CN205046029U - Silicon glue lens - Google Patents

Abstract

The utility model relates to a silicon glue lens, silicon glue lens are including the lens body of utensil internal surface and surface, and the lens body comprises central optics district and marginal zone, and central optics district diameter is between 5 -10mm, and thickness is distinguished between 0.04 -0.15mm to central optics, and marginal zone thickness is 0.22mm, and the lens is personally experienced sth. Part of the body and is synthesized by the substrate of the linear chain type polysiloxanes mixture that has the hydrophilicity side chain.

Description

A kind of silicon glue eyeglass

Technical field

The utility model is about a kind of contact lens and base material thereof, espespecially a kind of with the silicon glue eyeglass made containing the silicon glue of hydrophilic functional group's silicon monomer.

Background technology

Contact lens comprise hard contact lenses and Soft contact lens, compared to hard contact lenses, Soft contact lens due to oxygen value lower, easily cause canthus anoxic, and soft needs keep its shape with moisture content, after its moisture loss, the tear of wearer can be absorbed, therefore wear for a long time and easily cause eyes dry and astringent and bring uncomfortable sensation.

Due to oxygen transmission rate and the water ratio of the silicon glue tool height of tool hydrophilic functional group, therefore the base material of Chang Zuowei Soft contact lens, but known techniques is usually comparatively complicated, such as disclose a kind of with three step synthetic methods of Glacial acetic acid ring-opening reaction in No. US4259467th, U.S. Patent Bulletin, or disclose a kind of after eyeglass completes in U.S. Patent Bulletin US4332922, lens surface is changed into the compound reaction of SiOH base or other C=C containing the SiH base on the oligomerization siloxanes of SiH base, and make the surperficial tool wetting ability of eyeglass, and announce in No. TWI434865 at Taiwan Patent, then disclosing one utilizes two step hydrosilation reactions (hydrosilation) to make the polysiloxane of the hydrophilic side-chains such as amide functional base or phosphorylcholine functional group, but its hydrosilation reaction needs to use the comparatively high rhodium-containing catalyst of price, and its temperature of reaction needs on boiling point more, therefore higher cost of manufacture is needed.

Therefore how to simplify the synthesis step of the silicon glue of tool hydrophilic functional group and reduce its cost of manufacture, and the silicon glue eyeglass of synthesis tool height oxygen transmission rate and water ratio is the technical task of this case for solving.

Utility model content

In order to solve the problem described in background technology, main purpose of the present utility model is to provide a kind of silicon glue eyeglass, it is characterized in that the lens body comprising tool internal surface and outside surface, lens body is made up of central optical zone and marginarium, central optical zone diameter is between 5-10mm, central optical zone thickness is between 0.04-0.15mm, and marginarium thickness is 0.22mm, wherein eyeglass system by have hydrophilic side-chains polysiloxane mixture base material made by.

Described base material comprises: the polysiloxane mixture with hydrophilic side-chains represented with formula (I):

In formula (I), R is hydrophilic side-chains, x value between 0-10, n:m value be 1:6, n value between 1-800, m value between 50-5000.

Described hydrophilic side-chains R has the chemical structure of formula (II):

In formula (II), R1 is: hydroxyl (OH), methyl (CH ₃), hydrogen base (H), methylol (CH ₂oH), ethyl (C ₂h ₅) in any one, R2 is: any one in hydrogen base (H), hydroxyl (OH), h value between 0-30, j value between 0-10, k value between 0-10, y value between 0-100, z value between 0-30.

Described hydrophilic side-chains R system is selected from: 3-allyloxy-1,2, at least one in propylene glycol (3-allyloxy-1,2-propanediol), 2-allyloxyethanol (2-Allyloxyethanol), trimethylammonium alcohol propane-allyl ether (Trimethylolpropaneallylether).

Described central optical zone diameter is between 6.5-9mm.

Described central optical zone thickness is between 0.06-0.1mm.

The water ratio of described silicon glue eyeglass is 35 to 38%.

The oxygen transmission rate of described silicon glue eyeglass is 35 to 90.

Accompanying drawing explanation

Fig. 1 is vertical view (A) and the side-view (B) of the silicon glue eyeglass of this creation embodiment 3.

