JP3329899B2 - Water-containing ophthalmic lens material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrous ophthalmic lens material. The hydrous ophthalmic lens material provided by the present invention has good transparency and is useful as a material for soft contact lenses, intraocular lenses, artificial cornea, artificial vitreous body, and the like. In particular, it can be suitably used as a soft contact lens material.

[0002]

2. Description of the Related Art As a water-containing soft contact lens material, conventionally, 2-hydroxyethyl methacrylate (H
Hydrogels based on EMA) have been widely used. However, it has been pointed out that a soft contact lens using this hydrogel has a low water content of 40% or less, and thus has poor oxygen permeability, and the cornea may be deficient in oxygen, resulting in corneal damage. . Further, the corneal damage due to the poor stain resistance and dirt attached to the lens has also been reported.

Therefore, in order to improve oxygen permeability,
A hydrogel mainly composed of a monomer having higher hydrophilicity than HEMA has been developed. As monomers having high hydrophilicity, methacrylic acid, dimethylacrylamide, alkylene oxide monomethacrylate, N-vinyl lactam and the like are known. Among them, when N-vinyl-2-pyrrolidone (NVP) is used, cutting is performed. Since a contact lens can be manufactured by any of a polishing method, a molding method, and a spin casting method, it is used as a main component of a high water content soft contact lens. However, hydrogels made with only NVP have low strength and are not practical. Therefore, a method of copolymerizing NVP with a hydrophobic monomer has been attempted for the purpose of reinforcing the strength of the hydrogel.

In recent years, hydrogels having excellent resistance to protein contamination and oxygen permeability have been developed by using fluorine-containing monomers as hydrophobic monomers. For example, Japanese Patent Application Laid-Open No. 57-111119 discloses a hydrogel. JP-A-63-30820 discloses a soft contact lens comprising a copolymer containing alkylene glycol monomethacrylate, trifluoroethyl methacrylate and / or hexafluoroisopropyl methacrylate as a main component. Alternatively, a soft contact lens comprising a copolymer containing alkylene oxide (meth) acrylate and N-vinyllactam as main components is described.

[0005]

The above-mentioned JP-A-57-2
In Japanese Patent No. 11119 and JP-A-63-30820, trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate, which are specifically described as fluorine monomers, are obtained by copolymerizing with a hydrophilic monomer such as N-vinyl lactam. It was difficult to obtain a copolymer excellent in phase separation and excellent transparency, and was not always satisfactory as a soft contact lens material.

An object of the present invention is to provide a water-containing ophthalmic lens material having excellent optical transparency.

[0007]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a (meth) acrylate having a fluoroalkyl group having a specific structure, that is, fluorine represented by the following general formula (I): The present inventors have found that the monomer has excellent copolymerizability, and that the copolymer with N-vinyllactam has extremely excellent transparency, and the present invention has been accomplished.

[0008] According to the present invention, the object is to provide N-vinyllactam , a compound represented by the following general formula (I) :
This is achieved by providing a water-containing ophthalmic lens material comprising a copolymer obtained by copolymerizing a (meth) acrylate having a fluoroalkyl group and a crosslinking agent .

[0009]

Embedded image

(Wherein, R ¹ represents a hydrogen atom or a methyl group; n represents an integer of 1 to 4; m represents an integer of 1 to 10)

[0011] N-vinyl lactam is a component for imparting hydrophilicity to the copolymer. Examples of N-vinyl lactam include N-vinyl-2-piperidone, N-vinyl-2-pyrrolidone, N-vinyl-2-caprolactam, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-3 -Methyl-2-piperidone, N-vinyl-3-
Methyl-2-caprolactam, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-4-methyl-2-caprolactam, N-vinyl-5-methyl- 2-pyrrolidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-3-
Ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-
2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinyl-5-methyl-5-ethyl-2-pyrrolidone, N-vinyl-3,4,5-trimethyl-3- Ethyl-2-pyrrolidone, N-vinyl-6
Methyl-2-piperidone, N-vinyl-6-ethyl-2
-Piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam,
N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7- Trimethyl-2-caprolactam and the like can be mentioned. Among them, N-vinyl-2
-Piperidone, N-vinyl-2-pyrrolidone are preferred. These N-vinyl lactams are used alone or in combination of two or more.

When the amount of N-vinyl lactam used is less than 40% by weight based on the total amount of the raw material monomers, the water content of the obtained ophthalmic lens material is reduced, and the oxygen permeability is also low. If the amount of N-vinyl lactam exceeds 90% by weight based on the total amount of the raw material monomers, the strength of the obtained ophthalmic lens material will be remarkably reduced, and the durability will be poor. Therefore, the amount of N-vinyl lactam used is 40 to 90 to the total amount of the raw material monomers.
% By weight, more preferably 50 to 80% by weight.

