JPH04301813A - Soft contact lens - Google Patents

Abstract

PURPOSE:To enhance hardness at the time of containing no water and to enhance oxygen permeability and strength at the time of containing water by polymerizing composition containing a fluorinated monomer, N-vinyl lactam, and unsaturated dicarboxylic alkyl ester, and specifying the water content of the polymer. CONSTITUTION:The composition containing the fluorinated monomer, the N-vinyl lactam, and the mono- or di-alkyl unsaturated dicarboxylate as essential components is polymerized. The water-content of the copolymer is controlled to >=30wt.%. When the fluorinated monomer component is too much, the water content of gel at the time of wetting lowers and when too little, staining resistance lowers, and when the N-vinyl lactam is too much, the mechanical strength of the gel at the time of wetting reduces, and when too little, the water content reduces, and when the ester is too much, the water content of the gel lowers, and when too little hardness and mechanical strength at the time of wetting lowers, therefore, it is preferred to select the composition comprising the 1-50wt.% fluorinated monomer, the 15-90wt.% N-vinyl lactam, and the 1-50wt.% unsaturated dicarboxylic alkyl ester to embody the soft contact lens.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to soft contact lenses. More specifically, it has excellent water absorption and strength,
The present invention also relates to a soft contact lens that has high hardness when anhydrous.

0002

[Prior Art] Various water-containing soft contact lenses have been known, and materials for such contact lenses include 2-hydroxyethyl methacrylate (
Many of them contain alkylene glycol monomethacrylate as a main component and have a water content of about 30 to 40%, such as 2-HEMA). However, since 2-HEMA is hydrophilic, contact lenses containing it as a main component have some degree of wearability, but do not have sufficient oxygen permeability.
It was difficult to wear it continuously for a long time.

[0003] As an improvement on this, for example, N-
A high water content soft contact lens made of a copolymer obtained by copolymerizing vinylpyrrolidone with methyl methacrylate, 2-HEMA, etc. as a main component has been developed and is already on the market. It is a generally known fact that the higher the water content of the material for soft contact lenses, the higher the oxygen permeability.

[0004] For example, soft contact lens materials containing fluorine for the purpose of improving stain resistance include:
JP-A No. 57-211119 discloses a contact lens material made of poly-2-hydroxyethyl methacrylate containing fluorinated alkyl methacrylate, and JP-A No. 63-30820 discloses a contact lens material made of poly-2-hydroxyethyl methacrylate containing a fluorinated alkyl methacrylate. A contact lens material made of a copolymer of N-vinylpyrrolidone and alkyl methacrylate is disclosed.

[0005]

[Problems to be Solved by the Invention] However, although such lenses have excellent oxygen permeability, their strength when hydrated is low, and their durability has not led to their widespread use. Further, in order to manufacture soft contact lenses by cutting a hydrous soft contact lens material, a certain degree of hardness in an anhydrous state is required. Moreover, the higher the hardness, the fewer scratches occur during contact lens processing. Therefore, an object of the present invention is to provide a soft contact lens that has appropriate water content and oxygen permeability, and has high hardness in an anhydrous state.

[0006]

[Means for Solving the Problems] In order to achieve the above object, the present inventors have made extensive studies and have discovered that soft contact lenses made of a copolymer obtained by polymerizing a composition containing a specific monomer as an essential component have a high oxygen content. It was discovered that it has permeability, good gel strength, and high hardness, and the present invention was completed.

That is, the present invention provides a soft contact with a water content of 30% or more, which is made of a copolymer obtained by polymerizing a composition containing as essential components a fluorine monomer, N-vinyl lactam, and a mono- or dialkyl ester of an unsaturated dicarboxylic acid. It's a lens.

