JPS63268714A - Contact lens material - Google Patents

Abstract

PURPOSE:To provide the titled easily producible material having high oxygen permeability and excellent machinability, giving agreeable feeling to eyes and composed of a (co)polymer produced by polymerizing a polyfunctional monomer containing fluorinated alkyl (ether) group. CONSTITUTION:A polyfunctional monomer having fluorinated group on side chain is produced by reacting (A) a compound having plural radically polymerizable functional groups and hydroxyl groups (preferably tetramethylolmethane trimethacrylate, etc.) with (B) a compound of formula RfCOX [Rf is 1-30C fluorinated alkyl (ether) group; X is Cl or F) (e.g. trifluoroacetic acid chloride). The polyfunctional monomer is homopolymerized or >=15wt.% of said polyfunctional monomer is copolymerized with <=85wt.% of copolymerizable monomer and the obtained (co)polymer is used as the objective material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a contact lens material, and more specifically to a contact lens material made of a fluorine-containing polymer with good oxygen permeability.

[Conventional technology and its problems]

Generally, contact lenses are used along with spectacle lenses to correct vision, but at present, there are fewer people who wear contact lenses than people who wear glasses, and the reason for this is the contact lens materials that are commonly used in the past. This is thought to be due to various problems. Polymethyl methacrylate can be mentioned as a material for contact lenses that has been widely used in the past. This polymethyl methacrylate is preferred as a contact lens material because it is easy to machine and has high optical transparency (and excellent durability), but on the other hand, it has too high hardness. They also have problems in that they are uncomfortable to wear and cannot be worn for long periods of time due to their low oxygen permeability.

Hydrogel-based lenses and silicone rubber-based lenses have been proposed as soft lenses that have improved these problems. Hydrogel lenses are preferable in that they have a high water content and high oxygen permeability and provide a good wearing feeling, but on the other hand, they have drawbacks such as low strength and easy to become a culture medium for fungi. Furthermore, it has been pointed out that it is difficult to obtain desired optical characteristics.

Additionally, silicone rubber lenses are soft and have good oxygen permeability, but since this material is essentially non-wetting, contamination with proteins and fats is a problem, and movement on the cornea is a problem. In fact, there have been reports of cases in which serious disorders such as corneal damage occurred in contact lens wearers.

On the other hand, fluororesin is known as a contact lens material with good oxygen permeability.
05, JP 56-118408, JP 59-19918, JP 51-46614, JP 57-211119, JP 54-2
Copolymers such as fluorinated acrylates and fluorinated methacrylates are disclosed in JP-A No. 9660, and JP-A-58-127914 reports polymers in which perfluorooxyalkyl groups are introduced into the main chain. ing. However, these contact lens materials do not necessarily have well-balanced properties in terms of oxygen permeability, hardness, machinability, comfort, etc.

[Purpose of the invention]

The present invention does not have the various drawbacks of conventional contact lens materials, has good oxygen permeability, has excellent machinability, and provides a comfortable wearing feeling. It is an object of the present invention to provide a contact lens material that has the following properties and can be easily manufactured.

[Means to achieve the purpose]

The present invention achieves the above object by using a contact lens material as a polymer or copolymer obtained by polymerizing a polyfunctional monomer having a fluorinated alkyl group or a fluorinated alkyl ether group. It is characterized by a compound having two or more radically polymerizable functional groups and one or more hydroxyl group, and a compound having the general formula (wherein Rt is a fluorinated alkyl group having 1 to 30 carbon atoms or a fluorinated A polyfunctional monomer having a fluorinated group in the side chain obtained by esterification reaction with a compound represented by an alkyl ether group (X represents a chlorine atom or a fluorine atom) is polymerized alone. or obtained by copolymerizing 15% by weight or more of the polyfunctional monomer with 85 or less double wall parts of a monomer copolymerizable with the polyfunctional monomer. It is made of a copolymer.

