CN106033150B - Composite contact lens - Google Patents
Composite contact lens Download PDFInfo
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- CN106033150B CN106033150B CN201510116676.1A CN201510116676A CN106033150B CN 106033150 B CN106033150 B CN 106033150B CN 201510116676 A CN201510116676 A CN 201510116676A CN 106033150 B CN106033150 B CN 106033150B
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Abstract
A kind of composite contact lens, by sequentially including one layer of hydrophilic siliceous gelatine layer and one layer of hydrophilic gelatine layer close to eyeball surface to the direction far from eyeball surface.The hydrophilic siliceous gelatine layer has the OTR oxygen transmission rate of 60 to 180 equivalents and the water content of 30~60wt%.The present invention separately provides the preparation method of the composite contact lens.Composite contact lens of the present invention are able to allow the structure of composite contact lens and processing procedure more simple and can maintain required OTR oxygen transmission rate and water content simultaneously due to having the hydrophilic siliceous gelatine layer of the OTR oxygen transmission rate of particular range and water content containing this.
Description
Technical field
The present invention relates to a kind of Soft contact lens, and particularly relating to a kind of have both can allow wearer to have long-term comfort
The composite contact lens of OTR oxygen transmission rate and water content.
Background technique
The main material of Soft contact lens is siloxanes aquogel (silicone hydrogel), according to U.S. FDA pair
In the classification of contact lenses, aquogel type contact lenses can be generally divided into two kinds: (water content is small for the contact lenses of low water content
In 50wt%)；And the contact lenses of high-moisture (water content is equal to or higher than 50wt%).Other than water content, work as oxygen
When transmitance is low, it would be possible to lead to the corneas anoxic syndrome such as keratitis, ulcer of the cornea, xerophthalmia, so, hyperoxia vapor permeability
And high-moisture is all the prerequisite feature of contact lenses.However, Jacob et al. is in Contact Lens Spectrum,
Issue:September 2011 points out that the silica structure (Si-O) in silicone hydrogel lenses can be migrated to eyeglass-air
Interface causes the lens surface of such material can be more and more hydrophobic.So allow silicone hydrogel lenses have suitable hydrophily and
It reduces the frictional force of lens surface and makes the target made great efforts for contact lenses.
TaiWan, China patent of invention announces No. 311120 and discloses a kind of composite contact lens, contains main substance and parent
Aqueous coating.There is reactive base on the main substance surface, the reactivity base be originally present in the main substance or
It is prepared then by plasma-based surface on the main substance surface.The hydrophilic coating contains carbohydrate, be it is direct or
It is covalently connected to the reactive base on the main substance surface via the functional group of few function based compound, widow's function
Based compound is selected from epihalohydrin (epihalohydrin), ethylene oxide and isocyanates.This patent announcement it is compound hidden
Although shape glasses increase the hydrophily of main substance (such as siloxanes aquogel), but because reactive base is by plasma-based
Reason (such as embodiment 3) or direct impregnation are formed in the solution containing reactive base (such as embodiment 21~24), so this is anti-
Ying Xingji is formed on the outer surface of the main substance.Carbohydrate in the hydrophilic coating is to direct or through this
Few function based compound is reacted with the reactivity base, so the hydrophilic coating is the outer surface for covering the main substance.It is aforementioned
Although structure design can effectively improve hydrophily because extraneous oxygen at least need by hydrophilic coating → main substance →
Hydrophilic coating three-decker, but it is bad plus the OTR oxygen transmission rate of hydrophilic coating itself, cause composite contact lens whole
OTR oxygen transmission rate reduce.
The aqueous silicone hydrogel contact lens of US 2012/0026458 include front surface, opposite rear surface and Jie
Layer structure between a front surface and a rear surface.This layer of structure includes preceding gelatine layer, silicone hydrogel material internal layer and rear water
Glue-line.In this patent disclosure case, extraneous oxygen will equally pass through preceding gelatine layer → silicone hydrogel material internal layer → rear water
Glue-line just reaches cornea, and the OTR oxygen transmission rate of composite contact lens entirety is caused to reduce.
The production of the preceding gelatine layer and rear gelatine layer of the contact lenses of aforementioned patent case is with stacking (layer-by-
Layer) processing procedure, thickness control is not easy when will lead to the molding of contact lenses perched aquifer, and the too thin wearing that will lead to of gelatine layer is relaxed
Appropriateness decline.In addition, the degree of difficulty of the three-decker processing procedure of aforementioned patent case is higher, and still easily occur homogeneity of product it is bad,
The problems such as production cost is excessively high.
By preceding description it is found that existing composite contact lens are all to coat the siloxanes aquogel layer with hydrophilic gelatine layer
Outer surface also results in OTR oxygen transmission rate reduction, surface layer water content not other than structure is at least three layers and processing procedure is more complex
It is good, wear comfort level it is bad the problems such as.Therefore, how to allow OTR oxygen transmission rate and surface layer water content to reach balance, and then make to wear
Person feels comfortable after extended wear, still wants the target promoted for existing composite contact lens.
Summary of the invention
That the purpose of the present invention is to provide a kind of structures is simple, have both hyperoxia vapor permeability and surface layer high-moisture it is compound
Contact lenses.
Composite contact lens of the present invention, by sequentially including one layer hydrophilic close to eyeball surface to the direction far from eyeball surface
Siliceous gelatine layer and one layer of hydrophilic gelatine layer.The hydrophilic siliceous gelatine layer has the OTR oxygen transmission rate and 30 of 60 to 180 equivalents
The water content of~60wt%.
The beneficial effects of the present invention are: contained by using the hydrophilic of OTR oxygen transmission rate and water content for having particular range
Silicon gelatine layer, without forming hydrophilic gelatine layer on the contact surface between the hydrophilic siliceous gelatine layer and eyeball surface, thus
Oxygen is avoided to need more oxygen to be allowed to be accessible to eyeball surface by two layers of hydrophilic gelatine layer.Furthermore the present invention is compound hidden
Shape glasses can improve eyeglass wettability and reduce eyeglass by having the hydrophilic gelatine layer on the surface contacted with air and eyelid
With the frictional force of eyelid, and then is promoted and whole wear comfort level.
