GB1588744A - Creation of Inventions and Patents with Artificial Intelligence

GB1588744A – Cross-linked polymer composition for use in soft contact lenses
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GB1588744A – Cross-linked polymer composition for use in soft contact lenses
– Google Patents
Cross-linked polymer composition for use in soft contact lenses

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Publication number
GB1588744A

GB1588744A
GB44644/77A
GB4464477A
GB1588744A
GB 1588744 A
GB1588744 A
GB 1588744A
GB 44644/77 A
GB44644/77 A
GB 44644/77A
GB 4464477 A
GB4464477 A
GB 4464477A
GB 1588744 A
GB1588744 A
GB 1588744A
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Prior art keywords
cross
composition according
weight
polymerization
linking agent
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1976-11-04
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Toray Industries Inc

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Toray Industries Inc
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1976-11-04
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1977-10-26
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1981-04-29

1977-10-26
Application filed by Toray Industries Inc
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Toray Industries Inc

1981-04-29
Publication of GB1588744A
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patent/GB1588744A/en

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Classifications

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen

C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof

C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof

C08F220/10—Esters

C08F220/12—Esters of monohydric alcohols or phenols

G—PHYSICS

G02—OPTICS

G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS

G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

G02B1/041—Lenses

G02B1/043—Contact lenses

Description

PATENT SPECIFICATION ( 11) 1588 744
r ( 21) Application No 44644/77 ( 22) Filed 26 Oct 1977 Fd 199 ( 31) Convention Application No 51/132538 ( 32) Filed 4 Nov 1976 in > ( 33) Japan (JP) O
X ( 44) Complete Specification Published 29 Apr 1981
U ( 51) INT CL 3 CO 8 F 226/06 GO 2 C 7/04 (C 08 F 226/06 220/18) ( 52) Index at Acceptance C 3 P 154 202 216 220 222 234 252 254 260 266 302 304 306 316 328 FE C 3 Y B 370 F 205 G 220 G 230 G 2 J 56 C ( 54) CROSS-LINKED POLYMER COMPOSITION FOR USE IN SOFT CONTACT LENSES ( 71) We, TORAY INDUSTRIES, INC, a Company organized and existing under the laws of Japan of 2, Nihonbashi Muromachi 2-chome, Chuo-ku, Tokyo, Japan, do hereby declare the invention for which we pray that a Patent may be granted to us, and the method by which it is to be performed to be particularly described in and by the following statement: 5
Water-containing gels of 2-hydroxyethyl methacrylate (hereinafter referred to as “HEMA” for brevity) polymers have been widely used in so-called “soft contact lenses”, because soft contact lenses made from such water-containing gels possess good transparency and do not irritate the eyeballs during wearing However, these soft contact lenses are poor in permeability to some substances such as oxygen When the soft contact lenses are 10 worn during sleeping, cornea lesions sometimes occurred due to shortage of oxygen.
Therefore, such lens must be removed before sleeping.
In general, permeability of water-containing polymeric gels to oxygen increases with an increase of the water content Therefore, HEMA/N-vinylpyrrolidone copolymer gels have recently been proposed for use in making soft contact lenses Such gels are prepared by 15 copolymerizing HEMA with N-vinylpyrrolidone or graft-copolymerizing HEMA onto poly-N-vinylpyrrolidone The HEMA/N-vinylpyrrolidone copolymer gels exhibit an equilibrium water content of 70 % or more at 370 C although a HEMA homopolymer gel has an equilibrium water content of less than about 40 % However, the HEMA/ N-vinylpyrrolidone copolymer gels are still not satisfactory in that they are poor in 20 mechanical strengths Accordingly, soft contact lenses made therefrom are liable to be fragile.
Cross-linked copolymers of N-vinyllactams and other methacrylic acid esters such as methyl methacrylate have also been proposed for use in soft contact lenses Watercontaining gels of these cross-linked copolymers generally exhibit somewhat improved 25 mechanical strengths as compared with HEMA/N-vinylpyrrolidone copolymers Various cross-linking agents have been proposed for use in the preparation of these cross-linked copolymers For example, U S Patent 3,532,679 discloses the use of tetraethylene glycol dimethacrylate British Patent 1,391,438 discloses the use of divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylate, and diethylene glycol bis (allylcarbonate) 30 However, these cross-linked N-vinyllactam/methacrylic acid ester copolymers are still not satisfactory as materials for use in soft contact lenses which can be worn continuously for a long period of time, because they do not completely satisfy the requisites stated below.
