CN106318370A

CN106318370A - Photochromic optical product and method for preparing same

Info

Publication number: CN106318370A
Application number: CN201610807643.6A
Authority: CN
Inventors: 黄肃明
Original assignee: Wenzhou Fuqi Shi Photoelectric Material Co Ltd
Current assignee: Wenzhou Fuqi Shi Photoelectric Material Co Ltd
Priority date: 2016-09-04
Filing date: 2016-09-04
Publication date: 2017-01-11
Also published as: WO2018041098A1

Abstract

The invention discloses a photochromic optical product. The photochromic optical product comprises an upper base material (a), a lower base material (b), a first photochromic coating (c), a second photochromic coating (c) and an adhesive layer (d). The first photochromic coating is coated on the lower surface of the upper base material, the second photochromic coating is coated on the upper surface of the lower base material, and the adhesive layer is arranged between the upper base material and the lower base material and is at least partially simultaneously coated on the first photochromic coating and the second photochromic coating, so that the upper base material and the lower base material can cling to each other. The invention further discloses a method for preparing the photochromic optical product.

Description

Photochromic optical article and preparation method thereof

Technical field

The present invention relates to optical element technology field, more particularly it relates to an photochromic optical article and system thereof Preparation Method.

Background technology

Photochromic is a kind of phenomenon, and this phenomenon includes photochromic compound, or the color of the goods containing this compound, Be exposed under the light containing ultraviolet irradiates is reversible change, and recovers turning of primitive color when ultraviolet irradiates and stops Become.Light irradiation source containing ultraviolet includes, such as, and sunlight and the light of mercury lamp.Stop ultraviolet irradiating and can pass through such as Photochromic compound or goods it is placed at dark or comes real by removing ultraviolet irradiation source (such as, in the way of optical filtering) Existing.

In prior art, main obstacle is applied to be for photochromic article large-scale commercial, on the one hand, to gather at solid In compound matrix, rate of photochromic activation is slow and fades, on the other hand, owing to being exposed repeatedly to ultraviolet light (UV) for a long time Under, they lose the ability of Show Color reversible transition, aging seriously.

Hence it is highly desirable to by technological improvement, with obtain a kind of can excellent photochromic of the ageing-resistant performance of life-time service Optical goods.

Summary of the invention

In order to solve the problems referred to above, one aspect of the present invention provides a kind of photochromic optical article, including:

(a) upper base material；

Base material under (b)；

(c) the first photochromic coating and the second photochromic coating, described first photochromic coatings base on described The lower surface of material, described second photochromic coatings is at the upper surface of described lower base material；With

D () adhesive layer, described adhesive layer is arranged between base material and lower base material, and is simultaneously coated on institute at least in part State on the first photochromic coating and described second photochromic coating, make base material fit with lower base material.

In one embodiment, described upper base material can be identical or different with lower base material, and is each independently selected from poly-to benzene In the copolymer of naphthalate, norborene and ethylene, acetylbutyrylcellulose and Triafol T at least A kind of.

In one embodiment, described photochromic coating is obtained by coating photochromic coating, described photochromic painting The raw material of preparing of material includes:

Base resin 100 weight portion；

Photochromic compound 0.1-30 weight portion；With

Organic solvent 10-1000 weight portion.

In one embodiment, described base resin is selected from polyurethane polymer, amino resins base polymer and propylene At least one in esters of gallic acid polymer.

In one embodiment, described organic solvent selected from ether solvents, alcoholic solvent, ester solvent, sulfoxide solvent, alkane solvent and At least one in ketone solvent.

In one embodiment, described adhesive is selected from (methyl) esters of acrylic acid adhesive, epoxy resin tackifier, gathers At least one in ammonia ester adhesive and polyimide adhesive.

The method that photochromic optical article is prepared in the another aspect offer of present aspect, including:

Base material and lower base material in offer；

Photochromic coating is coated on the lower surface of described upper base material and the upper surface of described lower base material, respectively obtains One photochromic coating and the second photochromic coating；And

Adhesive is covered on the lower surface of base material on described and the upper surface of described lower base material the most simultaneously, make Upper base material is fitted with lower base material.

In one embodiment, described photochromic optical article selected from ophthalmic articles, display goods, window, mirror, with And the one in active liquid crystal wafer goods and passive liquid crystal wafer goods.

In one embodiment, described ophthalmic articles is selected from correcting lens, non-correcting lens, contact lens, intraocular lens, puts One in big lens, protection lens and protective eye lens.

In one embodiment, described display goods one in screen, monitor and safety element.

It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.

Accompanying drawing explanation

In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing skill In art description, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only the present invention Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to These accompanying drawings obtain other accompanying drawing.

Fig. 1: photochromic optical article schematic diagram, wherein, 1 represents upper base material, and 2 represent the first photochromic coating, 3 adhesive Layer, 4 represent the second photochromic coating, and 5 represent lower base material.

Detailed description of the invention

Participate in the election of the detailed description being preferable to carry out method of the invention below and the embodiment that includes can be more easily understood in the disclosure Hold.Can mention a large amount of term in description below and claims, these terms are defined as following meanings.

Singulative includes that plural number discusses object, unless the context clearly dictates otherwise.

" optional " or " any one " refer to that the item described thereafter or event may or may not occur, and this description The situation that the situation occurred including event and event do not occur.

Express a scope and include all integers in the range of this and its mark.Express a scope and also include the end of this scope Point, does not consider that this scope indicates whether a numerical value of some described numerical value " interior " or " between " or " ".Present disclosure and Scope described in claim is intended to particularly including four corner and is not only one or more end points.Such as, 0 to 10 institute All integers that the scope intention illustrated discloses between 0 and 10, such as 1,2,3,4 etc., all marks between 0 and 10, such as 1.5,2.3,4.57,6.1113 etc., and end points 0 and 10.