By using a (meth) acrylate having a fluoroalkyl group represented by the above general formula (I) as a raw material monomer, not only oxygen permeability, mechanical strength and protein stain resistance are excellent, but also A very transparent ophthalmic lens material is obtained.

When n is 5 or more in the general formula (I), the content of fluorine atoms in the monomer is reduced.
Since oxygen permeability and protein contamination resistance cannot be sufficiently imparted to the obtained ophthalmic lens material, n
Is an integer of 1 to 4, and n is preferably 1 or 2. When m is 11 or more, the hydrophobicity of the monomer increases, the compatibility with N-vinyllactam decreases, and it becomes difficult to obtain an ophthalmic lens material having excellent transparency. Thus, m is an integer from 1 to 10,
m is preferably an integer of 1 to 7, and more preferably m is an integer of 1 to 3.

The (meth) acrylate having a fluoroalkyl group represented by the general formula (I) includes, for example, 2,2,3,3-tetrafluoropropyl (meth)
Acrylate, 2,2,3,3,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,3,4
4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl (meth) acrylate, 2,2,3
3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate, 2,2,3,3,4
4,5,5,6,6,7,7,8,8-tetradecafluorooctyl (meth) acrylate, 2,2,3,3
4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl (meth) acrylate and the like can be mentioned. Among them, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3
4,4-hexafluorobutyl (meth) acrylate,
It is preferred to use 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate.
These fluorine monomers can be used alone or in combination of two or more.

When the amount of the (meth) acrylate having a fluoroalkyl group represented by the general formula (I) is less than 10% of the total amount of the raw material monomers, the mechanical strength of the obtained ophthalmic lens material , And sufficient protein stain resistance and oxygen permeability cannot be obtained. When the amount of the (meth) acrylate having a fluoroalkyl group exceeds 60% of the total amount of the raw material monomers, the water content of the obtained ophthalmic lens material is reduced and the flexibility is also lacking. It is not suitable as an ophthalmic lens material. Therefore, the amount of the (meth) acrylate having a fluoroalkyl group is preferably from 10 to 60% by weight based on the total amount of the raw material monomers, and from 20 to 20% by weight.
50% by weight is more preferred.

By using a cross-linking agent, shape stability and mechanical strength can be imparted to the ophthalmic lens material. As the crosslinking agent, a polyfunctional monomer is used.
For example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis [p- (γ-methacryloxy-β-hydroxypropoxy) phenyl] propane, methylene bismethacrylamide, Examples include methylene bisacrylamide, allyl (meth) acrylate, vinyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl isophthalate, divinyl adipate, diallyl adipate and the like. In order to obtain a more transparent ophthalmic lens material, it is necessary to increase the copolymerizability of N-vinyllactam and a (meth) acrylate having a fluoroalkyl group, and the effect of enhancing the copolymerizability as a crosslinking agent is required. It is preferred to use allyl (meth) acrylate and vinyl (meth) acrylate having. If the degree of cross-linking is high, the moisture content of the ophthalmic lens material is reduced to be hard, and if the degree of cross-linking is low, the shape stability and mechanical strength of the ophthalmic lens material tend to be inferior. Therefore, the amount of the crosslinking agent used is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, based on the total amount of the raw material monomers.

Examples of the polymerization initiator include benzoyl peroxide, 2,2'-azobisisobutyronitrile,
2'-azobismethylisobutyrate, 2,2'-azobisdimethylvaleronitrile and the like can be used. The amount of the polymerization initiator used is 0.01 to the total amount of the raw material monomers.
~ 5% by weight is preferred.

Other copolymerizable monomers may be used as long as they do not impair the present invention. For the purpose of improving the hydrophilicity and flexibility of the obtained ophthalmic lens material, a hydrophilic monomer such as dimethylacrylamide, methacrylic acid and HEMA can be added. Further, for the purpose of improving the mechanical strength and the flexibility, a hydrophobic monomer such as (meth) acrylate and organic acid vinyl can be added.

The polymerization method may be any of ordinary bulk polymerization or solution polymerization. In the case of solution polymerization, a solvent used can dissolve all monomers to be subjected to polymerization, for example, acetonitrile, N-methylpyrrolidone, dimethylsulfoxide, dimethylformamide, ethanol, methanol and the like can be used. In any of the polymerization methods, it is preferable to carry out heat polymerization. When performing this heat polymerization, using a constant temperature water tank or a hot air circulating drier or the like that is easy to control the temperature, heat polymerization is performed at about 40 to 60 ° C. for several hours to several tens of hours, and then at about 100 ° C. for several hours. It is preferable to carry out heat polymerization for a period of time to complete the polymerization. In order to remove the polymerization distortion of the copolymer, a heat treatment can be further performed at about 80 to 120 ° C. for several hours after the completion of the polymerization. A polymerization method such as photopolymerization or radiation polymerization other than heat polymerization may be employed.