It will be described in detail below with regard to the content of present invention:
" (methyl) acrylic acid " used hereinafter word includes methacrylic acid and acrylic acid.Similarly, " (methyl)
An acrylate " word includes methacrylate and acrylate.
Composite contact lens of the present invention are by sequentially including one layer hydrophilic close to eyeball surface to the direction far from eyeball surface
Siliceous gelatine layer and one layer of hydrophilic gelatine layer.
[hydrophilic siliceous gelatine layer]
The hydrophilic siliceous gelatine layer is to contact with eyeball surface (it is, vitreous layer) and have the oxygen of 60 to 180 equivalents
The water content of vapor permeability and 30~60wt%.
Preferably, the hydrophilic siliceous gelatine layer is by a hydrophilic siliceous glue material in ultraviolet light or the lower progress of heating
Polymerization forming and formed.The hydrophilic siliceous glue material is hydrophilic material and includes preferably containing at least one double bond end
Polysiloxanes or polysiloxanes giant molecule, double bond containing hydrophilic monomer, crosslinking agent, initiator and the company containing reactive group and double bond
Statement of account body.Each ingredient will be described in detail respectively below:
(1) polysiloxanes or polysiloxanes giant molecule containing at least one double bond end
The polysiloxanes of (1-1) containing at least one double bond end: should the polysiloxanes containing at least one double bond end
It can be used double containing at least one in such as 5,352,714,5,358,995,5,760,100,2013/0172574 patent of US
The polysiloxanes of key end.Preferably, being somebody's turn to do the polysiloxanes containing at least one double bond end is containing there are two double bond ends
Polysiloxanes (such as, but not limited to X-22-164, X-22- manufactured by SHIN-ETSU HANTOTAI's silicon benefit light (Shin-Etsu Silicone)
164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E etc.).
The polysiloxanes giant molecule of (1-2) containing at least one double bond end: preferably, at least one double bond end should be contained
The polysiloxanes giant molecule at end be by end be isocyanate group prepolymer with have at least one hydroxyl and at least one
Obtained by the reactant of double bond is reacted.The dosage of the prepolymer and the reactant can be intended to obtained gather according to subsequent
The property requirements of siloxanes giant molecule are adjusted.Preferably, with the dosage of the prepolymer for 100 parts by weight, the reactant
Amount ranges be 5 to 200 parts by weight.Preferably, the prepolymer and the reactant be 60~90 DEG C temperature range with
It is carried out under nitrogen environment.Each ingredient will be illustrated respectively below:
The end (1-2-1) is the prepolymer of isocyanate group
The prepolymer is carried out obtained by polymerization reaction in the presence of a catalyst as a starting material.The starting material
Polysiloxanes, (B) multicomponent isocyanate and (C) polyalcohol including (A) containing C-terminal.Preferably, the prepolymer
Weight average molecular weight range is 2000~200000.
(A) containing the polysiloxanes of C-terminal
The polysiloxanes for containing C-terminal indicates the polysiloxanes at least one C-terminal.Preferably, should
Polysiloxanes containing C-terminal has lower formula (I) structure:
The R1、R2、R3Respectively indicate alkyl, hydroxyl ,-(CH2)x1OH、-(CH2)x2(OCH2CH2)x3OH、-(CH2)x4OCH2CH
(OH)(CH2)x5CH3Or-(CH2)x6OCH2CH(OH)CH2OH, the integer that x1, x2, x3, x4, x5 and x6 are 1 to 6；
The R4Indicate hydrogen, alkyl ,-(CH2)y1OH、-(CH2)y2(OCH2CH2)y3OH、-(CH2)y4OCH2CH(OH)(CH2)y5CH3Or-(CH2)y6OCH2CH(OH)CH2OH, the integer that y1, y2, y3, y4, y5 and y6 are 0 to 6；
The integer that n is 1 to 100；And
Its condition is to work as R4When for alkyl, R1、R2And R3At least one of them be necessary for hydroxyl ,-(CH2)x1OH、-
(CH2)x2(OCH2CH2)x3OH、-(CH2)x4OCH2CH(OH)(CH2)x5CH3Or-(CH2)x6OCH2CH(OH)CH2OH。
Preferably, the weight average molecular weight range for being somebody's turn to do the polysiloxanes containing C-terminal is 300 to 6000.Commercially available quotient
(it has product double end (dual end type) type reaction siloxanes fluids KF-6001 as manufactured by Gui Liguang company, SHIN-ETSU HANTOTAI
Two C-terminals), Gelest product DMS series of products and Dow Corning silanol group liquid (Silanol Fluid) series
Product.
(B) multicomponent isocyanate
The multicomponent isocyanate is that the polysiloxanes for containing C-terminal for this and polyalcohol are reacted.Preferably,
The multicomponent isocyanate is diisocyanate；More preferably, the multicomponent isocyanate be selected from 2,4- toluene di-isocyanate(TDI) (2,
4-toluene diisocyanate, 2,4-TDI), 2,6- toluene di-isocyanate(TDI) (2,6-toluene diisocyanate,
2,6-TDI), n-hexane -1,6- diisocyanate (n-hexane-diisocyanate, 1,6-HDI), diphenyl-methane -4,4 ' -
Diisocyanate (diphenyl methane-4,4 '-diisocyanate, MDI), hydrogenated diphenyl methane diisocyanate
(hydrogenated diphenyl methane-4,4 '-diisocyanate, H12-MDI), different Buddhist ketone diisocyanate
(isophorone diisocyanate, IPDI) or combination above-mentioned.
(C) polyalcohol
Preferably, the polyalcohol is poly-dihydric alcohol；More preferably, which is straight chain type polyethylene glycol or the poly- second of branched chain type
Glycol.The weight average molecular weight range of the straight chain type polyethylene glycol is preferably 300 to 2000.The branched chain type polyethylene glycol is preferable
There can be 3,4,6 or 8 branches (branched), and weight average molecular weight range is preferably 1000 to 10000.
