JPH04332760A - Material for medical treatment - Google Patents

Abstract

PURPOSE:To provide a medical treatment material comprising a three- dimensionally crosslinked net structure polymer obtained by polymerizing a specific monomer component, having good handling property, excellent oxygen permeability, excellent hydrophilicity, excellent flexibility and good stain resistance, and suitable for contact lenses, etc. CONSTITUTION:A medical treatment material comprising a three-dimensional crosslinked net-like structure polymer produced by polymerizing at least (A) an organosiloxane of formula I (a is 1 or larger; b is 1-5; R1 is H, methyl; X1-X3 are a group of formula II; c is 0-3; Y1 and Y2 are a group of formula III; d is 0-2), (B) a fluoroorgano siloxane consisting of a monomer of formula IV [e is 0-700; R2 is (CH<2>)f; f is 1-25); R3 is 1-30C alkyl, alkoxy, etc.; A is a group of formula V (i is 0-250; R5 is H, methyl); Z1-Z6 are a group of formula (j is 0-10; R6-R8 are R3, 6-12C aryl)] in which one or more 2-30C fluorinated hydrocarbon groups having three or more fluorine atoms are graft-bonded to the carbon atoms of the alkylene groups in the main chain of the monomer, (C) a (meth)acrylate ester, and (D) a tear film-stabilizing agent.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to medical materials such as contact lenses.

0002

BACKGROUND OF THE INVENTION There are two types of contact lenses: water-containing ones that absorb water and swell, and non-water-containing ones that do not swell. By the way, water-containing soft contact lenses made of, for example, 2-hydroxyethyl methacrylate have poor shape stability and mechanical strength, and are prone to breeding of bacteria and mold, so they are frequently sterilized by boiling. However, it has problems such as being troublesome to handle.

On the other hand, non-hydrous materials made of copolymers of alkyl acrylic esters, long-chain alkyl methacrylic esters, esterified copolymers of acrylic acid, silicone rubber, etc. Contact lenses are known. However, contact lenses made of silicone rubber, for example, have extremely high oxygen permeability, can be worn continuously for long periods of time, and do not require complicated handling.
In order to exhibit water repellency, a surface treatment must be applied to improve water wettability. It should be noted that hydrophilic coatings formed by surface treatment are not only troublesome to form, but also have drawbacks such as poor durability and easy staining.

[0004] Also, (meth)acrylic acid ester materials,
For example, a non-hydrous contact lens made of a copolymer containing butyl acrylate as a main component has a sticky surface, easily attracts dirt such as lipids, and easily becomes cloudy. In addition, the oxygen permeability is not good and the mechanical strength is not satisfactory.

[0005]

[Disclosure of the Invention] The purpose of the present invention is to have good handling properties because bacteria and mold do not breed easily, and to have excellent oxygen permeability so that it can be worn continuously on the eyes for a long time, and to be easy to fit into the eyes. It is an object of the present invention to provide a medical material that has hydrophilicity and flexibility, is resistant to adhesion of stains such as lipids, and has mechanical strength that is practically satisfactory.

The object of the present invention is (a) to obtain the following general formula (
1) A monomer represented by

[0007]

[Chemical formula 8]

(However, a is an integer of 1 or more, b is an integer of 1 to 5, R1 is a hydrogen atom or a methyl group, and X1
~X3 is

[0009]

[Chemical formula 9]

0010, c is an integer of 0 to 3, Y1 and Y
2 is

[0011]

[Chemical formula 10]

(d is an integer of 0 to 2) (b) Carbon atoms having at least three fluorine atoms in the alkylene group carbon atoms in the main chain of the monomer represented by the following general formula (2) A fluorine-containing organosiloxane monomer in which 2 to 30 fluorine-substituted hydrocarbon groups are grafted to one or more per molecule of the monomer of general formula (2);

[0013]

[Chemical formula 11]

(In the formula, e is an integer of 0 to 700, R2 is -(CH2)f -, f is an integer of 1 to 25, R3
is an alkyl group having 1 to 30 carbon atoms, an alkoxy group, or

[0015]

[Chemical formula 12]

0016, g is an integer of 1 to 25, h is 0 to 2
an integer of 50, R4 represents a hydrogen atom or a methyl group,
A is

[0017]

[Chemical formula 13]

[0018] where i is an integer of 0 to 250, R5 is a hydrogen atom or a methyl group, and Z1 to Z6 are

0
019]

[Chemical formula 14]

[0020], j is an integer of 0 to 10, R6 to R
8 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group or an aryl group having 6 to 12 carbon atoms) (c) (meth)acrylic acid ester and (d) a tear film stabilizer are used at least to polymerize. This is achieved by a medical material characterized by being made of a polymer with a three-dimensional crosslinked network structure.

