CN102675658A - Method for preparing polysiloxane hydrogel with high moisture content - Google Patents
Method for preparing polysiloxane hydrogel with high moisture content Download PDFInfo
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Abstract
The invention provides a method for preparing polysiloxane hydrogel with high moisture content. The method includes the following steps: polymerizing monomer mixtures to form the polysiloxane hydrogel, wherein the monomer mixtures comprise at least one silicon-containing monomer and at least one ionic monomer; and placing the polysiloxane hydrogel into an alkaline solution for at least 20 minutes, wherein, the PH of the alkaline solution is not smaller than 7.5, and the content of the ionic monomer is no less than 0.7 wt. % of total weight of overall polysiloxane hydrogel dry weight.
Description
Technical field
The present invention relates to the method for manufacture of eye with object.Particularly, the present invention relates to the method for gathering silicone hydrogel that a kind of manufacturing has high-moisture percentage.
Background technology
Contact lens development is the history of existing last 100 years so far, one of important medical device of generally using for general spectacle family.In generation nineteen fifty, the Czech scientist utilizes poly hydroxy ethyl acrylate (poly (hydroxyethyl methacrylate); HEMA) material is processed hydrogel, has invented Soft contact lens, and this kind material still is used so far.Along with the progress of science and technology, the evolution of contact lens material is also towards high oxygen permeability and high-comfort development.
Gathering silicone hydrogel as the also existing history for many years of the development of the contact lens of material, these Products Development targets of past mainly are to promote characteristics such as the oxygen-permeable of gathering silicone hydrogel and water ratio.The oxygen value that gathers the silicone hydrogel product that is sold on the market at present all can reach more than the 100barriers, yet the water ratio that gathers silicone hydrogel but can't promote effectively.
Generally speaking, gather silicone hydrogel and mainly be made up of the reaction product of silicon-containing monomer and the water that is comprised thereof, wherein water shared ratio in gathering silicone hydrogel also can be described as the water cut of gathering silicone hydrogel.Because silicon-containing monomer and its reaction product is all more hydrophobic and wettability is poor; Be prone to make not good and water ratio is lower with the wetting effect of the contact lens surface of its manufacturing; Eyes feel that easily dryness and discomfort of the eye is right when causing wearing, and this also is the current direction that silicone hydrogel contact lenses is needed positive improvement badly of gathering.
For the problem that improves contact lens water ratio and surface wettability, the existing relevant announcement that utilizes various physics or chemical process to improve in the prior art.For example, USP the 4th, 158 No. 089 and the 6th, 242, is disclosed in for No. 508 and adds other hydrophilic monomers in the prescription and carry out copolymerization; USP the 5th, 969 No. 076 and the 6th, 596, then discloses for No. 294 and chemically to synthesize the hydrophilic siliceous molecule of various tools, and it is added in the prescription to promote wetting ability and wettability; USP the 6th, 367, high-molecular weight hydrophilic macromolecule (like PVP) is added in No. 929 exposure in gathering the silicone hydrogel principal constituent, promote wettability and wetting ability whereby.Yet with regard to present technology, these methods are not remarkable for the effect that lifting gathers the silicone hydrogel water ratio, and its water ratio is all less than 50%.
In addition, many researchs that utilize physics mode to promote contact lens water ratio or surface wettability are also arranged.For example, USP the 6th, 867, No. 245 and the 5th, 274, No. 008 announcement use has high polar mould and prepares contact lens; USP the 4th, 214 then discloses for No. 014 and to utilize plasma body that contact lens surface is handled.Though the processing of these physics modes can successfully improve the wetting effect of contact lens surface; But the water ratio to contact lens itself also can't promote effectively; Cause when wearing the contact lens that utilize the aforesaid way improvement; Of short duration comfortable effect is only arranged, and can't obtain to wear for a long time comfort.
With regard to comfortableness; Wearing contact lens for a long time can make eyes feel dry and astringent, uncomfortable usually; Cause the reason of these sensations to comprise, the moisture loss speed of contact lens is very fast, lachrymal gland can't provide sufficient tear or contact lens contacts with outside air for a long time and cause moisture lost gradually.Above situation possibly make contact lens wear person feel that eyes are drier and more astringent, or even possibly cause caliginous problem.
In sum, industry still needs a technical solution, can make that the contact lens behind the polymerization forming have the effect of high-moisture percentage and high-moisture-retention.
Summary of the invention
The object of the invention is to provide a kind of manufacturing to have the method that high-moisture percentage gathers silicone hydrogel, and it comprises:
(a) make the monomer mixture polymerization gather silicone hydrogel with formation, said monomer mixture comprises at least a silicon-containing monomer and at least a ionic comonomer; And
(b) the said silicone hydrogel that gathers was positioned in the basic soln 20 minutes at least,
Wherein, the pH of said basic soln is not less than 7.5, and the content of said ionic comonomer gathers the gross weight of silicone hydrogel dry weight in integral body, for being not less than 0.7 weight %.