The soft contact lens of the present invention is made of a copolymer obtained by polymerizing a composition containing specific monomers as essential components. Among these monomers, examples of fluorine monomers include fluorine monomers. Alkyl (
meth)acrylates, fluorinated hydroxyalkyl(meth)acrylates, fluorinated alkyl itaconates,
Examples include fluorinated alkyl fumarates and fluorinated styrenes. Examples of fluorinated alkyl (meth)acrylates include 2,2,2-trifluoroethyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2, 2,3,3-tetrafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,3.3-pentafluoropropyl acrylate, 2,2,2-trifluoro- 1-trifluoromethylethyl methacrylate, 2,
2,2-trifluoro-1-trifluoromethylethyl acrylate, 2,2,3,3-tetrafluoro-t-
Amyl methacrylate, 2,2,3,3-tetrafluoro-t-amyl acrylate, 2,2,3,4,4,4
-hexafluorobutyl methacrylate, 2,2,3,
4,4,4-hexafluorobutyl acrylate, 2,
2,3,4,4,4-hexafluoro-t-hexyl methacrylate, 2,2,3,4,4,4-hexafluoro-t-hexyl acrylate, 2,2,3,3,4,
4,5,5-octafluoropentyl methacrylate,
2,2,3,3,4,4,5,5-octafluoropentyl acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis(trifluoromethyl)pentyl methacrylate, 2 , 3,4,5,5,5-hexafluoro-2,4-bis(trifluoromethyl)pentyl acrylate, 2,2,3,3,4,4,5,5,6,6
, 7,7-dodecafluoroheptyl methacrylate, 2
, 2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 2-hydroxy-4
,4,5,5,6,7,7,7-octafluoro-6-
Trifluoromethylheptyl methacrylate, 2-hydroxy-4,4,5,5,6,7,7,7-octafluoro-6-trifluoromethylheptyl acrylate,
2-hydroxy-4,4,5,5,6,6,7,7,8
, 9,9,9-dodecafluoro-8-trifluoromethylnonyl methacrylate, 2-hydroxy-4,4,5
, 5,6,6,7,7,8,9,9,9-dodecafluoro-8-trifluoromethylnonyl acrylate, 2-
Hydroxy-4,4,5,5,6,6,7,7,8,8
,9,9,10,11,11,11-hexadecafluoro-10-trifluoromethylundecyl methacrylate, 2-hydroxy-4,4,5,5,6,6,7,7
, 8,8,9,9,10,11,11,11-hexadecafluoro-10-trifluoromethylundecyl acrylate. Further, examples of fluorinated alkyl itaconates, fluorinated alkyl fumarates, and fluorinated styrenes include bis-2,2,2-trifluoroethyl itaconate, t-butyl-(2,2,2-trifluoroethyl itaconate, Examples include fluoro-1-trifluoromethyl)ethyl fumarate, isopropyl-(1,1,2,2-tetrahydroperfluoro)octyl fumarate, and puntafluorostyrene. Among these, 2,2,2-trifluoroethyl methacrylate and 2,2,2-trifluoro-1-trifluoromethylethyl methacrylate having 5 to 10 carbon atoms are preferred. Moreover, these compounds may be used alone or in combination of two or more.

Examples of N-vinyl lactams used as monomers in the present invention include N-vinyl-2-piperidone, N-vinyl-2-pyrrolidone, and N-vinyl-2-pyrrolidone.
2-caprolactam, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-3-methyl-2-piperidone,
N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-4-
Methyl-2-piperidone, N-vinyl-4-methyl-2
-Caprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-piperidone, N
-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-
4,5-dimethyl-2-pyrrolidone, N-vinyl-5,
5-dimethyl-2-pyrrolidone, N-vinyl-3,3,
5-trimethyl-2-pyrrolidone, N-vinyl-5-methyl-5-ethyl-2-pyrrolidone, N-vinyl-3,
4,5-trimethyl-3-ethyl-2-pyrrolidone, N
-vinyl-6-methyl-2-piperidone, N-vinyl-
6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N- Vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl- Examples include 2-caprolactam, and one or a mixture of two or more of these can be used.

Examples of mono- or dialkyl esters of unsaturated dicarboxylic acids as monomers used in the present invention include mono- or dialkyl esters of fumaric acid, mono- or dialkyl esters of maleic acid, mono- or dialkyl esters of itaconic acid, etc. I can give an example. Among these, mono- or dialkyl esters of itaconic acid are preferred from the viewpoint of polymerizability. Examples of mono- or dialkyl itaconic acid esters include monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, monophenyl itaconate, diphenyl itaconate, methylethyl itaconate, methylphenyl itaconate, and itaconate. Examples include ethylphenyl acid, and one type or a mixture of two or more of these can be used.

The soft contact lens of the present invention is obtained by copolymerizing a composition containing the above-mentioned monomer as an essential component; however, if too much fluorine monomer is added, the water content of the gel when swollen decreases, and If it is scratched, the stain resistance tends to decrease, and if there is too much N-vinyl lactam, the mechanical strength of the gel when swollen will be reduced, and if it is too little, the water content will decrease, and the monomer of unsaturated dicarboxylic acid will decrease. Alternatively, if the dialkyl ester is too large, the water content of the gel when swollen decreases, and if it is too small, the hardness in anhydrous state decreases, resulting in decreased machinability and the mechanical strength of the gel when swollen, so it is preferable. is 1 to 50% by weight of fluorine monomer
, more preferably 3 to 40% by weight, preferably 15 to 90% by weight, even more preferably 50% by weight of N-vinyllactam.
~90% by weight, and preferably from 1 to 50% by weight, more preferably from 3 to 30% by weight of mono- or dialkyl esters of unsaturated dicarboxylic acids.