〔effect〕

The contact lens material of the present invention has a fluorinated alkyl group or alkyl ether group in the side chain, and
Because it is made of a polymer or copolymer containing a polyfunctional monomer having three or more radically polymerizable functional groups as an essential polymerization component, it has a high oxygen permeability and therefore has sufficient oxygen permeability when worn. A contact lens is obtained in which a large amount of oxygen is supplied to the cornea and can therefore be worn for a long period of time. In addition, this contact lens material
In addition to having mechanical strength and flexibility, it is also excellent in that it is less likely to be contaminated by proteins, lipids, etc. because it contains fluorine atoms.

The reason why the contact lens material of the present invention has such excellent properties is that the monomer, which is an essential component of the polymer or copolymer that is the material, contains relatively bulky fluorinated alkyl groups. Alternatively, since it has an alkyl ether group in its side chain, better oxygen permeability due to the fluorine-containing group can be obtained compared to those in which the carbon constituting the main chain is fluorinated. Furthermore, the monomer is easy to produce. Furthermore, since the monomer according to the present invention has two or more radically polymerizable functional groups, the polymer or copolymer thereof is highly crosslinked.
As a result, it is thought that mechanical strength and appropriate flexibility can be obtained.

The present invention will be specifically explained below.

The polymer or copolymer constituting the contact lens material according to the present invention is a specific polyfunctional monomer, that is, a compound having two or more radically polymerizable functional groups and one or more hydroxyl group (hereinafter referred to as "compound l"). ) and a compound represented by the general formula (in the formula, R2 is a fluorinated alkyl group or fluorinated alkyl ether group having 1 to 30 carbon atoms, and X represents a chlorine atom or a fluorine atom) (hereinafter referred to as a "compound"). It consists of a polymer or copolymer whose essential main component is a polyfunctional monomer obtained by esterification reaction of (also referred to as "2").

This polyfunctional monomer is a compound whose one component has both two or more radically polymerizable functional groups and one or more hydroxyl groups! And since the other component is compound (2) represented by the above general formula, the hydroxyl group of compound (1) and the functional group (-OX) as an acid halide of compound H undergo an esterification reaction, and as a result, the side chain It has a fluorinated alkyl group or a fluorinated alkyl ether group and two or more radically polymerizable functional groups.

Since the above polyfunctional monomers are copolymerized alone or together with monomers that can be copolymerized with them (hereinafter also referred to as "copolymerizable monomers"), the resulting polymer or The copolymer has many crosslinked structures formed as a result of polymerization by two or more radically polymerizable functional groups. Therefore, the contact lens material of the present invention obtained in this manner has sufficiently high mechanical strength, so that it can be subjected to desired machining and polishing. Moreover, since the polyfunctional monomer has a fluorinated alkyl group or alkyl ether group in its side chain, it has good oxygen permeability derived from the fluorine atom.

Compound 1 which is a component for obtaining the above polyfunctional monomer
Specific examples of compounds having one or more radically polymerizable functional groups and one or more, specifically 1 to 3, hydroxyl groups include 2-hydroxy-1,3-dimethacryloxypropane, tetramethylol, etc. Methane trimethacrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, N-hydroxyethyl diallyl isocyanurate, 1,2-bis(3-acryloxy-2
-hydroxypropoxy)ethane, 2-hydroxy-1
, 2-bis(3-acryloxy-2-hydroxypropoxy)propane, 2.2-bis(2-(3-methacryloxy-2-hydroxypropoxy)-1-methylethoxyphenyl)propane, 2+2-p-acryloxyphenyl Preferred examples include acryloxy esters, methacryloxy esters, and allyl compounds of polyhydric alcohols such as -p-hydroxyphenylpropane. Of course, the present invention is not limited to these.

In the present invention, the compound (2) to be esterified with the above compound (1), that is, the acid chloride or acid fluoride having a fluorinated alkyl group or a fluorinated alkyl ether group, is is 1 to 30.