Compared with prior art; The inventive method can be made the silicone hydrogel that gathers with high-moisture percentage; This method can reduce the moisture loss speed in the prepared contact lens, and improves the not good shortcoming of contact lens surface wettability, the problem that effectively solves prior art and faced.
Description of drawings
Fig. 1 representes that the carboxylic acid group can't dissociate voluntarily in acidic solution, be prone to by the hydrogen ion in the solution protonatedly and form hydrogen bond, thereby limits the network of hydrogel, has reduced the chance that water molecules gets into hydrogel.
Fig. 2 representes that the carboxylic acid group can dissociate in basic soln, with negative ion COO
-Form appears on the polymer segment, forms negatively charged ion and produces repulsive force, causes the bigger distance of the intersegmental generation of chain, makes more water molecules get into hydrogel.
Fig. 3 is instance 1 and 4 to 7 and the water ratio data of gathering the silicone hydrogel film of comparative example 1 and 2.
Embodiment
For making the feature and advantage of the present invention can be more obviously understandable, the hereinafter spy enumerates preferred implementation, and cooperates appended graphic detailed description following:
Manufacturing of the present invention has the method that high-moisture percentage gathers silicone hydrogel and comprises following steps:
(a) make the monomer mixture polymerization gather silicone hydrogel with formation, said monomer mixture comprises at least a silicon-containing monomer and at least a ionic comonomer; And
(b) the said silicone hydrogel that gathers was positioned in the basic soln 20 minutes at least,
Wherein, the pH of said basic soln is not less than 7.5, and the content of said ionic comonomer gathers the gross weight of silicone hydrogel dry weight in integral body, for being not less than 0.7 weight %.
In this article; Polymerisable low-molecular weight compound (promptly have usually and be lower than 700 number-average molecular weight) contained in term " monomer "; And polymerisable in to high-molecular weight compounds or polymkeric substance, be also referred to as macromonomer (promptly having number-average molecular weight usually) sometimes greater than 700.Therefore, should be appreciated that " silicon-containing monomer " among this paper and " " ionic comonomer " speech comprises monomer, macromonomer and prepolymer.Prepolymer is partially polymerized monomer or further monomer polymerized.
Gathering silicone hydrogel normally prepares through the monomer mixture that polymerization contains at least a silicon-containing monomer." gather silica (polysiloxane or silicone) " and mean material for comprising at least 5 weight % silica chains (OSi-chain), preferred 10 to 100 weight % silica chains, the more preferably material of the organic polymer of 30 to 90 weight % silica chains.
In the step (a) of the inventive method, ionic comonomer has can dissociated functional group, like hydroxy-acid group.The acid-basicity of environment is as follows to the dissociated influence of this kind group:
To cooperate graphic further specifying at present.As shown in Figure 1; PH less than 7 acidic solution in, the carboxylic acid group can't dissociate voluntarily, and protonated and form hydrogen bond by the hydrogen ion in the solution easily; Thereby limit the network of hydrogel; Also limit the motion of macromolecular chain in the hydrogel, and then reduced the chance that water molecules gets into hydrogel, reduced the swelling rate of hydrogel.
As shown in Figure 2, pH greater than 7 basic soln in, the carboxylic acid group can dissociate, and with negative ion COO
-Form appears on the polymer segment, and because there is negatively charged ion to form, and macromolecular chain is intersegmental to have repulsive force, makes the bigger distance of the intersegmental generation of chain, this spatial change and can make more water molecules get into hydrogel, and then improve the water ratio of hydrogel.
The ionic comonomer that is suitable among the present invention includes, but not limited to vinylformic acid (acrylic acid), methylacrylic acid (methacrylic acid; MA), FUMARIC ACID TECH GRADE (fumarate), furans-2-vinylformic acid (furan-2-acrylic acid), 3-(2-thienyl) vinylformic acid (3-(2-thienyl) acrylic acid), 6-methyl-2-(three silyls)-3-vinyl-6-heptenoic acid (6-methyl-2-(trimethylsilyl)-3-vinyl-6-heptenoic acid), 2-(trifluoromethyl) vinylformic acid (2-(trifluoromethyl) acrylic acid) or its mixture.
According to the present invention, the content of ionic comonomer is counted with the gross weight of gathering the silicone hydrogel dry weight and is not less than 0.7 weight %, is preferably 0.7 to 10 weight %, more preferably 1 to 3 weight %.
