JPH03257421A - Soft contact lens material - Google Patents

Abstract

PURPOSE:To provide the soft contact lens material having high oxygen permeability by using a copolymer consisting of a bifunctional org. soloxane monomer expressed by specific general formula and fluoroalkyl ester acrylate monomers, (meth)acrylate and a corsslinkable monomer, etc. CONSTITUTION:This soft contact lens material consists of the copolymer obtd. by mixing and polymerizing 15 to 60wt.% bifunctional org. siloxane monomer expressed by the general formula I, 10 to 60wt.% fluoroalkyl ester acrylate monomer, 5 to 50wt.% >=1 kinds of the monomers selected from the group consisting of the alkyl ester acrylate monomer of 1 to 20C alkyl group, fluoroalkyl ester mehacrylate monomer of 6 to 15C alkyl group, fluoroalkyl ester methacrylate monomer of 6 to 15C alkyl group, 0.5 to 10wt.% crosslinkable monomer, and 0.5 to 10wt.% hydrophilic monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel contact lens material. More specifically, the present invention relates to a substantially water-free soft contact lens material that has excellent oxygen permeability and optical and mechanical properties, has little dirt adhesion, and has no risk of adhesion to the cornea. be.

[Conventional technology]

Soft contact lenses are divided into hydrated soft contact lenses and non-hydrated soft contact lenses.

Water-containing soft contact lenses have the advantage of being soft and comfortable to wear, and higher water-containing types have higher oxygen permeability. Because it is easily contaminated and may cause bacterial growth, it is often inconvenient to handle, such as having to periodically sterilize it by boiling.

For non-hydroscopic soft contact lenses, for example, a platinum-based catalyst is added to a mixture of polydimethylsiloxane and methylhydrodiene polysiloxane, both ends of which are blocked with vinyldimethylsilyl groups, and the mixture is heated using a molding method. Silicone rubber lenses obtained by curing methods and soft contact lenses made of polymers mainly composed of polyperfluoroether with polymerizable groups such as methacryloxy groups added to both ends and hard contact lenses. Flexible lenses having an elastic modulus are known (Japanese Patent Laid-Open Nos. 54-81363, 1983).
-127914).

In addition, lenses are made by cutting from a hard substrate made by copolymerizing methacrylic acid, acrylic acid and methacrylic ester, or acrylic ester, and are then subjected to esterification and/or transesterification treatment to provide a comfortable wearing experience. A water-free soft contact lens with good properties has also been manufactured (Japanese Patent Laid-Open No. 75047/1983).

These non-water-containing soft contact lenses also have the following problems.

First of all, when silicone rubber lenses were first developed, there were drawbacks such as the hydrophilic treatment layer that was applied to improve the hydrophobicity of the lens surface peeling off, and the excessive elasticity causing it to stick to the cornea. However, recent advances in surface hydrophilic treatment technology, changes in lens design, and improvements in mechanical properties have significantly improved the above drawbacks. , L7 is still not completely satisfactory, and the reality is that it has not been widely used.

Next, non-hydrous lenses that are mainly composed of polyperfluoropolyether are more like semi-hard types than soft contact lenses, so they do not feel as comfortable when worn as soft contact lenses, and the lenses do not touch the cornea. The movement is also not satisfactory.

In addition, soft contact lenses mainly made of methacrylic esters or acrylic esters have poor oxygen permeability, and are therefore not suitable for long-term wear.

Contact lens materials mainly composed of polyfunctional polysiloxane and having high oxygen permeability are described in JP-A-54-24047 and JP-A-56-51715.

None of these polyfunctional polysiloxane-based materials take into account contamination by components in tear fluid, and since they are similar to silicone rubber lenses, there is a risk of them sticking to the cornea, making them difficult to put into practical use. has not been reached.

In recent years, there has been a demand for products that not only have high oxygen permeability, but also have good stain resistance, high safety, and wearability.

[Problems to be Solved by the Invention] Under these circumstances, the present invention provides a material with a high oxygen permeability coefficient DK value representing oxygen permeability, excellent optical and mechanical properties, and good stain resistance. The object of this invention is to provide a substantially water-free soft contact lens material that can provide a lens that has the following characteristics and is free from concerns about adhesion to the cornea.

[Means to solve the problem]

The present inventors have conducted intensive research to develop a water-free soft contact lens material with such favorable properties, and as a result, we have developed a bifunctional organosiloxane monomer with a specific structure and molecular weight and a fluoroalkyl acrylate. One or more monomers selected from the group of ester monomers, methacrylic acid alkyl ester monomers, acrylic acid alkyl ester monomers, and methacrylic acid fluoroalkyl ester monomers, crosslinkable monomers, and It was discovered that the object could be achieved by using a material made of a copolymer obtained by containing a hydrophilic monomer in a specific range, and based on this knowledge, the present invention was completed. .

That is, the present invention provides (A)-Noshiro: (RI+ RZI R3 and R4 each represent a methyl group or a trimethylsiloxy group, L and n are each an integer of 2 to 5, and m is an integer of 4 to 60. ) Difunctional organosiloxane monomers 15 to 60 represented by
Weight% (B) Acrylic acid fluoroalkyl ester monomer 10
~60% by weight, (C) Acrylic acid alkyl ester monomer whose alkyl group has 1 to 20 carbon atoms, and whose alkyl group has 6 to 1 carbon atoms.
5 to 50% by weight of one or more monomers selected from the group of methacrylic acid alkyl ester monomers having a carbon number of 5 and methacrylic acid fluoroalkyl ester monomers having an alkyl group of 6 to 15 carbon atoms. D) A substantially water-free copolymer obtained by mixing 0.5 to 10% by weight of a crosslinkable monomer (E) 0.5 to 10% by weight of a hydrophilic monomer and polymerizing the mixture. The present invention provides a soft contact lens material.

The present invention will be explained in detail below.

As the molecular weight of the bifunctional organosiloxane monomer represented by Noshiro (1) increases, the length of the open chain of the functional group increases, which improves oxygen permeability, lowers cohesive energy, and reduces glass transition. Since the point is also lower, when used as a soft contact lens, it has a great effect on physical properties such as softness, shape retention due to rubber elasticity, and returnability. Moreover, since it has a trifluoropropyl group in the side chain, it has water-repellent and oil-repellent properties due to the reduction in critical surface tension caused by the fluorine atom. It has the effect of suppressing contamination by the components of

However, if the monomer's 3.3.3 repeating number m of trifluoropropylmethylsiloxanyl units exceeds 50, the compatibility with other monomers will deteriorate7, resulting in cloudiness or phase separation. do. Regarding the oxygen permeability, when the number of repetitions m reaches a certain value (approximately 50), no significant difference is observed even if the number of repetitions is increased further. Furthermore, when the number of repetitions m is 4 or less, oxygen permeability decreases, and mechanical properties such as softness and returnability required for soft contact lenses deteriorate. Determine the molecular weight for the above reasons 3, 3.3) Repeating lifluoropropylmethylsiloxanyl units, the value of several m is 4 ~
60 preferably a range of 10 to 50 provides the most balanced material.

Examples of the difunctional organosiloxane monomer represented by -Noshiro (I) include α,ω-bis(3-methacryloxypropyldimethylsiloxy)3.3.3)lifluoropropylmethylpolysiloxane, α, ω-bis(3-
methacryloxypropyl)tetrakis(trimethylsiloxy)silyl3,3.3 trifluoropropylmethylbolysiloxane, α,ω-bis(2methacryloxypropyldimethylsiloxy)3,3.3 trifluoropropylmethylpolysiloxane, etc. Can be mentioned.

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

Next, the acrylic acid fluoroalkyl ester used as the monomer component (B) has water-repellent and oil-repellent properties due to a decrease in critical surface tension caused by fluorine atoms, which means that the surface of the contact lens can be absorbed into the tear fluid. It has the effect of suppressing contamination by components such as proteins and lipids.

In addition, in terms of physical properties, many of them have glass transition points below room temperature, so when copolymerized, they can exhibit the softness and flexibility necessary for soft contact lenses.

Specific examples of these acrylic acid fluoroalkyl esters include trifluoroethyl acrylate, tetrafluoroethyl acrylate, tetrafluoropropyl acrylate, pentafluoropropyl acrylate, hexafluorobutyl acrylate, hexafluoroisopropyl acrylate, and heptafluorobutyl. Acrylate, occufluoropentyl acrylate, etc. may be used, and one type of these monomers may be used, or 7.2
You may use it in combination of more than one kind.

Next, the methacrylic ester and acrylic ester monomers used as the monomer component (C) have the effect of improving the compatibility between the bifunctional organic siloxane (A) and the acrylic acid fluoroalkyl ester (B). Yes, it plays a role in expanding the scope of use of these two components. As a result, the glass transition point of the copolymer is lowered to room temperature or below 0°C, and the cohesive energy is lowered, which has the effect of imparting rubber elasticity and softness to the copolymer.

Specific examples of these methacrylic acid alkyl esters, acrylic acid alkyl esters, and methacrylic acid fluoroalkyl esters include n-propyl acrylate, n-
Butyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-hebutyl acrylate, n-nonyl acrylate, n-decyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, n
-dodecyl methacrylate, trifluoroethyl methacrylate, hexafluoropropyl methacrylate, etc., and these monomers may be used alone or in combination of two or more.

Next, the crosslinkable monomer used as the monomer component (D) is necessary to improve the dimensional stability of the lens.

Examples of these crosslinkable monomers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethac 1 12-lylate, vinyl Examples include methacrylate, allyl methacrylate, acrylates corresponding to these methacrylates, divinylhenzen, triallyl isocyanurate, and the like.

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

Furthermore, the hydrophilic monomer used as the monomer component (E) is necessary to improve the surface wettability of the lens.

These monomers for improving surface wettability include:
For example, methacrylic acid, acrylic acid, itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, glycerol methacrylate, polyethylene glycol methacrylate, N.

Examples include N'-dimethylacrylamide, N-methylacrylamide, and N-vinylpyrrolidone.

The copolymer used as the water-free soft contact lens material of the present invention has a bifunctional organosiloxane monomer content of component (A) of 15 to 60ffi1% (11).
The content of the fluoroalkyl acrylic ester monomer as a component is 10 to 60% by weight. The content of the methacrylic ester monomer and/or acrylic ester monomer as the component (C) is 5 to 50% by weight. Weight The content of the crosslinkable monomer in component D is 0.5 to 10% by weight.(The content of the hydrophilic monomer in component E is 0.5 to 10% by weight.) It is.

If the usage amount of each component exceeds the above range, for example, A
In the case of components, cloudiness may occur during polymerization due to compatibility,
Two-phase separation may occur when monomers are mixed. In the case of component B, component C, and component D, oxygen permeability, stain resistance, and softness and returnability deteriorate, respectively. Furthermore, if the amount used is less than the above range, it will have a negative effect on oxygen permeability and physical properties.

By changing the copolymerization ratio, etc., the copolymer of the present invention can be made into 30X10-" to 100XIO"mff1 cn+
A water-free soft contact lens material with well-balanced physical properties that corrects the oxygen permeability coefficient of about 1g/cTllsecmml7, is excellent optically and mechanically, and has stain resistance against lachrymal fluid that is equal to or better than that of commercially available products. It is.

The copolymer used as the contact lens material 7 of the present invention can be produced by a cast polymerization method using known radical polymerization by filling a mold with a monomer mixture, or by charging the monomer mixture into a rotating half-sided mold and polymerizing it. A contact lens can be formed by a method such as a method of cryo-cutting a copolymer at a low temperature, or the like.

For copolymerization, a photopolymerization initiator such as benzoin, benzophenone, benzyldimethylketanol, etc. is present in the monomer mixture, and polymerization is carried out by irradiation with ultraviolet rays, or azobisisobutyronitrile, benzoyl peroxide, etc. , a method of thermal polymerization using an azo compound such as lauroyl peroxide or an organic peroxide is preferable.

By considering the copolymerization ratio, etc., the copolymer according to the present invention can improve rubber hardness (Shore A) without reducing other physical properties.
) can be easily increased to 60-65 or more.

There have been various discussions regarding the corneal fixation of contact lenses, for example, in the Journal of the Japanese Contact Lens Society, Vol.
According to Vol. 8, pp. 191-197 (1986), as a measure to prevent silicone rubber lenses from sticking, by increasing the hardness of the material, making the rubber hardness (Shore A) 60 to 65 or higher, and considering the lens design. It has been reported that there is no need to worry about stickiness.

Considering this, it is predicted that the copolymer of the present invention will not cause corneal fixation. Since the material is also substituted with a fluorinated alkyl group, it is safer from sticking.

〔Example〕

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.

In addition, each physical property and molecular weight were calculated|required as follows.

(1) Oxygen permeability coefficient 15 16 -31 for gas permeability measuring device manufactured by Rika Seiki Kogyo Co., Ltd.
5-N was used. The sample piece has a diameter of 30 mm and a thickness of 0.3 mm.
A disk-shaped object was subjected to measurement, and the oxygen permeability coefficient was calculated from the slope of the straight line on the obtained chart. The measurements were carried out in a constant temperature room at 25°C, with the sample piece set at 35°C.

(2) Contact Angle manufactured by Kyowa Interface Science Co., Ltd.
Meter CA-A was used. Before measurement, the sample pieces were mirror-polished, surface dirt was removed using a surfactant, and then immersed in physiological saline for 24 hours before being used for measurement. For measurement, the sample piece is placed in pure water, a bubble with a diameter of 1.5 to 2.0 strokes is brought into contact with the bottom surface of the sample piece using a syringe, and the angle formed between the bubble and the sample piece is read and the contact angle is calculated. I asked for

(3) Tensile strength Universal tensile compression tester 5V-5 manufactured by Imada Seisakusho Co., Ltd.
0 was used. A sample piece having a thickness of 0.3 mm, a width of 5.0 mm, and a length of 30 mm was used for measurement. Pulling speed is 10mm
/min. The measurement was performed three times on the same sample piece, and the tensile strength was determined from the obtained values according to the calculation method described in JIS-6301.

(4) Dirt adhesion Journal of the Japanese Contact Lens Society, Vol. 24, No. 277-2
A stain adhesion test was conducted according to the method described on page 83 (1982). The sample piece has a thickness of 2 mm and a width of 5111 II.
+, a length of 30 barrels was used. Judgment was made using PM as a control.
Based on the dirt adhesion when the MA sample piece was operated in the same way, when the degree of dirt adhesion was less than that when observed with the naked eye, it was called "less", when it was more, it was called "more", and when it was the same, it was called "same". . In addition, mucin (7) is used as a model for dirt substances.
Three types were used: antemortem mucosa), lysozyme (Urashi), and lecithin (egg yolk).

(5) Hardness Hardness according to the method described in JIS-6301 (Shor
e A) was measured.

(6) Measurement of molecular weight 7 8 Mn of bifunctional organosiloxane mass (A) Liquid chromatograph: LC-3A model (Shimadzu Corporation ■
Column: 5hoclex 802
+803+805 (Showa Denko (I)) Detector: ERC-751O5 (manufactured by Elma Optical) Inch Gray Coo 77000A (manufactured by System Instruments) Developing solvent: Toluene Temperature: 25°C Standard polymer for molecular weight calibration curve: : Various types of monodisperse polystyrene (manufactured by Toyo Soda ■) (Mw/Mn=1.2 (max)) Mn and m are determined from the above analysis results.

