CN101573222A - Colorants for use in tinted contact lenses and methods for their production - Google Patents
Colorants for use in tinted contact lenses and methods for their production Download PDFInfo
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- CN101573222A CN101573222A CNA2007800490761A CN200780049076A CN101573222A CN 101573222 A CN101573222 A CN 101573222A CN A2007800490761 A CNA2007800490761 A CN A2007800490761A CN 200780049076 A CN200780049076 A CN 200780049076A CN 101573222 A CN101573222 A CN 101573222A
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Abstract
The present invention relates to compositions comprising a light absorbing prepolymer having a molecular weight of between about 7,000 and about 100,000 and polymeric units derived from and least one reactive colorant and monomers selected from the group consisting of hydrophilic monomers, hydrophobic monomers and mixtures thereof. The compositions of the present invention are useful for the manufacture of ophthalmic devices, including contact lenses.
Description
Invention field
The present invention relates to be used to make the coloring agent of tinted contact lenses.Specifically, the invention provides a kind of coloring agent that is used to make the one step process of contact lens dyeing and is used for described method.
Background of invention
The natural color of using tinted contact lenses to change iris is familiar with by us.Usually, the coloured portions of eyeglass is positioned at the center of eyeglass, just that part of the overlapping eyeglass wearer's of eyeglass pupil and iris.Whole eyeglass can slightly dye and also is familiar with by us into observability or positioning dyeing in contact lens dyeing.
The coloring agent that is used to make tinted lens generally is made up of adhesive polymer and pigment.In order to form stable tinted lens, known coloring agent need form covalent bond with crosslinking agent between lens materials and adhesive polymer." stable tinted lens " is meant not from the eyeglass bleeding or fades or be seeped into another part from a part of eyeglass.In addition, in some known methods that form tinted lens, need before being added on the eyeglass, coloring agent form the eyeglass body.Additive method and coloring agent need separately or close a plurality of steps of use with special-purpose loops, so that the Outboard Sections of eyeglass is protected under coloring agent.
Therefore, known coloring agent and the method for making tinted lens introduced general eyeglass manufacture process with one of extra time and additional materials or both.Therefore, the method that needs to eliminate the coloring agent of some or all of these shortcomings and make contact lens with coloring agent.
Detailed Description Of The Invention and preferred embodiment
The invention provides the method that is used to make the coloring agent of tinted contact lenses and makes contact lens dyeing with coloring agent of the present invention.Coloring agent of the present invention in the mode that produces finished product eyeglass with coloring agent with high-resolution printed patterns image when lens materials is transferred on the mould surface.
In one embodiment, the invention provides a kind of coloring agent that is used to make contact lens dyeing, described coloring agent comprises one or more light absorption prepolymers, is made up of one or more light absorption prepolymers substantially and is made up of one or more light absorption prepolymers.In another embodiment, the invention provides a kind of method of making tinted contact lenses, said method comprising the steps of, be made up of following steps substantially and be made up of following steps: at least a coloring composition of the effective dose that a) will dye is applied to the molded surface of mould, and described coloring composition comprises at least a light absorption prepolymer; B) lens materials with eyeglass formation amount is assigned in the mould; C) make coloring composition swelling in lens materials, and make lens materials diffuse into coloring composition; And d) under the condition that is fit to the formation tinted contact lenses, lens materials is solidified in mould.In another embodiment, the invention provides a kind of mould that is used to make tinted contact lenses, described mould comprises first half module and second half module, is made up of first half module and second half module substantially and is made up of first half module and second half module, wherein at least one molded surface of first half module and second half module comprises coloring composition, is made up of coloring composition substantially and is made up of coloring composition, described coloring composition comprises one or more light absorption prepolymers, and wherein said light absorption prepolymer can form interpenetrating polymer networks with lens materials.
According to the invention is intended to, " interpenetrating polymer networks " or " IPN " is defined as the combination of wherein a kind of polymer two or more synthetic and/or crosslinked independent polymers in the presence of another kind of polymer.Therefore, in network structure, there is certain IPN degree.The used independent polymers of general formation IPN is a latticed form.One type IPN (being specially half IPN) is made up of one or more crosslinked polymer and the not crosslinked polymer of one or more essence, as " Interpenetrating Polymer Networks:An Overview " (interpenetrating polymer networks: overview), Sperling, L.H., Interpenetrating Polymer Networks, Klempner, Sperling and Utracki edit, and pp 3-6 (1994) is described.According to the invention is intended to, used interpenetrating polymer networks type is half IPN.In one embodiment, half IPN forms with crosslinked lens materials and the coloring composition that comprises the not crosslinked light absorption prepolymer of at least a essence.According to the invention is intended to, essence is not crosslinked be meant with uncrosslinked material before lens materials contacts without the crosslinked condition of routine.Half IPN can form in a step, or forms (being also referred to as sequence half IPN) in a sequence step.Those of ordinary skill in the art it should be understood that this environment helps forming the sequence interpenetrating polymer networks by adding or existing crosslinking agent can produce a kind of reaction environment as impurity.
According to the invention is intended to, " molded surface " is meant the mould surface that is used to form lens surface.
