JP2001142034A - Soft contact lens material and manufacturing method - Google Patents

Abstract

(57) [Problem] To provide a soft contact lens material excellent in moderate mechanical strength, stain resistance and biocompatibility, and a method for producing the same. A soft contact lens material obtained by polymerizing a polymerizable monomer in the presence of a polymerization solvent, wherein the polymerizable monomer is 80 mol% to 99.9 mol% of a phosphorylcholine-like group-containing monomer of component A and ethylenic of component B Unsaturated crosslinker monomer 0.1mol% ~ 20mo
1% by weight of a soft contact lens material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soft contact lens material comprising a polymer suitable for use in a contact lens and a method of manufacturing the same. More specifically, the present invention relates to a soft contact lens material excellent in stain resistance and biocompatibility and a method for producing the same.

[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 water-containing soft contact lenses mainly composed of a hydrophilic monomer such as 2-hydroxyethyl methacrylate. , Widely used. Hard contact lenses made of methyl methacrylate have been used for the longest time and have 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, they have drawbacks such as dirt such as proteins and lipids in tears are easily attached and easily broken. .
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 than a hard contact lens and is excellent in wearing feeling. However, those having a low water content of 40% or less have insufficient oxygen permeability and feeling of wearing in many cases. Therefore, recently, methacrylic acid, N
Highly hydrous soft contact lenses containing vinylpyrrolidone have also been used. In general, a high water content soft contact lens has the characteristics of high oxygen permeability and excellent wearing feeling, but has the disadvantage of deteriorating the performance because proteins, lipids, and the like in tears are easily deposited.

[0003] Contact lens materials obtained by polymerizing 2-methacryloyloxyethyl phosphorylcholine in order to improve the adsorption of proteins and lipids in these tears (Japanese Unexamined Patent Publication No. Hei 6-502200, Japanese Unexamined Patent Publication No. Hei 6-43401, JP-A-6-313865, JP-A-7-159
736) has been proposed. However, although these contact lenses have anti-staining properties such as anti-protein adsorption and anti-lipid adsorption, they require diluent monomers or need to blend a large amount of strength maintaining polymer. there were. Therefore, the content of the structural unit based on the phosphorylcholine-like group-containing monomer is limited, and the performance such as stain resistance and biocompatibility is not always sufficient. Therefore, there has been a demand for a soft contact lens material capable of increasing the content of a structural unit based on a phosphorylcholine-like group-containing monomer and further improving stain resistance and biocompatibility.

[0004]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a soft contact lens material having an improved content of a structural unit based on a phosphorylcholine-like group-containing monomer and having improved stain resistance and biocompatibility. To provide. A second object of the present invention is to provide a method for producing the above soft contact lens material.

[0005]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a soft contact lens material obtained by polymerizing a polymerizable monomer in the presence of a polymerization solvent is not polymerizable. The inventors have found that the above problem can be solved by using only two components, a monomer containing a phosphorylcholine-like group as the component A and an ethylenically unsaturated crosslinking agent monomer as the component B, and completed the present invention. The present invention includes the following (a) to (e).

(A) A soft contact lens material obtained by polymerizing a polymerizable monomer in the presence of a polymerization solvent, wherein a polymerizable monomer having a phosphorylcholine analogous group as component A and an ethylenically unsaturated crosslinking agent as component B are used as polymerizable monomers. A soft contact lens material using two components of a monomer, wherein the component A is 80 mol% to 99.9 mol% of the polymerizable monomer and the component B is 0.1 mol% to 20 mol% of the polymerizable monomer. . (B) The soft contact lens material as described in (a) above, wherein the total concentration of the component A phosphorylcholine-containing group-containing monomer and the component B ethylenically unsaturated crosslinking agent monomer is 50 to 90% by weight. (C) A component is represented by the following formula (1)

[0007]

Embedded image

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are the same or different groups and represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydroxycarbon group. Shows a hydrogen group. X represents a divalent organic residue; Y represents an alkyleneoxy group having 1 to 6 carbon atoms; Z represents hydrogen or R ⁵ —O—CO— (where R ⁵ represents an alkyl group having 1 to 10 carbon atoms). A hydroxyalkyl group having 1 to 10 carbon atoms). Further, m represents 0 or 1, and n represents an integer of 2 to 4. The above (a) or (b) which is a phosphorylcholine analog-containing monomer represented by モ ノ マ ー
2. The soft contact lens material according to item 1. (D) Component B is a difunctional monomer or a monomer having three or more functionalities, and has the following formula (2)

