JPH0511220A - High oxygen permeability contact lens - Google Patents

Abstract

PURPOSE:To provide the contact lens which has an excellent effect of correcting sight, has high oxygen permeability and allows long-term continuous wearing by forming the contact lens from a copolymer of specific fumaric diester and specific styrene deriv. CONSTITUTION:This contact lens consists of the copolymer obtd. by polymerizing the raw material monomers consisting essentially of the fumaric diester of formula I and the styrene deriv. of formula II. In the formula I, X and Y are the same or different groups and denote >=3C branched alkyl group, >=4C cycloalkyl group, >=4C cycloalkyl group having >=3C branched alkyl group, or aryl group having >=3C alkyl group, etc. In the formula II, Z denotes 1 to 12C fluoroalkyl group, 4 to 10C cyclofluoroalkyl group, 4 to 10C cyclofluoroalkyl group having 1 to 12C fluoroalkyl group, or aryl group having 1 to 12C fluoroalkyl group, etc.; n denotes 1 to 5 integer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly oxygen permeable contact lens which is excellent in heat resistance and stain resistance and has high selective permeability.

[0002]

2. Description of the Related Art Conventionally, as contact lenses, oxygen permeable hard contact lenses and water-containing soft contact lenses are known.

Although the above-mentioned water-containing soft contact lens has the characteristics that it easily fits in the eyes and is excellent in wearing sensation, the oxygen permeability of the contact lens material is insufficient. Therefore, a method of increasing the water content of the contact lens material has been considered in order to improve the oxygen permeability, but there is a problem that it is easily contaminated by various bacteria and causes complications to the cornea and conjunctiva. On the other hand, oxygen-permeable hard contact lenses have characteristics such as high oxygen permeability, astigmatism correction effect, durability, and safety, and are becoming the mainstream of contact lenses. Along with this, the development of oxygen permeable hard contact lenses is being actively conducted. For example, JP-A-56-39450 discloses a copolymer of a (meth) acrylate having a siloxane group in the side chain and an alkyl (meth) acrylate, and JP-A-57-51705 discloses. , A fluoroalkyl (meth) acrylate-based copolymer, and in JP-A-61-176909, oxygen comprising a cross-linked polymer having a fumaric acid ester skeleton and a (meth) acrylic acid ester skeleton. Transparent contact lenses and the like have been proposed. However, all of the above contact lenses are still insufficient in terms of oxygen permeability, shape stability and stain resistance.

[0004]

The object of the present invention is to have excellent visual acuity correction effect, high oxygen permeability, and long-term continuous wear. Further, the shape stability, stain resistance and durability are improved. An object is to provide an excellent high oxygen permeability hard contact lens.

[0005]

According to the present invention, the following general formula 3

[0006]

[Chemical 3]

(Wherein X and Y are the same or different groups and have a branched alkyl group having 3 or more carbon atoms, a cycloalkyl group having 4 or more carbon atoms, and a carbon having a branched alkyl group having 3 or more carbon atoms. An aryl group having a cycloalkyl group having 4 or more carbon atoms, an alkyl group having 3 or more carbon atoms, or a cycloalkyl group having 4 or more carbon atoms, wherein some or all of hydrogen atoms in the alkyl group or cycloalkyl group are fluorine atoms. And a fumaric acid diester represented by the following general formula 4

[0008]

[Chemical 4]

(In the formula, Z is a fluoroalkyl group having 1 to 12 carbon atoms, a cyclofluoroalkyl group having 4 to 10 carbon atoms, or a cyclofluoroalkyl group having 4 to 10 carbon atoms and having a fluoroalkyl group having 1 to 12 carbon atoms. Group or a fluoroalkyl group having 1 to 12 carbon atoms or an aryl group having a cyclofluoroalkyl group having 4 to 10 or more carbon atoms, and n represents an integer of 1 to 5) (hereinafter referred to as styrene derivative) And a high oxygen-permeable contact lens made of a copolymer obtained by polymerizing a raw material monomer having a main component of 2).

The high oxygen permeable contact lens of the present invention is characterized by comprising a copolymer obtained by polymerizing a raw material monomer containing a specific diester of fumaric acid and a specific styrene derivative as main components. .