Be applicable to that silicon-containing monomer of the present invention does not have any special restriction; The silicon-containing monomer of any convention all can be applied among the present invention; It comprises; But be not limited to (trimethylsiloxy)-3-methacryloxypropyl silane ((trimethylsiloxy)-3-methacryloxypropylsilane; TRIS); Methylacrylic acid 3-(triethoxysilyl) propyl ester (3-(triethoxysilyl) propyl methacrylate); Methylacrylic acid 3-(diethoxymethyl silyl) propyl ester (3-diethoxymethylsilyl)-propyl methacrylate); Vinyltrimethoxy silane (vinyltrimethoxysilane); Vinyltriethoxysilane (vinyltriethoxysilane); Diethoxy (methyl) vinyl silanes (diethoxy (methyl) vinylsilane); 3-(methacryloxypropyl) methyl dimethoxysilane (3-methacryloxypropyl-methyldimethoxysilane); 3-(methacryloxypropyl) methyldiethoxysilane (3-methacryloxypropyl-methyldiethoxysilane); 3-(methacryloxypropyl) Trimethoxy silane (3-methacryloxypropyl-trimethoxysilane); 3-(methacryloxypropyl) triethoxyl silane (3-methacryloxypropyl-triethoxysilane); Vinyl three (isopropoxy) silane (vinyltri (isopropoxy) silane); Vinyl tripropoxy silane (vinyltripropoxysilane); Methylacrylic acid three (trimethylsiloxy) silyl propyl ester (tris (trimethylsiloxy) silylpropyl methacrylate); Two (trimethylsiloxy) methyl-silicane base propyl ester (bis (trimethylsiloxy) methylsilylpropyl methacrylate) of methylacrylic acid; Methylacrylic acid pentamethyl disiloxane propyl ester (pentamethyldisiloxanepropyl methacrylate); Methylacrylic acid three (trimethylsiloxy) silyl propoxy-ethyl ester (tris (trimethylsiloxy) silyl propyloxyethyl methacrylate); Methylacrylic acid three (polydimethyl siloxy-) silyl propyl ester (tris (polydimethylsiloxy) silylpropyl methacrylate) or its mixture.
According to the present invention, the content of silicon-containing monomer is at least 40 weight % to gather the gross weight of silicone hydrogel dry weight, is preferably 40 to 60 weight %, more preferably 45 to 55 weight %.
Step of the present invention (b) is that the silicone hydrogel that gathers that is polymerized is positioned over and carries out alkaline purification in the basic soln, and wherein the pH of basic soln is not less than 7.5, is preferably 7.5 to 11, more preferably 8 to 10; The time that said alkaline purification is carried out is at least 20 minutes, is preferably 30 to 480 minutes.
The basic soln that is applicable to step of the present invention (b) includes, but not limited to LiOH, NaOH, KOH, Mg (OH)
2, Ca (OH)
2, NH
4OH, Na
2CO
3, K
2CO
3, MgCO
3, CaCO
2, (NH
4)
2CO
3, BaCO
3, NaHCO
3, KHCO
3, CaO, BaO, NaNH
2, KNH
2, Mg (NH
2)
2, Ca (NH
2)
2, Zn (NH
2)
2, Al (NH
2)
3Or it makes up the aqueous solution that is mixed with, preferred NaOH or NaHCO
3The aqueous solution.
In the hydration of hydrogel, the crosslinking polymerization system; Contain the water that is equilibrium state; Physics between water molecules and the macromolecular chain or chemical related very important; The different behaviors of water molecules in hydrogel are then played the part of different and crucial role (synthetic and characteristic (the Synthesis and Characterization of a pH-and Ionic Strength-Responsive Hydrogel of pH value and ionic strength water reactive gel (soft material) with state; Soft Materials), 5:4,183-195; Journal of applied (Journal of Applied Polymer Science), the 101st volume, 3227-3232 (2006)).
Water molecules mainly has two kinds of kenels in hydrogel: free water (free water) and combination water.Wherein, combination water can further be divided into freezing combination water (freezing bound water again; Or claim freezing irreducible water) and non-freezing combination water (non-freezing bound water; Or claim non-freezing irreducible water).
Free water is meant water molecules in the network of whole macromolecular chain, and no any magnetism or repulsive force between macromolecular chain, so it can move freely in the network of macromolecular chain.Non-freezing combination water then refers to have the water molecules of pretending exert oneself very much (hydrogen bond) with the functional group of macromolecule surface, can be considered a high molecular part usually.This kind water molecules is can't be in the network of macromolecular chain freely movable, thus when temperature reaches the zero pour of water, arrangement that can't generation rule between this kind water molecules, thereby be difficult to form crystal form.In addition, the water molecules reactive force of freezing combination water then is between the former two, and itself and key knot has only slight reactive force (Van der Waals force) between the water on the macromolecular chain, its crystallinity when zero pour than general water molecules slightly a little less than.