Light absorption prepolymer of the present invention can be formed by any monomer of making ophthalmic device (being contact lens in one embodiment) that is applicable to.For example, the light absorption prepolymer can be generated by the monomer that comprises hydrophilic monomer, hydrophobic monomer and composition thereof.The hydrophilic monomer that one class is fit to comprises acrylic compounds or contains the monomer of vinyl.Term " vinyl type " or " containing vinyl " monomer are meant and comprise vinyl (CH=CH
2) monomer, and be generally high activity.Known this type of hydrophilic polymerisation of vinyl-containing monomers is relatively easy.
" acrylic-type " or " containing acrylic compounds " monomer is for containing acrylic groups (CH
2=CRCOX) those monomers of same known easy polymerization, wherein R is H or CH
3, X is O or N, as N,N-DMAA (DMA), 2-hydroxyethyl methacrylate (HEMA), glyceral methacrylate, 2-hydroxyethyl Methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid and acrylic acid.
The hydrophilic vinyl-containing monomers that can incorporate light absorption prepolymer of the present invention into comprises for example monomer of N-vinylamide, N-vinyl lactam (for example NVP), N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl-formamide, N-vinyl formamide, and NVP is preferred.
Other hydrophilic monomers that can use in the present invention comprise the polyoxyethylene polyols that replaces one or more terminal hydroxyls with the functional group that contains polymerizable double bond.Example comprises with one or more molar equivalent end-capping groups (as methacrylic acid isocyanate group ethyl ester (" IEM "), methacrylic anhydride, methacrylic chloride, vinyl benzene formyl chloride etc.) reaction has one or more terminal polymerizable alkylene hydrocarbyl groups to be attached to polyethylene glycol, ethoxylated alkyl glucoside and the ethoxylation bisphenol-A of polyethylene polyalcohol by coupling part (as carbamate groups or ester group) with generation.
Further example is a United States Patent (USP) 5,070,215 disclosed hydrophilic carbon vinyl acetates or carbamic acid vinyl acetate monomer and United States Patent (USP) 4,910,277 disclosed close water azolactone monomers.Other hydrophilic monomers that are fit to are apparent to those skilled in the art.
In one embodiment, hydrophilic monomer comprises for example DMA, HEMA, glyceral methacrylate, 2-hydroxyethyl Methacrylamide, NVP, N-vinyl-N methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid and acrylic acid at least a hydrophilic monomer, and DMA is most preferred.
According to the concrete balance of required character, the amount that hydrophilic monomer can wide region is present in the light absorption prepolymer.Can accept based on used all components about 10 to the hydrophilic monomer of about 100% weight of preparation light absorption prepolymer, about in some embodiments 1 to about 50% weight, and about in other embodiments 1 to about 30% weight.
When ophthalmic device is the silicone hydrogel contact lens, can desirably comprises at least a hydrophobic components and (in some embodiments) at least a component that contains polysiloxanes and prepare the light absorption prepolymer as monomer.The one class hydrophobic monomer that can comprise is for comprising " component that contains polysiloxanes " of at least one [Si-O-].The O of preferred all Si and combination is present in greater than the amount of about 20% weight and contains in the polysiloxanes component to contain polysiloxanes component total molecular weight, more preferably greater than 30% weight.The available polysiloxanes component that contains is a simple function, preferably comprises a polymerizable functional group, as acrylate, methacrylate, acrylamide, Methacrylamide, vinyl, N-vinyl lactam, N-vinylamide and styryl functional group.What be fit to contains the compound that the polysiloxanes component comprises formula I
Wherein
R
1Independently be selected from unit price active group, monovalent alkyl or unit price aryl; Any aforementioned group that can further comprise the functional group that is selected from hydroxyl, amino, oxa-, carboxyl, alkyl carboxyl, alkoxyl, acylamino-, carbamate, carbonic ester, halogen or its combination; With the monovalent siloxane chain that comprises 1-100 Si-O repetitive, described monovalent siloxane chain can further comprise the functional group that is selected from alkyl, hydroxyl, amino, oxa-, carboxyl, alkyl carboxyl, alkoxyl, acylamino-, carbamate, halogen or its combination;
Wherein b=0 to 500 should be appreciated that at this, and when b was not 0, b was the distribution with the model that equals described value;
One of them R
1Comprise the unit price active group.
" unit price active group " used herein is can be through the group of free radical and/or cationic polymerization.The unrestricted example of free radical activity group comprises (methyl) acrylate, styryl, vinyl, vinyl ethers, (methyl) acrylic acid C
1-6Arrcostab, (methyl) acrylamide, C
1-6Alkyl (methyl) acrylamide, N-vinyl lactam, N-vinylamide, C
2-12Thiazolinyl, C
2-12Thiazolinyl phenyl, C
2-12Thiazolinyl naphthyl, C
2-6Thiazolinyl phenyl C
1-6Alkyl, O-vinyl carbamate and O-vinyl carbonic ester.The unrestricted example of cation activity group comprises vinyl ethers or epoxy radicals and composition thereof.In one embodiment, the free radical activity group comprises (methyl) acrylate, acryloxy, (methyl) acrylamide and composition thereof.
The monovalent alkyl and the aryl that are fit to comprise unsubstituted unit price C
1To C
16Alkyl, C
6To C
14Aryl is as replacing and unsubstituted methyl, ethyl, propyl group, butyl, 2-hydroxypropyl, propoxyl group propyl group, polyethyleneoxy propyl group, it makes up etc.
