TW200418631A - Reactive dye and method for producing such a dye - Google Patents

Abstract

A reactive dye is a reactive dye-monomer compound and applicable in the preparation of a color lens. The reactive dye-monomer compound includes at least an absorption color group and an unsaturated reactive type vinyl group. Such compound has a high reactivity. Furthermore, the present invention provides a method for producing such a reactive dye-monomer compound. Such a production method is simple and the produced product has a high purity and a high reactivity. Moreover, the present invention provides a method for producing a color lens by using such a reactive dye-monomer compound without tedious washing and developing steps while obtaining a full color lens with uniform dyeing. The obtained dyed lens has excellent color stability and will not be dissolved and released and discolored pre-maturely after receiving multiple autoclave sterilization treatments.

Description

200418631 Rose, description of the invention: [Technical field to which the invention belongs] The present invention relates to a reactive dye compound and a method for manufacturing the same. The reactive dye compound can be used to manufacture colored soft contact lens lenses. More specifically, the present invention relates to a reactive dye compound that can be covalently bonded to a soft contact lens and a method for manufacturing the same. The reactive dye compound can be used to make colored hydrophilic soft contact lenses. Even if the lens is subjected to multiple autoclave sterilization treatment, it will not cause discoloration, and the dye will not be interpreted from the lens. [Previous Technology] Many different processes have been used to make full-color or color vision lenses with different functionalities. Taking contact lens lenses as an example, full-color contact lenses can not only change the apparent color of the user's iris, but because they have cedar, they can be easily identified in a clear solution in the lens storage, disinfection, or cleaning container. Where the lens is. When making k color 1¾-shaped spectacle lenses, color dyes need to be added. Generally, color dyes can be added to the lens before or after polymerizing the lens-forming material. One of the conventional methods is to dissolve or disperse an inorganic pigment (Inorganic pigment) or a long-chain organic dye in a monomer precursor (Monoma precursor) or a molecule in the formation of the lens. Matrix (Polymer mat) rix). Inorganic pigments or long-bond organic dyes can later be fixed in the lens, revealing the desired color. However, this method is not suitable for the dyeing of Hydrophi Uc 200418631-shaped spectacle lenses, because the water content of such lenses is very high, which often leads to migration or dissolution of colorants. Out, causing color shift. During high-pressure thermal sterilization, which is commonly used for hydrophilic soft contact lens lenses, the migration or dissolution of such dyes may appear more severe. The method proposed in U.S. Patent No. 4,252,421 is to use a water-insoluble dye on soft contact lenses to alleviate the aforementioned problem of poor dyeing. This kind of lens is made by insoluble peptide-thalocyanine dye and the monomer forming the hydrophilic lens through heat curing. Such a peptide cyanine dye is, for example, copper peptide cyanocyanine. The peptide cyanine dye is fixed in the prepared lens, and can still exist stably in an environment with a maximum water content of 35.7%. However, if 2-Hydroxyxyyi methacrylate (HEMA) is used as the hydrophilic monomer (HydrophylHc monomer) and the water content is 40%, the water-insoluble Peptide cyanine dyes are still soluble from the lenses. To make matters worse, the problem explained by this solution will worsen as the proportion of water content rises. A method for preparing a full-color contact lens using a copper peptide cyanine pigment [Color Index (Pigment BlUel 5)] is also disclosed in U.S. Patent No. 6,149,842. The copper peptide cyanine pigment is first dispersed in an aqueous solution. Polyvinyl alcohol (PVA) is first added to the aqueous solution as a dispersing agent. It is then weighed with Crosslinkable polyvinyl alcohol. The precursors (PVA precursors) are mixed and then photopolymerized (photopolinerized) in a mold to form a lens. However, this patent does not disclose details of the efficacy of the dyes used. As mentioned earlier, the dissolution of dyes in environments with large amounts of water content explains that this is still a potential problem with this method. A similar concept is also disclosed in U.S. Patent No. 5,516,467, in which a Vat dye, such as Vat Blue 6, is first converted into a Leuco COmpound and dissolved in the hydrophilic N, N-Dimethyl acrylamide (N, N-Dimethyl acrylamide) monomer to prepare a full-color monomer solution (Tintedmommersomution). Then, the solution and other ingredients are polymerized in a heated environment to form a lens. The lens then converts the dissolved leuco into an insoluble vat dye under boiling water. Although this vat dye is non-covalently bonded to the lens-forming material, it is also reported to have excellent stability and does not fade in boiling water for 200 hours. However, the disadvantage is that if it is located in a suitable alkaline environment, the fixed vat dye can also be converted back to the dissolved leuco, and if it is in an acidic environment, the reaction of the dye is not uniform (Unevenly reacted ). The method for applying color to a contact lens lens is to apply it to the completed lens_L by a printing or transfer printing method. Basically, the method usually transfers a color solvent ink (coining) to the lens by means of a silicon rubber pad. This transfer method has disadvantages, because it cannot dry the lens surface and carry out pigments-flawless close-packed coloring. Many different methods have been proposed to solve the problem. 