As used herein, term " photochromic " and similar terms such as " photochromic compound " represent at least may be used Seeing that light has absorption spectrum, it is in response to the absorption of at least photochemical radiation and changes.Additionally, as used herein, art Language " photochromic material " represents any such material, and it is suitable to show that photochromic properties (that is, is suitable to have at least may be used Seeing the absorption spectrum of light, it is in response to the absorption of at least photochemical radiation and changes), and it includes at least one light-induced variable Color compound.

As used herein, term " photochromic compound " includes the photochromic compound of thermal reversion and non-thermoreversible Photochromic compound.As used herein, term " photochromic compound/material of thermal reversion " represents such chemical combination Thing/material, it can be converted into the second state from the first state such as " pellucidity " when response light chemical radiation and such as " Color state ", and it is restored back to the first state when responding heat energy.As used herein, term " non-thermoreversible photochromic Compound/material " represent such compound/material, it can be such as " transparent from the first state when response light chemical radiation State " change into the second state such as " colored state ", and responding the wavelength essentially identical with the absorption of the state of coloring Photochemical radiation time be restored back to the first state (such as, stop be exposed to such photochemical radiation).

As used herein, term " optics " represents and belongs to or relevant with light and/or vision.Such as according to disclosed herein Different nonlimiting embodiments, these optical goods or element or device can be selected from ophthalmic articles, element and device, display Goods, element and device, window, mirror, and active and passive liquid crystal wafer goods, element and device.

As used herein, term " ophthalmology " represents and belongs to or relevant with eyes and vision.Ophthalmic articles or element are non- Determinate example includes correcting and non-correcting lens, and including single vision or many visions lens, it can be segmentation or overstepping one's bounds Many visions lens (such as but not limited to bifocal lens, three focus lens and progressive lens) of section, and other are used for correcting, protecting Protect or strengthen (cosmetic or other) vision element, including but not limited to contact lens, intraocular lens, amplifying lens and protection Lens or protective eye lens.

As used herein, term " ophthalmology substrate " represents lens, the lens of part formation and lens base substrate.

As used herein, term " show " represent the word of visible or machine-readable, numeral, symbol, design or The information representation that person draws.The example of display goods, element and device indefiniteness includes screen, monitor and safety element, Such as safety label.

As used herein, term " window " expression is used for allowing light transmitted through hole therein.The example of window indefiniteness Including automobile and aircraft clear glass, wave filter, shutter and optical converter.

As used herein, term " mirror " represents the surface of the incident illumination of direct reflection major part or essential part.

As used herein, term " liquid crystal cell " refers to the structure containing the liquid crystal material that can orient.Active liquid crystal Wafer is such box, and wherein by applying external force such as electric field or magnetic field, liquid crystal material can be between orderly and disordered state Or switching reversible He controlled between two order states or conversion.Passive liquid crystal wafer is such box, wherein Liquid crystal material keeps order state.The example of active liquid crystal wafer element or one indefiniteness of device is liquid crystal display.

As used herein, term " coating " represents the loaded film deriving from flowable composition, and it may or may not have There is uniform thickness, and specifically get rid of polymer sheet.The prime coat of the photochromic article of the present invention, Photochromic-Dichroic Layer and optional top coat can be coatings in some embodiments independently of one another.

As used herein, term " sheet " represents the film of a kind of preforming, and it has the most uniform thickness and can control oneself.

As used herein, term " polymer " " represent homopolymer (such as being prepared), copolymer (example by single monomeric substance As prepared by least two monomeric substance) and graft polymers.

As used herein, term " (methyl) acrylate " and similar terms such as " (methyl) acrylate " represent methyl Acrylate and/or acrylate.As used herein, term " (methyl) acrylic acid " represents methacrylic acid and/or third Olefin(e) acid.

As used herein, space or direction term such as "left", "right", " interior ", " outward ", " on ", D score etc. work as the present invention Associated during expression in the accompanying drawings.It is to be understood, however, that the present invention can assume that different selectable orientations, and therefore this The term of sample is not qualified as determinate.

As used herein, term " ... upper formation ", " ... upper deposition ", " provide and exist ... on ", " it is administered to ... on ", " occupy ... on " or " it is arranged in ... on " represent and formed on following element or elements below surface, deposit, provide, execute With, reside or arrange, but nonessential therewith directly (or adjacent) contact.The layer such as " being arranged in substrate " is not excluded for one Or the existence of other layers, coating or the film of multiple identical or different composition, layer that is that it is positioned at location or that formed and substrate Between.

One aspect of the present invention provides a kind of photochromic optical article, including:

(a) upper base material；

Base material under (b)；

Upper base material and lower base material

The plastics of upper base material and lower base material for forming the application are not particularly limited, and can be commercially available or experiment synthesis 's.

In one embodiment, described upper base material can be identical or different with lower base material, and is each independently selected from poly-to benzene In the copolymer of naphthalate, norborene and ethylene, acetylbutyrylcellulose and Triafol T at least A kind of；Preferably, described upper base material and the lower identical material of base material employing, and all use Triafol T.

First photochromic coating and the second photochromic coating

First photochromic coating of the application and the second photochromic coating obtain by coating identical photochromic coating, This photochromic coating can be commercially available or experiment synthesis.

Base resin 100 weight portion；

Photochromic compound 0.1-30 weight portion；With

Organic solvent 10-1000 weight portion.

