JPS63210115A - Oxygen-permeable material - Google Patents

Abstract

PURPOSE:To obtain an oxygen-permeable material suitable for contact lenses and excellent in wearability, stain resistance, and biocompatibility, formed from a fluorinated copolymer obtained from a specified fluorinated unsaturated dicarboxylate monomer and a fluorinated (meth)acrylate monomer. CONSTITUTION:A fluorinated copolymer is obtained by polymerizing 2-95wt.% fluorinated unsaturated dicarboxylate monomer (A) of formula I (wherein R<f1-f2> are each a 1-30 C fluorinated hydrocarbon group which may contain an 0 atom and which at least three F atoms are bonded, and m and n are each 0-4) with 98-5wt.% fluorinated (meth)acrylate monomer (B) of formula II (wherein R<f3> is R<f1>, R<1> as H or CH3, and l is m) and, optionally, another functional monomer (C) (e.g., ethylene glycol dimethacrylate) as a crosslinking agent at 40-200 deg.C for 0.5-5,000min in the presence of a thermal polymerization radical initiator (D) such as azobisisobutyronitrile. This polymer is molded into any desired shape under melting conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an oxygen permeable body formed from a fluorine-containing polymer that has excellent oxygen permeability, wear comfort, and stain resistance. More specifically, the present invention relates to an oxygen permeable material that has excellent biocompatibility when used as a medical oxygen permeable material such as a contact lens, can be worn for a long time, and exhibits excellent performance.

[Conventional technology]

Since the cornea of the eye is a tissue without blood vessels, the oxygen necessary for its respiratory metabolism is obtained by diffusion from the eyelid mucosa and aqueous humor when we are asleep, but when we are awake, it is taken in from the atmosphere. ing. Therefore, wearing contact lenses, whether hard or soft, tends to impede oxygen supply, and wearing them for a long time often causes hyperemia, edema, and other corneal damage. Therefore, materials for contact lenses are required to have excellent optical, chemical, physical, and mechanical properties as well as oxygen permeability.

In addition, materials for contact lenses have excellent stain resistance against proteins, lipids, mucin, etc. that are components of tear fluid, as well as stain resistance against bacteria and fungi.
It is required that the product be comfortable to wear and have excellent biocompatibility.

Conventionally, polymethyl methacrylate (PMMA) and polymers of various methacrylic acid ester monomers have been widely used as materials for contact lenses, but most of these have poor oxygen permeability and are difficult to wear for long periods of time. It was unbearable. A silicone methacrylate polymer in which a siloxane bond is introduced into the methacrylate ester molecule in order to improve the oxygen permeability of conventional methacrylate ester polymers (Japanese Patent Publication No. 33502/1983)
, an oxygen-permeable polymer mainly composed of cellulose acetate butyrate, and a fluorine-containing methacrylate polymer (Japanese Patent Application Laid-Open No. 1987-
51705 and Japanese Unexamined Patent Publication No. 61-111308), contact lenses have been proposed.

However, although these polymers have improved oxygen permeability compared to conventional methacrylic acid ester polymers such as PMMA, it is still not sufficient, and there is a need for polymers with further improved oxygen permeability. ing. Furthermore, these polymers are not satisfactory in terms of stain resistance, wear comfort, and other properties.

[Problems to be solved by the present invention]

The present inventors recognized that the prior art of conventional oxygen permeable materials, especially contact lenses, is in the above situation, and conducted intensive studies on oxygen permeable materials that have excellent oxygen permeability, wear comfort, and stain resistance. As a result, it was discovered that a specific fluorine-containing copolymer satisfies the above-mentioned object, and the present invention was achieved.