The raw material monomer is polymerized in a mold having a desired lens shape, and a lens having a desired shape can be directly obtained. Further, a method of forming the copolymer into a lens shape by machining such as cutting and polishing may be employed. By hydrating and swelling the lens-shaped molded product thus obtained, a water-containing ophthalmic lens is obtained.

In general, ophthalmic lens materials must be optically clear and have excellent transparency. Optical clarity can be evaluated by measuring the light transmittance and haze of the ophthalmic lens material in distilled water.
The light transmittance indicates the ratio of the amount of light transmitted through the ophthalmic lens material to the amount of incident light, and the haze indicates the ratio of the amount of light scattered when transmitting through the ophthalmic lens material relative to the amount of incident light. It is. The value of this light transmittance is 100
%, And as the haze value approaches 0%, the material is more excellent in transparency. As an ophthalmic lens material, the light transmittance is 98% or more and the haze is 0.5%.
The following is preferred.

[0023]

EXAMPLES The present invention will be described specifically with reference to Examples.
The present invention is not limited to these.

Examples 1 to 11 Each of the monomer compositions of Examples 1 to 11 shown in Table 1
After mixing 0 g and 0.02 g of 2,2′-azobisdimethylvaleronitrile as a polymerization initiator, the mixture was placed in a polypropylene test tube, replaced with nitrogen, and sealed. This is 4
It was immersed in a constant temperature water bath at 0 ° C. for 24 hours. Then, at 50 ° C
After being immersed in a constant temperature water bath for 24 hours, it was transferred into a constant temperature water bath at 60 ° C. for 5 hours, further immersed in a constant temperature water bath at 80 ° C. for 2 hours, and finally immersed in a constant temperature water bath at 100 ° C. for 1 hour. After cooling, take out the copolymer from the test tube and measure 15m in diameter.
m and a thickness of 10 mm, and formed into a contact lens by a normal cutting and polishing technique. Then, it was immersed in 0.9% physiological saline for several tens of hours, the base curve was 8.4 mm, the center thickness was 0.12 mm, and the power was -3.
A 0 diopter soft contact lens was obtained.

The water content, light transmittance and haze of the soft contact lens obtained by the above method were measured according to the following test methods. [Water content] The weight (Wa) of the soft contact lens at the time of swelling with water and the weight (Wb) at the time of dehydration and drying were measured, and the water content was calculated by the following equation. Water content (% by weight) = [(Wa−Wb) / Wa] × 100

[Light transmittance and haze] Tokyo Denshoku Co., Ltd.
It was measured using a haze meter (MODEL TC-HIII type). A halogen lamp was used as a light source. In the state where the soft contact lens is immersed in distilled water at 25 ° C., the amount of incident light from a halogen lamp (T ₁ ), the amount of light transmitted through the soft contact lens and distilled water (T ₂ ), and the amount of light diffused by distilled water (T ₃ ) and the amount of light (T ₄ ) diffused by the soft contact lens and distilled water were measured, and the light transmittance and haze were calculated by the following formulas. Light transmittance (%) = (T ₂ / T ₁ ) × 100 Haze (%) = [(T ₄ / T ₂ ) − (T ₃ / T ₁ )] × 100

Table 2 shows the water content, light transmittance and haze of the soft contact lens measured by the above method. All soft contact lenses have a light transmittance of 9
The haze was 8% or more and the haze was 0.5% or less, and the transparency was very excellent.

[0028]

[Table 1]

[0029]

[Table 2]

Comparative Examples 1 to 7 Using the monomer compositions of Comparative Examples 1 to 7 shown in Table 3, soft contact lenses were prepared in the same manner as in Example 1, and the water content of each soft contact lens was determined. Table 4 shows the measurement results of the light transmittance and the haze. In any of the soft contact lenses, the light transmittance was less than 98% and the haze was 1.0% or more, and the transparency was insufficient.

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

According to the present invention, N-vinyllactam has the general formula (I)
By using a (meth) acrylate having a fluoroalkyl group consisting of only the compound represented by and a crosslinking agent , a highly transparent water-containing ophthalmic lens material can be obtained. This ophthalmic lens material is particularly suitable as a soft contact lens material.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 220/22 C08F 226/06 A61L 27/00 G02C 7/04 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A water-containing composition comprising a copolymer obtained by copolymerizing N-vinyl lactam , a (meth) acrylate having a fluoroalkyl group comprising only a compound represented by the following general formula (I) and a crosslinking agent . Ophthalmic lens material. Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group. N represents an integer of 1 to 4, and m represents an integer of 1 to 10.)