JPH02269306A - Fluorine based contact lens - Google Patents

Abstract

PURPOSE:To obtain the contact lens which has excellent oxygen permeability, stain resistance and water leakability in combination and has a good wearing feel by constituting the lens of a polymer consisting of a specific perfluorovinyl ether monomer and a specific acrylate monomer as its essential components. CONSTITUTION:The oxygen permeable contact lens is constituted of the polymer consisting of the perfluorovinyl ether monomer expressed by formula I and the acrylate monomer expressed by formula II as its essential component. In the formula I, m is 0 to 2 integer; n is 1 to 5 integer; M is a sulfonyl group, carboxylate group or F group. In the formula II, R1 is a hydrogen atom or methyl group; R2 is a straight chain or branched fluorinated alkyl group. The perfluorovinyl ether monomer may be used alone or >=2 kinds thereof may be combined. This monomer plays the role of imparting resilience and oxygen permeability to the contact lens. The fluorine contact lens having the excellent oxygen permeability, strength, flexibility and water leakability is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a fluorine-containing contact lens that has excellent oxygen permeability, stain resistance, and wear comfort.

(Conventional technology) Conventionally, contact lenses were made of polymethyl methacrylate (
Polymers of various acrylate monomers, mainly PMMA), have been widely used, but since PMMA contact lenses do not have the ability to permeate oxygen, oxygen Transparent materials have come into use. As these materials, for example, contact lenses made of polymers using various siloxanyl methacrylates in which siloxane bonds are introduced into the acrylate molecules and fluorine-containing acrylates in which fluorine is introduced have been proposed (USP No. 152073, USP 3808).
178), but these polymers are similar to conventional P
Although the oxygen permeability has been improved compared to MMA, it is still not sufficient, and the stain resistance and wearing comfort are also unsatisfactory.

Polyhydroxyethyl methacrylate (PHEMA) and polyvinylpyrrolidone (PNVP) are used to improve wearing comfort.
) and other hydrogels are known.

Although these materials have greatly improved wearing comfort, they have problems in that they have insufficient oxygen permeability and mechanical strength, and are easily contaminated by fungi and lachrymal fluid components.

Although non-hydrous silicone rubber contact lenses have excellent oxygen permeability, they are highly lipophilic, making it easy for lipids in tear fluid to adhere to them, and their surface water repellency makes them poorly compatible with tear fluid, resulting in a foreign body sensation. There are problems such as causing

By the way, perfluorovinyl ether type contact lenses (USP No. 3,940,207) are known as fluorine type contact lenses.

This product has excellent stain resistance due to the inert properties of the fluorine-containing polymer, and has a refractive index close to that of tear fluid, so it has good optical properties between the tear fluid and the contact lens, and the contact lens does not affect the cornea. It is known to have the effect of facilitating adaptation. However, as shown in the patent, perfluorovinyl ether monomers have limited polymerization methods and polymers that can be obtained, and the copolymers obtained therefrom also have insufficient oxygen permeability. It does not polymerize with various siloxanyl methacrylate monomers and hydrocarbon acrylate monomers such as methyl methacrylate, which are often used in contact lens materials, and no contact lenses copolymerized with these monomers have been obtained. .

Additionally, telechelic perfluoropolyether contact lenses (LJSP340473) are known, but since the monomers used here are acrylate-based, they are copolymerized with various acrylate-based monomers. Although the properties and oxygen permeability have been improved significantly, there are the following problems in purifying the monomer.

That is, contact lenses are optical products and must meet strict optical standards.

For f, the raw material monomer must be of high purity, and the polymerization conditions must be strictly controlled.

In the case of the above-mentioned telechelic perfluoropolyether monomer, the molecular weight is high, and distillation purification, which is a common purification method for monomers, cannot be used, and it is difficult to purify it to a high degree of purity.

(Problems to be Solved by the Present Invention) The present invention overcomes the drawbacks of conventional oxygen permeable contact lenses, and provides excellent oxygen permeability, stain resistance,
The purpose of the present invention is to provide a contact lens that is water-resistant and comfortable to wear.