It, should with the gross weight of the polysiloxanes of (A) containing C-terminal for 100 listed as parts by weight in the starting material
(B) amount ranges of multicomponent isocyanate are 10 to 100 parts by weight, and being somebody's turn to do the amount ranges of (C) polyalcohol is 10 to 100 weight
Part.
The starting material is will to be somebody's turn to do the polysiloxanes containing C-terminal, the multicomponent isocyanate and polyalcohol to mix
And it obtains, and the starting material is that polymerization reaction is carried out in the presence of a catalyst.The catalyst can be used polyalcohol with it is polynary
Used catalyst when isocyanates is reacted.Preferably, the catalyst is selected from dibutyl tin dilaurate
(dibutyltin diaurate, DBTDL), iron chloride (FeCl3), tin octoate (stannous octoate) or triethylamine
(triethylamine)。
Preferably, the starting material contains solvent.The solvent is such as, but not limited to ketone (such as methyl ethyl ketone) or esters (such as second
Acetoacetic ester).With the gross weight of the polysiloxanes for containing C-terminal for 100 listed as parts by weight, the amount ranges of the solvent are 50
To 300 parts by weight.
Preferably, the polymerization reaction of the starting material is carried out under 60~90 DEG C of temperature range and nitrogen environment.
(1-2-2) has at least one hydroxyl and the reactant of at least one double bond
The reactant be reacted in the presence of catalyst by mixing material obtained by, the mixing material include (D) hydroxyl and
The monomer or oligomer of double bond, the biocompatibility macromolecule of (E) hydroxyl and (F) multicomponent isocyanate.It below will respectively
Each ingredient is illustrated:
(D) hydroxyl and the monomer or oligomer of double bond
The monomer or oligomer of the hydroxyl and double bond be mainly used for having with this prepolymer of isocyanate group into
Row reaction.Preferably, the hydroxyl and the monomer of double bond are selected from hydroxyalkyl (methyl) acrylate, dihydroxyalkyl (methyl)
Acrylate or combination above-mentioned.
Hydroxyalkyl (methyl) acrylate is such as, but not limited to (2- hydroxyethyl) methacrylate [2-
Hydroxyethyl methacrylate, HEMA], (2- hydroxyethyl) acrylate [2-hydroxyethyl
Acrylate], (4- hydroxybutyl) acrylate [4-hydroxybutyl acrylate], (3- hydroxypropyl) acrylate
[3-hydroxypropyl acrylate] or combination above-mentioned.
Dihydroxyalkyl (methyl) acrylate is such as, but not limited to (2,3- dihydroxypropyl), and methacrylate is [also
It is glyceryl methacrylate, glycerol monomethacrylate, GMMA].
The oligomer equally contains hydroxyl and double bond, such as poly(ethylene glycol) methacrylate [Poly (ethylene
Glycol) methacrylate], weight average molecular weight is 360~1200.
(E) biocompatibility macromolecule of hydroxyl
Should " biocompatibility macromolecule of hydroxyl " refer to containing at least one hydroxyl and with mammalian tissues or the food in one's mouth
Newborn animal fluid has the macromolecule of compatibility；Preferably there is with human tissue or body fluid the hydroxyl macromolecule of compatibility.
Preferably, the biocompatibility macromolecule of the hydroxyl be selected from polyvinyl alcohol (polyvinyl alcohol),
Poly- [(2- hydroxyethyl) methacrylate] [poly (2-hydroxyethyl) methacrylate, PHEMA], poly- [(2,3-
Dihydroxypropyl) methacrylate] [poly (2,3-dihydroxypropyl) methacrylate], (2- hydroxyethyl)
Copolymer [P (the HEMA-co- of methacrylate and N- vinyl -2- Pyrrolizidine ketone (N-vinyl-2-pyrrolidone)
NVP)], (2- hydroxyethyl) methacrylate and the copolymer [P (HEMA-co-MAA)] of acrylic acid, (2- hydroxyethyl) first
The copolymer [P (HEMA-co-NVP-co-MAA)] or aforementioned of base acrylate and N- vinyl -2- Pyrrolizidine ketone and acrylic acid
Combination.
Preferably, the weight average molecular weight range of the biocompatibility macromolecule of the hydroxyl is 1000~100000.
(F) multicomponent isocyanate
The multicomponent isocyanate can be identical or different with (B) multicomponent isocyanate used in the starting material.It should
The multicomponent isocyanate in mixing material can refer to explanation above-mentioned.
In the mixing material, with the gross weight of the monomer or oligomer of (D) hydroxyl and double bond for 100 listed as parts by weight,
The amount ranges for being somebody's turn to do the biocompatibility macromolecule of (E) hydroxyl are 10 to 300 parts by weight, and should (F) multicomponent isocyanate
Amount ranges be 20 to 300 parts by weight.
The mixing material be monomer by the hydroxyl and double bond or oligomer, the hydroxyl biocompatibility macromolecule and
The multicomponent isocyanate is mixed and is obtained.The mixing material is to be reacted in the presence of a catalyst.The catalyst with it is aforementioned
The catalyst mentioned is identical.The catalyst in the mixing material can refer to explanation above-mentioned.
Preferably, the mixing material contains solvent.The solvent is such as, but not limited to ketone (such as methyl ethyl ketone) or esters (such as acetic acid
Ethyl ester).With the gross weight of the monomer or oligomer of the hydroxyl and double bond for 100 listed as parts by weight, the amount ranges of the solvent are
50 to 1500 parts by weight.
Preferably, the reaction of the mixing material is carried out under 60~90 DEG C of temperature range and nitrogen environment.
The double bond quantity of polysiloxanes giant molecule containing at least one double bond end of the invention can by adjusting with
Hydroxyl and the monomer of double bond or the dosage of oligomer in the mixing material for generating reactant are changed, so as to can show compared with
High reactivity also can more meet subsequent applications demand.