'Some suggested to use multiple transfer (M is called plus this Printing) step to apply mottled spots on the lens surface; some use pigment / monomer suspension (Pigment / M〇n〇mer is called coated on the lens mold, this mold is embossed or printed a specific shape or time 200418631: by the traditional spin casting (Spin casting) technology to form a full color =: glasses lens' such as the United States Disclosed in Patent No. 4,640,805. Although the word -remedy can alleviate the phenomenon of Blemish defect2, due to the use of non-covalently bonded dyes, the potential of P I and pigment migration during autoclaving Risk. Therefore, in order to remove this disadvantage, reactive color dyes can meet this need. Because it co-polymerizes with the lens material to form a covalent bond, it can be used in different environments. It can prevent the dye from being dissolved out of the lens. For example, US Patent No. 5,352,245 discloses a reactive color dye, which is used to prepare transfer printing inks so that To compensate for the migration problem mentioned above (Migrati Shon Uge). This patent uses a reactive color dye, such as: Ramazol Black B, together with polyvinyl pyrolidone (PVP) The main agent (Binder) is mixed with a nonionic surfactant (Surfactant) to prepare an ink, which is then transferred to a hydrophilic contact lens' to form a full-color contact lens lens with a desired pattern. After completing the follow-up After the lye immersion procedure, the reactive dye can form a covalent bond with the lens material. However, the performance details of the full-color contact lens are still undisclosed. In addition, this method is very complicated, It also has the general disadvantages involved in soaking-to-fix technology. Many patents such as US Patent No. 4,559,059, US Patent No. 4,468,229, US Patent No. 4,157,892, US Patent No. 4,891 No. 046, U.S. Patent No. 4,553,975, U.S. Patent No. 4,929,250 'U.S. Patent No. 5,292,350, U.S. Patent No. 5,480,927, all proposed full-color coloring in The method of contact lens, 200418631, is to immerse the dye in the test solution with the formed lens in order to form a chemical bond between the dye and the lens material. This reactive color dye can be used before the polymerization step. And mixed with the lens to form monomer mixtures, or added to the alkaline solution after the lens polymerization step. In addition to the different types of reactive color dyes and production procedures proposed in the above patents, these patents usually take a long time (Time_consuming) and require multiple steps, such as neutralization (Extraction). n), and the steps of washing (rinsing) can be colored in the contact lens. In addition, the process variables of the above patents must be carefully controlled to avoid the occurrence of uneven dispersion (DiSpersion) and uneven staining (c0101rizati〇 ^). More than two patents proposed more effective lens staining methods, which are By forming a covalent bond between the preform or the prepolymer and the reactive color dye, the functionalized (Funeti 嶋 lized) prepolymer is refined after being refined into a lens mold for curing. (:: This method can effectively alleviate the process problems described in the aforementioned soaking-to-fix method. The following patents are 'such as US Patent No. 4,252,421, and US Patent No.' US Patent No. 5,938,795 'U.S. Patent No. 5,871,675, U.S. Patent No. 6,149,692, U.S. Patent No. 4,795,794 1, and U.S. = Patent No. 6,162,844, using the aforementioned technique to polymerize the dye in the polymerization step M' Chemically fixed to the lens-forming material. The difference between these patents is mainly in the type of reactive color dyes and precursors. Although these patented methods have the advantages described, they still exist Missing j: For example, tedious purification (Purificati) steps, and premature discoloration after periodic autoclaving (prmatwe 200418631 fading). Summarizing the methods disclosed in the aforementioned patents, usually including a Or several shortcomings. These shortcomings, such as 'lengthy process time, low conversion (l0w degree of conen)', explain the dissolution of weakly-bonded dyes, fading, lens tint:-caused, and complicated Reaction or purification process due to & preparation of colored contact lenses with excellent color stability 'but without the disadvantages mentioned above. See: see the wood used in the film' and use this dye to make colored contact lens lenses. There is a great demand in the industry. [Summary of the Invention] One of the objects of the present invention is to provide a reactive dye-monomer compound (Reacmve dye-monommer cmomund), which can be used for preparing Color lens, the dye-monomer compound contains at least one absorbing moiety) and an unsaturated vinyl group. The compound has high reactivity (R eacUvit ^. It can be covalently bonded to the lens material through a polymerization process. Another object of the present invention is to provide a method for manufacturing a reactive dye-monomer compound, which can be used. In the preparation of colored lenses. By this method, a novel reactive dye-monomer compound can be prepared. This manufacturing method is simple, and the single functional dye-monomer (M0H0-fUnCti0naldye_m) prepared by the method is simple. 〇n〇mer) compounds with high purity

