CN102675561B - silicone hydrogel with high water content - Google Patents
silicone hydrogel with high water content Download PDFInfo
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Abstract
The invention provides a silicone hydrogel. The silicone hydrogel comprises a reaction product of a monomer mixture for forming the silicone hydrogel, and water, wherein the water is not less than 50 percent of the total weight of the integral silicone hydrogel; the monomer mixture comprises at least one silicon-containing monomer and at least one ionic monomer; and the ionic monomer is not less than 0.7 percent of the total weight of the dry weight of the integral silicone hydrogel. The invention also provides an ophthalmic object prepared from the silicone hydrogel.
Description
Technical field
The present invention relates to a kind of poly-silicone hydrogel with high-moisture percentage.Modified form the eye object, particularly contact lens that the present invention also relates to make thus or intraocular lens (IOL).
Background technology
Contact lens are developed so far the history of existing last 100 years, one of important medical device of generally using for glasses family.In generation nineteen fifty, Czech scientist utilizes poly hydroxy ethyl acrylate (poly (hydroxyethyl methacrylate); HEMA) material is made hydrogel, has invented Soft contact lens, and this kind of material still used so far.Along with scientific and technological progress, the evolution of contact lens material is also towards high oxygen permeability and high-comfort development.
Using and gather silicone hydrogel as the development of the contact lens of material also existing history for many years, the development goal of these products of past is mainly to promote and gathers the characteristics such as the oxygen-permeable of silicone hydrogel and water ratio.More than the oxygen value of the poly-silicone hydrogel product that sold on the market at present all can reach 100barriers, yet the water ratio of poly-silicone hydrogel but cannot promote effectively.
Generally speaking, poly-silicone hydrogel is mainly comprised of the reaction product of silicon-containing monomer and the water comprising thereof, and wherein water shared ratio in poly-silicone hydrogel, also can be described as the water content of gathering silicone hydrogel.Because silicon-containing monomer and its reaction product are all more hydrophobic and wettability is poor, easily make that wetting effect with the contact lens surface of its manufacture is not good and water ratio is lower, while causing wearing, eyes easily feel that dryness and discomfort of the eye is suitable, and this is also the direction that current poly-silicone hydrogel contact lenses is needed positive improvement badly.
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 prior art.For example, United States Patent (USP) the 4th, 158, No. 089 and the 6th, is disclosed in for 242, No. 508 and in formula, adds other hydrophilic monomers and carry out copolymerization; United States Patent (USP) the 5th, 969, No. 076 and the 6th, discloses and chemically synthesizes the hydrophilic siliceous molecule of various tools for 596, No. 294, and added in formula to promote wetting ability and wettability; United States Patent (USP) the 6th, discloses the hydrophilic macromolecule (as PVP) that adds high molecular in poly-silicone hydrogel principal constituent for 367, No. 929, promotes whereby wettability and wetting ability.Yet with regard to current technology, these methods are not remarkable for the effect that promotes poly-silicone hydrogel water ratio, its water ratio is all less than 50%.
In addition, also there is the much research that utilizes physics mode to promote contact lens water ratio or surface wettability.For example, United States Patent (USP) the 6th, 867, No. 245 can be with the 5th, discloses for 274, No. 008 and use the mould with high polarity to prepare contact lens; United States Patent (USP) the 4th, discloses and utilizes plasma body to process contact lens surface for 214, No. 014.Though the processing of these physics modes can successfully improve the wetting effect of contact lens surface, but also cannot effectively promote the water ratio of contact lens itself, cause when wearing the contact lens that utilize aforesaid way improvement, only have of short duration comfortable effect, and cannot obtain, wear for a long time comfort.
With regard to comfortableness; wearing for a long time contact lens can make eyes feel dry and astringent, uncomfortable conventionally; cause the reason of these sensations to comprise, the moisture loss speed of contact lens is very fast, lachrymal gland cannot provide sufficient tear or contact lens contacts with outside air for a long time and cause moisture lost gradually.Above situation may make contact lens wear person feel that eyes are drier and more astringent, or even may cause caliginous problem.
In sum, industry still needs a technical solution, can make contact lens after polymerization forming have the effect of high-moisture percentage and high-moisture-retention.