When having many hydrophilic radicals on the macromolecular chain, will produce hydration between hydrogel material and water molecules, thereby improve the content of combination water, have influence on the swelling property and the water cut of hydrogel significantly.Usually the water cut of hydrogel is greater than 5 weight %, and preferably between 10 to 80 weight %.The content of various water moleculess in hydrogel can record by means of DSC (differential scanning calorimetry) and thermogravimetric analyzer (thermogravimetric analyzer).
The prepared whole water content meter that gathers the content of non-freezing combination water in the silicone hydrogel with free water, freezing combination water and non-freezing combination water of the inventive method for being no less than 20%, is preferably 20 to 40%, and more preferably 20 to 37%.Under this situation, the said silicone hydrogel that gathers has the ability of adsorbing more water molecules.Owing to have reactive force between non-freezing combination water and hydrogel material; Can make moisture loss slower; Thereby this characteristic is applied on the contact lens, then can slow down the moisture evapotranspiration rate in the contact lens, make contact lens in the process of wearing, can possess better water profit comfort.
The prepared water ratio that gathers silicone hydrogel of the inventive method is not less than 50%, is preferably 50 to 70%, and more preferably 55 to 63%.
Gather in the silicone hydrogel in that the inventive method is prepared; Monomer mixture can be chosen wantonly and further comprise at least a wetting ability nonionic monomers; Said wetting ability nonionic monomers includes, but not limited to methylacrylic acid 2-hydroxyethyl ester (2-hydroxyethyl methacrylate; HEMA), vinylformic acid 2-hydroxyethyl ester (2-hydroxyethyl acrylate), glyceral methacrylate (glycerol methacrylate), vinylformic acid 2-dimethylamino ethyl ester (2-dimethylaminoethyl acrylate), N-vinyl-methane amide (N-vinyl-formamide), N-vinyl pyrrolidone (N-vinyl pyrrolidone; NVP), acryloyl morpholine (acryloylmorpholine), USAF RH-1 (methacrylamide), N, N-DMAA (N, N-dimethylacrylamide; DMA), N, N-diethylammonium acrylic amide (N, N-diethylacrylamide), dihydroxy ethyl USAF RH-1 (2-hydroxyethyl methacrylamide), N-NSC 11448 (N-isopropylacrylamide) or its mixture.
The usage quantity of wetting ability nonionic monomers for not being higher than 60 weight %, is preferably 30 to 60 weight % to gather the gross weight of silicone hydrogel dry weight, and more preferably 35 to 55 weight % most preferably are 40 to 50 weight %.
Method of manufacture of the present invention can be through adding suitable initiator when copolymerization, and utilize to make such as methods such as UV, heat or its combinations and gather silicone hydrogel and curing takes place with casting forming.Representative thermal initiator is an organo-peroxide; For example acetylperoxide, lauroyl peroxide, decanoyl peroxide, stearoyl, Lucidol, the peroxo-trimethylacetic acid tert-butyl ester, peroxy dicarbonate and such as LUPERSOL
256; 225 (An Tuofeina chemical company (Atofina Chemical); Be positioned at philadelphia, pa (Philadelphia; PA)) commercially available thermal initiator and analogue thereof, these initiators use with the concentration that accounts for about 0.01 to the 2 weight % of total monomer mixture.Representative UV initiator is a known initiator in this field, such as, but be not limited to the benzil methyl ether; The benzil ether; DAROCUR
1173,1164,2273,1116,2959,3331; IGRACURE
651 and 184 (Ciba (Ciba Specialty Chemicals); Be positioned at New York A Zili (Ardsley, New York)).
Understood like affiliated field those skilled in the art; Except that above-mentioned polymerization initiator; The inventive method is prepared gathers and optionally in the silicone hydrogel also can comprise other component; For example, extra tinting material, UV absorption agent and extra processing aid etc. are such as well known in the contact lens technology.
The prepared silicone hydrogel that gathers of the inventive method has effects such as good oxygen-permeable, high-moisture and high-moisture-retention, therefore is suitable as very much eye and uses object, particularly contact lens or intraocular lens (IOL).Measure appearance through surface contact angle and record, the surface contact angle that the present invention gathers the prepared object of silicone hydrogel is not more than 30 °, is preferably 10 to 30 °, more preferably 15 to 25 °.
Capable of using such as being disclosed in the 3rd, 408, No. 429 patents and the 3rd of the U.S.; Rotated mold filing (spin cast molding) technology in 496, No. 254 patents, such as being disclosed in the U.S. the 5th, 271; Fixedly casting (cast molding) technology in No. 875 patents or such as being disclosed in the 4th, 084, No. 459 patents and the 4th of the U.S.; Prior art method such as compression moulding in 197, No. 266 patents make by the prepared silicone hydrogel that gathers of the inventive method and are configured as contact lens.The polymerization of monomer mixture can be carried out in corresponding to the rotating mold of want contact lens shape or fixed mould.In case of necessity, can further stand machine finish with these contact lens that obtain.Also can in suitable mold or container, carry out polymerization obtaining being the ocular lens material of button shaped, dish type or rod, its then can treated (for example via lathe or laser cutting or polishing) to obtain having the contact lens of the shape of being wanted.
