JPH0570527A - Contact lens material and contact lens - Google Patents

Abstract

PURPOSE:To obtain the title material having such hardness as to facilitate machining such as cutting and polishing and being desirable for obtaining a low-or medium-water content contact lens by copolymerizing a monomer mixture comprising a specified fluorinated monomer and an amide monomer. CONSTITUTION:100 pts.wt. monomer mixture containing 35-65 pts.wt. fluorinated monomer of formula I (wherein R1 is CH3; R2 is H or CH3; a is 1-9; m is 1-5; n is 4-10; p>=8; q>=0; and p+q=2n+1) (e.g. a compound of formula II) and 30-45 pts.wt. amide monomer [e.g. N,N-dimethyl (meth)acrylamide] as essential components and containing other monomers as optional components is copolymerized. In this way, a contact lens material having such hardness as to facilate machining such as cutting and polishing and being desirable for obtaining a low-or medium-water content contact lens can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a contact lens material and a contact lens, and more particularly to a contact lens material suitable for machining such as cutting and polishing, and a water-containing contact lens obtained from the contact lens material. Is.

[0002]

BACKGROUND ART Contact lenses currently generally used are roughly classified into hydrous contact lenses and non-hydrous contact lenses.

Among hydrous contact lenses, a high hydrous contact lens usually refers to a lens having a water content of 60% or more. However, the high hydrous contact lens has problems such as lack of mechanical strength and easy stain. is there. On the other hand, contact lenses with a water content of less than 60% often have insufficient oxygen permeability in low and medium water content contact lenses. The present inventors have proposed PCT / JP90 / 0 as a high water content contact lens and low / medium water content contact lens of this kind.
The invention described in 0973 (International filing date: July 31, 1990) was proposed.

[0004]

It cannot be said that the high water content contact lenses obtained by the present invention can completely solve the problems of the high water content contact lenses described above. In addition, the copolymers for obtaining low and medium hydrous contact lenses have low hardness,
It cannot be said that it has such an excellent hardness that machining such as polishing can be easily carried out. The present invention has been made to solve the above problems, and an object of the present invention is suitable for obtaining a contact lens having low / medium water content, and is subjected to machining such as cutting / polishing. (EN) Provided is a contact lens material having such a hardness as possible and a low / medium hydrous contact lens obtained from the material.

[0005]

The present invention has been made in order to achieve the above-mentioned object, and in 100 parts by weight of a monomer mixture to be copolymerized, the general formula

[Chemical 2] (In the formula, R ₁ is CH ₃ , R ₂ is H or CH ₃ , and may be the same or different, and a is an integer of 1 to 9,
m is an integer of 1 to 5, n is an integer of 4 to 10, p is an integer of 8 or more, q is an integer of 0 or more, and p + q = 2n + 1. ) At least one fluorine-containing monomer: 35 to 65 parts by weight, and at least one amide group-containing monomer: 30 to 45 parts by weight as essential components, and optionally other monomers. The subject matter is a contact lens material comprising a copolymer obtained by copolymerizing a monomer mixture contained as a component, and a hydrous contact lens obtained by machining this contact lens material.

The present invention will be described in detail below. The amount of each composition component used is important for obtaining the contact lens material and contact lens of the present invention. The fluorine-containing monomer represented by the general formula (I), which is the first essential component constituting the copolymer obtained in the present invention, imparts oxygen permeability to the copolymer and prevents an increase in water content. Contribute to. The amount used for that purpose is 35 to 65 parts by weight. If the amount is less than 35 parts by weight, the resulting water-containing contact lens tends to be high in water content, so that it tends to be soiled and insufficient in mechanical strength. And even if it becomes a low / medium water content contact lens, practical oxygen permeability cannot be obtained. on the other hand,
When it is used in an amount of more than 65 parts by weight, the hardness of the dry copolymer before hydration is lowered, so that machining becomes difficult. Further, when it is used in an amount of more than 65 parts by weight, the shape recoverability is often lowered. Preferably 50-63
Parts by weight.