Summary of the invention
Object of the present invention is for providing a kind of poly-silicone hydrogel of using object for eye, reaction product and water that it comprises the monomer mixture that is used to form poly-silicone hydrogel, wherein the content of water is in the poly-silicone hydrogel gross weight of integral body, for being not less than 50 % by weight, and described monomer mixture comprises at least one silicon-containing monomer and at least one ionic comonomer, the content of wherein said ionic comonomer is in the gross weight of the poly-silicone hydrogel dry weight of integral body, for being not less than 0.7 % by weight.
Another object of the present invention is for providing a kind of by the prepared eye object of poly-silicone hydrogel of the present invention.
Compared with prior art, poly-silicone hydrogel itself of the present invention has high-moisture percentage, it can reduce the moisture loss speed in prepared contact lens, and improves the not good shortcoming of contact lens surface wettability, effectively solves the problem that prior art faces.
Accompanying drawing explanation
Fig. 1 represents that carboxylic acid group cannot dissociate voluntarily in acidic solution, easily protonated by the hydrogen ion in solution and form hydrogen bond, thereby limits the network of hydrogel, has reduced the chance that water molecules enters hydrogel.
Fig. 2 represents that carboxylic acid group can dissociate in basic solution, with negative ion COO
-form appears on polymer segment, forms negatively charged ion and produces repulsive force, causes the larger distance of the intersegmental generation of chain, makes more water molecules enter hydrogel.
Fig. 3 is example 1 and 4 to 7 and the water ratio data of the poly-silicone hydrogel film of comparative example 1.
Embodiment
For the features and advantages of the present invention can be become apparent, cited below particularlyly go out preferred implementation, and coordinate appended graphic being described in detail as follows:
The present invention relates to a kind of poly-silicone hydrogel of using object for eye, reaction product and water that it comprises the monomer mixture that is used to form poly-silicone hydrogel, wherein the content of water is in the poly-silicone hydrogel gross weight of integral body, for being not less than 50 % by weight, described monomer mixture comprises at least one silicon-containing monomer and at least one ionic comonomer, the content of wherein said ionic comonomer is in the gross weight of the poly-silicone hydrogel dry weight of integral body, for being not less than 0.7 % by weight.
In this article, polymerisable low-molecular weight compound (conventionally having the number-average molecular weight lower than 700) contained in term " monomer ", and in polymerisable to high-molecular weight compounds or polymkeric substance, sometimes also referred to as macromonomer (conventionally thering is the number-average molecular weight that is greater than 700).Therefore, should be appreciated that " silicon-containing monomer " and " ionic comonomer " word herein comprises monomer, macromonomer and prepolymer.Prepolymer is partially polymerized monomer or the further monomer of polymerization.
Prepared by the monomer mixture that poly-silicone hydrogel normally contains at least one silicon-containing monomer by polymerization." poly-silica (polysiloxane or silicone) " means material for comprising at least 5 % by weight silica chains (OSi-chain), preferably 10 to 100 % by weight silica chains, the more preferably material of the organic polymer of 30 to 90 % by weight silica chains.
The monomer mixture that is used to form the poly-silicone hydrogel of the present invention comprises at least one ionic comonomer, and this ionic comonomer has the functional group that can dissociate, as hydroxy-acid group.The impact that the acid-basicity of environment dissociates on this kind of group is as follows:
Now further illustrate cooperation is graphic.As shown in Figure 1, in pH is less than 7 acidic solution, carboxylic acid group cannot dissociate voluntarily, and easily protonated by the hydrogen ion in solution and form hydrogen bond, thereby limit the network of hydrogel, also limit the motion of macromolecular chain in hydrogel, and then reduced the chance that water molecules enters hydrogel, reduced the swelling rate of hydrogel.
As shown in Figure 2, in pH is greater than 7 basic solution, carboxylic acid group can dissociate, and with negative ion COO
-form appears on polymer segment, and because there is negatively charged ion to form, and macromolecular chain is intersegmental has repulsive force, makes the larger distance of the intersegmental generation of chain, and the change in this space can make more water molecules enter hydrogel, and then improves the water ratio of hydrogel.
The ionic comonomer being suitable in the present invention includes, but not limited to vinylformic acid (acrylic acid), methacrylic 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 and is not less than 0.7 % by weight to gather the gross weight of silicone hydrogel dry weight, is preferably 0.7 to 10 % by weight, more preferably 1 to 3 % by weight.
