JPH0446311A - Production of polysiloxane contact lens - Google Patents

Abstract

PURPOSE:To obtain an unhydrated soft contact lens material not causing sticking to the cornea by mixing an org. siloxane oligomer represented by a prescribed formula with a monomer represented by a prescribed formula in a prescribed ratio and adding diisocyanate represented by a prescribed formula to the mixture. CONSTITUTION:An org. siloxane oligomer represented by formula I is mixed with a monomer represented by formula II in 2.0-2.6 molar ratio of the monomer to the oligomer and diisocyanate represented by formula III is added to the mixture and brought into a reaction. The resulting macrocomputer is mixed with one or more kinds of monomers copolymerizable with the macromonomer and a polysiloxane-based contact lens is produced. In the formula I, R1 is 2-7C divalent hydrocarbon or -(CH2CH2O)-p (p is 1-20), R2 is methyl or trifluoropropyl, Y is -OH or -SH and n is an integer of 0-100. In the formula II, R3 is H or methyl and R4 is 2-4C hydrocarbon contg. one or more active H atoms or -(CH2 CH2O)-pH (p is 2-20). In the formula III, R5 is a residue obtd. by removing -NCO from aliphatic, alicyclic or arom. diisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel contact lens material. More specifically, the present invention provides a substantially water-free soft contact lens material that has excellent oxygen permeability, optical and mechanical properties, is comfortable to wear, and has no risk of sticking to the cornea. The present invention relates to a manufacturing method.

[Conventional technology]

Soft contact lenses are divided into hydrated soft contact lenses and non-hydrated soft contact lenses.

Water-containing soft contact lenses are made of a copolymer mainly composed of hydrophilic lenses such as hydroxyethyl methacrylate and N-vinylpyrrolidone.The lenses are made by cutting or casting and then swollen in physiological saline. The treated lens has a water content of approximately 40-70%.

Non-hydroscopic soft contact lenses can be produced, for example, by adding a platinum-based catalyst to a mixture of polydimethylsiloxane and methylhydrodiene polysiloxane whose molecular chain ends are blocked with vinyldimethylsilyl groups, and then heating and curing the mixture using a molding method. A silicone rubber lens obtained by a method of There are known flexible lenses having
-127914).

In addition, lenses are made by cutting a hard base material made by copolymerizing (meth)acrylic acid and (meth)acrylic acid ester, and this is then subjected to esterification and/or transesterification treatment to create a lens that is comfortable to wear. Non-water-containing soft contact lenses are also manufactured (Japanese Unexamined Patent Publication No. 75047/1983).
.

Contact lens materials with high oxygen permeability based on polyfunctional polysiloxane are also disclosed in JP-A No. 54-24047,
It is described in Japanese Patent Application Laid-Open No. 56-51715.

Water-containing soft contact lenses have the advantage of being soft and comfortable to wear, and higher water-containing types have higher oxygen permeability. It is often inconvenient to handle, such as having to periodically sterilize it by boiling, as it is easily contaminated by bacteria and there is a risk of bacterial growth.

Non-water-containing contact lenses also have the following problems.

First of all, when silicone rubber lenses were first developed, they had drawbacks such as the hydrophilic treatment layer applied to improve the hydrophobicity of the lens surface peeling off, and their excessive elasticity causing them to stick to the cornea. However, recent advances in surface hydrophilic treatment technology, changes in lens design, and improvements in mechanical properties have significantly improved the above drawbacks. However, the actual situation is that it is still not completely satisfactory and has not yet been widely used.

Next, non-hydrous lenses that are mainly composed of polyperfluoroether are more like semi-hard types than soft contact lenses, so they do not feel as comfortable when worn as soft contact lenses. The movement is also not satisfactory.

In addition, soft contact lenses mainly composed of (meth)acrylic acid esters have poor oxygen permeability and are therefore not suitable for long-term wear.

All materials based on polyfunctional polysiloxane do not take contamination by components in lachrymal fluid into account, and are more similar to silicone rubber lenses.

[Problem to be solved by the invention]

Under these circumstances, the present invention has developed a material that has a very high oxygen permeability coefficient (DK value) that indicates oxygen permeability, excellent optical and mechanical properties, and has good wearing comfort and stain resistance. death,
The purpose of this invention is to provide a substantially water-free soft contact lens material that does not have to worry about sticking to the cornea.

[Means to solve the problem]

The present inventors have conducted extensive research in order to develop a water-free soft contact lens material having the above-mentioned favorable properties. It was discovered that the object could be achieved using a material made of a copolymer, and the present invention was completed based on this knowledge.