(Means for Solving the Problem) As a result of intensive research into a new contact lens that has excellent oxygen permeability, stain resistance, and water resistance, the present inventors discovered that a specific perfluorovinyl ether monomer The inventors have discovered that a polymer containing a specific fluorine-containing acrylate monomer as essential components can achieve the above object, and based on this knowledge, they have completed the present invention. That is, the present invention is based on (A) the general formula % (1) (where m is an integer of 0 to 2, n is an integer of 1 to 5, and M is a sulfonyl group, a carboxylic acid ester group, or an F group). ) Perfluorovinyl ether monomer represented by (B) general formula % formula % () (R1 in the formula is a hydrogen atom or a methyl group R2 is a linear or branched fluorinated alkyl group.) The present invention provides an oxygen-permeable contact lens made of a polymer containing an acrylate monomer represented by the following as an essential component.

The present invention will be explained in detail below.

IA) of the raw material monomer in the contact lens of the present invention
General formula CF2=CF (OCF2CF) a o-(CF2) as a component
, -M・---・(1)-Fs (m in the formula is an integer of O to 2, and n4 is an integer of 1 to 5.

M is a sulfonyl group, a carboxylic acid ester group, or a 41F group. ) is used. Regarding the physical properties of this monomer and its manufacturing method, please refer to U
SP4329434, υ5P4329435, SI
'390937 USP No. 3132123, Special Publication No. 45-
No. 22327, JP-A No. 52-28586, and the like.

Further, as the substituent M represented by the general formula (1), in the case of a sulfonyl group, S Oz F is preferable, and as the carboxylic acid ester group, a carboxylic acid alkyl ester group such as methyl carboxylate or ethyl carboxylate group is preferable. An example is CFz-CF OCF2OF -0-(CF2) 2C
OOCH3CF 3 CF2■CF OCFzc F2OOOC) (3CF2
40FO(CF2)3COOCH3CFz=CFO(C
F2) 4COOCR3F3 CF2=CFO (CF2)ssOzF, CFt CFO
(CF,) gcF3, etc.

These perfluorovinyl ether monomers may be used alone or in combination of two or more.

This monomer plays a role in contributing flexibility and oxygen permeability to contact lenses.

In the case of copolymerized contact lenses using perfluorovinylether monomers having a sulfonyl group or a carboxylic acid ester group at the end, one surface of the contact lens is immersed for a short time in a 5% aqueous sodium hydroxide solution using a known method. 50 on top
By generating 3 Na and COONa groups, it is also possible to impart ho properties.

In the contact lens of the present invention, the fluorine-containing acrylate monomer used as the raw material (B) component has a structure represented by the general formula (B) (in which R1 and R2 have the meanings as above). This monomer is compatible with the monomer (A), does not impair the oxygen permeability and flexibility imparting effect of the monomer (A), and has the (^) It has the effect of making it possible to copolymerize with hydrocarbon-based acrylate monomers, which are drawbacks of monomers, and with acrylate monomers having siloxane bonds.

Specific examples of the fluorine acrylate monomer represented by the above formula (rl) include methacrylates such as trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate, and hexafluoroisobutyl methacrylate; Corresponding acrylic children can be mentioned. Each of these acrylate monomers may be used alone.

It is also true that two or more types are combined.

In the contact lens of the present invention, the ratio of the monomer (^) to the monomer (B) is 5:95 to 50:5.
0. Preferably, it is selected in the range of 5295 to 35:65.

In the contact lens of the present invention, the above-mentioned (A) and (B)
) In addition to the monomers, hydrocarbon-based acrylate monomers, acrylate monomers containing siloxane, and monomers containing hydrophilic groups are used.

Among the specific examples of these various monomers, hydrocarbon acrylates include methyl methacrylate and medacrylic acid n.
-butyl, n-butyl acrylate.

Examples of acrylate monomers having a siloxanyl bond include methacryl and n-hexyl, and examples include the general formula, where X and Y are selected from the group consisting of a C to C5 alkyl group, a phenyl group, and a Z group; Z is a group having the structural formula (%), A is selected from the group consisting of 00 to C5 alkyl groups, phenyl groups, and Z groups, R is selected from hydrogen atoms or methyl groups, and m is 1 to 5. is an integer of n
is an integer from 1 to 3. ) is an acrylate monomer with a siloxanyl bond (equity 52-33502
), preferably tris(trimethylsiloxy)silylpropyl methacrylate, becitamethyldisiloxanylmethyl methacrylate, heptamethylsiloxanyl ethyl acrylate, etc. Examples of monomers having hydrophilic groups include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, N-vinylpyrrolidone, and methacrylic acid.