With high reactivity. X It is still another object of the present invention to provide a method for manufacturing a colored contact lens using a reactive dye-monomer compound to color a reactive agent in a lens. According to this method, a reactive dye 10 200418631 material-monomer compound is mixed with a lens forming material, and the mixture is cured on a lens mold to prepare a full-color soft contact lens. This method does not require tedious cleaning and development steps to obtain the uniformly colored full-color lens. Another object of the present invention is to provide a colored contact lens manufactured by using a reactive dye-monomer compound. The dyeing lens has excellent coloring properties, and is resistant to multiple hydration autoclave sterilization treatments. After that, the problem of premature fading does not occur. This exceptional durability is because the dye-monomer compound can form a covalent bond with the lens-forming material upon curing, and the polymer chain has excellent stability at high temperatures. Dye-monomer compounds can be represented by the following chemical formulae, which include at least one absorbing color group (c0rab absorbing moiety) and an unsaturated reactive vinyl group:

AB wherein A represents an unsaturated reactive ethylene group; and B represents an absorbing color group which can absorb visible light radiation. A can be derived from a hydrophilic hydro vinylic monomer, which has a reactive hydroxyl and unsaturated vinyl group. For example, it can be derived from acrylate or methacrylic acid. ester. More specific examples may include ethyl 2-hydroxymethyl acrylate, hydroxyethyl acrylate, methacrylamide, acrylic acid, ethyl alcohol, ethyl methacrylate, and ethyl bipyro copper. Or trimethylglycerol. B can be derived from a commercial reactive dye. The reactive dye can be 11 200418631. Water> gluten and at least β-sulfate-based ethyl sulfate (β- sulphatoethyl sulphone) or its derivatives, and its Color Index can be C · l Reactive Yeilow 14, c. I ·

Reactive Yellow 15 ^ C. I. Reactive Yellow 17 ^ C. I. Reactive Orange 7 > C. I. Reactive Orange 16 ^ C. I. Reactive Orange 72, C. I. Reactive Red 23, C. I. Reactive Red 49, C. I.

Reactive Red 180 ^ C. I. Reactive Blue 19 ^ C. I. Reactive

Blue 20, or C.I.Reactive Blue 21. In addition to the above-mentioned reactive dyes, they can be obtained from existing products, or they can be prepared by conventional techniques in the field of organic synthesis. The above-mentioned reactive dye-monomer compound can be applied to the dyeing of soft contact lens lenses. Such lenses can be calibrated ... with "non-corrective ..." Manufacture provided by the present invention The method of reactive dye_monomer compound is to react a reactive dye with another reactant providing a vinyl group, and functionalize the reactive vinyl grOUp to the molecular structure of the reactive dye. The reactive dyestuff-monomer compound produced by this method only needs to go through a simple purification process and does not require other activation steps, and can be directly used in the manufacture of colored contact lenses. A method for manufacturing a color contact lens using a reactive dye-monomer compound, which uses a reactive dye-monomer compound to polymerize a hydrophilic monomer that forms a lens material, and fixes the dye to the monomer by chemical action. Body, and does not require any subsequent dyeing or developing steps. At the same time, 'this method does not require testing solution or dye water after lens formation Developed and soaked in liquid for coloring. 12 200418631 ^ 'Dry-made compound made of raw color contact lenses, which, upon curing, the dye-overcoat entangled the premature compound with the mirror-forming material to form a covalent bond' and therefore did not There will be a 'discoloration problem' of dye dissolution and this polymer chain has excellent stability at high temperatures: early