In the general formula (I), the fluorine-containing hydrocarbon group represented by C _n F _p H _q is involved in increasing the oxygen permeability of the contact lens. n is 4 to 1
It is an integer of 0. This is because when n is an integer of 3 or less, p is an integer of 7 or less and oxygen permeability is insufficient, and when n is an integer of 11 or more, the lens becomes brittle, which is not preferable. Further, since oxygen permeability increases as the number of fluorine atoms increases, an integer of 8 or more is suitable for p. Also, q is 0
It is the above integer, which means that C _n F _p H _q may be a fluoroalkyl group containing an H atom other than the perfluoroalkyl group (q = 0). Also, p
+ Q = 2n + 1 indicates that C _n F _p H _q does not contain an unsaturated bond. In addition, C _n F _p H _q is preferably linear. Of down group, oxyethylene group - (- CH ₂ CH ₂ O
-) _a -, Okishipuropire It contributes to impart hydrophilicity to the base monomer and the obtained copolymer, and also has a function of improving compatibility with the amide group-containing monomer which is another essential component of the present invention. It is suitable that a is an integer of 1 to 9. This is because when a is 0, the compatibility with the amide group-containing monomer is poor and it is difficult to obtain a transparent polymer by ordinary bulk polymerization. Further, when a is an integer of 10 or more, when a monomer is synthesized, a distribution is generated in a, so that it is difficult to obtain a pure product, and thus it is difficult to stabilize the physical properties of the copolymer obtained after the polymerization. More preferably, a is an integer of 1-5. Also, the number of oxyethylene-oxypropylene groups,
That is, a'is preferably an integer of 2-9. This is because when a'is 1, it does not form an oxyethylene-oxypropylene group, and when it is an integer of 10 or more, the physical properties of the copolymer become unstable as in the above case. Preferred a'is an integer of 2-5.

[0008] _{- (- CH 2 -) m} - is to avoid problems such as hydrolysis of the fluorine-containing monomer, it is necessary to maintain a stable compound. M is 1 for stability
An integer of 5 is suitable, and 1 or 2 is more preferable. Specific preferred examples of the fluorine-containing monomer represented by the general formula (I) include the following.

[0009]

[Chemical 3]

[0010]

[Chemical 4]

[0011]

[Chemical 5]

[0012]

[Chemical 6]

[0013]

[Chemical 7]

[0014]

[Chemical 8]

[0015]

[Chemical 9]

[0016]

[Chemical 10]

[0017]

[Chemical 11]

[0018]

[Chemical formula 12]

[0019]

[Chemical 13]

[0020]

[Chemical 14]

[0021]

[Chemical 15]

[0022]

[Chemical 16]

[0023]

[Chemical 17]

[0024]

[Chemical 18]

[0025]

[Chemical 19]

[0026]

[Chemical 20] In the fluorine-containing monomer of the general formula (I), R ₁ is CH ₃
Since it is methacrylate, it has better machinability than acrylate. Particularly preferred are perfluorooctylethyloxypropylene methacrylate, perfluorooctylethyldioxypropylene methacrylate, perfluorooctylethyloxyethylene methacrylate, and perfluorooctylethyldioxyethylene methacrylate.

Second Component of Copolymer Obtained by the Present Invention
The amide group-containing monomer, which is an essential component of the above, imparts water content to the contact lens material and the contact lens, and contributes to the improvement of the lens wearing feeling.
Used by weight. If the amount is less than 30 parts by weight, the hardness of the copolymer before hydration is insufficient, which makes machining difficult. In addition, since the water content is insufficient, plasticization during hydration is insufficient, and as a result, the obtained contact lens has hardness or stiffness and is uncomfortable to wear. 45
When it is used in excess of the weight part, the water content becomes high and the contact lens has a water content of more than 55%, so that the stain resistance is lowered and the lens is easily soiled. In addition, the compatibility of the monomers decreases and the possibility of white turbidity increases. Preferably, it is 35 to 43 parts by weight.