Base resin

Base resin for the application is not particularly limited, and can be commercially available or experiment synthesis.

In one embodiment, described base resin is selected from polyurethane polymer, amino resins base polymer and propylene At least one in esters of gallic acid polymer；Preferably, described base resin is the aqueous dispersion of polyurethane resin, and it is derived from poly-carbon The skeleton of acid esters and percentage elongation are 200～1000%.The aqueous dispersion of polyurethane resin is defined as wherein disperseing to meet this " aqueous dispersion of polyurethane resin " (is only claimed below as the case may be by the aqueous dispersion of the polyurethane resin of class physical property For " (A)-component ").

Being derived from the skeleton of Merlon owing to polyurethane resin has, therefore it comprises polycarbonate polyol and polyisocyanates Product.Usually as the polyhydric alcohol of composition polyurethane resin, use poly alkylene glycol, PEPA, polyethers many Unit alcohol, polyester ether polylol etc..However, it is contemplated that improve the adaptation relative to various optical elements and the effect of resistance to impact Really, it is important that use polycarbonate polyol.It is to say, according to the present invention, had by use and be derived from Merlon The polyurethane resin of skeleton can obtain the effect of excellence.

As polycarbonate polyol, can unrestrictedly use known polycarbonate polyol, and can poly-(the alkylidene carbon of example Acid esters) such as poly-(hexa-methylene carbonic ester) etc..

The illustrative examples of above-mentioned polyisocyanates include aromatic isocyanate compound such as toluene di-isocyanate(TDI), 4,4-bis- Phenylmethane diisocyanate, XDI, 1,5-naphthalene diisocyanate, toluidine diisocyanate, penylene two are different Cyanate, 4,4-diphenyl diisocyanate, dianisidine diisocyanate, 4,4-diphenyl ether diisocyanate, three Phenylmethane triisocyanate, tri o cresyl thiophosphate phenyl isocyanate, tetramethylxylene diisocyanate etc., and aliphatic is different Cyanate esters such as 1,3,3-trimethyl hexamethylene diisocyanates, 4,4 '-, 2,4 '-or 2,2 '-dicyclohexyl methyl hydride two Isocyanates or its mixture, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylen two Carbimide. Ester, lysinediisocyanate, lysine ester triisocyanate (lysineestertriisocyanate), 1,6,11-ten one Alkane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, 1,3,6-hexa-methylene triisocyanates, dicyclo Heptane triisocyanate etc..

The polyurethane resin used in the present invention is made up of above-mentioned polycarbonate polyol and above-mentioned polyisocyanurate, but can wrap Contain the polyisocyanates with more than one sulphur atom or halogen atom, and denaturant such as biuret, isocyanuric acid ester, urea groups first Acid esters, carbodiimide etc..

Additionally, as the polyurethane resin used in the present invention, the polyurethane resin with cross-linked structure is preferably used.By making With molecule has the polyurethane resin of cross-linked structure, the coating composition being used for being formed hard conating is applied to silane coupling agent coating Time upper, the silane coupling agent coating dissolubility resistent to coating composition can be strengthened to shorten the manufacturing time of duplexer.Further, thus obtain The duplexer obtained is excellent in terms of outward appearance and resistance to impact.

In the present invention, can use have 200～1000% the polyurethane resin of percentage elongation as above-mentioned polyurethane resin.Work as elongation When rate is less than 200%, the resistance to impact of the optical goods with the silane coupling agent coating being formed on is not enough；Its reason is probably The reduction of pliability of the silane coupling agent coating obtained.When percentage elongation more than 1000% time, it is thus achieved that optical goods performance adversely Deterioration；Its reason is probably silane coupling agent coating and becomes excessively soft.Specifically, wrapped by solidification when being formed in silane coupling agent coating During the hard conating obtained containing the coating composition of inorganic oxide fine particle and organo-silicon compound, the marresistance of hard conating Reducing, the resistance to impact of the duplexer (having the optical goods of hard conating) simultaneously obtained reduces.Therefore, not preferably this type of elongation The rate situation more than 1000%.

In the purposes (purposes of first, second, and third laminate) improving photochromic coating and the adaptation of optical element In, it is undesirable that the percentage elongation of polyurethane resin is unsatisfactory for the situation of above-mentioned scope, this is because can not improve close fully Conjunction property.

Accordingly, it is considered to the optical goods obtained, duplexer, the performance of first cascade goods, the percentage elongation of polyurethane resin is excellent Select 250 to 900%.

In the present invention, the percentage elongation of polyurethane resin is measured with methods described below: first, will comprise the moisture of polyurethane resin A prose style free from parallelism loads in container such as cell (chalet) so that the film thickness of dried polyurethane resin becomes about 500 μm, at room temperature It is dried 24 hours, is dried at a temperature of 80 DEG C 6 hours, is then dried 20 minutes at a temperature of 120 DEG C, thus prepares polyurethane The film of resin.Hereafter, the film of polyurethane resin is cut into the size of 15mm (width) × 200mm (length), then with The equal intervals of 50mm makes the mid portion of labelling and prepares test film.This test film thus prepared is fixed to tension test Machine, then by drawing test film to make it rupture to measure and stretch with the speed of 200mm/ minute and handgrip (grips) spacing of 100mm Long rate.Measuring temperature is 23 DEG C.Method calculating percentage elongation with as described below:

Percentage elongation (%)=((during fracture before distance-test between labelling distance) between labelling/(before test between labelling away from From)) × 100

Optimization polyurethane resin has 200 measured in the manner～the percentage elongation of 1000% and has simultaneously 100% modulus of 1.5 to 18N/mm2.100% modulus is the value simultaneously measured with above-mentioned percentage elongation and refers to when above-mentioned poly-ammonia The length of the film (test film) of ester resin is 2 (two) times (100% percentage elongation) of the front length (the handgrip spacing before test) of test Time stress.Owing to 100% modulus of polyurethane resin meets above-mentioned scope, so optical goods, the stacking obtained can be improved The performance of body, first cascade goods etc..