Formula Formula Implementation rL The present invention mainly uses a simple procedure to synthesize a reactive monomer compound. 4 It promotes the reaction of 0-sulfate ethyl group in dyes and provides reactants of ethylene group. For example, the hydrophilic vinyl monomer (Hydroxyxyl gr〇), so Use a test substance to raise the call. In addition, in order to avoid vinyl groups (Vinyl groups) showing unwanted premature response (p 简 at㈣reaeti ° n), so 'polymerization inhibitor 0ymerization inhibit0r' is also used. The synthesis method is summarized as follows. The reactive dye is first activated in an aqueous solution with a predetermined amount of hydrazine and scopolamine base, and the preferred temperature for this activation step is H fρ of 30 to 80 ° C. Between Japan and Japan, the reaction time is preferably from 0.5 to 4 hours. Bran, dirty π A,…, and then add a pre-emulsion amount of a reactant providing a vinyl group and a polymerization inhibitor to p, and π y to an activated reactive dye reactant solution 'and seal it in a full N brother rain rat in a messy bottle. The reaction is performed at a predetermined temperature for a period of time, and the predetermined temperature may be about 50 to 50, and the reaction time is preferably 12 to 24 hours. From Doda I. HPLC results show that this method can obtain a product with a relatively high yield. The temperature and time used by the iron person, the field, etc. in the synthesis reaction depend on the reactants used in the preparation of the chromophore and the saccharin-early body compound. Commercially-available reactive dyes suitable for the above reactions include β- 13 200418631 sulfate-based ethyl stone wind (β-2004) with different substitution types containing water-soluble sulfonate groups (SlUf V uHonate grup). sulphatoethyl sulphone), the color index of this reactive dye can be listed, but not limited to c. L Reactive Yell〇w 14 C · I · Reactive Yellow 15, CI Reactive Yellow 17, C · I. Reactive Orange 7, C I. Reactive Orange 16, C. I ·