Examples of the amide group-containing monomer include amide group-containing monomers such as N, N-dialkyl (meth) acrylamide and monoalkyl (meth) acrylamide represented by N, N-dimethyl (meth) acrylamide. Be done. Among them, N, N-dimethylacrylamide (DMAA) is particularly preferable from the viewpoint of compatibility with other monomers such as fluorine-containing monomers. Further, in the case of producing by bulk polymerization, in order to obtain a transparent and good quality copolymer,
For example, DMAA is preferably 30 to 45 parts by weight.

The contact lens material of the present invention and the copolymer constituting the contact lens can be polymerized by adding optional components as required in order to further improve the physical properties thereof.

For example, a crosslinking monomer can be added for the purpose of improving the shape retention of the obtained contact lens. Examples of the crosslinkable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) arylate, allyl (meth) acrylate, glycerol di (meth) acrylate, trimethylol. Propane tri (meth) acrylate, triallyl isothianurate, 1,4-butanediol di (meth)
Acrylate, divinylbenzene, etc. are mentioned, and they are used individually or in combination of 2 or more types.

The amount of the crosslinkable monomer used is preferably 0.01 to 10 parts by weight in 100 parts by weight of the total monomer mixture (including the crosslinkable monomer) to be subjected to the copolymerization. If it is less than 0.01 part by weight, the crosslinking effect cannot be obtained, and if it exceeds 10 parts by weight, the copolymer becomes brittle, which is not preferable.

In order to improve the mechanical properties and the like of the contact lens, an alkyl (meth) acrylate, a fluorine-containing alkyl (meth) acrylate other than the fluorine-containing monomer represented by the general formula (I), a silicone-containing (meth) acrylate, It is also possible to copolymerize by adding alicyclic or aromatic (meth) acrylate.

As the alkyl (meth) acrylate,
For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, is
Examples thereof include o-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate and the like. These can be used alone or in combination of two or more.

Further, for example, an alkyl (meth) acrylate containing one or more hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate can be used. Is.

Examples of the silicone-containing (meth) acrylate include γ- (meth) acryloxypropyltris (trimethylsiloxy) silane, pentamethyldisiloxanylmethyl (meth) acrylate, tert-butyltetramethyldisiloxanylethyl. Examples thereof include (meth) acrylate and triphenyldimethyldisiloxanylmethyl (meth) acrylate, and these can be used alone or in combination of two or more.

Examples of the fluorine-containing alkyl (meth) acrylate other than the fluorine-containing monomer of the general formula (I) include monomers of the following general formula (II).

General formula

[Chemical 21] (In the formula, R ₃ is H or CH ₃ , r is an integer of 1 to 4, s is 1 to 10, t is an integer of 3 or more, and u is an integer of 0 or more.) General Formula (II ), Preferably s
Is a monomer represented by 3 to 10 and t is an integer of 6 or more. Specifically, hexafluoroisopyropyr (meta)
Acrylate, hexafluorobutyl (meth) acrylate, heptafluoropropyl-methyl (meth) acrylate, nonafluorobutyl-methyl (meth) acrylate, nonafluorobutyl-ethyl (meth) acrylate, tridecafluorohexyl-methyl (meth) Acrylate, tridecafluorohexyl-ethyl (meth) acrylate, heptadecafluorooctyl-methyl (meth) acrylate, heptadecafluorooctyl-ethyl (meth) acrylate, trifluoroethyl (meth)
Fluoroalkyl (meth) represented by acrylate
An acrylate is mentioned.

By adding the fluoroalkyl (meth) acrylate represented by the above general formula (II), the hardness of the copolymer before hydration is further increased to further improve the machinability, or water is added. It is also possible to improve the instantaneous shape recovery of the contact lens after the Japanese swelling. However, the amount used is preferably 35 to 70 parts by weight in total with the fluorine-containing monomer represented by the general formula (I), but is low in compatibility with the above-mentioned amide group-containing monomer, Not more than the fluorine-containing monomer of (I).

In the case of a contact lens having a water content of 55% or more, there is a problem that the lens is easily soiled, and if the water content is less than 25%, an unhydrated copolymer having a hardness that facilitates machining can be obtained. When trying to obtain a polymer, the flexibility of the contact lens after hydration swelling may be insufficient. Therefore, the water content in the present invention is 2
The range of 5 to 55% is preferable.

