Improved method of forming shaped hydrogel alticles including contact lenses using inert, displaceable diluents
19 claims: 2 independent, 17 dependent
- 1Szabadalmi igénypontok 1. Eljárás alakos hidrogél termékek, főként kontakt- lencsék előállítására, azzal jellemezve, hogy az (1) lépésben (alakozunk vagy kiőntünk egy polimerizációs keveréket - amely (a) egy monomer keveréket tartalmaz, amelynek nagyobb része egy vagy több hidrofil monomer, így (2-hidroxi-etil)-metakrilát, valamint egy vagy több térhálósí tó monomer;és olyan körülmények között, hogy a monomer keverék polimerizál, s így a fenti monomereket és a fenti hígítószert tartalmazó, alakozott kopolimer gél kép67 ződik;és (2) ezt követően a fenti hígítószert vízzel cseréljük, azzal a megkötéssel, hogy az inért, kicserélhető, nemvizes hígítószert úgy választjuk meg, hogy ha a fenti polimerizációs keveréket egy foto-differenciál letapogató kaloriméterben polimerizáljuk - ahol a polimerizációt ibolyántúli fénnyel besugározva váltjuk ki körülbelül 2,5-3 mW/cm 2 fényerőséggel akkor a polimerizáció maximális hőtermelésének elérésére szükséges idő körülbelül 0,2 és körülbelül 3,5 perc között van, és a maximális hőtermelés időpontjában a monomer keverék polimerré végbemenő konverziójának százalékos értéke legalább 40 százalék .
- 2Az 1. igénypont szerinti eljárás, azzal jellemezve, hogy az inért, kicserélhető, nemvizes hígítószert úgy választjuk meg, hogy ha a polimerizációs keveréket foto-differenciál letapogató kaloriméterben polimerizáljuk - ahol a polimerizációt ibolyántúli fénnyel besugározva körülbelül 2,5-3 mW/cm 2 fényerősséggel váltjuk ki - akkor a polimerizáció maximális hőtermelésének elérésére szükséges idő körülbelül 0,4 és körülbelül 2,5 perc között van, és a maximális hőtermelés időpontjában a monomer keverék polimerré végbemenő konverziójának százalékos értéke legalább 50 százalék.
- 3Az 1. igénypont szerinti eljárás, azzal jellemezve, hogy inért hígítószerként egy (I) általános képletű terméket vagy termékek keverékét alkalmazzuk - ahol az (I) képletben R 1 jelentése 1-6 szénatomos alkilcsoport;mindegyik R egyedileg -CH2-CH2- vagy -CH2-CH(CH3)- képletű csoportot jelent;és w, x, y és z összege körülbelül 5 és 50 közötti érték, azzal a megkötéssel, hogy az (I) általános képletű vegyületek keverékében az R csoportok túlnyomó része -CH2-CH2-csoportot jelent.
- 4A 3. igénypont szerinti eljárás, azzal jellemezve, hogy w, x, y és z összege körülbelül 5-től 30-ig terjedő tartományban van.
- 5A 3. igénypont szerinti eljárás, azzal jellemezve, hogy valamennyi R csoport -CH2-CH2- csoportot jelent.
- 6A 4. igénypont szerinti eljárás, azzal jellemezve, hogy valamennyi R csoport -CH2-CH2- csoportot jelent.
- 7Az 1. igénypont szerinti eljárás, azzal jellemez- ve, hogy inért hígítószerként (II) általános képletű vegyületet alkalmazunk, ahol a (II) képletben R 2 jelentése -CH2-CH2- képletű csoport;és m + n értéke körülbelül 2-től körülbelül 100-ig terjedő tartományban van.
- 8A 7. igénypont szerinti eljárás, azzal jellemezve, hogy m + n értéke körülbelül 4-től 20-ig terjedő tartományban van.
- 9Az 1. igénypont szerinti eljárás, azzal jellemez- ve, hogy inért hígítószerként (III) általános képletű polietilénglikol H0- (CH 2 -CH 2 O) n -H vegyületet alkalmazunk, ahol n olyan számot jelent, amellyel • · ♦· W4 ♦ « « - 69 a polietilénglikol molekulatömege körülbelül 300 és körülbelül 10 000 közötti tartományban van.
- 10A 9. igénypont szerinti eljárás, azzal jellemez- ve, hogy n olyan számot jelent, amellyel a polietilénglikol molekulatömege körülbelül 400 és körülbelül 5000 közötti tartományban van.
- 11Az 1. igénypont szerinti eljárás, azzal jellemez- ve, hogy inért hígítószerként egy 9. igénypont szerinti polietilénglikol és egy 6. igénypont szerinti, etoxilezett biszfenol A keverékét alkalmazzuk.
- 12Az 1. igénypont szerinti eljárás, azzal jellemez- ve, hogy inért hígítószerként egy 10. igénypont szerinti polietilénglikol és egy 3. igénypont szerinti, etoxilezett alkil—glükozid keverékét alkalmazzuk, ahol az (I) általános képletű vegyületek keverékében az R csoportok -CH2-CH2- csoportokat jelentenk.
- 13Az 1. igénypont szerinti eljárás, azzal jellemez- ve, hogy inért hígítószerként egy 3. igénypont szerinti (I) általános képletű propoxilezett alkil-glükozid - amelyben R jelentése -CH2-CH(CH3)- csoport - és egy legfeljebb 12 szénatomos kétértékű alkohol egyfázisú keverékét alkalmazzuk.
- 14A 13. igénypont szerinti eljárás, azzal jellemez- ve, hogy inért hígítószerként egy 3. igénypont szerinti (I) általános képletű propoxilezett alkil-glükozid - amelyben R jelentése -CH2-CH(CH3)- csoport - és egy legfeljebb 6 szénatomos kétértékű alkohol egyfázisú keverékét alkalmazzuk.
- 15Az 1. igénypont szerinti eljárás, azzal jellemez- ve, hogy inért hígítószerként ε-kaprolakton és valamilyen al • ·« - 70 kándiol vagy -triói adduktumát alkalmazzuk.
- 16A 15. igénypont szerinti eljárás, azzal jellemezve, hogy inért hígítószerként e-kaprolakton és glicerin adduktumát alkalmazzuk.
- 17Az 1. igénypont szerinti eljárás, azzal jellemezve, hogy inért hígítószerként egy 6. igénypont szerinti, etoxilezett biszfenol A és egy 2. igénypont szerinti, etoxilezett glükozid - ahol R -CH2-CH(CH3)- csoportot jelent - keverékét alkalmazzuk.
- 18Vizsgálati (tesztelő) eljárás egy vegyület alkalmazhatóságának (hasznosságának) meghatározására inért, kicserélhető oldószerként kontaktlencse előállítási eljárásában, azzal jellemezve, hogy előre meghatározott formában formázunk vagy kiöntünk egy polimerizációs keveréket, amely (a) egy monomer keveréket tartalmaz, amely nagyobb (túlnyomó) részében egy vagy több hidrofil monomerből, valamint egy vagy több térhálósító monomerből áll;és (b) valamilyen inért, kicserélhető, nemvizes hígítószert tartalmaz, olyan körülmények között tartunk, hogy a fenti monomer keverék polimerizál, s így a fenti monomerekből és a fenti hígítószerből álló kopolimer gélt kapunk, s amely vizsgálati módszer abban áll, hogy a fenti polimerizációs keverékben lévő monomereket egy foto-differenciál letapogató kaloriméterben polimerizáljuk, ahol a polimerizációt ibolyántúli sugárzással, körülbelül 2,5-3 mW/cm 2 fényerősséggel váltjuk ki, meghatározzuk a polimerizáció maximális hőtermeléséig eltelt időt, és ezt az időtartamot körülbelül 0,2 és körülbelül 3,5 perc közötti standard időtartammal összeha- 71 •·· sonlítjuk, valamint meghatározzuk a fenti monomer keverék polimerré végbemenő konverziójának százalékos értékét, és ezt a konverziós százalékot egy legalább 40 százalékos standarddal vetjük össze.
- 19A 18. igénypont szerinti vizsgálati eljárás, azzal jellemezve, hogy a polimerizációs keverékben lévő monomerek polimerizációját foto-differenciál letapogató kaloriméterben hajtjuk végre, ahol a polimerizációt ibolyántúli besugárzással körülbelül 2,5-3 mW/cm 2 fényerősséggel váltjuk ki, meghatározzuk a polimerizáció maximális hőtermeléséig eltelt időtartamot, és ezt az időt körülbelül 0,4 és körülbelül 2,5 perc közötti standard időtartammal vetjük össze, valamint meghatározzuk a monomer keverék polimerré alakulásának (konverziójának) százalékos értékét, és ezt a konverziós százalékot egy legalább 50 százalékos standard értékkel vetjük össze.
Independent claims19
937 paragraphs in 6 sections, as filed
The present invention relates to a process for the production of shaped hydrogel products, in particular soft contact lenses, and more specifically to the direct formation of such products using a novel class of interchangeable solvents.
So far, soft hydrogel-type contact lenses have been manufactured by turning machining or rotary molding. Turning machining involves mechanically cutting a bare lens or lens head consisting of a substantially anhydrous hydrophilic polymer (xerogel) and then grinding it on a fine lathe to form a lens, contacting it with water or saline to hydrate the polymer so as to hydrate the polymer. The mechanical steps used in turning machining are similar to those used in making hard contact lenses, except that play distance is required as the lens swells as the polymer is hydrated.
During the molding process, a small amount of the hydrophilic monomer mixture is placed in a concave, optically polished (polished) template, and the template is rotated while the monomers polymerize to form an xerogel lens. The two optical surfaces of the lens are formed simultaneously during polymerization; the outer surface is formed by the combined effect of the centrifugal force generated by the rotating template and the surface tension of the polymerization mixture. The lens thus obtained is contacted with water or saline to hydrate the polymer and to form it into a hydrogel lens as in the case of a lens obtained during turning machining.
I
- 3 Recently improved processes for the production of hydrogel contact lenses have been developed. Not only is this method more economical than either lathe machining or rotary casting, it also has the advantage that the final shape of the hydrated lens can be more precisely controlled. This new method involves directly forming a monomer mixture by dissolving the mixture in a non-aqueous, exchangeable solvent, placing the resulting mixture in a template that exactly matches the shape of the desired final hydrogel, i.e., water-swollen lens, and then subjecting the mixture of monomer and solvent to conditions under which the monomer (s) polymerizes to obtain the desired polymer-solvent mixture, in the form of a final hydrogel lens. (The polymerization is preferably carried out in a non-aqueous medium since water can interfere with the polymerization reaction and adversely affect the properties of the resulting polymer.) After the polymerization is complete, the solvent is replaced with water to produce a hydrated lens having a final size and its shape is exactly the same size and shape as the original shaped product containing the polymer and solvent. Such direct formation of hydrogel contact lenses is described in U.S. Patent Nos. 4,495,313 to Larsen and 4,680,336, 4,889,664 and 5,039,459 to Larsen et al.
U.S. Patent Nos. 4,495,313 to Larsen and U.S. Patent Nos. 4,889,664 and 5,039,459 to Larsen et al. Disclose that interchangeable diluents are water-exchangeable boric acid esters of polyhydric alcohols. Lar • ·
<img file="HUT68045A_D0001.tif" />
sen et al., U.S. Patent No. 4,680,336, disclose that interchangeable diluents are selected from water-exchangeable organic compounds selected from a comparison of their viscosity and Hansen's cohesion parameters with those of the hydrogel polymer component to be produced.
The present invention is based on the discovery of a new class of formulations which can be used as replaceable diluents for the direct formulation of hydrogel products such as soft contact lenses.