In one embodiment, b is 0, one R
1Be the unit price active group, at least 3 R
1Be selected from monovalent alkyl, be selected from monovalent alkyl in another embodiment with 1 to 6 carbon atom with 1 to 16 carbon atom.The unrestricted example of the polysiloxanes component of this embodiment comprise the 2-methyl-, 2-hydroxyl-3-[3-[1,3,3,3-tetramethyl-1-[(trimethyl silyl) oxygen base] disiloxanyl] propoxyl group] propyl diester (" SiMMA "), 2-hydroxy-3-methyl acryloxy propyl group oxygen base propyl group-three (trimethylsiloxy) silane, 3-methacryloxypropyl three (trimethylsiloxy) silane (" TRIS "), two (trimethylsiloxy) methyl-monosilanes of 3-methacryloxypropyl, 3-methacryloxypropyl pentamethyl disiloxane and combination thereof.
In another embodiment, b is 2 to 20,3 to 15, or in some embodiments 3 to 10; At least one terminal R
1Comprise the unit price active group, all the other R
1Be selected from monovalent alkyl, be selected from monovalent alkyl in another embodiment with 1 to 6 carbon atom with 1 to 16 carbon atom.In another embodiment, b is 3 to 15, one terminal R
1Comprise the unit price active group, other terminal R
1Comprise monovalent alkyl, all the other R with 1 to 6 carbon atom
1Comprise monovalent alkyl with 1 to 3 carbon atom.The unrestricted example of the polysiloxanes component of this embodiment comprises polydialkysiloxane, as the dimethyl silicone polymer (800-1000MW) (" mPDMS ") of (dimethyl silicone polymer (400-1000MW) of list-(2-hydroxy-3-methyl acryloxy propyl group)-propyl ether end-blocking) (" OH-mPDMS "), monomethyl acryloxy propyl group end-blocking list normal-butyl end-blocking.
In another embodiment, b is 5 to 400 or 10 to 300, two terminal R
1Include the unit price active group, all the other R
1Independently be selected from the monovalent alkyl with 1 to 18 carbon atom, described monovalent alkyl can have ehter bond between carbon atom, and can further comprise halogen.
In another embodiment, 1 to 4 R
1The ethylene carbonate or the carbamic acid ethene ester that comprise following formula:
Formula II
Wherein:
Y represents O-, S-or NH-;
R represents hydrogen or methyl;
D is 1,2,3 or 4; And
Q is 0 or 1.
The ethylene carbonate or the carbamic acid vinyl acetate monomer that contain polysiloxanes specifically comprise 1, two [4-(the vinyl oxygen base ketonic oxygen base) fourth-1-yl] tetramethyl-disiloxane of 3-; 3-(vinyl oxygen base carbonyl sulfenyl) propyl group-[three (trimethylsiloxy) silane]; 3-[three (trimethylsiloxy) silicyl] propyl group allyl amino formic acid esters; 3-[three (trimethylsiloxy) silicyl] propyl vinyl carbamate; Trimethyl silyl ethyl vinyl carbonic ester; Trimethyl silyl methyl ethylene carbonic ester.
In one embodiment, generate the used component of prepolymer and be selected from the used component of manufacturing ophthalmic device.In another embodiment, ophthalmic device is formed by silicone hydrogel, and the light absorption prepolymer comprise at least a 2-of being selected from methyl-, 2-hydroxyl-3-[3-[1,3,3,3-tetramethyl-1-[(trimethyl silyl) oxygen base] disiloxanyl] propoxyl group] propyl diester (" SiMMA "), 2-hydroxy-3-methyl acryloxy propyl group oxygen base propyl group-three (trimethylsiloxy) silane, 3-methacryloxypropyl three (trimethylsiloxy) silane (" TRIS "), two (trimethylsiloxy) methyl-monosilanes of 3-methacryloxypropyl, 3-methacryloxypropyl pentamethyl disiloxane, (dimethyl silicone polymer (400-1000MW) of list-(2-hydroxy-3-methyl acryloxy propyl group)-propyl ether end-blocking) (" OH-mPDMS "), the dimethyl silicone polymer (800-1000MW) of monomethyl acryloxy propyl group end-blocking list normal-butyl end-blocking, its mixture etc. contain the polysiloxanes component.In another embodiment, the light absorption prepolymer comprises the repetitive of dimethyl silicone polymer (800-1000MW) derived from 3-methacryloxypropyl pentamethyl disiloxane, (dimethyl silicone polymer (400-1000MW) of list-(2-hydroxy-3-methyl acryloxy propyl group)-propyl ether end-blocking) (" OH-mPDMS "), monomethyl acryloxy propyl group end-blocking list normal-butyl end-blocking, its mixture etc.
The light absorption prepolymer also can comprise at least a vital staining agent that is covalently bound to above it.The vital staining agent can be added to and generate the used active mixture of light absorption prepolymer, perhaps can be grafted to the prepolymer main chain.In one embodiment, the light absorption prepolymer is grafted on the prepolymer main chain.A lot of light-absorbing compounds are huge, and have relatively slow reaction rate.In these embodiments, grafting allows to prepare the prepolymer main chain with the molecular weight distribution of catering to the need with the reaction condition of certain limit.Therefore, the vital staining agent of Shi Heing comprises active group.
