CA1195127A - Polymeric scrub - Google Patents
Polymeric scrubInfo
- Publication number
- CA1195127A CA1195127A CA000401225A CA401225A CA1195127A CA 1195127 A CA1195127 A CA 1195127A CA 000401225 A CA000401225 A CA 000401225A CA 401225 A CA401225 A CA 401225A CA 1195127 A CA1195127 A CA 1195127A
- Authority
- CA
- Canada
- Prior art keywords
- nylon
- range
- particulate polymer
- cellulose
- recited
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0078—Compositions for cleaning contact lenses, spectacles or lenses
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Eyeglasses (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
POLYMERIC SCRUB
ABSTRACT
Soft and hard contact lenses are freed from deposits by rubbing them with a particulate organic polymer with a carrier, the polymer having a particular size in the range from about one micron to about 600 microns and a Rockwell hardness in the range of from about R120 to about M68, or a shore hardness in the range from about A15 to about D100.
ABSTRACT
Soft and hard contact lenses are freed from deposits by rubbing them with a particulate organic polymer with a carrier, the polymer having a particular size in the range from about one micron to about 600 microns and a Rockwell hardness in the range of from about R120 to about M68, or a shore hardness in the range from about A15 to about D100.
Description
~s~
POLYMERIC SCRUB
This invention relates to 3 rleansing composition for optical surfaces such as contact lenses and similar optic apparatuses.
Cleansing composition5 containing various abrasive materials have been used in the past. The abradant material is added to the composition to increase the effectiveness of the composition in removing undesired matter from the surface being cleanedO Hereto~ore the abradants, even when in fine particle form, were harsh and had a tendency t~ scratch optical surfaces~
Efficient cleaning of optical surfaces wlthout damaging them when such surfaces become encrusted with foreign matter sometimes presents difficult problems.
Contact lenses that have developed heavy proteinaceous or other encrustations present particularly difficult cleaning problems~ Encrustations that form on contact lenses may be proteinaceous in nature or may be lipids ?0 or other ma~erials foreign ~o ~he eye such as lady's mascara which usually is a soap or wax in gelatin.
Success in wearing and properly using contact lenses is a function Gf maintaining them in a clean condition without the buildup of foreign matter, particularly encrustations which physically or chemically attach to the lens sur~Eace. Buildup of ~uch material i5 gradualO
but will ultimately render the lens opaqueO Even before the len5 becomes opaque, however 9 the presence of encrustations on ~he lens causes the wearer of the lens increased discomfort and irrita~ionO Hard contact lenses may be buffed to remove encrustationsi but such a process requires skill and is not easily done by the user at home withou~ ~he considerable danger oE
scratching the lensO The surface of a soft contact lens 35 is particularly prone to develop encrustations and presents particularly difficult clearling problems since 5~
soft contac~ lenses canno~ be cleaned except by professionals and then only with limited swccess.
Many different solutions have been formulated for cleaning eQntact lensesO The ~ompositions, however, are primarily directed to disinfecting lenses and generally do not remove encrustations. Those compositions that have been formulated for the purpose of removing encrustations have met wi~h limited success.
Soft contact lenses may be divided into ~wo broad categories/ namely, hydrophilic and hydrophobic lenses ~ydrophobic contact lenses are usually based on elastic and flexible silicone rubber (polysiloxane), and are generally made from cross-linked dimethyl 15 polysiloxane.
Hydrophilic soft contact lenses are a hydrated gel, and the ability to absorb water resul~s in swelling to a transpa.rent sof t mass o good mechanical strength which is very eomfortable ~o the wearer. Hydrated gel lenses c~n contain: hydroxyethylmethacrylate (HEMA) ~r its analogs, ethylene-glycol dimethacrylate ~EGMA) or its analogs, polymethylmethacryla~e (PM~A) or i~s analogs~ polyvinylpyrrolidone (PVP) or its analogs~
monomers, inhibitors, traces of catalysts and waterO
Hydrophilic groups of these plastic lenses attract and hold large amoun~s of water in the gel. These virtues, however, lead to difficulties in cleaning and sterilizing the lenses ~ydrophilic soft lenses may be disinfected by chemical treatment or by boiling. A5 indicated~ neither procedure is entirely successful in removing encrustations. Some chemicals are ineffeetive in removing proteins, others in removing lipidsO Boiling may ~ven denature pro~einaceous m~terial on ~he lenses thereby attaching encrustat.ions all the more firmly to the lenses. United S~ates Pa~ent No 3,910,296 to ~ ~3S~7 Karageozian et al., discus~es a method for re~oving proteinaceous deposits from contact lenses with the use of a protease, however, lenses may become encru~ted and contaminated with other deleterious materials such as lipids which prokease enzyme will not remove~
The highly hydrophobic nature of the contact lenses based upon silicone r~bber interferes with their uniform and effective cleaning, United Sta~es Pa~en~
No, 4,127,423 to Rankin discusses a method of cleansing encrusted ~oft contact lenses including silicone lenses, wi~h aqueous solutlons of sodium silicatesO Deionized water is required and boiling is required when the lenses are heavily encrustedO
United States Patent No. 3,954,644 to 15 Krezanoski et alO discusses a contact lens cleaniny, stor.ing and wetting solution. The solution discussed contains a poly(oxyethylene)-poly(oxypropylene) block copolymer which is the primary wetting and cleaning agent of the composi~ion. Elimination of encru~tations from the surface of the lens is not discussed.
A need exists9 therefore, or a cleansing compo~ition which can remove fore.ign deposits and encrustation~ Erom both hard and soft surfaces without adversely affecting ~he surfaces thereof, More particularly~ a need exîsts for a cleansing composition which can clean and remove foreign deposi~s from both sof~ and hard contac~ lenses, and particul~rly from 80ft contac~ lensesO
In accordance with the present invention, the use of particulate organic polymers or polysiloxane having particle sizes between one and six hundred microns suspended in a -~uitable carrier unexpectedly provides a composition which can clean, without damage, goft or delica~e ~urfaces including hard or 80f t cont~c~
3~ lenses.
To provide a cleansing composi~ion, the ~ ~5~L~7 particulate polymer is mixed with a carrier containing a thickening agent such as Carbopol (a registered trademark of ~.F. ~oodrich Chemical Co~), cellulose or polyethylene glycol with a molecular wei~ht distribu~ion of 400 to 4000 to form a suspension~ The carrier can be any ocular compatible composition in which the polymeric particulates rernain in ~uspension. Most generally the carrier is water ~o whir~h various optional ingredients may be added. The end product may be a fluid or may be 1~ a thixotropic ointmen~ or gelO ~ surfactant such as Pluronic, (a regis~ered trademark of Wyanclotte Chemicals Co.), Tween, (a registered trademark of Atlas Powder Company) or tyloxapol may optionally be added to the cleaning composition to increase its effectiveness.
