CN100368828C - Lens and method of manufacturing lens - Google Patents
Lens and method of manufacturing lens Download PDFInfo
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- CN100368828C CN100368828C CNB2005101128145A CN200510112814A CN100368828C CN 100368828 C CN100368828 C CN 100368828C CN B2005101128145 A CNB2005101128145 A CN B2005101128145A CN 200510112814 A CN200510112814 A CN 200510112814A CN 100368828 C CN100368828 C CN 100368828C
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Abstract
A lens including a lens base material, a hard coat layer that is laminated on the lens base material directly or via a primer layer and includes a metal oxide fine particle, an organic silicon compound and a polyfunctional epoxy compound as a principal component, and an antireflection layer that is laminated on the hard coat layer and includes a porous silica fine particle and an organic silicon compound as a principal component.
Description
Technical field
The present invention relates to be used for the plastics system lens of glasses etc. or the dyeing of glass lens.
Background technology
Correcting vision has constituting base material or constituting the plastic lens of substrate or the eyeglass lens that glass lens dyes with in the tinted glasses lens such as lens and sunglasses.In addition, after deliberation the functional layer (for example hard conating) of lamination on substrate is dyeed to substitute lens are dyeed.Can under the situation of lens substrate not being had influence, have color to the dye lens of type of functional layer, and its concentration can be adjusted also.Therefore, the eyeglass lens of the varied color that meets customer requirements can be provided.
[patent documentation 1] spy opens the 2001-295185 communique
Following method is disclosed in the patent documentation 1: form dye layer on plastic lens substrate, at this hard conating is set above the dye layer, come dye layer dye (painted) by this hard conating.This method can dye after forming hard conating, and this in this method is excellent, and the dyeing lens can be kept at the stage that has formed hard conating, and according to the desirable color of user dye, shipment.
But,, on hard conating, overlap to form the antireflection film of low-refraction for most of eyeglass lens.Under a lot of situations, also to further on antireflection film, overlap to form and be used for antifouling waterproof membrane.So, after the dyeing, in when, in the film forming procedure at these layers problem taking place when, must use other stock to carry out dyeing process and film formation process again, perhaps, must after removing all layers that comprise dye layer on the lens substrate, generate dye layer and hard conating once more, and the later operation that dyes once more.Therefore, the yield rate of the film formation process of the film formation process of antireflection film and waterproof membrane is big to the cost impact of dilivery term and goods.
Compared with the dyeing lens, the demand of non-dyeing lens is bigger.Therefore, with non-dyeing lens be the technology and the tricks of the trade of the center manufacturing of having established relevant lens.For non-dyeing lens, carry out the film formation process of hard conating after, then carry out the film formation process of multilayer film, lamination antireflection film on hard conating.On the other hand, for according to the technology manufacturing of patent documentation 1 dyeing lens, carry out the film formation process of hard conating after, be immersed in and carry out dyeing process in the disperse dyes, then, the goods for after the dyeing wait the film formation process of carrying out antireflection film by evaporation.Therefore, be necessary further to establish and carry out the technology used in the film forming of antireflection film on the goods after dyeing.
That is, the lens for after the dyeing are necessary to accumulate again the technology and the tricks of the trade of coming the film forming antireflection film with high yield rate.Therefore, do not need the film technique of the lens that dye and tricks of the trade can not be applicable to fully in the manufacturing of dyeing lens.Therefore, patent documentation 1 disclosed method is the technology that need further accumulate production technology and tricks of the trade from now on.
Summary of the invention
Wherein, the object of the present invention is to provide lens and manufacture method thereof; In described lens and the manufacture method thereof, the production technology of the non-dyeing lens of accumulation before can further effectively utilizing; In addition, described lens and manufacture method thereof can be with short dilivery term and the low-cost lens that are coloured to the desirable color of user that provide.
Lens of the present invention have lens substrate, hard conating, prevent the reflection horizon; Described hard conating directly or across substrate layer is laminated on the described lens substrate, and contains metal oxide microparticle, organo-silicon compound and multi-functional epoxy compound as principal ingredient; The described reflective layer that prevents is pressed on the described hard conating, and contains poriness silicon oxide (silica) particulate and organo-silicon compound as principal ingredient.
In these lens, hard conating can be colored, and prevents that the reflection horizon from being porous.Therefore, by will having formed hard conating and prevent that the lens in reflection horizon are immersed in the disperse dyes, can be across preventing that the reflection horizon from dyeing to hard conating.Further, for lens of the present invention, even also can dye to hard conating across water barrier.
Lens of the present invention have lens substrate, the hard conating that can be colored, the porous reflection horizon that prevents; The described hard conating that can be colored directly or across substrate layer is laminated on the described lens substrate, and the described porous reflective layer that prevents is pressed on the described hard conating, and can dye to described hard conating across the described reflection horizon that prevents.
These lens are the lens that can be colored, and when making these lens simultaneously, can proceed to the manufacturing process that prevents the reflection horizon continuously, and without dyeing process.Therefore stay dyeing process, by with the identical manufacturing process of non-dyeing lens, the manufacturing of lens is finished to the state that does not dye, and is stored lens at this state.Then, can the lens of storing be dyeed.Therefore, the state before dyeing can be made in the lens process that can be colored among the application by making with non-dyeing lens operation much at one, has effectively utilized the manufacturing technology of non-dyeing lens.Therefore, can high finished product rate, make the lens that can be colored at low cost.
Lens of the present invention have lens substrate, the hard conating that can be colored, porous reflection horizon, the water barrier of preventing; The described hard conating that can be colored directly or across substrate layer is laminated on the described lens substrate, the described porous reflective layer that prevents is pressed on the described hard conating, described water barrier is laminated to and prevents on the reflection horizon, and can dye to described hard conating across described reflection horizon and the described water barrier of preventing.
According to present inventor's test, water barrier does not almost have influence to dyeability, even prevent overlapping water barrier on the reflection horizon porous, can similarly dye to hard conating with the lens that do not have above-mentioned water barrier yet.These lens, though be the lens that can be colored, can not carry out dyeing process earlier, can prevent the film formation process in reflection horizon and the film formation process of water barrier continuously, or do not have dyeing process, carry out film formation process continuously from the film formation process of hard conating to water barrier.This process is identical with the non-staining lens, finish the manufacturing of lens, store, can after this dye with water barrier, even therefore in having the lens manufacturing process that can be colored of water barrier, also can effectively utilize the manufacturing technology of non-dyeing lens.Therefore, can high finished product rate, make the lens that can be colored at low cost with water barrier.
Among the present invention, the lens that are colored have lens substrate, hard conating, poriness and prevent the reflection horizon; The described hard conating that has been colored directly or across substrate layer is laminated on the described lens substrate, and described poriness prevents that reflective layer is pressed on the described hard conating, and described hard conating is by across preventing that the reflection horizon from dyeing.
According to the present invention, for the dyeing lens, after being dyeed, sell immediately by the lens of storing, so the lens of the desired color of user can be provided in the short dilivery term.According to the present invention, as long as technology or the utensil that dyes arranged, just can dye to lens of the present invention, offer the client then.Therefore, even be not lens manufacturers, franchised dealer or shop, also can come lens of the present invention are dyeed, thereby the dyeing lens are provided according to the color of user's needs.