The silicon-containing monomer that is suitable for forming the poly-silicone hydrogel of the present invention there is no any special restriction, any known silicon-containing monomer all can be applied in the present invention, it comprises, but be not limited to (trimethylsiloxy)-3-methacryloxypropyl silane ((trimethylsiloxy)-3-methacryloxypropylsilane; TRIS), methacrylic acid 3-(triethoxysilyl) propyl ester (3-(triethoxysilyl) propyl methacrylate), methacrylic 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), methacrylic acid three (trimethylsiloxy) silyl propyl ester (tris (trimethylsiloxy) silylpropyl methacrylate), two (trimethylsiloxy) methyl-silicane base propyl ester (bis (trimethylsiloxy) methylsilylpropyl methacrylate) of methacrylic acid, methacrylic acid pentamethyl disiloxane propyl ester (pentamethyldisiloxanepropyl methacrylate), methacrylic acid three (trimethylsiloxy) silyl propoxy-ethyl ester (tris (trimethylsiloxy) silyl propyloxyethyl methacrylate), methacrylic 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, to gather the gross weight of silicone hydrogel dry weight, is at least 40 % by weight, is preferably 40 to 60 % by weight, more preferably 45 to 55 % by weight.
In the hydration of hydrogel, crosslinking polymerization system, containing the water that is equilibrium state, physics between water molecules and macromolecular chain or chemical associated very important, the different behaviors of water molecules in hydrogel are played the part of different and crucial role (synthetic and feature (the Synthesis and Characterization of a pH-and Ionic Strength-Responsive Hydrogel of pH value and ionic strength water reactive gel (soft material) from 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) with in conjunction with water.Wherein, in conjunction with water, can further divide into again freezing combination water (freezing bound water; Or claim freezing irreducible water) and non-freezing combination water (non-freezing bound water; Or claim non-freezing irreducible water).
Free water refers to that water molecules is in the network of whole macromolecular chain, and between macromolecular chain without any magnetism or repulsive force, therefore it can move freely in the network of macromolecular chain.Non-freezing combination water refers to have with the functional group of macromolecule surface the water molecules of pretending exert oneself very much (hydrogen bond), conventionally can be considered a high molecular part.This kind of water molecules cannot be freely movable in the network of macromolecular chain, thus when temperature reaches the zero pour of water, arrangement that cannot generation rule between this kind of water molecules, thereby be difficult to form crystal form.In addition, the water molecules reactive force of freezing combination water is between the former two, only has slight reactive force (Van der Waals force) between itself and the bond water on macromolecular chain, its crystallinity when zero pour than general water molecules slightly a little less than.
While thering is many hydrophilic radicals on macromolecular chain, between hydrogel material and water molecules, will produce hydration, thereby improve the content of freezing combination water and non-freezing combination water, have influence on significantly swelling and the water content of hydrogel.Conventionally the water content of hydrogel is greater than 5 % by weight, and preferably between 10 to 80 % by weight.The content of various water moleculess in hydrogel can record by means of differential scanning calorimeter (differential scanning calorimetry) and thermogravimetric analyzer (thermogravimetric analyzer).
The content of the poly-contained non-freezing combination water of silicone hydrogel of the present invention, with the whole water content meter of free water, freezing combination water and non-freezing combination water, for being no less than 20%, is preferably 20 to 40%, and more preferably 20 to 37%.Under this situation, described poly-silicone hydrogel has the ability of the more water molecules of absorption.Owing to thering is reactive force between non-freezing combination water and hydrogel material, can make moisture loss slower, thereby this characteristic is applied on contact lens, can slow down the moisture evapotranspiration rate in contact lens, make contact lens in the process of wearing, can possess better water profit comfort.
The water ratio of the poly-silicone hydrogel of the present invention is not less than 50%, is preferably 50 to 70%, and more preferably 55 to 63%.
The poly-contained monomer mixture of silicone hydrogel of the present invention can optionally further comprise at least one wetting ability nonionic monomers, described wetting ability nonionic monomers comprises, but be not limited to HEMA (2-hydroxyethyl methacrylate; HEMA), HEA (2-hydroxyethyl acrylate), glyceral methacrylate (glycerol methacrylate), vinylformic acid 2-dimethylamino ethyl ester (2-dimethylaminoethyl acrylate), N-vinyl-methane amide (N-vinyl-formamide), NVP (N-vinyl pyrrolidone; NVP), acryloyl morpholine (acryloylmorpholine), Methacrylamide (methacrylamide), N,N-DMAA (N, N-dimethylacrylamide; DMA), N, N-diethyl acrylamide (N, N-diethylacrylamide), dihydroxy ethyl Methacrylamide (2-hydroxyethyl methacrylamide), NIPA (N-isopropylacrylamide) or its mixture.