According to the invention, shaped hydrogel products, such as soft contact lenses, are prepared by forming or molding in a step (1) a polymerization mixture comprising (a) a monomer mixture, the majority of which is one or more hydrophilic monomers such as (2-). hydroxyethyl) methacrylate and one or more crosslinking monomers, and
<td>(b) inquired,</td><td>as a replaceable non-aqueous diluent</td>
<td>(I)</td><td>ethoxylated alkyl glucoside,</td>
<td>(Ii)</td><td>ethoxylated bisphenol A,</td>
<td>(Iii)</td><td>polyethylene glycol,</td>
<td>(arc)</td><td>propoxylated and ethoxylated alkyl glucosides mixture</td>
<td>(V)</td><td>a single-phase mixture of ethoxylated or propoxylated alkyl glucoside with a divalent alcohol having up to 12 carbon atoms,</td>
<td>(Vi)</td><td>e-caprolactone and C2-C6 alkanediols</td>
and triols adduct, (vii) ethoxylated C 3 -C 6 alkanetriol, and (viii) a mixture of one or more of the materials listed under (i) to (vii) above, under conditions such that the monomer mixture polymerizes, thereby forming a formed copolymer gel containing the above monomers and the diluent; and (2) subsequently exchanging said diluent with water.
In addition to the patents cited above by Larsen and Larsen et al., Relevant publications in the state of the art include:
Larsen, U.S. Patent 4,565,348;
Ohkada et al., U.S. Patent No. 4,347,198;
Shepherd, U.S. Patent No. 4,208,364;
Müller et al., EP-A-0 493 320 A2; and Wichterle et al., Re. 27,401 (U.S. Patent No. 3,220,960).
Suitable inert, non-aqueous, replaceable diluents for use in the process of the invention are selected from the group consisting of:
(i) ethoxylated alkyl glucoside, (ii) ethoxylated bisphenol A,
A mixture of propoxylated and ethoxylated alkyl glucosides, (iii) polyethylene glycol, (iv) arc) ethoxylated or propoxylated alkyl glucoside and a monovalent mixture of bivalent alcohols with up to 12 carbon atoms, ε-caprolactone and C2-6 alkanediols or triols (vii) ethoxylated C 3 -C 6 alkanetriol; and (viii) mixtures of one or more of the foregoing (i) to (vii).
All of the diluents used can be replaced (replaced) with water; that is, the gel of the copolymer formed from the above monomers and said diluent are treated with a solvent so that the diluent is removed and eventually replaced with water.
In most cases, the solvent used to remove the inert diluent is water (or an aqueous solution, such as physiological saline). If desired
and depending on the solubility characteristics of the inert diluent used in the process of the invention, the first solvent used to replace the inert diluent is an organic liquid such as ethanol, methanol, acetone, glycerol or a mixture thereof, or a mixture of one or more organic liquids with water. may be followed by an extraction with pure water (or physiological saline) and thus a water-swollen copolymer of the above monomers, a gel is obtained.
The structure of the ethoxylated and propoxylated alkyl glucosides is represented by the formula (I)
R<sup>1</sup> is (1-6C) alkyl (preferably methyl);
each R alone is -CH 2 -CH 2 - or -CH 2 -CH (CH 3) -;
w, x, y and z are from about 5 to about 50 (preferably from 5 to about 30) and represent the total number of ethylene and propylene oxide units present in the product.
The diluent of formula (I) may be: (i) ethoxylated alkyl glucoside; (ii) propoxylated alkyl glucose;
(iii) a mixture of ethoxylated and propoxylated alkyl glucose; or a mixture of two or more of the substances mentioned under (i), (ii) and (iii) above, provided that the majority of the R groups in the mixture of the products of formula (I) are -CH 2 -CH 2 -. Ethoxylated and propoxylated alkyl glucosides are commercially available products obtained by reaction of ethylene oxide or propylene oxide with an alkyl glucoside.
The ethoxylated or propoxylated glycoside may also be used as a mixture with a divalent alcohol having up to C atoms, preferably with a divalent alcohol having up to 6 carbon atoms. The two substances must be present in the mixture in such proportion that the mixture remains single phase. Examples of suitable divalent alcohols are ethylene glycol, propylene glycol, 1,4-butenediol and 1,6-hexanediol.
The structure of the ethoxylated bisphenol A is represented by the formula (II) wherein
R<sup>2</sup> is -CH2-CH2-; and the sum of m + n is from about 2 to about 100 (preferably from about 4 to about 20), which represents the total number of ethylene oxide units present in the product.
Ethoxylated bisphenol A is a commercially available product obtained by reaction of ethylene oxide with bisphenol A.
The structure of the polyethylene glycols is shown in (III).
HO- (CH<sub>2</sub>CH<sub>2</sub>SHE)<sub>n</sub>-H expresses a formula wherein n is such that the molecular weight of the polyethylene glycol is from about 300 to about 10,000, preferably from about 400 to about 5000. These polyethylene glycols are also marketable products.
The adducts of C2-C6 alkanediols and triols with e-caprolactone are prepared by reacting e-caprolactone with C2-C6 alkanediol or triol in the presence of a suitable catalyst. Additives having a molecular weight of about 300 to about 500 are preferred for use in the present invention. Adducts of e-caprolactone with alkanediols and triols are commercially available.
Ethoxylated triols such as ethoxylated trimethylolpropane, ethoxylated glycerol or ethoxylated 1,2,6-hexanetriol may also be used as inert diluents. Such products generally have a molecular weight of from about 200 to about 1000.
* the
Mixtures of one or more of the above products may also be used in the process of the invention. For example, a mixture of polyethylene glycol and ethoxylated bisphenol A is preferred; mixtures of polyethylene glycol and ethoxylated alkyl glucoside; mixtures of the ethoxylated and / or propoxylated alkyl glucoside with ethoxylated bisphenol A; and mixtures of ethoxylated alkyl glucoside with ethoxylated triols.
The monomer mixture used in the process of the present invention consists predominantly of a hydrophilic monomer such as (2-hydroxyethyl) methacrylate (abbreviated as HEMA) and additionally one or more crosslinking monomers and optionally minor amounts of additional monomers such as methacrylic acid. HEMA is the preferred hydrophilic monomer. Other monomers used in the process include: (2-hydroxyethyl) acrylate, (2-hydroxypropyl) methacrylate, (2-hydroxypropyl) acrylate, (3-hydroxypropyl) methacrylate, N vinylpyrrolidone, glycerol (mono-methacrylate), and glycerol (mono-acrylate).
Polyoxyethylene polyols which are substituted by one or more of the terminal hydroxyl functionalizable functional groups containing a polymerizable double bond may also be used as hydrophilic monomers. Examples include polyethylene glycol ethoxylated on ethoxylated glycol or ethoxylated with one or more molar equivalents of terminally introduced groups such as isocyanatoethyl methacrylate (abbreviated as IEM), methacrylic acid anhydride, methacrylic acid chloride, vinyl benzoyl chloride, derivative; so polite
- 10 lene polyols having one or more terminal, polymerizable olefinic groups attached to the polyethylene polyol by linking moieties, for example carbamate or ester groups. The examples illustrate the preparation of a plurality of end-to-end polyoxyethylene polyols.
Crosslinking monomers which may be used alone or in combination are, for example: ethylene glycol dimethacrylate (EGDMA for short), trimethylol propane trimethacrylate (abbreviated as: TMPTMA), glycerol trimethacrylate, polyethylene glycol dimethacrylate (where, for example, polyethylene glycol has a molecular weight of up to about 5000), and other polyacrylate and polymethacrylate esters, such as two or more terminal methacryl poly (oxy-Ethylenic) polyols. The crosslinking monomer is employed in conventional amounts, for example, from about 0.000415 to about 0.0156 moles per 100 grams of reactive monomer mixture. The crosslinking monomer may be a hydrophilic monomer.
Another suitable monomer is, for example, methacrylic acid, which can be used to influence the amount of water absorbed by the hydrogel at equilibrium. Methacrylic acid is generally employed in an amount of from about 0.2 to about 8 parts by weight per 100 parts of hydrophilic monomer. The monomer may also be present in the polymerization mixture as (methoxyethyl) methacrylate, acrylic acid or ultraviolet absorptive monomers.
A polymerization catalyst is also added to the monomer mixture. This polymerization catalyst can be, for example, a chemical.
-Allet, such as lauroyl peroxide, dibenzoid peroxide, isopropyl percarbonate, azobis (isobutyronitrile), which causes the formation of free radicals at moderately elevated temperatures; furthermore, the polymerization catalyst may be a photoinitiator (which produces free radicals by exposure to light), such as an aromatic α-hydroxy ketone, or a combination of a tertiary amine and a diketone. Examples of photoinitiator systems include 2-hydroxy-2-methyl-1-phenylpropan-1-one and the combination of camphorquinone and ethyl [4- (N, N-dimethylamino) benzoate]. The catalyst is used in a catalytically effective amount in the polymerization reaction mixture, for example, in an amount of from about 0.1 to about 2 parts by weight per 100 parts of a hydrophilic monomer (such as HEMA).
The following examples illustrate the practice of the invention. The chemical names of some of the products used in the examples are:
ethoxylated bisphenol A [chemically: ethoxylated 2,2-bis (4-hydroxyphenyl) propane], Photonol 7025 [sum of m + n in formula II] and Photonol 7028 [m + in formula II] sum of n 4];
ethoxylated trimethylol propane, Photonol 7158 (molecular weight 73 0);
4-methoxyphenol (hydroquinone monomethyl ether), designated MEHQ; (isocyanatoethyl) methacrylate, designated IEM;
N, N-dimethylacrylic acid, sign DMA; polyethylene glycol, PEG nnnn, where nnnn refers to molecular weight;
ethoxylated (or propoxylated) methylglucose:
GLUCAM's E-5, P-10, E-10 and E-20 (E-5 means that a total of 5 ethylene oxide units are added to the methyl glucoside; P-10 means that a total of 10 propylene —Oxide unit addition, and so on);
isophorone diisocyanate [5-isocyanato-1- (isocyanato-methyl) -1,3,3-trimethylcyclohexane], designated IPDI;
nnn boronic ester of polyethylene glycol, designated PEG nnn BAE; an ester of boric acid with 1,4-butanediol, designated 1,4-BDBAE;
(hydroxyethyl) methacrylate, designated HEMA;
methacrylic acid, sign MAA;
ethylene glycol dimethacrylate, designated EGDMA; trimethylol propane trimethacrylate, designated TMPTMA;
2-hydroxy-2-methyl-1-phenylpropan-1-one, designated DAROCURE 1173;
polycaprolactone triol: product (ester) of glycerol with e-caprolactone, molecular weight about 300, designated PCLT300;
1,2,6-trihydroxyhexane, designated 1,2,6-THH; diethylene glycol, present DEG;
ethylene glycol, designated EG;
1,4-butanediol, designated 1,4-BuDiol;
an ester of boric acid with 1,4-butanediol, designated 1,4-BDBAE;
1,2-propanediol, designated 1,2-ProDiol; and the glycerol ester of boric acid, designated BAGE.
Testing methods
<img file="HUT68045A_D0002.tif" />
The following test methods were used in the examples.
First test method
PhotoDSC definitions
Photocalorimetric measurements were performed on a BuPont DSC Model 910 instrument supplemented with Photocalorimeter No. 830 and the Omnitherm program. in each case a sample weight of 4.5 to 6.0 mg was used. Working conditions: temperature 45 ° C; nitrogen atmosphere (flushed with nitrogen for 10 minutes before irradiation at a rate of 10 ml / min), intensity of UV light source 2.5-3.0 mW / cm<sup>2</sup>.