The hard conating of preferred lens of the present invention contains Titanium Dioxide Rutile Top grade as metal oxide microparticle.So Titanium Dioxide Rutile Top grade is excellent owing to having high index of refraction as the composition that its upper strata is pressed with the hard conating of machine class antireflection film.In addition, because the photolytic activity of Titanium Dioxide Rutile Top grade is low, the hard conating dyeability that therefore contains Titanium Dioxide Rutile Top grade is good, and permanance is also high.
The manufacture method of lens of the present invention has the 1st operation, the 2nd operation and dyeing process; In described the 1st operation, on lens substrate, form the hard conating that can be colored directly or across substrate layer; In described the 2nd operation, on hard conating, form poriness and prevent the reflection horizon with damp process; In the described dyeing process, the object that dyes comprises hard conating.
In this manufacture method, can be from the series of processes of the functional layer relevant with lens itself being carried out film forming dyeing process be separated or independent.Therefore, can with non-dyeing lens same or similarly operation carry out the series of processes that film forming prevents reflection horizon and water barrier, thereby can fully effectively utilize under non-dyeing lens, accumulate or the manufacturing technology of exploitation from now on.
Have following operation in the lens manufacturing method of the present invention: the hard conating that can be colored directly or across substrate layer is laminated on the lens substrate, and the porous reflective layer that prevents is pressed on the hard conating, and the lens of above-mentioned formation are dyeed.
In this manufacture method, for the structure of the basic function of having finished relevant lens, be the lens of film forming of the various functional layers of lens, the operation that it is dyeed is arranged.Therefore, for keeping, store or the dyeing of circulation before lens, can be by suitable place or suitable people, shop even user itself for example, the color that becomes the user to wish lens staining.
Like this, according to the present invention, can completely effectively utilize the manufacturing technology of non-dyeing lens and make the dyeing lens.Therefore, can high finished product rate, make the dyeing lens at low cost.And, owing to do not have film formation process behind the dyeing process, can will finish the shipment of dyeing lens in the short period of time.Therefore, for this dyeing lens, can significantly shorten and determine the dilivery term of color after ordered.In addition, owing to can before the lens circulation or in the circulation at lens, carry out dyeing process, so can reduce storage.In addition, even owing to also can dye in the shop, so, can realize the supply of material of the shortest so far dilivery term by store and dye the back sale in the shop.
Among the present invention, hard conating preferably contains metal oxide microparticle, organo-silicon compound and multi-functional epoxy compound as principal ingredient.Prevent that the reflection horizon from preferably containing poriness silicon oxide particulate and organo-silicon compound as principal ingredient.
That is, the hard conating of preferred lens of the present invention is harder, be difficult for being scratched, further, preferably to fixing of dye ability excellence.Therefore, preferably in the composition that hardness is provided such as silane compound etc., add the multi-functional epoxy compound.Because the multi-functional epoxy compound further provides flexibility or stickability, therefore estimate to improve hard conating and substrate, and hard conating on the stickability that prevents the reflection horizon.
In order to obtain the porous reflection horizon that prevents of lens of the present invention, preferably contain poriness silicon oxide particulate and organo-silicon compound as principal ingredient.
The reflection horizon that prevents of preferred lens of the present invention is contained the organo-silicon compound of the poriness silicon oxide particulate of 40 weight %～85 weight %, 5 weight %～60 weight %, mostly is the multi-functional epoxyization thing of 10 weight % most.If the poriness silicon oxide particulate is very few, then can not form the poriness layer that can make lower floor's dyeing.On the other hand, if the poriness silicon oxide particulate is too much, the reflection horizon that prevents that then can not obtain having abundant hardness.Further, a spot of multi-functional epoxyization thing is contained in the reflection horizon that prevents of preferred lens of the present invention.Its stickability of reflection horizon that prevents that contains a small amount of multi-functional epoxyization thing improves.
The hard conating of preferred lens of the present invention contains the Titanium Dioxide Rutile Top grade of 40 weight %～70 weight % as metal oxide microparticle.Titanium Dioxide Rutile Top grade is the same with titanium dioxide to have high index of refraction, has about 1.67 high index of refraction.On the other hand, the photolytic activity of Titanium Dioxide Rutile Top grade is strong unlike the photolytic activity of anatase-type titanium oxide etc.Therefore, contain in the hard conating of Titanium Dioxide Rutile Top grade, can not be decomposed, thereby the hard conating of the performance of playing stably can be provided as the silane coupling agent organism such as (silane compounds) of other principal ingredient of hard conating.In addition, Titanium Dioxide Rutile Top grade can not decompose as organic dyestuff.Therefore, the hard conating that contains Titanium Dioxide Rutile Top grade seldom fades.
Among the present invention, hard conating or prevent the multi-functional epoxy compound that use in the reflection horizon can be enumerated for example following substances: the polyolefins epoxy resin that the peroxidating method is synthetic; The alicyclic ring epoxide resins such as poly glycidyl ester that obtain by cyclopentadiene oxide, cyclohexene oxide or hexahydrophthalic acid and chloropropylene oxide; The polyglycidyl ether that obtains by polynary alkanols such as polyhydric phenol such as bisphenol-A, catechol, resorcinol or (gathering) ethylene glycol, (gathering) propylene glycol, neopentyl glycol, glycerine, trimethylolpropane, pentaerythrite, two glycerine, D-sorbite and chloropropylene oxide; The epoxy novolac (epoxynovolak) that obtains by epoxidized vegetable oil, novolac type phenol resin (novolak phenol) and chloropropylene oxide; The epoxy resin that obtains by phenolphthalein and chloropropylene oxide; The multipolymer of glycidyl methacrylate and methyl methacrylate acrylic monomer or styrene etc.; And by above-mentioned epoxy compound with contain the epoxy acrylate that (methyl) acrylic acid glycidyl ring-opening reaction of monocarboxylic acid obtains.
Further, as multi-functional epoxy compound, can enumerate for example subordinate's material: the aliphatic epoxy compound, for example 1, the 6-hexanediol diglycidyl ether, ethylene glycol diglycidylether, the diethylene glycol diglycidyl ether, the triethylene glycol diglycidyl ether, the TEG diglycidyl ether, nine ethylene glycol diglycidylethers, propylene glycol diglycidylether, the dipropylene glycol diglycidyl ether, tripropyleneglycol diglycidyl ether, four propylene glycol diglycidylethers, nine propylene glycol diglycidylethers, neopentylglycol diglycidyl ether, the diglycidyl ether of neopentyl glycol hydroxyl trimethylace tonitric ester, the trimethylolpropane diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, glycerin diglycidyl ether, T 55, two glycerin diglycidyl ethers, two T 55s, two glycerine, four glycidol ethers, the pentaerythrite diglycidyl ether, the pentaerythrite triglycidyl ether, pentaerythrite four glycidol ethers, dipentaerythritol four glycidol ethers, D-sorbite four glycidol ethers, the diglycidyl ether of three (2-hydroxyethyl) chlorinated isocyanurates, the triglycidyl ether of three (2-hydroxyethyl) chlorinated isocyanurates etc.; Alicyclic epoxide compound, isophorone glycol (isophorone diol) diglycidyl ether, two-2 for example, 2-hydroxy-cyclohexyl propane diglycidyl ether etc.; Aromatic epoxy compound, for example resorcinolformaldehyde resin, bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol-S diglycidyl ether, o-phthalic acid diglycidyl ester, phenol phenolic aldehyde (phenol novolak) polyglycidyl ether, cresols phenolic aldehyde (cresolnovolak) polyglycidyl ether etc.