The fumaric acid diester used as an essential raw material monomer component in the present invention is the fumaric acid diester 1 represented by the above general formula 3. At this time, X and Y
The alkyl group of has a carbon number of preferably 3 to 12,
The carbon number of the cycloalkyl group is preferably 4-14. Specific examples of the fumaric acid diester 1 include diisopropyl fumarate, disec-butyl fumarate, diisobutyl fumarate, ditert-butyl fumarate, ditert-amyl fumarate, and di (3-pentyl fumarate). ), Di (2,3-dimethyl-2-butyl fumarate), 3-pentyl-tert-amyl fumarate, 3-pentyl-tert-butyl fumarate, 3-pentyl-2,3-dimethyl-2 fumarate. -Butyl, dicyclopentyl fumarate, dicyclohexyl fumarate, di (4-tert-butyl-cyclohexyl) fumarate, isopropyl-sec-butyl fumarate, isopropyl isobutyl fumarate, isopropyl-tert-butyl fumarate, tert-fumarate Butyl-4-methyl-2-pentyl, fumaric acid tert- Chill -n- pentyl, fumaric acid tert- butyl-3-pentyl, ter fumarate
t-butyl-isobutyl, cyclohexyl fumarate-t
tert-butyl, fumaric acid (tert-butyl) -cyclohexyl-tert-butyl, fumaric acid (tert-)
Butyl) cyclohexyl-4-methyl-2-pentyl,
Isopropyl-2,2,2-trifluoroethyl fumarate, isopropyl-1,1,1-trifluoromethyl fumarate, tert-butyl fumarate-1,1,1,3
3,3-hexafluoro-2-pentyl, fumaric acid te
rt-Butyl-1,1,1-trifluoromethyl, tert-butyl-2,2,2-trifluoroethyl fumarate, cyclohexyl fumarate-1,1,1,3,3,3
-Hexafluoro-2-pentyl, fumaric acid tert-
Butyl-cyclohexyl-1,1,1,3,3,3-hexafluoro-2-pentyl and the like can be preferably mentioned.

To prepare the fumaric acid diester 1, for example, fumaric acid is added to isobutene or 2-methyl-butene-1,2,3-dimethyl-in the presence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid. Known esterification reactions such as a method of adding a corresponding olefin such as butene-1, a method of reacting a fumaric acid chloride with a corresponding alcohol, a method of reacting a fumaric acid chloride with an alkali metal alkoxide of the corresponding alcohol, and the like Alternatively, it can be easily obtained by a method such as once converting maleic acid into a maleic acid diester by the above-mentioned esterification reaction and then converting into a fumaric acid diester using an isomerization catalyst such as thiourea or amine. Incidentally, at this time, with respect to the acid group of fumaric acid or maleic acid, the charged amount of olefins, alcohols or alkali metal alkoxides is set to ½ equivalent, and then reacted with different olefins or alcohols, Asymmetric fumaric acid diesters can be synthesized.

In the present invention, the styrene derivative used as an essential raw material monomer component is the styrene derivative 2 represented by the general formula (4). At this time, if the fluoroalkyl group of Z has 13 or more carbon atoms or the cycloalkyl group has 11 or more carbon atoms, the production is difficult. Specific examples of the styrene derivative 2 include 4-
(2 ', 2', 3 ', 3', 3'-pentafluoropropyloxymethyl) styrene, 4- (2 ', 2', 3 ', 3'-tetrafluoropropyloxymethyl) styrene, 4- ( 2 ',
2 ', 3', 3 ', 4', 4 ', 5', 5'-octafluoropentyloxymethyl) styrene, 4- (2 ', 2', 3 ', 3',
4 ', 4', 5 ', 5', 6 ', 6', 7 ', 7'-dodecafluoroheptyloxymethyl) styrene, 4- (2', 2 ', 3',
3 ', 4', 4 ', 5', 5 ', 6', 6 ', 7', 7 ', 8', 8 ', 9',
Preferable examples include 9 ', 10', 10 ', 10'-heptadecafluorodecyloxymethyl) styrene.

To prepare the styrene derivative 2, it corresponds to chloromethylstyrene (the number of chloromethyl groups is 1 to 5) in the presence of a catalyst such as tetranormal butylammonium hydrogensulfate or tetranormal butylammonium bromide. It can be easily obtained by dehydrochlorinating a fluoroalkyl alcohol.

The weight ratio of the diesters 1 to the styrene derivative 2 is preferably 100: 20-40. If the blending ratio is less than 20, oxygen permeability is lowered, and if it exceeds 40, stain resistance and hardness are lowered, which is not preferable.