The usage quantity of wetting ability nonionic monomers, to gather the gross weight of silicone hydrogel dry weight, for not higher than 60 % by weight, is preferably 30 to 60 % by weight, and more preferably 35 to 55 % by weight, most preferably are 40 to 50 % by weight.
Poly-silicone hydrogel of the present invention can be by adding suitable initiator when copolymerization, and it is curing with casting forming to utilize methods such as UV, heat or its combination to occur.Representative thermal initiator is organo-peroxide, for example acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl, benzoyl peroxide, the peroxidation 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 are used to account for the concentration of total monomer mixture approximately 0.01 to 2 % by weight.Representative UV initiator is initiator known in this field, such as, but be not limited to benzil methyl ether; Benzil ether; DAROCUR
1173,1164,2273,1116,2959,3331; IGRACURE
651 and 184 (Ciba (Ciba Specialty Chemicals) is positioned at New York A Zili (Ardsley, New York)).
As affiliated field those skilled in the art understand, except above-mentioned polymerization initiator, in poly-silicone hydrogel of the present invention, optionally also can comprise other component, for example, extra tinting material, UV absorption agent and extra processing aid etc., such as known person in contact lens technology.
The poly-silicone hydrogel of the present invention has the effects such as good oxygen-permeable, high-moisture and high-moisture-retention, is therefore suitable as very much eye object, particularly contact lens or intraocular lens (IOL).Through surface contact angle measurement instrument, record, the surface contact angle of the poly-prepared object of silicone hydrogel of the present invention is not more than 30 °, is preferably 10 to 30 °, more preferably 15 to 25 °.
Can utilize such as being disclosed in the U.S. the 3rd, 408, No. 429 patents and the 3rd, 496, rotated mold filing in No. 254 patents (spin cast molding) technique, such as being disclosed in the U.S. the 5th, fixedly casting in 271, No. 875 patents (cast molding) technique or such as being disclosed in the U.S. the 4th, 084, No. 459 patents and the 4th, the prior art method such as compression moulding in 197, No. 266 patents, making copolymer molded by poly-silicone hydrogel gained of the present invention is contact lens.The polymerization of monomer mixture can be carried out in the rotating mold corresponding to wanted contact lens shape or fixed mould.If desired, the contact lens that obtain with this can further stand machine finish.Also can in suitable mould or container, carry out polymerization to obtain 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 wanted shape.
Following examples will be for further illustrating the present invention, but not in order to limit the scope of the invention.Modification and change that under any, field those skilled in the art can reach easily include in the scope of this case specification sheets disclosure and appended claims.
Embodiment
Synthetic chemistry medicine
1. HEMA (be called for short HEMA):
purchased from Sigma company (Sigma).
2.N-vinyl pyrrolidone (being called for short NVP):
purchased from Sigma company.
3. methacrylic acid (MA):
purchased from Sigma company.
4. (trimethylsiloxy)-3-methacryloxypropyl silane (TRIS):
purchased from Sigma company.
5.CoatOsil:
purchased from Mai Tu company (Momentive).
6. Ethylene glycol dimethacrylate (EGDMA):
purchased from Sigma company.
7.D1173 light trigger: purchased from Ciba (Ciba Chemicals).
The preparation of poly-silicone hydrogel material
Example 1:
According to the composition shown in 1 and the content of filling a prescription in table 1, each composition is evenly mixed, and through ultraviolet lighting crosslinking polymerization 60 minutes, the polymkeric substance completing is soaked in 50% alcohol to 20 minutes, then with 70% alcoholic extract 60 minutes to remove unreacted monomer.It is 8 sodium bicarbonate (NaHCO that prepared poly-silicone hydrogel film is soaked in to pH
3) in solution 60 minutes, then be soaked in normal saline solution 60 minutes to replace, and finally gained film is placed in to normal saline solution and soaks 120 minutes, reach balancing water content.
Example 2:
Charge ratio and reaction conditions with example 1, but it is in 9 sodium hydroxide (NaOH) solution 60 minutes that prepared poly-silicone hydrogel film is soaked in to pH, be soaked in again in normal saline solution 60 minutes to replace, finally gained film is placed in to normal saline solution and soaks 120 minutes, reach balancing water content.