Can enumerate for example following substances as metal oxide: the composite oxide sol that contains the titanium dioxide that is applied by sb oxide that is disperseed by methyl alcohol; Or contain the particulate or the composite particles of at least a kind the metal oxide that is selected from Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, Ti; Outmost surface to metal oxide microparticle has been implemented the particulate that modification is handled with organo-silicon compound; Contain potpourri, the solid solution of above-mentioned substance, the material of other combined state.Titanium dioxide can be unformed, also can be Detitanium-ore-type, rutile-type, brookite type or Ca-Ti ore type titanium compound.Wherein, Titanium Dioxide Rutile Top grade most preferably.
Metal oxide is the form that for example is dispersed into colloidal at dispersion medium in water, alkanols or other organic solvent.In addition, can carry out modification to it with the surface that organo-silicon compound or aminated compounds are handled composite oxide particle.This moment, used organo-silicon compound for example had simple function silane or two functional silanes, trifunctional silane, four functional silanes etc.When handling, can just carry out modification and handle hydrolization group not being handled, also can be hydrolyzed and carry out modification after handling and handle.In addition, after the processing, though selective hydrolysis group and particulate-mode of OH radical reaction, even a remaining part there is not influence to stability yet.In addition, as aminated compounds, ammonium is arranged; Alkyl amines such as ethamine, triethylamine, isopropylamine, n-propylamine; Aralkylamines such as benzyl amine; Aliphatic cyclic amines such as piperidines; Alkanolamine such as monoethanolamine, triethanolamine.With respect to the weight of particulate, the addition of described organo-silicon compound and amines is necessary in about 1%～15% scope.Preferred above-mentioned any one particle diameter is about 1 millimicron～300 millimicrons.
Hard conating or prevent that silane compound that the reflection horizon is contained is preferably the organo-silicon compound of following general formula (A) expression.
R
1R
2 nSiX
1 3-n (A)
In the formula, n is 0 or 1.
Wherein, R
1It is the organic group that has the organic group of reactive group that can polymerization or have functional group that can hydrolysis.As the object lesson of reactive group that can polymerization, can enumerate for example following substances: vinyl, allyl, propenyl, methylpropenyl, epoxy radicals, sulfydryl, cyano group, amino etc.; Object lesson as functional group that can hydrolysis has alkoxys such as methoxyl, ethoxy, methoxy ethoxy; Halogen such as chloro, bromo; Acyloxy.
R
2Be that carbon number is 1～6 alkyl.As object lesson, can enumerate for example following substances: methyl, ethyl, butyl, ethylidene, phenyl etc.
In addition, X
1Be can hydrolysis functional group, can enumerate for example following substances: alkoxys such as methoxyl, ethoxy, methoxy ethoxy; Halogen such as chloro, bromo; Acyloxy.
As X
1Object lesson, can enumerate for example following substances: vinyl trialkyl oxysilane, vinyl trichlorosilane, vinyl three ('beta '-methoxy-ethoxy) silane, the allyl trialkoxy silane, the acryloxy propyl trialkoxy silane, the methacryloxypropyl trialkoxy silane, methacryloxypropyl dialkoxy methyl-monosilane, γ-glycidoxypropyl trialkoxy silane, β-(3,4-epoxy radicals cyclohexyl)-ethyl trialkoxy silane, the mercapto propyl trialkoxy silane, the gamma-amino propyl trialkoxy silane, N-β-(amino-ethyl)-gamma-amino propyl group methyl dialkoxy silicane, tetramethoxy-silicane, γ-glycidoxypropyltrimewasxysilane.As X
1, can mix at least 2 kinds of these functional groups and use.In addition, with X
1Re-use more effective after being hydrolyzed.
As dyestuff, preferably use disperse dyes in order to suppress uneven dyeing.In dyeing process, preferably lens are immersed in the dye bath and are colored and contaminate; Described dye bath is to obtain by disperse dyes are dispersed in the water.The preferred high dyestuff of permanance.Operable dyestuff for example has anthraquinone class, quinophthalone class dyestuff, nitrodiphenyl amines dyestuff, azo dyes etc. to disperse dyestuff.Object lesson as disperse dyes, can enumerate for example following substances: benzene class intermediate, for example P-nethoxyaniline, aniline, para aminoacet anilide, para-aminophenol, 1-chloro-2,4-dinitro benzene, 2-chloro-4-nitroaniline, o-chloronitrobenzene, diphenylamine, meta nitro aniline, paranitroanilinum, N, N-two (2-hydroxyethyl) aniline, 1-phenyl-3-methyl-5-pyrazolones ketone, phenol etc.; Toluene class intermediate, for example fixed (6-methoxyl-meta-aminotoluene), metacresol of metacresol, paracresol, meta-aminotoluene, 2-nitro-para-totuidine, para-nitrotoluene etc.; Naphthalene class intermediate, for example naphthalidine, beta naphthal etc.; Phthalic anhydride, anthraquinone class intermediate, for example 1-amino-4-bromo anthraquinone-2-sulfonic acid (bromamine acid), 1-anthraquinone sulfonic acid, 1,4-diamino-anthraquinone, 1,5-dichloroanthraquinone, 1,4-dihydroxy anthraquinone (quinizarin), 1,5-dihydroxy anthraquinone (anthrarufin), 1,2,4-trihydroxyanthraquinone (alizarinopurpurin), 2-methylanthraquinone etc.In addition, can use disperse dyes or at least 2 kinds of disperse dyes of mixing to use separately.Usually disperse dyes are dispersed in and obtain dye bath in the water.As solvent, can and use organic solvent such as methyl alcohol, ethanol, phenmethylol etc.
In dye bath,, can further add surfactant as spreading agent for dyestuff.As surfactant, can list following substances: anionic surfactant, for example alkyl benzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfo succinate, aromatic sulphonate formaldehyde condensation products, lauryl sulfate etc.; Non-ionic surfactant, for example polyoxy ethyl alkyl ether, alkyl ether amine, polyoxyethylene sorbitol fatty acid ester etc.Corresponding to lens colour saturation, it is preferred that to use the amount with respect to dyestuff be the surfactant of 5 weight %～200 weight %.In the dip-dye, disperse dyes and surfactant-dispersed are modulated dye bath in the potpourri of water or water and organic solvent, then plastic lens is immersed in this dye bath, under set point of temperature, the process stipulated time dyes.Dyeing temperature and time change according to desired the different of colour saturation.Usually, under 95 ℃ or lower temperature, can dye several minutes～30 minutes, the dye strength of preferred dye bath is 0.01 weight %～5 weight %.
The composition that hard conating contains is not limited to above-mentioned.For example, when forming hard conating, can use the adjuvant except mentioned component in case of necessity.As curing catalysts, can enumerate for example following substances: perchloric acid classes such as perchloric acid, ammonium perchlorate, magnesium perchlorate; With Cu (II), Zn (II), Co (II), Ni (II), Be (II), Ce (III), Ta (III), Ti (III), Mn (III), La (III), Cr (III), V (III), Co (III), Fe (III), Al (III), Ce (IV), Zr (IV), V (IV) etc. is the acetylacetonate of central metal atom; Amine; Amino acid such as glycocoll; Lewis acid; Metal salts of organic acids.Wherein, can enumerate magnesium perchlorate as most preferred curing catalysts; The acetylacetonate of Al (III), Fe (III).For addition, preferred solid component concentration is in the scope of 0.01 weight %～5.0 weight %.
