JPH0823630B2 - Contact lens material - Google Patents

Description

TECHNICAL FIELD The present invention relates to contact lens materials. More specifically, the present invention relates to contact lens materials having high oxygen permeability.

[Prior Art] Conventionally, as a contact lens material, a contact lens material mainly made of polymethyl methacrylate, which is excellent in cutting workability and elasticity and is lightweight, has been used.

However, since the contact lens material made of polymethylmethacrylate has a low oxygen permeability, there is a problem that when the obtained contact lens is worn for a long time, the corneal tissue is impaired in metabolism.

Therefore, in recent years, research and development of contact lens materials having excellent oxygen permeability that can replace polymethylmethacrylate have been made. For example, those mainly composed of silicone rubber such as polydimethylsiloxane, vinyl polymerization of (poly) organosiloxane, etc. It is obtained by introducing a group and then polymerizing it with another vinyl monomer.

Although a contact lens material mainly composed of silicone rubber such as polydimethylsiloxane has excellent oxygen permeability, it exhibits water repellency and is therefore usually used after being subjected to a discharge treatment or the like.

However, even if the hydrophilic treatment as described above is applied, the hydrophilicity decreases during use, and since the material is flexible, there is a phenomenon that it is adsorbed to the eye and causes corneal damage. There is.

(Poly) organosiloxane with a vinyl polymer group introduced and copolymerized with other vinyl monomers has oxygen permeability mainly derived from the organosiloxane site, so that it has less oxygen permeability than silicone rubber. It is possible to improve the oxygen permeability of a highly transparent and transparent acrylic resin, help the absorption of oxygen in the cornea when worn as a contact lens, and prevent the deterioration of corneal function due to lack of oxygen.

However, in order to copolymerize a (poly) organosiloxane having a vinyl polymerizable group introduced therein with an acrylic monomer and to impart sufficient oxygen permeability to the contact lens, the monomer must be added in a large amount. As a result, the obtained copolymer has a problem that the machinability at the time of manufacturing a contact lens is poor and the toughness of the lens is poor. On the other hand, in order to maintain the hardness that can withstand machining during lens manufacturing, it is not possible to add a large amount of (poly) organosiloxane with a vinyl polymer group introduced. A contact lens material having sufficient oxygen permeability to achieve this cannot be obtained.

In recent years, contact lenses using an ester of fumaric acid have been developed. For example, Japanese Patent Application Laid-Open No. 61-176909 discloses a contact lens obtained by copolymerizing a mono- or dialkyl fumarate with a conventional (meth) acrylic acid ester. Japanese Laid-Open Patent Publication No. 61-279821 discloses a contact lens comprising a copolymer of an ester of fumaric acid such as alkyl, phenyl and benzyl and a (meth) acrylic acid-based cross-linking agent. In these publications, fumaric acid diester is disclosed. As the t-
It is stated that butyl fumarate is preferably used.

However, since the yield of di-t-butyl fumarate during synthesis is low, the obtained contact lens is inevitably expensive, and it is solid (melting point is about 70 ° C.) at room temperature. Therefore, when it is copolymerized with another monomer, it must be heated in order to melt it, which not only complicates the polymerization operation, but also causes another monomer to start the polymerization by heating.

[Problems to be Solved by the Invention] Therefore, the present inventor has solved the above-mentioned problems of the prior art, has a desired hardness and hardness as a hard contact lens, and has a higher oxygen permeability. As a result of intensive studies to develop a hard contact lens which has good workability and is inexpensive, isopropyl-t-butyl fumarate and / or cyclohexyl-t-butyl fumarate is added to 30 parts of 100 parts by weight of fumaric acid ester.
When a copolymer of a monomer mixture added in an amount of not less than 1 part by mole is used, the monomer mixture is inexpensive, workability is good, and the copolymer exhibits excellent oxygen permeability,
Moreover, we found the fact that it has appropriate mechanical strength,
The present invention has been completed.