Thimerosal (a product of Rli Lilly & Co.), sorbic acid, or ethylenediamintetraa~etic acid (EDTA), as preservatives or bactericides, sodium chloride, and purified water may be optionally employed as is known in the art to provide a ~erile, buffered, isotonic cleansing composi~ion ~or contac~ lenses~
According to the present invention, a suspension is prepared containing a particulate organic polymer or polysiloxane of a particle size of one to six hundred microns and forming 1 to 25 percent by weight of the suspensionD a surfactant, and a sufficient amount of a thiGkener to give the suspension a viscosity of between about 150 and about 1500 Cp5~ The thickener keeps the polymeric particles in suspension and any viscosity suspension ~ha~ will accomplish thls result may be usedO The polymeric particles are preferably ~phericalJ have a particle size range preferably between about twenty and about one hundre~ microns, and preferably form 5 to 20 percent by weight of the suspensionO ~ particle size above and below the twen~y to one hundred micron range will function, however, ~he smaller sized par~icles will ~ake longer to comple~e ~ ~ ~ 5 ~ ~
their cleaning function and larger particles will feel gritty to the user.
Nylon 6 which has the formula (CH2 cH2 CH2 CH2 CH2 C-NH)~ Nylon 11, which S has the formula (CH2 (CM2)8-CH2CN), N~lon 12~
which has the formula (CH2 (CH2)3 CH2 C-NH) or mixtures ~hereof with Rockwell hardnesses of R80-83, ~-108, and R-106, respec~i~ely, and particle size ranges of 1 to 80 microns, 1 to 80 microns, and 20 to 45 microns, respectively, all may be used as polymeric particulates. Nylon 11 is a preferred polymerO
Polyethylene glycol is a preferred thickener in amount~
of between about 20 and about 80 percent by weight of the 6uspension, preferably between about 25 and about 50 percent by weight. The following polymers with their hardnesses as indicated in TABLE 1 will serve as a suitable particula~e polymer.
3S~
T~BLE I
SUITABLE PARTICULATE POLYMERS*
POLYMER SKORE ROCKWELL
~IARDNESS HARDNESS
5 acrylonitrile-butadiene R75-115 styrene acetal M94 polymethylmethacrylate IPMM~) M85-105 methylmethacrylate/styrene 10 copolymer M75 ethyl cellulose R50-115 cellulose acetate butyrate R30-115 cellulose acetate R85 120 polytetrafluoroethylene D50-55 15 polychlorotrifluorethylene R75-95 modiied poolyethylene-tetrafluoroethylene (PE TFE) R50 ionomer (copolymers of ethylene) D50-65 20 fluoro ethylene polymer (FEP) fluo~oplastic D5~65 ~ ~s~
Nylon 6 R80-83 ':
Nylon 6/6 Nylon 11 R108 Nylon 12 R106 5 polyutadiene R40 polyarylethex R117 polycarbonate M70 PBT polyester ~68 78 polyethylene R50 10 polypropylene R80 pol~sulf~2 ~88 silicone A15-65 *ASTM test method D785 applies to the Rockwell Hardness figure given, ~nd ASTM te~t method D22450 applies to the Shore ~ardness figure~ given.
Pluronic F-127 is a preferred ~urfactant and is an ethylene oxide propylene oxide-propylene glycol condensation product sol~ by Wyandotte Chemical Corporation. The ~urfactant ~ a 20~ gel by welght in purified wat r i5 optionally added to the suspension in an amount of between about 5 to 15 percent by weight of the ~u~pension, preferably between about 8 and about 12 percent by weightO
S~,7 The particulate polymer, the polyethylene glycsl and Pluronic E~ 127l as a 20% gel in purified water, may be mixed with thimerosal, sorbic acid, EDTA~
~odi~m chloridet and purified water to provide a ~terile isotonlc cleaning suspension.
To prepare a cleansing suspension polyethylene glycol having a molecular weight range form 400 to 4yO00 is melted by suspending a ~uitable sized container~ such as a beaker~ containing the glycol in hot water, When the polyethylene glycol is completPly melted, the beaker is removed from the heat ssurce. The Pluronic F-127 is added with s~irring un~ he mixture is cooled ~o room temperature. Upon cooling the particulate polymer is added with s~irring. The op~ional salts and preservative are then added together with the required amount of water to provide a cleansing suspension of the desired viscosity.
For a clearer understanding of the invention, specific examples are set forth below. These examples are merely illustrative, and are not to be understood as limiting the ~cope and underlying principles of the invention in any way. In ~he following Examples the particulate polymer~ which 's co~nercially purchased, has a range of particle sizes. A certain percentage of the ~ubstance may have a particle size below 5 or even 1 micron. Hence, the particle sizes expressed in the ~xamples will be set forth a~ a range from between 0 and a size at ~che larger end of ~he range~
EXAMPLE I
A mixture of 25 grams of polyethylene glycol of a molecular weight of approximately 4000, and 30 grams of polyethylene glycol of a molecular welgh~ of approximately 400 wa~ melted and thoroughly mixed. With stirring 20 grams of a 20~ gel in purified water 3f 35 P1UEOniC ~ 127 W~ added ~o the polyethylene glycol mix. ~he re~ulting mixture wa5 ~itrred until coo1ed to 5~'7 room temperatureD Upon cooling 10 grams of Natural (10/15~ ES (which is a tr~demark of Rislan Corporation and is Nylon-ll electrostatic extrude of a particl.e size range between 0 to 44 microns) was added wi~h stirring to the polyethylene g,ycol and Plurnnic mixture. With stirring 15 ml of purified water was added to the mixture and stir~eing was continued until a s~nooth suspension was formed~
EXAMPLE II
As in Example ~, 25 ~rams of Pluronic F-127 20%
gel was added with stirring to ~ melted mixture of 25 grams of polyethylene glycol of a molecular weight of approximately 4000, and 30 grams of polyethylene glycol of a molecular weight of approximately 400. The lS resulting mixture was stirred until cooled to room temperature, whereupon 10 grams of Polymer H0050/80 ~which is a trademark of ~islan Corporation and is Nylon ll of a particle size range between 0 to 80 microns) was added wi~h stirring to the polyethylene ~lycol and Pluronic mixtureO With stirring 10 ml of purified water was ~dded to the mixture and stirring was continued until a smooth suspension was formed.