Example 3:
Charge ratio and reaction conditions with example 1, but it is in 10 sodium hydroxide (NaOH) solution 60 minutes that prepared poly-silicone hydrogel film is soaked in to pH, be soaked in again in normal saline solution 60 minutes to replace, finally gained film is placed in to normal saline solution and soaks 120 minutes, reach balancing water content.
Comparative example 1:
With the charging of example 1 reaction conditions when, but prepared poly-silicone hydrogel film is directly soaked in normal saline solution, without the program of soaking basic solution.
Example 4:
With charge ratio and the reaction conditions of example 1, but prepared poly-silicone hydrogel film is soaked in to pH, be 8 sodium bicarbonate (NaHCO
3) in solution 30 minutes, then be soaked in normal saline solution 60 minutes to replace, and finally gained film is placed in to normal saline solution and soaks 120 minutes, reach balancing water content.
Example 5:
With charge ratio and the reaction conditions of example 1, but prepared poly-silicone hydrogel film is soaked in to pH, be 8 sodium bicarbonate (NaHCO
3) in solution 120 minutes, then be soaked in normal saline solution 60 minutes to replace, and finally gained film is placed in to normal saline solution and soaks 120 minutes, reach balancing water content.
Example 6:
With charge ratio and the reaction conditions of example 1, but prepared poly-silicone hydrogel film is soaked in to pH, be 8 sodium bicarbonate (NaHCO
3) in solution 240 minutes, then be soaked in normal saline solution 60 minutes to replace, and finally gained film is placed in to normal saline solution and soaks 120 minutes, reach balancing water content.
Example 7:
With charge ratio and the reaction conditions of example 1, but prepared poly-silicone hydrogel film is soaked in to pH, be 8 sodium bicarbonate (NaHCO
3) in solution 480 minutes, then be soaked in normal saline solution 60 minutes to replace, and finally gained film is placed in to normal saline solution and soaks 120 minutes, reach balancing water content.
Example 8:
According to the composition shown in 2 and the content of filling a prescription in table 1, each composition is evenly mixed, and through ultraviolet lighting crosslinking polymerization 60 minutes, the polymkeric substance completing is soaked in 50% alcohol to 20 minutes, then with 70% alcoholic extract 60 minutes to remove unreacted monomer.It is 8 sodium bicarbonate (NaHCO that prepared poly-silicone hydrogel film is soaked in to pH
3) in solution 60 minutes, then be soaked in normal saline solution 60 minutes to replace, and finally gained film is placed in to normal saline solution and soaks 120 minutes, reach balancing water content.
Comparative example 2:
According to the composition shown in 3 and the content of filling a prescription in table 1, each composition is evenly mixed, and through ultraviolet lighting crosslinking polymerization 60 minutes, the polymkeric substance completing is soaked in 50% alcohol to 20 minutes, then with 70% alcoholic extract 60 minutes to remove unreacted monomer.It is 8 sodium bicarbonate (NaHCO that prepared poly-silicone hydrogel film is soaked in to pH
3) in solution 60 minutes, then be soaked in normal saline solution 60 minutes to replace, and finally gained film is placed in to normal saline solution and soaks 120 minutes, reach balancing water content.
Table 1
Water cut test
To in water, take out through the crosslinked example 1 to 8 being shaped of ultraviolet lighting and the poly-silicone hydrogel film of comparative example 1 and 2, and wipe away and do its surface-moisture, measuring weight in wet base is W
0.At 25 ℃ of room temperatures, by film standing 5 minutes and 10 minutes, recording respectively weight was W
1and W
2.Film is placed in baking oven, and with 110 ℃ of bakings 24 hours, to remove the moisture of material, and to measure film dry weight be W
3.Through following formula, calculate moisture loss rate and water ratio, it the results are shown in table 2.
Non-freezing combination water content test
To with the following step, measure respectively through the crosslinked example 1 to 8 being shaped of ultraviolet lighting and the poly-silicone hydrogel film of comparative example 1 and 2, acquired results is shown in table 2.
With thermogravimetric analyzer (Thermogravimetric Analyzer, TGA), measure the water content of poly-silicone hydrogel.Get approximately 0.1 gram of poly-silicone hydrogel and be positioned in sample disc, temperature setting is set to by room temperature and rises to 150C, and heat-up rate is 10 ℃/min, and gained residual quantity is the water content of poly-silicone hydrogel.