Although the polyurethane resin that use is not specially limited in the present invention, as long as its percentage elongation meets above-mentioned scope, but Its glass transition point (Tg) preferably smaller than 0 DEG C, more preferably less than-5 DEG C and most preferably less than-10 DEG C.Had little by use In the polyurethane resin of the Tg of 0 DEG C, can more improve the resistance to impact of optical goods, duplexer, first cascade goods etc. and close Conjunction property.Although the bottom line of the Tg without particular limitation of polyurethane resin, but consider productivity ratio and the acquisition of polyurethane resin Optical goods, duplexer, the performance of first cascade goods etc., its preferably more than-100 DEG C, more preferably more than-70 DEG C, and Preferably more than-50 DEG C.

The above-mentioned Tg of polyurethane resin is the value measured in following such mode: by be used for measuring stretching of urethane resin film The test film that the urethane resin film of long rate is similar to is used as Tg measurement test film.By using this test film, by means of " DMS 5600 " (trade name, the SII Co., Ltd. dynamic viscoelastic manufactured measures equipment) measures Tg.Survey under the following conditions Amount: i.e., deformation pattern: stretching, programming rate: 5 DEG C/min, measure frequency: 10Hz, measurement temperature range :-100 DEG C to 200 ℃。

In the present invention, use aqueous dispersion (the polyurethane tree being dispersed in water of the polyurethane resin meeting above-mentioned percentage elongation Fat).The mean diameter of the polyurethane resin in aqueous dispersion is preferably greater than below 50nm to 140nm.When mean diameter is for being more than During 140nm, when for improve the purpose to the wettability of plastic lens (optical goods) and during interpolation lower alcohol as described below, the end The bin stability of coating material composition self tends to declining.It is presumed that, this is because owing to polyurethane resin is prone to rudimentary In alcohol swelling, viscosity increases along with the increase of the addition of lower alcohol, and this makes the optical goods silane coupling agent group of the present invention Compound is unstable.On the other hand, when in aqueous dispersion, the mean diameter of polyurethane resin is below 50nm, it is difficult to prepare poly-ammonia The aqueous dispersion of ester resin self.Speculate, owing to the mean diameter of the polyurethane resin in aqueous dispersion meets above-mentioned scope, when When it is with following organic solvent combination, can be formed and there is the uniform films (silane coupling agent coating) of excellent flatness and therefore can get There are the optical goods of excellent appearance.Additionally, it is believed that owing to polyurethane resin meets the above-mentioned scope of mean diameter, storage can be improved Deposit stability.

The mean diameter of the polyurethane resin in aqueous dispersion is by laser diffraction and scattering particle diameter distribution measurement apparatus " LS230 " The value that (trade name of Beckman Coulter Co.Ltd.) is measured.In the present invention, the particle diameter of polyurethane resin is by making apparatus Laser and this type of measurement equipment of having 750nm wavelength are measured by means of optical diffraction method.Mean diameter in the present invention is logical Cross the bulk averaged value that this type of method is measured.

In the present invention, the concentration (concentration of the solid composition of polyurethane resin) of the polyurethane resin in aqueous dispersion can be according to difference Demand type, such as application target and suitably determine, and preferable 3 to 60 quality %.For improving polyurethane resin Stability or the purpose of film property, in the aqueous dispersion of the polyurethane resin that can use in the present invention with preferably 10 mass % with Under, add below more preferably 7 mass % in addition to water there is high boiling organic solvent such as N-Methyl pyrrolidone etc..

As the aqueous dispersion of the polyurethane resin meeting above-mentioned requirements, those being obtained commercially, concrete example can be used " SUPERFLEX " series (being manufactured and for registered trade mark by Dai-ichi Kogyou Seiyaku Co.Ltd.), " NEOSTECKER " series and " EVAFANOL " series (are registrations by NICA CHEMICAL Co., Ltd.'s manufacture and both of which Trade mark), " HYDRAN " series (manufactured by DIC Corporation and for registered trade mark).

Photochromic compound

Photochromic compound without particular limitation of, and known compound can be used.Such as, can use described in documents below Photochromic compound: Japan patent applicant announce (Toku-kai-Hei) 2-28165, Japan patent applicant announce (Toku- Kai-Sho) 62-288830, International Publication WO94/22850 pamphlet, International Publication WO96/14596 pamphlet, International Publication WO01/60811 pamphlet, United States Patent (USP) 4913544 and United States Patent (USP) 5623005.The amount of photochromic compound can be according to light Mutagens color smears or the purposes of cast curing property compositions and suitably determine.

In one embodiment, the non-limitative example of described photochromic compound is to have desired chrominance color Photochromic compounds.They are generally of the absworption peak of at least one activation in the range of about 400-700nm.They Can be used alone or be used in combination with supplementing its photochromic compound activating color.