Embodiment

Because the utility model discloses the preparation technology of silicon glue lens substrate, wherein utilized ring-opening polymerization (ringopeningpolymerization) and hydrosilation reaction (hydrosilation), usually know that the knowledgeable can understand for correlative technology field has, therefore with explanation hereinafter, no longer do complete description.

The utility model is for providing the preparation technology of a kind of silicon glue eyeglass and base material thereof, and this preparation technology comprises: ring-opening polymerization (ringopeningpolymerization) and hydrosilation reaction (hydrosilation).

First, carry out ring-opening polymerization, as shown in following chemical equation (a).

A strong acid (4) is added in the mixture of cyclosiloxane (1), ring hydrogen siloxane (2) and linear silicones (3), the mole number of strong acid (4) is the 1-10% of cyclosiloxane (1), ring hydrogen siloxane (2) and the total mole number of linear silicones (3) mixture, under normal temperature, carry out ring-opening polymerization, form the polysiloxane mixture (5) of tool si-h bond; Wherein, cyclosiloxane (1) can be at least one in prestox cyclisation tetrasiloxane (Octamethylcyclotetrasiloxane), hexamethyl cyclotrisiloxane (Hexamethylcyclotrisiloxane); And ring hydrogen siloxane (2) can be 2,4,6,8-polysiloxane (2,4,6,8-Tetramethylcyclotetrasiloxane); And the x value shown in linear silicones (3) is between 0-10, such as linear silicones (3) can be 1,3-bis-(3-propyl methacrylate) tetramethyl disiloxane (1,3-Bis (3-methacryloxypropyl) tetramethyldisiloxane); And described strong acid (4) is except the trifluoromethanesulfonic acid (Trifluoromethanesulfonicacid) shown in chemical equation (a), sulfuric acid (Sulfuricacid) also can be used to replace.

After at room temperature carrying out ring-opening polymerization, the polysiloxane mixture (5) of tool si-h bond can be obtained, wherein, the n value shown in polysiloxane mixture (5) of tool si-h bond is the quantity of si-h bond and is between 1-800, and m value is then between 1-5000.

Thereafter, hydrosilation reaction (hydrosilation) is carried out, as shown in chemical equation (b).

Add hydrophilic compounds (6) in the polysiloxane mixture (5) of above-mentioned tool si-h bond, at temperature 85-90 DEG C, hydrosilation reaction is carried out, in order to obtain the polysiloxane mixture (7) of tool hydrophilic side-chains with platiniferous catalyst (Pt/C) catalysis.

Above-mentioned hydrophilic compounds (6) can be hydroxyl (OH), methyl (CH with the R1 shown in polysiloxane mixture (7) of tool hydrophilic side-chains ₃), hydrogen base (H), methylol (CH ₂oH), ethyl (C ₂h ₅) in any one, R2 can be any one in hydrogen base (H), hydroxyl (OH), h value between 0-30, j value between 0-10, k value between 0-10, y value between 0-100, z value between 0-30.Such as, hydrophilic compounds (6) can be 3-allyloxy-1,2, at least one in propylene glycol (3-allyloxy-1,2-propanediol), 2-allyloxyethanol (2-Allyloxyethanol), trimethylammonium alcohol propane-allyl ether (Trimethylolpropaneallylether).

In addition, in chemical equation (b), this hydrophilic compounds (6) equals n+A:1 with the Moore ratio of the polysiloxane mixture (5) of this tool si-h bond, wherein n value is the quantity of si-h bond in the polysiloxane mixture (5) of aforementioned tool si-h bond, and A value is the constant between 5-100.

Embodiment 1

Ring-opening polymerization: the building-up reactions of the polysiloxane mixture (n=22.6, m=113) of tool si-h bond.