Specific examples of such fluorinated alkyl acid chlorides or acid fluorides include, for example, trifluoroacetic acid chloride or fluoride, 1,1,2,3,3°3-hexafluoropropyl-rupoxylisoquacid chloride or fluoride, Perfluoro-n-hexylmethylcarboxylisoquasidochloride or fluoride, perfluoro-n-octylmethylcarboxylic acid chloride or fluoride, perfluoro-n-decanemethylcarbosilic acid chloride or fluoride, perfluoro-n-dodecane Mention may be made of methylcarboxylic acid chloride or fluoride, 1,1.2.2-tetrafluoroethylcarboxylic acid chloride or fluoride, perfluorooctanic acid chloride or fluoride, and mixtures thereof. However, it is not limited to these.

Specific examples of fluorinated alkyl ether acid fluorides include oligomers obtained by oligomerization of perfluoroepoxides such as hexafluoropropylene oxide or tetrafluoroethylene oxide, which have 3 carbon atoms and are represented by the following structural formula.
Mention may be made of acid fluorides of up to 0.

CFa CFt O+CFt CFz O+n
CFx CF These acid fluoride oligomers are
As will be understood from the description of Examples below, it can be obtained by oligomerizing hexafluoropropylene oxide or tetrafluoroethylene oxide using an amine such as cesium fluoride or pyridine as a catalyst.

The above compound (■) includes the Rt group in the above general formula,
That is, a fluorinated alkyl group or a fluorinated alkyl ether group having a carbon number of 1 to 30 is used. When using a compound with a large number of carbon atoms in this R7 group, the compound
This is advantageous in that a contact lens material with better oxygen permeability is obtained, but on the other hand, if one uses a large number of carbon atoms in the Rf group, , since the proportion of radically polymerizable functional groups in the polyfunctional monomer is relatively small,
Polymers or copolymers obtained using such polyfunctional monomers have inferior machinability and polishing properties.Since the number of carbon atoms in this compound It may be selected depending on the purpose of use, etc.

In addition, in the compound (2), the carbon atoms of the Rf group in the general formula may be all or partially fluorinated.

The above-mentioned compound I having two or more radically polymerizable functional groups and one or more hydroxyl groups, and the above-mentioned general formula Rt CO'
It is mixed with the compound (■) represented by X and undergoes an esterification reaction, but this esterification reaction
can be carried out using a dehydrated organic solvent that does not cause a reaction, or can be carried out in a system in which no organic solvent is present. By mixing both Compound I and Compound II, an esterification reaction occurs and hydrogen chloride or hydrogen fluoride is produced, so the reaction can be proceeded by removing this under reduced pressure, but it is more common In this method, a tertiary amine that reacts with hydrogen chloride or hydrogen fluoride to form a salt is present in the reaction system, thereby allowing the ester reaction to proceed. The degree of esterification reaction can be arbitrarily set depending on the oxygen permeability and other properties to be obtained for the target contact lens material, but usually,
It is sufficient to esterify 45 to 100% of all hydroxyl groups.

By the above esterification reaction, a polyfunctional monomer having a fluorinated alkyl group or a fluorinated alkyl ether group in the side chain and two or more radically polymerizable functional groups is obtained.

In the present invention, the polyfunctional monomer thus obtained may be polymerized alone as it is, and the resulting polymer may be used as a contact lens material, or it may be co-polymerized with this polyfunctional monomer. A polymerizable monomer, ie, a multifunctional monomer (details of which will be described later), and a copolymerizable monomer may be polymerized, and the resulting copolymer may be used as a contact lens material. When obtaining the latter copolymer, the proportion of polyfunctional monomers among all monomer components is reduced to 1.
It is necessary to set the content to 5% by weight or more, preferably 20% by weight or more. If this proportion is less than 15% by weight, the resulting contact lens material may not only have low oxygen permeability but also poor machinability and polishability.

However, copolymerizable monomers account for 85% by weight of the total monomer components.
The following excellent effects can be obtained in the resulting contact lens material by using the contact lens material preferably at a ratio of 80 years or less.

(a) A contact lens with improved hydrophilicity and good compatibility with the tear fluid on the cornea can be obtained.

(b) Oxygen permeability is further improved.

(c) Hardness and mechanical strength are further improved.

(d) The refractive index becomes even larger.

