic acid and hexamethylene methacrylate
Monomer. Similarly, for the polymerization of divinyl monomers of formulas V and VII
Here, if desired, a trace amount of a crosslinking agent may be used.   The monomer of formula V is free hydroxy, isocyanato, carboxy or amide.
If it has a phenyl group, a suitable crosslinking agent is an addition or
It contains di- or polyfunctional co-reactive groups that form condensation reaction products.   If desired, the monomer reaction mixture may comprise a catalytic amount of a conventional catalyst, preferably free radicals.
A catalyst may be contained. Hydrogen peroxide, benzoyl peroxide, tert-butyl per
Octoate, benzoyl peroxide or azobis (isobutyronitrile)
Of particular interest are the usual peroxide and azo catalysts.   The polymerization is generally carried out at a temperature of about 20 to about 150 ° C. for about 1 to about 24 hours.
You. It is understood that the time and temperature in such a reaction are inversely proportional. Accordingly
When the temperature at the upper limit of the temperature range is used, the reaction time is near the lower limit of the time range.
Preferably, the polymerization is performed in the presence of actinic radiation, such as UV light.   Depending on the nature of the polymer mixture, the polymer obtained by such polymerization
For example, it is desirable to post cure at a rather high temperature, such as about 60 to about 150C.   To manufacture contact lenses, the polymer mixture is directly shaped into the lens shape.
Forming or polymerizing further polymerization, such as a small cylindrical or "button" shape
Machining in a mold having a shape that is convenient for machining.
Can be.   Also, in a further embodiment of the present invention, an intraocular device, preferably a contact lens.
Essentially has the formula IX:     EY¹-D- (ALD)_w-A-Y¹-E (IX) And the following formula X:     (E¹)_t-G (X) Prepared from a polymer consisting of the addition product of   In the above formula, A, L, D and w are as defined above;   t is an integer from 2 to 4;   G has a valence corresponding to the value of t, and is an aliphatic or aromatic having about 24 or less carbon atoms.
, An araliphatic, carbocyclic or heterocyclic residue, or t is 2. Is:     -Y¹-D- (ALD)_w-A-Y¹− May represent a divalent group of Where Y¹Is oxy, carbonyloxy, amino, aminocarbonyl, oxyca
Interrupted by rubonyl, ureido, oxycarbonylamino or carbonyl
A divalent aliphatic group having 14 or less carbon atoms; a divalent aliphatic group having 14 or less carbon atoms
An aliphatic hydrocarbon carbonyl or -aminocarbonyl group (here,
The rubonyl group is adjacent to oxygen or -N (R¹⁹) —Covalently bonded to a group); charcoal
Divalent 5- to 7-membered alicyclic group having 5 to 14 carbon atoms; divalent aryl having 6 to 14 carbon atoms
A divalent aralkyl or alkaryl group having 7 to 14 carbon atoms;
Divalent 5-7 membered alicyclic carbonyl or aminocarboni having 6-15 atoms
(Wherein the carbonyl group is adjacent to oxygen or -N (R¹⁹) -Part
Or a divalent arylene-, aralkyl or a
Lucaryl-carbonyl or -aminocarbonyl groups (where aryl
The alkenyl group has 6 to 14 carbon atoms and the aralkyl or alicalyl group has
An oxygen atom having 7 to 14 atoms and an adjacent carbonyl group or -N (R¹⁹)
-Is covalently bonded to a group); or Y¹Is a direct bond (where E is water
Is prime).   E¹When is isocyanato or isothiocyanato, E is hydrogen, hydro
Xy or amino;¹When is hydroxy or amino, E is
Isocyanato or isothiocyanato.   Advantageously, in order to obtain a suitable crosslink, at least one fine concept
In an amount, for example, about 0.2% by weight, based on the amount of the compound of formula VI used, when t is 3
Is used. In general, stoichiometric equivalents of the compounds of formulas IX and X
Things are used together. However, a slight excess of di- or polyisocyanate
Or-use iothiocyanate to obtain sufficient cross-linking to achieve product dimensional stability
May be maintained. Instead, use additional conventional crosslinkers to reduce product dimensions.