[Means for solving problems]

According to the present invention, general formula (1) % formula % [wherein Rfl and Rf2 are each a fluorine-substituted carbon having 1 to 30 carbon atoms which may contain an oxygen atom to which at least 3 fluorine atoms are bonded] Indicates a hydrogen group.1. and are integers from 1 to 4, respectively] fluorine-containing unsaturated dicarboxylic acid ester monomer component units (al is 2 to 95% by weight and general formula (II) I CH2=C-CD□( CI(2)J” (II)
[In the formula, Rfl represents a fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom to which at least 3 fluorine atoms are bonded, R' represents a hydrogen atom or a methyl group, and R' represents a hydrogen atom or a methyl group; is an integer from 0 to 4] is an oxygen permeable fluorine-containing copolymer formed from a randomly arranged fluorine-containing copolymer with BL of 5 to 98% by weight. The body is provided.

The fluorine-containing unsaturated dicarboxylic acid ester monomer component unit (a
) is represented by the general formula (1) % formula % [wherein Rfl and 1lfl are each at least 3
represents a fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom to which 1 fluorine atoms are bonded;
and and each represent an integer from O to 4] are fluorine-containing unsaturated dicarboxylic acid ester monomer component units. In the general formula (I), 1 (fl and R
Each ff is preferably a fluorine-substituted hydrocarbon group having 2 to 25 carbon atoms which may contain an oxygen atom to which at least three fluorine atoms are bonded.1. and a are preferably I to 4, respectively. Specifically, the fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms, which may contain an oxygen atom to which at least three fluorine atoms are bonded, is, for example, (CF,)4CF3, -(CF
g) wcFs, -(CF z ) q CF 3, -(
CFz)++CFs, -CI(CFa)z, -C(C
F3)3, (CFri3C(CF3)s, (CFz)
sCH(CJs)z, etc. can be exemplified. Among these fluorine-substituted hydrocarbon groups, (CFg)yc
Fs, yes.

The fluorine-containing unsaturated dicarboxylic acid ester monomer component unit (al specifically, for example, CH2=C-C
0□(CHz)z (CF2)tcFsCH,CD□(
CHri2 (Ch) tcF+,CH,=C-CD□(
Examples include CL)z (CFz)3C(CF+)3■C)IzCOz(CHz)z(CFt)qCF3. Among these fluorine-containing unsaturated dicarboxylic acid ester monomer component units (al), +1 and the like are preferred.

Further, the fluorine-containing (meth)acrylic acid ester monomer component unit mass constituting the fluorine-containing copolymer of the oxygen permeable material of the present invention has the general formula (II) CHz=CC0z(CHt)
KaRt'' (II) [In the formula, If3 represents a fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom to which at least three fluorine atoms are bonded, and R1 is a hydrogen atom or a methyl is a fluorine-containing (meth)acrylic acid ester monomer component unit represented by the following formula (If), where at least three fluorine atoms are It is preferably a fluorine-substituted alkyl group having 2 to 25 carbon atoms, which may contain a bonded oxygen atom, and R is preferably 1 to 4. Specifically, the fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms, which may contain an oxygen atom,
The fluorine-substituted hydrocarbon groups exemplified as lfl and Rfz in the general formula (1) above can be similarly exemplified.

Specifically, the fluorine-containing (meth)acrylic acid ester monomer component unit (bl is, for example, C1, CH.

ll CH3CH3 CHs CHaCH,C
H.

CH3C113 CHz=CCOCH(CF+)z C)Iz=CC
OCHzCHz(CFz)3cH(CJs)g・CH.

CH2:CC0CHCH2C6F+3 I 1 0 CHzOCCaF+? For example, These fluorine-containing (meth)acrylic acid ester component units (in bl, CH3CH3 CH3 cuz=ccoco□CHI (CFz)3CH(CJ
s) gCH3 CHz=CCOCHCHzCJ+ 3 0 CHzOCCeF+t etc. are preferred.

The fluorine-containing copolymer forming the oxygen permeable body of the present invention is a fluorine-containing unsaturated dicarboxylic acid ester monomer component unit represented by the general formula [I] (2 to 95% by weight of Al).
, preferably 5 to 90% by weight, particularly preferably 2
0 to 70 weight range and a fluorine-containing (meth)acrylic acid ester component unit represented by the general formula (11) (
5 to 98% by weight of bl, preferably 10 to 95% by weight
It may be contained in an amount of 30 to 80% by weight, particularly preferably 30 to 80% by weight.