In addition, fluorine-containing monofunctional and/or polyfunctional (
This is achieved by a medical material characterized by comprising a polymer having a three-dimensional crosslinked network structure obtained by polymerizing a meth)acrylic acid ester monomer. In addition, in this medical material, the monomer (a) contains 1 to 85 parts by weight,
Desirably about 5 to 70 parts by weight, and 5 to 9 parts by weight of monomer (b).
5 parts by weight, preferably about 10 to 80 parts by weight, 1 to 60 parts by weight, preferably about 5 to 30 parts by weight of monomer (c),
The monomer (d) is 1 to 30 parts by weight, preferably about 1 to 1 part by weight.
A polymer having a three-dimensional crosslinked network structure polymerized using 0 parts by weight is preferable, and when a fluorine-containing monofunctional and/or polyfunctional (meth)acrylic acid ester monomer is further used. contains 1 to 8 monomers of (a)
5 parts by weight, 5 to 95 parts by weight of monomer (b), 1 to 60 parts by weight of monomer (c), and 1 to 30 parts by weight of monomer (d), totaling 100 parts by weight. , the fluorine-containing monofunctional and/or polyfunctional (meth)acrylic acid ester monomer is
~50 parts by weight (5-50% by weight), preferably about 5-4
It is preferable to use a polymer having a three-dimensional crosslinked network structure, which is polymerized using a proportion of 0 parts by weight (5 to 40% by weight).

[0022] Furthermore, in order to improve the shape stability, chemical resistance, solvent resistance, heat resistance, etc. of the material of the present invention, and to reduce the amount of eluate, it is preferable to use a crosslinking agent. The blending amount of the crosslinking agent is 1 to 15 parts by weight based on 100 parts by weight of the total amount of the monomers.
parts by weight (1-15% by weight), more preferably about 2-10
Weight%. Among the monomer components of the medical material (copolymer) of the present invention constituting an intraocular insert such as a non-hydrous soft contact lens, the organosiloxane monomer represented by the general formula (1) includes, for example, methacrylate. Roxyethoxypropylpentamethyldisiloxane, acryloxyethoxypropylpentamethyldisiloxane, methacryloxyethoxypropylheptamethyltrisiloxane, acryloxyethoxypropylheptamethyltrisiloxane, methacryloxyethoxypropyltris(trimethylsiloxy)silane, acryloxyethoxypropyl Tris(trimethylsiloxy)silane, methacryloxyethoxypropylphenyltetramethyldisiloxane, acryloxyethoxypropylphenyltetramethyldisiloxane, methacryloxyethoxypropyltribenzyldiethyldisiloxane, acryloxyethoxypropyltribenzyldiethyldisiloxane, methacryloxyethoxypropyltribenzyldiethyldisiloxane Propyl n-pentylhexamethyltrisiloxane, acryloxyethoxypropyl n-pentylhexamethyltrisiloxane, methacryloxyethoxypropyl di-n-propylpentamethyltrisiloxane,
Acryloxyethoxypropyldi-n-propylpentamethyltrisiloxane, methacryloxyethoxypropylphenyloctamethyltetrasiloxane, acryloxyethoxypropylphenyloctamethyltetrasiloxane, methacryloxyethoxypropylisobutyltetramethyldisiloxane, acryloxyethoxypropylisobutyltetramethyl Disiloxane, methacryloxyethoxypropylmethylbis(trimethylsiloxy)silane, acryloxyethoxypropylmethylbis(trimethylsiloxy)silane, methacryloxyethoxypropyltris(dimethylcyclohexylsiloxy)silane,
Acryloxyethoxypropyl tris(dimethylcyclohexylsiloxy)silane, methacryloxyethoxypropylpentamethyldisiloxybis(trimethylsiloxy)silane, acryloxyethoxypropylpentamethyldisiloxybis(trimethylsiloxy)silane, acryloxyethoxypropylpentamethyldisiloxy Bis(trimethylsiloxy)silane, methacryloxyethoxypropylheptamethylcyclotetrasiloxane, acryloxyethoxypropylheptamethylcyclotetrasiloxane, methacryloxyethoxypropyltetramethyltripropylcyclotetrasiloxane, acryloxyethoxypropyltetramethyltripropylcyclotetrasiloxane etc. can be mentioned. Note that two or more types of these organosiloxane monomers can be used in combination.