[0012] In addition to these monomers, a difunctional or more functional monomer can be added as a crosslinking agent. For example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetradecaethylene glycol dimethacrylate, tetradecaethylene glycol diacrylate, allyl methacrylate, allyl Acrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, 1,3-butanediol dimethacrylate, 1,3-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,9-nonanediol diacrylate,
1,10-decanediol dimethacrylate, 1,10
-decanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 2,2'-bis[p-(γ-methacryloxy-β-hydroxypropoxy)phenyl]propane, methylenebismethacrylamide, methylenebisacrylamide, These include vinyl methacrylate, triallyl cyanurate, dipentaerythritol hexaacrylate, polyethylene glycol #400 dimethacrylate, polypropylene glycol #400 dimethacrylate, and the like. The above-mentioned crosslinking agent is usually used in an amount of 0.01 to 5.0% by weight, preferably 0.05 to 2.0% by weight of the total composition.

In addition to these essential monomers, other monomers may be added to the extent that the effects of the present invention are not impaired. Examples include hydrophilic monomers such as dimethyl methacrylamide, dimethyl acrylamide, and 2-HEMA, and hydrophobic monomers such as methyl methacrylate, ethyl methacrylate, and styrenes.

When copolymerizing the above composition, when using a polymerization catalyst, for example, benzoyl peroxide, 2,
Catalysts such as 2'-azobisisobutyronitrile, 2,2'-azobismethylisobutyrate, and 2,2'-azobisdimethylvaleronitrile can be used. The addition ratio of the polymerization catalyst is preferably 0.01 to 5% by weight based on the total mixture. Other polymerization methods such as photopolymerization and radiation polymerization may also be used.

Contact lenses may be produced by cutting and polishing the above polymer, or by directly polymerizing a mixture of the monomers in a mold. good. The soft contact lens of the present invention can be obtained by swelling the lens obtained by these methods in physiological saline until it reaches equilibrium. Further, if necessary, a colored lens can be obtained by adding a coloring agent such as a dye or a pigment to the monomer mixture in advance, or by dyeing the lens.

[0016]

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by these in any way. In the examples, all "parts" represent parts by weight, and each physical property was measured in the following manner. Moisture content: A blow dryer with a temperature of 100°C was used. Oxygen permeability coefficient (DK): A Seikaken film oxygen permeability meter manufactured by Rika Seiki Kogyo Co., Ltd. was used. Vickers hardness: Micro hardness meter manufactured by Akashi Seisakusho Co., Ltd. (
Model MVK-F) was used. Tensile test: Conducted in water at 25°C.

Examples 1 to 18, Comparative Examples 1 to 6; 10.0 g of each composition shown in Table 1 and 0.2 g of 2,2'-azobisdimethylvaleronitrile as a catalyst were mixed to make polypropylene. The mixture was placed in a test tube, purged with nitrogen, and then sealed. This was immersed in a constant temperature water bath at 40°C for 24 hours. Next, it was immersed in a constant temperature water bath at 50°C for 24 hours, then transferred to a constant temperature bath at 60°C for 5 hours, further left in a constant temperature bath at 80°C for 2 hours, and finally left in a constant temperature bath at 100°C for 1 hour. After cooling, the polymer was taken out from the test tube, cut, and its hardness was measured. Water content, DK, tensile strength, and appearance were measured after the samples were hydrated in water for 24 hours or more. The results are shown in Table 1. Furthermore, when contact lenses were made by cutting these polymers, all of the polymers were transparent in the lens state.

[0018]

[Table 1]

[0019]

[Effect of the invention] The present invention provides high hardness in anhydrous state.
A soft contact lens having high water content and high strength in a water-containing state can be provided. Since such lenses have high hardness, they have excellent machinability, high strength, and high water content, so they are useful as long-term continuous wear contact lenses with excellent durability.

Claims (1)

[Claims] 1. A soft contact lens with a water content of 30% or more, comprising a copolymer obtained by polymerizing a composition containing as essential components a fluorine monomer, N-vinyl lactam, and a mono- or dialkyl ester of an unsaturated dicarboxylic acid.