(2) double bond containing hydrophilic monomer
Preferably, the double bond containing hydrophilic monomer is containing at least one double bond, to contain at least one double bond with this
The polysiloxanes or polysiloxanes giant molecule of end are reacted.The double bond containing hydrophilic monomer is such as, but not limited to (2- hydroxyl
Base ethyl) methacrylate (2-hydroxyethyl methacrylate, HEMA), (2- hydroxyethyl) acrylate (2-
Hydroxyethyl acrylate), (4- hydroxybutyl) acrylate (4-hydroxybutyl acrylate), (3- hydroxyl
Propyl) acrylate (3-hydroxypropyl acrylate), 3- (1,1,2,2- tetrafluoro ethyoxyl) -2- hydroxypropylmethyl
Acrylate (3- (1,1,2,2-tetrafluoroethoxy) -2-hydroxypropyl methacrylate), (2,3- bis-
Hydroxypropyl) methacrylate (glycerol methacrylate, GMA), N- vinyl -2- Pyrrolizidine ketone (N-vinyl-
2-pyrrolidone, NVP), methacrylic acid (methacrylic acid), acrylic acid (acrylic acid), itaconic acid
(itaconic acid), dimethylamino ethyl methacrylate (dimethylaminoethyl methacrylate), two
Ethylamino- ethylmethyl acrylate (diethylaminoethyl methacrylate), acrylamide (acrylamide),
Methacrylamide (methacrylamide), N, N '-dimethyl acrylamide (N, N'-dimethylacrylamide), N,
N '-acrylamide (N, N'-diethylacrylamide), 2- methacryloxyethyl phosphorylation choline (2-
Methacryloyloxyethyl phosphorylcholine, MPC) etc..In concrete example of the invention, the double bond containing parent
Aqueous monomers are selected from (2- hydroxyethyl) methacrylate, (2,3- dihydroxypropyl) methacrylate, N- ethylene
Base -2- Pyrrolizidine ketone, N, N '-dimethyl acrylamide or a combination above-mentioned.
(3) crosslinking agent
Preferably, the crosslinking agent is such as, but not limited to ethylene glycol dimethacrylate (ethylene glycol
Dimethacrylate, EGDMA), dimethacrylate (diethylene glycol
Dimethacrylate), tetraethylene glycol dimethylacrylate (tetraethylene glycol dimethacrylate),
Polyethylene glycol dimethacrylate (polyethylene glycol dimethacrylate), trimethylol propane trimethyl
Acrylate (trimethylolpropane trimethacrylate, TMPTMA), pentaerythritol tetramethylacrylate
(penterythritol tetramethacrylate), bisphenol a dimethacrylate (bisphenol A
Dimethacrylate), vinyl methacrylate (vinyl methacrylate) or combination above-mentioned.
(4) initiator
For any help to allow between double bond the initiator of radical reaction can occur for the initiator.Preferably, the starting
Agent is such as, but not limited to azodiisobutyronitrile (Azobisisobutyronitrile, AIBN), bis oxide (2,4,6- trimethylbenzenes
Formoxyl) Phenylphosphine (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide), commercial goods are such as
(the benzoin ethyl ether) , Benzyl base dimethyl ketal of IRGACURE 819, benzoin ethyl ether manufactured by BASF AG
(benzyl dimethyl ketal), α, α-diethoxy acetophenone (α, α-diethoxyacetophenone), 2- hydroxyl-
(2-hydroxy-2-methylpropiophenone, commercial goods are as manufactured by Ciba company for 2- methyl phenyl ketone
Darocure 1173) or combination above-mentioned.
(5) the connection monomer containing reactive group and double bond
The main function of the connection monomer containing reactive group and double bond is for keeping the hydrophilic siliceous gelatine layer hydrophilic with this
It is bonded together between gelatine layer by covalently bonded.The reactive group is selected from isocyanate group, isothiocyanates
Base, epoxy group, anhydride group, azalactone base (azalactone group), lactone group, silanol group, three alkoxysilane bases or preceding
State the combination of group.Preferably, it is selected from 3- (trimethoxy silicon substrate) propyl first that this, which contains reactive group and the connection monomer of double bond,
Base acrylate [3- (trimethoxysilyl) propyl methacrylate], 2- isocyanatoethylmethacrylate
(2-isocyanatoethyl methacrylate), epihydric alcohol methylpropenoic acid ester (glycidyl methacrylate),
(methyl) acrylic anhydride [(meth) acrylic acid anhydride], 4- vinyl -2,2- dimethyl azalactone (4-
) or combination above-mentioned vinyl-2,2-dimethylazlactone.More preferably, this contains reactive group and the connection monomer of double bond is
Epihydric alcohol methylpropenoic acid ester, 2- isocyanatoethylmethacrylate, 4- vinyl -2,2- dimethyl azalactone or
Combination above-mentioned.
(6) other reagents
The hydrophilic siliceous glue material selectively further includes other reagents, such as, but not limited to viscosity modifier, ultraviolet
Light absorber etc..
The viscosity modifier such as single methanol class (such as ethyl alcohol, isopropanol), polyalcohols [such as polyethylene glycol (such as PEG
600), glycerol etc.], esters (such as ethyl acetate), ketone (such as butanone) or it is above-mentioned combination etc..Preferably, being contained with this
The polysiloxanes of at least one double bond end or the gross weight of polysiloxanes giant molecule are 100 parts by weight, the use of the viscosity modifier
Amount range is 2.5~300 parts by weight.
The UV absorbers are such as, but not limited to benzophenone, 2- (2- hydroxy-5-methyl base acryloyl-oxyethyl benzene
Base) -2H- benzotriazole [2- (2-hydroxy-5-methacryloxyethylphenyl) -2H-benzo-triazole], benzene
And triazole (Benzotriazole, BTA), 2- dihydroxy benaophenonel (2-hydroxy-benzophenone), 2- (4- benzene first
Acyl group -3- hydroxyphenoxy) ethyl acrylate [2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate], 4-
Methacryloxy -2- dihydroxy benaophenonel (4-methacryloxy-2-hydroxybenzophenone) etc..