Sufficient crosslinking may be provided to maintain process stability. Therefore, of formulas IX and X In addition to the compounds, trace amounts, for example up to about 5% by weight, of toluene diisocyanate
, Isophorone diisocyanate, 4,4'-methylenebis (phenyl isocyanate
), Methylenebis (cyclohexyl isocyanate), melamine triisocy
Conventional di-isocyanates or triisocyanates such as anates
It may be added to the reaction mixture. On the other hand, a stoichiometric excess in the reaction of IX and X
If isocyanates are used, trace amounts, for example up to about 5% by weight, of amino and / or
Alternatively, a di- or polyfunctional crosslinking agent having a hydroxyl group may be used. This is a good thing
Such crosslinking agents include, for example, ethylene glycol, glycerin, diethylene glycol, and the like.
Recall, ethylenediamine, ethanolamine, triethanolamine, die
Tanolamine and the like.   The addition reaction between the compounds of the formulas IX and X, and any further crosslinking agents,
It can be carried out under conditions known per se. Thus, if necessary, the compound
Or in the presence of an inert diluent, if desired, from about 0 to about 100 ° C, preferably
At a reaction temperature of about 20-80 ° C., optionally with triethylamine or di-
It may simply be mixed in the presence of a condensation catalyst such as n-butyltin diacetate.   In the manufacture of intraocular devices such as contact lenses, the reaction mixture is applied to the lens
It may be molded directly into a shape, or the polymerization may be reduced to a small cylindrical or "button"
Performing in a mold with a shape that is convenient for further processing such as shape and then machining
May be performed.   The compounds of the formulas V, VII, IX and X are either known or are known per se.
It can be manufactured by a method.   For example, the vinyl monomer of Formula V is (a) the following Formula XI:     HO- (ALD)_w-AL- '' (XI) Wherein L ′ ″ is a monovalent aliphatic or alicyclic terminal group having 14 or less carbon atoms.
And A, L and w are as defined above) Or (b) the following formula XII:     HO- (ALD)_w-AH (XII) (Wherein, A, L and w are as defined above) With a stoichiometric amount of the following formula XIII: (Wherein X is an isocyanato group; anhydride, acid halide or carboxylic acid ester)
An activated carboxy group such as thiol; or a halide ion, sulfa
Is a residual group such as At a temperature of about 0 ° C. to about 100 ° C. in the presence of a conventional additional catalyst.
Or in the absence of an inert diluent, optionally in the presence of an inert diluent.
Manufactured by collecting the product. X is residual like halide ion
If it is a product of formula XII, the product of formula XII is an alkali metal alkoxide, such as
It may be in the form of an alkoxide salt.   Alternatively, such as aliphatic, aromatic, cycloaliphatic or araliphatic diisocyanates.
Such diisocyanates are converted to monools or diols of formula XI or XII, respectively.
To react the corresponding isocyanato-terminated product with acrylic acid or
Hydroxy-containing acrylates or methacrylates such as hydroxyethyl acrylate
Allylate or allylamine or methallylamine or allyl or metallyl
Alcohol and at a temperature of about 0-100 ° C in the presence or absence of an inert diluent
In the presence, optionally a tertiary amine such as triethylamine or organic
Reaction in the presence of an addition polymerization catalyst such as a compound of formula V to give the corresponding product of formula V
By forming and recovering the product of formula V, B and B 'are converted to -NHCO-
And the product of formula V wherein D is -O- can be obtained.   Further, a compound of formula XII is converted to a compound of formula XIV:           X-R-X (XIV) (Wherein, R and X are as defined above) With a compound of the formula XV:     X-R-B-D- (ALD)_w-ABRX (XV) Can be formed.   Compounds of formula XV further include co-reactive moieties of X that also contain a vinyl group, e.g.
The compound of formula V is obtained by reaction with hydroxyethyl acrylate.   The compounds of the formulas XI and XII are known or can be prepared by methods known per se.