In addition, in the manufacture process,, can also use solvent etc. except mentioned component.As the solvent that is used to dilute, alkanols, ester class, ketone, ethers, the fragrant same clan etc. are arranged.In addition, in case of necessity, add a spot of surfactant, antistatic agent, disperse dyes-oil-soluble dyes-fluorescent dye-pigment, light-sensitive compound etc., the performance of the coating after can improveing the coating of cambial coating liquid and can improveing curing.
Embodiment
Below, be illustrated for several embodiments of the invention and comparative example.
(embodiment 1)
(substrate layer)
Using " Seiko Super Sovereign " that Seiko Epson (strain) makes to form refractive index with lens raw material (hereinafter to be referred as SSV) is 1.67 plastic lens substrate.On this plastics system base material, form substrate layer (internal coating) by infusion process.Be used to form the coating fluid P1 of substrate layer as modulated.In 100 parts of commercial polyester resin " Pesresin A-160P " (high pine resin (strain) system, aqueous dispersion emulsion, solid component concentration is 27%) in sneak into 84 parts of Titanium Dioxide Rutile Top grade complex sols (catalyst change into industry (strain) system, Optolake 1120Z), 640 parts of methyl alcohol, 1 part of (Japan Unicar (strain) system of the silicone surfactant as levelling agent trade name: as diluting solvent, trade name " SILWETL-77 "), be stirred to the state of homogeneous, obtain coating fluid P1.
By dip-coating method (going up the pulling rate degree is per minute 15cm) this coating fluid P1 is coated on the lens substrate.By the lens substrate after will being coated with 80 ℃ air-dry 20 minutes, obtain the lens of belt material bottom.After using coating fluid P1 to come the substrate layer of film forming to smoke, solid constituent contains the Titanium Dioxide Rutile Top grade complex sol of 62 weight % vibrin, 38 weight %.
(hard conating)
The coating fluid H1 that is used for the hard conating film forming as modulated.(catalyst changes into industry (strain) system with 138 parts of methyl proxitols, 688 parts of Titanium Dioxide Rutile Top grade complex sols, trade name Optolake 1120Z) after the mixing, sneak into 106 parts of γ-glycidoxypropyltrimewasxysilane again, (Nagase changes into industry (strain) system for 38 parts of glycerine polyglycidyl ethers, trade name Denacol EX313), obtain mixed liquor, drip 30 parts of 0.1N aqueous hydrochloric acid solutions while stirring to this mixed liquor, further stir 4 hours after, slaking 1 is round the clock.Then, add 1.8 parts of Fe (III) acetylacetonate, 0.3 part of silicone surfactant (Japan Unicar (strain) system, trade name L-7001), obtain coating fluid H1 to this mixed liquor.
By dip-coating method (going up the pulling rate degree is per minute 35cm) this coating fluid H 1 is coated on the lens of belt material bottom.After the coating, by with lens 80 ℃ air-dry 30 minutes, smoked 120 minutes at 120 ℃ again, obtain having the lens of the thick hard conating of 2.3 μ m.Hard conating after the film forming contains sufficient multi-functional epoxy compound's glycerine polyglycidyl ether, and it is the hard conating that can be colored.
After utilizing coating fluid H1 to come the hard conating of film forming to smoke, its solid constituent contains 55 weight % metal oxide microparticles (Titanium Dioxide Rutile Top grade complex sol), 30 weight % organosilicons (γ-glycidoxypropyltrimewasxysilane), 15 weight % multi-functional epoxy compounds (glycerine polyglycidyl ether).
(preventing the reflection horizon)
Coating fluid (liquid of the low-refraction) AR1 that is used to prevent the reflection horizon film forming as modulated.In the potpourri of 14 parts of γ-glycidoxypropyltrimewasxysilane, 15 parts of tetramethoxy-silicanes, add 13 parts of 0.1N aqueous hydrochloric acid solutions while stir, further stir 4 hours after, slaking 1 is round the clock.Then, add 878 parts of methyl proxitols, 80 parts of hollow silicasol (hollow silica sol to this mixed liquor, catalyst changes into industry (strain) system, trade name Oscal special item), 0.04 part of magnesium perchlorate, 0.3 part of silicone surfactant (Japan Unicar (strain) system, trade name L-7001), obtain coating fluid AR1.
Before utilizing this coating fluid AR1 to form to prevent the reflection horizon, lens surface (surface of hard conating) is carried out hydrophiling by Cement Composite Treated by Plasma.Then, coating fluid is coated on the lens of band hard conating by damp process (dip-coating mode (going up the pulling rate degree is per minute 15cm)).After the coating, with lens 80 ℃ air-dry 30 minutes, and then smoked 60 minutes at 120 ℃, obtain having the thick porous lens that prevent reflection horizon (low refractive index film) of about 100nm.
To utilize coating fluid AR1 come film forming prevent that the reflection horizon from smoking after, its solid constituent contains 25 weight % γ-glycidoxypropyltrimewasxysilane, 15 weight % tetramethoxy-silicanes, 60 weight % hollow silicasol.Do not contain multi-functional epoxy compound's (glycerine polyglycidyl ether) in this liquid.
(water barrier)
Further, the described lens surface that prevents the reflection horizon that has is carried out water-proofing treatment with fluorine one type of silane compound, obtain lens with waterproof membrane.
(dyeing)
In the present embodiment, the lens of the band waterproof membrane so made were flooded 10 minutes in 94 ℃ disperse dye bath, dye.Disperse dyes for example can use the Seiko Plux Diamond Coat amber D of coloring agent (amber D).Dyeing lens for obtaining like this carry out test as described below, check each performance.To test and result's explanation of hereinafter summarizing thereof.
(embodiment 2)
(hard conating)
The coating fluid H2 that is used for the hard conating film forming as modulated.At first, (catalyst changes into industry (strain) system with 147 parts of methyl proxitols, 688 parts of Titanium Dioxide Rutile Top grade complex sols, trade name Optolake 1120Z) mixes, and then add 88 parts of γ-glycidoxypropyltrimewasxysilane, (Nagase changes into industry (strain) system for 50 parts of glycerine polyglycidyl ethers, trade name DenacolEX313), obtain mixed liquor, in this mixed liquor, drip 24 parts of 0.1N aqueous hydrochloric acid solutions while stirring, further stir after 4 hours, slaking 1 round the clock.Then, add 0.6 part of magnesium perchlorate, 1.9 parts of Fe (III) acetylacetonate, 0.3 part of silicone surfactant (Japan Unicar (strain) system, trade name L-7001), obtain coating fluid H2 to this mixed liquor.
By dip-coating method (going up the pulling rate degree is per minute 35cm) this coating fluid H2 is coated on the lens substrate (SSV, the lens of no substrate layer).After the coating, by with lens 80 ℃ air-dry 30 minutes, smoked 120 minutes at 120 ℃ again, obtain having the lens of the thick hard conating of 2.3 μ m.
After utilizing coating fluid H2 to come the hard conating of film forming to smoke, contain 55 weight % metal oxide microparticles (Titanium Dioxide Rutile Top grade complex sol), 25 weight % organosilicons (γ-glycidoxypropyltrimewasxysilane), 20 weight % multi-functional epoxy compounds (glycerine polyglycidyl ether) in the solid constituent.
