Process for the modification of a material surface

Details Process for the modification of a material surface Process for the modification of a material surface

2000-10-27

2003-02-18

Seidleck, James J. (Department: 1711)

Stock material or miscellaneous articles

Composite

Of addition polymer from unsaturated monomers

C428S704000, C428S423100, C428S424400, C351S16000R

Reexamination Certificate

active

06521352

ABSTRACT:

The present invention relates to a process for the manufacture of 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 a process for the modification of the surface of an article, such as a biomedical material or article, especially a contact lens including an extended-wear contact lens wherein the articles are at least partly coated with a polymer having a “bottle-brush” type structure composed of tethered “hairy” chains.
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 attract and stabilize 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 a monofunctional hydrophilic telomer having a bottle-brush type structure and then attaching the telomer to the material surface, for example, by reaction of its functional group with co-reactive groups being present on the material surface.
The present invention therefore in one aspect relates to a process for coating a material surface, comprising the steps of:
(a) providing a hydrophilic telomer of formula
(oligomer)-T  (1),
 wherein
T is hydroxy, epoxy, amino, C
1
-C
6
-alkylamino, carboxy or a suitable carboxy derivative, for example a carboxylic acid ester or an acid halide, and (oligomer) is the radical of a telomer of formula
-(Alk)-S&Brketopenst;Z &Brketclosest;
a
&Brketopenst;Z &Brketclosest;
b
Q  (2),
 wherein
(Alk) is C
2
-C
12
-alkylene which may be interrupted by —O— or —NH—,
Q is a monovalent group that is suitable to act as a polymerization chain-reaction terminator,
a and b are each independently of another an integer from 0 to 350, wherein the total of (a+b) is an integer from 2 to 350,
and Z and Z′ 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, which radical carries a hydrophilic side chain having a weight average molecular weight of ≧200; and
(b) covalently binding the hydrophilic telomer to the material surface.
The following meanings and preferences apply to the variables contained in the definition of the hydrophilic telomer of formula (1):
T as carboxy derivative is for example a radical —C(O)OC
1
-C
4
-alkyl or —C(O)Cl. T is preferably hydroxy, amino or carboxy, more preferably amino or carboxy and in particular amino.
(Alk) is preferably C
2
-C
8
-alkylene, more preferably C
2
-C
6
-alkylene, even more preferably C
2
-C
4
-alkylene and particularly preferably 1,2-ethylene. The alkylene radical (alk) may be branched or preferably linear alkylene.
Q is for example hydrogen.
The total of (a+b) is preferably an integer from 2 to 150, more preferably from 5 to 100, even more preferably from 5 to 75 and particularly preferably from 5 to 50. In a preferred embodiment of the invention b is 0 and a is an integer from 2 to 350, preferably from 2 to 150, more preferably from 5 to 100, even more preferably from 5 to 75, and particularly preferably from 5 to 50.
A suitable 1,2-ethylene radical Z or Z′ is, for example, a radical of formula
wherein
R
1
is hydrogen or C
1
-C
6
-alkyl or a radical —COOR′;
R, R′ and R
2
are each independently of the other hydrogen or C
1
-C
6
-alkyl; and
R
3
is, for example, a non-ionic substituent selected from the group consisting of a radical —COOY
10
, wherein Y
10
is a radical —CH
2
CH
2
—O—(CH
2
CH
2
O)
y
—E, E is hydrogen or C
1
-C
6
-alkyl and y is an integer from 3 to 24, or Y
10
is a radical —C
2
-C
6
-alkyl-NH—C(O)—O—G wherein —O—G is the radical of a saccharide or is a radical —O—(CH
2
CH
2
O)
y
—E wherein E and y are each as defined above; and a radical —CONY
11
Y
12
, wherein Y
11
is hydrogen or unsubstituted or, for example, hydroxy-substituted C
1
-C
24
-alkyl, and Y
12
is C
1
-C
12
-alkyl which is substituted by a radical —O—(CH
2
CH
2
O)
y
—E and wherein E and y are as defined above; and a zwitter-ionic substituent of formula
—C(O)O—CH
2
—CH(OY
13
)—CH
2
—O—PO
2
−
—(CH
2
)
2
—N(CH
3
)
3
+
,
wherein Y
13
is the acyl radical of a higher fatty acid; or
R
3
is a radical of formula
—A-(oligomer
1
)  (4),
wherein A is a direct bond or is a radical of formula
—C(O)—(A
1
)
n
—X—  (5a) or
—(A
2
)
m
—NH—C(O)—X—  (5b); or
—(A
2
)
m
—X—C(O)—  (5c); or
—C(O)—NH—C(O)—X—  (5d); or
—C(O)—X
1
—(alk*)X—C(O)—  (5e); 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 —O—C
2
-C
12
-alkylene-O—C(O)—NH—R
33
—NH—C(O)—, wherein R
33
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
1
) is
(i) the radical of a telomer of formula
-(alk)-S&Brketopenst;B&Brketclosest;
p
&Brketopenst;B′&Brketclosest;
q
Q
1
  (6a),
 wherein
(alk) is C
2
-C
12
-alkylene,
Q
1
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 350, wherein the total of (p+q) is an integer from 2 to 350,
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
19
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 X
2
is —O—, —NH— or —NC
1
-C
6
-alkyl- and R
19
and u are as defined above, or
(iv) the radical of an oligomer of formula
 wherein R
20
and R
20
′ 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
21
—C(O)—NH)
t
—CHR
21
—COOH  (6d)
or
—CHR
2

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