Can be easily manufactured.   For example, a compound of formula XII can be obtained by adding a diol of the formula: HO-AH
Compounds having functional reactive groups (where the reactive groups are isocyanate, anhydride, acid
An activated carboxy such as a halide or carboxylate, or
Such as halide ions, sulfato, etc.)
Therefore, it is manufactured. The molar ratio of the diol to the bifunctional reactive group containing compound is about
If two to one, the value of w in the resulting adduct of formula XII is about 1 and about 3
When moles of diol are reacted with about 2 moles of bifunctional group containing compound,
The average value of w obtained in the adduct of formula XII is about 2. w
Said reaction to obtain one or more such compounds of formula XII comprises:
At a reaction temperature of about -10 to about 100 ° C depending on the relative reactivity of the
In the presence or absence of, if desired or appropriate,
In the presence of a catalyst for addition polymerization.   Preferred polyols of the formula HD-AH wherein A represents a divalent moiety of the formula I and amino
Polyethers are generally known substances or can be prepared in a manner known per se.
Therefore, it can be manufactured.   Thus, polyols of the formula: HO-AH generally have xq moles of the following formula:
XVI:(Where R¹~ R⁶, B, x and q are as defined above. And yq mol of the following formula XVII: (Where R⁷~ R¹², D, y and q are as defined above) And zq mole of the following formula XVIII: (Where R¹³~ R¹⁸, F, z and q are as defined above) In the presence of an epoxide of the formula
Under pressure from ambient pressure to about 3,000 kPa gauge pressure, temperature from 0 to about 130 ° C,
It is optionally prepared by an addition reaction in the presence of an inert diluent. Desired
If applicable, prior to the reaction of the evoxides, aliphatic or aromatic compounds having 14 or less carbon atoms
Add an aromatic or cycloaliphatic alcohol, acid or amine to the reaction mixture and add
Corresponding monols with D as a terminal group may be prepared.   When a polyol of the formula: HO-AH is obtained using a mixture of various epoxides
The epoxide is mixed by mixing the epoxides,
A dumb copolymer or terpolymer can be obtained or added
To form a block copolymer having terminal hydroxyl groups.
it can. Suitable catalysts include alkaline earth metal oxides, alkaline earth metal carbonates
Salts, alkyl zinc compounds, aluminum alkoxides, chloride, bromide and vinegar
Hydrates of ferric acid and gamma radiation. The reaction is ethylene glycol
Or the presence of a glycol such as propylene glycol
Or with a highly functional polyol such as sucrose,
Is also initiated by amines such as ethylenediamine, toluenediamine, etc.
Can be made. In general, the length of the reaction time depends in part on the alkylene oxide used.
Depending on the sid, it is generally less than one hour to several tens of hours. Therefore, ethylene The oxides generally exhibit about three times the activity of propylene oxide, and moreover, 1,2-butylene.
Reacts faster than lenoxide. Polyoxyethanes and polytetrahydrides
The production of lofurans is generally carried out using trialkyloxonium salts, carboxonium,
To form a ring-opening oxonium using a salt such as
Begun.   Suitable diols of the formula: HO-AH include 1,2-propylene oxide
1,2-butylene oxide; 1,2-epoxydecane; 1,2-epoxidede
1,2-epoxyoctane; 2,3-epoxynorbornane; 1,2-d
Poxy-3-ethoxypropane; 1,2-epoxy-3-phenoxypropane;
2,3-epoxypropyl-4-methoxyphenyl ether; tetrahydrofura
1,2-epoxy-3-cyclohexyloxypropane; oxetane;
2-epoxy-5-hexene; 1,2-epoxyethylbenzene; 1,2-epoxy
Xy-1-methoxy-2-methylpropane; perfluorohexylethoxypro
Epoxides such as pyrene oxide and benzyloxypropylene oxide
And those obtained from Similarly, the epoxides can be used with these mixtures.
You may use it. Further, the formulas XVI, XVII and XVIII (where b or d
Or each f is 3 and the carbocyclic portion of the ring is substituted).