The fluorine-containing organosiloxane monomer represented by the general formula (2) is as follows:

[0024]

[Chemical formula 15]

[0025]

[Chemical formula 16]

[0026]

[Chemical formula 17]

[0027]

[Chemical formula 18]

[0028] etc. Note that two or more of these fluorine-containing organosiloxane monomers can be used in combination. As the (meth)acrylic ester, for example, methyl (
meth)acrylate, ethyl(meth)acrylate, n
-Butyl (meth)acrylate, n-propyl (meth)
Acrylate, 1-propyl (meth)acrylate, t
-Butyl (meth)acrylate, n-pentyl (meth)
Acrylate, n-hexyl (meth)acrylate, 2
-Ethylhexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tetradecyl (meth)acrylate, n-hexadecyl (meth)acrylate, lauryl (meth)acrylate, etc. (meth)acrylic acid alkyl ester, alkoxyalkyl ester group is -
CH2 CH2 OR, -CH2 CH2 (OR)C
H3, -CH2 CH2 CH2OR, -CH(CH
3) CH2 OR, -CH2 CH2 CH2 OR
(Meth)acrylic acid alkoxyalkyl ester having an alkoxyalkyl group represented by (R is an alkyl group having 1 to 7 carbon atoms), and other cyclohexyl (meth)
Acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl Oxyethyl (meth)acrylate, 1
, 3-dioxolane (meth)acrylate, and the like. Note that two or more of these (meth)acrylic acid esters can be used in combination.

As the tear film stabilizer, (meth)acrylic acid such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, dihydroxypropyl (meth)acrylate, dihydroxybutyl (meth)acrylate, etc. Acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate,
-OH group-containing (meth)acrylates such as dipropylene glycol mono(meth)acrylate, such as N-vinylpyrrolidone, α-methylene-N-methylpyrrolidone,
Vinyl lactams such as N-vinylcaprolactam and N-(meth)acryloylpyrrolidone, (meth)acrylamides such as (meth)acrylamide and N-methylolmethacrylamide, such as aminoethyl (meth)acrylate, N-methylaminoethyl Aminoalkyl (meth)acrylates such as (meth)acrylate, such as alkoxy group-containing (meth)acrylate such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, etc.
Examples include acrylates. Two or more of these tear film stabilizers can be used in combination.

Examples of the fluorine-containing (meth)acrylic ester include 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (
meth)acrylate, 2,2,3,3-tetrafluoro-t-pentyl (meth)acrylate, 2,2,3,4
, 4,4-hexafluorobutyl (meth)acrylate, 2,2,3,4,4,4-hexafluoro-t-hexyl (meth)acrylate, 2,3,4,5,5,5-
Hexafluoro-2,4-bis(trifluoromethyl)
Pentyl (meth)acrylate, 2,2,3,3,4,
4-hexafluorobutyl (meth)acrylate, 2,
2,2,2',2',2'-hexafluoroisopropyl (meth)acrylate, 2,2,3,3,4,4,4
-heptafluorobutyl (meth)acrylate, 2,2
,3,3,4,4,5,5-octafluoropentyl (
meth)acrylate, 2,2,3,3,4,4,5,5
, 5-nonafluoropentyl (meth)acrylate, 2
, 2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth)acrylate, 3,3,4
, 4,5,5,6,6,7,7,8,8-dodecafluorooctyl (meth)acrylate, 3,3,4,4,5
, 5,6,6,7,7,8,8,8-tridodecafluorooctyl (meth)acrylate, 2,2,3,3,4
, 4,5,5,6,6,7,7,7-tridecafluoroheptyl (meth)acrylate, 3,3,4,4,5,
5,6,6,7,7,8,8,9,9,10,10-hexadecafluorodecyl (meth)acrylate, 3,3
,4,4,5,5,6,6,7,7,8,8,9,9,
10,10,10-heptadecafluorodecyl (meth)
Acrylate, 3, 3, 4, 4, 5, 5, 6, 6, 7,
7,8,8,9,9,10,10,11,11-octadecafluoroundecyl (meth)acrylate, 3,3
,4,4,5,5,6,6,7,7,8,8,9,9,
10,10,11,11,11-nonadecafluoroundecyl (meth)acrylate, 3,3,4,4,5,5
,6,6,7,7,8,8,9,9,10,10,11
, 11,12,12-eicosafluorododecyl (meth)acrylate, 2-hydroxy-4,4,5,5,6
, 7,7,7-octafluoro-6-trifluoromethylheptyl (meth)acrylate, 2-hydroxy-4
, 4,5,5,6,6,7,7,8,9,9,9-dodecafluoro-8-trifluoromethylnonyl (meth)acrylate, 2-hydroxy-4,4,5,5,6 ,6
,7,7,8,8,9,9,10,11,11,11-
Examples include hexadecafluoro-10-trifluoromethylundecyl (meth)acrylate. Two or more of these fluorine-containing (meth)acrylic esters can be used in combination.