The requisites for water-containing polymeric gels for use in soft contact lenses which can be worn continuously for a long period of time will be explained in the following First, the 35 water-containing polymeric gels should possess an equilibrium water content of at least % by weight, preferably from 65 % to 80 %, at 37 C for providing the desired permeability to oxygen In general, as the equilibrium water content increases, the mechanical properties of the polymeric gels are liable to become undesirable It is preferable that the polymeric gels possess a tensile strength of at least 10 kg/cm 2 an 40 1 588 744 elongation at break of at least 100 %, and more preferably a product of the tensile strength and the elongation being at least 1,500 % kg/Cm 2 Secondly, the polymeric gels should not become opaque, distorted, or colored Their mechanical strengths should not become reduced upon immersing in boiling water, which immersion is popularly carried out for sterilization Furthermore, the polymeric gels should contain little or no water-soluble, 5 extractable matter which can be dissolved during wearing of the soft contact lenses.
U.S Patent 3,949,021 discloses a cross-linked N-vinylpyrrolidone polymer for use in soft contact lenses, which polymer is prepared by polymerizing Nvinylpyrrolidone in the presence of (i) a water-insoluble polymer, dissolved in Nvinylpyrrolidone, such as polymethyl methacrylate, and (ii) a cross-linking agent However, the polymer product is 10 mainly comprised of polymethyl methacrylate and a cross-linked poly-Nvinylpyrrolidone, and is not satisfactory in the following First, soft contact lenses made from the polymer product are poor in dimensional stability upon immersion in boiling water Second, a polymethyl methacrylate solution in N-vinylpyrrolidone is too viscous to be easily handled for the polymerization operation That is, it is difficult to prepare the polymer solution of a 15 concentration of more than approximately 20 % by weight, to filter the polymer solution for the removal of foreign matters therefrom, and, furthermore, to uniformly dissolve a polymerization initiator in the polymer solution Third, the resulting polymer product is poor in resistance to organic solvents.
Embodiments of the present invention seek to provide a cross-linked polymer 20 composition which can become a transparent polymeric gel for use in soft contact lenses, which polymeric gel completely satisfies the above-mentioned requisites, i e a gel which possesses an equilibrium water content of at least 60 % by weight and improved mechanical properties, and which contains little or no water-soluble, extractable matter and is not changed both in shape and dimension upon immersion in boiling water 25 According to the invention there is provided a cross-linked polymer composition providing a transparent aqueous polymeric gel having an equilibrium water content of at least 60 % by weight for use in soft contact lenses, which polymer composition is prepared by polymerizing, using a bulk polymerization procedure, a monomer mixture comprising an alkyl methacrylate and an N-vinyllactam in the presence of a crosslinking agent comprising 30 triallyl isocyanurate.
N-vinyllactams and alkyl methacrylates have poor capability for being copolymerized with each other When they are co-polymerized, the resulting polymer product is mainly comprised of two copolymer ingredients: a copolymer ingredient derived from a major amount of an alkyl methacrylate and a minor amount of an N-vinyllactam, and a copolymer 35 ingredient derived from a major amount of an N-vinyllactam and a minor amount of an alkyl methacrylate The alkyl-methacrylate-rich copolymer ingredient and the Nvinyllactam-rich copolymer ingredient are liable to be subject to phaseseparation, and therefore, the polymer product comprising these two copolymer ingredients tends to become undesirably opaque In order to overcome this defect, the respective copolymers 40 should have a cross-linked structure possessing a moderate degree of cross-linking.
However, most conventional cross-linking agents tend to produce a polymer product of which one copolymer ingredient (usually, the alkyl acrylate-rich copolymer ingredient) exhibits a far enhanced degree of cross-linking as compared with the other copolymer ingredient In contrast to this fact, the cross-linking agent used in the present invention can 45 advantageously provide a moderate degree of cross-linking to the two copolymer ingredients.
The alkyl methacrylates used for the preparation of the polymer composition of the invention are preferably those methacrylates whose alkyl group possesses 1 to 4 carbon atoms The N-vinyllactams used for such preparation are, for example, Nvinyl-2 50 pyrrolidone, N-vinyl-2-piperidone and N-vinylcaprolactam A combination of methyl methacrylate as the alkyl methacrylate and N-vinylpyrrolidone as the Nvinyllactam is preferable because these two monomers are readily available.