[Means for Solving the Problems] That is, the present invention contains isopropyl-t-butyl fumarate and / or cyclohexyl-t-butyl fumarate and a silicon-containing fumarate, And / or cyclohexyl-t-butyl fumarate relates to a contact lens material comprising a copolymer of a comonomer mixture in which fumaric acid is added in an amount of 30 parts by mole or more based on 100 parts by mole of the fumaric acid ester.

[Example] The contact lens material of the present invention is isopropyl-t
-Butyl fumarate (hereinafter referred to as IPTBF) and / or cyclohexyl-t-butyl fumarate (hereinafter referred to as CH
TBF) and a silicon-containing fumarate,
Total IPTBF and / or CHTBF is 10 total fumaric acid ester
It is composed of a copolymer of a monomer mixture in which 30 parts by mole or more is added to 0 parts by mole.

The IPTBF has the formula: CHTBF is represented by the formula: Is a compound represented by.

Examples of the monomers other than IPTBF and CHTBF used in the present invention include bis (silicon-containing alkyl) fumarate, other dialkyl fumarate, bis (fluoroalkyl) fumarate, alkyl (fluoroalkyl) fumarate, alkyl (silicon-containing alkyl) fumarate. , Fluoroalkyl (alkyl containing silicon)
Examples thereof include fumarate, alkyl (hydroxyalkyl) fumarate and monoalkyl fumarate.

The bis (silicon-containing alkyl) fumarate has the general formula: (In the formula, R ₁ and R ₂ are respectively (X ₁ , Y ₁ and Z ₁ are -R ₃ or R3 is an alkyl group phenyl group having 1 to ₃ carbon atoms, q is 2 or 3), (X ₂ , Y ₂ and Z ₂ are each -R ₃ (R ₃ is the same as above),-
OZ ₃ (Z ₃ is a general formula: R ₄ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and r represents an integer of 2 to 4) and (X ₁ , Y ₁ and Z ₁ are the same as defined above), -Si (OSi (CH ₃ ) ₃ ) _3-s (OSiH (CH ₃ ) ₂ ) _s (s
Represents an integer of 1 to 3) and -Z ₃ (Z ₃ is the same as above)
A group selected from the group consisting of, n ₁ and n ₂ are each 1
Or 3, p ₁ and p ₂ each represent 0 or 1), and specific examples of the bis (silicon-containing alkyl) fumarate include bis (trimethylsilylpropyl) fumarate and bis (pentamethyl). Disiloxanylpropyl) fumarate, bis ((trimethylsilyloxy) tetramethyldisiloxanylpropyl) fumarate, bis ((trimethylbis (trimethylsilyloxy) disiloxanyl) propyl) fumarate, bis ((tetrakis (trimethylsilyloxy)
Trimethyltrisiloxanyl) propyl) fumarate,
Examples thereof include bis (tetramethyltriisopropylcyclotetrasiloxanylpropyl) fumarate and bis (tetramethyltriisopropylcyclotetrasilyloxybis (trimethylsilyloxy) silylpropyl) fumarate. Among these bis (silicon-containing alkyl) fumarate, the general formula: A bis (silicon-containing alkyl) fumarate represented by (in the formula, X ₃ represents a methyl group or a trimethylsilyloxy group, respectively) can be preferably used because its synthesis is easy and purification is easy.

The other dialkyl fumarate has the general formula: (In the formula, each of R ₅ and R ₆ is a straight chain having 1 to 13 carbon atoms,
A branched or cyclic alkyl group) is used, and specific examples of such dialkyl fumarate include diethyl fumarate, dipropyl fumarate, diisopropyl fumarate, dibutyl fumarate,
Linear or branched dialkyl fumarate such as ditertiary butyl fumarate, dipentyl fumarate, dioctyl fumarate, ditertiary amyl fumarate, didodecyl fumarate, di (2-ethylhexyl) fumarate, dicyclohexyl fumarate, Examples thereof include cyclic alkyl fumarate such as bis (tert-butylcyclohexyl) fumarate and bis (trimethylcyclohexyl) fumarate.