Examples of the crosslinking agent component include diesters, triesters, and tetraesters of polyhydric alcohols having 10 or less carbon atoms and methacrylic acid or acrylic acid. For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate,
Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3
-Butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , pentaerythritol tetra(meth)acrylate, and the like. Moreover, a macromonomer having two or more polymerizable groups in the molecule can also be used as a crosslinking agent. Note that two or more of these crosslinking agents can be used in combination.

Furthermore, for the purpose of adjusting the mechanical strength, one type or Two or more types of reinforcing monomers may be blended in an amount of 10% by weight or less. In addition, it can be added with ultraviolet absorbency, colored,
In addition to copolymerized components, ultraviolet absorbers (including polymerizable types) and pigments, especially ultraviolet absorbing dyes (polymerizable type 2% by weight or less, e.g. 0
．． It may be used in an amount of 1 to 1% by weight.

[0033] The method for obtaining the medical material of the present invention is as follows:
In addition to the essential components organosiloxane monomer, fluorine-containing organosiloxane monomer, (meth)acrylic acid ester, and tear film stabilizer, a fluorine-containing monofunctional and/or polyfunctional (meth)acrylic ester is optionally added. Monomers, crosslinking agents, and reinforcing monomers are appropriately blended, a radical polymerization agent is added thereto, and polymerization is performed by thermal polymerization or irradiation with electromagnetic waves such as ultraviolet rays, microwaves, and radiation (γ rays).

In this case, as the radical polymerization initiator,
Dimethyl-2,2'-azobisisobutyrate, 2,2
'-Azobis(4-methoxy-2,4'-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutylnitrile, benzoyl peroxide, di- Examples include tert-butyl peroxide, methyl ethyl ketone peroxide, isobutyl peroxide, diisopropyl peroxydicarbonate, and the like. These radical polymerization initiators can be used in combination.

A cutting method can be used to obtain, for example, a contact lens from the substantially water-free medical material obtained as described above. Incidentally, since the material of the present invention is soft and flexible, it is more preferable to employ a molding method such as a spin casting method or a static casting method. Hereinafter, this will be explained in detail using examples.

[0036]

[Example 1] General formula (1) (R1 = methyl group, a = 1, b = 3
, c=1, d=0) (hereinafter referred to as METS)
11 parts by weight General formula (2) (e=60, f=3, g
=3, h=1, i=1, j=0, R4 =R5 =R6
= R7 = R8 = methyl group) A fluorine-containing polyorganosiloxane monomer (hereinafter referred to as FPOS) in which -CF2 CHFCF3 is grafted to the carbon atom of the ethoxy group in the main chain of the polyorganosiloxane monomer represented by
70 parts by weight n-butyl methacrylate

10 parts by weight N-vinylpyrrolidone

5 parts by weight triethylene glycol dimethacrylate
4 parts by weight 2,2'
-Azobis-(2,4-dimethylvaleronitrile)
0.01 part by weight The above composition was poured into a contact lens mold, heated continuously from room temperature to 95°C, and after being released from the mold, a secondary heat treatment was performed at 130°C using a dryer. A colorless and transparent contact lens was obtained.

[0037]

[Example 2] METS

10 parts by weight FPOS

50 parts by weight n-butyl methacrylate

10 parts by weight N-vinylpyrrolidone

5 parts by weight 2, 2, 2, 2', 2'
,2'-hexafluoroisopropyl methacrylate


20 parts by weight triethylene glycol dimethacrylate
5 parts by weight 2,2'-azobis-(2,4-dimethylvaleronitrile) 0.
01 parts by weight A colorless and transparent contact lens was obtained in the same manner as in Example 1 using the above composition.