(preventing the reflection horizon)
Then, this lens surface is carried out hydrophiling by Cement Composite Treated by Plasma.Then, will prevent the coating fluid AR1 of reflection horizon film forming, be coated on the lens that have hard conating by dip-coating mode (going up the pulling rate degree is per minute 15cm) with embodiment 1 identical being used to.After the coating, 80 ℃ air-dry 30 minutes, smoked 60 minutes at 120 ℃ again, obtain having the thick porous lens that prevent the reflection horizon of about 100nm.
(water barrier)
Further, the described lens surface that prevents the reflection horizon that has is carried out water-proofing treatment with fluorine one type of silane compound, obtain lens with waterproof membrane.
(dyeing)
The lens of band waterproof membrane were flooded 10 minutes in 94 ℃ disperse dye bath, dye.Dyeing lens for obtaining like this carry out test as described below, check each performance.
(embodiment 3)
(hard conating)
The coating fluid H3 that is used for the hard conating film forming as modulated.(catalyst changes into industry (strain) system with 156 parts of methyl proxitols, 688 parts of Titanium Dioxide Rutile Top grade complex sols, trade name Optolake 1120Z) after the mixing, sneak into 71 parts of γ-glycidoxypropyltrimewasxysilane again, (Nagase changes into industry (strain) system for 63 parts of glycerine polyglycidyl ethers, trade name Denacol EX313), obtain mixed liquor, drip 20 parts of 0.1N aqueous hydrochloric acid solutions while stirring to this mixed liquor, further stir 4 hours after, slaking 1 is round the clock.Then, add 4 parts of Fe (III) acetylacetonate, 0.3 part of silicone surfactant (Japan Unicar (strain) system, trade name L-7001), obtain coating fluid H3 to this mixed liquor.
By dip-coating method (going up the pulling rate degree is per minute 35cm) this coating fluid H3 is coated on the lens substrate (SSV, the lens of no substrate layer).After the coating, by with lens 80 ℃ air-dry 30 minutes, smoked 120 minutes at 120 ℃ again, obtain having the lens of the thick hard conating of 2.5 μ m.
After utilizing coating fluid H3 to come the hard conating of film forming to smoke, its solid constituent contains 55 weight % metal oxide microparticles (Titanium Dioxide Rutile Top grade complex sol), 20 weight % organosilicons (γ-glycidoxypropyltrimewasxysilane), 25 weight % multi-functional epoxy compounds (glycerine polyglycidyl ether).
(preventing the reflection horizon)
The coating fluid AR2 that is used to prevent the reflection horizon film forming as modulated.In the potpourri of 14 parts of γ-glycidoxypropyltrimewasxysilane, 15 parts of tetramethoxy-silicanes, add 13 parts of 0.1N aqueous hydrochloric acid solutions while stir, further stir 4 hours after, slaking 1 obtains mixed liquor round the clock.Then, to this mixed liquor add 883 parts of methyl proxitols, (catalyst changes into industry (strain) system to 73 parts of hollow silicasol, trade name Oscal special item), (Nagase changes into industry (strain) system to 2 parts of glycerine polyglycidyl ethers, trade name Denacol EX313), 0.07 part of magnesium perchlorate, 0.3 part silicone surfactant (Japan Unicar (strain) system, trade name L-7001), obtain coating fluid AR2.
Prevent that in formation reflection horizon (being film forming) is preceding, hydrophiling is carried out by Cement Composite Treated by Plasma in the surface of hard conating.Coating fluid AR2 by dip-coating mode (go up pulling rate degree be per minute 15cm) be coated on the lens of band hard conating on thereafter.After the coating, with lens 80 ℃ air-dry 30 minutes, smoked 120 minutes at 120 ℃ again, obtain having the thick porous lens that prevent the reflection horizon of about 100nm.
To utilize coating fluid AR2 come film forming prevent that the reflection horizon from smoking after, its solid constituent contains 25 weight % γ-glycidoxypropyltrimewasxysilane, 15 weight % tetramethoxy-silicanes, 55 weight % hollow silicasol.Further, the multi-functional epoxy compound's (glycerine polyglycidyl ether) who also contains 5 weight %.
(water barrier)
The described lens surface that prevents the reflection horizon that has is carried out water-proofing treatment with fluorine one type of silane compound, obtain lens with waterproof membrane.
(dyeing)
The lens of band waterproof membrane were flooded 10 minutes in 94 ℃ disperse dye bath, dye.Dyeing lens for obtaining like this carry out test as described below, check each performance.
(embodiment 4)
(hard conating)
The coating fluid H4 that is used for the hard conating film forming as modulated.(catalyst changes into industry (strain) system with 207 parts of methyl proxitols, 625 parts of Titanium Dioxide Rutile Top grade complex sols, trade name Optolake 1120Z) mixes, and then add 71 parts of γ-glycidoxypropyltrimewasxysilane, (Nagase changes into industry (strain) system for 75 parts of glycerine polyglycidyl ethers, trade name Denacol EX313), obtain mixed liquor, drip 20 parts of 0.1N aqueous hydrochloric acid solutions while stirring to this mixed liquor, further stir 4 hours after, slaking 1 is round the clock.Then, add 2.3 parts of Fe (III) acetylacetonate, 0.3 part of silicone surfactant (Japan Unicar (strain) system, trade name L-7001), obtain coating fluid H4 to this mixed liquor.
By dip-coating method (going up the pulling rate degree is per minute 35cm) this coating fluid H4 is coated on the lens substrate (SSV, the lens of no substrate layer).After the coating, by with lens 80 ℃ air-dry 30 minutes, smoked 120 minutes at 120 ℃ again, obtain having the lens of the thick hard conating of 2.5 μ m.
After utilizing coating fluid H4 to come the hard conating of film forming to smoke, its solid constituent contains 50 weight % metal oxide microparticles (Titanium Dioxide Rutile Top grade complex sol), 20 weight % organosilicons (γ-glycidoxypropyltrimewasxysilane), 30 weight % multi-functional epoxy compounds (glycerine polyglycidyl ether).
(preventing the reflection horizon)
Then, this lens surface is carried out hydrophiling by Cement Composite Treated by Plasma.Then, will prevent the coating fluid AR2 of reflection horizon film forming, be coated on the lens that have hard conating by dip-coating mode (going up the pulling rate degree is per minute 15cm) with embodiment 3 identical being used to.After the coating, 80 ℃ air-dry 30 minutes, smoked 120 minutes at 120 ℃ again, obtain having the thick porous lens that prevent the reflection horizon of about 100nm.
(water barrier)
The described lens surface that prevents the reflection horizon that has is carried out water-proofing treatment with fluorine one type of silane compound, obtain lens with waterproof membrane.
(dyeing)
The lens of band waterproof membrane were flooded 10 minutes in 94 ℃ disperse dye bath, dye.Dyeing lens for obtaining like this carry out test as described below, check each performance.
(embodiment 5)
(hard conating)
The coating fluid H5 that is used for the hard conating film forming as modulated.With 162 parts of methyl proxitols, (catalyst changes into industry (strain) system to 625 parts of Titanium Dioxide Rutile Top grade complex sols, trade name Optolake 1120Z) mixes, and then add 53 parts of γ-glycidoxypropyltrimewasxysilane, 35 parts of 3-methacryloxypropyl trimethoxy silane, 32 parts of tetramethoxy-silicanes, 50 part 1, (Nagase changes into industry (strain) system to the 6-hexanediol diglycidyl ether, trade name Denacol EX212), obtain mixed liquor, drip 43 parts of 0.1N aqueous hydrochloric acid solutions while stirring to this mixed liquor, further stir after 4 hours, slaking 1 round the clock.Then, add 1.8 parts of Al (III) acetylacetonate, 0.3 part of silicone surfactant (Japan Unicar (strain) system, trade name L-7001), obtain coating fluid H5 to this mixed liquor.