Can use any can non-essence makes the coloring agent of vital staining agent intensity or tone degradation to comprise active group through modification.The coloring agent compound that is fit to comprises vinyl sulfone dyestuff, phthalocyanine dye, halo triasine dyes, chloro acetyl group dyestuff, α-bromocryloyl dyestuff, its combination etc.In one embodiment, the coloring agent compound comprises at least a vinyl sulfone, chloro triazine and composition thereof.But can use any can with monomer in the active mixture or with prepolymer on any reactive functionality reactive activity group.The active group that is fit to can be selected according to the used monomer of preparation adhesive polymer by those skilled in the art easily.For example, add the embodiment of active mixture, can comprise the free radical activity group with the preparation prepolymer for the vital staining agent.Want grafting to be attached in the embodiment of prepolymer in the vital staining agent, can select the suitable active group in the vital staining agent, with prepolymer on utilized radical reaction.For example, if prepare prepolymer with 2-hydroxyethyl methacrylate as monomer, then the active group in the vital staining agent is selected from the active group that forms covalent bond with hydroxyl, for example ester or acid.Other suitable groups that are used for grafting comprise the group that can pass through condensation type reaction, nucleophilic aromatic substitution reaction, the addition reaction of Michael type, traditional SN2 reaction etc.In one embodiment, coloring agent comprises at least a vinyl sulfone, and vinyl sulfone is grafted on the prepolymer main chain by the addition reaction of Michael type.
The instantiation that is fit to the vital staining agent comprises the C.I. reactive black 5, C.I. reactive black 14, C.I. active blue 19, C.I. reactive blue 20, C.I. REACTIVE Blue 21, C.I. reactive blue 27, C.I. reactive blue 28, C.I. reactive blue 37, C.I. reactive blue 38, C.I. reactive orange 7, C.I. reactive orange 14, C.I. reactive orange 15, C.I. reactive orange 16, C.I. reactive orange 23, C.I. reactive orange 24, C.I. reactive orange 78, C.I. reactive yellow 13, C.I. active 14, C.I. reactive yellow 15, C.I. reactive yellow 17, C.I. reactive yellow 23, C.I. reactive yellow 24, C.I. reactive yellow 37, C.I. reactive yellow 42, C.I. reactive red 21, C.I. reactive red 22, C.I. reactive red 23, C.I. reactive red 34, C.I. Reactive Red 35, C.I. reactive red 36, C.I. reactive red 49, C.I. reactive red 50, C.I. reactive red 63, C.I. reactive red 64, C.I. reactive red 180, C.I. reactive violet, C.I. Reactive Violet 5, C.I. active palm fibre 16, with be disclosed in US 7,060,829, US 6,689,828, US 5, those coloring agents of 944,853 (its disclosure is attached to herein by reference), its combination etc.
In another embodiment, the vital staining agent comprises at least a active photochromic compound, and is disclosed as PCT/US2006/013005.
The vital staining agent is contained in the light absorption prepolymer with the amount (" dyeing effective dose ") that required color and color intensity effectively are provided.The amount of vital staining agent is with the Strength Changes of vital staining agent, more by force, stronger coloring agent uses with the littler concentration of more weak coloring agent.For the vital staining agent, as vinyl sulfone, about 0.2 is enough to the amount of about 25% weight vital staining agent in light-absorbing polymers.In one embodiment, the light absorption prepolymer can add based on the amount of light absorption prepolymer weight about 1 to about 10% weight.Can use the combination of a certain proportion of vital staining agent according to required color, the depth and tone.
A discovery of the present invention is, by using the light absorption prepolymer that can form interpenetrating polymer networks with lens materials, can get rid of and forms covalent bond form the needs of stablizing tinted lens between coloring agent and lens materials.The stability of tinted lens is tangled by light absorption prepolymer and eyeglass base polymer and is provided.
Light absorption prepolymer of the present invention is used to have the homopolymers of similar solubility parameter or copolymer or its combination to lens materials and makes.These light absorption prepolymers can comprise make prepolymer can with self and the interactional functional group of lens materials.Interaction between the functional group can be shifted recombination property for polarity, dispersiveness or electric charge.Functional group can be positioned on polymer or the copolymer chain, perhaps can dangle from main chain.
For example, in order to generate the light absorption prepolymer, the mixture that generates a kind of monomer of the polymer with positive charge or monomer can be used in combination with one or more monomers that generation has a polymer of negative electrical charge.As example more specifically, available methacrylic acid (" MAA ") and 2-hydroxyethyl methacrylate (" HEMA ") provide MAA/HEMA copolymer, mix with HEMA/3-(N, N-dimethyl) propyl group acrylamide copolymer then, to generate adhesive polymer.
The molecular weight of light absorption prepolymer must make it be dissolved in lens materials and swelling therein a little.Lens materials diffuses into the light absorption prepolymer, polymerization and/or crosslinked.Yet the molecular weight of light absorption this moment prepolymer can not highly must influence the quality of printing image.The molecular weight that preferred light absorbs prepolymer is about 7,000 to about 100,000, and more preferably from about 7,000 to about 65,000, and most preferably from about 15,000 to about 55,000M
The peak, be equivalent to top molecular weight (=(M in SEC analyzes
n* M
w)
1/2).
According to the invention is intended to, use the gel permeation chromatography molecular weight, and utilize 90 ° of light scattering and refractive index detector.Two post PW4000 and PW2500 are adjusted to 75/25 w/w methanol-water eluent of 50mM sodium chloride, use polystyrene as reference material.