Of the several methods known to date for manufacturing contact lenses, the method with the most practical advantage is the method of cutting and polishing. the suitable hardness to easily fabricated, Rockwell hardness (H _R L) is in the case of at least 60 or more.

Then, in the normal all-day wear of contact lenses, the oxygen permeability coefficient is 15 × 10 ^-11 cm ³ (O ₂ ).
・ There is no problem if it has oxygen permeability of cm / (cm ²・ sec ・ mmHg) or more. The contact lens of the present invention has at least 15 × 10 ⁻¹¹ cm ³ (O ₂ ) · cm / (cm ² · sec · mm).
It has an oxygen permeability coefficient of Hg) or higher, and has practically no problem oxygen permeability when worn all day.

In the production of the contact lens material and contact lens of the present invention, first, the above composition components are mixed to form a comonomer solution, and then a polymerization initiator is added and mixed, and this solution is mixed with metal, glass or After injection into a polymerization container made of plastic with a desired shape (eg, cylindrical container, test tube, lens-shaped container) and sealing, then polymerizing by heating or light, the lens material or water Obtain a lens-shaped object. As the polymerization initiator, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, which are usual radical generators,
Bis-4-t-butylcyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate,
Organic peroxide-based polymerization initiator represented by t-butylperoxy (2-ethylhexanoate), or 2,2 ′
-Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azo Bisisobutyrate, 1,1'-
Azobis (cyclohexane-1-carbonitrile),
At least one of azo-based polymerization initiators such as 2,2′-azobis (2-amidinopropane) dihydrochloride and photopolymerization initiators such as benzoin methyl ether and benzoin ethyl ether is used. The addition amount of the polymerization initiator is preferably 0.01 to 3.0 parts by weight based on 100 parts by weight of the total monomer mixture to be subjected to the copolymerization (this mixture does not contain the polymerization initiator). When heat-polymerization is carried out, a water tank capable of temperature control and stirring or a vessel sealed in a hot-air circulation type dryer is allowed to stand, and the temperature is gradually raised from room temperature to carry out the polymerization. In the case of photopolymerization, a highly transparent polymerization container is used, and ultraviolet rays or visible rays are irradiated to perform polymerization.
At this time, it is more preferable to polymerize under heating and under a stream of an inert gas. In either thermal polymerization or photopolymerization, in order to eliminate polymerization distortion, after completion of polymerization, the resin is kept in the polymerization container or taken out from the polymerization container at 80 ° C to 120 ° C.
The heat treatment may be performed. After the completion of the polymerization and the heat treatment, the mixture is cooled to room temperature, the polymer is cut into a desired lens shape and polished, and then hydrated and swollen to obtain a water-containing contact lens. When directly obtaining a lens-shaped polymer,
After the polymerization and the heat treatment, it is possible to obtain a contact lens which is hydrated and swollen to contain water.

[0043]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The evaluation of each physical property in Examples and Comparative Examples was performed by the following methods.

[0044] (A) hardness (H _R L) (Co.) using a Rockwell hardness tester of Akashi Seisakusho, diameter 15 mm, wall thickness 6mm flat plate, L scale (hereinafter, H _R
(Abbreviated as L).

(B) Gel Transparency (Light Transmittance) For the purpose of evaluating the transparency of the gel, Hitachi Autograph Spectrophotometer U
-3210 was used to measure a water-containing sample having a thickness of 0.2 mm saturated with 0.9% physiological saline in 0.9% physiological saline, and a light transmittance of 90% or more is indicated by a circle as a transparent body. The white turbidity with a transmittance of less than 90% was indicated by x.

(C) Moisture content (% by weight) = [(W ₁ -W ₂ ) / W ₁ ] × 100 W ₁ : Weight at saturated water content. W ₂ : Weight when dehydrated.

(D) Shape retention / shape recovery The shape recovery when a water-containing flat plate having a central wall thickness of 0.15 mm was pinched with fingers and folded in half was evaluated. ◯: Good (shape recovery similar to that of a hydroxyethyl methacrylate polymer in a water-containing state). ×: The crease remains and the original state is not restored. XX ... Has cracked because it is hard and brittle.

