JP2000111847A - Soft contact lens material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent mechanical strength and durability by polymerizing monomers having specified phosphorylcholine analog groups, monomers copolymerizable with the first monomers, and crosslinking monomers having >=4 functional groups. SOLUTION: This material is produced by polymerizing monomers having phosphorylcholine analog groups expressed by the formula, monomers copolymerizable with the first monomers, and crosslinking monomers having >=4 functional groups. In the formula, R1 is a hydrogen atom or methyl group, R2 is (CH2CHR6)n, (CH2CHR6O)nCH2CHR6 (wherein R6 is a hydrogen atom or methyl group and n is an integer 1 to 8) or 3-10C hydrocarbon group, m is an integer 2 to 4, and R3 to R5 are 1-8C alkyl groups. As for the monomers expressed by the formula, for example, 2-(meth)acryloyloxyethy1-2-(trimethylammonio)ethylphosphate can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a soft contact lens material. More specifically, the present invention relates to a soft contact lens material having excellent mechanical strength and durability.

[0002]

2. Description of the Related Art Contact lenses are classified into hard contact lenses mainly composed of a hydrophobic monomer such as methyl methacrylate and hydrous soft contact lenses mainly composed of a hydrophilic monomer such as 2-hydroxyethyl methacrylate. , Widely used. The hard contact lens made of methyl methacrylate has been used for the longest time and has excellent mechanical strength and antifouling resistance. More recently, from the viewpoint of supplying oxygen to the cornea, a hard contact lens containing an organic silane compound or a fluorine compound and having high oxygen permeability has been replaced. However, although these hard contact lenses are provided with oxygen permeability by containing an organic silane compound, they have drawbacks such as easy attachment of stains such as proteins and lipids in tears, and fragility. ing.

On the other hand, a water-containing soft contact lens containing 2-hydroxyethyl methacrylate as a main component is a lens that is more familiar to the eyes and is more comfortable to wear than a hard contact lens. However, those having a low water content of 40% or less have insufficient oxygen permeability and feeling of wearing in many cases, and recently contain methacrylic acid and N-vinylpyrrolidone for the purpose of improving the feeling of wearing. Highly hydrous soft contact lenses have also been used. In general, high water content soft contact lenses have the characteristics of high oxygen permeability and excellent feeling of wearing, but on the contrary, proteins and lipids in tears are more likely to be deposited, so that the performance of contact lenses is reduced. There are drawbacks.

A contact lens material containing 2-methacryloyloxyethyl phosphorylcholine has been proposed to improve the adsorption of proteins and lipids in these tears (Japanese Patent Publication No. Hei 6-502200, Japanese Patent Application Laid-Open No. 5-107).
511, JP-A-6-43400, JP-A-6-43400
JP-43401, JP-A-6-313865,
JP-A-7-159736). However, although contact lenses made from this material have excellent anti-staining properties such as anti-protein adsorbing property and anti-lipid adsorbing property, they are not always sufficient in strength and durability. Therefore, in order to solve the above-mentioned problems, the contact lens material of the present invention is to provide a soft contact lens having excellent mechanical strength and durability when a contact lens is manufactured.

[0005]

An object of the present invention is to provide a soft contact lens material having excellent mechanical strength and durability.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a monomer having a specific phosphorylcholine-like group, a monomer copolymerizable therewith,
Further, when a crosslinkable monomer having four or more functional groups is polymerized, it has been found that a contact lens material having excellent mechanical strength and excellent durability has been obtained, and the present invention has been completed. That is, the present invention includes the following (1) to (3).

(1) As the component A, the following general formula [1]

[0008]

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In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents (CH ₂ CHR ⁶ ) n or (CH ₂ CHR)
⁶ O) nCH ₂ CHR ⁶ (where R ⁶ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8), or a hydrocarbon group having 3 to 10 carbon atoms, and m represents 2 And R ³ , R ⁴ and R ⁵ represent an alkyl group having 1 to 8 carbon atoms. The monomer represented by｝ and the B component are monofunctional vinyl monomers copolymerizable with the monomer of the general formula [1], and the C component is a crosslinkable monomer having four or more functional groups. A soft contact lens material obtained by polymerizing a monomer composition containing

(2) As the component A, the following general formula [2]

[0011]

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In the formula, R ¹ represents a hydrogen atom or a methyl group. A) a monofunctional vinyl monomer copolymerizable with the monomer of the general formula [2] as the component B, and a crosslinkable monomer having four or more functional groups as the component C. A soft contact lens material obtained by polymerizing a contained monomer composition.

(3) The monomer of component A is 5 to 89.99% by weight, the monomer of component B is 10 to 99.99% by weight, and the crosslinkable monomer of component C is 0.01 to 20% by weight. % Of the above-mentioned soft contact lens material obtained by polymerizing a monomer composition containing

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The contact lens material of the present invention has the following general formula [1] as the component A:

[0015]

Embedded image

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents (CH ₂ CHR ³ ) n or (CH ₂ CHR
³ O) nCH ₂ CHR ³ (where R ³ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8) or a hydrocarbon group having 3 to 10 carbon atoms; Is 2-4
Indicates an integer. ｝, A monofunctional vinyl monomer copolymerizable with the monomer of the general formula [1] as the B component, and a crosslinkable monomer having four or more functional groups as the C component. A soft contact lens material obtained by polymerizing a contained monomer composition.