In a non-limiting detailed description of the invention, described photochromic compound includes chromene, such as aphthopyrans, benzo Pyrans, indole aphthopyrans and phenanthro-pyrans；Spiro-pyrans, such as spiral shell (benzo indoline) aphthopyrans, spiral shell (indoline) .alpha.-5:6-benzopyran, spiral shell (indoline) aphthopyrans, spiral shell (indoline) quinopyrans and spiral shell (indoline) pyrans；Piperazine, example Such as spiral shell (indoline) azophenlyene, spiral shell (indoline) pyridobenzoxazines, spiral shell (benzo indoline) pyrido benzo Piperazine, spiral shell (benzo indoline) azophenlyene and spiral shell (indoline) benzimidazole dihydrochloride；The dithizonate of hydrargyrum, fulgide, floating essence acyl Amine, and the mixture of these photochromic compounds.These photochromic compounds United States Patent (USP) US5,645,767, US6,153,126 and US6,296,785B1 the 30th walks to be described in the 31st hurdle the 5th row in hurdle the 44th.

Organic solvent

Organic solvent for the application is not particularly limited, in one embodiment, described organic solvent selected from ether solvents, At least one in alcoholic solvent, ester solvent, sulfoxide solvent, alkane solvent and ketone solvent；Preferably, described organic solvent is that ether is molten Agent, and selected from ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol list n-propyl ether, second two Alcohol list n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol list n-propyl ether, Propylene glycol list n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl acetas, dioxane etc.；Ketone such as two Pyruvic alcohol etc..Above-mentioned all in, it may be preferred to DAA, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol list At least one in n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl.

Further, the raw material of preparing of described photochromic coating also includes: the organo-silicon compound 1-20 containing hydrolyzable groups Weight portion and inorganic oxide fine particle 10-200 weight portion.

Organo-silicon compound containing hydrolyzable groups

The optical goods primer composition of the present invention can comprise the organo-silicon compound containing hydrolyzable groups.Contain by being blended The organo-silicon compound of hydrolyzable groups, can improve the closely sealed of formed silane coupling agent coating and optical element (plastic lens) Property, the silane coupling agent coating formed and the adaptation of hard conating, and the silane coupling agent coating formed further is with photochromic The adaptation of coating.

The preferably illustrative examples of the organo-silicon compound containing hydrolyzable groups includes γ-glycidoxypropyl trimethoxy silicon Alkane, γ-glycidoxypropyl dimethoxysilane, γ-glycidoxypropyl diethoxy silane, γ-epoxy third Oxygen propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, tetraethoxysilane, vinyl front three TMOS, VTES, vinyltriacetoxy silane, MTMS, methyl three ethoxy Silane, methyl triple phenoxyl silane, dimethyldimethoxysil,ne, trimethylmethoxysilane, phenyltrimethoxysila,e, two Phenyidimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, n-pro-pyl trimethoxy silane, normal-butyl trimethoxy silicon Alkane, trimethoxysilane, isobutyl triethoxy silane, n-hexyl trimethoxy silane, n-hexyl triethoxysilicane Alkane, n-octytriethoxysilane, positive decyl trimethoxy silane, 1,6-double trimethoxy silane, 3-ureido-propyl three ethoxy Base silane, double [3-(diethoxymethyl silicyl) propyl group] carbonic ester, trifluoro propyl trimethoxy silane, perfluor Flos Magnoliae base Triethoxysilane, γ-r-chloropropyl trimethoxyl silane, vinyl three ('beta '-methoxy-ethyoxyl) silane, pi-allyl trimethoxy Base silane, γ-acryloxypropyl trimethoxy silane, γ-acryloxypropyl triethoxysilane, γ-methyl-prop Alkene acryloxypropylethoxysilane trimethoxy silane, γ-methacryloxypropyl, γ-methacryloxy Dimethylamine epoxide methyl-monosilane, γ-mercaptopropyi trialkoxy silane, γ-aminopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-Asia Butyl) propylamine, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxy silicon Alkane, N-2-(aminoethyl)-3-aminopropyltriethoxy dimethoxysilane, to styryl trimethoxy silane, 3-isocyanates third Ethyl triethoxy silicane alkane etc. and their part or all of hydrolyzate or partial condensation products thereof.Wherein, preferable γ- Glycidoxy-propyltrimethoxy silane, γ-glycidoxypropyl dimethoxysilane, tetraethoxysilane, methyl three Ethoxy silane, γ-acryloxypropyl trimethoxy silane, γ-acryloxypropyl triethoxysilane, γ-metering system Monomethacryloxypropyl trimethoxy silane and their part or all of hydrolyzate, or partial condensation products thereof, in order to improve optics The adaptation of base material and (it comprises inorganic oxide fine particle and siliconated containing hydrolyzable groups by solidification to hard conating The coating composition of compound obtains, and is laminated on silane coupling agent coating or photochromic coating) adaptation.Above-mentioned have Organic silicon compound can being applied in combination individually or with two or more.

Inorganic oxide fine particle

By adding inorganic oxide fine particle, the refractive index of the silane coupling agent coating obtained can be improved, and can more improve hard painting The marresistance of layer.Inorganic oxide fine particle can be used together with the above-mentioned organo-silicon compound containing hydrolyzable groups or individually Use.It addition, when in order to improve the refractive index of photochromic coating and improve hard painting by adding inorganic oxide fine particle The marresistance of layer.