Those of ordinary skill in the art will be appreciated that, by in the preparation of light absorption prepolymer, using chain-transferring agent, by using a large amount of initators, by using living polymerization, by monomer and the initiator concentration of selecting to be fit to, amount and type or its combination by selective solvent can obtain required light absorption prepolymer molecular weight.The preference chain transfer agent is used in combination with initator, or more preferably is used in combination with initator and one or more solvents, to obtain required molecular weight.Perhaps, a spot of high molecule light absorption prepolymer can be used in combination with a large amount of solvents, to keep the required viscosity of light absorption prepolymer.
Generate the used chain-transferring agent of light absorption prepolymer in the present invention and have greater than about 0.01 chain and shift steady state value, be preferably greater than about 7, more preferably greater than about 25,000.This type of chain-transferring agent that is fit to is known, includes but not limited to that (wherein R is C to formula R-SH
1To C
12Aliphatic group, benzyl, alicyclic group) or CH
3(CH
2)
xAliphatic mercaptan, benzene, n-butyl chloride, tertiary butyl chloride, n-butyl bromide, 2 mercapto ethanol, 1-dodecyl mercaptans, Sec-Butyl Chloride, acetone, acetate, chloroform, butylamine, triethylamine, di-n-butyl thioether and di-n-butyl two sulphur, carbon tetrachloride and the carbon tetrabromide of-SH (wherein x is 1 to 24) (carbon tetrachloride and bromide) etc. and combination thereof.Usually use based on polymer formulations gross weight about 0 to about 7% weight.Preferably use dodecyl mercaptans, decyl mercaptan, spicy thioalcohol or its combination as chain-transferring agent.
Any desirable initator be can use, ultraviolet initiator, visible light initiator, thermal initiator etc. and combination thereof included but not limited to.The preferred thermal initiator that uses, more preferably 2,2-azobis isobutyronitrile and 2, the two 2-methylbutyronitriles of 2-azo.The amount of used initator is to about 5% weight based on total formulation weight amount about 0.1.2, the two 2-methylbutyronitriles of 2-azo preferably use with dodecyl mercaptans.
Light absorption prepolymer of the present invention be can prepare by suitable polymerization, radical chain polymerization, progressively polymerization, emulsion polymerisation, ion chain polymerization, open loop, GTP, atom transfer polymerization etc. included but not limited to.The preferred heat of using causes radical polymerization.The condition of carrying out polymerization is in those of ordinary skills' ken.
The used solvent of preparation light absorption prepolymer is that boiling point about 120 is to about 230 ℃ medium-boiling solvent.The selection of solvent for use is based on the light absorption prepolymer type and the molecular weight thereof that will prepare.The solvent that is fit to includes but not limited to diacetone alcohol, cyclohexanone, isopropyl lactate, 3-methoxyl group 1-butanols, 1-ethyoxyl-2-propyl alcohol, N, dinethylformamide, methyl pyrrolidone etc.
With regard to regard to the expansion factor in the water, light absorption prepolymer of the present invention should adapt to the lens materials that uses together.The expansion factor of light absorption prepolymer with fill the expansion factor coupling of solidifying lens materials in the solution or essence coupling and avoid causing the generation of the eyeglass internal stress that bad optics and lens parameters shift.In addition, the light absorption prepolymer must can be in lens materials swelling, to allow image swelling with coloring agent printing of the present invention.Because this swelling, image become be retained in the lens materials and to the eyeglass comfortableness without any influence.
Except the light absorption prepolymer, coloring composition of the present invention also comprises one or more and helps coloring composition to be coated to lip-deep solvent.Another discovery of the present invention is, guarantee the coloring composition indiffusion or moves on the surface that it applies, and caters to the need and preferred coloring composition has the surface tension that is lower than about 27mN/m.Can obtain this surface tension by surface treatment, for example handle the mould surface that will apply coloring agent.Can carry out surface treatment by methods known in the art, as but be not limited to plasma and sided corona treatment.Perhaps also preferably obtain required surface tension by the used solvent of selective staining agent composition.
Therefore, the used solvent of coloring composition of the present invention is those solvents that can increase or reduce coloring agent viscosity and help control surface tension force.The solvent that is fit to includes but not limited to cyclopentanone, 4-methyl-2 pentanone, 1-methoxyl group-2-propyl alcohol, 1-ethyoxyl-2-propyl alcohol, isopropyl lactate, N, dinethylformamide, methyl pyrrolidone etc. and combination thereof.Preferred use 1-ethyoxyl-2-propyl alcohol, isopropyl lactate, N, dinethylformamide, methyl pyrrolidone and combination thereof.
In another embodiment, in coloring composition of the present invention, use at least three kinds of different solvents.Preceding two kinds (being medium-boiling solvent) of these solvents are used to prepare adhesive polymer.Though can after generation, slough these solvents, preferably they be kept from adhesive polymer.Preferred medium-boiling solvent is selected from 1-ethyoxyl-2-propyl alcohol, isopropyl lactate, N, dinethylformamide, methyl pyrrolidone and composition thereof.Other low boiling point solvent (refer to boiling point be about 75 ℃ to about 120 ℃ solvent) be used for reducing as required the viscosity of coloring agent.The low boiling point solvent that is fit to includes but not limited to 2-propyl alcohol, 1-methoxyl group-2-propyl alcohol, 1-propyl alcohol etc. and combination thereof.The preferred 1-propyl alcohol that uses.