With differential scanning calorimeter (Differential Scanning Calorimetry, DSC), measure the endotherm(ic)peak area of water in poly-silicone hydrogel.Get approximately 0.1 gram of poly-silicone hydrogel and be positioned over the sealing of sample aluminium dish, temperature condition is set to-30 to 20 ℃, and heat-up rate is 5 ℃/min, through measuring thermogram spectrum.Respectively approximately 0 ℃ of peace treaty-1 in gained collection of illustrative plates to the endotherm(ic)peak area of-3 ℃ can be obtained to the weight of free water and freezing combination water divided by the heat content (333.3 joule/gram) of pure water.
Poly-silicone hydrogel total water content deduction free water by thermogravimetric analyzer gained and the content of freezing combination water can be obtained to the content of non-freezing combination water, and can calculate its content ratio.
Table 2
In table 2, example 1 to 3 and comparative example 1 show that prepared poly-silicone hydrogel film is soaked in every data measured under different pH; Example 1 and 4 to 7 and comparative example 1 show that prepared poly-silicone hydrogel film processes measured every data through the basic solution of different time; Example 1 and 8 and comparative example 2 show with the measured every data of the prepared poly-silicone hydrogel film of different ions type monomer content.
From every data shown in table 2 and Fig. 3, the content of the non-freezing combination water in poly-silicone hydrogel be no less than whole water content 20% time, the water ratio of the poly-silicone hydrogel of the present invention increases along with the increase of non-freezing combination water content, and the moisture loss rate of poly-silicone hydrogel inside is also slower, thereby there is the effect of water conservation.
Surface contact angle test
Utilize contact angle measurement instrument practical measuring examples 1 to 3 and 8 and the surface contact angle of the poly-silicone hydrogel film of comparative example 1 and 2.When fluid drips is on solid surface, the angle of solid surface and tangent is " contact angle ".When contact angle is 0 while spending, express liquid is moistening solid surface fully; When contact angle is 180 while spending, represent that liquid completely can not moistening solid surface.The data of contact angle test are as shown in table 3 below.
Table 3
| Surface contact angle | |
| Example 1 (pH 8) | 18.80±4.22 |
| Example 2 (pH 9) | 18.77±6.97 |
| Example 3 (pH 10) | 18.10±4.62 |
| Example 8 (pH 8) | 18.30±4.65 |
| Comparative example 1 (pH 7) | 51.14±5.48 |
| Comparative example 2 (pH 8) | 58.20±5.25 |
Because the ionic comonomer dissociation degree in the poly-silicone hydrogel of processing through basic solution is higher, can attract more water molecules, the wetting ability on poly-silicone hydrogel surface is promoted, there is preferably wetting effect, so the numerical value of surface contact angle obviously declines.
Should easily to understand various improvement of the present invention be feasible and be that one of ordinary skill in the art easily associate and expect.
Claims (17)
1. one kind for the poly-silicone hydrogel of object for eye, reaction product and water that it comprises the monomer mixture that is used to form poly-silicone hydrogel, the content of wherein said water is in the gross weight of the poly-silicone hydrogel of integral body, for being not less than 50 % by weight, described monomer mixture comprises at least one silicon-containing monomer, a kind of wetting ability nonionic monomers and at least one ionic comonomer, the content of wherein said ionic comonomer is in the gross weight of the poly-silicone hydrogel dry weight of integral body, it is 0.7 to 10 % by weight, the content of described silicon-containing monomer is in the gross weight of the poly-silicone hydrogel dry weight of integral body, be 40 to 60 % by weight, the content of described wetting ability nonionic monomers is in the gross weight of the poly-silicone hydrogel dry weight of integral body, be 30 to 60 % by weight, wherein said poly-silicone hydrogel contained humidity attached bag is containing free water, freezing combination water and non-freezing combination water, and the content of described non-freezing combination water is no less than 20% with whole water content meter.
2. poly-silicone hydrogel according to claim 1, the content of wherein said ionic comonomer, in the gross weight of the poly-silicone hydrogel dry weight of integral body, is 1 to 3 % by weight.
3. poly-silicone hydrogel according to claim 1, the content of wherein said silicon-containing monomer, in the gross weight of the poly-silicone hydrogel dry weight of integral body, is at least 40 % by weight.
4. poly-silicone hydrogel according to claim 1, the content of wherein said silicon-containing monomer, in the gross weight of the poly-silicone hydrogel dry weight of integral body, is 45 to 55 % by weight.