Following examples will be used to further specify the present invention, but be not in order to limit scope of the present invention.The field those skilled in the art can reach easily under any modification and change include in the scope of this case specification sheets disclosure and appended claims.
Embodiment
The synthetic chemistry medicine
1. methylacrylic acid 2-hydroxyethyl ester (be called for short HEMA):
is available from Sigma company (Sigma).
2.N-vinyl pyrrolidone (being called for short NVP):
is available from Sigma company (Sigma).
3. methylacrylic acid (MA):
is available from Sigma company (Sigma).
4. (trimethylsiloxy)-3-metacryloxy propyl silane (TRIS):
is available from Sigma company (Sigma).
5.CoatOsil:
is available from Mai Tu company (Momentive).
6. TGM 1 (EGDMA):
is available from Sigma company.
7.D1173 light trigger: available from Ciba (Ciba Chemicals).
The preparation that gathers the silicone hydrogel material
Instance 1:
According to composition and the content of prescription shown in 1 in the table 1, with each composition uniform mixing, and through ultraviolet lighting crosslinking polymerization 60 minutes, the polymkeric substance of accomplishing was soaked in 50% alcohol 20 minutes, again with 70% alcoholic extract 60 minutes to remove unreacted monomer.Gather the silicone hydrogel film to be soaked in pH be 8 sodium hydrogencarbonate (NaHCO prepared
3) in the solution 60 minutes, be soaked in the normal saline solution 60 minutes again to replace, the gained film is positioned in the normal saline solution soaked 120 minutes at last, reach balancing water content.
Instance 2:
Charge ratio and reaction conditions with instance 1; But gather the silicone hydrogel film to be soaked in pH be in 9 sodium hydroxide (NaOH) solution 60 minutes prepared; Be soaked in the normal saline solution 60 minutes again to replace; At last the gained film is positioned in the normal saline solution and soaked 120 minutes, reach balancing water content.
Instance 3:
Charge ratio and reaction conditions with instance 1; But gather the silicone hydrogel film to be soaked in pH be in 10 sodium hydroxide (NaOH) solution 60 minutes prepared; Be soaked in the normal saline solution 60 minutes again to replace; At last the gained film is positioned in the normal saline solution and soaked 120 minutes, reach balancing water content.
Comparative example 1:
With the charge ratio and the reaction conditions of instance 1, but the prepared silicone hydrogel film that gathers directly is soaked in the normal saline solution, without the program of soaking basic soln.
Comparative example 2:
With the charge ratio and the reaction conditions of instance 1, but gather the silicone hydrogel film to be soaked in pH be 8 sodium hydrogencarbonate (NaHCO prepared
3) in the solution 15 minutes, be soaked in the normal saline solution 60 minutes again to replace, the gained film is positioned in the normal saline solution soaked 120 minutes at last, reach balancing water content.
Instance 4:
With the charge ratio and the reaction conditions of instance 1, but gather the silicone hydrogel film to be soaked in pH be 8 sodium hydrogencarbonate (NaHCO prepared
3) in the solution 30 minutes, be soaked in the normal saline solution 60 minutes again to replace, the gained film is positioned in the normal saline solution soaked 120 minutes at last, reach balancing water content.
Instance 5:
With the charge ratio and the reaction conditions of instance 1, but gather the silicone hydrogel film to be soaked in pH be 8 sodium hydrogencarbonate (NaHCO prepared
3) in the solution 120 minutes, be soaked in the normal saline solution 60 minutes again to replace, the gained film is positioned in the normal saline solution soaked 120 minutes at last, reach balancing water content.
Instance 6:
With the charge ratio and the reaction conditions of instance 1, but gather the silicone hydrogel film to be soaked in pH be 8 sodium hydrogencarbonate (NaHCO prepared
3) in the solution 240 minutes, be soaked in the normal saline solution 60 minutes again to replace, the gained film is positioned in the normal saline solution soaked 120 minutes at last, reach balancing water content.
Instance 7:
With the charge ratio and the reaction conditions of instance 1, but gather the silicone hydrogel film to be soaked in pH be 8 sodium hydrogencarbonate (NaHCO prepared
3) in the solution 480 minutes, be soaked in the normal saline solution 60 minutes again to replace, place normal saline solution to soak 120 minutes the gained film at last, reach balancing water content.
Instance 8:
According to composition and the content of prescription shown in 2 in the table 1, with each composition uniform mixing, and through ultraviolet lighting crosslinking polymerization 60 minutes, the polymkeric substance of accomplishing was soaked in 50% alcohol 20 minutes, again with 70% alcoholic extract 60 minutes to remove unreacted monomer.Gather the silicone hydrogel film to be soaked in pH be 8 sodium hydrogencarbonate (NaHCO prepared
3) in the solution 60 minutes, be soaked in the normal saline solution 60 minutes again to replace, the gained film is positioned in the normal saline solution soaked 120 minutes at last, reach balancing water content.