The concrete amount of solvent for use depends on multiple factor.For example, the amount of generation adhesive polymer solvent for use depends on the molecular weight and the used component of adhesive polymer (as monomer and copolymer) of required adhesive polymer.The amount of used low boiling point solvent depends on viscosity and the surface tension that coloring composition is required.In addition, if the light absorption prepolymer is applied on the mould and solidifies with lens materials, the amount of solvent for use depends on used eyeglass and mold materials and whether mold materials has passed through surface treatment to increase its wettability.The accurate amount of determining solvent for use is in those of ordinary skills' technical scope.Usually, the gross weight of solvent for use for the solvent that will use about 40 to about 75% weight.
Except solvent, also can and preferably at least a plasticizer be joined coloring composition, to reduce cracking between coloring composition and optical mode plastic dry period, improve the final quality of the image that produces with coloring composition and strengthen lens materials diffusion and swelling coloring agent.The type of used plasticizer and amount depend on the molecular weight of used light absorption prepolymer and required pot-life stability (for the coloring composition on the mould of placing that stores before use).Used plasticizer includes but not limited to silicone oil, contains the surfactant of polysiloxanes, glycerine, propane diols, DPG, tripropylene glycol, Macrogol 200,400 or 600 etc. and combination.In one embodiment, plasticizer comprises propane diols.The amount of used plasticizer is generally based on adhesive polymer weight 0 to about 10% weight.
The opacity of coloring composition can be by changing light absorption prepolymer in the coloring composition concentration and the concentration control of used light absorption prepolymer, the concentration of light absorption prepolymer can be easy in one embodiment by multi-layer dyeing agent composition being applied to eyeglass or the eyeglass mould is controlled.Perhaps can use opacifying agent.The opacifying agent that is fit to can be buied, for example titanium dioxide or zinc oxide.
By light absorption prepolymer and adhesive polymer (prepolymer that does not contain light-absorbing compound) and solvent, also can control the absorption of coloring composition.For example, in some embodiments, can comprise in coloring composition based on about 0 adhesive polymer to about 40% weight of all components in the coloring composition, about 5 to about 15% weight in other embodiments.
In preferred coloring agent mixture of the present invention, use about 0.30 to about 45% weight light absorption prepolymer, about 0 to about 40% weight adhesive polymer, about 40 to about 70% weight solvent, about 0 to about 25% weight titanium dioxide and about 0.2 to about 7% weight plasticizer.Weight percent is based on the gross weight of coloring agent mixture.
Those of ordinary skill in the art it should be understood that also can comprise the additive in addition of discussing in coloring composition of the present invention.The additive that is fit to includes but not limited to help to flow and the additive of homogenizing, the additive that prevents foam, the additive etc. that changes rheology and combination thereof.
Light absorption prepolymer of the present invention becomes when material cured and is embedded in the lens materials.Therefore, the surface of the mould that applies according to the eyeglass coloring agent, eyeglass absorbs prepolymer and can imbed near the front surface or the rear surface of the eyeglass that forms.In addition, can apply one or more coloring agent layers by any order.In another embodiment, can be used in combination transparent adhesive polymer layer with coloring composition.For example, in the method for the invention, can before applying coloring composition, transparent adhesive polymer layer be applied to the molded surface of half module.Transparent adhesive polymer can be by the identical or different hydrophilic monomer and the hydrophobic monomer generation that are used to prepare the light absorption prepolymer.If transparent adhesive polymer is different from the light absorption prepolymer, then must be compatible with regard to expansion factor and swellability with light absorption prepolymer and lens materials, and must swelling enter lens materials.
The available hard or soft contact lens of making by any known lens materials or the suitable material of making this type of eyeglass of dyeing that the invention provides.Preferred eyeglass of the present invention is to have the about 0 soft contact lens to about 90% water content.More preferably eyeglass is made by hydroxyl, carboxyl or both monomers, is perhaps made by the polymer that contains polysiloxanes, as siloxanes, hydrogel, silicone hydrogel and combination thereof.Mixture and additive (as polymerization initiator) reaction by macromonomer, monomer and combination thereof can prepare formation eyeglass material therefor of the present invention.Suitable material includes but not limited to the silicone hydrogel and the combination thereof of making by the component that contains polysiloxanes and above listed hydrophilic component, by polysiloxanes macromonomer and hydrophilic component.The examples of formulations that comprises the monomer that contains polysiloxanes includes but not limited to those preparations of finding in WO03/022321.The example of polysiloxanes macromonomer includes but not limited to the dimethyl silicone polymer with the acidifying of water-wet side ylmethyl propylene, as United States Patent (USP) 4,259, and 467,4,260,725 and 4,261,875 is described; Polydimethylsiloxanemacromer macromer with polymerizable functionalities is as United States Patent (USP) 4,136,250,4,153,641,4,189,546,4,182,822,4,343,927,4,254,248,4,355,147,4,276,402,4,327,203,4,341,889,4,486,577,4,605,712,4,543,398,4,661,575,4,703,097,4,837,289,4,954,586,4,954,587,5,346,946,5,358,995,5,387,632,5,451,617,5,486,579,5,962,548,5,981,615,5,981,675 and 6,039,913 is described; And combination.Their preparation also can be used the polysiloxanes macromonomer in conjunction with hydrophilic monomer, as United States Patent (USP) 5,010, and 141,5,057,578,5,314,960,5,371,147 and 5,336,797,6,867,245 is described; Or comprise the macromonomer of dimethyl silicone polymer block and polyether block, and as United States Patent (USP) 4,871,785 and 5,034,461 is described.All are mentioned patent and all are attached to herein by reference in full.