That is, the present invention provides 2(I) (wherein R1 is a linear or branched divalent hydrocarbon group having 2 to 7 carbon atoms or p is 1 to 20 +CHzCHzO
+p group, R2 is methyl group or trifluoropropyl group, Y is 10H group or -SH group, n is 0
is an integer of 100 to 100) and the organosiloxane oligomer represented by the formula (II) (
In the formula, R3 is hydrogen or a methyl group, and R4 is a hydrocarbon group having 2 to 4 carbon atoms containing one or more active hydrogen, or P is 2 to 20 + cl (zcHzo +, H group) The monomer represented by (II)/(I) is 2.0 to 2
．． 6 molar ratio, and to this mixture, the formula (I
A macromer obtained by adding and reacting a diisocyanate represented by the formula %([) (wherein R6 is a residue obtained by removing the NGO group from an aliphatic, cycloaliphatic or aromatic diisocyanate) and one or more heptamers copolymerizable with the macromer.

As the molecular weight of the siloxane oligomer represented by the general formula (I) increases, the length of the open chain of the functional group increases, which improves oxygen permeability, lowers the cohesive energy, and lowers the glass transition point. Therefore, when made into soft contact lenses, it has a great effect on physical properties such as softness, shape retention indicated by rubber elasticity, and returnability. However, the organosiloxane oligomer (
If the repeating number n of the siloxanyl units in I) exceeds 100, the compatibility with other monomers will deteriorate, resulting in cloudiness or phase separation. Not only was there no significant difference in oxygen permeability,
The properties of the silicone rubber lens become stronger, causing increased contamination by components in tear fluid. In view of the softness and flexibility required for oxygen permeable soft contact lenses, a value of the repeating number n in the range of 10 to 100, preferably 20 to 80 provides the most balanced material.

In 2 (I), R3 is a straight chain or branched chain having 2 to 2 carbon atoms.
7 divalent hydrocarbon group or P is 1 to 20+CH2
C1 (20+, group. Preferably 3 to 4 carbon atoms
is a divalent linear hydrocarbon group.

R2 is a methyl group or a trifluoropropyl group, and these organic siloxane oligomers can be used alone or in combination.

Y is an 10H group or a -SH group, and these organic siloxane oligomers can be used alone or in combination.

The hexamer represented by formula (II) is an acrylic ester or methacrylic ester containing active hydrogen.
In I), R4 has 2 to 4 carbon atoms and contains one or more active hydrogen.
or +CI(zC)Iz where p is 2-2o
O-)-, H group. Preferably, it is at least one selected from 2-hydroxy methacrylate, 2-hydroxy acrylate, 3-hydroxypropyl methacrylate, 3-hydroxy acrylate, diethyl glycol methacrylate, diethylene glycol acrylate, and the like.

Organosiloxane oligomers represented by 2 (r) and 2 (
The mixing ratio of monomers represented by IT) is (II)/(
I) is in a range of 2.0 to 2.6 molar ratio.

If this ratio is less than 2, the resulting macromer may become cloudy or have reduced strength when polymerized.

Moreover, if it is larger than 2 or 6, the softness of the obtained contact lens will be insufficient or it will become cloudy.

The compatibility of the macromer with other monomers is evaluated from the viewpoint of the transparency of the polymer, and the balance of physical properties such as strength and elasticity (f
f) B) is preferably in a molar ratio of about 2.0 to 2.3. The diisocyanate represented by II (III) has the formula (
Among II), R6 is one or more selected from aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbon residues. Hexamethylene diisocyanate, tetramethylene diisocyanate,
2゜4.4-Trimethyl-1,6-hexamethylene diisocyanate, 2.6-diycyanatomethyl caproate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4 '-diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, xylylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, etc. are used.

The macromer of the present invention is obtained by reacting a mixture of the above-mentioned organosiloxane oligomer (I) and active hydrogen-containing upper parter (I[) with diisocyanate (III). The amount of diisocyanate (I[r) added to the mixture of organic siloxane oligomer (I) and active hydrogen-containing monomer (II) is such that the isocyanate group equivalent is 0.8 to 1.5 per equivalent of active hydrogen. The equivalent ratio is preferably 0.9 to 1.1 from the viewpoint of the balance of properties such as optical properties, mechanical properties, and dirt adhesion of the contact lens.