The maximum polymerization rate (Rp<sup>up</sup>) was calculated from the following equation:
<sub>rp</sub>up <sub>=</sub> ([Mlo / Qoo) (dQ / dt)<sub>up</sub> (1) where ζ)<sub>ω</sub> represents the total amount of heat generated by the sample, and [M]<sub>She</sub> the concentration of double bonds in methacrylate; (DQ / dt)<sub>up</sub> is the observed maximum rate of heat evolution (t = T)<sub>up</sub> (T)<sub>up</sub> the time needed to reach the exothermic peak, which is the same as the time at which the maximum rate of polymerization reaction is reached). Note that Q is obtained from the DSC trace by subtracting the area under the exotherm (the total amount per unit mass of the sample, i.e. Q<sub>m</sub> heat content) and multiply the resultant amount by the weight of the sample. [M]<sub>She</sub>is obtained by simply calculating the concentration of the double bond in the product together with the diluent. Reactive monomer ke · «··
- The density of 14 bullion (RMM in short) should be determined so that [M]<sub>She</sub> amount, i.e. the methacrylate moiety present in a unit volume of RMM, is obtained.
We found that T<sub>up</sub> normally between about 0.2 and about 3.5 minutes; is preferably between about 0.4 and about 2.5 minutes for inert, exchangeable diluents that can be successfully used in the particular reactive monomer mixture. Therefore, with the PhotoDSC test described above, T<sub>up</sub> is a suitable assay to determine whether a proposed inert, exchangeable diluent is suitable for the conversion of a particular reactive monomer mixture into a shaped gel (this applies to any shape other than the contact lens form assumed in the test). Suitable inert, replaceable diluents for the specified RMM are within the limits given above.<sub>up</sub> values.
We also found that in most cases, the percent conversion of the reactive monomer mixture (defined as below the DSC trace, <sup>T</sup>area up to max is divided by the total area under the DCS trace) in the PhotoDSC test described above T<sub>up</sub>at least 40%, preferably at least 50%, to obtain an optically pure gel.
Second test method
Measurement of the Density of RMM and Diluent The density of each fluid was measured using the Archimedes principle. For this purpose, we used the Sartorius Research Balance, which is suitable for measuring the density of liquids
<img file="HUT68045A_D0003.tif" />
complete with kit (available from the manufacturer), which was suitable for all our measurements. The procedure involves measuring a glass weight in the liquid to be tested and then measuring it outside. The volume of glass weight is predetermined with a liquid of known density (e.g., water).
The density of high-viscosity liquids (e.g., boric acid esters) was determined with an aluminum pycnometer, the volume of which was measured using deionized water at a given temperature.
Third test method
Tensile properties (modulus, elongation and rigidity)
The lens to be examined was cut to the desired sample size and shape, and its cross-sectional area was measured, and then the sample was connected with the upper support of a cross-head motion type device with a force measuring cell. The crosshead was lowered to the initial length and the sample was attached to the fixed support. The sample was then stretched at a constant drawing speed and the tensile-tension force roller was applied. Elongation is expressed as a percentage, tensile modulus and tensile strength in kPa. The shaped gel has been found to be suitable for contact lenses if the shaped gel has a modulus of at least about 140 kPa, preferably at least about 170 kPa.
4th test method
Gravimetric determination of water content
Samples for gravimetric water content measurements were prepared as follows:
Cylindrical polystyrene cavities with a diameter of 3 mm and a depth of 3 mm were filled with degassed HEMA-based formulations and cured under fluorescent fluorescent tubes under nitrogen for approximately 20 minutes. According to the measurement, the total energy dose is 1.2-1.6 Joules / cm<sup>2</sup>. The discs containing the polymer and diluent were then removed from the polystyrene bottles using a hot plate and cut into disks 9-10 mm in diameter using a cork drill # 7. The polystriol cavities generally contained sufficient reactive monomer mixture to provide a disc of 1.5 mm thickness. The swellable polymer disks were hydrated in deionized water for 3 hours at 70 ° C and allowed to stand at room temperature for a further 3 days. The discs were then removed from the deionized water bath and air-dried for 10-15 hours and then heated at 100 ° C for 2 hours under vacuum of 200 Pa. The weight of each disk was measured and the disk was kept in physiological saline for 2 days. At this point, the polymer discs were removed from the saline solution, and the water was carefully wiped from the surface and weighed again. The water content was calculated using the following equation:
Water content-h = 100 x (m<sub>nec</sub>j<sub>ves</sub> my<sub>s</sub>^<sub>raz</sub>) / ^ wet (2) where m<sub>s</sub>^<sub>raz</sub> and m<sub>not(</sub>^<sub>ves</sub> represents the weight of the polymer disk before or after hydration.
• »
5th test method
Oxygen permeability (DK)
The permeability of oxygen was measured by the method of Fatt et al. [Measurement of oxygen permeability and permeability on hydrogel lenses and materials; International Contact Lens Clinic, Volume 9, Issue 2, March-April 1982, p. 76]. For this procedure, a polarographic oxygen sensor consisting of a gold cathode with a diameter of 4 mm and a silver / silver chloride annular anode were used. The measured oxygen permeability is denoted by DK, where D is the diffusion coefficient of oxygen and k is the solubility of oxygen in the test substance. Unit of permeability (DK) (cm<sup>2</sup>/ s) (ml 02 / ml x Hgmm).
The following six examples illustrate the preparation of reactive crosslinking agents (Examples 1-4) and the preparation of two diluents known in the art (Examples 5-6).
First example
Preparation of Dicapped, Ethoxylated Bisphenol A (BPA 890) at both ends in a 72-L, three-necked round bottom flask, dried Photonol 7025 (molecular weight: 580 g / mol), 1.5 L of dry acetonitrile, 1.0 g of methoxyphenol (MEHQ) and 0.5 g tin (II) octoate (about 0.1 mol% w / w). The resulting solution was flushed with dry oxygen for 30-45 minutes (gas diffuser was used). After completion of the oxygen purge, 365 g (2.35 moles) of isocyanatoethyl methacrylate (IEM) and 730 g of ace tonitrile are charged into a 1 liter addition funnel (preferably under nitrogen).
The contents of the addition funnel (i.e., the IEM solution) are added dropwise to the above mixture with vigorous stirring. This addition takes about 2-3 hours. After completion of the IEM addition, the addition funnel was rinsed with 50-100 mL of acetonitrile. The progress of the reaction is monitored by observing the disappearance of NCO absorption in the infrared spectrum at 2270 cm<sup>_1</sup>-than. The acetonitrile is then removed in vacuo and the bisphenol A 890 product obtained as a viscous liquid, coated at both ends, is used as such.
Second example
Production of coated polyethylene glycol (PEG) 4000 at both ends
200 g (0.05 mol) of dry PEG 4000 product was placed in a 1 liter round bottom flask equipped with a mechanical stirrer and a gas inlet flask and a dry nitrogen pad was added to the reaction vessel. 375 g of dry acetonitrile are weighed into the flask and allowed to stand with PEG 4000 until completely dissolved. At this time, 2 drops of tin (II) octoate and 500 ppm of MEHQ were added. Into a 100 mL addition funnel was placed 15.52 g (0.100 mol) of IEM and 50 mL of acetonitrile. After completion of the IEM administration, the progress of the reaction is monitored by observing the disappearance of NCO absorption in the infrared spectrum at 2270 cm<sup>_1</sup>-than. After completion of the reaction, acetonitrile is removed in vacuo and the remaining white, waxy, doubly-coated PEG 4000 product is used as is.
Third example
Preparation of Double-Coated Polyethylene Glycol (PEG) 4500
A one-liter, three-necked round bottom flask equipped with mechanical stirrer and gas inlet was charged with 22534 g (0.05 mole) of dry PEG 4500 and rinsed with dry nitrogen followed by dry oxygen. To the contents of the flask was added 375 g of dry acetonitrile and the PEG 4500 was allowed to settle until completely dissolved. 2 drops of tin (II) octoate and 500 ppm of MEHQ are then added. Into a 100 mL addition funnel was poured 15.52 g (0.100 mol) of IEM and 50 mL of acetonitrile, and after completion of the addition of IEM, the reaction progress was monitored with the disappearance of the NCO absorption band (2270 cm).<sup>-1</sup> wavenumber). After completion of the reaction, acetonitrile is removed in vacuo and the remaining white, waxy title product is used as is.
4th example
Preparation of Glucam Ε-20 / polyethylene glycol (PEG) 4500
A one-liter, three-necked round bottom flask equipped with a mechanical stirrer and a gas inlet was charged with 100 g (0.022 moles) of dry PEG 4500 and rinsed with dry nitrogen followed by dry oxygen, respectively. Then 375 g of dry acetonitrile was poured into the flask and the PEG 4500 was allowed to settle until completely dissolved. 2 drops of tin (II) octoate and 500 ppm MEHQ are then added and a mixture of 3.41 g (0.022 mol) of IEM and 10 ml of acetonitrile is added via a addition funnel.
- 20 for the mix. After the addition of IEM, the progress of the reaction is followed by the disappearance of the NCO absorption band (2270 cm<sup>-1</sup> wave number in the infrared spectrum). When this peak disappears completely, the above reaction mixture is transferred to a 500 ml addition funnel and the contents of the funnel are slowly added to a two-liter, three-necked round bottom flask containing 4.89 g (0.022 mol) of isophorone diisocyanate (200 g in dry acetonitrile). contain. Effective mechanical mixing must be ensured during the addition. Upon completion of the addition, the reaction was concentrated to the hydroxyl peak (center 3400 cm) of PEG<sup>_1</sup>on the infrared spectrum) with its disappearance. To this mixture was added a solution of Glucam E-20 (6.0 g, 0.006 mol) in acetonitrile (50 mL). After the disappearance of NCO absorption (2270 cm<sup>-1</sup>acetonitrile was removed in vacuo and the resulting white powdered Glucam E-20 / PEG 4500 solid was used as such.
5th example
Preparation of PEG 400 Boric Acid Ester (PEG 400 BAE) Diluent
Polyethylene glycol 400 (PEG-400) (400 g, 1 mole) was added to a two-liter rotary evaporator flask, and boric acid (123.7 g, 2.0 mole) was added to the flask, and the contents of the flask were distilled on a rotary evaporator. reduced to. Upon reaching the vacuum, slowly increase the bath temperature to 92 ° C and evaporate the water formed during the formation of the boric ester. The transparent viscous PEG 400 BAE fluid is used in this state. (This diluent is a representative example according to Larsen et al.
<img file="HUT68045A_D0004.tif" />
···· >· « • · ··: : » ·· ·. :
889 U.S. Patent No. 664, known diluents.
6th example
Preparation of boric acid ester of 1,4-butanediol (1,4-BDBAE)
To a three liter rotary evaporator flask was charged 277.7 g (4.5 moles) of boric acid, 1,223 g (13.6 moles) of 1,4-butanediol was placed on the rotary evaporator and the pressure was slowly reduced to 65-130 Pa. After reaching the final vacuum, the bath temperature is slowly raised to 85 ° C by increasing the temperature every 20 minutes by about 5 ° C. The water liberated during the formation of the boronic ester is distilled off. The remaining viscous, clear, liquid
1,4-BDBAE is used in this state. This diluent exemplifies the diluents already known in Larsen et al., U.S. Patent Nos. 5,039,459 and 4,889,664.
7-35. example
In these examples, various diluents are used to prepare soft contact lenses from the following reactive monomer mixture:
96.8% by weight ΗΕΜΆ; A mixture of 1.97% methacrylic acid, 0.78% ethylene glycol dimethacrylate (EGDMA), 0.1% trimethylolpropane trimethacrylate (TMPTMA) and 0.34% Darocur 1173 was prepared. To this monomer mixture is added the inhalable interchangeable diluent to be evaluated. The mixture is stirred thoroughly at ambient temperature and then allowed to stir under reduced pressure at 276 kPa (25 ° C),
Ύ. · '
- 22 and then transferred to contact lens templates. Filled templates with UV wavelength 300-380 nm 1.2-1.6 Joule / cm<sup>2 </sup>irradiation (at about 50 ° C for 20 minutes). The templates were then separated and kept at 70 ° C for 3.0 hours to remove the inert diluent and any unreacted monomer remaining. After this initial period of hydration, the lenses are equilibrated at room temperature in fresh saline and then tested using test methods 3, 4 and 5.