By prestox cyclisation tetrasiloxane (Octamethylcyclotetrasiloxane) (40g), 2,4,6,8-polysiloxane (2,4,6,8-Tetramethylcyclotetrasiloxane) (8.3g), 1,3-bis-(3-propyl methacrylate) tetramethyl disiloxane (1,3-bis (3-methacryloxypropyl) tetramethyldisiloxane) (2.1g) mix with a solvent trichloromethane (33mL) and be placed in 250mL two-neck bottle, and after two-neck bottle mouth loads onto serum plug and check valve, nitrogen is passed into check valve; Afterwards, get trifluoromethanesulfonic acid (trifluoromethanesulfonicacid) (0.22mL) with syringe and inject the two-neck bottle of aforementioned 250mL, and under the condition of temperature 35 DEG C, allow the prestox cyclisation tetrasiloxane, 2 being dissolved in trichloromethane, 4,6,8-polysiloxane and 1, the mixture of 3-bis-(3-propyl methacrylate) tetramethyl disiloxane is under trifluoromethanesulfonic acid exists, react 72 hours in nitrogen, the serum plug of opening unit on two-neck bottle, adds saturated aqueous sodium carbonate (0.5mL), to stop ring-opening polymerization subsequently.

Concentrating under reduced pressure instrument is utilized to remove organic solvent trichloromethane, afterwards, carrying out an extraction step, is utilize ethyl acetate (200mL) and saturated aqueous common salt (150mL) to extract five times, collect top organic layer, recycling concentrating under reduced pressure machine removing organic solvent ethyl acetate; Then, with 10mL acetone solution, then carry out redeposition in the methyl alcohol instilling 50mL; Afterwards, after carrying out gravity filtration with filter paper, then with the washed with methanol upper strata dope of 500mL, collect upper strata dope and remove organic solvent-acetone with spin concentration instrument; Afterwards, then repeat the aforementioned reppd step of secondary, collect upper strata dope, the polysiloxane mixture of the colourless sticky tool si-h bond of about 26g can be obtained.

The hydrogen nuclear magnetic resonance spectral results of the polysiloxane mixture of above-mentioned tool si-h bond is as follows: 1HNMR (CDCl3,400MHz): 6.1 (s, 2H), 5.56 (s, 2H), 4.70 (m, 22.6H), 4.10 (t, 4H), 1.95 (s, 6H), 1.65-1.75 (m, 4H), 0.54-0.60 (m, 4H), 0.04-0.20 (m, Si-CH3), wherein 4.70 (m, 22.6H) represent the formation of si-h bond.

Then, hydrosilation reaction is carried out: the building-up reactions of namely carrying out the polysiloxane mixture (n=22.6, m=135) of tool hydrophilic side-chains.

First, by 3-allyloxy-1,2, propylene glycol (3-allyloxy-1,2-propanediol) (11.78g, 89.1mmol) and platiniferous catalyst (Pt/C) (5%oncarbon, 2.3g) are placed in 500mL two-neck bottle; Then, after loading onto return line and dripping pipe, carry out vacuumizing and pour into nitrogen three times; Again then, getting solvent dry toluene (80mL) with syringe injects among 500mL two-neck bottle; Afterwards, will be dissolved in the 3-allyloxy-1,2 of dry toluene, propylene glycol and platiniferous catalyst (Pt/C) to be inserted in oil bath pan and are heated to 85-90 DEG C.

The polysiloxane mixture (by NMR, n=22.6, m=113 calculate that molecular weight is about 10100) (20g, 1.98mmol) of tool si-h bond synthesized in aforementioned ring-opening polymerization is placed in the two-neck bottle of another 100mL; Afterwards, after the two-neck bottle mouth of 100mL loads onto serum plug and check valve, carry out vacuumizing and fill with nitrogen three times; Afterwards, injection solvent dry toluene (55mL) and stablizer 4-mequinol (4-methoxyphenol) (2mg) is to the two-neck bottle of 100mL, extract out with the polysiloxane mixture solution of the tool si-h bond of dry toluene dissolving in 100mL two-neck bottle with syringe again, by the dropping pipe of injection device on 500mL two-neck bottle, and instilled in 500mL two-neck bottle (time for adding is about 5 minutes) by dropping pipe.If still have resistates in 100mL two-neck bottle, available syringe gets the resistates in the dry toluene cleaning 100mL two-neck bottle of 15mL, and is reinjected by the resistates washed out in dropping pipe, then instills in 500mL two-neck bottle.

Under the condition of temperature 85-90 DEG C, react 24 hours in nitrogen, collected by vacuum filtration liquid afterwards, recycling concentrating under reduced pressure instrument removing organic solvent dry toluene.

With acetone (13.6mL) lysate, redeposition, in pure water (68.6mL), does gravity filtration with filter paper, then cleans upper strata dope with about 500mL pure water.