By dip-coating method (going up the pulling rate degree is per minute 35cm) this coating fluid H5 is coated on the lens of belt material bottom.After the coating, by with lens 80 ℃ air-dry 30 minutes, smoked 120 minutes at 120 ℃ again, obtain having the lens of the thick hard conating of 2.3 μ m.
After utilizing coating fluid H5 to come the hard conating of film forming to smoke, its solid constituent contains 50 weight % metal oxide microparticles (Titanium Dioxide Rutile Top grade complex sol), 30 weight % organosilicons (γ-glycidoxypropyltrimewasxysilane, 3-methacryloxypropyl trimethoxy silane, tetramethoxy-silicane), 15 weight % multi-functional epoxy compounds (1, the 6-hexanediol diglycidyl ether).
(preventing the reflection horizon)
Then, with of the potpourri polishing of this lens surface with cerium oxide particulate and water.Then, will prevent the coating fluid AR1 of reflection horizon film forming, coat on the lens that have hard conating by dip-coating mode (going up the pulling rate degree is per minute 15cm) with embodiment 1 identical being used to.After the coating, 80 ℃ air-dry 30 minutes, smoked 60 minutes at 120 ℃ again, obtain having the thick porous lens that prevent the reflection horizon of about 100nm.
(water barrier)
Further, the described lens surface that prevents the reflection horizon that has is carried out water-proofing treatment with fluorine one type of silane compound, obtain lens with waterproof membrane.
(dyeing)
The lens of band waterproof membrane were flooded 10 minutes in 94 ℃ disperse dye bath, dye.Dyeing lens for obtaining like this carry out test as described below, check each performance.
(embodiment 6)
(hard conating)
The coating fluid H6 that is used for the hard conating film forming as modulated.(catalyst changes into industry (strain) system with 139 parts of methyl proxitols, 688 parts of Titanium Dioxide Rutile Top grade complex sols, trade name Optolake 1120Z) mixes, and then add 88 parts of γ-glycidoxypropyltrimewasxysilane, 17 parts of 3-methacryloxypropyl trimethoxy silane, (Nagase changes into industry (strain) system to 38 parts of T 55s, trade name Denacol EX314), obtain mixed liquor, drip 29 parts of 0.1N aqueous hydrochloric acid solutions while stirring to this mixed liquor, further stir after 4 hours, slaking 1 round the clock.Then, add 1.8 parts of Al (III) acetylacetonate, 1.1 parts of magnesium perchlorates, 0.3 part of silicone surfactant (Japan Unicar (strain) system, trade name L-7001), obtain coating fluid H6 to this mixed liquor.
By dip-coating method (going up the pulling rate degree is per minute 35cm) this coating fluid H6 is coated on the lens of belt material bottom.After the coating, by with lens 80 ℃ air-dry 30 minutes, smoked 120 minutes at 120 ℃ again, obtain having the lens of the thick hard conating of 2.2 μ m.
After utilizing coating fluid H6 to come the hard conating of film forming to smoke, its solid constituent contains 55 weight % metal oxide microparticles (Titanium Dioxide Rutile Top grade complex sol), 30 weight % organosilicons (γ-glycidoxypropyltrimewasxysilane, 3-methacryloxypropyl trimethoxy silane), 15 weight % multi-functional epoxy compounds (T 55).
(preventing the reflection horizon)
Then, with of the potpourri polishing of this lens surface with cerium oxide particulate and water.Then, will prevent the coating fluid AR2 of reflection horizon film forming, coat on the lens that have hard conating by dip-coating mode (going up the pulling rate degree is per minute 15cm) with embodiment 3 identical being used to.After the coating, 80 ℃ air-dry 30 minutes, smoked 60 minutes at 120 ℃ again, obtain having the thick porous lens that prevent the reflection horizon of about 100nm.
(water barrier)
Further, the described lens surface that prevents the reflection horizon that has is carried out water-proofing treatment with fluorine one type of silane compound, obtain lens with waterproof membrane.
(dyeing)
The lens of band waterproof membrane were flooded 10 minutes in 94 ℃ disperse dye bath, dye.Dyeing lens for obtaining like this carry out test as described below, check each performance.
(comparative example 1)
(substrate layer and hard conating)
On substrate (SSV) similarly to Example 1, similarly, be used for the coating fluid P1 of substrate layer film forming, form substrate layer by identical processing, thereby obtain the lens of belt material bottom.On the lens of this belt material bottom, use the coating fluid H1 that be used for hard conating film forming identical with embodiment 1, form hard conating by identical processing, thereby obtain lens with hard conating.
(preventing the reflection horizon)
Be used to form coating fluid (liquid of the low-refraction) AR3 that prevents the reflection horizon as modulated.In 25 parts of γ-glycidoxypropyltrimewasxysilane, 25 parts of tetramethoxy-silicane alkylating mixtures, add 21 parts of 0.1N aqueous hydrochloric acid solutions while stir, further stir 4 hours after, slaking 1 obtains mixed liquor round the clock.Then, to this mixed liquor add 889 parts of methyl proxitols, (catalyst changes into industry (strain) system to 40 parts of hollow silicasol, trade name Oscal special item), 0.08 part of magnesium perchlorate, 0.3 part of silicone surfactant (Japan Unicar (strain) system, trade name L-7001), obtain coating fluid AR3.
Before preventing the reflection horizon film forming, hydrophiling is carried out by Cement Composite Treated by Plasma in the surface of hard conating.Coating fluid AR3 by dip-coating mode (go up pulling rate degree be per minute kind 15cm) be coated on the lens of band hard conating on thereafter.After the coating, with lens 80 ℃ air-dry 30 minutes, smoked 60 minutes at 120 ℃ again, obtain having the thick porous lens that prevent the reflection horizon of about 100nm.
To adopt coating fluid AR3 come film forming prevent that the reflection horizon from smoking after, its solid constituent contains 45 weight % γ-glycidoxypropyltrimewasxysilane, 25 weight % tetramethoxy-silicanes, 30 weight % hollow silicasol.This liquid does not contain multi-functional epoxy compound's (glycerine polyglycidyl ether).
(water barrier)
The described lens surface that prevents the reflection horizon that has is carried out water-proofing treatment with fluorine one type of silane compound, obtain lens with waterproof membrane.
(dyeing)
The lens of band waterproof membrane were flooded 10 minutes in 94 ℃ disperse dye bath, dye.Dyeing lens for obtaining like this carry out test as described below, check each performance.
(comparative example 2)
On substrate (SSV) similarly to Example 1, use the same coating liquid P1 that is used for the substrate layer film forming, carry out substrate layer film forming (formation substrate layer) by same processing, thereby obtain the lens of belt material bottom.
(hard conating)
The coating fluid H5 that is used for the hard conating film forming as modulated.With 69 fens methyl proxitols, (catalyst changes into industry (strain) system to 750 parts of Titanium Dioxide Rutile Top grade complex sols, trade name Optolake 1120Z) mixes, and then add 141 parts of γ-glycidoxypropyltrimewasxysilane, obtain mixed liquor, drip 39 parts of 0.1N aqueous hydrochloric acid solutions while stirring to this mixed liquor, further stir after 4 hours, slaking 1 round the clock.Then, add 0.4 part of magnesium perchlorate, 0.3 part of silicone surfactant (Japan Unicar (strain) system, trade name L-7001), obtain coating fluid H5 to this mixed liquor.