As the bis (fluoroalkyl) fumarate,
General formula: (In the formula, R ₇ and R ₈ are —C _a H _b F _{2a + 1-b} , a is an integer of 1 to 21, b is 0 or _1, and m ₁ and m ₂ are each an integer of 0 to 3. ) Is used, and specific examples of the bis (fluoroalkyl) fumarate include bis (trifluoroethyl) fumarate, bis (tetrafluoropropyl) fumarate, bis (hexafluoroisopropyl) fumarate, and bis (octa Examples thereof include fluoropentyl) fumarate and bis (dodecafluoroheptyl) fumarate. Among these bis (fluoroalkyl) fumarates, bis (trifluoroethyl) fumarate, bis (hexafluoroisopropyl)
Fumarate, bis (tetrafluoropropyl) fumarate, bis (octafluoropentyl) fumarate and the like can be preferably used since the monomer can be easily synthesized and the monomer raw material can be easily obtained.

Examples of the alkyl (fluoroalkyl) fumarate include the general formula: (In the formula, R ₅ is the same as above, R ₉ is CH _{2 k} C _a H _b F
_{2a + 1-b} (in the formula, a and b are the same as above, k represents an integer of 0 to 3), and specific examples of the alkyl (fluoroalkyl) fumarate are as follows. Is methyl (trifluoroethyl) fumarate, ethyl (trifluoroethyl) fumarate, isopropyl (trifluoroethyl) fumarate, tertiary butyl (trifluoroethyl) fumarate, octyl (trifluoroethyl) fumarate, cyclohexyl (trifluoroethyl) Fumarate, methyl (hexafluoroisopropyl) fumarate, ethyl (hexafluoroisopropyl) fumarate, isopropyl (hexafluoroisopropyl) fumarate, tertiary butyl (hexafluoroisopropyl) fumarate, octyl (hexafluorooi) Sopropyl) fumarate, cyclohexyl (hexafluoroisopropyl) fumarate,
Methyl (octafluoropentyl) fumarate, ethyl (octafluoropentyl) fumarate, isopropyl (octafluoropentyl) fumarate, tertiary butyl (octafluoropentyl) fumarate, octyl (octafluoropentyl) fumarate, cyclohexyl (octafluoropentyl) fumarate, etc. Can be given.

Examples of the alkyl (silicon-containing alkyl) fumarate include the general formula: (In the formula, R ₅ is the same as above, R ₁₀ is (In the formula, 1 is 1 or 3, and A is -CH ₃ or, respectively. Are used as the alkyl (silicon-containing alkyl) fumarate, methyl (trimethylsilylpropyl) fumarate, ethyl (trimethylsilylpropyl) fumarate,
Isopropyl (trimethylsilylpropyl) fumarate, tertiary butyl (trimethylsilylpropyl)
Fumarate, octyl (trimethylsilylpropyl) fumarate, cyclohexyl (trimethylsilylpropyl) fumarate, methyl (pentamethyldisiloxanylpropyl) fumarate, ethyl (pentamethyldisiloxanylpropyl) fumarate, isopropyl (pentamethyldisiloxanylpropyl) Fumarate, tert-butyl (pentamethylrudisiloxanylpropyl) fumarate, octyl (pentamethyldisiloxanylpropyl) fumarate, cyclohexyl (pentamethyldisiloxanylpropyl) fumarate, methyl ((tetramethyl (trimethylsilyloxy) disiloxanil ) Propyl) fumarate, ethyl ((tetramethyl (trimethylsilyloxy) disiloxanyl) propyl) fumarate, isopropyl ( Tetramethyl (trimethylsilyloxy) disiloxanyl) propyl) fumarate, tert-butyl ((tetramethyl (trimethylsilyloxy) disiloxanyl) propyl) fumarate, octyl ((tetramethyl (trimethylsilyloxy) disiloxanyl) propyl) fumarate, cyclohexyl ((tetramethyl ( Trimethylsilyloxy) disiloxanyl) propyl) fumarate, methyl ((trimethylbis (trimethylsilyloxy) disiloxanyl) propyl) fumarate, ethyl ((trimethylbis (trimethylsilyloxy) disiloxanyl) propyl) fumarate, isopropyl ((trimethylbis (trimethylsilyloxy) disiloxanyl) Propyl) fumarate,
Tert-butyl ((trimethylbis (trimethylsilyloxy) disiloxanyl) propyl) fumarate,
Octyl ((trimethylbis (trimethylsilyloxy) disiloxanyl) propyl) fumarate, cyclohexyl ((trimethylbis (trimethylsilyloxy))
Disiloxanyl) propyl) fumarate and the like.