[0009]

Embedded image

In the formula, R ⁶ and R ⁷ may be the same or different and each represent a hydrogen atom or a methyl group, and L ¹ and L ³ represent-
(C = O) -O-,-(C = O) NH-, -O- (C =
O) -, - O -, - O- (C = O) represents a group selected from -O-, L ² _{is, -O -, - (CH 2} CHR 8) n-,
^{_{- {(CH 2 CHR 8)}} p-O} n- ( provided that R ⁸ represents a hydrogen atom or a methyl group, n represents 1 to 24 integer, p is 1
8 represents an integer of), and ^{- (- R 9 SiR 9 -O} ) q
—R ⁹ SiR ⁹ — (where R ⁹ is an alkyl group and q is 1 to
And an integer of 50). (A) which is an ethylenically unsaturated crosslinking agent monomer represented by｝
-The soft contact lens material according to (d). (E) The method according to any one of the above (a) to (d), wherein the phosphorylcholine analog-containing monomer of the component A is 80 mol%.
A soft contact lens obtained by polymerizing 99.9 mol% and an ethylenically unsaturated crosslinking agent monomer of component B from 0.1 mol% to 20 mol% in water or an alcohol or a mixture of water and an alcohol. Material manufacturing method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The present invention relates to a soft contact lens material obtained by polymerizing a polymerizable monomer in the presence of a polymerization solvent, wherein the polymerizable monomer comprises a phosphorylcholine-like group-containing monomer of component A and an ethylenically unsaturated crosslinking agent monomer of component B. A soft contact lens material obtained by using only two components and polymerizing in the presence of a polymerization solvent. In the soft contact lens material of the present invention, only two components of the phosphorylcholine-like group-containing monomer of component A and the ethylenically unsaturated crosslinking agent monomer of component B can be used as the polymerizable monomers. In particular,
The soft contact lens material of the present invention is characterized in that a diluent monomer which is usually used for dissolving a monomer component is not substantially used as a polymerizable monomer. The phosphorylcholine analog-containing monomer of component A used in the soft contact lens material of the present invention includes the following formula (1)

[0012]

Embedded image

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ are the same or different groups and represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydroxycarbon group. Shows a hydrogen group. X represents a divalent organic residue; Y represents an alkyleneoxy group having 1 to 6 carbon atoms; Z represents hydrogen or R ⁵ —O—CO— (where R ⁵ represents an alkyl group having 1 to 10 carbon atoms). A hydroxyalkyl group having 1 to 10 carbon atoms). In addition, m represents 0 or 1, and n represents an integer of 2 to 4. One or more phosphorylcholine analog-containing monomers represented by｝ can be used.

Specific examples of the zwitterionic monomer represented by the formula (1) include, for example, 2- (meth) acryloyloxyethyl-2 '-(trimethylammonio) ethyl phosphate and 3- (meth) acryloyloxy Propyl-2 '-(trimethylammonio) ethyl phosphate, 4- (meth) acryloyloxybutyl-2'-
(Trimethylammonio) ethyl phosphate, 6-
(Meth) acryloyloxyhexyl-2 '-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl-2'-(triethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl-2'- (Tripropylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl-2 '-(tributylammonio) ethylphosphate, 2- (meth) acryloyloxypropyl-2'-
(Trimethylammonio) ethyl phosphate, 2-
(Meth) acryloyloxybutyl-2 '-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxypentyl-2'-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyhexyl-2'- (Trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl-3 '-(trimethylammonio) propyl phosphate, 3- (meth) acryloyloxypropyl-3'-
(Trimethylammonio) propyl phosphate, 4-
(Meth) acryloyloxybutyl-3 '-(trimethylammonio) propyl phosphate, 5- (meth) acryloyloxypentyl-3'-(trimethylammonio) propyl phosphate, 6- (meth) acryloyloxyhexyl-3'- (Trimethylammonio) propyl phosphate, 2- (meth) acryloyloxyethyl-4 '-(trimethylammonio) butylphosphate, 3- (meth) acryloyloxypropyl-
4 '-(trimethylammonio) butyl phosphate,
4- (meth) acryloyloxybutyl-4 '-(trimethylammonio) butyl phosphate, 5- (meth)
Acryloyloxypentyl-4 '-(trimethylammonio) butyl phosphate, 6- (meth) acryloyloxyhexyl-4'-(trimethylammonio) butyl phosphate and the like can be mentioned. Particularly, 2-methacryloyloxyethyl-2 '-(trimethylammonio) ethyl phosphate (hereinafter abbreviated as MPC) is preferably exemplified from the viewpoint of availability and the like. As the ethylenically unsaturated crosslinking agent monomer of the component B used in the soft contact lens material of the present invention, any substance can be used as long as it is an ethylenically unsaturated crosslinking agent monomer.
Particularly, a bifunctional monomer or a monomer having three or more functional groups is used, and the following formula (2)