By dip-coating method (going up the pulling rate degree is per minute 35cm) this coating fluid H5 is coated on the lens of belt material bottom.After the coating, by with lens 80 ℃ air-dry 30 minutes, further, smoked 120 minutes at 120 ℃, obtain having the lens of the thick hard conating of 2.1 μ m.
After adopting coating fluid H5 to come the hard conating of film forming to smoke, its solid constituent contains 60 weight % metal oxide microparticles (Titanium Dioxide Rutile Top grade complex sol), 40 weight % organosilicons (γ-glycidoxypropyltrimewasxysilane) do not contain the multi-functional epoxy compound.
(preventing the reflection horizon)
Then, this lens surface is carried out hydrophiling by Cement Composite Treated by Plasma.Then, will prevent the coating fluid AR1 of reflection horizon film forming, be coated on the lens of band hard conating by dip-coating mode (going up the pulling rate degree is per minute 15cm) with embodiment 1 identical being used to.After the coating, 80 ℃ air-dry 30 minutes, smoked 60 minutes at 120 ℃ again, obtain having the thick porous lens that prevent the reflection horizon of about 100nm.
(water barrier)
Further, the described lens surface that prevents the reflection horizon that has is carried out water-proofing treatment with fluorine one type of silane compound, obtain having the lens of waterproof membrane.
(dyeing)
The lens of band waterproof membrane were flooded 10 minutes in 94 ℃ disperse dye bath, dye.Dyeing lens for obtaining like this carry out test as described below, check each performance.
(test and evaluation)
The lens that to be made by embodiment 1～embodiment 6 and the dyeing color lens made by comparative example 1 and comparative example 2 carry out the test and the evaluation of relevant dyeability, thermotolerance, anti-reflection effect, stickability, mar resistance as subjects.The results are summarized in table 1.
For dyeability, estimate dyeing concentration, the dyeing inhomogeneity of the lens after the dyeing with visual inspection.Specifically, the degree of dyeing is come classification by visual inspection." ◎ " expression does not have inhomogeneity, and is coloured to full concentration, and " zero " expression does not have inhomogeneity but concentration is not enough, and " △ " expression dyeing inhomogeneity is obvious, or dyeing concentration is not enough, the serious or not dyeing of " * " dyeing inhomogeneity.
For thermotolerance, estimate by the temperature that mensuration cracks.Particularly, the lens of subjects are put into spectacle-frame after, be placed in 40 ℃ the baking oven with spectacle-frame, heated 30 minutes, from baking oven, after spectacle-frame takes out, at room temperature placed 30 minutes, use camera bellows to estimate on lens and whether crack by visual inspection.When not cracking, the temperature of baking oven is raise 10 ℃ again, once more subjects was heated 30 minutes with spectacle-frame.Then, take out, carry out and above-mentioned same evaluation from baking oven.Heat up with 10 ℃ temperature strides and to test, rise to 100 ℃ to the temperature of baking oven.In its process, the temperature when confirming to produce serious crackle is as cracking temperature.In this stable on heating evaluation criterion, " ◎ " expression crackle produces temperature and be 100 ℃ or do not crack yet that thermotolerance is high in the time of 100 ℃; The temperature that " zero " expression cracks is 80 ℃～90 ℃, the thermotolerance height; The temperature that " * " expression cracks is smaller or equal to 70 ℃, poor heat resistance.
With the surface reflectivity of the lens of spectrophotometer (U-3500 of Hitachi) determination test object and to preventing reflecting effect evaluation.Use spectrophotometer, measure the visible region (average reflectance (simultaneously) of 400nm～800nm).This prevents in the evaluation criterion of reflecting effect that " ◎ " expression average reflectance prevents that smaller or equal to 2% reflecting effect is splendid; " zero " expression average reflectance has to prevent reflecting effect fully smaller or equal to 3.5%; " * " expression average reflectance surpasses 3.5%, does not almost have the reflecting effect of preventing.
In order to estimate stickability, at first the lens with subjects are in sunlight weatherability case (placing 120 hours) in having the sunshine weather meter of xenon lamp, it are positioned under constant temperature and humidity again and (place 7 days in constant temperature and humidity cabinet 60 ℃ * 99% atmosphere gas).Then, for these subjects lens, estimate the stickability of lens substrate and surface-treated layer (substrate layer (being only limited to the lens of formation substrate layer), hard conating and prevent the reflection horizon).Specifically, for the subjects lens, carry out crosscut girdle tests (cross-cut tape test) according to the JISD-0202 standard.In this test, use pocket knife, on the substrate surface of each lens, every interval 1mm adds score, forms 100 1 square millimeter grid.Then, (Nichiban (strain) system, trade name " Cellotape (registered trademark) " is pressed thereon securely, spends directions from the surface with 90 and promptly draws and peel off with adhesive tape.Then, will detect by an unaided eye at the residual grid of coated film (surface-treated layer) as adhesive index.For adhesive evaluation criterion, the remaining area of " ◎ " expression coated film is 100%, and stickability is high; The remaining area of " zero " expression coated film is 95%～100%, the stickability height; The remaining area of " △ " expression coated film is 50%～95%, and stickability is relatively poor; " * " represents the remaining area of coated film less than 50%, poor adherence.
In the evaluation of mar resistance,, apply the loading of 1kg, reciprocating friction 10 times, the degree of visual inspection scratch with Bonstar#0000 steel wool (Japanese steel wool (strain) system) for the lens surface of subjects after the dyeing.The metewand of this mar resistance is divided into 10 grades (1 (poor)～10 (good)) by visual inspection, and wherein, " ◎ " is 10～8 grades, and mar resistance is high; " zero " is 7～6 grades, the mar resistance height; " △ " is 5～4 grades, and mar resistance is lower; " * " is 3～1 grades, and mar resistance is low.
The evaluation result of table 1 embodiment and comparative example lens
| Dyeability | Thermotolerance | Prevent reflecting effect | Stickability | Mar resistance | |
| Embodiment 1 | ◎ | ◎ | ◎ | ◎ | ◎ |
| Embodiment 2 | ◎ | ◎ | ◎ | ◎ | ◎ |
| Embodiment 3 | ◎ | ◎ | ◎ | ◎ | ◎ |
| Embodiment 4 | ◎ | ◎ | ◎ | ◎ | ◎ |
| Embodiment 5 | ◎ | ◎ | ◎ | ◎ | ◎ |
| Embodiment 6 | ◎ | ◎ | ◎ | ◎ | ◎ |
| Comparative example 1 | × | ◎ | ○ | ◎ | ◎ |
| Comparative example 2 | × | ◎ | ◎ | ○ | ◎ |
As shown in Table 1, by the dyeing lens that embodiment 1～embodiment 6 makes, dyeability, thermotolerance, prevent that whole evaluation results of reflecting effect, stickability, mar resistance from being " ◎ ".Therefore, be that dyeability is splendid, the lens that mar resistance is also high.Further, also be all good dyeing lens of endurance quality and look performance.Therefore, according to these tests as can be known, can obtain forming and prevent the lens that still can dye behind reflection horizon and the water barrier.