Comparative example 3:
According to composition and the content of prescription shown in 3 in the table 1, with each composition uniform mixing, and through ultraviolet lighting crosslinking polymerization 60 minutes, the polymkeric substance of accomplishing was soaked in 50% alcohol 20 minutes, again with 70% alcoholic extract 60 minutes to remove unreacted monomer.Gather the silicone hydrogel film to be soaked in pH be 8 sodium hydrogencarbonate (NaHCO prepared
3) in the solution 60 minutes, be soaked in the normal saline solution 60 minutes again to replace, the gained film is positioned in the normal saline solution soaked 120 minutes at last, reach balancing water content.
Table 1
Water cut test
To in water, take out through the instance 1 to 8 of the crosslinked shaping of ultraviolet lighting and the silicone hydrogel film that gathers of comparative example 1 to 3, and wipe away and do its surface-moisture, measuring weight in wet base is W
0Under 25 ℃ of room temperatures, film was left standstill 5 minutes and 10 minutes, recording weight respectively is W
1And W
2Film is placed in the baking oven, and with 110 ℃ of bakings 24 hours, removing the moisture of material, and to measure the film dry weight be W
3Calculate moisture loss rate and water ratio through following formula, its result is shown in the table 2.
Table 2
In table 2; Instance 1 to 3 shows that with comparative example 1 the prepared silicone hydrogel film that gathers is soaked in each measured under different pH association; To be immersed in pH be in the basic soln more than 8 time when gathering the silicone hydrogel film; Can promote water ratio wherein significantly, and reduce the moisture loss speed of gathering the silicone hydrogel film; Instance 1 and 4 to 7 shows prepared each measured association of basic soln processing of gathering the silicone hydrogel film through different time with comparative example 1 and 2; Be immersed in the basic soln at least 30 minutes as long as gather the silicone hydrogel film, just can make and gather the silicone hydrogel film and reach and have high-moisture percentage and the effect that reduces moisture loss; Instance 1 and 8 shows with prepared each the measured association of silicone hydrogel film of gathering of different ions type monomer content with comparative example 3; When the ionic comonomer content in gathering the silicone hydrogel film is not less than 1.0wt%, just can makes and gather the silicone hydrogel film and reach and have high-moisture percentage and the effect that reduces moisture loss.
Can know by table 2 and each association shown in Figure 3; To gather silicone hydrogel was soaked in the sodium hydrogen carbonate solution about 30 minutes; Just can make the water ratio that gathers silicone hydrogel promote about 8 to 10%; Thereby have the water ratio more than 50%, and it is also slower to gather the inner moisture loss rate of silicone hydrogel, thereby has effect of water keeping.
The surface contact angle test
Utilize contact angle measure appearance practical measuring examples 1 to 3 and 8 with the surface contact angle that gathers the silicone hydrogel film of comparative example 1 and 2.When fluid drips was on solid surface, the angle of solid surface and tangent was " contact angle ".When contact angle is 0 when spending, express liquid can fully moistening solid surface; When contact angle is 180 when spending, represent the liquid fully can not moistening solid surface.The data of contact angle test are as shown in table 3 below.
Table 3
| Surface contact angle | |
| Instance 1 (pH 8) | 18.80±4.22 |
| Instance 2 (pH 9) | 18.77±6.97 |
| Instance 3 (pH 10) | 18.10±4.62 |
| Instance 8 (pH 8) | 18.30±4.65 |
| Comparative example 1 (pH 7) | 51.14±5.48 |
| Comparative example 3 (pH 8) | 58.20±5.25 |
Because the ionic comonomer dissociation degree of gathering in the silicone hydrogel through alkaline purification is higher, can attract more water, the wetting ability of gathering the silicone hydrogel surface is promoted, have preferable wetting effect, so the numerical value of surface contact angle descends obviously.
Should to understand various improvement of the present invention easily be feasible and be that one of ordinary skill in the art associate easily and expect.
Claims (20)
1. a manufacturing has the method that high-moisture percentage gathers silicone hydrogel, and it comprises:
(a) make the monomer mixture polymerization to form the said silicone hydrogel that gathers, said monomer mixture comprises at least a silicon-containing monomer and at least a ionic comonomer; And
(b) the said silicone hydrogel that gathers was positioned in the basic soln 20 minutes at least,
Wherein, the pH of said basic soln is not less than 7.5, and the content of said ionic comonomer gathers the gross weight of silicone hydrogel dry weight in integral body, for being not less than 0.7 weight %.
2. method according to claim 1, the pH of wherein said basic soln is 7.5 to 11.