The hydrophilic siliceous glue material is by that will be somebody's turn to do polysiloxanes or polysiloxanes containing at least one double bond end
Giant molecule, the double bond containing hydrophilic monomer, the crosslinking agent, the initiator, this contain connection monomer and the choosing of reactive group and double bond
Other reagents for selecting addition are mixed and are obtained.Each composition dosage of the hydrophilic siliceous glue material can be hydrophilic according to this
Property needed for siliceous gelatine layer is adjusted.Preferably, containing the polysiloxanes or poly- silicon of at least one double bond end with this
The gross weight of oxygen alkane giant molecule is 100 parts by weight, and the amount ranges of the double bond containing hydrophilic monomer are 100~400 parts by weight, should
The amount ranges of crosslinking agent are 0.2~10 parts by weight, and the amount ranges of the initiator are 0.1~10 parts by weight, this contains reactive group
And the amount ranges of the connection monomer of double bond are 0.1~100 parts by weight.
The hydrophilic siliceous gelatine layer is polymerize under ultraviolet light or heating by above-mentioned hydrophilic siliceous glue material
It forms and is formed.Above-mentioned steps are selected according to initiator and type of crosslinking agent.Preferably, the wave-length coverage of the ultraviolet light
For 254~390nm, exposure intensity range is 0.2~50mW/cm2.Preferably, the heating temperature range is 50~110 DEG C.
[hydrophilic gelatine layer]
Preferably, the hydrophilic gelatine layer has the water content greater than 40wt%；More preferably, has 40wt% to 90wt%'s
Water content.
Preferably, the hydrophilic gelatine layer is by hydrophilic glue constituent in ultraviolet light or the lower progress polymerization forming of heating
And formed, which includes hydrophilic monomer, crosslinking agent and initiator.
Preferably, the hydrophilic monomer is selected from (2- hydroxyethyl) methacrylate, (2,3- dihydroxypropyl)
Methacrylate, (2- hydroxyethyl) acrylate, (4- hydroxybutyl) acrylate, (3- hydroxypropyl) acrylate,
3- (1,1,2,2- tetrafluoro ethyoxyl) -2- hydroxy propyl methacrylate [3- (1,1,2,2-tetrafluoroethoxy) -
2-hydroxypropyl meth-acrylate], methacrylic acid, acrylic acid, itaconic acid (itaconic acid), dimethylamine
Base ethylmethyl acrylate (dimethylaminoethyl methacrylate), diethylin ethylmethyl acrylate
(diethylaminoethyl methacrylate), acrylamide (acrylamide), Methacrylamide
(methacrylamide), N, N '-dimethyl acrylamide (N, N'-dimethylacrylamide), N, N '-diethyl propylene
Amide (N, N'-diethylacrylamide) or N- vinyl -2- Pyrrolizidine ketone (N-vinyl-2-pyrrolidone, NVP).
The crosslinking agent can refer to preceding description and be selected.The initiator can refer to preceding description and be selected.
The hydrophilic glue constituent selectively includes other foregoing reagents.Preferably, with the hydrophilic monomer
Gross weight be 100 parts by weight, the amount ranges of the viscosity modifier are 5~100 parts by weight.
The hydrophilic glue constituent is its by adding the hydrophilic monomer, the crosslinking agent, the initiator and selection
He mixes and obtains reagent.Each composition dosage of the hydrophilic glue constituent can be according to needed for the hydrophilic gelatine layer
Property is adjusted.Preferably, the amount ranges of the crosslinking agent are 0.25 with the gross weight of the hydrophilic monomer for 100 parts by weight
~5 parts by weight and the amount ranges of the initiator are 0.1~5 parts by weight.
The hydrophilic gelatine layer be by above-mentioned hydrophilic glue constituent in ultraviolet light or heating it is lower carry out polymerization forming and
It is formed.Above-mentioned steps are selected according to initiator and type of crosslinking agent.Preferably, the wave-length coverage of the ultraviolet light is 254
~390nm, exposure intensity range are 0.2~50mW/cm2.Preferably, the heating temperature range is 50~110 DEG C.
[articulamentum]
Preferably, composite contact lens of the present invention, which also include one layer, is set to the hydrophilic siliceous gelatine layer and the hydrophilic glue
Articulamentum between layer, the articulamentum pass through covalent bond with the hydrophilic siliceous gelatine layer in conjunction with the hydrophilic gelatine layer respectively.
Preferably, the articulamentum is will to connect material to be coated on the hydrophilic gelatine layer and be dried and formed.Preferably,
The connection material includes the connection monomer containing reactive group and double bond, which can contain at least with the hydrophilic monomer and this respectively
The polysiloxanes or its giant molecule generation covalent bond of one double bond end.The reactive group, this contain the connection list of reactive group and double bond
Body can refer to content above-mentioned.
Preferably, the connection material further includes initiator.The concrete example of the initiator is as previously described.
Preferably, the connection material further includes hydrophilic monomer.The concrete example of the hydrophilic monomer is as previously described.
Preferably, the connection material further includes crosslinking agent.The concrete example of the crosslinking agent is as previously described.
Preferably, the connection material selectively includes foregoing viscosity modifier and foregoing UV Absorption
Agent.
The connection material is by the way that this to be contained to the connection monomer of reactive group and double bond, the initiator and the viscosity tune of selection addition
Whole dose is mixed with UV absorbers and is obtained.Each composition dosage of the connection material can contain needed for articulamentum according to this
Property be adjusted.Preferably, with the gross weight of the connection monomer containing reactive group and double bond for 100 parts by weight, the initiator
Amount ranges be 0.01~10 parts by weight.
[functional layer]
Preferably, composite contact lens of the present invention also include one layer be set to the articulamentum and the hydrophilic siliceous gelatine layer it
Between functional layer.The functional layer is not influence under the hydrophilic siliceous gelatine layer, the articulamentum and the property of the hydrophilic gelatine layer
It is configured, generation type can be adjusted variation according to the function material of actual use.
Preferably, the functional layer is such as, but not limited to: coat of colo(u)r, medicine layer, microwafer, printed circuit, optical element, micro-
Type battery etc..