Examples of the monomer represented by the general formula [1] of the component A include 2- (meth) acryloyloxyethyl-2- (trimethylammonio) ethyl phosphate and 2- (meth) acryloyloxy. Propyl-2-
(Trimethylammonio) ethyl phosphate, 4-
(Meth) acryloyloxybutyl-4- (trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethoxyethyl-2- (trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxydiethoxyethyl-2- (Trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl-2- (trimethylammonio) propyl phosphate, 2- (meth) acryloyloxypropyl-2- (trimethylammonio) propyl phosphate, 4- (meta) ) Acryloyloxybutyl-4- (trimethylammonio) propyl phosphate, 2- (meth) acryloyloxyethoxypropyl-2- (trimethylammonio) propyl phosphate, 2- (meth) acryloyloxy Ethoxy-2- (trimethylammonio) propyl phosphate, and the like. More preferably, from the viewpoint of availability and the like, 2
-(Meth) acryloyloxyethyl-2- (trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl-2- (trimethylammonio)
Propyl phosphate.

The monofunctional vinyl monomer of the component B may be any one having copolymerizability with the general formula [1].
For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glyceroyl mono Acrylate or methacrylate such as (meth) acrylate, carboxyl group-containing monomer such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, N-vinylpyrrolidone, N-vinylcaprolactam, N, N-dimethyl (meth) Other examples include acrylamide, styrene, and methyl nucleus-substituted styrene.

Examples of the crosslinking agent monomer having four or more functional groups of the component C include pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa (meth) acrylate, Hexa (meth) acrylate of caprolactone adduct of dipentaerythritol, dipentaerythritol hexa (meth) acrylate propionate, pentaerythritol triacrylate, tolylene diisocyanate urethane prepolymer and the like can be mentioned.

The mixing ratio of the monomer is 5 to 89.99% by weight of the monomer represented by the general formula [1] of the component A,
10 to 99.99% by weight of a vinyl monomer as a component;
A crosslinking agent monomer having four or more functional groups
A range of 1 to 20% by weight is preferred.

The soft contact lens material obtained in the present invention can be obtained by copolymerizing the monomers of the above-mentioned components A, B and C. The polymerization is performed by a radical polymerization method using a general radical polymerization initiator. For example, it can be performed by a known technique such as bulk polymerization. Examples of the radical polymerization initiator include benzoyl peroxide, lauroyl peroxide, diisopropyl dicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate,
t-butyl peroxydiisobutyrate, azobisisobutyronitrile, azobisdimethylvaleronitrile, azobis (2-amidinopropane) dihydrochloride, azobis (4-cyanovaleric acid), azobisisobutylamide dihydrate, Potassium persulfate or the like can be used. The amount of the polymerization initiator to be used is 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of all monomers.
Parts by weight.

This polymerization can also be carried out in the presence of a suitable solvent, based on 100 parts by weight of the monomer mixture.
It can be used in the range of 100 to 5000 parts by weight.

Examples of usable solvents include water, methanol, ethanol, chloroform, methylene chloride, dimethylformamide, dimethylsulfoxide, acetone, ethyl acetate and the like.

The polymerization temperature varies depending on the type of polymerization initiator, but is preferably from 20 to 140 ° C.
~ 120 hours are preferred.

Further, a dye, a dye, a pigment, an ultraviolet absorber and the like may be contained as long as the physical properties of the obtained contact lens are not affected. For example, Blue No. 201, Blue 2
04, purple 201, red 404, green 202,
Dyes or pigments such as Blue No. 404, and ultraviolet absorbers such as 2- (2'-hydroxyphenyl) benzotriazole and 2- (hydroxy) benzophenone.

In order to make the soft contact lens material of the present invention into a desired lens shape, for example, (a) the above-mentioned raw material monomer is mixed in an appropriate container such as a test tube based on the above radical polymerization conditions. After polymerizing to obtain a round bar or block, mechanical processing such as cutting, polishing, etc. (b)
A method in which the raw material monomer and the polymerization initiator are injected into a predetermined mold and a contact lens is directly molded by mold polymerization, (c) a method of casting while heating or irradiating light, or (d) a radical polymerization method in advance After producing the polymer by the method described above, the polymer can be obtained by dissolving the polymer in an appropriate solvent and removing the solvent by a casting method.

The water content of the soft contact lens made from the soft contact lens material of the present invention is 10 to 8
0% is preferred. If the water content is less than 10%, the feeling of wearing decreases, and if it exceeds 80%, the strength decreases, which is not preferable.

[0028]

The soft contact lens material of the present invention comprises a copolymerizable monofunctional vinyl monomer of a component A containing a phosphorylcholine-like group and a component B;
A soft contact lens material obtained by polymerizing a monomer composition with a crosslinkable monomer having four or more functional groups of the component, and has anti-protein and anti-lipid absorption properties due to the A component. With excellent wearability and C
Excellent mechanical strength and durability due to components.