As the fluoroalkyl (silicon-containing alkyl) fumarate, for example, a compound represented by the general formula: (Wherein R ₉ and R ₁₀ are the same as above) are used. Specific examples of such fluoroalkyl (silicon-containing alkyl) fumarate include trifluoroethyl (trimethylsilylpropyl) fumarate and hexafluoroisopropyl. (Trimethylsilylpropyl) fumarate, octafluoropentyl (trimethylsilylpropyl) fumarate, trifluoroethyl ((tetramethyl (trimethylsilyloxy) disiloxanyl) propyl) fumarate, hexafluoroisopropyl ((tetramethyl (trimethylsilyloxy) disiloxanyl) propyl) fumarate, octa Fluoropentyl ((tetramethyl (trimethylsilyloxy)
Disiloxanyl) propyl) fumarate, trifluoroethyl ((trimethylbis (trimethylsilyloxy)
Disiloxanyl) propyl) fumarate, hexafluoroisopropyl ((trimethylbis (trimethylsilyloxy) disiloxanyl) propyl) fumarate, octafluoropentyl ((trimethylbis (trimethylsilyloxy) disiloxanyl) propyl) fumarate and the like.

IPTBF, CHTBF, bis (silicon containing alkyl) fumarate, other dialkyl fumarate, bis (fluoroalkyl) fumarate, alkyl (fluoroalkyl) fumarate, alkyl (silicon containing alkyl) fumarate, fluoroalkyl (silicon containing alkyl)
Among the fumarate, bis (silicon-containing alkyl) fumarate, fluoroalkyl (silicon-containing alkyl)
When using a silicon-containing fumarate such as fumarate, alkyl (silicon-containing alkyl) fumarate,
It is particularly preferably used because a contact lens material having high oxygen permeability can be obtained.

Incidentally, among the above-mentioned various monomers, those which are homopolymerized are only the above IPTBF, CHTBF and the other dialkyl fumarate, and among them, ditertiary butyl fumarate (hereinafter referred to as DTBF), IPTBF and CHTBF are homopolymerizable. Is used because it is very high, but DTBF
As described above, the workability is deteriorated as described above. Therefore, in the present invention, it is necessary to use 30 parts by mole or more of IPTBF and / or CHTBF per 100 parts by mole of the fumarate ester.
When a monomer that is solid at room temperature is used as the other alkyl fumarate, the total amount of fumaric acid ester is
The monomer is adjusted to be used in an amount of 30 parts by mole or less, preferably 20 parts by mole or less in 100 parts by mole.

Since the bis (silicon-containing alkyl) fumarate, bis (fluoroalkyl) fumarate, alkyl (fluoroalkyl) fumarate fluoroalkyl (silicon-containing alkyl) fumarate and alkyl (silicon-containing alkyl) fumarate do not substantially homopolymerize,
The total amount of fumaric acid ester must be 50 parts by mole or less based on 100 parts by mole, and preferably 10 to 45 parts by mole.

In order to impart hydrophilicity to the obtained copolymer and obtain a hard contact lens having good wettability, it is preferable to add a hydrophilic monomer. Examples of such a hydrophilic monomer include N-vinylpyrrolidone, N, N-dimethylacrylamide, 3-methyl-1-buten-3-ol, and the general formula (I): (Wherein R ₅ is the same as above, R ₁₁ is a hydroxyalkyl group having 1 to 8 carbon atoms), and alkyl (hydroxyalkyl) fumarate, monoalkyl fumarate, and the like are listed. One kind or two or more kinds can be selected and used, and among these, alkyl (hydroxyalkyl) fumarate can be preferably used.