-Ethers are resistant to homopolymerization but are more reactive cyclic ethers.
And copolymerize very quickly. Suitable comonomers include, for example, 2-methyl
-Tetrahydrofuran and 3-methyl-tetrahydrofuran. As well
Alternatively, ethylene oxide may be used as a comonomer.
Mers are used in accordance with the invention in the absence of larger units of hydrophobicity.
Characteristic of being too hydrophilic to absorb too much aqueous fluid
Is shown. However, it contains more than 60% propylene oxide on a molar basis.
Ethylene oxide / propylene oxide copolymerized diols are
Hydrophobic enough to qualitatively show no swelling, less than 60 °, preferably 40 °
Less, more preferably less than 25 °, even more preferably less than 15 °, most preferably
It still has sufficient hydrophilicity to show a contact angle with water of less than 10 °.   In general, the ethoxy units in the polymer backbone of the polymeric intraocular device of the present invention The upper limit depends on the amount of water absorbed by such polymers under the conditions of use. Book
The polymer used in the invention is characteristically about 10 ply based on the total weight of the polymer.
% Water absorption, preferably up to about 7% by weight, most preferably up to about 5% by weight
Indicates the amount. The amount of water absorbed is about 20 ° C., distilled water or, if desired,
It is usually or conveniently measured using an isotonic solution.   Many polymer diols of the formula: HO-AH are commercially available. Therefore
Suitable diol products have the general formula: (Where b ′ has a value of about 16 to 70 and the sum of a ′ and c ′ is about 4 to about 100
Is) And polyoxamers having the formula: Examples of such polyoxamers and
And the average values of a ′, b ′ and c ′ of these are polyoxamer 101 (a
'Is 2, b' is 16, c 'is 2); polyoxamer 105 (a' is 11, b 'is
16, c 'is 11); polyoxamer 108 (a' is 46, b 'is 16, c' is
46); polyoxamer 122 (a 'is 5, b' is 21, c 'is 5);
Summer 124 (a 'is 11, b' is 21, c 'is 11); polyoxamer 181
(A 'is 3, b' is 30, c 'is 3); polyoxamer 182 (a' is 8, b '
Is 30, c 'is 8); polyoxamer 183 (a' is 10, b 'is 30, c' is
10); polyoxamer 185 (a 'is 19, b' is 30, and c 'is 19);
Oxamer 212 (a 'is 8, b' is 35, c 'is 8); polyoxamer 231
(A 'is 6, b' is 39, c 'is 6); polyoxamer 282 (a' is 10, b
'Is 47, c' is 10); polyoxamer 331 (a 'is 7, b' is 54, c '
7); polyoxamer 401 (a 'is 6, b' is 67, c 'is 6)
You. It is commercially available under the product name.   As the polypropylene ether glycols, a range of about 400 to about 4,000 is used.
Commercial products having the molecular weights in the box are included. Relatively low molecular weight, usually about 1,000 to 2,000 polytetramethylene ether glycols, and 1,
Polymers of 2-butylene oxide, i.e. polybutyl ether glycol, are also
It is commercially available.   As mentioned above, the polymers used in the present invention are less than 60 ° at 20 ° C, preferably
Or less than 40 °, more preferably less than 25 °, even more preferably less than 15 °,
Also preferably shows a receding contact angle of less than 10 °. Measurement of such contact angles
For example, J. D. "Surface and Interface Aspects of Biomedical Polymers" by Androde et al. (S
urface and Interfacial Aspects of Biomedical Polymers), Volume 1, “Surfaces
Chemistry and Physics ", published by Plenum Press, 19
1985, using the modified "Wilhelmy Plate" method described in
This can be done conveniently, where a flat plate of known dimensions
A sample is placed in pure water, which is a wet solution, at a controlled speed, for example, 2 to 20 mm.