[0038]

[Example 3] METS

20 parts by weight FPOS

45 parts by weight ethyl methacrylate

19 parts by weight acrylic acid

3 parts by weight 2,2,
2,2',2',2'-hexafluoroisopropyl methacrylate

9 parts by weight ethylene glycol dimethacrylate
4 parts by weight 2,2'-azobis-(2,4-dimethylvaleronitrile) 0.01 part by weight The procedure was carried out in the same manner as in Example 1 using the above composition to obtain a colorless and transparent contact lens.

[0039]

[Example 4] METS

45 parts by weight FPOS

20 parts by weight n-butyl methacrylate

17 parts by weight N-vinylpyrrolidone

6 parts by weight 2, 2, 2, 2', 2'
,2'-hexafluoroisopropyl methacrylate


6 parts by weight triethylene glycol dimethacrylate
6 parts by weight 2,2'-azobis-(2,4-dimethylvaleronitrile) 0
．． 01 parts by weight A colorless and transparent contact lens was obtained in the same manner as in Example 1 using the above composition.

[0040]

[Example 5] METS

61 parts by weight FPOS

10 parts by weight n-butyl methacrylate

8 parts by weight N-vinylpyrrolidone

5 parts by weight 2, 2, 2, 2', 2
',2'-hexafluoroisopropyl methacrylate

10 parts by weight triethylene glycol dimethacrylate
6 parts by weight 2,2'-azobis-(2,4-dimethylvaleronitrile) 0
．． 01 parts by weight A colorless and transparent contact lens was obtained in the same manner as in Example 1 using the above composition.

[0041]

[Characteristics] In order to examine the characteristics of the contact lenses obtained in each of the above examples, we prepared films of the same material and examined their tensile strength, elongation at break, hardness, and oxygen permeability coefficient.The results are shown below. Shown in 1.

Claims (4)

[Claims] Claim 1: (a) a monomer represented by the following general formula (1);
represents a hydrogen atom or a methyl group, and X1 to X3 are [
Chemical formula 2], c is an integer of 0 to 3, Y1 and Y2 are [Chemical formula 3
] (d is an integer of 0 to 2) (b) A monomer represented by the following general formula (2) having at least 3 fluorine atoms in the carbon atoms of the alkylene group in the main chain; A fluorine-containing organosiloxane monomer in which ~30 fluorine-substituted hydrocarbon groups are grafted to one or more per molecule of the monomer of general formula (2);
embedded image (where e is an integer of 0 to 700, R2 is -(CH2
)f −, f is an integer of 1 to 25, R3 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group, or
], g is an integer from 1 to 25, h is an integer from 0 to 250,
R4 represents a hydrogen atom or a methyl group, A represents [Chemical formula 6], i represents an integer of 0 to 250, R5 represents a hydrogen atom or a methyl group, Z1 to Z6 represent [Chemical formula 7], and j represents An integer of 0 to 10, R6 to R8 are an alkyl group having 1 to 30 carbon atoms, an alkoxy group, or an alkyl group having 6 to 30 carbon atoms.
12 aryl group) (c) (meth)acrylic acid ester, and (d)
1. A medical material comprising a polymer having a three-dimensional crosslinked network structure obtained by polymerizing at least a tear film stabilizer. [Claim 2] Fluorine-containing monofunctional and/or polyfunctional (
2. The medical material according to claim 1, comprising a polymer having a three-dimensional crosslinked network structure obtained by polymerizing further using a meth)acrylic acid ester monomer. 3. Monomer (a) contains 1 to 85 parts by weight, (
5 to 95 parts by weight of monomer b), 1 to 95 parts by weight of monomer (c)
2. The medical material according to claim 1, comprising a polymer having a three-dimensional crosslinked network structure obtained by polymerizing 60 parts by weight of the monomer (d) in a proportion of 1 to 30 parts by weight. 4. Monomer (a) contains 1 to 85 parts by weight, (
5 to 95 parts by weight of monomer b), 1 to 95 parts by weight of monomer (c)
60 parts by weight, fluorine-containing monofunctional and/or polyfunctional (meth)acrylic acid ester monomer is used at a ratio of 5 to 50% by weight based on the total of 1 to 30 parts by weight of the monomer (d). 3. The medical material according to claim 2, comprising a polymer having a three-dimensional crosslinked network structure obtained by polymerization.