[0029]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Example 1 15 parts by weight of 2-methacryloyloxyethyl-2- (trimethylammonio) ethyl phosphate (MEPC), 2-hydroxyethyl methacrylate (HEM)
A) 83 parts by weight, 2 parts by weight of pentaerythritol tetraacrylate (PETMA) and 0.2 parts by weight of azobisisobutyronitrile are poured into a test glass-type polymerization tube,
The system was purged with nitrogen and deaerated, sealed, and heat-cured. The heating was carried out in a constant temperature bath by raising the temperature to 30 to 100 ° C. over 50 hours. After completion of the polymerization, the cured product was taken out of the mold, cut and polished by a usual processing method to prepare a predetermined test piece, and each physical property value was evaluated by the following measurement methods. The results are shown in Table 1.

(1) Water Content After immersion in 0.9% by weight of physiological saline to obtain a saturated water content, the weight was measured and calculated by the following equation. Water content (%) = {(W ₁ −W ₂ ) / W ₁ } × 100 where W ₁ : weight at saturated water content, and W ₂ : dry weight.

(2) Oxygen Permeability The oxygen permeability coefficient in 0.9% by weight physiological saline at 35 ° C. was measured using a Kaken type film oxygen permeability measuring device (manufactured by Rika Seiki Kogyo Co., Ltd.).

(3) Mechanical strength A flat plate saturated at room temperature 23 ° C. and 0.9% by weight of physiological saline was cut into a strip having a width of 2 mm, a length of 10 mm and a thickness of 0.2 mm to obtain a test piece. Using a tensile tester (manufactured by Yamaden Co., Ltd., Leoner RE3305), 1 mm
/ Sec.

Examples 2 to 10 Polymerization was carried out in the same manner as in Example 1 except that the monomer components of Example 1 were changed to the respective compositions and mixing ratios shown in Tables 1 and 2, and physical properties were measured. . The results are shown in Tables 1 and 2.

Comparative Examples 1 to 3 Polymerization was carried out in the same manner as in Example 1 except that the polymerization components were changed to the respective compositions and compounding ratios shown in Table 3, and physical properties were measured. Table 3 shows the results.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

The abbreviations in the table indicate the following compounds. A component; MEPC: 2- (methacryloyloxy) ethyl-2 ′
-(Trimethylammonio) ethyl phosphate, MPPC: 3- (methacryloyloxy) propyl-
2 ′-(trimethylammonio) ethyl phosphate, B component; HEMA: 2-hydroxyethyl methacrylate, MA: methacrylic acid, NVP: N-vinylpyrrolidone, MMA: methyl methacrylate, C component; PETMA: pentaerythritol tetramethacrylate PDPEHA: Dipentaerythritol hexaacrylate propionate DPETHA: dipentaerythritol hexaacrylate Other components; DEGMA: diethylene glycol dimethacrylate TEGMA: triethylene glycol dimethacrylate Note * Unit for oxygen permeability; (*) × 10 ^-11 ml (ST
P) cm / cm ² · sec · mmHg

From the above results, it can be seen that the examples of the present invention are superior in mechanical strength and superior as a soft contact lens material as compared with the comparative example using a bifunctional monomer.

Continued on the front page (72) Inventor Norio Nakabayashi 5-6-20 Koganehara, Matsudo-shi, Chiba (72) Inventor Kazuhiko Ishihara 3-16-37, Josuihoncho, Kodaira-shi, Tokyo F-term (reference) 2H006 BB01 BB06 4J100 AL08P AL08Q AL63R AL65R BA21R BA32P BA32Q BA63P BA63Q CA06 FA03 FA19 JA34

Claims (3)

[Claims] 1. A component represented by the following general formula [1]: In the formula, R ¹ represents a hydrogen atom or a methyl group;
² is (CH ₂ CHR ⁶ ) n or (CH ₂ CHR ⁶ O) n
CH ₂ CHR ⁶ (where R ⁶ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 8), or a hydrocarbon group having 3 to 10 carbon atoms, and m represents 2 to 4 carbon atoms. integer,
R ³ , R ⁴ and R ⁵ represent an alkyl group having 1 to 8 carbon atoms. As the monomer represented by｝ and the B component, general formula [1]
A monofunctional vinyl monomer copolymerizable with a monomer of
A soft contact lens material obtained by polymerizing a monomer composition containing, as a component, a crosslinkable monomer having four or more functional groups. 2. A component represented by the following general formula [2]: In the formula, R ¹ represents a hydrogen atom or a methyl group. A) a monofunctional vinyl monomer copolymerizable with the monomer of the general formula [2] as the component B, and a crosslinkable monomer having four or more functional groups as the component C. A soft contact lens material obtained by polymerizing a contained monomer composition. 3. The composition according to claim 1, wherein the monomer of the component A is 5 to 89.99% by weight,
The monomer composition comprising 10 to 94.9% by weight of the monomer of the component B and 0.01 to 20% by weight of the crosslinkable monomer of the component C is polymerized. Soft contact lens material.