These above-mentioned monomers may be used alone or in combination of two or more, and these monomers (A) (
B) What monomers are added to the monomer?

Usually, a range of 3 to 50% by weight of the total amount of monomers is selected. In addition, in addition to these, for the purpose of improving the mechanical strength of the contact lens, a crosslinking agent such as ethylene glycol dimethacrylate, trimethylolpropane, trimethacrylate, vinyl methacrylate, etc. can also be used in a range of about 10% by weight. .

According to the present invention, this contact lens can be manufactured by a known method of placing a raw material monomer mixture and a polymerization catalyst in a mold and carrying out radical polymerization. This method is not particularly limited, and methods commonly used in radical polymerization, such as thermal polymerization and photopolymerization using ultraviolet irradiation, can be used. In the WI thermal polymerization method, a thermal polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, etc. is usually used in an amount of 0.01 to 5% based on the total amount of monomers. % by weight, and the mixture was heated at a temperature ranging from 25 to 120°C for 50 minutes.
Contact lenses can be obtained from the desired copolymer by carrying out the polymerization reaction for about 100 hours.

On the other hand, in the photopolymerization method, thermal polymerization initiators are usually used, such as benzoin ethyl ether, benzoin n-butyl ether,
-thyl, benzyl dimethyl ketal, acetophenone,
α, α′-Jethoxyacetophenone, anthraquinone, etc. are added at a ratio of 0.05 to 3% by weight based on the total amount of monomers, and this mixture is poured into an ultraviolet-transparent contact lens-shaped mold and irradiated with ultraviolet rays. After a polymerization reaction is carried out, a contact lens can be obtained from the mold.

(Effect of the invention) The contact lens of the invention has excellent oxygen permeability, strength,
It has good flexibility and water wettability, making it extremely suitable for use as contact lenses.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1゜CF2-CF20CF2CFOCF2CF2COOCH
3(F-1) CF.

10 parts by weight hexafluoroisopropyl acrylate 9
0 parts by weight and 1 part by weight of benzyl dimethyl ketal were thoroughly mixed, and the mixture was poured into an ultraviolet-transparent contact lens mold, irradiated with a chemical lamp of 8 mw/cm2 for 1 hour, and further heat-treated at 80°C for 1 hour.

This lens is flexible and transparent, and is produced using a pressure method (vacuum method) using a 307 μm film made under the same polymerization conditions.
When oxygen permeability was measured by
0-10cm'(STP) ・am/ am2・se
c-cmHg, and the tensile strength is 369g/m
m2, elongation was 438%. The contact angle with water was measured by the bubble method and was 48 degrees, indicating good water wettability. As a pretreatment for contact angle measurement, the surface of the sample film was washed with a surfactant, and the film was soaked in physiological saline for 2 hours.
After 4 hours of immersion, the contact angle was measured.

Examples 2 to 5 Contact lenses and films were prepared by polymerization in the same manner as in Example 1, except that the monomer composition in Example 1 was changed as shown in the following table, and their physical properties were determined. Monomer compatibility and physical properties are shown in the table.

Comparative example 1. 2 The following table shows the compatibility and physical properties of the monomers when the monomer composition in Example 1 was changed as shown in the table below.

Margin below

Claims (1)

[Claims] (A) General formula▲ Numerical formulas, chemical formulas, tables, etc.▼……(I) (In the formula, m is an integer of 0 to 2, n is an integer of 1 to 5, M is a sulfonyl group , represents a carboxylic acid ester group or F group) and a perfluorovinyl ether monomer represented by (B
) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼‥‥‥(II) (In the formula, R_1 represents a hydrogen atom or a methyl group, and R_2 represents a linear or branched fluorinated alkyl group.) A contact lens made of a polymer containing acrylate monomer as an essential component.