Reactive Orange 72 ^ C. I. Reactive Red 23 ^ C. I. Reactive

Red 49, C. I. Reactive Red 180, C. I. Reactive Blue 19 (RB 19), C. I. Reactive Blue 20, and C. I. Reactive Blue 21 (RB 21). These reactive dyes can be obtained from existing commercial products or can be prepared by conventional techniques in the field of organic synthesis. The structure of the vinyl-providing reactant used in the preparation of the reactive dye-monomer compound of the present invention should include a hydroxyl group (or an amine group) and a vinyl group (Vinyl group). A hydrophilic hydrophilicvinylic reactant. Suitable reactants for providing ethylene groups are copolymer monomers (Comonomers) containing ethylene hydrophilic reactants, which can be exemplified, but not limited to the following compounds: 2-Hhydroxyethyl methacrylate, HEMA), Hydroxylethyl acrylate, Methacrylamide, Acrylicacid, Vinyl alcohol, Vinyl pyridine, Vinyl pyridine j ( N-Vinylpyrrolidone), glycerol methacrylate, and the like. The alkaline substances used to promote the reaction may be exemplified by Ammonia, Triethyl amine, Alkaline metal hydroxide (such as sodium hydroxide), and Alkaline metal salts (such as sodium bicarbonate 14 200418631 (Sodium bicarbonate)). Its function is to first activate the reactive dye to convert β-sulfate ethyl sulfone into reactive vinyl sulfone. The molar equivalent added by the basic substance is preferably larger than the molar equivalent added by the reactive dye reactant in order to improve the efficiency and yield of the reaction. Generally, the molar ratio of the test substance to the reactive dye ranges from 1: 1 to 5: 1. However, the actual amount of test substance used will be very closely related to the strength of the test substance. In the foregoing reaction, one molecule of the reactive dye system is bonded to one molecule of a vinyl monomer (Vinylic monomer) (a reactant providing a vinyl group), and the bonding system is converted by the reactive dye The reactive vinyl sulfone group reacts with a hydroxyl group (Hydroxyl grOUp) on the ethylene-containing monomer. Therefore, the molar ratio of the reactive dye to the ethylene-containing monomer is preferably between 1: 1 and U in order to improve the efficiency and reaction rate of the reaction. The addition of a 'polymerization inhibitor' in the above reaction is to prevent the vinyl (νίηγ1 groups) from exhibiting an undesired preniature reaction during the synthesis. The polymerization inhibitor may be selected from at least one of the following compounds: hydroquinone, methyl hydroquinone, hydroq uinone monomethyl ether, Catechol and Pyrogallol. The polymerization inhibitor is added in an amount based on the weight of the unsaturated vinylic reactant, which is between 0.02% and 6%. In this synthetic reaction, the reaction conditions will be determined according to the selected reactive dyes and reactants that provide vinyl groups, although many dyes are auxiliary 15 200418631 sub-drugs, such as Dispersant, Salt Wetting agent (FiUlng agent), fixing agent (Fixing agent), etc., are often used in the bleaching process, but in the reactive dye-monomer (Dye_monomer) compound process of the present invention, do not need to add these Dyeing aids. Once the above synthesis reaction is completed, unwanted by-products, unreacted reactants, and water can be easily separated from the dye-early body product by conventional methods. The known methods referred to herein may be crystallization, extraction, filtration, and the like. The reactive dye-monomer compound prepared according to this method, after repeated operations according to the above separation method, and then analyzed by high performance liquid chromatography (HPLC), has a purity of at least 85%. The purity of this reactive dye 'monomer compound is greater than 80% *, which can be used to make dyed contact lens lenses without further purification. In the above reaction, it should be noted that the reactive dye selected and the reactant providing the vinyl group (for example, Hydrophiiic vinyl reactant) should be sufficiently dissolved in the aqueous solution. Before and after the reaction, both reactants should form a homogeneous aqueous solution. In addition, the method for manufacturing a color contact lens using a dye-monomer compound provided in the present invention is to perform a polymerization reaction on a lens-forming material, and inject the reactive dye-monomer compound prepared according to the above method into It is formed in lens forming material and then polymerized. The reactive dye-monomer compound is provided with a vinyl group (% groups) for reaction grafting, which can perform photo-initiated free radical polymerization reaction with acetamyl groups on a lens forming material (ph. t〇initiated radical polymerization). Wherein, the lens forming material may be ethyl 2-hydroxymethyl methacrylate (HEMA). 