/ Min. Poly (hydroxyethyl methacrylate) is generally
Have a receding contact angle of 39-43 °.   As mentioned above, the polymers used in the present invention have a high degree of oxygen permeability. acid
Elemental permeability: Dk (× 10^-Ten) Is (a) 21% oxygen, ie 99-100%
(B) The surface area of the sample used is 100 square meters, using air instead of oxygen.
Is 0.50 square meters, and the relative humidity is 0% relative humidity.
ASTM Standard D with modification to control to 95 to 100% relative humidity
It is measured using the method of 3985-81. The unit of Dk is [(cm · mm / s) (ml
O_Two/ Ml · mmHg)].   Normal, fully swollen polymethacrylic acid usually with little cross-linking
The droxyethyl lens is Dk (× 10^-Ten) Value about 5-7 [(cmm / s) (mlO_Two
/ Ml · mmHg)].   The polymers of the present invention for use in intraocular devices such as contact lenses are advantageously
Greater than 7, preferably greater than about 15, more preferably greater than about 20
Most preferably, Dk (× 10^-Ten) Value.   The following examples are for illustrative purposes and are to be construed as limiting the invention.
Should not be. All parts are by weight unless otherwise indicated.   The following examples all have common procedures. These common steps and
Is:   1. Dry all glassware in an oven at 150 ° C for at least 5-6 hours.
Was.   2. During assembly, the reaction system must be maintained under a steady nitrogen atmosphere.
Absent.   3. All isocyanates used must be freshly distilled.   4. All polyglycol materials must contain more than 0.005% water.
No. For these examples, all diols were used at 65 ° C. using a Pope removal membrane.
And water was removed while maintaining the pressure at less than 265 Pa.   5. After assembling the reaction glass container and placing it under a nitrogen atmosphere, set the apparatus on fire for 20 minutes.
Flame dried to ensure that all water was removed from the system.   6. The methylene chloride used in these reactions was all glass helices.
ices) and distilled into molecular sieves through a 200 mm column
.   7. All temperatures shown are degrees Celsius. Vacuum evaporation is 2 unless otherwise specified.
Performed at １３13 kPa. Abbreviations used in this specification   PPG: polypropylene glycol   HEMA: hydroxyethyl methacrylate   TDI: Toluene diisocyanate   PEG: polyethylene glycol Example 1   Reaction vessel carefully dried 2.105 mol of 2,4-toluene diisocyanate
And add 9% by weight of methylene chloride to the total prepolymer to be produced.
I got it. Add 1.053 mol of PPG to the dried dropping funnel and add all the prepolymer
51% by weight of methylene chloride to stannous octoa
te) (Catalyst) was added thereto with 0.0029 mol. Diisocyanate PPG mixture
The nate mixture was added over 2-4 hours. The reaction is based on IR spectroscopy. About 3,500cm^-1Monitored by disappearance of the OH peak at. At this point, HE
2.105 moles of MA were added to the mixture and the reaction was analyzed by IR spectroscopy to 2,270
cm^-1Was monitored by the disappearance of the NCO peak. next, To the solution was added methylpropane-1-one under reduced pressure at 25 ° C under reduced pressure.
Was removed. The material thus produced is placed in a UV furnace at about 3-5 milliwatts.
It was cured. Next, the crosslinked polymer is extracted in isopropanol for 5-6 hours,
The desired contact lens material was obtained. Examples 2 to 10   The same operation as in Example 1 was performed using the amounts specified in the table below. Isoshi
If the anate / diol ratio is 3: 2, add the diol to the isocyanate
Instead, it was preferred to add the isocyanate to the diol.   The above table contains the molar ratios of several diol / diisocyanate reactions. these
All numerical values were based on an initial amount of 500 g of diol. These reactions are based on HEM
All capped with A.   In the examples below, all amounts of reactants are in grams and the corresponding molar amounts are
It is shown in parentheses and the Dk value is × 10^-TenIt is an order. Contact angle in degrees Show. Example 11   Air-cooled coagulator, dropping funnel, Claisen adaptor, and nitrogen
Three-port round bottom hula equipped with an inlet / outlet (a drying tube is attached to the outlet)
To the flask were added 152.6 g (1.053 mol) of TDI and 200 g of methylene chloride.