Specific examples of copolymerizable monomers mainly used from the above point of view include styrene, α-methylstyrene, p-chlorostyrene,
Aromatic vinyl compounds such as vinyltoluene, vinylnaphthalene, diisopropenylbenzene, isopropenylnaphthalene, p-vinylphenol, methyl p-vinylbenzoate, divinylbenzene, vinylpyrrolidone, butadiene, 4-vinyl-1-cyclohexene, chloride Aliphatic vinyl compounds such as vinyl and vinyl acetate, methyl methacrylate, methyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, glycerin trimethacrylate,
Trimethylolpropane trimethacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane diacrylate, 2-hydroxyethyl acrylate,
Acrylate compounds of aliphatic or aromatic monovalent or polyhydric alcohols such as tetramethylolmethane trimethacrylate, phenyl methacrylate, methacryloxy-polyethoxybenzene, 2,2-bis(4-acryloxy-ethoxyphenyl)propane, or Metafrylate compounds, acrylic acid, acrylamide, methacrylic acid.

Methacrylamide, derivatives of acrylic acid or methacrylic acid such as N-methylolmethacryamide, allyl alcohol, allylphenol/triallyl isocyanurate, diethylene glycol bisallyl carbonate,
Examples include aliphatic or aromatic allyl compounds such as diallyl phthalate.

Among the monomers used as the copolymerizable monomers mentioned above, water-soluble monomers are particularly preferred in that they can impart suitable hydrophilicity to the resulting copolymer. be. Specific examples of such water-soluble monomers include acrylic acid, methacrylic acid, acrylamide, methacrylamide, 2-hydroxyethyl methacrylate,
-Hydroxyethyl acrylate, allyl alcohol,
Vinylpyrrolidone, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2.3-
Dihydroxypropyl acrylate, 2.3-dihydroxypropyl methacrylate, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, 2
-Sulfoethyl acrylate, 2-sulfoethyl methacrylate, 2-sulfamidoethyl acrylate, 2-
Examples include sulfamide ethyl methacrylate and vinyl sulfonic acid.

In addition to the above, in the present invention, as a copolymerizable monomer, acrylic acid-2,2,3,3-tetrafluoropropyl ester, methacryl ll-2,2,3°4.4
．． 4-hexafluorobutyl ester, methacrylic acid trifluoroethyl ester, acrylic acid-2-(perfluoro-n-hexyl)ethyl ester, methacrylic acid-2-(perfluoro-n-octyl)ethyl ester, methacrylic acid-2-(perfluoro-n-hexyl)ethyl ester 2-(perfluoro-n-decane)ethyl ester, acrylic acid-2-(perfluoro-n-
Various fluorinated acrylates or fluorinated methacrylates can be used, such as (dodecane) ethyl ester, methacrylic ester of p-fluorophenol, and perfluorophenyl acrylate. It is preferable to use monomers having these fluorine-containing alkyl groups as copolymerizable monomers, since this can provide the resulting contact lens material with even higher oxygen permeability.

In addition to the above, acryloxypropyltris(trimethylsiloxy)silane, methacryloxypropylpentamethyldisiloxane, methyldi(trimethylsiloxy)silylpropylglycerol methacrylate, methacryloxypropyltris(pentamethyldisiloxanyl)silane, bis(methacryloxy) Acrylate or methacrylate compounds having an organosilane group such as (butyl)tetramethyldisilazane are also useful as copolymerizable monomers that can provide good oxygen permeability.

Of course, in the present invention, the copolymerizable monomers are not limited to the monomers listed above.

That is, in the present invention, a copolymerizable monomer selected from the above monomers or other monomers depending on the purpose of the final contact lens material and others is used. can do.

The contact lens material of the present invention can be obtained by polymerizing the above-mentioned polyfunctional monomer or by copolymerizing a polyfunctional monomer and a copolymerizable monomer, but this polymerization reaction For this purpose, an ordinary radical polymerization method using a radical polymerization initiator is used. In practice, this polymerization reaction uses a mold having a mold space of a desired shape, such as a lens shape, and injects a polyfunctional monomer or a monomer copolymerizable with the polyfunctional monomer into the mold. , the polymerization reaction can be carried out within this mold. According to this method, it is possible to easily produce a contact lens material having a desired final shape in a single step.