Examples of the alkyl (hydroxyalkyl) fumarate represented by the general formula (I) include isopropyl (2-hydroxyethyl) fumarate and ethyl (2-
Hydroxyethyl) fumarate, n-butyl (2-hydroxyethyl) fumarate, ethyl (2-hydroxypropyl) fumarate, isopropyl (2-hydroxypropyl) fumarate, n-butyl (2-hydroxypropyl) fumarate, ethyl (2-hydroxy) Butyl) fumarate, isopropyl (2-hydroxybutyl) fumarate, n-butyl (2-hydroxybutyl) fumarate and the like. Further, instead of using monoalkyl fumarate, alkyl (trimethylsilyl) fumarate may be copolymerized, and after molding, hydrolysis may be performed to remove the trimethylsilyl group. The amount of the hydrophilic monomer used is preferably in the range of about 0 to 20 parts by mol based on 100 parts by mol of the total monomer mixture used for the copolymerization. If a large amount of these hydrophilic monomers is used in an amount exceeding the above range, the oxygen permeability will decrease, which is not preferable.

A crosslinkable monomer is effective for the purpose of stabilizing the specifications and shape of the contact lens such as size and power (frequency) and improving chemical resistance. Specific examples of such crosslinkable monomers include diallyl fumarate, allyl methacrylate, allyl acrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, divinylbenzene and general formula (II). : (In the formula, R ₁₂ and R ₁₃ are each independently a group selected from the above R ₅ , R ₉ and R ₁₀ , X ₄ is a branched or straight chain alkylene group having 1 to 4 carbon atoms, and a general formula -CH ₂ CH ₂ OCH ₂ CH _2
n3 (wherein, n ₃ is an integer of 1-5) or the general formula: (In the formula, R ₁₄ is —CH ₃ or and t represents an integer of 0 to 55), and it is preferable to use one or more selected from these crosslinking agents. Among them, diallyl fumarate and the crosslinking agent represented by the general formula (II) are preferable. The amount of the cross-linking agent used is preferably in the range of 0 to about 20 parts by mol with respect to 100 parts by mol of the total monomer mixture used for the copolymerization.

Instead of or in addition to the use of the hydrophilic monomer, for example, the obtained hard contact lens is subjected to discharge treatment such as corona discharge or plasma discharge, or the hydrophilic monomer is graft-polymerized after the discharge treatment, or hydrochloric acid or By treating with a strong acid such as nitric acid or a strong alkali, it is possible to impart effective hydrophilicity to the surface.

Further, in the present invention, a monomerized dye such as Seikagen-0-Real Black (manufactured by Dainichiseika Co., Ltd.) or 2-hydroxy-5-acryloxyphenyl-2-hydroxybenzo may be used, if necessary. Monomerized UV absorbers such as triazoles can also be used. These are preferably used in an amount of 5% by weight or less in order to maintain high oxygen permeability with respect to the total amount of monomers.

Examples of the method for copolymerizing the monomer mixture include a method in which heating is performed in a temperature range of room temperature to about 110 ° C. to carry out the polymerization by an ordinary radical polymerization method. Examples of the polymerization initiator that can be used include benzoyl peroxide, azobisisobutyronitrile, azobisdimethylvaleronitrile and the like, and one or more of them are selected and used. In addition, the amount used is preferably 0.01 to 1.0 part by mol based on 100 parts by mol of the total amount of the monomer mixture to be copolymerized.

The molding method for forming a contact lens from the monomer mixture can be carried out by a usual method. For example, the copolymerization reaction of the monomer mixture is carried out in a mold corresponding to the shape of the contact lens to directly form the shape of the contact lens, and further, if necessary, mechanically,
For example, finishing processing such as cutting and polishing can be performed. In addition, after performing copolymerization in a suitable mold or container to form a block-shaped, plate-shaped or round bar-shaped material, cutting,
A contact lens having a desired shape may be formed by a usual mechanical processing method such as polishing.