Specifically, silicon dioxide can be used as inorganic oxide fine particle.When adding inorganic oxide to increase refractive index During fine grained, preferably use and comprise in the group selecting free Si, Al, Ti, Fe, In, Zr, Ag, Au, Sn, Sb, W and Ce composition The inorganic oxide of at least one element or the fine grained of composite inorganic oxide；More particularly, it may be more preferable to use and comprise choosing The inorganic oxide of at least one element in the group of free Si, Al, Ag, Ti, Fe, Zr, Sb and W composition or composite inorganic oxidation The fine grained of thing.As composite inorganic oxide fine particle, preferably comprise the nano silicon of 10 mass %, 30 mass % Stannum oxide, the antimony pentoxide of 10 mass %, the silver oxide of 10 mass and the iron sesquioxide of 40 mass %；

Make that the particle diameter of inorganic oxide fine particle is preferably observed by transmission electron microscope (TEM) about 1～the one of 300nm Secondary particle diameter.The fine grained with this particle diameter is generally scattered in the water of disperse medium using it or the aftermentioned organic solvent of part State in (especially, alcohol race solvent) uses；Colloidal dispersion is commonly used to prevent fine grained and condenses.Such as, in the present invention, From inorganic oxide fine particle homodisperse viewpoint in optical goods primer composition, preferably that inorganic oxide is thin The solation that granule is scattered in water-miscible organic solvent such as methanol, ethanol, isopropanol etc. or water with them adds optics to In goods primer composition.

As it has been described above, as the water-miscible organic solvent for inorganic oxide fine particle disperse medium, preferable alcoholic solvent Such as methanol, ethanol, isopropanol etc.；But it is used as butanone, methyl iso-butyl ketone (MIBK), dimethyl acetylamide etc..

That is, in the present invention, preferably it is dispersed in water with inorganic oxide fine particle or colloidal sol in above-mentioned water-miscible organic solvent Form, specifically with silicon dioxide gel, inorganic oxide fine particle colloidal sol or the shape of composite inorganic oxide fine particle colloidal sol Formula, mixes inorganic oxide fine particle with other component.The order mixed with other component by inorganic oxide fine particle is not It is particularly limited to.

Silica sol can be obtained commercially；Such as, the colloidal sol of disperse medium is comprised water as from NISSAN CHEMICAL INDUSTRIES, LTD registered trade mark is that " Snowtex ", " Snowtex OS ", " Snowtex O " or " Snowtex O-40 " purchases ?.Comprise the water-miscible organic solvent colloidal sol as disperse medium from NISSAN CHEMICAL INDUSTRIES, LTD trade name For " methanol silica sol ", " MA-ST-MS " (disperse medium: methanol), " IPA-ST " (disperse medium: isopropanol) etc. Buy.

The colloidal sol of composite inorganic oxide fine particle can also be obtained commercially；Such as, example is by NISSAN CHEMICAL " HX series ", " HIT series " or " HT series " that INDUSTRIES, LTD manufacture and by JGC Catalyst and " OPTLAKE " (registered trade mark) that Chemicals Ltd. manufactures.

Other component:

Additionally, for the purpose of the flatness improving the silane coupling agent coating obtained, preferably by levelling agent (leveling agent) Make an addition in the optical goods primer composition used in the present invention.Known levelling agent can be used not limit, and Preferably example includes silicone-based, fluorine system, acryloyl base system, ethylene base system etc..Preferably with 10～10000ppm, more preferably with 50～5000ppm add levelling agents in the optical goods primer composition of the present invention.

Adhesive

Adhesive for the application is not particularly limited, and can be commercially available or experiment synthesis.It is selected from acrylate In class adhesive, epoxy resin tackifier, polyurethane tackifier and polyimide adhesive any one or many Kind.

Preferably, adhesive used by the present invention is esters of acrylic acid adhesive, and described esters of acrylic acid adhesive, and it is prepared Raw material includes:

The acrylate copolymer of 100 weight portions；

The ester plasticiser of 0.01～20 weight portions；

The alkali metal salt of 0.001～7 weight portions；

Amino silane modified beta-schardinger dextrin--graphene oxide-the polybenzimidazole compound of 0.01～10 weight portions and

The epoxy-capped polyetheramine of 0.01～10 weight portions；

Weight average molecular weight Mw of described acrylate copolymer is 100000～2000000, and dispersion Mw/Mn is 4～20；

Described ester plasticiser is selected from diethylene glycol-two 2-ethylhexanoate, TEG two-2-ethylhexanoate, Polyethylene Glycol Two-2-ethylhexanoate, triethylene glycol diethyl butyrate, Polyethylene Glycol diethyl butyrate, polypropylene glycol diethyl caproic acid Ester, triethylene glycol dibenzoate, polyethylene glycol dibenzoate, dibenzonate and Polyethylene Glycol-2-ethyl Any one or more in caproate benzoate；

Described alkali metal salt any one or more in lithium perchlorate, trifluoromethanesulfonic acid lithium and sodium perchlorate.

In one embodiment, described acrylate copolymer is to be caused comonomer to be gathered by solution by radical initiator Conjunction obtains；Initiator is the one in azo-bis-isobutyl cyanide or dibenzoyl peroxide, and the gross weight that initiator adds is single The 0.03%～0.6% of body gross weight；Copolymerization temperature is 50 DEG C～100 DEG C；Polymerization process uses N₂Protection；Polymerisation in solution is adopted Solvent be organic solvent, for aromatic hydrocarbon, esters, the mixture of one or more in alcohols and ketone.