The contact lens material of the present invention obtained by the above polymerization reaction can be subjected to machining or polishing using known techniques. Therefore, by the above-mentioned polymerization reaction, a contact lens material consisting of a rod-shaped, block-shaped or sheet-shaped polymer or copolymer is obtained, which is then cut into pieces.
It is also possible to manufacture contact lenses by performing mechanical processing such as polishing.

As described above, the contact lens material of the present invention is obtained by polymerizing a polyfunctional monomer having a fluorinated alkyl group or a fluorinated alkyl ether group in its side chain and having crosslinking properties as a polymerization component. Since it is made of a polymer or copolymer, it has good oxygen permeability and antifouling properties, and has excellent mechanical strength, making it tough and easy to machine and polish. contact lenses.

〔Example〕

The present invention will be described in detail below, but the present invention is not limited thereto.

Example 1 5 g of cesium fluoride heated and dried with a heater,
Dehydrated distilled diethylene glycol dimethyl ether 5
The temperature was controlled at 25 to 30° C., and about 600 d of hexafluoropropylene oxide dried with calcium chloride was slowly added thereto to perform oligomerization. Then, by distillation under reduced pressure, a colorless and transparent hexafluorinated propylene oxide oligomer represented by the following structural formula was obtained.

CF s CF 3 CF s CF * -CF x -0+ CF
CF z O÷nCF-CF This oligomer has a boiling point of 280 to 300°C or less when converted to normal pressure, and as a result of analysis, the value of n in the above formula is 6 or less, with an average of about n = 4.2. It was something.

Next, 300 g of A7Tone, 6.4 g of 2-hydroxy-t-acryloxy-3-methacryloxypropane, and 3.64 g of triethylamine were mixed, and the mixture was heated at a temperature of 0 to 5°C.
Cooled to . To this, 30.8 g of the above-mentioned 6-fufluorinated propylene oxide oligomer was slowly added dropwise to carry out the esterification reaction, and after removing the generated salt by filtration, acetone and triethylamine were removed in vacuo. A pale yellow polyfunctional monomer, which is a difunctional radically polymerizable monomer having a fluorinated alkyl ether group in its chain, was obtained.

20 g of the polyfunctional monomer obtained as above, 30 g of methyl methacrylate, and 15 g of vinylpyrrolidone.
and 35 g of 2,2,3.4,4.4-hexafluorobutyl methacrylate were added and mixed, and after adding 0.6 g of lauroyl peroxide as a polymerization initiator, a polymerization reaction was carried out at 60° C. for 16 hours. A rod-shaped contact lens material made of a pale yellow transparent copolymer was obtained.

This contact lens material has excellent machinability and can be polished, and contact lenses could be obtained extremely easily by cutting and polishing.

The physical properties of this contact lens material are as follows.

Parallel light transmittance 87% Specific gravity 1.393 Refractive index 1.444 Oxygen transmittance 2.6X10-th cc・CIl/clI!
・sec・IIMHgThe parallel light transmittance here is “
Haze meter (HAZE female TER) TC-Hl[
[J (manufactured by Tokyo Juishiki Co., Ltd.), the refractive index is the value measured using "Atsube Refractometer Type 3" (manufactured by Atago Co., Ltd.) at a temperature of 20°C, and the oxygen permeability is the value measured using the Seikaken method. This is a value measured using an oxygen permeability meter.

As is clear from these physical property values, this contact lens material has excellent oxygen permeability and machinability.

In addition, the same monomer composition as above was dissolved in a 100-layered wall portion and 1.0 parts by weight of lauroyl peroxide as a polymerization initiator was placed in a glass mold having a mold space in the shape of a contact lens. When the polymerization reaction was carried out at a temperature of 60° C. for 10 hours and then at 80° C. for 4 hours, it was possible to directly produce a pale yellow transparent contact lens.