The contact lens thus obtained has more excellent oxygen permeability than the conventional oxygen permeable contact lens, and has appropriate mechanical strength.

Next, the contact lens material of the present invention will be described in more detail based on examples, but the present invention is not limited to only these examples.

Example 1 78 mol parts of CHTBF, 20 mol parts of bis (tristrimethylsiloxysilylpropyl) fumarate, 2 mol parts of ethylene glycol bis (isopropyl fumarate) and 0.1 mol part of benzoyl peroxide as a polymerization initiator were placed in a glass ampoule and depressurized. (10 ^-3 mmHg or less), seal, and 50 ℃
Polymerization was carried out for 48 hours at 60 ° C. for 24 hours and at 70 ° C. for 24 hours. Open the ampoule, take out the obtained polymer, and
Heated at 0 ° C. for 2 hours. The obtained polymer was colorless and transparent. This polymer was cut to obtain a film having a diameter of 15 mm and a thickness of 0.2 mm. The oxygen permeation coefficient of this film was measured in a physiological saline solution at 35 ° C using a Seikaken-type film-oxygen permeation meter to obtain 61.3 x 10 ^-11 [(cm ³ · cm) /
(Cm ² · sec · mmHg)].

Examples 2 to 31 Table 1 shows the results of the same operation as in Example 1 except that the monomer composition was changed as shown in Table 1.

In Table 1, each abbreviation means the following.

DtBF: Ditert-butyl fumarate iP-tBF: Isopropyl-tert-butyl fumarate CH-tBF: Cyclohexyl-tert-butyl fumarate DS ₃ PF: Bis (trimethylsilyloxytetramethyldisiloxanylpropyl) fumarate DS ₄ PF: Bis (Tristrimethylsiloxysilylpropyl) fumarate DF ₃ F: Bis (trifluoroethyl) fumarate DF ₈ F: Bis (octafluoropentyl) fumarate iP-S ₄ F: Isopropyl-tristrimethylsiloxysilylpropyl fumarate iP- F ₃ F: Isopropyl-trifluoroethyl fumarate iP-F ₈ F: Isopropyl-octalfluoropentyl fumarate iP-OS ₄ F: Isopropyl-tristrimethylsiloxysilylproproxyethyl fumarate F ₃ S ₄ F: Trifluoroethyl- To Sutorime chill siloxy silyl propyl fumarate F ₆ S ₄ F: hexafluoroisopropyl - tri string siloxy silyl propyl fumarate iP-HEF: Isopropyl - hydroxyethyl off maleate EGBiPF: Ethylene glycol bis (isopropoxide Pirufumareto) BDBiPF: 2,3- Butanediol bis (isopropylpropyl fumarate) F ₆ S ₂ F: 1,1,3,3-tetramethyl (bis ((11,11,11-trifluoroethyltrimethylene) fumarate) disiloxane [Effect of the invention] The contact lens material of the present invention exhibits better oxygen permeability than conventional contact lens materials, and has appropriate mechanical strength, so there is no problem such as corneal metabolism disorder even when worn for a long time. The effect is that it can be suitably used for contact lenses.

In addition, a desired contact lens can be produced from the contact lens material of the present invention at low cost and efficiently (in good workability) as compared with a conventional contact lens made of a copolymer containing DTBF as a main component.

Claims (2)

[Claims] 1. Isopropyl-t-butyl fumarate and / or cyclohexyl-t-butyl fumarate,
A copolymer of a monomer mixture containing a silicon-containing fumarate and containing the isopropyl-t-butyl fumarate and / or cyclohexyl-t-butyl fumarate in an amount of 30 parts by mole or more based on 100 parts by weight of the fumarate ester. Contact lens material. 2. A silicon-containing fumarate having the general formula: The contact lens material according to claim 1, which contains a fumarate represented by the formula (wherein each X represents a methyl group or a trimethylsilyloxy group).