(E) Contamination resistance: Oleic acid was selected as an artificial lipid stain, and a hydrated plate was immersed in oleic acid while stirring and then washed with water to visually observe the residual oleic acid on the plate surface. The durability against lipid stain was evaluated by observing the presence or absence. ◯: It was easily removed by washing with water. ×: Sticky and cannot be removed.

Example 1 60 parts by weight of perfluorooctylethyloxypropylene methacrylate (hereinafter abbreviated as OPMA1), N, N
-Dimethylacrylamide (hereinafter abbreviated as DMAA) 3
9.5 parts by weight, ethylene glycol dimethacrylate (hereinafter abbreviated as EDMA) 0.5 parts by weight, and 2,2'-azobis- (2,4-dimethylvaleronitrile) (hereinafter, V-65) as a polymerization initiator. Was abbreviated) was added and dissolved in an amount of 0.2 parts by weight per 100 parts by weight of the total monomer mixed liquid (this mixed liquid does not contain a polymerization initiator). After pouring the obtained mixed liquid into a molding die and sealing the mold, the mixture was kept at 40 ° C. for 25 hours in a hot air circulation dryer, then 45 ° C. for 15 hours, and 45 ° C. to 60 ° C. for 10 hours. ℃ to 80 ℃
The temperature was raised from 80 ° C. to 100 ° C. over 4 hours, and the temperature was maintained at 100 ° C. for 8 hours to complete the polymerization. Then, it cooled to room temperature and took out the copolymer from the mold. The polymer colorless and transparent Rockwell hardness (H _R L) is 76
It was a hard material. This was cut and polished into a contact lens shape by a usual processing technique to manufacture a contact lens. Then, the contact lens was heated at 80 ° C. for 6 hours in 0.9% physiological saline to hydrate and swell.

As shown in Table 1, the water-containing soft contact lens is a colorless and transparent body having a water content of 41%, excellent shape retention / instantaneous shape recovery, and stain resistance.
(G), that is, (B) it is transparent in both dry and hydrated states, (B) it has practical oxygen permeability, and (C) it is soft, and it retains its shape even after being shaped into a lens and after deformation. (D) It is less likely to be contaminated by tear fluid components such as proteins and lipids. (E) Can maintain the wettability of the lens surface for a long time during wear. (F) Practical mechanical strength. All of the conditions such as the (g) copolymer having a hardness that allows a contact lens to be easily manufactured even by cutting and surface polishing are satisfied.

Examples 2 to 12 Only the constituents were changed within the limits of the present invention, and
A contact lens material was manufactured by the same method as in Example 1, and then cut and polished into a contact lens shape to manufacture a contact lens. The results of the physical property tests of the obtained products are shown in Tables 1 and 2. The water-containing copolymer obtained in any of the examples is a colorless and transparent hard material, and
The hydrous contact lens after being cut and polished into a contact lens shape also satisfied all of the above conditions (a) to (g).

Comparative Example 1 75 parts by weight of OPMA1, 24.5 parts by weight of DMAA, 0.5 parts by weight of triethylene glycol dimethacrylate (hereinafter abbreviated as 3G), and V-65 as a polymerization initiator were mixed in a total monomer mixture (this mixture). Liquid does not contain polymerization initiator) 1
A copolymer was obtained in the same manner as in Example 1 except that 0.2 part by weight per 100 parts by weight was added and dissolved.
Rockwell hardness (H _R L) -30 of the polymer was significantly flexible than the copolymer of the present invention. Attempts were made to produce a contact lens from the copolymer by cutting and polishing, but there were defects in the edge of the lens and scratches due to polishing,
Furthermore, since the curvature of the cutting surface is easily destroyed by the polishing pressure, the optical surface cannot be formed, and the function as a contact lens cannot be achieved. Table 3 for other physical properties
Shown in.