In concrete example of the invention, which is coat of colo(u)r.Preferably, the coat of colo(u)r is by pigment constituent in purple
Outer light, which irradiates, or heating is lower is formed, which includes pigment (and/or dyestuff), crosslinking agent and initiator, and optional
Add the monomer and other foregoing reagents as previously described containing reactive group and double bond with selecting.The pigment (and/or dyestuff)
Any pigments or dyes suitable for contact lenses can be selected, preferably, the pigments or dyes are Food and Drug Administration
The pigments or dyes of approval.The crosslinking agent can refer to preceding description and be selected.The initiator can refer to preceding description and be selected
With.
First concrete example of composite contact lens of the invention is comprising one layer of hydrophilic siliceous gelatine layer and one layer of hydrophilic water
Glue-line, the hydrophilic siliceous gelatine layer and the hydrophilic gelatine layer are in the hydrophilic siliceous glue material by the hydrophilic siliceous gelatine layer
Connection monomer containing reactive group and double bond and the hydrophilic monomer of the hydrophilic gelatine layer form covalent bond and combine.
Second concrete example of composite contact lens of the invention is comprising one layer of hydrophilic siliceous gelatine layer, one layer of hydrophilic glue
Layer and one layer of articulamentum being set between the hydrophilic siliceous gelatine layer and the hydrophilic gelatine layer.
The third concrete example of composite contact lens of the invention is comprising one layer of hydrophilic siliceous gelatine layer, one layer of hydrophilic glue
Layer, one layer of articulamentum being set between the hydrophilic siliceous gelatine layer and the hydrophilic gelatine layer and one layer are arranged in the articulamentum
With the functional layer between the hydrophilic siliceous gelatine layer.
The preparation method of first concrete example of composite contact lens of the present invention is to include:
(a) hydrophilic glue constituent is prepared, which includes hydrophilic monomer, crosslinking agent and initiator；
(b) in the way of printing (bat printing or wire mark), spraying, spin coating etc., which is coated in stealth
One layer of hydrophilic gelatine layer is formed on lens molds；
(c) hydrophilic siliceous glue material is coated on the hydrophilic gelatine layer and is gathered under ultraviolet light or heating
Synthesis type, forms one layer of hydrophilic siliceous gelatine layer, which includes poly- containing at least one double bond end
Siloxanes or polysiloxanes giant molecule, double bond containing hydrophilic monomer, crosslinking agent, initiator and the connection containing reactive group and double bond
Monomer；And
(d) contact lens molds are removed, and obtain composite contact lens.
Other than the step of being also contained in after step (b) (b1), the second concrete example of composite contact lens of the present invention
The step of preparation method is with the preparation method of the first concrete example is identical.The step (b1) is will to connect material to be placed on the hydrophilic gelatine layer and formed
One layer of articulamentum.
Other than the step of being also contained in after step (b) (b2), the third concrete example of composite contact lens of the present invention
The step of preparation method is with the preparation method of the first concrete example is identical.The step (b2) is to be placed in a connection material on the hydrophilic gelatine layer and shape
At one layer of articulamentum, then function material is placed on the articulamentum again and forms an one functional layer.Preferably, the functional layer is face
The bed of material and the function material include pigment (and/or dyestuff), crosslinking agent, initiator and the monomer containing reactive group and double bond, and can
Selectively add other foregoing reagents.
Other than coat of colo(u)r, which is selectively medicine layer, microwafer, printed circuit, optical element or miniature
Battery etc..
Detailed description of the invention
Nothing
Specific embodiment
The present invention will be described further with regard to following embodiment, however, it should be noted that the embodiment only illustrates
Purposes, and it is not necessarily to be construed as the limitation that the present invention is implemented.
The preparation of [preparation example 1] hydrophilic glue constituent
By (2- hydroxyethyl) methacrylate of 25wt%, (2,3- dihydroxypropyl) methacrylic acid of 50wt%
N- vinyl -2- Pyrrolizidine the ketone of ester and 25wt% are mixed and obtain a hydrophilic monomer.By the above-mentioned parent of 100 parts by weight
Aqueous monomers, the crosslinking agent (ethylene glycol dimethacrylate) of 1.25 parts by weight, 1.25 parts by weight initiator (2- hydroxyl-
2- methyl phenyl ketone, manufactured by Ciba company, the name of an article is Darocure 1173) and 22.5 parts by weight viscosity modifier [by
Poly- (the N- vinyl -2- Pyrrolizidine ketone) and the polyethylene glycol of 18.75 parts by weight of 3.75 parts by weight are formed] it is mixed and is obtained
Obtain a hydrophilic glue constituent.
The preparation of [preparation example 2] hydrophilic siliceous glue materials A
By 100 parts by weight containing two double bond ends polysiloxanes (as manufactured by the Gui Liguang company, SHIN-ETSU HANTOTAI, name of an article X-
22-164A), the double bond containing hydrophilic monomer of 257.5 parts by weight is (by the N of 150 parts by weight, N '-dimethyl acrylamide, 95
N- vinyl -2- Pyrrolizidine the ketone of parts by weight and the methacrylic acid of 12.5 parts by weight are formed), the crosslinking agents of 2.5 parts by weight
(ethylene glycol dimethacrylate), 2.5 parts by weight initiator (2- hydroxy-2-methyl propiophenone, manufactured by Ciba company,
The name of an article is Darocure 1173), connection monomer [3- (trimethoxy silicon substrate) propyl containing reactive group and double bond of 75 parts by weight
Methacrylate] and the viscosity modifier (butanone) of 62.5 parts by weight mixed and obtain hydrophilic siliceous glue materials A.