3. method according to claim 2, the pH of wherein said basic soln is 8 to 10.
4. method according to claim 1, wherein said basic soln are selected from by LiOH, NaOH, KOH, Mg (OH)
2, Ca (OH)
2, NH
4OH, Na
2CO
3, K
2CO
3, MgCO
3, CaCO
2, (NH
4)
2CO
3, BaCO
3, NaHCO
3, KHCO
3, CaO, BaO, NaNH
2, KNH
2, Mg (NH
2)
2, Ca (NH
2)
2, Zn (NH
2)
2, Al (NH
2)
3And the aqueous solution that is mixed with of combination.
5. method according to claim 4, wherein said basic soln are NaOH or NaHCO
3The aqueous solution.
6. method according to claim 1, the wherein said silicone hydrogel that gathers was positioned in the said basic soln 30 to 480 minutes.
7. method according to claim 1, the wherein said water ratio that gathers silicone hydrogel is not less than 50%.
8. method according to claim 1, the content of wherein said ionic comonomer gathers the gross weight of silicone hydrogel dry weight in integral body, is 0.7 to 10 weight %.
9. method according to claim 8, the content of wherein said ionic comonomer gathers the gross weight of silicone hydrogel dry weight in integral body, is 1 to 3 weight %.
10. the silicone hydrogel that gathers according to claim 1, the content of wherein said silicon-containing monomer gathers the gross weight of silicone hydrogel dry weight in integral body, is at least 40 weight %.
11. the silicone hydrogel that gathers according to claim 10, the content of wherein said silicon-containing monomer gathers the gross weight of silicone hydrogel dry weight in integral body, is 40 to 60 weight %.
12. the silicone hydrogel that gathers according to claim 11, the content of wherein said silicon-containing monomer gathers the gross weight of silicone hydrogel dry weight in integral body, is 45 to 55 weight %.
13. the silicone hydrogel that gathers according to claim 1, wherein said ionic comonomer are selected from by vinylformic acid (acrylic acid), methylacrylic acid (methacrylic acid; MA), the group that formed of FUMARIC ACID TECH GRADE (fumarate), furans-2-vinylformic acid (furan-2-acrylic acid), 3-(2-thienyl) vinylformic acid (3-(2-thienyl) acrylic acid), 6-methyl-2-(three silyls)-3-vinyl-6-heptenoic acid (6-methyl-2-(trimethylsilyl)-3-vinyl-6-heptenoic acid), 2-(trifluoromethyl) vinylformic acid (2-(trifluoromethyl) acrylic acid) and composition thereof.
14. the silicone hydrogel that gathers according to claim 1, wherein said silicon-containing monomer are selected from by (trimethylsiloxy)-3-methacryloxypropyl silane ((trimethylsiloxy)-3-methacryloxypropylsilane; TRIS); Methylacrylic acid 3-(triethoxysilyl) propyl ester (3-(triethoxysilyl) propyl methacrylate); Methylacrylic acid 3-(diethoxymethyl silyl) propyl ester (3-diethoxymethylsilyl)-propyl methacrylate); Vinyltrimethoxy silane (vinyltrimethoxysilane); Vinyltriethoxysilane (vinyltriethoxysilane); Diethoxy (methyl) vinyl silanes (diethoxy (methyl) vinylsilane); 3-(methacryloxypropyl) methyl dimethoxysilane (3-methacryloxypropyl-methyldimethoxysilane); 3-(methacryloxypropyl) methyldiethoxysilane (3-methacryloxypropyl-methyldiethoxysilane); 3-(methacryloxypropyl) Trimethoxy silane (3-methacryloxypropyl-trimethoxysilane); 3-(methacryloxypropyl) triethoxyl silane (3-methacryloxypropyl-triethoxysilane); Vinyl three (isopropoxy) silane (vinyltri (isopropoxy) silane); Vinyl tripropoxy silane (vinyltripropoxysilane); Methylacrylic acid three (trimethylsiloxy) silyl propyl ester (tris (trimethylsiloxy) silylpropyl methacrylate); Two (trimethylsiloxy) methyl-silicane base propyl ester (bis (trimethylsiloxy) methylsilylpropyl methacrylate) of methylacrylic acid; Methylacrylic acid pentamethyl disiloxane propyl ester (pentamethyldisiloxanepropyl methacrylate); Methylacrylic acid three (trimethylsiloxy) silyl propoxy-ethyl ester (tris (trimethylsiloxy) silyl propyloxyethyl methacrylate); The group that methylacrylic acid three (polydimethyl siloxy-) silyl propyl ester (tris (polydimethylsiloxy) silylpropyl methacrylate) and composition thereof is formed.
15. the silicone hydrogel that gathers according to claim 1, wherein said monomer mixture further comprises the wetting ability nonionic monomers.