Comparative Example 2 A copolymer was obtained in the same mixing ratio and method as in Example 1, except that perfluorooctylethyl methacrylate (hereinafter abbreviated as 17FMA) was used instead of OPMA1. Table 3 shows the physical properties of the obtained copolymer. The obtained copolymer was cloudy in both the dry and water-containing states.

Comparative Examples 3 to 4 In place of OPMA1, γ-methacryloxypropyltris (trimethylsiloxy) silane, which is a silicone-containing methacrylate, was used as a highly oxygen permeable component, and Example 1 was used.
It was processed into a contact lens shape in the same manner as in (1) and was saturated with water. Table 3 shows the physical properties of the obtained copolymer. Lipids were attached to any of the water-containing copolymers, and the once attached oleic acid could not be easily removed by washing with water using a surfactant. In particular, an attempt was made to wear a water-containing contact lens shaped article made of the copolymer of Comparative Example 4, but it was judged that the lens immediately after wearing was clouded and could not be put to practical use. Moreover, none of them has been provided with both flexibility and instantaneous shape recoverability at the same time.

Comparative Examples 5 to 8 Contact lenses were produced in the same manner as in Example 1 except that the constituent components were used as shown in Table 3. The water content of the contact lens of Comparative Example 5 was 72%, which was a high water content contact lens, and was inferior in stain resistance. Comparative Example 6
The copolymers of Nos. 8 and 9 were cloudy and had poor shape retention and shape recovery. Copolymer of Comparative Example 7 was as hardness (H _R L) is low.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3] Description of Monomer Abbreviations OPMA1: Perfluorooctylethyloxypropylene methacrylate OPMA2: Perfluorooctylethyldioxypropylene methacrylate OEMA1: Perfluorooctylethyloxyethylene methacrylate OEMA2: Perfluorooctylethyldioxyethylene methacrylate DMAA: N, N-dimethylacrylamide 17FMA: perfluorooctylethylmethacrylate n-BMA: n-butylmethacrylate TSiMA: γ-methacryloxypropyltris (trimethylsiloxy) silane HEMA: 2-hydroxyethylmethacrylate MAA: methacrylic acid 6FMA: hexafluoroisopropylmethacrylate EDMA: ethyleneglycoldi Methacrylate Allyl MA Allyl methacrylate TMPT: trimethylolpropane trimethacrylate 3G: triethylene glycol dimethacrylate

[0059]

EFFECTS OF THE INVENTION According to the present invention, a contact lens suitable for obtaining a contact lens having a low / medium water content and having a hardness such that machining such as cutting / polishing can be easily performed. The material can be obtained.

The low / medium hydrous contact lens of the present invention has good practically good balance of all physical properties, and can be efficiently manufactured from a contact lens material having a great advantage in the manufacturing process. Therefore, it has great practical significance.

Claims (6)

[Claims] 1. In 100 parts by weight of a monomer mixture used for copolymerization, a compound represented by the general formula: (In the formula, R ₁ is CH ₃ , R ₂ is H or CH ₃ , and may be the same or different, and a is an integer of 1 to 9,
m is an integer of 1 to 5, n is an integer of 4 to 10, p is an integer of 8 or more, q is an integer of 0 or more, and p + q = 2n + 1. ) At least one fluorine-containing monomer: 35 to 65 parts by weight, and at least one amide group-containing monomer: 30 to 45 parts by weight as essential components, and optionally other monomers. A contact lens material comprising a copolymer obtained by copolymerizing a monomer mixture contained as a component. 2. The contact lens material according to claim 1, wherein the optional component is a crosslinkable monomer. 3. The optional component is an alkyl (meth) acrylate, a fluorine-containing alkyl (meth) acrylate other than the fluorine-containing monomer represented by the general formula (I), a silicone-containing (meth) acrylate and an alicyclic or aromatic (meth) acrylate. The contact lens material according to claim 1, which is at least one selected from the group consisting of: 4. A hardness when dried the copolymer is 60 or more in Rockwell hardness (H _R L), the contact lens material according to any one of claims 1 to 5. 5. A hydrous contact lens obtained by processing the contact lens material according to any one of claims 1 to 4. 6. The contact lens according to claim 5, which has a water content of 25 to 55% after hydration and swelling.