[preparation example 3] includes the preparation of the hydrophilic siliceous glue material B of the connection monomer containing reactive group and double bond
By 100 parts by weight containing two double bond ends polysiloxanes (as manufactured by the Gui Liguang company, SHIN-ETSU HANTOTAI, name of an article X-
22-164A), 245 parts by weight double bond containing hydrophilic monomer (by the N of 150 parts by weight, N '-dimethyl acrylamide and 95 weights
Amount part N- vinyl -2- Pyrrolizidine ketone formed), the crosslinking agent (ethylene glycol dimethacrylate) of 2.5 parts by weight, 2.5
The initiator (2- hydroxy-2-methyl propiophenone, manufactured by Ciba company, the name of an article is Darocure 1173) of parts by weight, 75 weight
Part the connection monomer [2- isocyanatoethylmethacrylate] containing reactive group and double bond, 12.5 parts by weight methacrylic acid
And 62.5 the viscosity modifiers (butanone) of parts by weight mixed and obtain hydrophilic siliceous glue material B.
The preparation of [preparation example 4] connection material
By the connection monomer [2- isocyanatoethylmethacrylate] containing reactive group and double bond of 100 parts by weight, 33.3
The N- vinyl-of the poly(ethylene glycol) dimethylacrylates (weight average molecular weight 550) of parts by weight, 266.7 parts by weight
The viscosity modifier of 2- Pyrrolizidine ketone, the initiator (azodiisobutyronitrile) of 6.7 parts by weight and 262.6 parts by weight is [by 33.3 weights
Measure the ethyl acetate of poly- (the N- vinyl -2- Pyrrolizidine ketone) of part, the Macrogol 600 of 93.3 parts by weight and 133.3 parts by weight
Formed] it is mixed and obtains connection material.
The preparation of [preparation example 5] pigment constituent (function material) A
By the friendship of the iron oxide pigment of 100 parts by weight, N- vinyl -2- the Pyrrolizidine ketone, 2.5 parts by weight of 125 parts by weight
Join agent (ethylene glycol dimethacrylate), the initiator (azodiisobutyronitrile) of 5 parts by weight and the viscosity tune of 262.6 parts by weight
Whole dose [by the fourth of poly- (the N- vinyl -2- Pyrrolizidine ketone) of 50 parts by weight, the Macrogol 600 of 70 parts by weight and 75 parts by weight
Ketone is formed] it is mixed and obtains pigment constituent A.
The preparation of [preparation example 6] pigment constituent (function material) B
By the friendship of the iron oxide pigment of 100 parts by weight, N- vinyl -2- the Pyrrolizidine ketone, 2.5 parts by weight of 125 parts by weight
Join agent (ethylene glycol dimethacrylate), the initiator (azodiisobutyronitrile) of 5 parts by weight, 75 parts by weight containing reactive group and
The connection monomer (2- isocyanatoethylmethacrylate) of double bond and the viscosity modifier of 262.6 parts by weight are [by 50 parts by weight
Poly- (N- vinyl -2- Pyrrolizidine ketone), the Macrogol 600 of 70 parts by weight and 75 parts by weight butanone formed] mixed
It closes and obtains pigment constituent B.
[embodiment 1] composite contact lens I
(a) hydrophilic glue constituent obtained by the preparation example 1 is taken.
(b) the hydrophilic glue constituent is coated in a contact lenses plastic mould (material is polypropylene, the group of concave-convex mold
Close) cavity plate in, then under the ultraviolet light of wavelength 380nm irradiate (exposure intensity 3mW/cm2, irradiation time is about 2 points
Clock) under carry out curing molding, and form one layer of hydrophilic gelatine layer.
(c) by hydrophilic siliceous glue material B coating obtained by the preparation example 3 to the contact lenses plastic cement of the step (b)
On the cavity plate of mold and the hydrophilic gelatine layer is covered, then punch-pin in conjunction with cavity plate and is stood 10 to 30 minutes；Then, Yu Bochang
Ultraviolet light (the exposure intensity 3mW/cm of 380nm2, irradiation time is about 30 minutes) under carry out curing molding, and Yu Mo
Composite contact lens I is formed on tool (comprising the hydrophilic gelatine layer and the hydrophilic siliceous gelatine layer).
(d) the contact lenses plastic mould is removed, composite contact lens I is taken out, then with the alcohol of concentration 70wt%
Aqueous solution is extracted and is purified, then is placed in normal saline solution and is saved.
[embodiment 2] composite contact lens II
(a) hydrophilic glue constituent obtained by the preparation example 1 is taken.
(b) the hydrophilic glue constituent is coated in contact lenses plastic mould (material is polypropylene, the group of concave-convex mold
Close) cavity plate in, then under the ultraviolet light of wavelength 380nm irradiate (exposure intensity 3mW/cm2, irradiation time is about 2 points
Clock) under carry out curing molding, and form one layer of hydrophilic gelatine layer.
(b1) by the cavity plate of the contact lenses plastic mould of connection material coating obtained by the preparation example 4 to the step (b)
It goes up and covers the hydrophilic gelatine layer, then cavity plate is placed in 70 DEG C of baking oven and is toasted 20 minutes, to form the articulamentum.
(c) by hydrophilic siliceous glue materials A coating obtained by the preparation example 2 to the contact lenses plastic cement of the step (b1)
On the cavity plate of mold and the articulamentum is covered, then punch-pin in conjunction with cavity plate and is stood 10 to 30 minutes；Then, Yu Bochang
Ultraviolet light (the exposure intensity 3mW/cm of 380nm2, irradiation time is about 30 minutes) under carry out curing molding, and Yu Mo
Composite contact lens II is formed on tool (comprising the hydrophilic gelatine layer, the articulamentum and the hydrophilic siliceous gelatine layer).
(d) the contact lenses plastic mould is removed, composite contact lens II is taken out, then with the alcohol of concentration 70wt%
Aqueous solution is extracted and is purified, then is placed in normal saline solution and is saved.
[embodiment 3] composite contact lens III
(a) hydrophilic glue constituent obtained by the preparation example 1 is taken.
(b) the hydrophilic glue constituent is coated in contact lenses plastic mould (material is polypropylene, the group of concave-convex mold
Close) cavity plate in, then under the ultraviolet light of wavelength 380nm irradiate (exposure intensity 3mW/cm2, irradiation time is about 2 points
Clock) under carry out curing molding, and form one layer of hydrophilic gelatine layer.