In one embodiment, described amino silane modified beta-schardinger dextrin--graphene oxide-polybenzimidazole compound by with Lower section method prepares:

1) by 0.16 mole 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS) be first dissolved in containing 85wt% phosphorus pentoxide more than 1000 grams In polyphosphoric acid, then by the 1 of 0.1 mole, during between 3,5-, benzenetricarboxylic acid joins reactant liquor, after 200 DEG C of reactions 20 hours, it is down to Room temperature, in precipitating to water, then neutralizes with ammonia, filters, be vacuum dried, obtain amino-terminated hyperbranched polyphenyl at 100 DEG C And imidazoles；

2), after 10 grams of beta-schardinger dextrin-s being completely dissolved in acetum, add 10 grams of steps 1) described in amino-terminated hyperbranched poly- Benzimidazole, 3 grams of graphene oxides, 3 grams of amino silicane coupling agent KH-550,2 grams of glutaraldehydes and 2 gram 1,3-dibromopropane is also Ultrasonic disperse, regulation pH value of solution is between 8.0～9.0；At 55～65 DEG C, stir 1.5～2.5h, obtain precipitate, in cleaning extremely Property is also dried, and obtains amino silane modified beta-schardinger dextrin--graphene oxide-polybenzimidazole compound.

In one embodiment, described epoxy-capped polyetheramine is prepared by following methods:

The epoxy resin E51 of 100 grams and the benzylamine of 0.23 mole being dissolved in 2000 grams of propylene glycol monomethyl ethers, nitrogen is protected Under, after 100 DEG C are reacted 4 hours, it is down to room temperature and with after deionized water cyclic washing product, in vacuum drying oven, 50 DEG C are dried 5 Hour, obtain described epoxy-capped polyetheramine.

Base material and lower base material in offer；

Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following example are served only for right The present invention is described further, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field according to Some nonessential improvement and adjustment that the content of the invention described above is made, still fall within protection scope of the present invention.

It addition, illustrate without other, raw materials used is all commercially available, and number used by following material is weight portion.

Raw material:

A1: Triafol T

A2: polyethylene terephthalate

A3: acetylbutyrylcellulose

B1: photochromic coating, its preparation method is: by aqueous dispersion " SUPERFLEX420 " 100 weight of polyurethane resin Part, spiral shell (benzo indoline) aphthopyrans 15 weight portion, and ethylene glycol monomethyl ether 800 weight portion mix homogeneously obtain；

Described " SUPERFLEX420 " (registered trade mark is manufactured by Dai-ichi Kogyou Seiyaku Co.Ltd., average particle Footpath: 120nm, percentage elongation: 280%, Tg:-20 DEG C, 100% modulus: 15N/mm²Gu, composition (polyurethane resin) concentration: about 32 Quality %, water: about 65 mass %, contain the skeleton being derived from Merlon, cross-linking).

B2: photochromic coating, its preparation method is: by aqueous dispersion " SUPERFLEX420 " 100 weight of polyurethane resin Part, spiral shell (indoline) pyrans 15 weight portion, ethylene glycol monomethyl ether 800 weight portion, γ-glycidoxypropyl diethoxy Base silane 15 weight portion, nano silicon 25 weight portion mix homogeneously obtain；

B3: photochromic coating, its preparation method is: by aqueous dispersion " SUPERFLEX420 " 100 weight of polyurethane resin Part, spiral shell (indoline) pyrans 15 weight portion, ethylene glycol monomethyl ether 800 weight portion, γ-glycidoxypropyl diethoxy Base silane 15 weight portion, nano silicon 25 weight portion mix homogeneously obtain；

B4: photochromic coating, its preparation method is: by aqueous dispersion " SUPERFLEX420 " 100 weight of polyurethane resin Part, spiral shell (indoline) pyrans 15 weight portion, ethylene glycol monomethyl ether 800 weight portion, γ-glycidoxypropyl diethoxy Base silane 15 weight portion, composite inorganic oxide fine particle 25 weight portion mix homogeneously obtain；

Described " SUPERFLEX420 " (registered trade mark is manufactured by Dai-ichi Kogyou Seiyaku Co.Ltd., average particle Footpath: 120nm, percentage elongation: 280%, Tg:-20 DEG C, 100% modulus: 15N/mm²Gu, composition (polyurethane resin) concentration: about 32 Quality %, water: about 65 mass %, contain the skeleton being derived from Merlon, cross-linking)；

Described composite inorganic oxide fine particle is by the nano silicon of 10 mass parts, the stannum oxide of 30 mass parts, 10 mass The antimony pentoxide of part and the iron sesquioxide composition of 50 mass parts.

B5: photochromic coating, its preparation method is: by aqueous dispersion " SUPERFLEX420 " 100 weight of polyurethane resin Part, spiral shell (indoline) pyrans 15 weight portion, ethylene glycol monomethyl ether 800 weight portion, γ-glycidoxypropyl diethoxy Base silane 15 weight portion, composite inorganic oxide fine particle 25 weight portion mix homogeneously obtain；

Described composite inorganic oxide fine particle is by the nano silicon of 10 mass parts, the stannum oxide of 30 mass parts, 10 mass The iron sesquioxide composition of antimony pentoxide, the oxidation of 10 mass parts and 40 mass parts of part.

C1: Henkel Thailand happy pine Technomelt Q 8783

C2: esters of acrylic acid adhesive, the preparation method of described esters of acrylic acid adhesive is:

By the butyl polyacrylate of 100 weight portions, the tetraethylene glycol (TEG) two-2-ethylhexanoate of 5 weight portions, the perchloric acid of 4 weight portions The epoxy-capped polyetheramine mix homogeneously of lithium and 5 weight portions i.e. obtains described esters of acrylic acid adhesive；

Described epoxy-capped polyetheramine is prepared by following methods:

C3: esters of acrylic acid adhesive, the preparation method of described esters of acrylic acid adhesive is:

By the butyl polyacrylate of 100 weight portions, the tetraethylene glycol (TEG) two-2-ethylhexanoate of 5 weight portions, the perchloric acid of 4 weight portions Amino silane modified beta-schardinger dextrin--graphene oxide-polybenzimidazole compound the mix homogeneously of lithium and 5 weight portions i.e. obtains institute State esters of acrylic acid adhesive；

