JPH0699517B2 - Soft contact lens material - Google Patents

Description

The present invention relates to an oxygen-permeable soft contact lens material.

[Conventional technology]

Conventionally, various polymers have been proposed as contact lens materials, which are roughly classified into soft materials and hard materials.
It is well known that a soft material is preferable for obtaining a contact lens having a good wearing feeling.

As such a soft material, there is a hydrous contact lens material that absorbs water, swells, and is softened. Particularly, a high hydrous contact lens that absorbs a large amount of water has high oxygen permeability, and thus is actively studied. However, when the water content is increased in order to increase the oxygen permeability, there is a drawback in that the mechanical strength is poor.

On the other hand, a contact lens made of silicone rubber has a very high oxygen permeability, but has a defect that the surface of the contact lens is extremely water-repellent, and it has been reported to cause serious damage.

On the other hand, measures have been taken to obtain high oxygen permeability with a low water content. For example, JP-A-59-195621 discloses a combination of a long-chain alkyl methacrylate and a hydrophilic monomer such as N-vinylpyrrolidone. With a water content of about 40%, it has about three times the oxygen permeability of soft contact lenses with the same water content as before. Further, as disclosed in Japanese Patent Publication No. 53-31189, a contact lens composed of a copolymer of alkyl methacrylate and alkyl acrylate has been proposed. In particular, a contact lens mainly containing butyl methacrylate and butyl acrylate is proposed. Although a lens has been put into practical use, this lens is not preferable because its oxygen permeability is not so high. Furthermore, JP-A-59-
The soft contact lens of 195621 and the soft contact lens of Japanese Examined Patent Publication No. 53-31189 have the drawback that they are easily contaminated especially by eye oil.

Further, a contact lens containing siloxanyl (meth) acrylate is disclosed in, for example, Japanese Patent Publication No. 52-33502, but a (meth) acrylate having a siloxane bond is weak against hydrolysis and the (meth) acrylate having the siloxane bond is not When the contact lens contained is boiled and sterilized in a water-containing state as required as a sterilization method, there is a drawback that the siloxane bond is gradually cleaved to change the physical properties.

[Problems to be solved by the invention]

The present invention provides a soft contact lens which does not have the drawbacks of the soft contact lens as described above, that is, has a high durability against an operation of boiling disinfection and has high oxygen permeability that does not easily stain. is there.

[Means and Actions for Solving Problems]

That is, the present invention relates to a soft contact lens material characterized by containing 20 parts by weight or more of the radically polymerizable monomer having the formula (I) in 100 parts by weight of the total amount of the polymerizable component.

(Wherein, X is a hydrogen atom or a methyl radical, R is a group represented by the formula (II) or Formula (III).) (II) CH 2 3 O-CH 2 -CH 2 -OH (III) CH ₂ pOCH ₂ CH ₂ OqCH ₃ (In the formula, p is an integer of 3 to 5, and q is an integer of 1 to 4.) The radically polymerizable monomer having the formula (I) used in the present invention (hereinafter referred to as “ The term "component A") is a (meth) acrylate that not only provides a polymer with high oxygen permeability, but also does not have a siloxane bond and thus is not easily hydrolyzed by boiling. Examples thereof include (methoxyethoxyethoxypropyldimethylsilylpropyl) dimethylsilylpropyl (meth) acrylate and 1-methacryloyloxypropyldimethylsilyl-3-hydroxyethoxypropyldimethylsilylpropane.

In order to obtain the effect, the amount of the component A is preferably 20 parts by weight or more, and more preferably 30 parts by weight to 60 parts by weight based on 100 parts by weight of the total amount of the polymerizable monomers. preferable. If the amount used is too small, the oxygen permeability will be low, and if the amount used is too large, the material will have poor mechanical strength.

In the soft contact lens material of the present invention, in addition to the component A, for example, a hydrophilic monomer, a crosslinkable monomer, a monomer for further improving oxygen permeability, or the like can be used.

Examples of the hydrophilic monomer include N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, dimethylacrylamide and the like. Examples of the crosslinkable monomer include allyl methacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and divinylbenzene. Furthermore, oxygen permeability can be further improved by using trifluoroethyl methacrylate, perfluoroisopropoxytetrafluoroisopropyl methacrylate (formula (IV)), octafluoropentyl methacrylate, or the like. In addition, alkyl methacrylate such as methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and the like can be used.