5. poly-silicone hydrogel according to claim 1, wherein said ionic comonomer selects free vinylformic acid (acrylic acid), methacrylic acid (methacrylic acid; MA), the group that 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 form.
6. poly-silicone hydrogel according to claim 1, wherein said silicon-containing monomer choosing is (trimethylsiloxy)-3-methacryloxypropyl silane ((trimethylsiloxy)-3-methacryloxypropylsilane freely; TRIS), methacrylic acid 3-(triethoxysilyl) propyl ester (3-(triethoxysilyl) propyl methacrylate), methacrylic 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), methacrylic acid three (trimethylsiloxy) silyl propyl ester (tris (trimethylsiloxy) silylpropyl methacrylate), two (trimethylsiloxy) methyl-silicane base propyl ester (bis (trimethylsiloxy) methylsilylpropyl methacrylate) of methacrylic acid, methacrylic acid pentamethyl disiloxane propyl ester (pentamethyldisiloxanepropyl methacrylate), methacrylic acid three (trimethylsiloxy) silyl propoxy-ethyl ester (tris (trimethylsiloxy) silyl propyloxyethyl methacrylate), the group that methacrylic acid three (polydimethyl siloxy-) silyl propyl ester (tris (polydimethylsiloxy) silylpropyl methacrylate) and composition thereof forms.
7. poly-silicone hydrogel according to claim 1, the content of wherein said water counts 50 to 70% with the gross weight of the poly-silicone hydrogel of integral body.
8. poly-silicone hydrogel according to claim 7, the content of wherein said water counts 55 to 63% with the gross weight of the poly-silicone hydrogel of integral body.
9. poly-silicone hydrogel according to claim 1, the content of wherein said non-freezing combination water be take whole water content meter as 20 to 40%.
10. poly-silicone hydrogel according to claim 9, the content of wherein said non-freezing combination water be take whole water content meter as 20 to 37%.
11. poly-silicone hydrogels according to claim 1, the content of wherein said wetting ability nonionic monomers, to gather the gross weight of silicone hydrogel dry weight, is 35 to 55 % by weight.
12. poly-silicone hydrogels according to claim 11, the content of wherein said wetting ability nonionic monomers, to gather the gross weight of silicone hydrogel dry weight, is 40 to 50 % by weight.
13. poly-silicone hydrogels according to claim 1, wherein said wetting ability nonionic monomers is selected free HEMA (2-hydroxyethyl methacrylate; HEMA), HEA (2-hydroxyethyl acrylate), glyceral methacrylate (glycerol methacrylate), vinylformic acid 2-dimethylamino ethyl ester (2-dimethylaminoethyl acrylate), N-vinyl-methane amide (N-vinyl-formamide), NVP (N-vinyl pyrrolidone; NVP), acryloyl morpholine (acryloylmorpholine), Methacrylamide (methacrylamide), N,N-DMAA (N, N-dimethylacrylamide; DMA), N, the group that N-diethyl acrylamide (N, N-diethylacrylamide), dihydroxy ethyl Methacrylamide (2-hydroxyethyl methacrylamide), NIPA (N-isopropylacrylamide) and composition thereof form.
14. 1 kinds by according to the prepared eye object of the poly-silicone hydrogel described in arbitrary claim in claim 1 to 13, and it is contact lens or intraocular lens.
15. eye objects according to claim 14, it has the surface contact angle that is not more than 30 °.
16. eye objects according to claim 15, wherein said surface contact angle is 10 ° to 30 °.
17. eye objects according to claim 16, wherein said surface contact angle is 15 ° to 25 °.
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| JP6606652B2 (en) * | 2014-08-19 | 2019-11-20 | 国立大学法人北海道大学 | Composite material comprising fabric and amphoteric polyelectrolyte hydrogel and method for producing the same |
| CN104877068B (en) * | 2015-05-21 | 2017-08-25 | 爱生华(苏州)光学有限公司 | A kind of preparation method of practical silicone hydrogel contact mirror |
| CN105061674B (en) * | 2015-08-10 | 2018-04-13 | 爱生华(苏州)光学有限公司 | A kind of formulation selection and new process of the silicone hydrogel contact lens of novel fluorine siloxanes |
| CN106749877B (en) * | 2016-12-20 | 2018-12-28 | 无锡蕾明视康科技有限公司 | A kind of high oxygen permeability optical lens material and preparation method thereof |
| 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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