I got it. The mixture was stirred vigorously with a large magnetic stirring bar for about 20 minutes. PP in dropping funnel
G475 250 g, methylene chloride 323 g and stannous octoate 1.09 g
(0.0027 mol) was added. Gently flush the reactants over 4-5 hours.
Ko. After more than 4 hours, completion of the reaction was determined by IR spectroscopy to be 3,5
00cm^-1The disappearance of the hydroxyl group peak was examined. When this peak dissipates
136.99 g of HEMA was passed through a dropping funnel into a round bottom flask over 20 minutes.
added. The reaction was completed by IR at 2,270 cm^-1The disappearance of NCO absorption in Japan
By guessing, I was able to track again. After the reaction is completed, the prepolymer
Transfer the solution to a single-necked flask and then rotary rot to remove the methylene chloride.
Connected to the evaporator. This separation step is generally performed over 1 hour and 30 minutes,
30 minutes at 30 ° C. Then 0.6% of the prepolymer Films made from the polymer have a Dk of 3.2 and a better contact angle than HEMA
Had. Examples 12 to 16   Perform the same operation as in Example 11 except for using the reactants and amounts specified below.
The resulting Dk is shown in the table. Example 17   Air-cooled aggregator, dropping funnel, Claisen adapter, mechanical stirring bar, and nitrogen introduction
・ Three-necked round-bottom flask equipped with an outlet (a drying tube is attached to the outlet)
In addition, 250 g (0.5263 mol) of PPG475, 500 g of methylene chloride and
1.00 g (0.0025 mol) of stannous octoate was added. 45 reactants
Stir well for minutes. 102.75 g (0.7895 mol) of TDI was added to the dropping funnel.
And 237 g of methylene chloride. The diisocyanate mixture over 4-5 hours
It was added dropwise to the diol and the heat generated during the reaction of the reaction mixture was sometimes examined. Methyl chloride
Once the ren begins to reflux, simply add more diisocyanate and increase the amount.
Stopped and the reaction mixture was allowed to cool to ambient temperature using a water bath. After 3-4 hours
The completion of the reaction was determined by IR spectroscopy at 3,500 cm^-1Disappearance of hydroxyl absorption
Could be tracked. After this absorption has dissipated, 68.49 g of HEMA (
0.5263 mol) was added through the addition funnel over 20-30 minutes. Responsive
Completion is 2,270cm by IR^-1By observing the disappearance of NCO absorption
Could be tracked again. After the reaction is completed, the prepolymer solution is
To a rotary evaporator to remove methylene chloride.
Was. The above removal is at about 665 Pa at the ambient temperature for the first hour and then for the last 30 hours.
The minutes were performed at 30 ° C. Then 0.6% of the prepolymer Membranes made from the polymer have a Dk of 3.9 and have better contact than that of HEMA.
Had antennae. Examples 18 to 22   The polymers in these examples were the same as in the examples except that the reactants and amounts indicated below were used.
17, and the obtained Dk and contact angle were determined as follows.
It is shown in the table. Example 23   Air-cooled coagulator, dropping funnel, Claisen adapter, mechanical stirring bar, and nitrogen introduction
・ Three-necked round bottom flask equipped with an outlet (a drying tube is attached to the outlet)
In addition, 250 g (0.5263 mol) of PPG475, 350 g of methylene chloride and
0.60 g (0.0015 mol) of stannous octoate was added. 45 reactants
Stir well for minutes. 152.63 g of styrene isocyanate (1.
0526 mol) and 150 g of methylene chloride. 6 isocyanate mixture
The heat generated during the course of the reaction of the reaction mixture is adjusted occasionally,
Solid. The reaction temperature must not exceed 35 ° C. or else the reaction mixture will generally develop color
Occurs. When the temperature starts to rise, the contents of the reaction mixture are removed by using an ice bath.