In the present invention, examples of the monomers other than the diesters 1 and the styrene derivative 2 which can be used as the raw material monomers include, for example, methacrylic acid, methyl methacrylate, allyl methacrylate, maleic acid ester, styrene. And the like can be preferably mentioned. When using a monomer other than the diesters 1 and the styrene derivative 2, the amount used is preferably 50% by weight or less with respect to the entire raw material monomer.

In order to polymerize the above-mentioned polymerizable monomer to prepare a copolymer, it can be easily obtained by a generally used radical polymerization method. Specifically, for example, azobisisobutyronitrile, azo Azo radical polymerization initiators such as biscyclohexanecarbonitrile and azobisvaleronitrile; organic peroxide radical polymerization initiators such as benzoyl peroxide, tert-butyl hiddle peroxide, cumene peroxide, diacyl peroxide; ammonium persulfate , Various radical polymerization initiators such as inorganic radical polymerization initiators such as potassium persulfate or redox radical polymerization initiators such as hydrogen peroxide-sodium hydroxide, solution polymerization, bulk polymerization, emulsion polymerization, suspension Polymerization by general-purpose vinyl monomer radical polymerization such as polymerization and radiation polymerization It can be. At this time, the bulk polymerization method or the suspension polymerization method, which can sufficiently increase the concentration of the polymerizable monomer, is the most preferable because it can increase the molecular weight of the copolymer, and the polymerization method in which impurities are less mixed is preferable. It is preferably used. When the polymerization temperature is higher than the 10-hour half-life temperature of the radical polymerization initiator used,
The polymerization temperature is preferably lower than the 10-hour half-life temperature of the radical polymerization initiator to be used, because the molecular weight of the obtained copolymer becomes small.

The average molecular weight of the copolymer is 10,000.
The range of 0 to 1,000,000 is preferable, and 20,000
The range of 0 to 500,000 is particularly preferable. When the average molecular weight is less than 10,000, the mechanical strength and long-term stability of the obtained film are lowered, and further the hardness is lowered,
Further, if it exceeds 1,000,000, polymerization becomes difficult, which is not preferable.

To prepare the highly oxygen permeable contact lens of the present invention, for example, the above raw material components are copolymerized in a suitable container such as a test tube based on the above copolymerization conditions, and a round bar or block is formed. After obtaining, cutting, a method of machining such as polishing, injecting the raw material components and a polymerization initiator into a desired mold, a method of directly forming a contact lens by template polymerization or pre-based on the copolymerization conditions After the copolymer is produced, it can be obtained by a method of dissolving the copolymer in a suitable solvent and removing the solvent by a casting method.

The oxygen permeability coefficient (DK value) of the highly oxygen permeable contact lens of the present invention is preferably in the range of 20 or more. When the DK value is less than 20, oxygen permeability is lowered and continuous wearing becomes difficult, which is not preferable.

Further, in the present invention, the above-mentioned raw material monomer
A dye, a coloring agent such as a pigment is added to copolymerize, or the coloring agent is dissolved in a solution in which the copolymer is dissolved to prepare a contact lens by the casting method. It is possible to obtain a contact lens that is colored. It is also possible to add additives such as an ultraviolet absorber to the raw material monomer. Furthermore, the highly oxygen permeable contact lens of the present invention can be surface-modified by subjecting it to acid or alkali treatment, low-temperature plasma treatment, or the like, or by graft-polymerizing a hydrophilic monomer by low-temperature plasma treatment. It is also possible to improve the feeling of wearing.

[0022]

The highly oxygen permeable contact lens of the present invention comprises a copolymer of a raw material monomer containing a specific fumaric acid diester and a specific styrene derivative as main components, and therefore has high mechanical strength, heat resistance, and It has excellent physical properties such as surface strength, and has a high oxygen permeability coefficient, so continuous wear is possible. Further, it has excellent properties that it is possible to prevent the deposition of proteins, lipids, inorganic substances such as calcium, etc. on the lens surface, and prevent water from penetrating into the lens.

[0023]

EXAMPLES The present invention will be specifically described below with reference to examples, but the examples do not limit the scope of the present invention.