By the dyeing lens that comparative example 1 and comparative example 2 are made, obtain the result of dyeability difference.In the lens of comparative example 1, prevent to contain 30 weight % hollow silicasol among the coating fluid AR3 in reflection horizon, poriness is insufficient, prevents that the reflection horizon from can not fully see through dyestuff.In addition,, prevent that the reflection horizon can not have sufficient low-refraction, therefore prevent that reflecting effect is not good because the hollow silicasol is not enough.In the lens of comparative example 2, the coating fluid H5 of hard conating does not contain the multi-functional epoxy compound, and the dyeability of hard conating is poor, so can not dye, find in addition, because multi-functional epoxy compound's deficiency, thereby stickability reduces.
Therefore, in the lens of the present invention, on lens substrate, form hard conating and prevent the reflection horizon; Further also form water barrier; Can be colored then,, prevent that preferably the reflection horizon from containing 40%～85 weight % poriness silicon oxide particulate, 5%～60 weight % organo-silicon compound, at least 10 weight % multi-functional epoxy compounds for said lens of the present invention.In addition, preferably contain 60%～80 weight % poriness silicon oxide particulate, 20%～40 weight % organo-silicon compound.
In addition, preferred hard conating contains 40 weight %～70 weight % Titanium Dioxide Rutile Top grade particulates; More preferably contain 50 weight %～above-mentioned particulate of 60 weight %.
As substrate layer, preferably contain 20 weight %～80 weight % vibrin, 20 weight %～80 weight % Titanium Dioxide Rutile Top grade particulates; More preferably above-mentioned content is 40 weight %～60 weight %.
In addition, though above for example in, be that the example of plastic lens describes with substrate,, even glass lens also can obtain same effect.Further, in above giving an example, employed plastic lens in the glasses is fabricated to the dyeing lens, though except dyeability, also estimated permanance such as stickability, mar resistance, but going for dyeing lens of the present invention (optical element) and be not limited to eyeglass lens, also can be the camera lens.Further, the present invention's optical element prism for example of going for other.
Claims (12)
1. lens, it has lens substrate, hard conating, prevents the reflection horizon; Described hard conating directly or across substrate layer is laminated on the described lens substrate, and contains metal oxide microparticle, organo-silicon compound and multi-functional epoxy compound as principal ingredient; The described reflective layer that prevents is pressed on the described hard conating, and contains poriness silicon oxide particulate and organo-silicon compound as principal ingredient.
2. lens as claimed in claim 1, wherein, described hard conating contains Titanium Dioxide Rutile Top grade as metal oxide microparticle.
3. lens, hard conating, poriness that it has lens substrate, be colored prevent the reflection horizon; The described hard conating that has been colored directly or across substrate layer is laminated on the described lens substrate, and described poriness prevents that reflective layer is pressed on the described hard conating, and hard conating is dyeed across the described reflection horizon that prevents.
4. lens as claimed in claim 3, wherein, described hard conating contains Titanium Dioxide Rutile Top grade as metal oxide microparticle.
5. the manufacture method of lens, it has the 1st operation, the 2nd operation and dyeing process; In described the 1st operation, on lens substrate, form the hard conating that can be colored directly or across substrate layer; In described the 2nd operation, on described hard conating, form poriness and prevent the reflection horizon with damp process; In the described dyeing process, the object that dyes comprises described hard conating.
6. the manufacture method of lens as claimed in claim 5, wherein, described hard conating contains metal oxide microparticle, organo-silicon compound and multi-functional epoxy compound as principal ingredient; The described reflective layer that prevents contains poriness silicon oxide particulate and organo-silicon compound as principal ingredient.
7. the manufacture method of lens as claimed in claim 6, wherein, 40 weight %～described poriness silicon oxide particulate of 85 weight %, the 5 weight %～described organo-silicon compound of 60 weight %, the described multi-functional epoxy compound of maximum 10 weight % are contained in the described reflection horizon that prevents.
8. the manufacture method of lens as claimed in claim 6, wherein, described hard conating contains 40 weight %～70 weight % Titanium Dioxide Rutile Top grades as described metal oxide microparticle.
9. the manufacture method of lens, it has following operation: the hard conating that can be colored directly or across substrate layer is laminated on the lens substrate, and the described porous reflective layer that prevents is pressed on the hard conating, and the lens of above-mentioned formation are dyeed.
10. the manufacture method of lens as claimed in claim 9, wherein, described hard conating contains metal oxide microparticle, organo-silicon compound and multi-functional epoxy compound as principal ingredient; Poriness silicon oxide particulate and organo-silicon compound are contained as principal ingredient in the described reflection horizon that prevents.
11. the manufacture method of lens as claimed in claim 9, wherein, 40 weight %～described poriness silicon oxide particulate of 85 weight %, the 5 weight %～described organo-silicon compound of 60 weight %, the described multi-functional epoxy compound of maximum 10 weight % are contained in the described reflection horizon that prevents.
12. the manufacture method of lens as claimed in claim 10, wherein, described hard conating contains 40 weight %～70 weight % Titanium Dioxide Rutile Top grades as described metal oxide microparticle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004297211 | 2004-10-12 | ||
| JP2004297211 | 2004-10-12 | ||
| JP2005180204 | 2005-06-21 |
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| CN1760698A CN1760698A (en) | 2006-04-19 |
| CN100368828C true CN100368828C (en) | 2008-02-13 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8960899B2 (en) * | 2012-09-26 | 2015-02-24 | Google Inc. | Assembling thin silicon chips on a contact lens |
| WO2015163465A1 (en) * | 2014-04-24 | 2015-10-29 | ホヤ レンズ タイランド リミテッド | Eyeglass lens |
| EP3136140B1 (en) * | 2014-04-24 | 2021-02-17 | Hoya Lens Thailand Ltd. | Eyeglass lens |
| CN105319612B (en) * | 2014-07-22 | 2017-04-19 | 江苏淘镜有限公司 | Preparation method for colored eyeglass with colored coating |
| CN105572904B (en) * | 2016-01-21 | 2019-06-21 | 江苏视博光学眼镜有限公司 | Myopia sunglasses piece, preparation method |
| CN106950722B (en) * | 2017-04-12 | 2023-05-23 | 厦门腾诺光学科技有限公司 | Matte sun lens and production process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10319206A (en) * | 1997-05-20 | 1998-12-04 | Seiko Epson Corp | Laminated body |
| US20020018886A1 (en) * | 2000-02-23 | 2002-02-14 | Akihiro Matsufuji | Hard coat film and display device having same |
| US20030202137A1 (en) * | 1999-09-28 | 2003-10-30 | Fuji Photo Film Co., Ltd. | Anti-reflection film, polarizing plate comprising the same, and image display device using the anti-reflection film or the polarizing plate |
| CN1463367A (en) * | 2001-04-17 | 2003-12-24 | 索尼公司 | Antireflection film and antireflection layer-affixed plastic substrate |
-
2005
- 2005-10-12 CN CNB2005101128145A patent/CN100368828C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10319206A (en) * | 1997-05-20 | 1998-12-04 | Seiko Epson Corp | Laminated body |
| US20030202137A1 (en) * | 1999-09-28 | 2003-10-30 | Fuji Photo Film Co., Ltd. | Anti-reflection film, polarizing plate comprising the same, and image display device using the anti-reflection film or the polarizing plate |
| US20020018886A1 (en) * | 2000-02-23 | 2002-02-14 | Akihiro Matsufuji | Hard coat film and display device having same |
| CN1463367A (en) * | 2001-04-17 | 2003-12-24 | 索尼公司 | Antireflection film and antireflection layer-affixed plastic substrate |
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