16 200418631 In this reaction, the amount of dye-monomer compound added is based on the hue and color required by the formulation of the lens, based on the weight of the lens-forming material, preferably 0.01% to 0.25%. between. Important ^ ^ ° Text, before or after curing, the dye-monomer compound should be completely and uniformly dissolved in the lens-forming material to avoid lens defects, for example, the lens color is uniform for two weeks 'Or the disadvantage of inconsistent hue of different batches of lenses. The colored contact lens formed according to the present invention has excellent stability after repeated tests of high-pressure hot salt bacteria treatment. The present invention is further described below with specific examples. The following examples are intended to clarify the present invention, but not to limit the scope of the present invention. Anyone skilled in organic synthesis technology can make partial modifications and changes without departing from the spirit and perspective of this creation. Any equivalent changes and modifications made in accordance with the scope of the patent application for this creation are covered by the patent for this invention range. Synthesis of reactive dye-monomer compound with reactive dye RB 19 '25 g of RB 19, 2 g of sodium argon oxide, and 500 g of distilled water were mixed in a 1-liter round-bottomed flask and stirred uniformly for 10 minute. After this uniformity, the temperature was raised to 40 ° C for 1 hour. Next, 8 g of HEMA and 0.02 g of hydroquinone were added to the aforementioned solution and stirred uniformly. This solution was reacted in an oil bath at 30 ° C for 24 hours. After that, it is cooled to the chamber ^ ', the product is dried under vacuum, and then the purification step is performed. This purification step is extraction with 95% ethanol, transition and vacuum drying, and the aforementioned purification steps are repeated to obtain the desired purity. The product produced by this synthesis reaction was a dark powder of about 丄 lg. Analysis of HpLc indicated that the purity of the purified product was close to 87%. 2 Synthesis of Reactive Dye-Monomer Compound with Reactive Dye RB 21 A mixture of 25 g of RB 21, 2 g of sodium hydroxide, and 500 g of distilled water was uniformly stirred in a 1-liter round-bottomed flask for 1 Q minutes. After this uniformity ', the temperature was raised to 400c for 1 hour. Next, 8 g of HEMA and 0.02 g of hydroquinone were added to the aforementioned solution and stirred uniformly, and this solution was reacted in an oil bath at 30 ° C for 24 hours. After that, the cold part was brought to room temperature, and the product was vacuum-dried, followed by a purification step. This purification step is performed according to the purification step in Example 1, extraction, filtration, and vacuum drying are performed repeatedly to obtain the desired purity. The product produced by this synthesis reaction was about 10 g of a dark powder. HPLC analysis indicated that the purity of the product after purification was close to 90%. "Imperial Golden Example" · Synthesis of reactive dyes with C · L Reactive Yellow 15 _ Monomer Compound A mixture of 25 g of reactive dye c. I. Reactive Yellow 15, 5 g of sodium carbonate and 5 g of steamed crane water in a 1 liter round bottom Flask 'evenly mix for 10 minutes. After mixing well, the temperature was increased to 400c for 1 hour. Next, 8 g of HEMA and 0.02 g of hydroquinone were added to the above solution and stirred uniformly. The solution was reacted in an oil bath at 30 ° C for 24 hours. After that, it was cooled to room temperature, the product was dried under vacuum, and then the purification step was performed. This purification step was performed in accordance with the purification step 18 200418631 in Example 丨, extraction, filtration, and vacuum drying were performed, and repeated to obtain the desired purity. The product produced by this synthesis reaction was about 8 g of yellow umbrella scorched HPLC. The purity of the purified product was close to 92%. The reaction dye was synthesized by C · I · Reactive Red 180. A mixture of 25 g of C. I. Reactive Red 180, 5 g of sodium carbonate, and 500 g of Luohe water was uniformly stirred in a 1-liter round-bottomed flask for 10 minutes. After mixing well, raise the temperature to 40 ° C for 1 hour. Next, 8 g of HEMA and 0.02 g of hydroquinone were added to the aforementioned solution and uniformly mixed. This solution was reacted in a 30aC oil bath for 24 hours. After that, the product was cooled to room temperature ', the product was dried under vacuum, and then the purification step was performed. This purification step is performed according to the purification steps in Example 丨, extraction, filtration, and vacuum drying are performed repeatedly to obtain the desired purity. The product produced by this synthesis reaction was about 7 g of a yellow powder. HPLC analysis indicated that the purity of the purified product was close to 93%. Example 5 Preparation of colored soft contact lens lenses The basic formulation of colored soft contact lens lenses is listed below: 55% moisture content, 100 parts of hydroxyethyl methacrylate (HEMA), 15 parts N-Vinyl pyrrolidone, 0.2 parts of 2-Chlorothioxanthone (phOtoinitiator), 1.2 parts of Methacrylic acid , 1.5 parts of ethylene glycol dimethacrylate (Ethylene glyc〇1 19 200418631 dimethacrylate) crosslinker (Crosslinker), 0.04 parts of the dye-monomer compound (as prepared in Examples 1-4), and 1 〇〇part of glycerin (Glycerin) 〇The above formula is in an ultrasonic tank, after sufficient mixing and filtering, placed in polystyrene lens molds, at 60 degrees Celsius A 250 Watt UV lamp is cured by irradiating UV light with a wavelength of 300 to 410 nanometers (nm) for 15 minutes. The total accumulated light energy is 1900 millijoules / cm 2 (mJ / cm2). After curing, the lens was removed from the k mold and washed in hot water at 80 ° C for 20 minutes to remove the unreacted diluent glycerol and unreacted residual constituents. Then at 25 C / f; f shows the hydration of the quasi-saline solution for 24 hours. Before and after autoclaving, the lenses synthesized by the above method were analyzed for their UV / VIS spectrum with a Perkin-Elmer uv-VIS 8453 Spectrophotometer. The UV / VIS spectrum of the lens is scanned from 190 to 1200 nm with a resolution of 1 nm.