The following tables show the evaluated diluents, monomer to diluent ratios, and Table 7-35. Examples 3 to 4 are the results obtained using Test Methods 3, 4 and 5.
- 23 ····
<td></td><td>Example 7</td><td>Example 8</td><td>Example 9</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 96,8</td><td> 96,8</td><td> 96,8</td>
<td>MAA</td><td> 1,97</td><td> 1,97</td><td> 1, 97</td>
<td>EGDMA</td><td> 0,78</td><td> 0,78</td><td> 0, 78</td>
<td>TMPTMA</td><td> 0,1</td><td> 0,1</td><td> 0,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>GLUCAM E20</td><td>GLUCAM E10</td><td>GLUBAM E5</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 234±28</td><td> 248±21</td><td> 227±28</td>
<td>Elongation (%)</td><td> 149±50</td><td> 148±63</td><td> 174±46</td>
<td>Tensile strength</td><td> 280±69</td><td> 280±83</td><td> 318±63</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 57,4+0,7</td><td> 54,4+0,2</td><td> 59,9±0,3</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (min)</td><td> 1,75</td><td> 1,65</td><td> 1,48</td>
<td>Conversion% T<sub>up</sub>-at</td><td> 64,5</td><td> 64,7</td><td> 61,4</td>
<td></td><td>Example 10 control (known)</td><td>Example 11 control (known)</td><td>Example 12</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 96,8</td><td> 96,8</td><td> 96,8</td>
<td>ΜΆΑ</td><td> 1,97</td><td> 1,97</td><td> 1,97</td>
<td>EGDMA</td><td> 0,78</td><td> 0,78</td><td> 0,78</td>
<td>TMPTMA</td><td> 0,1</td><td> 0,1</td><td> 0,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>1,2,6-THH</td><td>glycerol</td><td>Phot 7158</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 170±14</td><td> 280±21</td><td> 186±14</td>
<td>Elongation (%)</td><td> 183±53</td><td> 119±33</td><td> 174±49</td>
<td>Tensile strength</td><td> 248±550</td><td> 255±496</td><td> 255±48</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 59,9+0,1</td><td> 60,6 + 0,6</td><td> 59,5±0,3</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (min)</td><td> 1,80</td><td> 1,53</td><td> 2,15</td>
<td>Conversion% T<sub>up</sub>-at</td><td> 73,4</td><td> 70,9</td><td> 65,1</td>
<td></td><td>Example 13</td><td>Example 14</td><td>Example 15</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 96,8</td><td> 96,8</td><td> 96,8</td>
<td>ΜΆΑ</td><td> 1,97</td><td> 1,97</td><td> 1,97</td>
<td>EGDMA</td><td> 0,78</td><td> 0,78</td><td> 0,78</td>
<td>TMPTMA</td><td> 0,1</td><td> 0,1</td><td> 0,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0, 34</td><td> 0,34</td>
<td>The diluents:</td><td>Phot 7025</td><td>Phot 7028</td><td>PCLT300</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48 : 52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 227±21</td><td> 234±21</td><td> 200±21</td>
<td>Elongation (%)</td><td> 200+76</td><td> 191+48</td><td> 179±55</td>
<td>Tensile strength</td><td> 331±103</td><td> 324±63</td><td> 280±63</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 62,2 + 0,2</td><td> 59,3±0,5</td><td> 61,0±0,6</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (min)</td><td> 1,52</td><td> 1,47</td><td> 1,72</td>
<td>Conversion% T<sub>up</sub>-at</td><td> 62,2</td><td> 61,2</td><td> 69,0</td>
*·♦· • ·
<td></td><td>Example 16 control (known)</td><td>Example 17 control (Ovako)</td><td>Example 18 Control (known)</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 96,8</td><td> 96,8</td><td> 96,8</td>
<td>ΜΆΑ</td><td> 1,97</td><td> 1,97</td><td> 1, 97</td>
<td>EGDMA</td><td> 0,78</td><td> 0,78</td><td> 0,78</td>
<td>TMPTMA</td><td> 0,1</td><td> 0,1</td><td> 0,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>1,4-BDBAE</td><td>GLUCAM P10</td><td>DEG</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48 : 52</td><td> 48:52</td><td> 48 : 52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 186±14</td><td> 110±28</td><td> 97±21</td>
<td>Elongation (%)</td><td> 124±20</td><td> 266±35</td><td> 203±56</td>
<td>Tensile strength</td><td> 194±241</td><td> 331±83</td><td> 170±28</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 62,6+0,6</td><td> 63,5 + 0,5</td><td> 65,4±0,8</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (min)</td><td> 1,08</td><td> 0,87</td><td> 4,83</td>
<td>Conversion% T<sub>up</sub>-at</td><td> 59,5</td><td> 31,5</td><td> 83,3</td>
<img file="HUT68045A_D0005.tif" />
<td></td><td>Example 19 control (known)</td><td>Example 20 control (known)</td><td>Example 21</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 96,8</td><td> 96,8</td><td> 96,8</td>
<td>MAA</td><td> 1,97</td><td> 1,97</td><td> 1,97</td>
<td>EGDMA</td><td> 0,78</td><td> 0,78</td><td> 0,78</td>
<td>TMPTMA</td><td> 0,1</td><td> 0,1</td><td> 0,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>PEG 400BAE</td><td>BAGE</td><td>PEG 400</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 227±14</td><td> 234±14</td><td> 170±21</td>
<td>Elongation (%)</td><td> 134±29</td><td> 114+42</td><td> 179±35</td>
<td>Tensile strength</td><td> 241±34</td><td> 234±55</td><td> 131±14</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 60,4 + 0,2</td><td> 62,7±0,3</td><td> 62,7±0,8</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td>Tmax (Minutes)</td><td> 0,52</td><td> 1,37</td><td> 3,61</td>
<td>Conversion% T<sub>up</sub>-at</td><td> 34,8</td><td> 68,8</td><td> 68,9</td>
<img file="HUT68045A_D0006.tif" />
<td></td><td>Example 22 (low modulus)</td><td>Example 23 Control (known)</td><td>Example 24 Control (known)</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 96,8</td><td> 96,8</td><td> 96,8</td>
<td>MAA</td><td> 1, 97</td><td> 1,97</td><td> 1,97</td>
<td>EGDMA</td><td> 0,78</td><td> 0,78</td><td> 0,78</td>
<td>TMPTMA</td><td> 0, 1</td><td> 0, 1</td><td> 0,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>1,4-BuDiol</td><td>1,2-ProDiol</td><td>SKY</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48 : 52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 90±7</td><td> 110±7</td><td> 159+14</td>
<td>Elongation (%)</td><td> 215±66</td><td> 215±53</td><td> 168±30</td>
<td>Tensile strength</td><td> 159±41</td><td> 193±41</td><td> 186+28</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 66,4+0,6</td><td> -</td><td> 59,9+0,2</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (min)</td><td> 3,42</td><td> 5,48</td><td> 4,80</td>
<td>Conversion% T<sub>up</sub>-at</td><td> 65,4</td><td> 71,5</td><td> 75,0</td>
<td></td><td>Example 25 control (Opaque)</td><td>Example 26 control (Opaque)</td><td>Example 27 control (Opaque)</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 96, 8</td><td> 96, 8</td><td> 96,8</td>
<td>ΜΆΑ</td><td> 1,97</td><td> 1,97</td><td> 1,97</td>
<td>EGDMA</td><td> 0,78</td><td> 0,78</td><td> 0,78</td>
<td>TMPTMA</td><td> 0,1</td><td> 0,1</td><td> 0,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td></td><td></td><td></td>
<td>GLUCAM P-10</td><td> 95</td><td> 85</td><td> 70</td>
<td>GLUCAM E-10</td><td> 5</td><td> 15</td><td> 30</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 83 + 7</td><td> 117±14</td><td> 145±14</td>
<td>Elongation (%)</td><td> 282+56</td><td> 233±45</td><td> 192±42</td>
<td>Tensile strength</td><td> 296+63</td><td> 303±55</td><td> 280±76</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 68,7±0,4</td><td> 69,8±0,6</td><td> 68,9±0,4</td>
<td>hydrogel</td><td>opaque</td><td>opaque</td><td>opaque</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td>Tmax (minutes)</td><td> 0,85</td><td> 0,98</td><td> 1,14</td>
<td>Conversion% T<sub>up</sub>-at</td><td> 28,8</td><td> 38,5</td><td> 49,1</td>
<td></td><td>Example 28</td><td>Example 29</td>
<td>Composition (%):</td><td></td><td></td>
<td>HEMA</td><td> 96,8</td><td> 96,8</td>
<td>MAA</td><td> 1,97</td><td> 1,97</td>
<td>EGDMA</td><td> 0,78</td><td> 0,78</td>
<td>TMPTMA</td><td> 0,1</td><td> 0,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td></td><td></td>
<td>GLUCAM P-10</td><td> 40</td><td> 20</td>
<td>GLUCAM E-10</td><td> 60</td><td> 80</td>
<td>Monomer ratio a</td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td>
<td>Modulus (kPa)</td><td> 262±21</td><td> 262±28</td>
<td>Elongation (%)</td><td> 162±32</td><td> 199±55</td>
<td>Tensile strength</td><td> 303±63</td><td> 338±76</td>
<td>(KPa)</td><td></td><td></td>
<td>Water content (%)</td><td> 59,5+0,2</td><td> 58,4+0,5</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td>
<td><sup>T</sup>max (Minutes)</td><td> 1,47</td><td> 1,56</td>
<td>Conversion% T<sub>up</sub>-at</td><td> 62,2</td><td> 64,1</td>
<img file="HUT68045A_D0007.tif" />
<td></td><td>Example 30 control (Ooak)</td><td>Example 31 control (Opaque)</td><td>Example 32</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 96,8</td><td> 96,8</td><td> 96,8</td>
<td>MAA</td><td> 1,97</td><td> 1,97</td><td> 1,97</td>
<td>EGDMA</td><td> 0,78</td><td> 0,78</td><td> 0,78</td>
<td>TMPTMA</td><td> 0,1</td><td> 0,1</td><td> 0,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td></td><td></td><td></td>
<td>GLUCAM P-10</td><td> 95</td><td> 85</td><td> 70</td>
<td>1,4-BuDiol</td><td> 5</td><td> 15</td><td> 30</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48 : 52</td><td> 48:52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 97±7</td><td> 145+21</td><td> 170+28</td>
<td>Elongation (%)</td><td> 209±49</td><td> 194+43</td><td> 175±59</td>
<td>Tensile strength</td><td> 241+63</td><td> 283±69</td><td> 214±69</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 69,3 + 0,6</td><td> 70,1+0,3</td><td> 62,2±0,3</td>
<td>hydrogel</td><td>opaque</td><td>opaque</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (Minutes)</td><td> 0,96</td><td> 1,21</td><td> 2,24</td>
<td>Conversion% T<sub>up</sub>-at</td><td> 37,5</td><td> 51,6</td><td> 66,2</td>
<td></td><td>Example 33</td><td>Example 34</td><td>Example 35</td>
<td></td><td>(extreme</td><td>(extreme</td><td>(extreme</td>
<td></td><td>modulus)</td><td>modulus)</td><td>modulus)</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 96,8</td><td> 96,8</td><td> 96,8</td>
<td>MAA</td><td> 1,97</td><td> 1,97</td><td> 1,97</td>
<td>EGDMA</td><td> 0,78</td><td> 0,78</td><td> 0,78</td>
<td>TMPTMA</td><td> 0,1</td><td> 0,1</td><td> 0,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td></td><td></td><td></td>
<td>GLUCAM P-10</td><td> 50</td><td> 40</td><td> 20</td>
<td>1,4-BuDiol</td><td> 50</td><td> 60</td><td> 80</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48 : 52</td><td> 48:52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 140±21</td><td> 145+14</td><td> 131±7</td>
<td>Elongation (%)</td><td> 160±41</td><td> 201±63</td><td> 258+80</td>
<td>Tensile strength</td><td> 159±48</td><td> 214±414</td><td> 248±630</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 62,2±0,3</td><td> 62,4±0,4</td><td> 62,9 + 0,1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (Minutes)</td><td> 2,81</td><td> 3,23</td><td> 3,43</td>
<td>Conversion% T<sub>up</sub>-at</td><td> 69,4</td><td> 68,9</td><td> 60,2</td>
36-39. example
In these examples, the diluent used was Photonol 7025 in combination with a reactive monomer mixture containing HEMA, the reactive crosslinking agent prepared in Example 4 and Darocur 1173, which were obtained in varying proportions. The preparation is illustrated in the following description:
by weight, the PEG 4500-Glucam E-20 derivative described in Example 4, 0.35% Darocur 1173 and 74.7% HEMA was mixed with Photonol 7025 in a replaceable diluent such that 48% of the monomer and % diluent ratio should be maintained. The mixture was stirred vigorously at 65 ° C and stirred at 5.2 kPa for 30 minutes and then transferred to contact lens templates. The filled templates are irradiated with ultraviolet light (at 300-380 nm,
1.2-1.6 Joule / cm<sup>2</sup> dose for about 20 minutes at about 65 ° C). The templates were then separated and kept at 70 ° C for 3.0 hours to remove the inert diluent and some unreacted monomer residue. After this initial hydration period, the lenses are equilibrated at room temperature in a fresh saline bath and then tested with test methods 3, 4, and 5, as detailed above.