The fluorine-containing copolymer may consist of only two components: the fluorine-containing unsaturated dicarboxylic acid ester monomer component unit +al and the fluorine-containing (meth)acrylic acid ester monomer component unit (bl). However, in addition to these two essential components, other copolymerization components may be copolymerized within a range that does not impair the performance of the oxygen permeable material.For example, ethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, tetradeca A polyfunctional monomer such as ethylene glycol dimethacrylate, nonapropylene glycol dimethacrylate, allyl methacrylate, or trimethylolpropane trimethacrylate can be added as a crosslinking agent in any proportion.

In addition, additives such as various stabilizers, pigments, thickeners, etc. can be added to the polymer forming the oxygen permeable body of the present invention or at a stage before polymerization in arbitrary proportions.

As a method for producing the fluorine-containing copolymer forming the oxygen permeable body of the present invention, the fluorine-containing unsaturated dicarboxylic acid ester monomer +al and the fluorine-containing (meth)acrylic ester monomer (b ), a method of reacting a monomer mixture consisting of other copolymerization components added as necessary, and a mixture consisting of a polymerization initiator.

Among polymerization initiators, radical initiators for thermal polymerization include azobisisobutyronitrile, azobiscyclohexanecarbonitrile, phenylazobisbutyronitrile, asohisdimethylvaleronitrile, benzoyl peroxide, di-t-butyl Specific examples of photopolymerization initiators include benzoin ethers such as subbutyl, benzophenones such as benzophenone and benzoate, xanthones,
Xanthone such as thioxanthone, can be removed. The temperature during thermal polymerization is usually in the range of 40 to 200°C, preferably 45 to 120°C, and the time required for polymerization is usually 0.
5 to 5000 minutes, preferably 30 to 2000 minutes.

In the case of photopolymerization, the time required for polymerization varies depending on the type and amount of monomers and photopolymerization initiators used, as well as the type of light source used. A polymer with sufficient strength for practical use can be obtained in a short period of time.

As a method for producing the oxygen permeable material of the present invention, a method may be adopted in which the fluorine-containing copolymer obtained by the above method is molded into a desired shape under melting conditions, or a method may be adopted in which the fluorine-containing copolymer obtained by the above method is molded into a desired shape. It is also possible to adopt a method of obtaining a fluorine-containing polymer in a desired shape by polymerizing a mixture consisting of a polymerization initiator and a polymerization initiator in a polymerization mold.

The intrinsic viscosity [η] of the fluorine-containing polymer measured in ethyl acetate at 30° C. is usually 0.1 to 3.0 dl/g. If the fluorine content of the fluorine-containing polymer is high, it may become insoluble in solvents and the intrinsic viscosity [η] may not be measurable, but it can also be used in the oxygen permeable material of the present invention.

The glass transition temperature (Tg) of the fluorine-containing polymer measured with a differential scanning calorimeter (DSC) is usually -80 to 20
0°C, preferably in the range of -50 to 200°C.

In addition, the fluorine-containing copolymer has excellent oxygen permeability,
Its oxygen permeability coefficient (DK value
TP) cm/cd-sec, mm1g) is usually in the range of 10 or more, preferably 15 or more, particularly preferably 20 or more.

Here, the oxygen permeability coefficient of the fluorine-containing copolymer was measured using a film oxygen permeability meter manufactured by Seikaken.

The fluorine-containing polymer has excellent stain resistance against lachrymal fluid components such as proteins, lipids, and mucin.

The oxygen permeable body made of the fluorine-containing copolymer of the present invention has excellent wearing comfort and stain resistance, has extremely good oxygen permeability, and has excellent biocompatibility. For example, it is suitable for applications such as hard contact lenses or various separation membranes. In particular, when the oxygen permeability of the present invention is used as a hard contact lens, it has superior oxygen permeability, wear comfort, and stain resistance against tear fluid components compared to conventional ones, and has excellent biocompatibility, so it can be used for long periods of time. This has the advantage that it can be installed.