Must be cooled. After 3-4 hours, complete the reaction by IR spectroscopy
By 3,500cm^-1Can be tracked by disappearance of hydroxyl absorption
. The reaction was also completed by IR at 2,270 cm^-1Of NCO absorption disappeared
Was also able to be tracked. After the reaction is completed, the prepolymer solution is
Transfer to single-necked flask, then rotary evaporate to remove methylene chloride
Connected to the monitor. The above removal is about 665 Pa and the first hour is at ambient temperature
The last 30 minutes were performed at 30 ° C. Then 0.6% in the prepolymer Membrane made from repolymer has a Dk of 10.00 and is comparable to HEMA
Had antennae. Examples 24 to 28   The polymers in these examples were the same as in the examples except that the reactants and amounts indicated below were used.
The same Dk and contact angle were obtained as described below.
It is shown in the table. Example 29   Air-cooled aggregator, Claisen adapter, electromagnetic stir bar, (drying tube is installed at the outlet
A three-necked round bottom flask with a nitrogen inlet and outlet and a dropping funnel
, TDI 21.67 g (0.1250 mol) and methylene chloride 200 g
Was. The mixture was thoroughly stirred before adding additional reagents. PPG in dropping funnel
4000 250 g (0.0625 mol), 323 g of methylene chloride and octane
0.66 g (0.0020 mol) of stannous acid was added. PPG4000 and Ok
The solution of stannous titanate was added to the TDI solution over 4-5 hours. Another 4-5 hours
After the elapse, the reaction was completed by IR spectroscopy at 3,500 cm^-1Hydroxy in
Judgment was made by showing the disappearance of the functionality of the di-group. The IR spectrum has two more
Important 2, corresponding to NCO carbonyl and carbamate carbonyl respectively
270cm^-1And 1,750cm^-1It also had near absorption. Judge that the reaction is completed
Once done, 18.75 g (0.0313 mol) of PEG 600 and methylene chloride
100 g was added slowly through the addition funnel over 2 hours. The completion of the reaction
3,500 cm by IR spectroscopy^-1The disappearance of the hydroxy functional group in water
By guessing, I was able to track again. PEG600 reacts completely
After that, 8.14 g (0.0625 mol) of HEMA was passed through a dropping funnel for 20 to 3 hours.
Added to flask over 0 minutes. Completion of the reaction is 2,270 cm^-1NCO peak of
Monitored by extinction. After the reaction is completed, transfer the prepolymer solution to a single-necked flask.
Then, it was connected to a rotary evaporator to remove methylene chloride. This
The separation step generally takes 1.5 hours and lasts 30 minutes at 30 ° C. For 30 to 90 minutes. A membrane made from this prepolymer is Dk33
Had. Examples 30 to 36   The polymers of these examples were prepared from the second glycol and the chloride used with it.
Example 2 except that the amount of styrene was as shown in the table below together with the value of Dk obtained.
Manufactured in the same manner as 29.Example 37   After completion of the reaction, before removing the methylene chloride, 10% by weight of N-vinylpyrrolidone was used.
The operation was performed in the same manner as in Example 28 except that% was added. Remove methylene chloride and add 0.6
% Durocur was added. Curing was performed in the same manner as in Example 28. The resulting polymer
Had a water content of 9.8%.