Suitable material also can be by the combined preparation of oxyperm and ionoperm component, as United States Patent (USP) 5,760, and 100,5,776,999,5,789,461,5,807,944,5,965,631 and 5,958,440 is described.Hydrophilic monomer also can be incorporated in this analog copolymer, comprise 2-hydroxyethyl methacrylate (" HEMA "), acrylic acid 2-hydroxy methacrylate, N, N-DMAA (" DMA "), N-vinyl pyrrolidone, 2-vinyl-4,4 '-dimethyl-2-oxazoline-5-ketone, methacrylic acid and 2-hydroxyethyl Methacrylamide.Can incorporate other siloxanyl monomers into, for example methacrylic acid three (trimethylsiloxy) silicyl propyl ester or United States Patent (USP) 5,998,498,3,808,178,4,139,513,5,070,215,5,710,302,5,714,557 and 5,908,906 described siloxanyl monomers.They also can comprise various flexibilizer, UV blocking agent and wetting agent.Their available diluent preparations, as United States Patent (USP) 6,020,445 described primary alconols or the secondary alcohol or the tertiary alcohol.All are mentioned patent and all are attached to herein by reference in full.
Manufacturing contact lens material therefor is familiar with by us and can be buied.In another embodiment, used lens materials is HEMA based aquagel (as etafilcon A) or polyvinyl alcohol based aquagel.In one embodiment, when lens materials was the HEMA base, the light absorption prepolymer comprised the repetitive that is formed by methacrylic acid (" MAA "), 2-hydroxyethyl methacrylate (" HMA ") and lauryl methacrylate (" LMA "); The linear statistic copolymer of MAA and HEMA; The linear statistic copolymer of HEMA and LMA; Or HEMA homopolymers.
In another embodiment, used lens materials is a silicone hydrogel, as galyfilcon, senofilcon, comfilcon, lotrafilcon A, lotrafilcon B or balafilcon.
The used coloring composition of eyeglass of the present invention can be applied on the lens surface by any appropriate method.In a preferred method of the invention, use the thermoplasticity optical mode of making by any suitable material, include but not limited to polypropylene or polystyrene resin.The coloring composition of dyeing effective dose is applied to the required part of the molded surface of mould.Apply and to be undertaken by any appropriate methodology.Preferably apply by intaglio plate bat printing (pad printing) or bat printing (tampo printing).Also can apply coloring composition,, include but not limited to ink jet printing as in those methods known in the art by additive method.
The lens materials of eyeglass formation amount is assigned in the mould." eyeglass formation amount " is meant the amount of the eyeglass that is enough to make required size and thickness.About 10 to about 40mg the lens materials of general use.
Make coloring agent swelling in lens materials.Preferably to about 4 times condition, carry out swelling being fit to make coloring agent swell to its dry thickness about 1.This swelling generally can reach in about 30 minutes about 1 at about 40 to about 68 ℃.
Make the mould that contains lens materials and coloring agent be exposed to the condition that is fit to form tinted lens then.Accurately condition depends on the composition of selected coloring agent and lens materials, and in the scope that those of ordinary skills determine.In case solidify and to finish, just make the eyeglass demoulding, and can be in salt solution cushioning liquid balance.
The method for optimizing of making tinted lens carries out with the intaglio plate bat printing is following.Just become water-insoluble photoresist material covered metal plate with can in a single day solidifying, metallic plate is preferably made of steel, is more preferably made by stainless steel.Select or the used pattern of design coloring agent, become required size with some technology then,, place on the metallic plate, and the photoresist material is solidified as camera work.Carry out the used condition of pattern etching in those of ordinary skills' ken.
After forming pattern,, the image etching entering plate that obtains is reached the suitable degree of depth, for example about 20 microns subsequently with the plate solution washing.Coloring agent is deposited on the pattern, to fill recess with coloring agent.The silicon pad that will be fit to geometry and different hardness (general about 1 to about 10 Xiao A hardness meter units) is pressed on the image of plate, to remove coloring agent, makes coloring agent dry slightly by the solvent evaporation then.Pad is pressed on the molded surface of optical mode then, and makes the coloring agent drying.Made the mould degassing nearly 12 hours, and, filled mould with the lens materials of eyeglass formation amount subsequently to remove excessive solvent and oxygen.Finish membrane module with complementary mold halves then, and after making the image swelling of printing, membrane module is exposed to be fit to the condition that used lens materials is solidified.
Illustrate the present invention by studying following unrestricted embodiment now.
Embodiment
Embodiment 1
Add 2.4g (2.42mmol) reactive black #5 and 15mL DI water to the 100mL flask.Stirred content 30 minutes in environment temperature.Add the poly-HEMA of 5g (38.42mmol) to flask
MW=20,000To react and stir 20 minutes.Be added in 138.21mg (1.00mmol) K in the 5mL DI water to solution then
2CO
3Reaction is heated to 40 ℃, and stirred 96 hours.After 96 hours, will react cooling, and with capacity DI water washing, to remove any unreacted dyestuff.With the black polymer drying under reduced pressure, to obtain the hard black look polymer of quantitative yield.