The following table shows the ratios used in the reactive monomer mixtures, as well as the results of tests 36-39 in Test Methods 3, 4 and 5. in Example .
<td></td><td>Example 36</td><td>Example 37</td><td>Example 38</td><td>Example 39</td>
<td></td><td>(extreme</td><td>(extreme</td><td>(extreme</td><td>(extreme</td>
<td></td><td>modulus)</td><td>modulus)</td><td>modulus)</td><td>(modulus)</td>
<td>Composition (%):</td><td></td><td></td><td></td><td></td>
<td>HEMA</td><td> 74,7</td><td> 64,7</td><td> 49,7</td><td> 39,7</td>
<td>PEG4500-GLUE20</td><td> 25</td><td> 35</td><td> 50</td><td> 60</td>
<td>Darocur 1173</td><td> 0,35</td><td> 0,35</td><td> 0,35</td><td> 0,35</td>
<td>The diluents:</td><td>Pho 7025</td><td>Pho 7025</td><td>Pho 7025</td><td>Pho 7025</td>
<td>Monomer ratio a</td><td></td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48:52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 152±7</td><td> 131±7</td><td> 152±55</td><td> 140±21</td>
<td>Elongation (%)</td><td> 266±42</td><td> 218±44</td><td> 180±76</td><td> 160±41</td>
<td>Break! fall-</td><td></td><td></td><td></td><td></td>
<td>strength (kPa)</td><td> 241±34</td><td> 210±34</td><td> 104±14</td><td> 159±48</td>
<td>Water content (%)</td><td> 55±2</td><td> 69±1</td><td>70 ± l</td><td> 80±2</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>dk</td><td> 31,5</td><td> 40,3</td><td> 60,5</td><td> 41,3</td>
40-44. example
In these examples, Photonol 7025 was used as a diluent in HEMA, MAA, PEG 4500XL (Example 3),
BPA890XL (Example 1) and Darocur 1173 have different ratios 35
<img file="HUT68045A_D0008.tif" />
in a reactive monomer mixture. The method of preparation is described below:
5.78% by weight of the PEG 4500 crosslinker described in Example 3, 11.1% of the ethoxylated bisphenol A crosslinker described in Example 1, 0.34% Darocur 1173, 1.98% matacrylic acid and 80.8%
The HEMA reactive monomer mixture is supplemented with a sufficient amount of Photonol 7025 so that the percentage of the monomer mixture and diluent is 48-52. The mixture was thoroughly mixed at 65 ° C, then stirred under reduced pressure at 65 ° C for 30 minutes and then transferred into contact lens templates. The filled templates were irradiated with ultraviolet light at a wavelength of 300-380 nm at a dose of 1.2-1.6 Joules / cm 2 for 20 minutes at about 65 ° C. The templates were then separated and kept in saline for 3.0 hours at 70 ° C to remove the inert diluent and some unreacted monomer. After this initial hydration period, the lenses are equilibrated in a fresh saline bath at room temperature and then tested with the assay methods of 3, 4 and 5.
The following table shows the results of Figures 40-44. monomer ratios of Examples 1 to 4, and the results obtained using test methods 3, 4 and 5.
<img file="HUT68045A_D0009.tif" />
<td></td><td>Example 40</td><td>Example 41</td><td>42. example</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 80,8</td><td> 75,3</td><td> 64,5</td>
<td>MAA</td><td> 1,98</td><td> 1, 98</td><td> 1,98</td>
<td>PEG 4500XL</td><td> 5,78</td><td> 11,1</td><td> 22,1</td>
<td>BPA890XL</td><td> 11,1</td><td> 11,1</td><td> 11,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>Thinner.</td><td>Phot 7025</td><td>Phot 7025</td><td>Phot 7025</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48 : 52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 468±41</td><td> 580+63</td><td> 550±63</td>
<td>Elongation (%)</td><td> 57±16</td><td> 59±13</td><td> 90±27</td>
<td>Tensile strength</td><td> 331±83</td><td> 352±63</td><td> 524±131</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 36±1</td><td> 41 + 1</td><td> 52±1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>dk</td><td> 20,5</td><td> 23,0</td><td> 28,8</td>
<td></td><td>Example 43</td><td>Example 44</td>
<td>Composition (%):</td><td></td><td></td>
<td>HEMA</td><td> 53,9</td><td> 41,9</td>
<td>MAA</td><td> 1,98</td><td> 1,98</td>
<td>PEG 4500XL</td><td> 32,7</td><td> 44,7</td>
<td>BPA890XL</td><td> 11,1</td><td> 11,1</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>Phot 7025</td><td>Phot 7025</td>
<td>Monomer ratio a</td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td>
<td>Modulus (kPa)</td><td> 580±55</td><td> 558±63</td>
<td>Elongation (%)</td><td> 84±22</td><td> 80 + 32</td>
<td>Tensile strength</td><td> 504±110</td><td> 538±234</td>
<td>(KPa)</td><td></td><td></td>
<td>Water content (%)</td><td> 59±1</td><td> 63±1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td>
<td>dk</td><td> 35,7</td><td> 39,7</td>
<img file="HUT68045A_D0010.tif" />
45-59. example
In these examples, Photonol 7025 was used as a diluent together with a mixture of HEMA, MAA, PEG 4000XL (Example 2), diglycidyl bisphenol A dimethacrylate (Example 1) and Darocur 1173 in varying proportions. The preparation is described below:
90.6% by weight of HEMA, 1.98% by weight of MAA, 5% by weight of the PEG 4000XL crosslinking agent described in Example 2, 2.04% by weight of the diglycidyl bisphenol A described in Example 1 and 0.34% by weight of Darocur 1173 an amount of Photonol 7025 is added so that the ratio of monomer mixture to diluent in the mixture is 48:52. This mixture was thoroughly stirred at 65 ° C, stirred under reduced pressure (5,2 kPa) for 30 minutes at 65 ° C and transferred to contact lens templates. Filled templates with 300-380 nm wavelength ultraviolet light, 1.2-1.6 Joule / cm<sup>2</sup> irradiated at a dose of about 65 ° C for 20 minutes, and the templates were separated and kept at 70 ° C for 3.0 hours in saline to remove the inert diluent and some unreacted monomer. After this initial hydration period, the lenses are equilibrated at room temperature in a fresh saline bath and then tested with test methods 3, 4 and 5.
The following tables show the proportions of the monomers and the test methods 45-59 for Test Methods 3, 4 and 5. The results obtained on the products of Examples 1 to 8 are shown.
<img file="HUT68045A_D0011.tif" />
<td colspan="2">Example 45 (extreme</td><td rowspan="2">Example 46 (extreme modulus)</td><td rowspan="2">Example 47 (extreme modulus)</td><td rowspan="2">Example 48 (extreme (modulus)</td>
<td></td><td>modulus)</td>
<td>Composition (%):</td><td></td><td></td><td></td><td></td>
<td>HEMA</td><td> 90,6</td><td> 85,6</td><td> 75,6</td><td> 65,6</td>
<td>MAA</td><td> 1,98</td><td> 1,98</td><td> 1, 98</td><td> 1,98</td>
<td>PEG 4000XL</td><td> 5</td><td> 10</td><td> 20</td><td> 30</td>
<td>DGBPA510</td><td> 2,04</td><td> 2,04</td><td> 2,04</td><td> 2,04</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>Pho 7025</td><td>Pho 7025</td><td>Pho 7025</td><td>Pho 7025</td>
<td>Monomer ratio a</td><td></td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48 : 52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 296±21</td><td> 303±21</td><td> 345±14</td><td> 338±41</td>
<td>Elongation (%)</td><td> 133±35</td><td> 148±34</td><td> 135±35</td><td> 139±38</td>
<td>Breaking Si-</td><td></td><td></td><td></td><td></td>
<td>strength (kPa)</td><td> 303+76</td><td> 318±69</td><td> 338±63</td><td> 366±90</td>
<td>Water content (%)</td><td> 42±1</td><td> 45±1</td><td> 52±1</td><td> 56±1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>dk</td><td> 30,3</td><td> 33,6</td><td> 39,4</td><td> 42,7</td>
Kinetic parameters:
<td><sup>T</sup>max (min)</td><td> 1,52</td><td> 1,19</td><td colspan="2"> 1,26</td>
<td>Conversion%</td><td></td><td></td><td></td><td></td>
<td><sup>T</sup>up<sup>n</sup>false</td><td> 53,8</td><td> 59,3</td><td> 49,2</td><td> -</td>
<img file="HUT68045A_D0012.tif" />
<td></td><td>Example 49</td><td>Example 50</td><td>Example 51</td><td>Example 52</td>
<td>Composition (%):</td><td></td><td></td><td></td><td></td>
<td>HEMA</td><td> 55,6</td><td> 89,2</td><td> 84,2</td><td> 73,8</td>
<td>MAA</td><td> 1,98</td><td> 1,98</td><td> 1,98</td><td> 1,98</td>
<td>PEG 4000XL</td><td> 40</td><td> 5</td><td> 10</td><td> 20</td>
<td>DGBPA510</td><td> 2,04</td><td> 3,84</td><td> 2,04</td><td> 2,04</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>Pho 7025</td><td>Pho 7025</td><td>Pho 7025</td><td>Pho 7025</td>
<td>Monomer ratio a</td><td></td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48:52</td><td> 48 : 52</td>
<td>Features:</td><td></td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 324+48</td><td> 410±28</td><td> 410±34</td><td> 427+21</td>
<td>Elongation (%)</td><td> 118+33</td><td> 94±29</td><td> 126±25</td><td> 129±33</td>
<td>Breaking Si-</td><td></td><td></td><td></td><td></td>
<td>strength (kPa)</td><td> 303±83</td><td> 331±76</td><td> 441±103</td><td> 441+103</td>
<td>Water content (%)</td><td> 61±1</td><td> 37 + 1</td><td>40 ± l</td><td> 47+1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>dk</td><td> 49,5</td><td> 25,4</td><td> 27,6</td><td> 35,1</td>
<img file="HUT68045A_D0013.tif" />
<td></td><td>Example 53</td><td>54. example</td><td>Example 55</td><td>Example 56</td>
<td>Composition (%):</td><td></td><td></td><td></td><td></td>
<td>HEMA</td><td> 63,8</td><td> 53,8</td><td> 91,6</td><td> 86,6</td>
<td>MAA</td><td> 1,98</td><td> 1,98</td><td> 0,98</td><td> 0,98</td>
<td>PEG 4000XL</td><td> 30</td><td> 40</td><td> 5</td><td> 10</td>