(b1) by the cavity plate of the contact lenses plastic mould of connection material coating obtained by the preparation example 4 to the step (b)
It goes up and covers the hydrophilic gelatine layer, then cavity plate is placed in 70 DEG C of baking oven and is toasted 20 minutes, to form the articulamentum.
(b2) by the recessed of the contact lenses plastic mould of pigment material A coating obtained by the preparation example 5 to the step (b1)
On mould and the articulamentum is covered, (exposure intensity 3mW/cm is then irradiated under the ultraviolet light of wavelength 380nm2, irradiation time is about
Be 2 minutes) under carry out curing molding, to form the coat of colo(u)r.
(c) by hydrophilic siliceous glue materials A coating obtained by the preparation example 2 to the contact lenses plastic cement of the step (b2)
On the cavity plate of mold and the coat of colo(u)r is covered, then punch-pin in conjunction with cavity plate and is stood 10 to 30 minutes；Then, Yu Bochang
Ultraviolet light (the exposure intensity 3mW/cm of 380nm2, irradiation time is about 30 minutes) under carry out curing molding, and Yu Mo
Composite contact lens III is formed on tool (comprising the hydrophilic gelatine layer, the articulamentum, the coat of colo(u)r and the hydrophilic siliceous glue
Layer).
(d) the contact lenses plastic mould is removed, composite contact lens III is taken out, then with the wine of concentration 70wt%
Smart aqueous solution is extracted and is purified, then is placed in normal saline solution and is saved.
[test]
Contact lenses I, II and III of embodiment 1,2 and 3 are subjected to following test respectively, as a result such as the following table 1:
Water content (%) test: contact lenses are taken out, the normal saline solution of lens surface is removed and carries out weighing and obtain
To weight in wet base.Then contact lenses are put into 60 DEG C of baking ovens and are dried 24 hours, then carried out weighing and obtain dry weight.Finally according to
Water content is calculated according to following formula.The water content of general silicon glue contact lenses is about 30~50%.
Oxygen permeating amount [equivalent (barrer)] test: referring to polarographic technique.General silicon glue stealth eye
The oxygen permeating amount of mirror is about 60~180 equivalents.
Table 1
| Water content (%) | Oxygen permeating amount (equivalent) | |
| Contact lenses I | 45±2 | 81 |
| Contact lenses II | 42±2 | 80 |
| Contact lenses III | 42±2 | 63 |
In conclusion composite contact lens of the present invention are by using the OTR oxygen transmission rate and water content for having particular range
Hydrophilic siliceous gelatine layer, without forming hydrophilic glue on the contact surface between the hydrophilic siliceous gelatine layer and eyeball surface
Layer, thus be avoided oxygen and need through two layers of hydrophilic gelatine layer, more allow oxygen to be accessible to eyeball surface, and of the invention
Hydrophilic gelatine layer can improve eyeglass wettability and reduce the frictional force of eyeglass and eyelid, and then promote whole wearing comfort level, institute
The purpose of the present invention can be reached really.
Claims (7)
1. a kind of composite contact lens, it is characterised in that: by sequentially including close to eyeball surface to the direction far from eyeball surface:
One layer of hydrophilic siliceous gelatine layer is to contact with eyeball surface, and in ultraviolet light or added by hydrophilic siliceous glue material
Heat is lower to be carried out polymerization forming and is formed, and has the OTR oxygen transmission rate of 60 to 180 equivalents and the water content of 30~60wt%, the parent
The siliceous glue material of water includes the polysiloxanes containing at least one double bond end or polysiloxanes giant molecule, double bond containing hydrophilic
Property monomer, connection monomer, crosslinking agent and initiator containing reactive group and double bond, which is selected from isocyanate group, different
Thiocyanate groups, epoxy group, anhydride group, azalactone base, lactone group, silanol group or three alkoxysilane bases；And
One layer of hydrophilic gelatine layer.
2. composite contact lens according to claim 1, it is characterised in that: the hydrophilic gelatine layer has 40wt% extremely
The water content of 90wt%.
3. composite contact lens according to claim 1, it is characterised in that: the hydrophilic gelatine layer is by chemical bonded refractory side
Formula and be formed on the hydrophilic siliceous gelatine layer.
4. composite contact lens according to claim 3, it is characterised in that: the hydrophilic gelatine layer is made of hydrophilic glue
Object is formed in ultraviolet light or the lower progress polymerization forming of heating, which includes hydrophilic monomer, crosslinking
Agent and initiator.
5. composite contact lens according to claim 1, it is characterised in that: it also includes one layer, and to be set to this hydrophilic siliceous
Articulamentum between gelatine layer and the hydrophilic gelatine layer, the articulamentum pass through covalent bond and the hydrophilic siliceous gelatine layer respectively and are somebody's turn to do
Hydrophilic gelatine layer combines.
6. composite contact lens according to claim 5, it is characterised in that: its also include one layer be set to the articulamentum with
Functional layer between the hydrophilic siliceous gelatine layer.
7. composite contact lens according to claim 6, it is characterised in that: the functional layer is coat of colo(u)r.
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| CN114942530B (en) * | 2022-04-12 | 2023-09-08 | 温州医科大学 | Contact lens and application thereof in diagnosis and treatment of infectious keratitis |
| CN116554719A (en) * | 2022-12-08 | 2023-08-08 | 华诺森（武汉）生物医药技术有限公司 | Coating process of hydrophilic silicon hydrogel cornea contact lens |
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| CN201035250Y (en) * | 2007-04-26 | 2008-03-12 | 朱守群 | Pressure sticking type anti-myopia edge convex combination glasses |
| CN103052364A (en) * | 2010-07-30 | 2013-04-17 | 诺瓦提斯公司 | Silicone hydrogel lenses with water-rich surfaces |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201035250Y (en) * | 2007-04-26 | 2008-03-12 | 朱守群 | Pressure sticking type anti-myopia edge convex combination glasses |
| CN103052364A (en) * | 2010-07-30 | 2013-04-17 | 诺瓦提斯公司 | Silicone hydrogel lenses with water-rich surfaces |
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