This reaction may be carried out by adding known catalysts such as organotin compounds or tertiary amines, or by heating. Furthermore, in order to inhibit the polymerization of acryloyl or methacryloyl groups, it is desirable to proceed with the reaction by adding a small amount of a polymerization inhibitor, such as hydroquinone, methylhydroquinone, isopropylhydroquinone, hydroquinone 7-methyl ether, or di-t-butyl para-cresol. .

For this reaction, the following macromer and copolymerizable,
In addition, a diluent which is inert to isocyanates may be used as a diluent.

The reason why the macromer of the present invention is excellent for use in contact lenses is that diisocyanate (
II[), compared to a macromer obtained by reacting a conventional organic siloxane oligomer with a diisocyanate oligomer at both ends, which is reacted with a diisocyanate, and an unsaturated monomer containing active hydrogen. It has excellent compatibility with the macromer and copolymerizable monomer, which will be described later, and the resulting copolymer has excellent mechanical strength, elastic modulus, and softness.

The details of this reason are unknown, but compared to the case where the reaction is carried out in two steps, the reaction between organosiloxane oligomer (I) and diisocyanate (I [ This is thought to be because the coexistence of Zummer (I[) causes the viscosity of the reaction system to be lower than that of organosiloxane oligomer (I) alone, and the reaction of isocyanate groups proceeds uniformly, reducing the number of unreacted isocyanate groups.

As an example of the macromer of the present invention, for example, a mixture of α,ω-bis(3-hydroxypropyl) to polydimethylsiloxane having a degree of polymerization of about 20 and 2-hydroxyethyl methacrylate is reacted with 16-hexamethylene diisocyanate. α, ω with a degree of polymerization of about 40
A product obtained by reacting a mixture of -bis(3-hydroxypropyl)-polydimethylsiloxane and 2-hydroxyethyl methacrylate with R6-hexamethylene diisocyanate, α,ω bis(3- hydroxypropyl dimethyl siloxy) polymethyl (trifluoropropyl) siloxane and 2-hydroxyethyl methacrylate and isophorone diisocyanate, obtained by reacting isophorone diisocyanate, α, ω- with a degree of polymerization of about 40
There are those obtained by reacting a mixture of bis(3-mercabutopropyl)-polydimethylsiloxane and 3-hydroxypropyl methacrylate with 1,6-hexamethylene diisocyanate.

The contact lens of the present invention is produced by polymerizing the macromer and one or more copolymerizable monomers. Examples of heptamers copolymerizable with the macromer include trifluoroethyl acrylate, tetrafluoroethyl acrylate, tetrafluoropropyl acrylate, pentafluoropropyl acrylate, hexafluorobutyl acrylate, hexafluoroisopropyl acrylate, heptafluorobutyl acrylate, and octafluorobutyl acrylate. Acrylic acid fluoroalkyl esters such as fluoropentyl acrylate and corresponding methacrylic acid fluoroalkyl esters, methacrylates such as methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and Acrylates corresponding to these, aromatic vinyl compounds such as styrene, t-butylstyrene, α-methylstyrene, methacrylic acid, acrylic acid, itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Hydrophilic monomers such as methacrylate, 2-hydroxypropyl acrylate, glycerol methacrylate, polyethylene glycol methacrylate, N,N'-dimethylacrylamide, N-methylacrylamide, N-vinylpyrrolidone, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Cross-linking materials such as dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, vinyl methacrylate, acrylic methacrylate and corresponding acrylate a, divinylbenzene, triallylisocyanurate, etc. - etc.

In order to improve the balance of contact lenses' optical properties, oxygen permeability, mechanical strength, deformation recovery, dirt adhesion when worn on the eye, dimensional stability in tear fluid and its change over time, etc. Mixed monomers combining copolymerizable monomers can be used.

Examples of mixed monomers copolymerizable with the macromer of the present invention include trifluoroethyl acrylate, n
-butyl acrylate, a combination of methacrylic acid and ethylene glycol dimethacrylate, hexafluoroisopropyl acrylate, n-butyl acrylate,
Examples include combinations of methacrylic acid and diethylene glycol dimethacrylate.

A known method can be used to manufacture contact lenses. For example, a method in which a photopolymerization initiator such as hensifhenone, hengeine, benzyl dimethyl ketal, etc. is mixed with a mixture of a macromer and a copolymerizable heptamer, and the mixture is filled into a lens mold and irradiated with ultraviolet rays to polymerize the macromer. A method in which a polymerization initiator such as azobisisobutyronitrile, hensyl peroxide, lauroyl peroxide, etc. is mixed with a mixture of and 7-mer, and the mixture is filled into a lens mold and thermally polymerized and molded.