16. the silicone hydrogel that gathers according to claim 15, the usage quantity of wherein said wetting ability nonionic monomers is to gather the gross weight of silicone hydrogel dry weight, for not being higher than 60 weight %.
17. the silicone hydrogel that gathers according to claim 16, the usage quantity of wherein said wetting ability nonionic monomers are 30 to 60 weight % to gather the gross weight of silicone hydrogel dry weight.
18. the silicone hydrogel that gathers according to claim 17, the usage quantity of wherein said wetting ability nonionic monomers are 35 to 55 weight % to gather the gross weight of silicone hydrogel dry weight.
19. the silicone hydrogel that gathers according to claim 18, the usage quantity of wherein said wetting ability nonionic monomers are 40 to 50 weight % to gather the gross weight of silicone hydrogel dry weight.
20. the silicone hydrogel that gathers according to claim 15, wherein said wetting ability nonionic monomers are selected from by methylacrylic acid 2-hydroxyethyl ester (2-hydroxyethyl methacrylate; HEMA), vinylformic acid 2-hydroxyethyl ester (2-hydroxyethyl acrylate), glyceral methacrylate (glycerol methacrylate), vinylformic acid 2-dimethylamino ethyl ester (2-dimethylaminoethyl acrylate), N-vinyl-methane amide (N-vinyl-formamide), N-vinyl pyrrolidone (N-vinyl pyrrolidone; NVP), acryloyl morpholine (acryloylmorpholine), USAF RH-1 (methacrylamide), N, N-DMAA (N, N-dimethylacrylamide; DMA), N; N-diethylammonium acrylic amide (N, N-diethylacrylamide), the group that formed of dihydroxy ethyl USAF RH-1 (2-hydroxyethyl methacrylamide), N-NSC 11448 (N-isopropylacrylamide) and composition thereof.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877068A (en) * | 2015-05-21 | 2015-09-02 | 爱生华(苏州)光学有限公司 | Novel and practical preparation method of silicone hydrogel contact lens |
| CN104945570A (en) * | 2015-07-03 | 2015-09-30 | 东南大学 | Silica gel contact lens and surface reversal processing method thereof |
| WO2018205350A1 (en) * | 2017-05-12 | 2018-11-15 | 李宗津 | Nanocomposite hydrogel material and preparation method therefor |
| CN110283273A (en) * | 2019-06-21 | 2019-09-27 | 甘肃天后光学科技有限公司 | A kind of high moisturizing flexible hydrophilic silicone-hydrogel and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144226A (en) * | 1990-11-27 | 1997-03-05 | 博士伦有限公司 | Method for preparing surface active random copolymer |
| WO1999057178A1 (en) * | 1998-05-05 | 1999-11-11 | Bausch & Lomb Incorporated | Plasma surface treatment of silicone hydrogel contact lenses |
| CN1242982A (en) * | 1998-06-15 | 2000-02-02 | 莱雅公司 | Cosmetic composition containing poly organo-silicone and acrylic ternary copolymer, and use of same for processing cutin material |
| CN101289541A (en) * | 2008-05-30 | 2008-10-22 | 浙江大学 | Organic-hybridization micro-hydrogels sensitive to pH value and temperature and method for preparing same |
-
2011
- 2011-03-07 CN CN2011100610390A patent/CN102675658A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144226A (en) * | 1990-11-27 | 1997-03-05 | 博士伦有限公司 | Method for preparing surface active random copolymer |
| WO1999057178A1 (en) * | 1998-05-05 | 1999-11-11 | Bausch & Lomb Incorporated | Plasma surface treatment of silicone hydrogel contact lenses |
| CN1242982A (en) * | 1998-06-15 | 2000-02-02 | 莱雅公司 | Cosmetic composition containing poly organo-silicone and acrylic ternary copolymer, and use of same for processing cutin material |
| CN101289541A (en) * | 2008-05-30 | 2008-10-22 | 浙江大学 | Organic-hybridization micro-hydrogels sensitive to pH value and temperature and method for preparing same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877068A (en) * | 2015-05-21 | 2015-09-02 | 爱生华(苏州)光学有限公司 | Novel and practical preparation method of silicone hydrogel contact lens |
| CN104945570A (en) * | 2015-07-03 | 2015-09-30 | 东南大学 | Silica gel contact lens and surface reversal processing method thereof |
| CN104945570B (en) * | 2015-07-03 | 2017-06-09 | 东南大学 | A kind of Silica hydrogel contact lens and its surface reversion processing method |
| WO2018205350A1 (en) * | 2017-05-12 | 2018-11-15 | 李宗津 | Nanocomposite hydrogel material and preparation method therefor |
| CN110283273A (en) * | 2019-06-21 | 2019-09-27 | 甘肃天后光学科技有限公司 | A kind of high moisturizing flexible hydrophilic silicone-hydrogel and preparation method thereof |
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