<td>DGBPA510</td><td> 2,04</td><td> 2,04</td><td> 2,04</td><td> 2,04</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>Pho 7025</td><td>Pho 7025</td><td>Pho 7025</td><td>Pho 7025</td>
<td>Monomer ratio a</td><td></td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48:52</td><td> 48 : 52</td>
<td>Features:</td><td></td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 410±28</td><td> 359±76</td><td> 296±21</td><td> 338±34</td>
<td>Elongation (%)</td><td> 109±41</td><td> 108±27</td><td> 124±37</td><td> 131+37</td>
<td>Breaking color</td><td></td><td></td><td></td><td></td>
<td>strength (kPa)</td><td> 340±103</td><td> 359±90</td><td> 290±63</td><td> 331±69</td>
<td>Water content (%)</td><td> 54 + 2</td><td> 57 + 1</td><td> 48±1</td><td> 52±1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>dk</td><td> 41,4</td><td> 46,3</td><td> 20,8</td><td> 48,10</td>
Kinetic parameters:
<td><sup>T</sup>max (min)</td><td> -</td><td> -</td><td> 1,18</td><td> 1,13</td>
<td>Conversion%</td><td></td><td></td><td></td><td></td>
<td><sup>T</sup>up<sup>-n</sup>false</td><td> -</td><td> -</td><td> 62,0</td><td> 60,0</td>
···· 99 1
<td></td><td>Example 57</td><td>Example 58</td><td>Example 59</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 76, 6</td><td> 66,6</td><td> 56,6</td>
<td>MAA</td><td> 0, 98</td><td> 0,98</td><td> 0,98</td>
<td>PEG 4000XL</td><td> 5,78</td><td> 11,1</td><td> 22,1</td>
<td>DGBPA510</td><td> 2,04</td><td> 2,04</td><td> 2,04</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>Phot 7025</td><td>Phot 7025</td><td>Phot 7025</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48 : 52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 338±21</td><td> 331±34</td><td> 318±14</td>
<td>Elongation (%)</td><td> 141±35</td><td> 123±43</td><td> 130±51</td>
<td>Tensile strength</td><td> 365±69</td><td> 338±28</td><td> 359±124</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td>60 ± l</td><td> 65±1</td><td>70 ± l</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>dk</td><td> 31,1</td><td> 40,2</td><td> 44,0</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (min)</td><td> 0,89</td><td> 0,82</td><td> 0,68</td>
<td>Conversion%</td><td></td><td></td><td></td>
<td><sup>T</sup>up<sup>-n</sup>false</td><td> 53,4</td><td> 52,7</td><td> 46,4</td>
60-69. example
In these examples, Glucam E-20 was used as a diluent, with varying proportions of HEMA, MAA, PEG 4500XL (Example 3), Digicidyl Bisphenol A dimethacrylate (Example 1), and Darocur 1173 monomer mixture. The following illustrates the method of preparation:
5.7% by weight of the PEG 4500 crosslinking agent described in Example 3, 4.98% by weight of a reactive monomer mixture of the ethoxylated bisphenol A described in Example 1, 0.35% Darocur 1173, 1.98% methacrylic acid and 87.0% HEMA products. The amount of E-20 is mixed so that the resulting mixture contains 48% monomer mixture and 52% diluent. After thorough mixing at 65 ° C, the mixture was further stirred under reduced pressure (5.2 kPa) for 30 minutes at 65 ° C and transferred to contact lens templates. Loaded templates with 300-380 nm wavelength ultraviolet light, 1.2-1.6 Joule / cm<sup>2</sup> irradiated at about 65 ° C for 20 minutes. The templates were then separated and kept in physiological saline for 3.0 hours at 70 ° C to remove the inert diluent and some unreacted monomer remaining. After this initial period of hydration, the lenses are equilibrated at room temperature in a fresh saline bath and the lenses are tested according to Test Methods 3, 4 and 5.
The following tables illustrate pages 60-69. and the results of tests according to Test Methods 3, 4 and 5.
- 44 »···
<td></td><td>Example 60</td><td>Example 61</td><td>Example 62</td><td>63. example</td>
<td>Composition (%):</td><td></td><td></td><td></td><td></td>
<td>HEMA</td><td> 87,0</td><td> 81,8</td><td> 73,7</td><td> 59,4</td>
<td>MAA</td><td> 1,98</td><td> 1,98</td><td> 1,98</td><td> 1,98</td>
<td>PEG 4500XL</td><td> 5,7</td><td> 10,9</td><td> 19</td><td> 33,3</td>
<td>BPA890XL</td><td> 4,98</td><td> 4,98</td><td> 4,98</td><td> 4,98</td>
<td>Darocur 1173</td><td> 0,35</td><td> 0,35</td><td> 0,35</td><td> 0,35</td>
<td>The diluents:</td><td>GLUCAM E20</td><td>GLUCAM E20</td><td>GLUCAM E20</td><td>GLUCAM E20</td>
<td>Monomer ratio a</td><td></td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48 : 52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 434148</td><td> 434+34</td><td> 455+28</td><td> 483±34</td>
<td>Elongation (%)</td><td> 119+23</td><td> 120+33</td><td> 142+35</td><td> 145+34</td>
<td>Breaking color</td><td></td><td></td><td></td><td></td>
<td>strength (kPa)</td><td> 228+83</td><td> 234+97</td><td> 318±124</td><td> 352+131</td>
<td>Water content (%)</td><td> 5611</td><td> 58 + 1</td><td> 62 + 1</td><td> 68 + 1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>dk</td><td> 25,9</td><td> 27,7</td><td> 32,3</td><td> 38,70</td>
<td></td><td>Example 64</td><td>Example 65</td><td>Example 66</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>ΗΕΜΆ</td><td> 48,5</td><td> 83,1</td><td> 77,9</td>
<td>MAA</td><td> 1,98</td><td> 1,98</td><td> 1,98</td>
<td>PEG 4500XL</td><td> 44,2</td><td> 5,7</td><td> 10,9</td>
<td>BPA890XL</td><td> 4,98</td><td> 8,9</td><td> 8,9</td>
<td>Darocur 1173</td><td> 0,35</td><td> 0,35</td><td> 0,35</td>
<td>The diluents:</td><td>GLUCAM E20</td><td>GLUCAM E20</td><td>GLUCAM E20</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48:52 ,</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 550±83</td><td> 593±55</td><td> 615±28</td>
<td>Elongation (%)</td><td> 159±36</td><td> 114±14</td><td> 120±30</td>
<td>Tensile strength</td><td> 468±165</td><td> 280±103</td><td> 296±131</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 71 + 1</td><td> 53±1</td><td> 55 + 1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>dk</td><td> 45,0</td><td> 21,0</td><td> 23,4</td>
• * · ·
<td></td><td>Example 67</td><td>Example 68</td><td>Example 69</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 69,8</td><td> 55,5</td><td> 44,6</td>
<td>MAA</td><td> 1,98</td><td> 1,98</td><td> 1,98</td>
<td>PEG 450OXL</td><td> 19</td><td> 33,3</td><td> 44,2</td>
<td>BPA890XL</td><td> 8,9</td><td> 8,9</td><td> 8,9</td>
<td>Darocur 1173</td><td> 0,35</td><td> 0,35</td><td> 0,35</td>
<td>The diluents:</td><td>GLUCAM E20</td><td>GLUCAM E20</td><td>GLUCAM E20</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 48:52</td><td> 48:52</td><td> 48:52</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 615±34</td><td> 662±41</td><td> 704±41</td>
<td>Elongation (%)</td><td> 127+35</td><td> 163±25</td><td> 162±25</td>
<td>Tensile strength</td><td> 338±170</td><td> 566±145</td><td> 600±103</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 60 + 1</td><td> 65±1</td><td> 69±2</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>dk</td><td> 29,2</td><td> 34,5</td><td> 40,3</td>
Example 70
At one end, production of a coated polyethylene glycol 3350 (designated PEG 3350MC)
With a mechanical stirrer, a three-necked flask with a gas inlet was charged with 200 g (0.060 mol) of dry PEG 3350 product and the system was purged with dry nitrogen and then with dry oxygen. To the PEG 3350 in the flask is added 600 g of dry acetonitrile and stirred until the PEG 3350 is completely dissolved. 2 drops of tin (II) octoate and 500 ppm of MEHQ are then added and 8.69 g (0.056 mol) of (isocyanatoethyl) methacrylate are added in a dropping funnel. The reaction is carried out at room temperature for 24-28 hours. The progress of the reaction in the infrared spectrum is 2270 cm<sup>_1</sup>at the disappearance of the NCO absorption band. The acetonitrile was then removed in vacuo and the resulting white waxy PEG 3350 coated at one end was used as such.
71-107. example
In these examples, various diluents and mixtures were added to the reactive monomer mixture containing HEMA, DMA, PEG 4000XL (Example 2), diglycidyl bisphenol A dimethacrylate (Example 1), PEG 3350MC (Example 70) and Darocur 1173. The following illustrates the method of preparation:
64.7% by weight HEMA, 20.0% N, N-dimethylacrylamide (DMA), the coated PEG 4000 crosslinker described in Example 2, 2.0% ethoxylated bisphenol A crosslinker prepared in Example 1, 6, 0% covered in one end as described in example 70 ····· ······· ···
A reactive monomer mixture of PEG 3350 and 0.34% Darocur 1173 was prepared. To 60% by weight of this monomer mixture is added 40% PEG 1000 inert replaceable diluent, the mixture is mixed thoroughly at 60 ° C, and the resulting mixture is stirred under reduced pressure at 60 ° C for 30 minutes and contact lens templates we carry it. Filled templates with ultraviolet light of 300-380 nm, 1.2-1.6 Joule / cm<sup>2</sup> irradiated at about 60 ° C for 20 minutes. The templates were then separated and kept at 70 ° C for 3.0 hours to remove the inert diluent and some remaining monomer. After this initial period of hydration, the lenses are equilibrated at room temperature in a fresh saline bath and the lenses are tested using the assay method 3, 4 and 5.
The ratio of monomers and assays of Test Methods 3, 4 and 5 are shown in Figures 71-107. The results of the products of Examples 1 to 4 are summarized in the tables below.