EX~MPLE III
As in Example I~ 35 gra~s of Pluronic F-127 20%
gel was added with stirring to a melted mixture of 25 grams of polyethylene glycol of a molecular weight of approximately 4000t and 30 grams of polyethylene glycol of a molecular wei~ht of approxima~ely 400. The resulting mixture was stirred until cooled to room temperature, whereupon 10 grams of French~Naturelle ES
twhi~h is a trademark of ~islan Corp4ration and is Nylon-ll electrostatic extrude of a particle size range between 0 to 80 microns) was added with stirring to the polye~hylene glycol and ~luronic mixture. ~tirring of the mixture was continued until a ~mooth suspenslon was formed~
EXAMPLE IV
As in Example X, 35 grams of Pluron.ic F-127 20 gel was added with stirring to a melked mixture of 25 grams of polyethylene glycol of a molecular weight of approximately 4000, and 30 grams of polyethylenQ glycol of a molec~lar weight of approximately 400. The resulting mixture was stirred until cooled to room temperature, whereupon 10 grams of C~B 381-20 (which is a trademark of Eastman Chemical Co. and i~ cellulose acetate bu~yrate of a particle size range between 0 to 120 microns) was added to the polyethylene glycol and Pluronic mixture~ Stirring of the mixture was continu2d until a smooth su~pension was formedd EX~MPLE V
lS As in Example I, 25 grams of Pluronic F-127 20%
gel was added with stirring to a melted mixture of 25 grams of polyethylene glycol of a molecular weight Gf approximately 4000, and 30 grams of polyethylene glycol of a molecular weight of approximately 4G0. The resulting mix~ure was stirred until cooled to r~om temperature, whereupon 1205 grams of Naturell Fine (which is a trademark of ~islan Corporation and is Nylon-ll of a particle size range between 0 to 45 microns) was added wi~h stixring to the polye~hylene glycol and Pluron.ic mixture. With constant agitation 0.02 grams of a lo 0~ aqueous solution of thlmerosal and 0.9 grams of sodium chloride were mixed in~o the glycol=Pluronic-Natur211 Fine mix~ure to form the -cleaning composition. After addition of the thimerosa and sodium chloride~ wi~h continued s~irring purified water was added to bring the total weight Df the composition to 100 grams ~n~ a .smoo~h suspension w~s formed.
EXAMPLE VI
As in Example I~ ~5 grams of Pluronic F 127 2G%
gel was added wi~h s~irring ~o a melted mi.xt~re of 25 ~ 5 ~ ~7 grams of polyethylene glycol of a molecul~r weight of approximately 4000, and 30 grams of polyethylene glycol of a molecular weight of approximately 400~ The re~ulting mixture was stirred until cooled ~o room temperature, whereupon 10.0 grams of polyethylene ~-N500 (which is a product of SO Industrial Chemicals and is low density polyethyler.e of a particle size of less than 20 microns) was added with stirring to the polyethylene glycol and Pluronic mixture, With constant agitation 10 0O 02 grams of an aqueous solution of ~himerosal and 0.9 grams of sodium chloride were mixed into the glycol-Pluronic- polyethylene mixture to form the cleaning composition. After the addition of the thimerosal and sodium chloride, with continuous stirring purified water was added to bring the tot~l weight of the composition ~o 100 grams and a smooth suspension was formed.
EXAMPLE VII
In a beaker 04 8 grams of hydroxy ethyl cellulose having a molecular weight of approximately 15,000 and 0.5 ~rams Tween 21 is dispersed into about 40 ml of purified water~ The mixture then is sterilized by autoclaving at 121C under a pressure of 18 psi for 1/2 hour. In another beaker n,s gram sodium chloride, 0~2 gram boric ~cid, 0.1 gram EDTA-disodium~ 0,25 gram sodium bora~e qs to pH 7.6 and 0.4 ml of a 1.0% aqueou~
solution of thimerosal is di~ olved and mixed with constant agi~ation in~o 40 ml o purified water~ This mixture is then pressure filtered into the first mixture using a sterile millipore ~etup fitted with a 0~2 micron filter. The ~wo mixtures are ~hen homogeneously mixed.
10 grams of French Naturelle beads~ sterilized at 121~C at lB psi for 1/2 hour~ are added to ~h~
homogeneous mixture with constant ayitation. With continuous ~tirring purified wa~er w2s added to the latter mixture to bring ~he ~o~~l weight of the composition ~o 100 grams and to form a smooth suspension.
EXAMPLE VIII
A mixture of 30 grams of polyethylene glycol of a molecular weight of approxima~ely 4000, and 40 grams of polyethy1ene glycol of a molecular weight of approxima~ely 400 was melted in a beaker by suspending the beaker into hot wa~er~ After the polye~hylene glycol was completely melted, i~ was thoroughly mixed with a glass rod to form a smooth ointment base. The ointment base was ~ranserred onts a porcelain tile and was mixed with a ~patula with 15 grams of Natural ES
(10/15) to form an ointment. With continued stirring purified water was incorporated into the ointment to bring the total weight of the composition to 100 grams and ~o so~en and gmooth the resul~ing cleansing ointment.
EXAMPLE IX
A mix~ure of 50 grams of polyethylene glycol of a molecular weight of approximately 4000~ and 30 grams o~ polyethylene glycol of a molecular weight of 400 was melted and mixed as in ~xample VIII. After mixing and melting, as in Example VIXI, the glycol mix~ure was mixed with 10 grams of Natural ES and further mixed with purified water to bring the total weighk of the composition to 100 grams and to pruvide a soft smooth cleansing ointment.
EXAMPLE X
A mixture of 25 grams of polyethylene glycol of a molecular weight of approximately 4000~ and 30 grams of polyethylene glycol of a molecular weight of 400 was melted and mixed a~ in Example VIIo After mixing and melting, 25 grams of a 20% gel in purifi~d water of Pluronic F-127 and 10 grams of polymer ~0050/80 ~ere added and mix2d in~o the polyethylene glyool to provide an ointmentO Wi~h con~inued mixiny purified water was incorporated in o the ointment to b~ing the ~otal weight of the composition to 100 grams and to soften and smooth the resulting cleansing ointment.
A study was designed to determine the non-abrasive nature of the polymeric cleaner formulation.
Five unused lenses of each of the six brands of contact lenses were selected for the non-abrasive test.
The six brands of contact lenses selected were:
Polycon - Syntex Tesicon - Uricon TRESOFT - Alcon Laboratories, Inc.
Silicon - Wohlk CAB - Danker Wohlk PMMA - Standard Hard Lenses Prior to starting the study to determine the non-abrasive nature of the polymeric cleaner formulations, all the lenses were viewed through the Bausch & Lomb Optical Microscope under 40X magnification for scrateches and/or cuts on lens surface. It was noted that almost all types of lenses had some sufrace scratches .