[0015]

Embedded image

In the formula, R ⁶ and R ⁷ may be the same or different and each represent a hydrogen atom or a methyl group, and L ¹ and L ³ represent-
(C = O) -O-,-(C = O) NH-, -O- (C =
O) -, - O -, - O- (C = O) represents a group selected from -O-, L ² _{is, -O -, - (CH 2} CHR 8) n-,
^{_{- {(CH 2 CHR 8)}} p-O} n- ( provided that R ⁸ represents a hydrogen atom or a methyl group, n represents 1 to 24 integer, p is 1
8 represents an integer of), and ^{- (- R 9 SiR 9 -O} ) q
—R ⁹ SiR ⁹ — (where R ⁹ is an alkyl group and q is 1 to
And an integer of 50). One or more ethylenically unsaturated crosslinking agent monomers represented by｝ can be preferably used.

Specific examples of the difunctional monomer and trifunctional or higher functional monomer represented by the formula (2) include, for example, ethylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, and triethylene glycol di (meth) acrylate. ) Acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, divinyltetramethyldisilane, 1,4-divinyltetramethyldisilylethane,
1,3-divinyltetramethyldisiloxane, 1,5 divinylhexamethyltrisiloxane, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, ditrimethylolpropane Tetraacrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol caprolactone adduct hexa (meth) acrylate, dipentaerythritol propionate hexa (meth) acrylate, pentaerythritol triacrylate tolylene diisocyanate urethane prepolymer, etc. Can be mentioned.

Further, the soft contact lens material of the present invention uses only two components of a phosphorylcholine-like group-containing monomer of component A and an ethylenically unsaturated cross-linking monomer of component B as the polymerizable monomer, and 80 mol% to 99.9 mol% of the whole polymerizable monomer, and B component is 0.1 mol% to 20 mol of the whole polymerizable monomer.
%, And can be obtained by polymerization in the presence of a solvent for polymerization, and more preferably, 83 to 99.5 mol% of a phosphorylcholine analog-containing monomer of Component A,
More preferably, the amount of the ethylenically unsaturated crosslinker monomer of the component B is 851 to 99 mol%, preferably 0.51 mol% to 17 mol%, more preferably 1 mol% to 15 mol%. Further, the concentration of the polymerizable monomer can be obtained by polymerizing at a concentration of 50 to 90% by weight in the presence of a polymerization solvent. Here, the polymerizable monomer means the total amount of the component A and the component B used. For example, in the present invention, the A component and the B component need not be present as a mixture from the beginning, and only one component is dissolved in the polymerization solvent before the polymerization reaction, or both components are dissolved. It may be present in a state of being dissolved in a solvent for polymerization or being mixed. The method for producing a soft contact lens material of the present invention uses a predetermined amount of two components of a phosphorylcholine analog-containing monomer of component A and an ethylenically unsaturated crosslinking agent monomer of component B, and in the presence of a polymerization solvent. It is characterized by being obtained by polymerization.

The polymerization solvent used for polymerizing the entire polymerizable monomer may be any solvent as long as it is a solvent used for polymerization, but may be water, alcohol, or a mixture of water and alcohol. Is preferably used. When the whole monomer for polymerization is dissolved in the solvent for polymerization, the concentration is preferably such that the whole polymerizable monomer is 50 to 90% by weight.