The monomer mixture may comprise, in addition to the alkyl methacrylate and the N-vinyllactam, a small amount of at least one other copolymerizable monoethylenically 55 unsaturated monomer for the purpose of, for example, forming a watercontaining polymeric gel having desirably controlled hardness and mechanical properties This additional monomer can be selected from, for example, alkyl acrylates (the alkyl group of which possesses 1 to 4 carbon atoms) acrylonitrile, styrene, vinyl acetate and 2hydroxyethyl methacrylate 60 The monomer mixture should preferably comprise 10 to 40 % by weight of alkyl methacrylate, 60 to 80 % by weight of an N-vinyllactam and 0 to 20 % by weight of one or more other copolymerizable monoethylenically unsaturated monomers, based on the total weight of the monomer mixture excluding the cross-linking agent.
In addition to the above-mentioned cross-linking agent, namely, triallyl isocyanurate, 65 1 588 744 minor amounts of at least one other cross-linking agent may be used Preferable cross-linking agents used in addition to the above-mentioned crosslinking agent are polyethylene glycol dimethacrylates which are expressed by the formula:
CH 3 CH 3 5 CH 2 =C-COO t CH 2 CH 2 O -),CO C=CH 2 (I) wherein N is an integer of from 2 to 6 Typical polyethylene glycol dimethacrylates of the formula (I) are di-, tri and tetra-ethylene glycol dimethacrylates The amount of this 10 additional cross-linking agent is less than 50 % by mole based on the total amounts of the cross-linking agents, i e less than one mole per mole of triallyl isocyanurate used.
Preferably, the amount of the additional cross-linking agent is below 0 5 mole per mole of triallyl isocyanurate used.
The bulk polymerization of the monomer mixture is carried out in the presence of a 15 polymerization initiator The polymerization initiator used may be selected from conventional free-radical initiators, which may be selected from, for example, organic and inorganic peroxides such as di-tert -butylperoxide and ammonium persulfate; and azo compounds such as 2,2 ‘-azobisisobutyronitrile, 2,2 ‘-azobis-2,4dimethylvaleronitrile, 2,2 ‘azobis( 4-methoxy-2,4-dimethyl-valeronitrile and 1,1 ‘-azobiscyclohexane1-carbonitrile 20 Besides these thermally decomposing-type polymerization initiators, photosensitizers may be used which include, for example, acetophenone, benzophenone, xanthone, benzoin and benzoin ethyl ether The amount of the polymerization initiator is from 0 001 to 1 0 % by mole, preferably 0 005 to 0 5 % by mole, based on the amount of the monomer mixture.
It is preferable that, as the polymerization proceeds, the polymerization temperature be 25 increased either in a stepwise manner or in a continuous manner When a thermally decomposing-type polymerization initiator is used, the polymerization temperature may preferably be set at a temperature of from 100 to 50 ‘C at the initial stage and at a temperature of from 900 to 160 ‘C at the final stage When a photosensitizer is used with, for example, ultraviolet light irradiation from a high pressure mercury lamp, the polymeriza 30 tion temperature may be set at a temperature of from 00 to 40 ‘C at the initial stage.
If desired, a combination of two or more thermally decomposing-type initiators having different decomposing temperatures or a combination of at least one thermally decomposing-type initiator and at least one photosensitizer may be used.
The polymerization product obtained may be in a desired shape such as a rod, plate or 35 any other block shapes However, a rod-shaped product with a circular cross-section is most preferable The rod-shaped polymer is formed by carrying out bulk polymerization within a tube exhibiting a circular cross-section, preferably disposed in a substantially vertical direction and having an inner diameter of from 10 to 20 mm and a wall thickness of from 0 5 to 3 mm In view of the fact that the polymer product can be separated from the inner wall 40 of the tube due to the shrinkage of the polymer product before completion of the polymerization, it is preferable that the tube is made of polypropylene, high density polyethylene or polyfluoroethylene Of these components, polypropylene is optimum The tube may be of a length of from 10 to 50 cm The bottom of the tube may be made of the same material as that of the tube wall 45 Soft contact lenses may be manufactured from the polymer block as described hereinafter Button-like articles are cut from the block, and then subjected to lathing, polishing and then swelling in physiological salt solution or water The water-soluble, extractable matter may be removed either by using the above-mentioned swelling treatment in physiological salt solution or water or by immersing the article, treated by swelling, 50 further in water at approximately 100 ‘C for a period of at least 6 hours, preferably from 10 to 30 hours.
The dry polymer composition of the invention exhibits an extractionretention percentage of from 85 % to 95 % by weight as measured after being immersed in water at 100 ‘C for 16 hours, although such an extraction-retention value is less than that of the 55 conventional polymer used in soft contact lens When the extractionretention percentage is too small, the resulting contact lenses are poor in elongation at break, and fragile In contrast, when the extraction-retention percentage is too large, it is difficult to completely remove the water-soluble, extractable matter therefrom and the soft contact lenses are poor in dimensional stability upon immersion in boiling water 60 It has been found that the water-containing polymeric gels in the form of discs or lenses obtained from a cylindrical polymer rod exhibit a substantially constant D value, which is defined by the following equation, i e a D value of 1 19 0 07.