Each brand of lenses was then cycled through a clenaing regimen. The lens was rubbed with 2 to 3 drops of polymeric cleaner of Example VIII in the palm of the hand with the index finger for a trotal of 20 seconds and rinsed with normal saline. This procedure was repeated for a total of fifty cyles on each lens. the lenses were viewed for scrateches after 5,10, 20. 30, 40 and 50 cleaning cycles using the Bausch & Lomb Optical Microscope under 20X and 100X magnifications.
Photographs were taken.
The lens photographs indicat4e no sign of new cuts and/ or scratches on the lens surfaces under study.
The efficacy of polymeric cleaner was determined on laboratory deposited as well as human worn soft contact lenses.
In the laboratory, soft contact lenses were ~ ~ ~5~
soiled with artificial deposition model solution, containing 0~05 percent by weigh~ lysozyme 3X protein and On 05% percent by weight mucin type 2 in isotonic solution to pH 7O0. The deposi~ion of clean lenses 5 involved heating the lenses with a 5ml of deposition model solution in s~oppered glass vial for one hour at 92C~ The above procedure was repeated two times with fresh depositions model ~olution to obtain heavier deposi~s of protein on the lens surface~
The deposited lens was then rubbed with 2 to 3 drops of ~he polymer cleaner of Example YIII in the palm of the hand with the inde~ finger for a total of 20 seconds (bo~h sides of the lens~ and rinsed with normal salineO Depending on the extent o protein deposit on the lens, one to two applicatons of polymeric cleaner of Example VIII was needed to clean the protein from the lens.
In another efficacy study~ human worn sof~
contact lenses having protein encrustations were collected and cleaning efficacy of the polymeric cleaner was determined followin~ a similar cleaning regimen as described above. Six ~ets of huMan worn lenses were used for the efficacy study and all the lenses w~re effectively cleaned, and the prote.in encrustat.ions were removedO
POLYMERIC SCRUB
This invention relates to 3 rleansing composition for optical surfaces such as contact lenses and similar optic apparatuses.
Cleansing composition5 containing various abrasive materials have been used in the past. The abradant material is added to the composition to increase the effectiveness of the composition in removing undesired matter from the surface being cleanedO Hereto~ore the abradants, even when in fine particle form, were harsh and had a tendency t~ scratch optical surfaces~
Efficient cleaning of optical surfaces wlthout damaging them when such surfaces become encrusted with foreign matter sometimes presents difficult problems.
Contact lenses that have developed heavy proteinaceous or other encrustations present particularly difficult cleaning problems~ Encrustations that form on contact lenses may be proteinaceous in nature or may be lipids ?0 or other ma~erials foreign ~o ~he eye such as lady's mascara which usually is a soap or wax in gelatin.
Success in wearing and properly using contact lenses is a function Gf maintaining them in a clean condition without the buildup of foreign matter, particularly encrustations which physically or chemically attach to the lens sur~Eace. Buildup of ~uch material i5 gradualO
but will ultimately render the lens opaqueO Even before the len5 becomes opaque, however 9 the presence of encrustations on ~he lens causes the wearer of the lens increased discomfort and irrita~ionO Hard contact lenses may be buffed to remove encrustationsi but such a process requires skill and is not easily done by the user at home withou~ ~he considerable danger oE
scratching the lensO The surface of a soft contact lens 35 is particularly prone to develop encrustations and presents particularly difficult clearling problems since 5~
soft contac~ lenses canno~ be cleaned except by professionals and then only with limited swccess.
Many different solutions have been formulated for cleaning eQntact lensesO The ~ompositions, however, are primarily directed to disinfecting lenses and generally do not remove encrustations. Those compositions that have been formulated for the purpose of removing encrustations have met wi~h limited success.
Soft contact lenses may be divided into ~wo broad categories/ namely, hydrophilic and hydrophobic lenses ~ydrophobic contact lenses are usually based on elastic and flexible silicone rubber (polysiloxane), and are generally made from cross-linked dimethyl 15 polysiloxane.
Hydrophilic soft contact lenses are a hydrated gel, and the ability to absorb water resul~s in swelling to a transpa.rent sof t mass o good mechanical strength which is very eomfortable ~o the wearer. Hydrated gel lenses c~n contain: hydroxyethylmethacrylate (HEMA) ~r its analogs, ethylene-glycol dimethacrylate ~EGMA) or its analogs, polymethylmethacryla~e (PM~A) or i~s analogs~ polyvinylpyrrolidone (PVP) or its analogs~
monomers, inhibitors, traces of catalysts and waterO
Hydrophilic groups of these plastic lenses attract and hold large amoun~s of water in the gel. These virtues, however, lead to difficulties in cleaning and sterilizing the lenses ~ydrophilic soft lenses may be disinfected by chemical treatment or by boiling. A5 indicated~ neither procedure is entirely successful in removing encrustations. Some chemicals are ineffeetive in removing proteins, others in removing lipidsO Boiling may ~ven denature pro~einaceous m~terial on ~he lenses thereby attaching encrustat.ions all the more firmly to the lenses. United S~ates Pa~ent No 3,910,296 to ~ ~3S~7 Karageozian et al., discus~es a method for re~oving proteinaceous deposits from contact lenses with the use of a protease, however, lenses may become encru~ted and contaminated with other deleterious materials such as lipids which prokease enzyme will not remove~
The highly hydrophobic nature of the contact lenses based upon silicone r~bber interferes with their uniform and effective cleaning, United Sta~es Pa~en~
No, 4,127,423 to Rankin discusses a method of cleansing encrusted ~oft contact lenses including silicone lenses, wi~h aqueous solutlons of sodium silicatesO Deionized water is required and boiling is required when the lenses are heavily encrustedO
United States Patent No. 3,954,644 to 15 Krezanoski et alO discusses a contact lens cleaniny, stor.ing and wetting solution. The solution discussed contains a poly(oxyethylene)-poly(oxypropylene) block copolymer which is the primary wetting and cleaning agent of the composi~ion. Elimination of encru~tations from the surface of the lens is not discussed.
A need exists9 therefore, or a cleansing compo~ition which can remove fore.ign deposits and encrustation~ Erom both hard and soft surfaces without adversely affecting ~he surfaces thereof, More particularly~ a need exîsts for a cleansing composition which can clean and remove foreign deposi~s from both sof~ and hard contac~ lenses, and particul~rly from 80ft contac~ lensesO
In accordance with the present invention, the use of particulate organic polymers or polysiloxane having particle sizes between one and six hundred microns suspended in a -~uitable carrier unexpectedly provides a composition which can clean, without damage, goft or delica~e ~urfaces including hard or 80f t cont~c~
3~ lenses.