Collect upper strata dope also with spin concentration instrument removing organic solvent-acetone, repeat abovementioned steps redeposition secondary, collect upper strata dope, the yellow of about 15g can be obtained and clarify the polysiloxane mixture of sticky tool hydrophilic side-chains.

The hydrogen nuclear magnetic resonance spectral results of the polysiloxane mixture of tool hydrophilic side-chains is as follows: 1HNMR (CDCl3,400MHz): 6.1 (s, 2H), 5.54 (s, 2H), 4.10 (t, 4H), 3.40-3.85 (m, 203H), 1.94 (s, 6H), 1.50-1.70 (m, 49H), 0.47-0.60 (m, 49H), 0.04-0.20 (m, Si-CH3), wherein 3.40-3.85 (m, 203H) represents the formation of hydrophilic side-chains.

Embodiment 2

With the prestox cyclisation tetrasiloxane (Octamethylcyclotetrasiloxane), 2 of different mole number ratio, 4,6,8-polysiloxane (2,4,6,8-Tetramethylcyclotetrasiloxane) with 1,3-bis-(3-propyl methacrylate) tetramethyl disiloxane (1,3-Bis (3-methacryloxypropyl) tetramethyldisiloxane) polysiloxane mixture of the tool hydrophilic side-chains of different n, m value ratio can be obtained, wherein, the higher representative of m value has more oxygen flow ends.

Result of study finds, as its n:m=1:6 of polysiloxane mixture of tool hydrophilic side-chains and m value between 50-5000 time, there is high oxygen transmission rate and stable water ratio.

With the silicon glue eyeglass that different n, m values makes, its character such as water ratio and oxygen transmission rate performance results is as shown in the table:

As seen from the above table, compared to US4259467 the silicon glue base material of n:m=1:3 is proposed, the silicon glue base material of n:m=1:6 proposed by the invention, water ratio EWC (%) can be allowed to be maintained at the interval of 35-38, and can by raising m value, improve oxygen transmission rate (Barrers), and can be applicable to the product of different oxygen flow demand, and the adjustment of oxygen transmission rate can not have an impact to its water ratio EWC (%).

Embodiment 3

A silicon glue eyeglass is made with the polysiloxane mixture of aforementioned synthesis tool hydrophilic side-chains, as shown in Figure 1, this silicon glue eyeglass has lens body 1, A represents the vertical view of lens body 1, B represents the side-view of lens body 1, lens body 1 has outside surface 13 and internal surface 14, lens body 1 is by central optical zone 11 and marginarium 12, wherein, central optical zone diameter D1 is between 5-10mm, in a better embodiment, central optical zone diameter D1 is between 6.5-9mm, in addition, described central optical zone thickness is between 0.04-0.15mm, in another better embodiment, central optical zone thickness is between 0.06-0.1mm, described marginarium thickness is 0.22mm.

Compared to prior art, the utility model can carry out the polysiloxane mixture that hydrosilation reaction forms tool hydrophilic side-chains under boiling point, in addition, this hydrosilation reaction of platiniferous catalyst catalysis that the utility model also uses price comparatively cheap, from the above, the utility model provides the silicon glue eyeglass of a kind of stable aqueous rate and high oxygen transmission rate, and uses energy expenditure reduction, the lower-cost synthesis mode of catalyst, promotes the efficiency of the polysiloxane mixture synthesis of tool hydrophilic side-chains significantly; Therefore the utility model is a creation having industrial value in fact.

Claims (5)

1. a silicon glue eyeglass, it is characterized in that comprising the lens body with internal surface and outside surface, described lens body is made up of central optical zone and marginarium, described central optical zone diameter is between 5-10mm, described central optical zone thickness is between 0.04-0.15mm, and described marginarium thickness is 0.22mm.

2. silicon glue eyeglass as claimed in claim 1, is characterized in that described central optical zone diameter is between 6.5-9mm.

3. silicon glue eyeglass as claimed in claim 1, is characterized in that described central optical zone thickness is between 0.06-0.1mm.

4. silicon glue eyeglass as claimed in claim 1, is characterized in that the water ratio of described silicon glue eyeglass is 35 to 38%.

5. silicon glue eyeglass as claimed in claim 1, is characterized in that the oxygen transmission rate of described silicon glue eyeglass is 35 to 90.