Claims (1)

[Claims] 1. Formula V: Wherein w is 0-8; D is each independently oxygen; L is each independently -BRB'-; B and B 'are each independently And the following formula: Wherein the carbonyl group is attached to the D or A; R is a C ₁ -C ₂₅ aliphatic group, C ₅ -C ₅ -C _{5, respectively.} ~ C
_7- membered alicyclic group, arylene having 6 to 25 carbon atoms, aralkyl or alkaryl having 7 to 25 carbon atoms, wherein the aliphatic group and the alkyl group are optionally represented by the following formula: And the aryl and arylene groups are unsubstituted or further substituted with a substituent selected from halogen, C ₁ -C ₄ alkyl and C ₁ -C ₁₂ perhaloalkyl. L 'is P'-RB-' and P'-BR-B'- (where B, R and B '
Is the same as defined above, wherein P ′ is a moiety containing a group that can be cross-linked when co-reacted with a cross-linking agent or when irradiated with actinic radiation); L "Is selected from -BR-P 'and -BR-B'-P', where B, R, B 'and P' are as defined above; And A is each of the formula I: Wherein b, d and f are each independently 0-4; q is 1-1,0
X, y and z are each independently 0 to (x + y + z)
X is a number such that q is 4-1,000; R ¹ -R ¹⁸ are each selected from a hydrogen atom, C ₁ -C ₄ alkyl and phenyl, provided that at least one of R ¹ -R ¹⁸ One is C ₁ -C ₄ alkyl or phenyl and R ¹ -R ¹⁸ , alone or in combination, exhibit sufficient hydrophobicity that the resulting polymer is substantially non-swellable in water Having a receding contact angle to distilled water of less than 60 ° when measured at 20 ° C., containing less than 10% of water, and being greater than 7 when measured at 20 ° C. Oxygen permeability: Dk (× 10 ⁻¹⁰ [cm · mm / sec] [mlO ₂ / ml · mmHg]), optically clear, wettable, flexible, stable to hydrolysis, Biologically inert, substantially siloxane-free, substantially non-swelling in intraocular tears , Oxygen permeable contact lenses. 2. R ^{1 to} R ¹⁸ are each independently selected from the group consisting of hydrogen and C _{1 to} C ₄ alkyl, wherein at least one of R ^{1 to} R ¹⁸ is C _{1 to} C ₄ alkyl. 2. The contact lens according to item 1, wherein 3. The contact lens according to claim 1, wherein the crosslinked polymer has a degree of crosslinking of 10% or less. 4. 4. The contact lens according to claim 3, wherein said crosslinked polymer has a degree of crosslinking of 5% or less. 5. The contact lens according to claim 4, wherein the crosslinked polymer has a degree of crosslinking of 1 to 4%. 6. The contact lens according to claim 5, wherein the crosslinked polymer has a degree of crosslinking of 2-3%. 7. 2. The contact lens according to claim 1, wherein said receding contact angle is less than 40 [deg.]. 8. The contact lens according to claim 7, wherein said receding contact angle is less than 25 °. 9. 9. The contact lens according to claim 8, wherein said receding contact angle is less than 15 °. Ten. 10. The contact lens according to claim 9, wherein said receding contact angle is less than 10 °. 11． 2. The contact lens according to claim 1, wherein said oxygen permeability is greater than 15. 12． The contact lens according to claim 11, wherein the oxygen permeability is greater than 20. 13. 13. The contact lens according to claim 12, wherein said oxygen permeability is greater than 40. 14. 2. The contact lens according to claim 1, wherein b, d, and f are each independently 0 to 3. 15． Claim 14 wherein b, d and f are each independently 0 to 2.
The contact lens according to the item. 16． 16. The contact lens according to claim 15, wherein b, d, and f are each independently 0 or 1. 17． wherein b, d and f are each 0 or 1, and R ^{1 to} R ¹⁸ are independently selected from hydrogen and methyl, wherein at least one of R ^{1 to} R ¹⁸ is methyl. 3. The contact lens according to item 1, wherein 18． N- (vinyl-containing group) -pyrrolidone and Wherein R is H or CH ₃ , wherein A is crosslinked in the presence of up to 10% by weight of an additional vinyl comonomer, Wherein b, d, f, x, y, z, q, R ⁵ , R ¹² and R ¹⁸ are the same as defined in claim 1. The contact lens according to claim 1, which is manufactured from: 19. b, d and f are each independently 0 or 1; R ^{1 to} R ¹⁸ are independently selected from hydrogen and methyl, provided that at least one of R ^{1 to} R ¹⁸ is L is P'-R'-B '; L "is -BR-P'; R 'is phenylene, toluylene Or-(
Phenyl or toluyl) -aminocarbonyloxyethyl-
The contact lens according to claim 1, wherein the phenyl ring of the above is bonded to the B or B ', and P' is vinyl or methacryloyloxy.