To provide a cleansing composi~ion, the ~ ~5~L~7 particulate polymer is mixed with a carrier containing a thickening agent such as Carbopol (a registered trademark of ~.F. ~oodrich Chemical Co~), cellulose or polyethylene glycol with a molecular wei~ht distribu~ion of 400 to 4000 to form a suspension~ The carrier can be any ocular compatible composition in which the polymeric particulates rernain in ~uspension. Most generally the carrier is water ~o whir~h various optional ingredients may be added. The end product may be a fluid or may be 1~ a thixotropic ointmen~ or gelO ~ surfactant such as Pluronic, (a regis~ered trademark of Wyanclotte Chemicals Co.), Tween, (a registered trademark of Atlas Powder Company) or tyloxapol may optionally be added to the cleaning composition to increase its effectiveness.
Thimerosal (a product of Rli Lilly & Co.), sorbic acid, or ethylenediamintetraa~etic acid (EDTA), as preservatives or bactericides, sodium chloride, and purified water may be optionally employed as is known in the art to provide a ~erile, buffered, isotonic cleansing composi~ion ~or contac~ lenses~
According to the present invention, a suspension is prepared containing a particulate organic polymer or polysiloxane of a particle size of one to six hundred microns and forming 1 to 25 percent by weight of the suspensionD a surfactant, and a sufficient amount of a thiGkener to give the suspension a viscosity of between about 150 and about 1500 Cp5~ The thickener keeps the polymeric particles in suspension and any viscosity suspension ~ha~ will accomplish thls result may be usedO The polymeric particles are preferably ~phericalJ have a particle size range preferably between about twenty and about one hundre~ microns, and preferably form 5 to 20 percent by weight of the suspensionO ~ particle size above and below the twen~y to one hundred micron range will function, however, ~he smaller sized par~icles will ~ake longer to comple~e ~ ~ ~ 5 ~ ~
their cleaning function and larger particles will feel gritty to the user.
Nylon 6 which has the formula (CH2 cH2 CH2 CH2 CH2 C-NH)~ Nylon 11, which S has the formula (CH2 (CM2)8-CH2CN), N~lon 12~
which has the formula (CH2 (CH2)3 CH2 C-NH) or mixtures ~hereof with Rockwell hardnesses of R80-83, ~-108, and R-106, respec~i~ely, and particle size ranges of 1 to 80 microns, 1 to 80 microns, and 20 to 45 microns, respectively, all may be used as polymeric particulates. Nylon 11 is a preferred polymerO
Polyethylene glycol is a preferred thickener in amount~
of between about 20 and about 80 percent by weight of the 6uspension, preferably between about 25 and about 50 percent by weight. The following polymers with their hardnesses as indicated in TABLE 1 will serve as a suitable particula~e polymer.
3S~
T~BLE I
SUITABLE PARTICULATE POLYMERS*
POLYMER SKORE ROCKWELL
~IARDNESS HARDNESS
5 acrylonitrile-butadiene R75-115 styrene acetal M94 polymethylmethacrylate IPMM~) M85-105 methylmethacrylate/styrene 10 copolymer M75 ethyl cellulose R50-115 cellulose acetate butyrate R30-115 cellulose acetate R85 120 polytetrafluoroethylene D50-55 15 polychlorotrifluorethylene R75-95 modiied poolyethylene-tetrafluoroethylene (PE TFE) R50 ionomer (copolymers of ethylene) D50-65 20 fluoro ethylene polymer (FEP) fluo~oplastic D5~65 ~ ~s~
Nylon 6 R80-83 ':
Nylon 6/6 Nylon 11 R108 Nylon 12 R106 5 polyutadiene R40 polyarylethex R117 polycarbonate M70 PBT polyester ~68 78 polyethylene R50 10 polypropylene R80 pol~sulf~2 ~88 silicone A15-65 *ASTM test method D785 applies to the Rockwell Hardness figure given, ~nd ASTM te~t method D22450 applies to the Shore ~ardness figure~ given.
Pluronic F-127 is a preferred ~urfactant and is an ethylene oxide propylene oxide-propylene glycol condensation product sol~ by Wyandotte Chemical Corporation. The ~urfactant ~ a 20~ gel by welght in purified wat r i5 optionally added to the suspension in an amount of between about 5 to 15 percent by weight of the ~u~pension, preferably between about 8 and about 12 percent by weightO
S~,7 The particulate polymer, the polyethylene glycsl and Pluronic E~ 127l as a 20% gel in purified water, may be mixed with thimerosal, sorbic acid, EDTA~
~odi~m chloridet and purified water to provide a ~terile isotonlc cleaning suspension.
To prepare a cleansing suspension polyethylene glycol having a molecular weight range form 400 to 4yO00 is melted by suspending a ~uitable sized container~ such as a beaker~ containing the glycol in hot water, When the polyethylene glycol is completPly melted, the beaker is removed from the heat ssurce. The Pluronic F-127 is added with s~irring un~ he mixture is cooled ~o room temperature. Upon cooling the particulate polymer is added with s~irring. The op~ional salts and preservative are then added together with the required amount of water to provide a cleansing suspension of the desired viscosity.
For a clearer understanding of the invention, specific examples are set forth below. These examples are merely illustrative, and are not to be understood as limiting the ~cope and underlying principles of the invention in any way. In ~he following Examples the particulate polymer~ which 's co~nercially purchased, has a range of particle sizes. A certain percentage of the ~ubstance may have a particle size below 5 or even 1 micron. Hence, the particle sizes expressed in the ~xamples will be set forth a~ a range from between 0 and a size at ~che larger end of ~he range~
EXAMPLE I
A mixture of 25 grams of polyethylene glycol of a molecular weight of approximately 4000, and 30 grams of polyethylene glycol of a molecular welgh~ of approximately 400 wa~ melted and thoroughly mixed. With stirring 20 grams of a 20~ gel in purified water 3f 35 P1UEOniC ~ 127 W~ added ~o the polyethylene glycol mix. ~he re~ulting mixture wa5 ~itrred until coo1ed to 5~'7 room temperatureD Upon cooling 10 grams of Natural (10/15~ ES (which is a tr~demark of Rislan Corporation and is Nylon-ll electrostatic extrude of a particl.e size range between 0 to 44 microns) was added wi~h stirring to the polyethylene g,ycol and Plurnnic mixture. With stirring 15 ml of purified water was added to the mixture and stir~eing was continued until a s~nooth suspension was formed~
EXAMPLE II
As in Example ~, 25 ~rams of Pluronic F-127 20%
gel was added with stirring to ~ melted mixture of 25 grams of polyethylene glycol of a molecular weight of approximately 4000, and 30 grams of polyethylene glycol of a molecular weight of approximately 400. The lS resulting mixture was stirred until cooled to room temperature, whereupon 10 grams of Polymer H0050/80 ~which is a trademark of ~islan Corporation and is Nylon ll of a particle size range between 0 to 80 microns) was added wi~h stirring to the polyethylene ~lycol and Pluronic mixtureO With stirring 10 ml of purified water was ~dded to the mixture and stirring was continued until a smooth suspension was formed.