A method that can be used is to polymerize a mixture of macromer and 7-mer to form a disk, round rod, etc., and then cut and polish the resulting shape at room temperature or low temperature.

〔Example〕

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.

In addition, each physical property and molecular weight were calculated|required as follows.

(I) Oxygen permeability coefficient -31 to the gas permeability measuring device manufactured by Rika Seiki Kogyo Co., Ltd.
5-N was used. A disk-shaped sample piece with a diameter of 30 mm and a thickness of 0.3 mm was used for measurement, and the oxygen permeability coefficient was calculated from the slope of the straight line on the obtained chart. The measurements were carried out in a constant temperature room at 25°C, with the sample piece set at 35°C.

(2) Contact Angle manufactured by Kyowa Interface Science Co., Ltd.
MeterCA-A was used. Before measurement, the sample pieces were mirror-polished, surface dirt was removed using a surfactant, and then immersed in physiological saline for 24 hours before being used for measurement. For measurement, the sample piece is placed in pure water, a bubble with a diameter of 1.5 to 2.0 cm is brought into contact with the bottom surface of the sample piece using a syringe, the angle formed between the bubble and the sample piece is read, and the contact angle is calculated by calculating the angle formed between the bubble and the sample piece. I asked for

(3) Tensile Strength A universal tensile compression tester 5V50 manufactured by Imada Seisakusho Co., Ltd. was used. A sample piece with a thickness of 0.3 m, a width of 5.0 mm, and a length of 30 m was used for measurement. The pulling speed is 10 a/
It was a win. Measurements were performed three times on the same sample piece.
From the obtained values, tensile strength was determined according to the calculation method described in JIS-6301.

(4) Dirt adhesion Journal of the Japanese Contact Lens Society, Vol. 24, No. 277-2
A stain adhesion test was conducted according to the method described on page 83 (I982). The sample piece is 2mm thick and 511Ifl wide.
1 and a length of 30 mm was used. The judgment is P as a control.
Based on the dirt adhesion when the MMA sample piece is operated in the same way, if the degree of dirt adhesion is less than that when observed with the naked eye, it is ``little'', if it is more, it is ``extensive'', and if it is the same, it is ``same''.
And so. Three types of dirt substances were used as models: mucin (bovine gastric mucosa), lysozyme (Uhaku), and lecithin (Uoji).

(5) Hardness According to the method described in JIS-6301, hardness (Sho
re A) Measured.

(6) Measurement of molecular weight Mn of organosiloxane oligomer (I) Liquid chromatograph: LC-3A model (manufactured by Shimadzu Corporation) Column: 5hodex
802+803+805 (manufactured by Showa Denko ■) Detector: ERC-751OS (manufactured by Elma Optical ■) Inch Grater Near 000A (manufactured by System Instruments) Solvent: Toluene Temperature: 25°C Standard polymer for molecular weight calibration curve: Monodisperse Various types of polystyrene (manufactured by Toyo Soda ■) (Mw/Mn= 1.2 (IIlax)) Mn and n
is calculated from the above analysis results.

Example 1 50 parts by weight of α,ω-bis(3-hydroxypropyl)-polydimethylsiloxane (n+30) and 6 parts by weight of 2-hydroxyethyl methacrylate were uniformly mixed.
I ratio 2.16), 7.2 parts by weight of 1.6-hexamethylene diisocyanate, 0.2 parts by weight of dibutyltin dilaurate, and 0.01 parts by weight of hydroquinone were placed in a flask equipped with a condenser, a thermometer, and a stirrer. The mixture was kept at 40°C and reacted for 24 hours while passing nitrogen gas. After confirming the disappearance of absorption based on isocyanate groups by infrared absorption spectrum, 40 parts by weight of hexafluoroisopropyl acrylate (abbreviated as AA-FTP), 10 parts by weight of n-butyl acrylate (hereinafter abbreviated as n-BA), and methacrylic acid (abbreviated as n-BA) were added. 5 parts by weight of diethylene glycol dimethacrylate (hereinafter abbreviated as 2ED), and benzyl dimethyl ketanol (manufactured by Ciba Geigy).
651) 0.5 part by weight was mixed. The mixture was injected into a cell made of two glass plates (10m++ thick, 50mm wide, 100mm long) with a silicone rubber gasket inserted between them, and the cell was heated at 50-60''C. A copolymer was obtained by irradiating with ultraviolet rays for 2 hours at the same temperature.The copolymer thus obtained was measured for oxygen permeability coefficient, contact angle, tensile strength, stain adhesion, and hardness.