1 588 744 D=(l-0 1) ( 10 _ 1) wherein f is the linear swelling coefficient of expansion, ER is the extraction-retention 5 percentage and W is the equilibrium water content (%) Determination of the values for f 3, ER and W will be further described below.
The present invention will be further illustrated in detail with reference to the following Examples wherein parts and percentages are by weight unless otherwise specified.
In the Examples, the performances of the polymeric gels were determined as follows 10 (i) Linear swelling coefficient of expansion (P 3) A disc-shaped specimen having a thickness of from 0 2 to 0 3 mm and a diameter of 11 mm was cut from a cylindrical polymer block.
The specimen was dried at 40 WC and 1 mm Hg for 16 hours, and its diameter “a” (in mm) was measured Then, the specimen was first immersed in pure water at boiling temperature 15 for 16 hours; further immersed in pure water at 370 C for two hours; and, then, its diameter “b” (in mm) was measured in pure water at 370 C The linear swelling coefficient of expansion (P) is expressed by the formula:
3 = b/a 20 (ii) Extraction-retention percentage (ER) The disc-shaped specimen was dried at 40 WC and 1 mm Hg for 16 hours, and its weight “im” (in grams) was measured Then, the specimen was immersed in pure water at boiling temperature for 16 hours and, then, dried at 40 WC and 1 mm Hg for 16 hours The weight 25 “n” (in grams) of the specimen was measured again The extractionretention percentage (ER) is expressed by the formula:
ER (%) (n/mi x 100 30 (iii) Equilibrium water content (W) After immersion of the disc-shaped specimen in boiling water for 16 hours and then in 370 C water for 2 hours, the weight of the specimen “p” (in grams) was measured The equilibrium water content (W) is expressed by the formula:
35 W (%) = l (p-n)/pl x 100 (iv) Dimensional change upon boiling The disc-shaped specimen used for the determination of its diameter “b” after immersion in boiling water for 16 hours, in the above-mentioned item (i), was further immersed in 40 boiling water for 100 hours and then in pure water at 370 C The diameter “c” (in mm) of the specimen was measured in the 370 C water The dimensional change upon boiling is expressed by the formula:
Dimensional change (%) = l(c-b)/bl x 100 45 (v) Mechanical properties Measurements of tensile strength, elongation and Young’s modulus were taken from a strip-shaped specimen having a width of 2 mm and a thickness of from 0 2 to 0 3 mm immersed in water maintained at a temperature of from 220 to 230 C after the specimen was 50 immersed in boiling water for 16 hours An Instron-type tensile tester was used with the clamp distance being set at 10 mm and the clamp separation speed being set at 100 mm/min.
“INSTRON” is a Registered Trade Mark.
(vi) Degree of transparency A plate-shaped specimen having a thickness of 5 mm was placed in pure water at a 55 temperature of from 220 to 230 C and the specimen’s light transmittance was measured by using a tungsten lamp a G filter (used in Hunter’s calorimeter) and a quartz cell As the reference, pure water was used The transparency of the specimen was expressed by using the grading system stated below.
1 588 744 Transparency of specimen Light transmittance A More than 90 % B 80 90 % 5 C Below 80 % -10 (vii) K Mn O 4 reduction value 10 The concentration (in water) of the materials capable of reducing K Mn O 4, which materials remain in the specimen after the specimen is immersed in boiling water for 16 hours, was determined as follows Forty disc-shaped specimens each similar to that used in the above-mentioned item (i), (ii), (iii) or (iv) were immersed in boiling water for 16 hours to become swollen The swollen specimens were placed in 50 ml of water and then boiled 15 for 30 minutes After the 50 ml of water were left to stand to cool to room temperature, 10 ml of the 50 ml water was placed in a conical flask Twenty ml of an aqueous 0 01 N potassium permanganate solution and 1 0 ml of 10 % sulfuric acid were added into the flask, and the contents of the flask were boiled for 3 minutes After the contents were cooled, 0 1 g of potassium iodide and 5 drops of an aqueous starch reagent solution were added to the 20 contents in the flask Then, the contents were titrated with an aqueous 0 01 N sodium thiosulfate solution The above-mentioned procedure was repeated wherein 10 ml of pure water were used instead of the water in which the swollen specimens were immersed The concentration (in water) of the materials capable of reducing K Mn O 4 was expressed by the difference in the amounts in ml of the aqueous 0 01 N sodium thiosulfate solution required 25 for the titrations, which difference is hereinafter referred to as the “K Mn O 4 reduction value” for brevity.