EX~MPLE III
As in Example I~ 35 gra~s of Pluronic F-127 20%
gel was added with stirring to a melted mixture of 25 grams of polyethylene glycol of a molecular weight of approximately 4000t and 30 grams of polyethylene glycol of a molecular wei~ht of approxima~ely 400. The resulting mixture was stirred until cooled to room temperature, whereupon 10 grams of French~Naturelle ES
twhi~h is a trademark of ~islan Corp4ration and is Nylon-ll electrostatic extrude of a particle size range between 0 to 80 microns) was added with stirring to the polye~hylene glycol and ~luronic mixture. ~tirring of the mixture was continued until a ~mooth suspenslon was formed~
EXAMPLE IV
As in Example X, 35 grams of Pluron.ic F-127 20 gel was added with stirring to a melked mixture of 25 grams of polyethylene glycol of a molecular weight of approximately 4000, and 30 grams of polyethylenQ glycol of a molec~lar weight of approximately 400. The resulting mixture was stirred until cooled to room temperature, whereupon 10 grams of C~B 381-20 (which is a trademark of Eastman Chemical Co. and i~ cellulose acetate bu~yrate of a particle size range between 0 to 120 microns) was added to the polyethylene glycol and Pluronic mixture~ Stirring of the mixture was continu2d until a smooth su~pension was formedd EX~MPLE V
lS As in Example I, 25 grams of Pluronic F-127 20%
gel was added with stirring to a melted mixture of 25 grams of polyethylene glycol of a molecular weight Gf approximately 4000, and 30 grams of polyethylene glycol of a molecular weight of approximately 4G0. The resulting mix~ure was stirred until cooled to r~om temperature, whereupon 1205 grams of Naturell Fine (which is a trademark of ~islan Corporation and is Nylon-ll of a particle size range between 0 to 45 microns) was added wi~h stixring to the polye~hylene glycol and Pluron.ic mixture. With constant agitation 0.02 grams of a lo 0~ aqueous solution of thlmerosal and 0.9 grams of sodium chloride were mixed in~o the glycol=Pluronic-Natur211 Fine mix~ure to form the -cleaning composition. After addition of the thimerosa and sodium chloride~ wi~h continued s~irring purified water was added to bring the total weight Df the composition to 100 grams ~n~ a .smoo~h suspension w~s formed.
EXAMPLE VI
As in Example I~ ~5 grams of Pluronic F 127 2G%
gel was added wi~h s~irring ~o a melted mi.xt~re of 25 ~ 5 ~ ~7 grams of polyethylene glycol of a molecul~r weight of approximately 4000, and 30 grams of polyethylene glycol of a molecular weight of approximately 400~ The re~ulting mixture was stirred until cooled ~o room temperature, whereupon 10.0 grams of polyethylene ~-N500 (which is a product of SO Industrial Chemicals and is low density polyethyler.e of a particle size of less than 20 microns) was added with stirring to the polyethylene glycol and Pluronic mixture, With constant agitation 10 0O 02 grams of an aqueous solution of ~himerosal and 0.9 grams of sodium chloride were mixed into the glycol-Pluronic- polyethylene mixture to form the cleaning composition. After the addition of the thimerosal and sodium chloride, with continuous stirring purified water was added to bring the tot~l weight of the composition ~o 100 grams and a smooth suspension was formed.
EXAMPLE VII
In a beaker 04 8 grams of hydroxy ethyl cellulose having a molecular weight of approximately 15,000 and 0.5 ~rams Tween 21 is dispersed into about 40 ml of purified water~ The mixture then is sterilized by autoclaving at 121C under a pressure of 18 psi for 1/2 hour. In another beaker n,s gram sodium chloride, 0~2 gram boric ~cid, 0.1 gram EDTA-disodium~ 0,25 gram sodium bora~e qs to pH 7.6 and 0.4 ml of a 1.0% aqueou~
solution of thimerosal is di~ olved and mixed with constant agi~ation in~o 40 ml o purified water~ This mixture is then pressure filtered into the first mixture using a sterile millipore ~etup fitted with a 0~2 micron filter. The ~wo mixtures are ~hen homogeneously mixed.
10 grams of French Naturelle beads~ sterilized at 121~C at lB psi for 1/2 hour~ are added to ~h~
homogeneous mixture with constant ayitation. With continuous ~tirring purified wa~er w2s added to the latter mixture to bring ~he ~o~~l weight of the composition ~o 100 grams and to form a smooth suspension.
EXAMPLE VIII
A mixture of 30 grams of polyethylene glycol of a molecular weight of approxima~ely 4000, and 40 grams of polyethy1ene glycol of a molecular weight of approxima~ely 400 was melted in a beaker by suspending the beaker into hot wa~er~ After the polye~hylene glycol was completely melted, i~ was thoroughly mixed with a glass rod to form a smooth ointment base. The ointment base was ~ranserred onts a porcelain tile and was mixed with a ~patula with 15 grams of Natural ES
(10/15) to form an ointment. With continued stirring purified water was incorporated into the ointment to bring the total weight of the composition to 100 grams and ~o so~en and gmooth the resul~ing cleansing ointment.
EXAMPLE IX
A mix~ure of 50 grams of polyethylene glycol of a molecular weight of approximately 4000~ and 30 grams o~ polyethylene glycol of a molecular weight of 400 was melted and mixed as in ~xample VIII. After mixing and melting, as in Example VIXI, the glycol mix~ure was mixed with 10 grams of Natural ES and further mixed with purified water to bring the total weighk of the composition to 100 grams and to pruvide a soft smooth cleansing ointment.
EXAMPLE X
A mixture of 25 grams of polyethylene glycol of a molecular weight of approximately 4000~ and 30 grams of polyethylene glycol of a molecular weight of 400 was melted and mixed a~ in Example VIIo After mixing and melting, 25 grams of a 20% gel in purifi~d water of Pluronic F-127 and 10 grams of polymer ~0050/80 ~ere added and mix2d in~o the polyethylene glyool to provide an ointmentO Wi~h con~inued mixiny purified water was incorporated in o the ointment to b~ing the ~otal weight of the composition to 100 grams and to soften and smooth the resulting cleansing ointment.
A study was designed to determine the non-abrasive nature of the polymeric cleaner formulation.