Income. The lenses obtained above were subjected to autoclaving, here: at 2 atmospheres, operating β at 12rc, one autoclaving cycle took about 30 minutes. This color > _ Yi soft contact lens color fastness is evaluated after three high-pressure heat-extinguishing g treatment cycles, the test = the results are shown in Table 1. e strength), you measured it with an Instron tensile tester, and the repetition rate,% li / m, and wheat: the Strain rate was 50 / min (mm / min). And there are + r UL s', /, tensile test pieces with two shapes and sizes 20 200418631 The self-cured lens is rolled out (Die-cut), and the cross-sectional area of the sample is measured. The obtained tensile strength and strain are shown in Table 1. Table 1: Properties of colored soft contact lens lenses prepared by the present invention. Dye-monomer compound moisture content (%) Lens diameter (mm) # Tensile strength (Kg / cm2) * Elongation (%) Color stability Property + Example 1 55.1 (0.9) $ 14.1 2.1 120 ± 12 Stable Example 2 54.6 (0.8) 14.0 2.2 118 ± 10 Stable Example 3 54.8 (0.7) 14.0 2.1 121 ± 13 Stable Example 4 54.3 (0.9) 14.1 2.1 122 + 12 Stable control group (without added dye-monomer compounds) 55.2 (0.7) 14.1 2.2 126 ± 11 (): Standard deviation. The confidence interval of 99% of the lens diameter is less than ± 0.2 mm. The standard deviation of tensile strength is less than 0.2 Kg / cm2. Stable: No significant fading and / or removal of the dye after autoclaving cycles. 21 200418631 [Schematic description] None

twenty two

Claims (1)