Example 1
A polymerization reactor in the form of a tube with a circular crosssection made of 30 polytetrafluoroethylene and having an inner diameter of 16 mm, an outer diameter of 18 mm and a length of 500 mm was vertically arranged The tubular reactor was provided with a polytetrafluoroethylene bottom plate The tubular reactor was charged with 80 g of a mixture comprised of 30 parts of methyl methacrylate, 70 parts of Nvinylpyrrolidone, 0 030 part (i e, 0 020 % by mole per mole of the total amount of methyl methacrylate and 35 N-vinylpyrrolidone) of azobisisobutyronitrile, and a cross-linking agent shown in Table I, below After the upper space inside the tubular reactor was flushed with nitrogen, the tubular reactor was sealed The tubular reactor was immersed in a constant temperature bath maintained at 450 C for 15 hours, and, then, the bath temperature was raised in a stepwise manner to 550 C, 60 WC, 70 WC and 90 WC at an hourly interval After the tubular 40 reactor was maintained at 90 WC for one hour, it was transferred into a constant temperature air oven maintained at 120 WC and kept at that temperature for two hours After the tubular reactor was gradually cooled, a colorless transparent polymer in a rodshape having a length of approximately 320 mm was obtained.
The properties of the discs cut from the rod are shown in Table I, below 45 6 1 588 744 6 TABLE I
Run No l 1 1 ‘ 2 ‘ 3 ‘ Cross-linking agent 2 TAIC DVB TEGDMA GMA 5 & its amount 0 068 0 135 0 340 1 610 (mole %/monomer) 10 Equilibrium water 68 68 71 71 content (%) Linear swelling coefficient of 1 51 1 45 1 49 1 50 15 of expansion Tensile strength (kg/cm 2) 22 26 22 24 Elongation at break (%) 180 200 160 200 20 Young’s modulus (kg/cm 2) 16 27 14 20 Transparency A C C B 25 25 Extraction-retention (%) 95 83 83 84 Dimensional change Below upon boiling (%) 10 21 -1 7 -3 5 -2 6 30 K Mn O 4 reduction 0 20 2 45 3 84 2 30 value (ml) D 3 1 23 35 Note: 1 Run Nos 1 ‘, 2 ‘ and 3 ‘ are comparative examples.
2 The abbreviations for the cross-linking agents are:
TAIC = Triallyl isocyanurate 40 DVB = Divinylbenzene TEGDMA = Triethylene glycol dimethacrylate GMA = Glycidyl methacrylate 45 3 D = O R O _ 1) ( 100 -1) ER (W Example 2 50
Following a procedure similar to that set forth in Example 1, a rodshaped colorless transparent polymer was manufactured In this procedure, a tubular reactor similar to that used in Example 1 but made of polypropylene was used The mixture charged in the tubular reactor was comprised of 25 parts of methyl methacrylate, 75 parts of Nvinylpyrrolidone, 0 017 part (i e 0 006 % by mole per mole of the total amount of methyl methacrylate and 55 N-vinylpyrrolidone) of 2,2 ‘-azobis ( 4-methoxy-2,4-dimethylvaleronitrile, 0 010 part (i e, 0.0044 % by mole per mole of the total amount of methyl methacrylate and Nvinylpyrrolidone) of 1,1 ‘-azobiscyclohexane-1-carbonitrile, and a crosslinking agent shown in Table II, below The tubular reactor charged with the above-mentioned mixture was immersed in a constant temperature bath maintained at 25 C for 15 hours Thereafter, the 60 bath temperature was raised to 30 C, maintained at that temperature for one hour and further raised in a stepwise manner to 40 C, 45 C, 50 C, 70 C and 90 C at intervals of 30 minutes After the reactor was maintained at 90 C for one hour, it was transferred into a constant temperature air oven maintained at 120 C and kept therein at that temperature for two hours 65 1 588 744 The properties of the thin discs cut from the rod-shaped polymer obtained by the above-mentioned bulk polymerization are shown in Table II, below.
TABLE II
5 Run No l 1 1 ‘ 2 ‘ 3 ‘ Cross-linking agent 2 TAIC DVB EGDMA GMA & its amount 0 146 0 146 0 730 5 400 10 (mole %/monomer) Equilibrium water 73 73 73 72 content (%) 15 Linear swelling coefficient 1 58 1 53 1 52 1 52 of expansion 20 Tensile strength (kg/cm 2) 10 14 12 12 Elongation at break (%) 180 220 210 180 Young’s modulus (kg/cm 2) 7 8 7 7 25 Transparency A B C C Extraction-retention (%) 93 82 81 83 30 Dimensional change Below upon boiling (%) 10 21 -2 0 -4 1 -3 2 K Mn O 4 reduction 0 15 2 28 4 26 3 34 value (ml) 35 D 1 20 Note: 1 Run Nos 1 ‘, 2 ‘ and 3 ‘ are comparative examples 40 2 The abbreviations for the cross-linking agents are:
TAIC, DVB and GMA are defined in the footnote in Table I.
EGDMA = Ethylene glycol dimethacrylate 45 Example 3
A tubular polymerization reactor with a circular cross-section made of polypropylene and having an inner diameter of 16 mm, an outer diameter of 18 mm and a length of 350 mm was 50 vertically arranged The tubular reactor was provided with a polypropylene bottom plate.
The tubular reactor was charged with a mixture comprised of 30 parts of methyl methacrylate, 70 parts of N-vinylpyrrolidone, 0 157 part (i e, 0 068 % by mole per mole of the total amount of methyl methacrylate and N-vinylpyrrolidone) of triallyl isocyanurate, 0 043 part (i e, 0 016 % by mole per mole of the total amount of methyl methacrylate and 55 N-vinylpyrrolidone) of triethylene glycol dimethacrylate and 0 031 part (i e, 0 020 % by mole per mole of the total amount of methyl methacrylate and Nvinylpyrrolidone) of azobisisobutyronitrile The amount of the mixture was such that the mixture occupies a height of 300 mm in the tubular reactor After the upper space inside the tubular reactor was flushed with argon, the tubular reactor was sealed and then immersed in a constant 60 temperature bath maintained at 40 C for 40 hours Then, the bath temperature was raised to 50 C and maintained at that temperature for 24 hours Furthermore, the tubular reactor was maintained at 70 C for 2 hours and then at 90 C for 2 hours Finally, the tubular reactor was transferred into a constant temperature air oven and maintained therein at 120 C for 2 hours 65 1 588 744 The properties of the thin discs cut from the rod-shaped polymer obtained by the above-mentioned bulk polymerization are shown in Table III, below.
Example 4
A tubular gasket made of an ethylene-propylene-terpolymer rubber and having an inner 5 diameter of 3 mm, an outer diameter of 8 mm and a shore hardness (A scale) of 50 was sandwiched between two glass sheets, each 200 mm in length, 200 mm in width and 5 mm in thickness, in a manner such that the gasket was disposed around the entire periphery of the interspace between the two glass sheets After the two glass sheets were clamped together with the gasket therebetween, the following mixture was injected into the interspace 10 between the two glass sheets The mixture used was comprised of 25 parts of methyl methacrylate, 75 parts of N-vinylpyrrolidone, 0 084 part of triallyl isocyanurate, 0 019 part of triethylene glycol dimethacrylate, 0 046 part of azobisisobutyronitrile and 0 0143 part of 2,2 ‘-azobis( 4-methoxy-2,4-dimethylvaleronitrile) (the amounts of the triallyl isocyanurate, triethylene glycol dimethacrylate, azobisisobutyronitrile and 2,2 ‘azobis ( 4-methoxy-2,4 15 dimethylvaleronitrile) were 0 039 % by mole, 0 006 % by mole, 0 030 % by mole and 0.050 % by mole, respectively, per mole of the total amount of methyl methacrylate and N-vinylpyrrolidone) The mixture-charged glass sheet molding unit was immersed in a constant temperature bath and maintained therein at 10 C for 120 hours The bath temperature was raised in a stepwise manner and the molding unit was maintained at 20 C 20 for 24 hours, at 30 C for 17 hours, at 45 C for 24 hours, at 55 C for 2 hours, at 60 C for 2 hours, at 70 C for 2 hours and then at 90 C for 2 5 hours Thereafter, the mold unit was transferred into a constant temperature air oven and maintained therein at 120 C for 16 hours.
The properties of the thin discs cut from the polymer plate obtained by the 25 above-mentioned procedure are shown in Table III below In Table III ” 10 21 ” means “+ 0 2 “.
TABLE III
30 Example No 3 4 Equilibrium water content (%) 70 75 35 Linear swelling coefficient of expansion 1 49 1 55 Tensile strength (kg/cm 2) 18 13 40 40 Elongation at break (%) 200 280 Young’s modulus (kg/cm 2 15 7 Transparency A A 45 Dimensional change upon Below Below boiling (%) 10 21 10 21 K Mn O 4 reduction value (ml) 0 20 0 40 50 D 1 16 Example 5 55
This example shows clinical demonstrations wherein soft contact lenses obtained in the preceding Examples were tested on patients.
Tested during the demonstrations were soft contact lenses each having a diameter of 12 5 mm and a thickness (at the center portion) of 0 2 mm prepared from the rod-shaped polymer of Example 1 by the processes of lathing, polishing and swelling Among 54 60 myopic patients, 47 patients could wear the soft contact lenses continuously over a period of at least seven days without removal of the lenses during sleeping.
These clinical demonstrations were repeated on the soft contact lenses respectively obtained from the polymers of Examples 2 through 4 The results thereof were approximately similar to those results mentioned above 65 1 588 744 Reference is directed to our co-pending Application No 7938230 (Serial No 1588745), which describes and claims a cross-linked polymer composition providing a transparent polymeric gel having an equilibrium water content of at least 60 % by weight for use in soft contact lenses, which polymer composition is prepared by polymerizing, using a bulk polymerization procedure, a monomer mixture comprising an alkyl methacrylate and an 5 N-vinyllactam in the presence of a cross-linking agent comprising at least one compoundselected from vinyl acrylate and vinyl methacrylate.
Reference is also directed to our co-pending Application No 7938231, (Serial No.
1588746) which describes and claims a cross-linked polymer composition providing a transparent polymeric gel having an equilibrium water content of at least 60 % by weight for 10 use in soft contact lenses, which polymer composition is prepared by polymerizing, using a bulk polymerization procedure, a monomer mixture comprising an alkyl methacrylate and an N-vinyllactam in the presence of a cross-linking agent comprising at least one compound selected from vinyl carboxylates expressed by the formula:
15 R COOCH=CH 2)n where R is a hydrocarbon radical having 1 to 10 carbon atoms and N is an integer of 2, 3 or 4.