The polymerization can be preferably carried out by a general radical polymerization method. Examples of the radical polymerization initiator used include general ones, and preferably, for example, benzoyl peroxide, lauroyl peroxide, diisopropyl dicarbonate, t-butylperoxy-
2-ethylhexanoate, t-butylperoxypivalate, t-peroxydiisobutyrate, azobisisobutyronitrile, azobisdimethylvaleronitrile,
Azobis (2-amidinopropane) dihydrochloride, azobis (4-cyanovaleric acid), azobisisobutylamide dihydrate, potassium persulfate and the like can be used.

The amount of the radical polymerization initiator 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 the total polymerizable monomers. The polymerization temperature varies depending on the type of the polymerization initiator.
To 140 ° C., and the polymerization time is preferably 6 to 120 hours. Further, a pigment, a dye, a pigment, and an ultraviolet absorber may be contained as long as the physical properties of the obtained contact lens are not affected.
And purple dye No. 201, red No. 404, green No. 202, blue No. 404 and the like, 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 polymerization solution is copolymerized in an appropriate container such as a test tube based on the above radical polymerization conditions. Then, after obtaining a round bar or a block, a method of machining such as cutting and polishing, (b) Injecting the polymerization solution and the radical polymerization initiator into a predetermined mold, and directly molding a contact lens by mold polymerization. how to,
(C) It can be obtained by a method of casting while heating or irradiating light.

The water content of the soft contact lens made from the soft contact lens material of the present invention is 10 to 9
0% is preferred. When the water content is less than 10%, the feeling of wearing decreases, and when it exceeds 90%, the strength decreases, which is not preferable.

[0024]

The soft contact lens material of the present invention comprises a phosphorylcholine-like group-containing monomer 80 of component A.
a material obtained by polymerization in the presence of a polymerization solvent using only 0.1 mol% to 20 mol% of the ethylenically unsaturated crosslinker monomer of the B component and 99.9 mol% of the B component, and has a moderate strength. It is a soft contact lens material with excellent stain resistance and biocompatibility. Further, the production method of the present invention relates to a method for producing a phosphorylcholine analog-containing monomer 8
Using 0 mol% to 99.9 mol% and 0.1 mol% to 20 mol% of the ethylenically unsaturated crosslinking agent monomer of the B component, it is possible to easily obtain a soft contact lens material by polymerizing in the presence of a polymerization solvent. It is a manufacturing method.

[0025]

The present invention will be described below in detail with reference to examples. Example 1 99 mol of 2-methacryloyloxyethyl-2- (trimethylammonio) ethyl phosphate (MPC)
% And 1 mol% of ethylene glycol dimethacrylate were dissolved in water such that the total monomer concentration became 65% by weight. After deoxygenation by passing N ₂ gas through the solution,
5% by weight of potassium persulfate was dissolved. This solution was combined with two sheets of glass and polytetrafluoroethylene sheets.
It was poured into a mold made of two sheets of polyethylene terephthalate film. Thereafter, the mixture was heated at 80 ° C. for 24 hours to perform polymerization. After the polymerization, the resulting colorless and transparent sheet-like polymer was removed from the mold, and swollen in physiological saline to prepare a hydrogel. About the obtained hydrogel, each physical property shown below was evaluated.

(1) Water Content The obtained hydrogel was dried in an oven at 100 ° C. for 24 hours, and the water content was determined by the following equation.

Water content (%) = {(W 1 −W 2) / W 1} × 100 The meanings of the symbols in the formula are as follows. W1: Weight when saturated with water W2: Dry weight

(2) Mechanical strength The obtained hydrogel was cut into strips having a width of 2 mm and a length of 10 mm to obtain test pieces, and the test pieces were obtained using a tensile strength tester (Leonar Re-3305, manufactured by Yamaden Corporation). 1.0m
The test was performed at a pulling speed of m / min.

(3) Evaluation of Protein Adsorption A hydrogel obtained by processing a contact lens into a protein solution obtained by dissolving 0.39 g of albumin, 0.17 g of lysozyme, and 0.11 g of γ-globulin in 100 g of physiological saline was used at 37 ° C. For 7 days. After rinsing with physiological saline, the protein is separated from the hydrogel using a 1% by weight aqueous solution of sodium dodecyl sulfate in a surfactant,
The adsorbed protein was quantified using a protein quantification kit. Table 1 shows the evaluation results of the properties.