The amount of these used is preferably 10 to 70 parts by weight, and more preferably 20 to 55 parts by weight, of the hydrophilic monomer in order to enhance hydrophilicity, based on 100 parts by weight of the total amount of the polymerizable monomer. The crosslinkable monomer is not always necessary, but it is preferably used in the range of 0.1 to 3.0 parts by weight in consideration of the standard stability and chemical resistance of the soft contact lens. Also,
The monomer used for improving the oxygen permeability can be used in an amount of 40 parts by weight or less. Further, the total amount of monomers other than the component A is preferably 70 parts by weight or less.

The following is an example of the synthesis of component A of the present invention.

There are the following three stages of synthesis.

(R in each formula is the same as formula (I)) Step (1) Synthesis of formula (i) Step (2) Synthesis of formula (ii) Step (3) Synthesis of Formula (I) In step (1), for example, the corresponding allyl compound may be reacted with dimethylallylsilane in a solvent such as cyclohexane in the presence of a platinum catalyst. For example, when R is a methoxyethoxyethoxypropyl group, the corresponding allyl compound is diethylene glycol allyl methyl ether.

In step (2), (i) and chloropropyldimethylsilane may be reacted in the presence of a platinum catalyst in a solvent such as cyclohexane as in step (1).

In step (3), if (meth) acrylic acid and (ii) are reacted in triethylamine, dehydrochlorination occurs to produce (I).

When R has a hydroxyl group, it is also possible to employ a method in which the hydroxyl group is protected with a trimethylsilyl group and then the steps 1, 2 and 3 are synthesized, and then detrimethylsilylation is performed to restore the hydroxyl group. . By doing so, the boiling point of the intermediate purified product is lowered, and the purification by distillation becomes easy.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to such embodiments.

(Synthesis example 1) 18.4 g of metallic sodium was added to 500 ml of ethyl ether,
At room temperature, 100 g of diethylene glycol monomethyl ether was added dropwise over 5 hours. After that, the mixture was left to stand overnight and completely reacted. Next, while heating the reaction mixture under reflux, 76.5 g of allyl chloride was added dropwise over 2 hours and then stirred for 4 hours to complete the reaction. The reaction solution was separated from salts by suction filtration, dried over magnesium sulfate overnight, distilled to remove ether, and distilled under reduced pressure to obtain diethylene glycol allyl methyl ether.

Obtained diethylene glycol allyl methyl ether 40
A mixture of 4 g of cyclohexane, 50 g of cyclohexane and 1 g of chloroplatinic acid in 30 ml of isopropanol was brought to reflux temperature, and a solution of 25 g of dimethylallylsilane diluted with 20 g of cyclohexane was added dropwise over 2 hours. After this, 3 more
The reaction was carried out at reflux temperature for hours. After the reaction, n-hexane 200m
l, and washed twice with 5% aqueous sodium carbonate solution,
Anhydrous magnesium sulfate was added to the hexane layer washed once with water and dried overnight. After removing hexane by distillation, methoxyethoxypropylallyldimethylsilane was obtained by vacuum distillation.

Next, methoxyethoxypropyl allyldimethylsilane
A mixture of 40 g of cyclohexane, 50 g of cyclohexane and 1 g of chloroplatinic acid in 30 ml of isopropanol was heated to 60 ° C, and a solution of 8.5 g of chloropropyldimethylsilane diluted with 10 ml of cyclohexane was added dropwise over 25 minutes. Then, the reflux was continued for another 4 hours. N-hexane in the reaction solution
200 ml was added and the mixture was washed twice with a 5% aqueous sodium carbonate solution and then once with water. After removing hexane by distillation, 1- (chloropropyldimethylsilyl)-
3- (Methoxyethoxyethoxypropyldimethylsilyl) propane was obtained.

Furthermore, 1- (chloropropyldimethylsilyl) -3- (methoxyethoxyethoxypropyldimethylsilyl) propane 50g, methacrylic acid 28g, triethylamine 38.2g,
A mixture of 100 g of dimethylformamide and 0.4 g of hydroquinone was heated to a reflux temperature (125 ° C.) and stirred for 16 hours to react. Thereafter, 500 ml of n-hexane was added to the reaction solution, and the mixture was washed twice with a 5% aqueous sodium carbonate solution and then once with water. Anhydrous magnesium sulfate and activated carbon were added to the hexane layer, and the mixture was left overnight, dried and decolorized. After this solution was filtered, the solvent was completely removed to obtain 1- (methacryloyloxypropyldimethylsilyl) -3- (methoxyethoxyethoxypropyldimethylsilyl) propane (hereinafter referred to as "silyl monomer").