Claims (14)

WHAT WE CLAIM IS: 20

1 A cross-linked polymer composition providing a transparent aqueous polymeric gel having an equilibrium water content of at least 60 % by weight for use in soft contact lenses, which polymer composition is prepared by polymerizing, using a bulk polymerization procedure, a monomer mixture comprising an alkyl methacrylate and an Nvinyllactam in the presence of a cross-linking agent comprising triallyl isocyanurate 25

2 The composition according to Claim 1, wherein the alkyl methacrylate is methyl methacrylate.

3 The composition according to Claim 1 or Claim 2, wherein the Nvinyllactam is N-vinyl-2-pyrrolidone.

4 The composition according to any one of Claims 1 to 3, wherein said monomer 30 mixture comprises 10 to 40 % by weight of an alkyl methacrylate, 60 to 80 % by weight of an N-vinyllactam and 0 to 20 % by weight of one or more other copolymerizable monoethylenically unsaturated monomers based on the weight of the monomer mixture excluding the cross-linking agent.

5 The composition according to any one of Claims 1 to 4, wherein the amount of triallyl 35 isocyanurate is from 0 01 to 5 0 % by mole based on the monomer mixture excluding the cross-linking agent.

6 The composition according to any one of Claims 1 to 5, wherein in addition to the said cross-linking agent there is used a further cross-linking agent which comprises at least one polyethylene glycol dimethacrylate expressed by the formula: 40 CH 3 CH 3 CH 2 =C COO(CH 2 CH 20)n CO C=CH 2 (I) 45 45 wherein N is an integer of from 2 to 6, and wherein the amount of the polyethylene glycol dimethacrylate is less than 50 % by mole based on the total amount of triallyl isocyanurate and the further cross-linking agent.

7 The composition according to Claim 6, wherein the amount of the polyethylene 50 glycol dimethacrylate is below 0 5 mole per mole of triallyl isocyanurate used.

8 The composition according to any one of Claims 1 to 7, which has an extraction retention of 85 % to 95 % by weight as measured after immersion in water at 100 C for 16 hours.

9 The composition according to any one of Claims 1 to 8, wherein said bulk 55 polymerization is carried out in the presence of a thermally decomposingtype polymerization initiator.
The composition according to any one of Claims 1 to 9, wherein said polymerization is carried out while the polymerization temperature is increased with the initial and final polymerization temperatures being from

10 to 50 C and from 90 to 160 C, respectively 60

11 The composition according to any one of Claims 1 to 10 wherein said bulk polymerization is carried out within a tube having a circular section.

12 The composition according to Claim 11, wherein said tube is of a circular cross-section, made of polypropylene, has an inner diameter of from 10 to 20 mm and a wall thickness of from 0 5 to 3 mm, and is disposed in a substantially vertical direction 65 1 588 744 10

13 A cross-linked polymer composition as claimed in Claim 1, substantially as hereinbefore described with reference to the Examples.

14 A soft contact lens wearable continuously for a long period of time, which is comprised of a transparent aqueous polymeric gel having an equilibrium water content of at least 60 % by weight, said polymeric gel comprising the cross-linked polymer composition 5 claimed in any one of Claims 1 to 13.
For the Applicants:
RAWORTH, MOSS AND COOK, Chartered Patent Agents, 10 36 Sydenham Road, Croydon CRO 2 EF.
and 6 Buckingham Gate, Westminster, 15 London SW 1 E 6 JP.
Printed for Her Majesty’s Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey, 1981.
Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A IAY, from which copies may be obtained.