200418631 Patent application scope: 1. A reactive dye-monomer compound (reactive dye-monomer compound), which can be used to prepare color lenses, the reactive dye-monomer compound contains at least one absorbing color group ( c〇1〇r absorbing moiety) and an unsaturated vinyl group ° 2 · Reactive dye-monomer compounds such as the scope of application for patent x, in which the absorbing color group is derived from Reactive dye. 3. The reactive dye-monomer compound according to item 2 of the patent application range, wherein the reactive dye is a β-sulfate-based ethyl stone wind (p) which is water-soluble and contains at least a sulfonate group. -suiphat〇ethyl sulphone) and its derivatives. 4. The reactive dye-monomer compound according to item 3 of the patent application scope, wherein the color index of the reactive dye is CI Reactive Yellow 14, CI Reactive Yellow 15, C.I. Reactive Yellow 17, C. I. Reactive Orange 7, C. I. Reactive Orange 16, C. I. Reactive Orange 72, C. I. Reactive Red 23, C. I. Reactive Red 49, C. I. Reactive Red 180, C. Selected from the group consisting of I · Reactive Blue 19, C · I · Reactive Blue 20, and C · I · Reactive Blue 21. 5. The reactive dye-monomer compound according to item 3 of the patent application scope, wherein the color index of the reactive dye is CI Reactive Yellow 15, C. I. Reactive Red 180, C. I. Reactive Blue 19 and C · I · Reactive Blue 21. 23 200418631 6. The reactive dye-monomer compound according to item i of the patent application, wherein the unsaturated reactive vinyl is derived from a hydrophilic vinylophilic monomer. 7. The reactive dye-monomer compound according to item 6 of the application, wherein the hydrophilic vinyl-containing monosystem is an acrylate or a methacrylate. 8. The reactive dye-monomer compound according to item 6 of the application, wherein the hydrophilic vinyl-containing monomer system is composed of 2-hydroxyethyl methacrylate, acrylic acid via ethyl, methacrylamide, and acrylic acid. , Vinyl alcohol, vinyl stone fluorene, ethynolone, and glyceryl methacrylate. 9. The reactive dye-monomer-compound according to the item of the scope of application for a patent, wherein the reactive dye-monomer compound can be covalently bonded to the lens material through a polymerization process. 10. The reactive dye-monomer compound according to item 9 of the application, wherein the lens material is a soft contact lens material. 11. The reactive dye-monomer compound according to item 1 of the application, wherein the lens is a soft contact lens. a 12. A method for manufacturing a reactive dye-monomer compound, which can be used to prepare colored lenses, the method includes at least the following steps: (a) obtaining a predetermined amount of reactive dye; b) mixing a predetermined amount of a basic substance with the reactive dye to activate the reactive dye at a predetermined temperature for a predetermined time; (c) a predetermined amount of a reactant providing a vinyl group and a predetermined amount of ❸ The polymerization inhibitor is added to the activated reactive dye solution: 24 200418631 to perform the reaction; (d) recovering the reactive dye-monomer compound obtained by the reaction. 13. The method for manufacturing a reactive dye-monomer compound as described in item 12 of the scope of application for a patent, wherein the reactive dye is a β-sulfate ethyl code and Selected from a group of derivatives. 14. The method for manufacturing a reactive dye-monomer compound as described in item 12 of the scope of application for a patent, wherein the color index of the reactive dye (c0100r Index) is determined by C · I · Reactive Yellow 14, C L Reactive Yellow 15 ^ CI Reactive Yellow 17 > C. L Reactive Orange 7, C. I. Reactive Orange 16, C. I. Reactive Orange 72, C. I. Reactive Red 23, C. I. Reactive Red 49 , C. I. Reactive Red 180 ^ CI Reactive Blue 19 > CI Reactive Blue 20, and c. I. Reactive Blue 21. 15. The method for manufacturing a reactive dye-monomer compound as described in item 12 of the scope of application for a patent, wherein the color index of the reactive dye (c0100r Index) is determined by CI Reactive Yellow 15, C · I · Selected from the group consisting of Reactive Red 180, C.I. Reactive Blue 19, and CI Reactive Blue 21. 16. The reactive dye-monomer compound method according to item 12 of the scope of the patent application, wherein the basic substance is a group consisting of ammonia, triethylamine, alkali metal hydroxide, and alkali metal salts. Selected in the group. 17. The method for producing a reactive dye-monomer compound according to item 16 of the scope of the patent application, wherein the basic substance is sodium hydroxide or sodium carbonate. 25 20041863 lS. The method for reacting a dye-monomer compound as described in item 12 of the scope of patent application, wherein the molar ratio of the basic substance to the reactive dye is 1: 1 to 5: 1. 19. The method of the reactive dye-monomer compound as described in item 12 of the scope of the patent application, wherein the predetermined temperature of (b) is 30 to 80 ° C. 20. The method for manufacturing a reactive dye-monomer compound as described in claim 12 of the patent scope, wherein the predetermined reaction time of (b) is 0.4 to 4 hours. 21. The method for producing a reactive dye-monomer compound as described in item 12 of the scope of patent application, wherein the reactant for providing a vinyl group is a hydrophilic vinyl-containing monomer. 22. The method for manufacturing a reactive dye-monomer compound as described in item 21 of the scope of patent application, wherein the hydrophilic vinyl-containing monosystem is composed of hydroxyethyl methacrylate, hydroxyethyl acrylate, and methacrylic acid Selected from the group consisting of amine, acrylic acid, ethylene alcohol, ethylene ^, ethylene fluorene, and glycerol methyl acrylate. 23. The method for manufacturing a reactive dye-monomer compound as described in item 12 of the scope of the patent application, in which the molar ratio of the reactive dye to the ethylenically-reactive reactant is 1: 1 to 1: 5 . 24. The method for producing a reactive dye-monomer compound as described in item 12 of the scope of the patent application, wherein the polymerization inhibitor is composed of hydroquinone, methyl hydroquinone, methyl hydroquinone, Selected from the group consisting of catechins and gallops. It is the "method for producing a reactive dye-monomer compound as described in Item 12 of the scope of the patent application", wherein the polymerization inhibitor is added in an amount of 0.02% by weight to the weight of the reactant that provides ethylene. 26 26. Production of reactive dye monomers 27 &, 'such as compound No. Dj, +, and η of the patent application range, wherein the reaction temperature of (C) is from room temperature to 50. (: The method for manufacturing a reactive dye-monomer product as described in item 12 of the patent application scope, wherein the reaction time of fluorene is "hours. The manufacturing reactive type as described in item 12 of each patent application scope Dye and material list: 'wherein (d) the recovery step further includes a step of purifying the dyed precursors to achieve the desired purity of the dye-monomer compound 0, The method for manufacturing reactive dyes-monomers and daggers according to item 28 of the stated patent, wherein the steps of purifying the dye-monomer compounds include alcohol extraction, filtration, and vacuum drying. 30. A method for manufacturing a color contact lens using a reactive dye-monomer compound, comprising at least the following steps: (1) obtaining a predetermined amount of a reactive dye-monomer compound, the reactive dye-monomer compound comprising At least one absorbing color group and an unsaturated reactive vinyl group; (2) Dissolve and mix a predetermined amount of the lens-forming material solution with the reactive dye-monomer compound; (3). Make the mixed solution of (b) solidify in the mold; (4) Wash to remove Remove the unreacted ingredients. 31. The method for manufacturing a color contact lens using a reactive dye-monomer compound as described in item 30 of the scope of the patent application, wherein the curing reaction is curing by ultraviolet light irradiation. 32. The method for manufacturing a color contact lens using a reactive dye-monomer compound as described in item 30 of the scope of the patent application, wherein the reactive dye 27 200418631 material-monomer compound is added to the weight of the lens forming material 0.001% to 0.25%. 33. The method for producing a color contact lens using a reactive dye-monomer 'compound as described in item 30 of the scope of the patent application, wherein the lens forming material comprises a hydrophilic vinyl-containing monomer. 34. The method for manufacturing a color contact lens using a reactive dye-monomer compound as described in item 30 of the scope of the patent application, wherein the lens-forming material comprises ethyl 2-hydroxymethacrylate (ΗΕΜΑ). 35. A color contact lens _ mirror lens made by using a reactive dye-monomer compound, the reactive dye-monomer compound includes at least one color-absorbing group and an unsaturated reactive vinyl group. 36. The color contact lens lens manufactured by using a reactive dye-monomer compound as described in item 35 of the patent scope of claim 2, wherein the lens forming material of the color contact lens comprises a hydrophilic vinyl-containing monomer. 37. The color contact lens lens manufactured by using the reactive dye-monofluorene compound as described in item 35 of the application patent scope, wherein the lens forming material package of the color contact lens will be 2 ^ 3 hydroxy methacrylic acid Ethyl ester W (HEMA) 〇28 200418631 柒. Designated representative map: (1) The designated representative map in this case is: None. (2) Brief description of the representative symbols of the components in this representative diagram: None. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: