Stock material or miscellaneous articles – Composite – Of polyamidoester
Reexamination Certificate
2000-10-27
2002-09-10
Tarazano, D. Lawrence (Department: 1773)
Stock material or miscellaneous articles
Composite
Of polyamidoester
C428S500000, C427S002240, C427S164000, C427S487000, C351S16000R
Reexamination Certificate
active
06447920
ABSTRACT:
The present invention relates to coated articles wherein the coating comprises a polymer having desirable characteristics regarding adherence to the substrate, durability, hydrophilicity, wettability, biocompatibility and permeability. More particular, the present invention relates to an article, such as a biomedical material or article, especially a contact lens including an extended-wear contact lens which is at least partly coated with a polymer having a “bottle-brush” type structure composed of tethered “hairy” chains. The inventive coatings are obtainable by grafting specific ethylenically unsaturated macromonomers onto the surface of a substrate which has been previously provided with initiator groups.
A variety of different types of processes for preparing polymeric coatings on a substrate have been disclosed in the prior art. For example, U.S. Pat. No. 5,527,925 describes functionalized photoinitiators and also organic substrates such as contact lenses containing said photoinitiators covalently bound to their surface. In one embodiment of said disclosure, the so modified surface of the contact lens is further coated with a photopolymerizable ethylenically unsaturated monomer which is then polymerized by irradiation thus forming a novel substrate surface. With this method, however, it is not always possible to obtain the desired coating characteristics, for example wettability characteristics which are necessary for the surface of biomedical devices including contact lenses. In particular, the ability of the known materials to hold a continuous layer of an aqueous solution, e.g. human body fluids such as tears or mucus layers, for a prolonged period of time which is an important feature for many biomedical applications is not yet satisfactory.
Surprisingly, it now has been found that articles, particularly biomedical devices such as contact lenses, with an improved wettability, water-retention ability and biocompatibility are obtained by first of all providing the article surface with covalently bound photoinitiator molecules, coating the modified surface with a layer of one or more different polymerizable macromonomers and then subjecting it to heat or radiation whereby the macromonomer is graft polymerized thus forming the novel article surface.
The present invention therefore in one aspect relates to a composite material comprising
(a) an inorganic or organic bulk material having covalently bonded to its surface initiator moieties for radical polymerization; and
(b) a hydrophilic surface coating obtainable by applying one or more different ethylenically unsaturated hydrophilic macromonomers to the bulk material surface provided with the initiator radicals and polymerizing said macromonomers,
wherein the macromonomers are each of formula
R
1
is hydrogen, C
1
-C
6
-alkyl or a radical —COOR′;
R, R′ and R
1
′ are each independently of the other hydrogen or C
1
-C
6
-alkyl;
A is a direct bond or is a radical of formula
—C(O)—(A
1
)
n
—X— (2a)
or
—(A
2
)
m
—NH—C(O)—X— (2b);
or
—(A
2
)
m
—X—C(O)— (2c);
or
—C(O)—NH—C(O)—X— (2d);
or
—C(O)—X
1
—(alk*)—X—C(O)— (2e);
or
A and R
1
, together with the adjacent double bond, are a radical of formula
A
1
is —O—C
2
-C
12
-alkylene which is unsubstituted or substituted by hydroxy, or is —O—C
2
-C
12
-alkylene-NH—C(O)— or —C
2
-C
12
-alkylene-O—C(O)—NH—R
11
—NH—C(O)—, wherein R
11
is linear or branched C
1
-C
18
-alkylene or unsubstituted or C
1
-C
4
-alkyl- or C
1
-C
4
-alkoxy-substituted C
6
-C
10
-arylene, C
7
-C
18
-aralkylene, C
6
-C
10
-arylene-C
1
-C
2
-alkylene-C
6
-C
10
-arylene, C
3
-C
8
-cycloalkylene, C
3
-C
8
-cycloalkylene-C
1
-C
6
-alkylene, C
3
-C
8
-cycloalkylene-C
1
-C
2
-alkylene-C
3
-C
8
-cycloalkylene or C
1
-C
6
-alkylene-C
3
-C
8
-cycloalkylene-C
1
-C
6
-alkylene;
A
2
is C
1
-C
8
-alkylene; phenylene or benzylene;
m and n are each independently of the other the number 0 or 1;
X, X
1
and X′ are each independently of the other a bivalent group —O— or —NR″, wherein R″ is hydrogen or C
1
-C
6
-alkyl;
(alk*) is C
2
-C
12
-alkylene;
and (oligomer) denotes
(i) the radical of a telomer of formula
wherein
(alk) is C
2
-C
12
-alkylene,
Q is a monovalent group that is suitable to act as a polymerization chain-reaction terminator,
p and q are each independently of another an integer from 0 to 100, wherein the total of (p+q) is an integer from 2 to 250,
and B and B′ are each independently of the other a 1,2-ethylene radical derivable from a copolymerizable vinyl monomer by replacing the vinylic double bond by a single bond, at least one of the radicals B and B′ being substituted by a hydrophilic substituent; or
(ii) the radical of an oligomer of the formula
wherein R
28
is hydrogen or unsubstituted or hydroxy-substituted C
1
-C
12
-alkyl, u is an integer from 2 to 250 and Q′ is a radical of a polymerization initiator; or
(iii) the radical of formula
wherein
R
28
, X and u are as defined above, or
(iv) the radical of an oligomer of formula
wherein R
2
and R
2
′ are each independently C
1
-C
4
-alkyl, An
−
is an anion, v is an integer from 2 to 250, and Q″ is a monovalent group that is suitable to act as a polymerization chain-reaction terminator; or
(v) the radical of an oligopeptide of formula
—(CHR
4
—C(O)—NH)
t
—CHR
4
—COOH (3d)
or
—CHR
4
—(NH—C(O)—CHR
4
)
t
—NH
2
(3d′),
wherein R
4
is hydrogen or C
1
-C
4
-alkyl which is unsubstituted or substituted by hydroxy, carboxy, carbamoyl, amino, phenyl, o-, m- or p-hydroxyphenyl, imidazolyl, indolyl or a radical —NH—C(═NH)—NH
2
and t is an integer from 2 to 250, or the radical of an oligopeptide based on proline or hydroxyproline; subject to the provisos that
A is not a direct bond if (oligomer) is a radical of formula (3a);
A is a radical of formula (2a), (2b) or (2d) or A and R
1
, together with the adjacent double bond, are a radical of formula (2f) if (oligomer) is a radical of formula (3b), (3c) or (3d);
A is a direct bond if (oligomer) is a radical of formula (3b′); and
A is a radical of formula (2c) or (2e) if (oligomer) is a radical of formula (3d′).
Examples of suitable bulk materials are quartz, ceramics, glasses, silicate minerals, silica gels, metals, metal oxides, carbon materials such as graphite or glassy carbon, natural or synthetic organic polymers, or laminates, composites or blends of said materials, in particular natural or synthetic organic polymers which are known in large number. Some examples of polymers are polyaddition and polycondensation polymers (polyurethanes, epoxy resins, polyethers, polyesters, polyamides and polyimides); vinyl polymers (poly-acrylates, polymethacrylates, polystyrene, polyethylene and halogenated derivatives thereof, polyvinyl acetate and polyacrylonitrile); elastomers (silicones, polybutadiene and polyisoprene); or modified or unmodified biopolymers (collagen, cellulose, chitosan and the like).
A preferred group of bulk materials are those being conventionally used for the manufacture of biomedical devices, e.g. contact lenses, in particular contact lenses for extended wear, which are not hydrophilic per se. Such materials are known to the skilled artisan and may comprise for example polysiloxanes, perfluoropolyethers, fluorinated poly(meth)acrylates or equivalent fluorinated polymers derived e.g. from other polymerizable carboxylic acids, polyalkyl (meth)acrylates or equivalent alkylester polymers derived from other polymerizable carboxylic acids, or fluorinated polyolefines, such as fluorinated ethylene propylene, or tetrafluoroethylene, preferably in combination with specific dioxols, such as perfluoro-2,2-dimethyl-1,3-dioxol. Examples of suitable bulk materials are e.g. Lotrafilcon A, Neofocon, Pasifocon, Telefocon, Silafocon, Fluorsilfocon, Paflufocon, Silafocon, Elastofilcon, Fluorofocon or Teflon AF materials, such as Teflon AF 1600 or Teflon AF 2400 which are copolymers of about 63 to 73 mol % of perfluoro-2,2-dimethyl-1,3-dioxol an
Chabrecek Peter
Höpken Jens
Lohmann Dieter
Gearhart Richard
Meece R. Scott
Novartis AG
Tarazano D. Lawrence
Zhou Jian S.
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