Example 2 35 g of the same polyfunctional monomer as obtained in Example 1, 15 g of vinylpyrrolidone, 30 g of methacryloxypropylpentamethyldisiloxane, 2°2,2-)
20 g of refluoroethyl methacrylate was mixed and polymerized according to a method similar to Example 1 to obtain a rod-shaped contact lens material made of a pale yellow transparent copolymer.

This contact lens material has excellent machinability and can be polished, and contact lenses could be obtained extremely easily by cutting and polishing.

The physical properties of this contact lens material are as follows.

Parallel light transmittance 90% Specific gravity 1.374 Refractive index 1.442 Oxygen transmittance 36 x 10-th cc-CIII10
I112·sec·lIIIIII (g Example 3 34.8 g of 2-hydroxy-1,2-bis(3-acryloxy-2-hydroxypropoxy)propane, which is a diacrylate compound having three hydroxyl groups in the molecule, was mixed with 300 g of acetone. 30.36 g of triethylamine was added to this solution and cooled to a temperature of 0 to 5°C.

To this, 99.1 g of perfluoro-〇-hexylmethylcarboxylic acid O-yide (Ch F +
s CHz COCJ ) was slowly added southward to carry out the esterification reaction. After filtering off the generated salt and removing acetone and triethylamine in vacuum, 2
A functional radically polymerizable monomer was obtained.

Ch F r a C in the side chain obtained in this way
70 g of a bifunctional monomer having an Hz group was mixed with 10 g of methyl methacrylate and 20 g of vinylpyrrolidone, and 0.6 g of lauroyl peroxide was added thereto and reacted at 60°C for 16 hours to form a copolymer round. A rod-shaped contact lens material was obtained.

This contact lens material has excellent machinability and can be polished, and contact lenses could be obtained extremely easily by cutting and polishing.

The physical properties of this contact lens material are as follows.

Parallel light transmittance 87% Specific gravity 1.459 Refractive index 1.428 Oxygen transmittance 31 X 10-” cc-cm/c
m''-sec-wllllHg or more, it is clear that this copolymer is a contact lens material with excellent properties.

Example 4 According to the method for producing a polyfunctional monomer in Example 3, 2
-hydroxy-1,3-dimethacryloxypropane,
Perfluoro-n-hexylmethylcarboxylisoquasidochloride is subjected to an esterification reaction in an equimolar ratio, whereby 2 having a fluorinated alkyl group in the side chain
A functional radically polymerizable monomer was obtained.

0 parts by weight of lauroyl peroxide in 100 parts by weight of this monomer.
．． 6 parts by weight were dissolved and a polymerization reaction was carried out at a temperature of 60° C. for 16 hours to obtain a rod-shaped contact lens material made of a polymer.

This contact lens material is hard and has excellent machinability, and is also easy to polish, making it easier to obtain contact lenses.

The physical properties of this contact lens material are as follows.

Parallel light transmittance 88% Specific gravity 1.523 Refractive index 1.414 Oxygen transmittance 40X 10-” cc-cm/ct
az-sec-mtaHgAs described above, the present invention has good oxygen permeability, excellent machinability, and provides a comfortable feeling when worn. However, it is possible to provide a contact lens material that can be easily manufactured.

Claims (1)

[Scope of Claims] 1) A compound having two or more radically polymerizable functional groups and one or more hydroxyl group, and a compound having the general formula R_fCOX (wherein R_f is a fluorinated alkyl group having 1 to 30 carbon atoms or a fluorinated A polyfunctional monomer having a fluorinated group in the side chain obtained by esterification reaction with a compound represented by an alkyl ether group (X represents a chlorine or fluorine atom) is polymerized alone. A polymer obtained by
or a copolymer obtained by polymerizing 15% by weight or more of the polyfunctional monomer and 85% by weight or less of a monomer copolymerizable with the polyfunctional monomer. contact lens materials. 2) The monomer copolymerizable with the polyfunctional monomer is (a) a monomer soluble in water, (b) a monoacrylate or monomethacrylate having a fluorine-containing alkyl group, and (c) an organosilane group. Contact lens material according to claim 1, characterized in that it is selected from acrylates and methacrylates.