[0030]

[Table 1]

The abbreviations used in Table 1 are as follows. MPC: 2-methacryloyloxyethyl-2- (trimethylammonio) ethyl phosphate EGMA: ethylene glycol dimethacrylate TEMMA: triethylene glycol dimethacrylate TMPTA: trimethylolpropane triacrylate

Examples 2 to 5 Polymerization was carried out in the same manner as in Example 1 except that the polymerization components were changed so as to have the compositions and compounding ratios shown in Table 1, and physical properties were measured. Table 1 shows the results.

Comparative Examples 1 to 5 Polymerization was carried out in the same manner as in Example 1 except that the polymerization components were changed so as to have the compositions and compounding ratios shown in Table 2, and physical properties were measured. Table 2 shows the results.

[0034]

[Table 2]

The new abbreviations used in Table 2 are as follows. HEMA: 2-hydroxyethyl methacrylate NVP: N-vinylpyrrolidone MA: methacrylic acid

From the above results, Comparative Example 1 in which MPC alone was polymerized had insufficient strength, whereas Examples 1 to 5 of the present invention had tensile strength, and Comparative Examples 1 to 5 outside the scope of the present invention. It can be seen that the soft contact lens is excellent in stain resistance and biocompatibility as compared with 2 to 5.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2H006 BB01 BB06 BC07 4J027 AC02 AC06 AC07 AF01 AF03 AF04 AF05 BA07 CB03 CB09 CC02 CC04 CD04 4J100 AL08P AL62Q AL63Q AL66Q AL67Q AP17Q BA02P BA02Q BA08Q BA15Q BA32P BA38Q BA63 CA81Q JA34

Claims (5)

[Claims] 1. A soft contact lens material obtained by polymerizing a polymerizable monomer in the presence of a polymerization solvent, wherein the polymerizable monomer is a phosphorylcholine-like group-containing monomer of component A and an ethylenically unsaturated crosslinking agent monomer of component B. And the component A is a polymerizable monomer of 8
A soft contact lens material, wherein 0 mol% to 99.9 mol% and the B component is 0.1 mol% to 20 mol% of the polymerizable monomer. 2. The soft contact lens material according to claim 1, wherein the polymerizable monomer has a concentration of 50 to 90% by weight. (3) The component A has the following formula (1): {Wherein, R ¹ represents a hydrogen atom or a methyl group, R ^2,
R ³ and R ⁴ are the same or different groups and represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydroxy hydrocarbon group. X represents a divalent organic residue; Y represents an alkyleneoxy group having 1 to 6 carbon atoms; Z represents hydrogen or R ⁵ —O—CO— (where R ⁵ represents an alkyl group having 1 to 10 carbon atoms). A hydroxyalkyl group having 1 to 10 carbon atoms). M represents 0 or 1, and n represents 2 to 4
The soft contact lens material according to claim 1, which is a phosphorylcholine-like group-containing monomer represented by｝, which represents an integer of: 4. The component B is a difunctional monomer or a monomer having three or more functional groups, and is represented by the following formula (2). In the formula, R ⁶ and R ⁷ may be the same or different and each represent a hydrogen atom or a methyl group, and L ¹ and L ³ represent — (C ＝ O) —
O-,-(C = O) NH-, -O- (C = O)-, -O
-, -O- (C = O) -O-, a group selected from
_{^2, -O -, - (CH 2} CHR 8) n -, - {(CH 2 C
^{HR 8) p-O} n-} ( provided that R ⁸ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 24, p is an integer of 1-8), and - (- R ⁹ SiR ⁹ - ^{O) q-R 9 SiR 9} -
(However, R ⁹ represents an alkyl group, and q represents an integer of 1 to 50). The soft contact lens material according to claim 1, wherein the soft contact lens material is an ethylenically unsaturated crosslinking agent monomer represented by｝. 5. The manufacturing method according to claim 1, wherein:
Phosphorylcholine analog-containing monomer 80mo of component A
1% to 99.9 mol% and 0.1 mol% to 20 mol% of an ethylenically unsaturated crosslinker monomer of the B component are polymerized in water or an alcohol or a mixture of water and an alcohol in a solvent. Manufacturing method of contact lens material.