Five unused lenses of each of the six brands of contact lenses were selected for the non-abrasive test.
The six brands of contact lenses selected were:
Polycon - Syntex Tesicon - Uricon TRESOFT - Alcon Laboratories, Inc.
Silicon - Wohlk CAB - Danker Wohlk PMMA - Standard Hard Lenses Prior to starting the study to determine the non-abrasive nature of the polymeric cleaner formulations, all the lenses were viewed through the Bausch & Lomb Optical Microscope under 40X magnification for scrateches and/or cuts on lens surface. It was noted that almost all types of lenses had some sufrace scratches .
Each brand of lenses was then cycled through a clenaing regimen. The lens was rubbed with 2 to 3 drops of polymeric cleaner of Example VIII in the palm of the hand with the index finger for a trotal of 20 seconds and rinsed with normal saline. This procedure was repeated for a total of fifty cyles on each lens. the lenses were viewed for scrateches after 5,10, 20. 30, 40 and 50 cleaning cycles using the Bausch & Lomb Optical Microscope under 20X and 100X magnifications.
Photographs were taken.
The lens photographs indicat4e no sign of new cuts and/ or scratches on the lens surfaces under study.
The efficacy of polymeric cleaner was determined on laboratory deposited as well as human worn soft contact lenses.
In the laboratory, soft contact lenses were ~ ~ ~5~
soiled with artificial deposition model solution, containing 0~05 percent by weigh~ lysozyme 3X protein and On 05% percent by weight mucin type 2 in isotonic solution to pH 7O0. The deposi~ion of clean lenses 5 involved heating the lenses with a 5ml of deposition model solution in s~oppered glass vial for one hour at 92C~ The above procedure was repeated two times with fresh depositions model ~olution to obtain heavier deposi~s of protein on the lens surface~
The deposited lens was then rubbed with 2 to 3 drops of ~he polymer cleaner of Example YIII in the palm of the hand with the inde~ finger for a total of 20 seconds (bo~h sides of the lens~ and rinsed with normal salineO Depending on the extent o protein deposit on the lens, one to two applicatons of polymeric cleaner of Example VIII was needed to clean the protein from the lens.
In another efficacy study~ human worn sof~
contact lenses having protein encrustations were collected and cleaning efficacy of the polymeric cleaner was determined followin~ a similar cleaning regimen as described above. Six ~ets of huMan worn lenses were used for the efficacy study and all the lenses w~re effectively cleaned, and the prote.in encrustat.ions were removedO
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIM ED ARE DEFINED AS FOLLOWS:
1.. A cleansing composition for cleaning optical surfaces, comprising: a particulate polymer selected from the group consisting of cellulose-acetate-butyrate, polyethylene, acrylonitrile-butadiene-styrene, acetal, polymethylmethacrylate, methylmethacrylate/styrene copolymer, ethyl cellulose, cellulose acetate, cellulose acetate butyrate polychlorotrifluoroethylene, modified polyethylene-tetrafluoroethylene, nylon 6, nylon 6/6, nylon 11, nylon 12, polybutadiene, polyarylether, poly-carbonate, polybutylene terephthalate polyester, polypropylene, polysulfone, polytetraflourethylene, ionomer fluoroethylene polymer, polysiloxane polymers and mixtures thereof, wherein said particulate polymer has a particle size in the range of from about one micron to about six hundred microns and a Rockwell hardness in the range of from about R120 to about M68 or a Shore hardness in the range from about A15 to about D100; and a carrier having a viscosity sufficient to keep said particulate polymer in suspension.
2. A cleansing composition as recited in claim 1, wherein said carrier is compatible with ocular tissue.
3. A cleansing composition as recited in claim 1, wherein said carrier, comprises: water and a thickener, wherein said thickener is selected from the group consisting of polyethylene glycol, Carbopol*, cellulose and mixtures thereof.
4. A cleansing composition as recited in claim 1, 2 or 3, wherein said particulate polymer has a Rockwell hardness in the range from about R120 to about M68.
*trade mark
*trade mark
5. A cleansing composition as recited in claim 1, 2 or 3, wherein said particulate polymer has a Shore hardness in the range from about A15 to about D100.
6. A cleansing composition as recited in claim 1, 2 or 3, wherein said particulate polymer is selected from the group consisting of cellulose-acetate-butyrate, polyethylene, acrylonitrile-butadiene-styrene, acetal, polymethylmethacrylate, methylmethacrylate/-styrene copolymer, ethyl cellulose, cellulose acetate, cellulose acetate butyrate polychlorotrifluoroethylene, modified polyethylene-tetrafluoroethylene, nylon 6, nylon 6/6, nylon 11, nylon 12, polybutadiene, polyaryl-ether, polycarbonate, polybutylene terephthalate polyester, polypropylene, polysulfone and mixtures thereof, and therein said particulate polymer has a Rockwell hardness in the range from about R120 to about M68.
7. A cleansing composition as recited in claim 1, 2 or 3, wherein said particulate polymer is selected from the group consisting of polytetraflourethylene, ionomer, fluoroethylene polymer, polysiloxane polymers and mixtures thereof, and wherein said particulate polymer has a Shore hardness in the range from about A15 to about D100.
8. A method for cleansing a contact lens, comprising: rubbing the contact lens with a composition, comprising a particulate polymer selected from the group consisting of cellulose-acetate-butyrate, polyethylene, acrylonitrile-butadiene-styrene, acetal, polymethylmeth-acrylate, methylmethacrylate/styrene copolymer, ethyl cellulose, cellulose acetate, cellulose acetate butyrate polychlorotrifluoroethylene, modified polyethylene-tetrafluoroethylene, nylon 6, nylon 6/6, nylon 11, nylon 12, polybutadiene, polyarylether, polycarbonate, polybutylene terephthalate polyester, polypropylene, polysulfone, polytetraflourethylene, ionomer, fluoro-ethylene polymer, polysiloxane polymers and mixtures thereof, wherein said particulate polymer has a particle size in the range of from about one micron to about six hundred microns and a Rockwell hardness in the range of from about R120 to about M68 or a Shore hardness in the range from about A15 to about D100; and a carrier having a viscosity sufficient to keep said particulate polymer in suspension.