[0024]

Example 1 tert-butyl-3-pentyl fumarate 25 parts by weight, diisopropyl-2,2,2-trifluoroethyl fumarate 25 parts by weight, 4- (2 ', 2', 3 ', 3',
3'-pentafluoropropyloxymethyl) styrene (F ₅ POMSt) 20 parts by weight methyl methacrylate 20
Parts by weight, 5 parts by weight of allyl methacrylate and 5 parts by weight of methacrylic acid were placed in a glass ampoule and 0.05 parts by weight of perbutyl I (trade name, manufactured by NOF CORPORATION) as a radical polymerization initiator, Further, 50 ppm of quinizaringulin was added as a dye. Then, the ampoule was thoroughly replaced with nitrogen and deaeration under reduced pressure was repeated.
Radical polymerization was carried out at 20 ° C. for 30 hours. After the completion of the polymerization, an annealing treatment was further performed at 120 ° C., and the obtained resin was cut and polished to have a diameter of 12.7 m.
A contact lens having a thickness of m and a thickness of 0.2 mm was prepared. The oxygen permeability and physical properties of the obtained contact lens were measured. The results are shown below. The measurement was performed by the following method.

Oxygen Permeability Coefficient: Zertex Corporation [made by Xertex Corporation, trade name [MODEL
2110] (Multirange Analyzer for Dissolved Oxyge
n)] at 35 ° C in 0.9% physiological saline
The value (cc · cm / cm ² · sec · mmHg) was measured. Contamination resistance: 3 test pieces with a diameter of 12.7 mm and a thickness of 0.2 mm were immersed in a 0.2 wt% saline solution of egg white lysozyme.
It was immersed at 7 ° C. for 24 hours, and the change in absorbance at 280 nm was measured to determine the amount of the egg white lysozyme aqueous solution adhered. Vickers hardness (HV): Measured using a Terasawa MM-2 type ultra-fine hardness meter manufactured by Taiyo Tester Co., Ltd.

[0026]

Examples 2 to 10 Polymerization, contact lenses were prepared and evaluated in the same manner as in Example 1 except that the raw material monomers shown in Table 1 were used. The results are shown in Table 1.

[0027]

Comparative Examples 1 to 3 Polymerization, production of contact lenses and evaluation were carried out in the same manner as in Example 1 except that the raw material monomers shown in Table 1 were used. The results are shown in Table 1.

[0028]

[Table 1]

The abbreviations in the table indicate the following compounds, respectively. tB / 3PF; fumarate -tert- butyl-3-pentyl iP / F ₃ EF; fumaric acid isopropyl-2,2,2
Trifluoroethyl tB / DM3PF; -tert-butyl fumarate-2,
5-Dimethyl-3-pentyl F ₅ POMSt; 4- (2 ′, 2 ′, 3 ′, 3 ′, 3′-pentafluoropropyloxymethyl) styrene F ₄ POMSt; 4- (2 ′, 2 ′, 3 ', 3'-tetramethyl-fluoropropyl oxy) styrene _{F 8 PeOMSt; 4- (2'} , 2 ', 3', 3 ', 4', 4 ',
5 ', 5'-octafluoropentyloxy) styrene _{F 12 HOMSt; 4- (2'} , 2 ', 3', 3 ', 4', 4 ', 5',
5 ', 6', 6 ', 7', 7'-dodecafluoroheptyl oxy) styrene _{F 17 DOMSt; 4- (3 '} , 3', 4 ', 4', 5 ', 5', 6 ',
6 ', 7', 7 ', 8', 8 ', 9', 9 ', 10', 10 ', 10'-heptadecafluorodecyloxymethyl) styrene MMA; methyl methacrylate AMA; allyl methacrylate MA; Methacrylic acid

Claims (1)

What is claimed is: (Claim 1) The following general formula 1 (Wherein X and Y are the same or different groups,
A branched alkyl group having 3 or more carbon atoms, a cycloalkyl group having 4 or more carbon atoms, a cycloalkyl group having 4 or more carbon atoms having a branched alkyl group having 3 or more carbon atoms, an alkyl group having 3 or more carbon atoms, or a carbon number 4 A fumaric acid diester represented by the above aryl group having a cycloalkyl group, wherein a part or all of the hydrogen atoms in the alkyl group or the cycloalkyl group may be substituted with a fluorine atom, and the following general formula: Chemical formula 2 (In the formula, Z is a fluoroalkyl group having 1 to 12 carbon atoms, a cyclofluoroalkyl group having 4 to 10 carbon atoms, and 1 to
A C4 to C10 cyclofluoroalkyl group having a 12 fluoroalkyl group, a C1 to C12 fluoroalkyl group, or an aryl group having a C4 to 10 or more cyclofluoroalkyl group is shown. N is 1
A high oxygen-permeable contact lens comprising a copolymer obtained by polymerizing a raw material monomer having a styrene derivative represented by the formula (1 to 5) as a main component.