<td></td><td>Example 71</td><td>Example 72</td><td>Example 73</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 64,7</td><td> 64,7</td><td> 64,7</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4000XL</td><td> 7</td><td> 7</td><td> 7</td>
<td>PEG 3350MC</td><td> 6</td><td> 6</td><td> 6</td>
<td>BPA890XL</td><td> 2</td><td> 2</td><td> 2</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>PEG 1000</td><td>PEG 750</td><td>PEG 600</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 60:40</td><td> 60:40</td><td> 60:40</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 170</td><td> 152</td><td> 131</td>
<td>Elongation (%)</td><td> 191</td><td> 200</td><td> 191</td>
<td>Tensile strength</td><td> 186</td><td> 145</td><td> 165</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 63,0</td><td> 61,7</td><td> 61,3</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (min)</td><td> 3,50</td><td> 3,90</td><td> 4,00</td>
<td>Conversion%</td><td></td><td></td><td></td>
<td><sup>T</sup>up<sup>-n</sup>false</td><td> 59,0</td><td> 58,0</td><td> 61,0</td>
<img file="HUT68045A_D0014.tif" />
. Example 75 (Extreme Control Module) (known)
Composition (%):
HEMA
DMA
PEG 4000XL
PEG 3350MC
BPA890XL
Darocur 1173
The diluents:
Ratio of monomer to diluent
Features:
Modulus (kPa)
Elongation (%)
Tensile strength (kPa)
Water content (%)
hydrogel
Kinetic parameters:
<sup>T</sup>max (min)
Conversion% <sup>T</sup>max ~<sup>n</sup>false
<td> 64,7</td><td> 64,7</td>
<td> 20</td><td> 20</td>
<td> 7</td><td> 7</td>
<td> 6</td><td> 6</td>
<td> 2</td><td> 2</td>
<td> 0,34</td><td> 0,34</td>
<td>PEG 400</td><td>PEG 400BAE</td>
<td> 60:40</td><td> 60:40</td>
<td> 124</td><td> 352</td>
<td> 189</td><td> 122</td>
<td> 179</td><td> 318</td>
<td> 62,1</td><td> 61,3</td>
<td>transparent</td><td>transparent</td>
<td> 4,30</td><td> 0,34</td>
<td> 63,0</td><td> 39,0</td>
·· ·4
<img file="HUT68045A_D0015.tif" />
<td></td><td>Example 76</td><td>Example 77</td><td>Example 78</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 64,7</td><td> 64,7</td><td> 64,7</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4000XL</td><td> 7</td><td> 7</td><td> 7</td>
<td>PEG 3350MC</td><td> 6</td><td> 6</td><td> 6</td>
<td>BPA890XL</td><td> 2</td><td> 2</td><td> 2</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>The diluents:</td><td>GLUCAM E10</td><td>GLUCAM E20</td><td>GLUCAM 7025</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 60:40</td><td> 60:40</td><td> 60:40</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 366</td><td> 352</td><td> 345</td>
<td>Elongation (%)</td><td> 135</td><td> 133</td><td> 165</td>
<td>Break! strength</td><td> 324</td><td> 303</td><td> 338</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 60,8</td><td> 60,5</td><td> 61,1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (min)</td><td> 1,10</td><td> 0,90</td><td> 1,10</td>
<td>Conversion%</td><td></td><td></td><td></td>
<td><sup>T</sup>max "<sup>n</sup>live</td><td> 42,0</td><td> 44,0</td><td> 39,0</td>
<img file="HUT68045A_D0016.tif" />
<td></td><td>Example 79</td><td>Example 80</td><td>Example 81</td><td>Example 82</td>
<td>Composition (%):</td><td></td><td></td><td></td><td></td>
<td>HEMA</td><td> 64,7</td><td> 64,7</td><td> 64,7</td><td> 64,7</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4000XL</td><td> 7</td><td> 7</td><td> 7</td><td> 7</td>
<td>BPA890</td><td> 2</td><td> 2</td><td> 2</td><td> 2</td>
<td>PEG 3350MC</td><td> 6</td><td> 6</td><td> 6</td><td> 6</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>Diluent (%):</td><td></td><td></td><td></td><td></td>
<td>PEG 400</td><td> 90</td><td> 75</td><td> 60</td><td> 50</td>
<td>Photonol 7025</td><td> 10</td><td> 25</td><td> 40</td><td> 50</td>
<td>Monomer ratio a</td><td></td><td></td><td></td><td></td>
<td>diluent</td><td> 60 -.40</td><td> 60:40</td><td> 60:40</td><td> 60:40</td>
<td>Features:</td><td></td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 186</td><td> 214</td><td> 210</td><td> 270</td>
<td>Elongation (%)</td><td> 200</td><td> 210</td><td> 190</td><td> 186</td>
<td>Breaking Si-</td><td></td><td></td><td></td><td></td>
<td>strength (kPa)</td><td> 193</td><td> 214</td><td> 200</td><td> 214</td>
<td>Water content (%)</td><td> 62,1</td><td> 61,9</td><td> 62,0</td><td> 61,2</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td><td>transparent</td>
Kinetic parameters:
<td><sup>T</sup>max (min)</td><td> 4,2</td><td> 4,0</td><td> 3,9</td><td> 3,4</td>
<td>Conversion%</td><td></td><td></td><td></td><td></td>
<td><sup>T</sup>up<sup>-n</sup>false</td><td> 59,0</td><td> 56,0</td><td> 52</td><td> 53</td>
• · · · • · * ·
<img file="HUT68045A_D0017.tif" />
<td></td><td>Example 83</td><td>Example 84</td><td>Example 85</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 64,7</td><td> 64,7</td><td> 64,7</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4000XL</td><td> 7</td><td> 7</td><td> 7</td>
<td>BPA890</td><td> 2</td><td> 2</td><td> 2</td>
<td>PEG 3350MC</td><td> 6</td><td> 6</td><td> 6</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>Diluent (%):</td><td></td><td></td><td></td>
<td>PEG 400</td><td> 35</td><td> 25</td><td> 15</td>
<td>Photonol 7025</td><td> 65</td><td> 75</td><td> 85</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 60:40</td><td> 60:40</td><td> 60:40</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 290</td><td> 352</td><td> 359</td>
<td>Stretching (¾)</td><td> 175</td><td> 185</td><td> 160</td>
<td>Tensile strength</td><td> 280</td><td> 280</td><td> 296</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 61,1</td><td> 60,9</td><td> 60,7</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (min)</td><td> 2,1</td><td> 1,6</td><td> 1,2</td>
<td>Conversion%</td><td></td><td></td><td></td>
<td><sup>T</sup>up<sup>-n</sup>false</td><td> 51,0</td><td> 48,0</td><td> 41,0</td>
<td></td><td>Example 86</td><td>Example 87</td><td>Example 88</td><td>Example 89</td>
<td>Composition (%):</td><td></td><td></td><td></td><td></td>
<td>HEMA</td><td> 64,7</td><td> 64,7</td><td> 64,7</td><td> 64,7</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 400OXL</td><td> 7</td><td> 7</td><td> 7</td><td> 7</td>
<td>BPA890</td><td> 2</td><td> 2</td><td> 2</td><td> 2</td>
<td>PEG 3350MC</td><td> 6</td><td> 6</td><td> 6</td><td> 6</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>Diluent (%).</td><td></td><td></td><td></td><td></td>
<td>PEG 400</td><td> 90</td><td> 75</td><td> 60</td><td> 50</td>
<td>GLUCAM E20</td><td> 10</td><td> 25</td><td> 40</td><td> 50</td>
<td>Monomer ratio a</td><td></td><td></td><td></td><td></td>
<td>diluent</td><td> 60:40</td><td> 60:40</td><td> 60:40</td><td> 60:40</td>
<td>Features:</td><td></td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 165</td><td> 200</td><td> 207</td><td> 255</td>
<td>Elongation (%)</td><td> 185</td><td> 190</td><td> 188</td><td> 178</td>
<td>Breaking Si-</td><td></td><td></td><td></td><td></td>
<td>strength (kPa)</td><td> 170</td><td> 200</td><td> 214</td><td> 234</td>
<td>Water content (%)</td><td> 61,8</td><td> 61,7</td><td> 61,2</td><td> 61,0</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td><td>transparent</td>
Kinetic parameters:
<td><sup>T</sup>max (min)</td><td> 4,1</td><td> 3,7</td><td> 3,2</td><td> 2,1</td>
<td>Conversion%</td><td></td><td></td><td></td><td></td>
<td>Tmax<sup>_naX</sup></td><td> 59,0</td><td> 50,0</td><td> 49,0</td><td> 46,0</td>
···· ·* · ··«· ·· • · · · · « · · ··· · * » · · • · · ♦ ♦ ·« · * · ·· ·· · · ·»
<td></td><td>Example 90</td><td>Example 91</td><td>Example 92</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 64,7</td><td> 64,7</td><td> 64,7</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4000XL</td><td> 7</td><td> 7</td><td> 7</td>
<td>BPA890</td><td> 2</td><td> 2</td><td> 2</td>
<td>PEG 3350MC</td><td> 6</td><td> 6</td><td> 6</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>Diluent (%):</td><td></td><td></td><td></td>
<td>PEG 400</td><td> 90</td><td> 75</td><td> 60</td>
<td>GLUCAM E20</td><td> 10</td><td> 25</td><td> 40</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 60:40</td><td> 60:40</td><td> 60:40</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 303</td><td> 331</td><td> 359</td>
<td>Elongation (%)</td><td> 150</td><td> 150</td><td> 141</td>
<td>Tensile strength</td><td> 283</td><td> 270</td><td> 310</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 60,8</td><td> 60,7</td><td> 60,5</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td>Tmax (Minutes)</td><td> 1,4</td><td> 1,0</td><td> 0,9</td>
<td>Conversion%</td><td></td><td></td><td></td>
<td>Tmax ~<sup>n</sup>false</td><td> 48,0</td><td> 44,0</td><td> 47,0</td>
'·· · 9 4 ♦ · · · * ··· 9 4 • * * ··· • «Μ ·
<td></td><td>Example 93</td><td>94. example (extreme modulus)</td><td>Example 95</td><td>Example 96</td>
<td>Composition (%):</td><td></td><td></td><td></td><td></td>
<td>HEMA</td><td> 64,7</td><td> 64,7</td><td> 64,7</td><td> 64,7</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4000XL</td><td> 7</td><td> 7</td><td> 7</td><td> 7</td>
<td>BPA890</td><td> 2</td><td> 2</td><td> 2</td><td> 2</td>
<td>PEG 3350MC</td><td> 6</td><td> 6</td><td> 6</td><td> 6</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>Diluent (%):</td><td></td><td></td><td></td><td></td>
<td>PEG 1000</td><td> 100</td><td> 90</td><td> 75</td><td> 60</td>
<td>GLUCAM E20</td><td> 0</td><td> 10</td><td> 25</td><td> 40</td>
<td>Monomer ratio a</td><td></td><td></td><td></td><td></td>
<td>diluent</td><td> 60:40</td><td> 60:40</td><td> 60:40</td><td> 60:40</td>
<td>Features:</td><td></td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 170</td><td> 145</td><td> 193</td><td> 228</td>
<td>Elongation (%)</td><td> 191</td><td> 190</td><td> 175</td><td> 184</td>
<td>Breaking Si-</td><td></td><td></td><td></td><td></td>
<td>strength (kPa)</td><td> 186</td><td> 210</td><td> 255</td><td> 214</td>
<td>Water content (%)</td><td> 63,0</td><td> 62,3</td><td> 62,0</td><td> 61,6</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td><td>transparent</td>
Kinetic parameters:
<td><sup>T</sup>max (min)</td><td> 3,5</td><td> 3,3</td><td> 2,9</td><td> 2,6</td>
<td>Conversion%</td><td></td><td></td><td></td><td></td>
<td><sup>T</sup>up<sup>n</sup>false</td><td> 59,0</td><td> 55,0</td><td> 53,0</td><td> 54,0</td>
97th Example 98 Example 98 Example 99 Example 100
Composition (%):
<td>HEMA</td><td> 64,7</td><td> 64,7</td><td> 64,7</td><td> 64,7</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4000XL</td><td> 7</td><td> 7</td><td> 7</td><td> 7</td>
<td>BPA890</td><td> 2</td><td> 2</td><td> 2</td><td> 2</td>
<td>PEG 3350MC</td><td> 6</td><td> 6</td><td> 6</td><td> 6</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>Diluent (%):</td><td></td><td></td><td></td><td></td>
<td>PEG 1000</td><td> 50</td><td> 35</td><td> 25</td><td> 15</td>
<td>GLUCAM E20</td><td> 50</td><td> 65</td><td> 75</td><td> 85</td>
<td>Monomer ratio a</td><td></td><td></td><td></td><td></td>