The results are shown in Table 1.

Example 2 The mixture of monomers and oligomers used in Example 1 was
It was filled into a polypropylene uneven mold made by injection molding and irradiated with ultraviolet rays for 2 hours. After irradiation, the lens taken out from the mold was transparent, soft, and had good strength and returnability.

When this lens was washed with an aqueous solution containing a surfactant and stored in pure water, a lens with good water wettability was obtained.

Examples 3 and 4 Except for using α,ω~bis(3-hydroxypropyl)polydimethylsiloxane (n+30) used in Example 1, n+40 was used in Example 3 and n:60 was used in Example 4. A copolymer was obtained in the same manner as in Example 1,
Its physical properties were measured. The results are shown in Table 1.

Example 5 A copolymer was obtained in the same manner as in Example 1, except that AA-PIF used in Example 1 was replaced with trifluoroethyl acrylate (hereinafter abbreviated as 3FA), and its physical properties were measured. The results are shown in Table 1.

Examples 6-11 α,ω-Bis(3-hydroxypropyl)polydimethylsiloxane (n+30), 8A-FIP, 3FA.

A mixture was prepared by mixing n-BA, MAA, and 2ED monomers in the proportions shown in Table 1, a copolymer was obtained in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table 1.

Example 12 A macromer was produced in the same manner as in Example 1, except that α1ω-bis(3-mercaptopropyl)-polydimethylsiloxane (n+40) was used, and a copolymerizable monomer was used in the same manner as in Example 1. Filled into a polypropylene uneven mold and irradiated with ultraviolet rays for 1 hour, the outer diameter was approximately 8.5 mm.
A ttm lens was manufactured. The obtained lens was transparent, soft, strong, and had good returnability.

Example 13 A macromer was produced in the same manner as in Example 1, except that 3-hydroxypropyl methacrylate and isophorone diisocyanate were used instead of 2-hydroxyethyl methacrylate and L6 hexamethylene diisocyanate.

Using the same copolymerizable monomer as in Example 1, a concavo-convex mold made of polypropylene was filled and irradiated with ultraviolet rays for 1 hour to produce a lens with an outer diameter of about 8.5=. The obtained lens was transparent, soft, had excellent strength and returnability, and had excellent performance with little dirt adhesion.

Comparative Example 1 50 parts by weight of α1ω-bis(3-hydroxypropyl)-polydimethylsiloxane (n+30), 7.2 parts by weight of 1,6-hexamethylene diisocyanate, and 0.2 parts by weight of dibutyltin dilaurate were placed in a cooler and a thermometer. , put it in a flask equipped with a stirrer, and pass nitrogen gas through it for 4 hours.
The reaction was maintained at 0°C for 24 hours, and then 6 parts by weight of 2-hydroxyethyl methacrylate and 0% of hydroquinone were added.
．． Add 1 part of 0.01 weight, and while passing nitrogen gas,
The reaction was maintained at 40°C for 24 hours.

After confirming the disappearance of absorption based on isocyanate groups by infrared absorption spectrum, the same monomers as in Example 1 were mixed and polymerized. The obtained copolymer was slightly cloudy, had a tensile strength of 200 g/lll112, and had a high stain adhesion property.

(The following is a blank space) [Effects of the Invention] The contact lens obtained by the present invention has hard oxygen permeability, excellent hydrophilicity, good mechanical properties, and has stain resistance comparable to that of PMMA-based hard contact lenses. It is something. In addition, the hardness can be easily adjusted, and there is no risk of corneal stickiness.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 is a straight chain or branched 2 having 2 to 7 carbon atoms.
a valent hydrocarbon group or a ▲ mathematical formula, chemical formula, table, etc. ▼ group in which p is 1 to 20, R_2 is a methyl group or trifluoropropyl group, and Y is an -OH group or -S
H group, n is an integer from 0 to 100) Organosiloxane oligomers represented by formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_3 is hydrogen or methyl group Yes, R_4 is 1
A monomer represented by (II)/(I ) is 2.0~2
．． 6 molar ratio, and to this mixture, the formula (I
II) Obtained by adding and reacting a diisocyanate represented by OCN-R_5-NCO (3) (wherein R_5 is a residue obtained by removing the NCO group from an aliphatic, alicyclic or aromatic diisocyanate) A method for producing a polysiloxane contact lens, which comprises polymerizing a macromer and one or more monomers copolymerizable with the macromer.