9. A method as recited in claim 8, wherein said carrier is compatible with ocular tissue.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25586181A | 1981-04-20 | 1981-04-20 | |
| US255,861 | 1981-04-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1195127A true CA1195127A (en) | 1985-10-15 |
Family
ID=22970167
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000401225A Expired CA1195127A (en) | 1981-04-20 | 1982-04-19 | Polymeric scrub |
| CA615,525A Expired - Lifetime CA1270119B (en) | 1981-04-20 | 1989-10-13 | Polymeric scrub |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA615,525A Expired - Lifetime CA1270119B (en) | 1981-04-20 | 1989-10-13 | Polymeric scrub |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0063472B1 (en) |
| JP (1) | JPS57192922A (en) |
| AT (1) | ATE32270T1 (en) |
| AU (1) | AU559965B2 (en) |
| BR (1) | BR8202239A (en) |
| CA (2) | CA1195127A (en) |
| DE (1) | DE3278049D1 (en) |
| MX (1) | MX166498B (en) |
| ZA (1) | ZA822496B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4693840A (en) * | 1982-07-26 | 1987-09-15 | The Procter & Gamble Company | No rinse liquid car cleaner with solid polymers |
| US4481126A (en) * | 1982-07-26 | 1984-11-06 | The Procter & Gamble Company | No rinse liquid car cleaner with solid polymers |
| US4678698A (en) * | 1983-04-12 | 1987-07-07 | Minnesota Mining And Manufacturing Company | Contact lens cleaning article |
| US4622258A (en) * | 1983-04-12 | 1986-11-11 | Minnesota Mining And Manufacturing Company | Contact lens cleaning article |
| US4533399A (en) * | 1983-04-12 | 1985-08-06 | Minnesota Mining And Manufacturing Company | Contact lens cleaning method |
| JPS60159721A (en) * | 1984-01-31 | 1985-08-21 | Nippon Contact Lens Seizo Kk | Cleaner for contact lens |
| US4655957A (en) * | 1984-06-25 | 1987-04-07 | Bausch & Lomb Incorporated | Contact lens cleaning composition with polymeric beads |
| AT380897B (en) * | 1984-12-10 | 1986-07-25 | Koller Anton | MIXTURE FOR THE CARE AND CLEANING OF CONTACT LENSES |
| GB2188744B (en) * | 1986-04-01 | 1989-11-15 | Donald James Highgate | Contact lens cleaners |
| JPH01501899A (en) * | 1986-12-24 | 1989-06-29 | アルコン ラボラトリーズ インコーポレイテッド | Contact lens cleaning agent and its usage |
| DE3852571T2 (en) * | 1987-05-28 | 1995-08-17 | Colgate Palmolive Co | Detergent composition for hard surfaces. |
| JPH01177014A (en) * | 1987-12-28 | 1989-07-13 | Tome Sangyo Kk | Detergent for contact lens |
| WO1989012842A1 (en) * | 1988-06-18 | 1989-12-28 | Tomei Sangyo Kabushiki Kaisha | Detergent for contact lens and method for washing contact lens |
| US4855067A (en) * | 1988-05-10 | 1989-08-08 | Colgate-Palmolive Company | Household cleaning composition |
| JPH01293314A (en) * | 1988-05-20 | 1989-11-27 | Daicel Chem Ind Ltd | Cleaning agent for contact lens |
| US4968447A (en) * | 1988-08-11 | 1990-11-06 | Gage Products Company | Cleaning composition and method |
| JPH0633415B2 (en) * | 1988-12-02 | 1994-05-02 | 花王株式会社 | Skin cleanser composition |
| US5128058A (en) * | 1989-05-31 | 1992-07-07 | Hoya Corporation | Contact lens cleaner containing a microcapsular polishing agent |
| US5017238A (en) * | 1989-08-30 | 1991-05-21 | Dow Corning Corporation | Aqueous cleaning dispersions using adsorptive polymeric powder and method of using |
| US5037485A (en) * | 1989-09-14 | 1991-08-06 | Dow Corning Corporation | Method of cleaning surfaces |
| CA2039378A1 (en) * | 1990-04-03 | 1991-10-04 | Toyoyasu Tanaka | Contact lens cleaning instrument |
| DE19808054C2 (en) * | 1998-02-26 | 2002-06-13 | Boehme Chem Fab Kg | Object for cleaning surfaces |
| GB0004898D0 (en) * | 2000-03-02 | 2000-04-19 | Ici Plc | Extrusion process |
| CN1965066A (en) * | 2004-06-07 | 2007-05-16 | 宝洁公司 | Detergent composition |
| JP4896650B2 (en) * | 2006-09-29 | 2012-03-14 | 株式会社コーセー | Novel water-soluble scrub agent and oil-based skin cleansing agent containing the scrub agent |
| DE102012222263A1 (en) * | 2012-12-05 | 2014-06-05 | Henkel Ag & Co. Kgaa | Removal of greasy soiling |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1295611A (en) * | 1970-07-16 | 1972-11-08 | ||
| US3884826A (en) * | 1973-07-20 | 1975-05-20 | Barnes Hind Pharm Inc | Thixotropic cleaning agent for hard contact lenses |
| US4048122A (en) * | 1976-01-23 | 1977-09-13 | Barnes-Hind Pharmaceuticals, Inc. | Cleaning agents for contact lenses |
| CA1152843A (en) * | 1979-06-25 | 1983-08-30 | Polymer Technology Corporation | Abrasive-containing contact lens cleaning materials |
-
1982
- 1982-04-13 ZA ZA822496A patent/ZA822496B/en unknown
- 1982-04-14 AU AU82587/82A patent/AU559965B2/en not_active Expired - Fee Related
- 1982-04-15 DE DE8282301936T patent/DE3278049D1/en not_active Expired
- 1982-04-15 EP EP82301936A patent/EP0063472B1/en not_active Expired
- 1982-04-15 AT AT82301936T patent/ATE32270T1/en not_active IP Right Cessation
- 1982-04-19 BR BR8202239A patent/BR8202239A/en not_active IP Right Cessation
- 1982-04-19 MX MX192307A patent/MX166498B/en unknown
- 1982-04-19 CA CA000401225A patent/CA1195127A/en not_active Expired
- 1982-04-20 JP JP57066174A patent/JPS57192922A/en active Granted
-
1989
- 1989-10-13 CA CA615,525A patent/CA1270119B/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU559965B2 (en) | 1987-03-26 |
| MX166498B (en) | 1993-01-12 |
| AU7372387A (en) | 1987-10-08 |
| ZA822496B (en) | 1983-02-23 |
| ATE32270T1 (en) | 1988-02-15 |
| EP0063472A3 (en) | 1983-05-04 |
| AU590848B2 (en) | 1989-11-16 |
| BR8202239A (en) | 1983-03-29 |
| AU8258782A (en) | 1982-10-28 |
| EP0063472B1 (en) | 1988-01-27 |
| JPS57192922A (en) | 1982-11-27 |
| CA1270119B (en) | 1990-06-12 |
| JPS632091B2 (en) | 1988-01-16 |
| EP0063472A2 (en) | 1982-10-27 |
| DE3278049D1 (en) | 1988-03-03 |
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