(Synthesis Example 2) A mixture of 102 g of ethylene glycol allyl ether, 111.1 g of triethylamine, and 300 g of n-hexane was ice-cooled. To this, 119.35 g of trimethylchlorosilane was added dropwise over 2 hours while the reaction liquid was kept at 10 ° C or lower with stirring. After completion of the dropping, the mixture was stirred for 30 minutes while cooling with ice, then heated to 50 ° C. and stirred for 3 hours to obtain a reaction liquid. The reaction solution was suction filtered to separate the hydrochloride, and the filtrate was washed with water. Anhydrous magnesium sulfate was added to this and dried overnight. After removing hexane by distillation, vacuum distillation was performed to obtain trimethylsiloxyethyl allyl ether.

Next, trimethylsiloxyethyl allyl ether 34.8
g, cyclohexane 40 g and a solution of 3 g of a solution of chloroplatinic acid 1 g dissolved in 30 ml of isopropanol were heated to 60 ° C. and 20 g of dimethylallylsilane was added to cyclohexane 2
The solution diluted with 0 g was added dropwise over 2 hours, and then the reaction was continued for another 4 hours. 300 ml of n-hexane was added to the reaction solution, which was washed twice with a 5% aqueous sodium carbonate solution and then once with water, anhydrous magnesium sulfate was added, and the mixture was dried overnight. After removing hexane by distillation, trimethylsiloxyethylpropylallyldimethylsilane was obtained by vacuum distillation.

Next, 29 g of trimethylsiloxyethylpropylallyldimethylsilane, 40 g of cyclohexane and 1 g of chloroplatinic acid were added.
A mixture of 3 drops of a solution in 30 ml of isopropanol
Heat to 60 ° C and add to it chloropropyldimethylsilane 1
A solution prepared by diluting 4.45 g with 17 g of cyclohexane was added dropwise over 40 minutes, and then stirring was continued for another 4 hours. N in the reaction solution
-Hexane (300 ml) was added, and the mixture was washed twice with a 5% aqueous sodium carbonate solution and then once with water. Anhydrous magnesium sulfate was added and the mixture was dried overnight. After removing hexane by distillation, vacuum distillation was performed to obtain 1-chloropropyldimethylsilyl-3-trimethylsiloxyethoxypropyldimethylsilylpropane.

In addition, 1-chloropropyldimethylsilyl-3-trimethylsiloxyethoxypropyldimethylsilylpropane 28
A mixture of g, methacrylic acid 20.19 g, triethylamine 20.66 g, dimethylformamide 70 g and hydroquinone 0.1 g was heated to a reflux temperature (125 ° C.) and stirred for 12 hours to cause a reaction. After cooling the reaction solution, the hydrochloride was separated by suction filtration. Thereafter, 500 ml of n-hexane was added to the reaction solution, and the solution was washed 3 times with a 5% aqueous sodium carbonate solution and then once with water. The solvent of this solution was completely removed. The obtained compound was dissolved in a mixed solvent of 20 g of water and 80 g of ethanol and refluxed for 4 hours to eliminate the trimethylsilyl group, and 1-methacryloyloxypropyldimethylsilyl-3-hydroxyethoxypropyldimethylsilylpropane (hereinafter referred to as " Silyl monomer II ") was obtained.

(Example 1) 50 parts by weight of a silyl monomer, 25 parts by weight of N-vinylpyrrolidone, 25 parts by weight of 2-hydroxyethyl methacrylate and 0.4 parts by weight of allyl methacrylate were dissolved in a mixture of 0.2 parts by weight of dimethylvaleronitrile as a polymerization initiator,
It was sealed in a silane-treated glass test tube having an inner diameter of 15 mm.
This test tube is heated in a constant temperature water layer at 40 ° C for 16 hours and at 50 ° C for 8 hours, and then in a circulation dryer at 50 ° C for 4 hours, 60 hours.
Polymerization was completed by heating at 70 ° C, 70 ° C, 80 ° C, 90 ° C, 100 ° C, and 110 ° C for 1.5 hours each. The polymerized bar was taken out of the test tube and heated at 90 ° C. for 2 hours.

This was subjected to cutting work, and was sufficiently absorbed in water to obtain a sample. The results are shown in Table 1 together with other examples. In addition, the measuring method and unit of each physical property in Table 1 are as follows.