Example 1 α,ω-bis(3-methacryloxypropyldimethylsiloxy) 3,3.3 trifluoropropylmethylpolysiloxane (molecular weight M n ”, 3500 m #
20) 40 parts by weight, 40 parts by weight of hexafluoroisopropyl acrylate-1- (hereinafter abbreviated as ^^-PIP), 20 parts by weight of n-butyl acrylate (hereinafter abbreviated as n-BA),
5 parts by weight of methacrylic acid (hereinafter abbreviated as MAA), 5 parts by weight of diethylene glycol dimethacrylate (hereinafter abbreviated as 2ED)
A monomer mixture for polymerization was prepared by stirring and mixing parts by weight and benzyl dimethyl ketanol (Ciba Geigy 1-651 >0.5 parts by weight) using a magnetic cooler for 1 hour.

The above monomer mixture for copolymerization was injected into a cell made up of two glass plates (thickness 10 mm, width 50 mm, length 100 mm) with a silicone rubber gasket inserted between them. A copolymer was obtained by irradiating with ultraviolet light for 2 hours at a temperature of 50 to 60°C.

The thus obtained copolymer was measured for oxygen permeability coefficient, contact angle, tensile strength, stain adhesion, and hardness. The results are shown in Table 1.

The monomer mixture for copolymerization was filled into a polypropylene uneven mold made by injection molding, and irradiated with ultraviolet rays for 2 hours. After irradiation, the lens taken out from the mold was transparent, soft, and had good strength and returnability. When this lens was washed with an aqueous solution containing a surfactant and stored in pure water, a lens with good water wettability was obtained.

Example 2 M n
#8000 with m4=i50, a monomer mixture for copolymerization having the same composition was prepared, a copolymer was obtained in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table 1.

Example 3 A copolymer was obtained in the same manner as in Example 1, except that A^-FTP used in Example 1 was changed to trifluoroethyl acrylate, and its physical properties were measured. Results first
Shown in the table.

Example 4 α,ω-bis(3-methacryloxypropyldimethylsiloxy)3.3.31-lifluoropropylmethylpolysiloxane (molecular weight Mn #3500 rn': 20)
50 parts by weight, 40 parts by weight of static FIP, 10 parts by weight of n-BA, 5% by weight of MAA, 5 parts by weight of 2E0 and 0.5 parts by weight of benzyl dimethyl ketanol were mixed, and the same operation as in Example 1 was carried out. A polymer was obtained. The physical property measurement results are shown in Table 1.

(Margins below) 1 2- [Notes] 1) PMMA 71 degrees * Not measured [Effects of the invention] The contact lens material of the present invention is composed of a difunctional organosiloxane monomer having a specific structure and molecular weight, and a fluoroacrylic acid. It consists of a copolymer obtained by polymerizing a mixture of a single alkyl ester, a (meth)acrylic acid ester, a crosslinking monomer, and a hydrophilic monomer within a specific range. It is possible to provide lenses that have high oxygen permeability, good mechanical properties, and dirt adhesion resistance that is comparable to PMMA hard contact lenses.The hardness can be easily adjusted, and there is no risk of sticking to the cornea. Can you provide lenses that are not available?

Claims (1)

[Claims] (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼…………(I) (In the formula, R_1, R_2, R_3 and R_4 each represent a methyl group or a trimethylsiloxy group, l and n
are each an integer of 2 to 5, and m is an integer of 4 to 60. ) Bifunctional organosiloxane monomers 15 to 60 represented by
Weight %, (B) Acrylic acid fluoroalkyl ester monomer 10
~60% by weight, (C) Acrylic acid alkyl ester monomer whose alkyl group has 1 to 20 carbon atoms, and whose alkyl group has 6 to 1 carbon atoms.
5 to 50% by weight of one or more monomers selected from the group of methacrylic acid alkyl ester monomers having a carbon number of 5 and methacrylic acid fluoroalkyl ester monomers having an alkyl group of 6 to 15 carbon atoms. A soft contact lens material comprising a copolymer obtained by mixing D) 0.5 to 10% by weight of a crosslinkable monomer and (E) 0.5 to 10% by weight of a hydrophilic monomer and polymerizing the mixture.