<td>diluent</td><td> 60:40</td><td> 60:40</td><td> 60:40</td><td> 60:40</td>
<td>Features:</td><td></td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 234</td><td> 228</td><td> 324</td><td> 338</td>
<td>Elongation (%)</td><td> 141</td><td> 132</td><td> 122</td><td> 111</td>
<td>Breaking Si-</td><td></td><td></td><td></td><td></td>
<td>strength (kPa)</td><td> 290</td><td> 283</td><td> 338</td><td> 283</td>
<td>Water content (%)</td><td> 61,0</td><td> 61,3</td><td> 60,8</td><td> 61,0</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td><td>transparent</td>
Kinetic parameters:
<td><sup>T</sup>max (min)</td><td> 2,1</td><td> 1,4</td><td> 1,1</td><td> 1,1</td>
<td>Conversion%</td><td></td><td></td><td></td><td></td>
<td><sup>T</sup>max "<sup>n</sup>a stirred</td><td> 49,0</td><td> 47,0</td><td> 46,0</td><td> 41,0</td>
One hundred and first Example 102 Example 103 Example 104 (Extreme Module)
Composition (%):
<td>HEMA</td><td> 64,7</td><td> 64,7</td><td> 64,7</td><td> 64,7</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4000XL</td><td> 7</td><td> 7</td><td> 7</td><td> 7</td>
<td>BPA890</td><td> 2</td><td> 2</td><td> 2</td><td> 2</td>
<td>PEG 3350MC</td><td> 6</td><td> 6</td><td> 6</td><td> 6</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>Diluent (%):</td><td></td><td></td><td></td><td></td>
<td>PEG 1000</td><td> 90</td><td> 75</td><td> 60</td><td> 50</td>
<td>GLUCAM E20</td><td> 10</td><td> 25</td><td> 40</td><td> 50</td>
<td>Monomer ratio a</td><td></td><td></td><td></td><td></td>
<td>diluent</td><td> 60:40</td><td> 60:40</td><td> 60:40</td><td> 60 :40</td>
<td>Features:</td><td></td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 131</td><td> 186</td><td> 221</td><td> 241</td>
<td>Elongation (%)</td><td> 183</td><td> 175</td><td> 181</td><td> 177</td>
<td>Breaking Si-</td><td></td><td></td><td></td><td></td>
<td>strength (kPa)</td><td> 248</td><td> 193</td><td> 214</td><td> 228</td>
<td>Water content (%)</td><td> 61,1</td><td> 62,8</td><td> 62,5</td><td> 62,1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td><td>transparent</td>
Kinetic parameters:
<td><sup>T</sup>max (min)</td><td> 3,6</td><td> 3,4</td><td> 3,1</td><td> 2,7</td>
<td>Conversion%</td><td></td><td></td><td></td><td></td>
<td><sup>T</sup>up<sup>-n</sup>false</td><td> 49,0</td><td> 51,0</td><td> 45,0</td><td> 39,0</td>
• ·
<img file="HUT68045A_D0018.tif" />
<td></td><td>Example 105</td><td>Example 106</td><td>Example 107</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 64,7</td><td> 64,7</td><td> 64,7</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4000XL</td><td> 7</td><td> 7</td><td> 7</td>
<td>BPA890</td><td> 2</td><td> 2</td><td> 2</td>
<td>PEG 3350MC</td><td> 6</td><td> 6</td><td> 6</td>
<td>Darocur 1173</td><td> 0,34</td><td> 0,34</td><td> 0,34</td>
<td>Diluent (%):</td><td></td><td></td><td></td>
<td>PEG 1000</td><td> 90</td><td> 75</td><td> 60</td>
<td>Photonol 7025</td><td> 10</td><td> 25</td><td> 40</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 60:40</td><td> 60:40</td><td> 60:40</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 270</td><td> 310</td><td> 318</td>
<td>Elongation (%)</td><td> 131</td><td> 125</td><td> 130</td>
<td>Tensile strength</td><td> 283</td><td> 283</td><td> 324</td>
<td>(KPa)</td><td></td><td></td><td></td>
<td>Water content (%)</td><td> 61,5</td><td> 60,7</td><td> 60,8</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<td>Kinetic parameters:</td><td></td><td></td><td></td>
<td><sup>T</sup>max (min)</td><td> 1,4</td><td> 1,1</td><td> 1,1</td>
<td>Conversion%</td><td></td><td></td><td></td>
<td><sup>T</sup>max "<sup>n</sup>false</td><td> 41,0</td><td> 42,0</td><td> 44,0</td>
<img file="HUT68045A_D0019.tif" />
108th example
Preparation of PEG 2000 Monomethyl Ether Covered at One End (Isocyanatoethyl) Methacrylate
200 Dry PEG 2000 monomethyl ether (0.10 mol) was weighed in a 1 liter three-necked flask with mechanical stirring and a gas inlet, 600 g of dry acetonitrile were added and allowed to stand until the PEG 2000 monomethyl ether was completely dissolved. The system was purged with dry nitrogen immediately followed by dry oxygen and two drops of stannous octoate and 500 ppm 4-methoxyhydroquinone (MEHQ) were added to the contents of the flask. A solution of 15.51 g (0.10 mol) of (isocyanatoethyl) methacrylate in 50 g of acetonitrile is then added dropwise to the contents of a 1 liter flask. The reaction mixture was allowed to stand at room temperature for 24-28 hours. The progress of the reaction is monitored by observing an infrared spectrum of 2270 cm<sup>1</sup> value of NCO absorption. After the reaction was complete (when 2270 cm<sup>-1</sup>absorbance is no longer detectable), the solvent is removed in vacuo and the white, waxy residue, coated PEG 2000 monomethyl ether, is carried on in this form.
109-120. example
Different amounts of HEMA, 20.0% N, N-dimethylacrylamide (DMA), 16.0% PEG 4500 cross-linked crosslinking agent (PEG 4500XL; see Example 3), 8.0% ethoxylated bisphenol in Example 1 using a crosslinking agent (BPA890) as described above and various amounts of one end coated PEG 2000 monomethyl ether as described in Example 108 and 0.4% Darocur 1173 to form a reactive monomer mixture. To 55% (w / w) of this monomer mixture is added a 45% inert, replaceable diluent, which in itself consists of 50% Glucam Ε-20 and 50% Photonol 7025. The above mixture was thoroughly mixed at 60 ° C, stirred under reduced pressure at 60 ° C for 30 minutes and then transferred to contact lens templates. Filled templates with ultraviolet light of 300-380 nm, 1.2-1.6 Joule / cm<sup>2</sup> irradiated at about 60 ° C for 20 minutes. At this point, the templates were separated and kept in physiological saline for 3.0 hours at 70 ° C to remove inhaled diluent and residual unreacted monomers. After this initial period of hydration, the lenses are equilibrated at room temperature in a fresh saline bath and then tested according to Test Methods 3, 5 and 5.
The following tables show the results of Figures 109-120. and the composition of the reactive monomer mixture.
<img file="HUT68045A_D0020.tif" />
<td></td><td>Example 109</td><td>Example 110</td><td>Example 111</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 43,6</td><td> 34,6</td><td> 20,6</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4500XL</td><td> 16</td><td> 16</td><td> 16</td>
<td>BPA890</td><td> 8</td><td> 8</td><td> 8</td>
<td>MC mPEG 2000</td><td> 12</td><td> 21</td><td> 35</td>
<td>Darocur 1173</td><td> 0,4</td><td> 0,4</td><td> 0,4</td>
<td>Diluent (%):</td><td></td><td></td><td></td>
<td>Photonol 7025</td><td> 50</td><td> 50</td><td> 50</td>
<td>GLUCAM E-20</td><td> 50</td><td> 50</td><td> 50</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 55:45</td><td> 55:45</td><td> 55:45</td>
<td>Features ·</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 523</td><td> 530</td><td> 517</td>
<td>Elongation (%)</td><td> 148</td><td> 113</td><td> 117</td>
<td>dk</td><td> 37</td><td> 42</td><td> 50</td>
<td>Water content (%)</td><td> 70,5</td><td> 73,8</td><td> 78,1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<img file="HUT68045A_D0021.tif" />
• ·
<td></td><td>Example 112</td><td>Example 113</td><td>Example 114</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 43,6</td><td> 34,6</td><td> 20,6</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4500XL</td><td> 16</td><td> 16</td><td> 16</td>
<td>BPA890</td><td> 8</td><td> 8</td><td> 8</td>
<td>MC mPEG 2000</td><td> 12</td><td> 21</td><td> 35</td>
<td>Darocur 1173</td><td> 0,4</td><td> 0,4</td><td> 0,4</td>
<td>Diluent (%):</td><td></td><td></td><td></td>
<td>Photonol 7025</td><td> 50</td><td> 50</td><td> 50</td>
<td>GLUCAM E-20</td><td> 50</td><td> 50</td><td> 50</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 45 : 55</td><td> 45:55</td><td> 45 : 55</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 352</td><td> 303</td><td> 324</td>
<td>Elongation (%)</td><td> 142</td><td> 119</td><td> 128</td>
<td>dk</td><td> 40</td><td> 47</td><td> 55</td>
<td>Water content (%)</td><td> 72,9</td><td> 76,6</td><td> 80,3</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<img file="HUT68045A_D0022.tif" />
<td></td><td>Example 115</td><td>Example 116</td><td>Example 117</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>HEMA</td><td> 36,6</td><td> 27,6</td><td> 13,6</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4500XL</td><td> 16</td><td> 16</td><td> 16</td>
<td>BPA890</td><td> 15</td><td> 15</td><td> 15</td>
<td>MC mPEG 2000</td><td> 12</td><td> 21</td><td> 35</td>
<td>Darocur 1173</td><td> 0,4</td><td> 0,4</td><td> 0,4</td>
<td>Diluent (%):</td><td></td><td></td><td></td>
<td>Photonol 7025</td><td> 50</td><td> 50</td><td> 50</td>
<td>GLUCAM E-20</td><td> 50</td><td> 50</td><td> 50</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 55:45</td><td> 55 :45</td><td> 55:45</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 897</td><td> 870</td><td> 862</td>
<td>Elongation (%)</td><td> 96</td><td> 81</td><td> 68</td>
<td>dk</td><td> 29</td><td> 33</td><td> 50</td>
<td>Water content (%)</td><td> 64,7</td><td> 68,2</td><td> 78,1</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<img file="HUT68045A_D0023.tif" />
<td></td><td>Example 118</td><td>Example 119</td><td>Example 120</td>
<td>Composition (%):</td><td></td><td></td><td></td>
<td>ΗΕΜΑ</td><td> 36,6</td><td> 27,6</td><td> 13,6</td>
<td>DMA</td><td> 20</td><td> 20</td><td> 20</td>
<td>PEG 4500XL</td><td> 16</td><td> 16</td><td> 16</td>
<td>BPA890</td><td> 15</td><td> 15</td><td> 15</td>
<td>MC mPEG 2000</td><td> 12</td><td> 21</td><td> 35</td>
<td>Darocur 1173</td><td> 0,4</td><td> 0,4</td><td> 0,4</td>
<td>Diluent (%):</td><td></td><td></td><td></td>
<td>Photonol 7025</td><td> 50</td><td> 50</td><td> 50</td>
<td>GLUCAM E-20</td><td> 50</td><td> 50</td><td> 50</td>
<td>Monomer ratio a</td><td></td><td></td><td></td>
<td>diluent</td><td> 45:55</td><td> 45:55</td><td> 45:55</td>
<td>Features:</td><td></td><td></td><td></td>
<td>Modulus (kPa)</td><td> 600</td><td> 620</td><td> 586</td>
<td>Elongation (%)</td><td> 122</td><td> 90</td><td> 78</td>
<td>dk</td><td> 40</td><td> 47</td><td> 55</td>
<td>Water content (%)</td><td> 7297</td><td> 76,6</td><td> 80,3</td>
<td>hydrogel</td><td>transparent</td><td>transparent</td><td>transparent</td>
<img file="HUT68045A_D0024.tif" />
Contents6
33 sheets
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1 legal event, as the office reported them to INPADOC
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Numbers
- Application
- 9402146
Titles
- English
- IMPROVED METHOD OF FORMING SHAPED HYDROGEL ALTICLES INCLUDING CONTACT LENSES USING INERT, DISPLACEABLE DILUENTS
Classification
- CPC, 6
- G02B1/043
- C08F2/00
- Y10S524/916
- C08F20/28
- C08F2/44
- C08F2/48
- IPC, 7
- B29D11 02
- C08F2 00
- C08J5 00
- C08F2 44
- C08F2 48
- C08L71 02
- G02B1 04