Moisture content ・ Measurement temperature: 20 ℃ ・ Unit:% ・ Calculation formula Equilibrium water content film weight = W1 Dry film weight = W2 Oxygen permeability coefficient ・ Measurement temperature: 35 ℃ ・ Measuring instrument: A Kaken film oxygen permeability meter (Rika Seiki Co., Ltd.) is used.

Punching strength (method described in Japanese Patent Application No. 61-182528) ・ Measuring temperature: room temperature ・ Unit: g ・ Measuring method Using an Instron type compression tester, press a needle with a diameter of 1/16 inch to the center of the film ( An indenter) was applied to measure the load at break.

Elongation rate (method described in Japanese Patent Application No. 61-182528) ・ Measurement temperature: Room temperature ・ Unit:% ・ Measurement device Same as punching load (measured simultaneously). The amount of elongation up to break is calculated as a percentage.

(Examples 2 to 13) The operation was performed in the same manner as in Example 1 except that the composition of the monomers was different. The results are shown in Table 1 together with Example 1.

(Example 14) Staining test with artificial eye oil The following formulation was added, polymerized in the same manner as in Example 1, and cut to obtain a sample film having a thickness of 0.2 mm.

Composition Table 45 parts by weight of silyl monomer 45 parts by weight of N-vinyl-2-pyrrolidone 45 parts by weight of 2-hydroxyethyl methacrylate 10 parts by weight of allyl methacrylate 0.4 parts by weight Separately, the following components were mixed to prepare artificial eye oil.

Artificial eye fat Tripalmitin 18.18g Cetyl alcohol 6.06g Palmitic acid 12.12g Oleic acid 12.12g Linoleic acid 12.12g Ester wax 18.18g Cholesterol 6.06g Cholesteryl palmitate 6.06g Lecithin 9.10g Put artificial eye oil 1g in 100ml of water at 70 ℃. While keeping the water temperature at 70 ° C., one sample film was put into this while stirring vigorously and stirred for 20 minutes. After that, the sample film was taken out and allowed to cool, and the film surface was washed with a soft contact lens cleaning sponge (trade name "Menicon Puff", manufactured by Toyo Contact Lens Co., Ltd.). The state of the film surface was observed with the naked eye, but adhesion of artificial eye oil was hardly observed.

(Example 15) The operation was performed in the same manner as in Example 14 except that the formulation was changed as follows. As a result, adhesion of artificial eye oil was hardly observed.

Recipe List 35 parts by weight of silyl monomer 35 parts by weight of N-vinyl-2-pyrrolidone 30 parts by weight of 2-hydroxyethyl methacrylate 30 parts by weight of allyl methacrylate 0.4 parts by weight (Comparative example) Water containing N-vinyl-2-pyrrolidone and lauryl methacrylate as main components A soft contact lens material with a rate of about 45% was used as a sample film in the same manner as in Example 14, and a stain test with artificial eye oil was performed.As a result, artificial eye oil adhered to one surface of the sample film, and the sample film was violent. It was transformed. It can be seen that artificial eye oil has penetrated to the inside.

(Test Example) The sample films prepared in Examples 14 and 15 were used as 300
Boiled in water for 500 hours and 500 hours, and observed changes in water content and diameter. The results are shown in the table below, indicating that there is almost no change.

Film of Example 14 Water content Diameter Before boiling 50.2% 12.63mm After boiling for 300 hours 50.1% 12.60mm After boiling for 5 hours 50.8% 12.60mm Film of Example 15 Water content Diameter Before boiling 47.0% 12.41mm After boiling for 4 hours 300% 47.6% 12.38mm 48.4% after boiling for 500 hours 12.40mm [Effect of the invention] The soft contact lens material of the present invention has a large oxygen permeability, is hard to stain, and does not change even when boiled in water. It can be suitably used for lenses.

Claims (1)

[Claims] 1. A soft contact lens material comprising a radically polymerizable monomer having the formula (I) in an amount of 20 parts by weight or more per 100 parts by weight of the total amount of the polymerizable component. (Wherein, X is a hydrogen atom or a methyl radical, R is a group represented by the formula (II) or Formula (III).) (II) CH 2 3 O-CH 2 -CH 2 -OH (III) CH ₂ pOCH ₂ CH ₂ OqCH ₃ (In the formula, p is an integer of 3 to 5, and q is an integer of 1 to 4.)