Embodiment 2
With poly-HEMA in the acetonitrile
MW=12,000Solution dry under vacuum, desolvate to remove from poly-HEMA polymer.In case remove all solvents, dry polymer is washed with water, removing any solvent impurity, and dry under vacuum, obtain white, crystalline polymer.Poly-HEMA with 5 gram (38.42mmol) dryings
MW=12,000Join reactive black #5[2.40g, 2.42mmol] and the solution of 25mL DI water.To react and stir 20 minutes.Be added in K in the 5mL DI water to solution then
2CO
3[165.85mg, 1.20mmol].Reaction is heated to 40 ℃, and stirred 96 hours.After 96 hours, will react cooling, and pH will be adjusted to 6.5 with rare HCl.Polymer is with capacity DI water washing, removing any unreacted dyestuff, and but spends the night in refrigerator and cooled.With the black polymer drying under reduced pressure, obtain the 3.40g black polymer.
Embodiment 3
With poly-HEMA in the acetonitrile
MW=12,000Solution dry under vacuum, desolvate to remove from poly-HEMA polymer.In case remove all solvents, dry polymer is washed with water, removing any solvent impurity, and dry under vacuum, obtain white, crystalline polymer.With the poly-HEMA of 5 grams
MW=12,000(38.42mmol) join the solution of Remazol light blue [1.52g, 2.42mmol] and 25mL DI water.To react and stir 30 minutes.Be added in K in the 5mL DI water to solution then
2CO
3[165.85mg, 1.20mmol].Reaction is heated to 40 ℃, and stirred 96 hours.After 96 hours, will react cooling, and pH will be adjusted to 7.0 with rare HCl.Polymer is with capacity DI water washing, removing any unreacted dyestuff, and but spends the night in refrigerator and cooled.With the blue polymer drying under reduced pressure, obtain the 3.20g blue polymer.
Claims (21)
1. composition that comprises the light absorption prepolymer, described light absorption prepolymer has about 7,000 to about 100,000 molecular weight, and comprise derived from least a vital staining agent and be selected from the polymer of monomers unit of hydrophilic monomer, hydrophobic monomer and composition thereof, its condition is that described composition essence does not contain initator.
2. the composition of claim 1, wherein said light absorption prepolymer has about 7,000 to about 65,000 molecular weight.
3. the composition of claim 1, wherein said light absorption prepolymer has about 15,000 to about 55,000 molecular weight.
4. the composition of claim 1, wherein said monomer comprises the hydrophilic monomer of at least a N-of being selected from vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl-formamide, N-vinyl formamide and composition thereof.
5. the composition of claim 1, wherein light absorption prepolymer essence is nonactive.
6. the composition of claim 1, wherein vital staining agent polymerization in the main chain of light absorption prepolymer.
7. the composition of claim 1, wherein the vital staining agent is grafted on the main chain of light absorption prepolymer.
8. coloring composition, described coloring composition comprises at least a solvent and at least a light absorption prepolymer, described light absorption prepolymer has less than about 65,000 molecular weight, and comprise derived from least a vital staining agent and be selected from the polymer of monomers unit of hydrophilic monomer, hydrophobic monomer and composition thereof.
9. the coloring agent of claim 8, wherein at least a solvent comprises at least a medium-boiling solvent and a kind of low boiling point solvent.
10. the coloring agent of claim 8, wherein said coloring agent comprises the surface tension that is lower than about 27mN/m.
11. the coloring agent of claim 8, wherein medium-boiling solvent comprises 1-ethyoxyl-2-propyl alcohol and isopropyl lactate.
12. the coloring agent of claim 8, described coloring agent further comprises plasticizer and opacifying agent.
13. the coloring agent of claim 8, wherein light absorption prepolymer essence is nonactive.
14. a method of making tinted contact lenses said method comprising the steps of:
A) will the dye coloring agent of effective dose is applied to the molded surface of mould, and described coloring agent comprises at least a light absorption prepolymer and one or more solvents; B) lens materials with eyeglass formation amount is assigned in the mould; C) make coloring agent swelling in lens materials; And d) lens materials is solidified in mould, to form tinted contact lenses.
15. the method for claim 14, wherein the light absorption prepolymer has the molecular weight less than about 65,000.
16. the method for claim 14, wherein light absorption prepolymer and lens materials form interpenetrating polymer networks.
17. the method for claim 14, wherein said monomer comprise the hydrophilic monomer of at least a N-of being selected from vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl-formamide, N-vinyl formamide and composition thereof.
18. the method for claim 14, wherein light absorption prepolymer essence is nonactive.
19. the method for claim 14, wherein at least a solvent comprises at least a medium-boiling solvent and a kind of low boiling point solvent.
20. the method for claim 14, wherein said coloring agent comprises the surface tension that is lower than about 27mN/m.
21. the method for claim 19, wherein medium-boiling solvent comprises 1-ethyoxyl-2-propyl alcohol and isopropyl lactate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86375006P | 2006-10-31 | 2006-10-31 | |
| US60/863,750 | 2006-10-31 | ||
| US11/868,771 | 2007-10-08 |
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| Publication Number | Publication Date |
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| CN101573222A true CN101573222A (en) | 2009-11-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800490761A Pending CN101573222A (en) | 2006-10-31 | 2007-10-31 | Colorants for use in tinted contact lenses and methods for their production |
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| Country | Link |
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| CN (1) | CN101573222A (en) |
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2007
- 2007-10-31 CN CNA2007800490761A patent/CN101573222A/en active Pending
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