GB44644/77A
1976-11-04
1977-10-26
Cross-linked polymer composition for use in soft contact lenses

Expired

GB1588744A
(en)

Applications Claiming Priority (1)

Application Number
Priority Date
Filing Date
Title

JP13253876A

JPS5374049A
(en)

1976-11-04
1976-11-04
Soft contact lens material

Publications (1)

Publication Number
Publication Date

GB1588744A
true

GB1588744A
(en)

1981-04-29

Family
ID=15083609
Family Applications (2)

Application Number
Title
Priority Date
Filing Date

GB44644/77A
Expired

GB1588744A
(en)

1976-11-04
1977-10-26
Cross-linked polymer composition for use in soft contact lenses

GB38230/79A
Expired

GB1588745A
(en)

1976-11-04
1977-10-26
Cross-linked polymer composition for use in soft contact lenses

Family Applications After (1)

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Title
Priority Date
Filing Date

GB38230/79A
Expired

GB1588745A
(en)

1976-11-04
1977-10-26
Cross-linked polymer composition for use in soft contact lenses

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US
(1)

US4184992A
(en)

JP
(1)

JPS5374049A
(en)

CA
(1)

CA1090937A
(en)

DE
(2)

DE2760058C2
(en)

FR
(1)

FR2370063A1
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GB
(2)

GB1588744A
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1977-12-27
1983-10-18
Schering Corporation
Hydrophilic polymers and contact lenses of high water content

JPS598177B2
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1979-07-20
1984-02-23
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Gel for gel filtration

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1981-11-12
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Bausch & Lomb Incorporated
N-Vinyl lactam based biomedical devices

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1982-02-17
1983-08-23
Silver Kogyo Kk
Burner wick and manufacture thereof

CA1272329C
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1985-01-09
1990-07-31

High water-absorptive soft contact lens

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1985-08-16
1987-05-26
Bausch & Lomb Incorporated
Sustained-release formulation containing and amino acid polymer

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1985-08-16
1987-12-15
Bausch & Lomb Incorporated
Sustained-release formulation containing an amino acid polymer with a lower alkyl (C1 -C4) polar solvent

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1985-11-25
1986-01-02
Highgate D J
Hydrophilic materials

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1986-01-28
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Smith & Nephew Ass
Hydrogel polymers

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Ethicon, Inc.
Process for augmenting soft tissue with cross-linked polyvinyl pyrrolidone

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1987-06-08
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1988-04-18
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1993-11-26
1998-01-27
Ciba Vision Corporation
Cross-linkable copolymers and hydrogels

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2000-05-31
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Hydrophilic, crosslinked copolymers based on N-vinylformamide, process for their preparation and their use

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1994-11-14
2002-01-29
Novartis Ag
Cross-linkable copolymers and hydrogels

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1995-11-16
1997-05-22
Roehm Gmbh

Plastisols based on polymer masses softened by the addition of plasticizers

US20120208965A1
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2011-02-15
2012-08-16
3M Innovative Properties Company
Addition-fragmentation agents

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2011-02-15
2019-08-06
3M Innovative Properties Company
Addition-fragmentation agents

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2013-03-20
2015-11-25
쓰리엠 이노베이티브 프로퍼티즈 컴파니
High refractive index addition-fragmentation agents

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2017-03-16
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A hardenable multi-part acrylic composition

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1969-04-07
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Robert Steckler
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1971-04-20
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Hydrophilic copolymers and articles formed therefrom

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1971-10-05
1973-11-13
Union Optics Corp
Copolymers and hydrogels of unsaturated heterocyclic compounds

FR2239486A1
(en)

1973-07-10
1975-02-28
Union Optics Corp
N-vinyl or n-allyl polymers – with unsatd esters and glycidyl esters forming hydrogels

JPS5510050B2
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1976-03-04
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Toray Ind Inc
Preparation of hydrophilic high polymers

1976

1976-11-04
JP
JP13253876A
patent/JPS5374049A/en
active
Granted

1977

1977-10-26
GB
GB44644/77A
patent/GB1588744A/en
not_active
Expired

1977-10-26
GB
GB38230/79A
patent/GB1588745A/en
not_active
Expired

1977-10-31
CA
CA289,905A
patent/CA1090937A/en
not_active
Expired

1977-11-02
DE
DE2760058A
patent/DE2760058C2/en
not_active
Expired

1977-11-02
DE
DE2748898A
patent/DE2748898C2/en
not_active
Expired

1977-11-03
US
US05/848,357
patent/US4184992A/en
not_active
Expired – Lifetime

1977-11-04
FR
FR7733301A
patent/FR2370063A1/en
active
Granted

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Publication date

DE2760058C2
(en)

1984-05-03

JPS5439741B2
(en)

1979-11-29

CA1090937A
(en)

1980-12-02

DE2748898A1
(en)

1978-05-11

DE2748898C2
(en)

1984-05-10

US4184992A
(en)

1980-01-22

JPS5374049A
(en)

1978-07-01

FR2370063B1
(en)

1984-09-14

GB1588745A
(en)

1981-04-29

FR2370063A1
(en)

1978-06-02

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