〔Example〕

Next, the oxygen permeable body of the present invention will be specifically explained with reference to Examples.

Reference example I IH, IH, 2H, 2) 1-pentadecafluoro-1-
decanol) 10cH2cH2 (CF2), CF369
．． 6g (0.15M), p-) was mixed with toluene and reacted at 140°C for 8 hours.

During this time, the water produced was removed from the system using a Dean-Stark reflux device to accelerate the reaction. After the reaction, toluene was distilled off from the reaction solution, the solution was dissolved in methylene chloride, and undissolved substances were removed. This filtrate was washed with an alkali and water, and then filtered with addition of boron salt, and the filtrate was evaporated to dryness. The obtained viscous liquid was further subjected to column separation to obtain a pale yellow transparent viscous liquid.

Reference example 2 1.1,2,3.3-pentahydroperfluorononylene-1,2-oxide CbF+ 3cHzcHcH□
13.16g (0,035M), perfluorononanoic acid C6FI? 0.28 g of potassium hydroxide was added to a mixed solution of 20 g (0,042 M) of C0OH, and the mixture was reacted at 100°C for 8 hours in a nitrogen atmosphere. Through a purification process, Cb
F+5CHtCHCHtOCCJ+q was obtained. 4.5 g of this compound and 15 mff1 of pyridine, p-
14.45 g of Itacone DCI (acid chloride Cth=CCHzCOC) was added dropwise to a solution containing 0.1 g of dimethylaminopyridine at room temperature, and the mixture was reacted at 60°C for 2 hours. After a purification process, 60 parts of Example 1 and 1. 0.5 part of 1,2.2-tetrahydroperfluorodecyl azobisisobutyronitrile was added, thoroughly stirred and mixed, and vacuum degassed for 10 minutes. This solution was poured in a nitrogen atmosphere between two glass plates with a 200μ Teflon backing as a spacer, fixed with a clamp, placed in a constant temperature bath, heated at 60℃ for 24 hours, 70℃ and 80℃.
Polymerization was carried out by heating at 90°C and 90°C for 2 hours each.

After the polymerization was completed, the produced transparent film was peeled off from the glass plate and the oxygen permeability coefficient was measured. The results are shown in Table 1.

Examples 2 and 3 Polymerization was carried out in the same manner as in Example 1, except that the ratio of 60 parts and 1.1.2.2-tetrahydroperfluorodecyl was changed, and the oxygen permeability coefficient was measured. The results are shown in Table 1.

Examples 4 to 6 Polymerization was performed in the same manner as in Example 1 except that the 1,1,2,2-tetrahydroperfluorodecyl meta ratio obtained in Reference Example 2 was changed, and the oxygen permeability coefficient was measured. The results are shown in Table 1.

Comparative example I C.I.

(2) Polymerization was carried out in the same manner as in Example 1 using only methyl methacrylate CHz=CCOOCHi, and the oxygen permeability coefficient was measured. The results are shown in Table 1.

Comparative Example 2 1.1,2.2-Tetrahydroperfluorodecylme C
H.

Reference rate CHz=CCOOCHzCHzCeF+w
Polymerization was carried out in the same manner as in Example 1 using only 10% of the polymer, and the oxygen permeability coefficient was measured.

Claims (1)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R^f^1 and R^f^2 each represent an oxygen atom to which at least three fluorine atoms are bonded. a fluorine-containing unsaturated dicarboxylic acid ester monomer component unit (representing a fluorine-substituted hydrocarbon group having 1 to 30 carbon atoms which may be contained, m and n each representing an integer of 0 to 4) a) is 2 to 95% by weight and the general formula [
II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, R^f^3 is a carbon atom number of 1 to 3 which may contain an oxygen atom to which at least 3 fluorine atoms are bonded.
0 fluorine-substituted hydrocarbon group, R^1 represents a hydrogen atom or a methyl group, and l represents an integer from 0 to 4] fluorine-containing (meth)acrylate monomer component unit ( An oxygen permeable body formed from a randomly arranged fluorine-containing copolymer comprising 5 to 98% by weight of b).