Described amino silane modified beta-schardinger dextrin--graphene oxide-polybenzimidazole compound is prepared by following methods:

C4: esters of acrylic acid adhesive, the preparation method of described esters of acrylic acid adhesive is:

By the butyl polyacrylate of 100 weight portions, the tetraethylene glycol (TEG) two-2-ethylhexanoate of 5 weight portions, the perchloric acid of 4 weight portions Lithium, the amino silane modified beta-schardinger dextrin--graphene oxide-polybenzimidazole compound of 5 weight portions and the epoxy of 5 weight portions End capped polyether amine mix homogeneously i.e. obtains described esters of acrylic acid adhesive；

2), after 10 grams of beta-schardinger dextrin-s being completely dissolved in acetum, add 10 grams of steps 1) described in amino-terminated hyperbranched poly- Benzimidazole, 3 grams of graphene oxides, 3 grams of amino silicane coupling agent KH-550,2 grams of glutaraldehydes and 2 gram 1,3-dibromopropane is also Ultrasonic disperse, regulation pH value of solution is between 8.0～9.0；At 55～65 DEG C, stir 1.5～2.5h, obtain precipitate, in cleaning extremely Property is also dried, and obtains amino silane modified beta-schardinger dextrin--graphene oxide-polybenzimidazole compound；

Described epoxy-capped polyetheramine is prepared by following methods:

Embodiment 1

Base material A1 and lower base material A1 in offer；B1 is coated in lower surface and the upper surface of described lower base material of described upper base material On, respectively obtain the first photochromic coating and the second photochromic coating；And

C1 is covered on the lower surface of base material on described and the upper surface of described lower base material the most simultaneously, make base Material is fitted with lower base material.

Embodiment 2

Base material A2 and lower base material A2 in offer；B1 is coated in lower surface and the upper surface of described lower base material of described upper base material On, respectively obtain the first photochromic coating and the second photochromic coating；And

Embodiment 3

Base material A3 and lower base material A3 in offer；B1 is coated in lower surface and the upper surface of described lower base material of described upper base material On, respectively obtain the first photochromic coating and the second photochromic coating；And

Embodiment 4

Base material A1 and lower base material A1 in offer；B2 is coated in lower surface and the upper surface of described lower base material of described upper base material On, respectively obtain the first photochromic coating and the second photochromic coating；And

Embodiment 5

Base material A1 and lower base material A1 in offer；B3 is coated in lower surface and the upper surface of described lower base material of described upper base material On, respectively obtain the first photochromic coating and the second photochromic coating；And

Embodiment 6

Base material A1 and lower base material A1 in offer；B4 is coated in lower surface and the upper surface of described lower base material of described upper base material On, respectively obtain the first photochromic coating and the second photochromic coating；And

Embodiment 7

Base material A1 and lower base material A1 in offer；B5 is coated in lower surface and the upper surface of described lower base material of described upper base material On, respectively obtain the first photochromic coating and the second photochromic coating；And

Embodiment 8

C2 is covered on the lower surface of base material on described and the upper surface of described lower base material the most simultaneously, make base Material is fitted with lower base material.

Embodiment 9

C3 is covered on the lower surface of base material on described and the upper surface of described lower base material the most simultaneously, make base Material is fitted with lower base material.

Embodiment 10

C4 is covered on the lower surface of base material on described and the upper surface of described lower base material the most simultaneously, make base Material is fitted with lower base material.

Method of testing

Photochromic properties is tested

Outdoor simulation (OS) test

In outdoor simulation (OS) test described herein, in PPG customization The light of preparation as described in embodiment 1-10 is tested on AdvanceBenchforMeasuringPhotochromics (A-BMP) The photochromic response of mutagens tinctorial pattern product.On A-BMP before test, this photochromic sample is activated as mentioned below Regulate with fading.Test sample is primarily exposed to 365 nano-ultraviolet lights about 10 minutes of the distance of 14 centimetres, activates This photochromic compound.With UVA (315-380nm) spoke at LicorModelLi-1800 spectroradiometric measurements sample Illumination, and it was found that be 22.2 watts/square metre.Then this activated sample is placed in 500 watts of high intensity the distance of 36 centimetres Under Halogen light about 10 minutes, make the bleaching of this photochromic compound or inactivation.Illumination at sample is to use Licor light splitting Measurement amount, and it was found that be 21.4Klux.Then this test sample covers at least 1 hour before test on A-BMP.

This A-BMP be provided with 150 watts of xenon arc lamps of 90 ° of arranged apart two (lamp provides the amount (lamp 1) of UV/VIS light, and One provides other visible ray to contribute (lamp 2)).Collimated output beam from this xenon arc lamp is merged and by 50/50 point Bundle device is directed to sample room.By single for each lamp optical filtering with block, and upon mixing, block before entering temperature control sample room. Light path from lamp 1 is directed through 3mmSchottKG-2 bandpass filter and suitable Midst density optical filter, and it contribute to institute The UV needed and some visible light irradiance level.Light path from lamp 2 is directed through 3mmSchottKG-2 bandpass filter, 400nm blocks optical filter and Midst density optical filter, provides supplementary visible light exposure degree.Proprietary software is used for A-BMP Controlling sequential, irradiance intensity, sample room temperature, block, optical filter selects and response measurement.By Zeiss spectrophotometer (model MCS601 has the fibre-optic cable for light carried sample) is for response and color measuring.By in sample room Sample use FTSTMSystemsAirJetTMXE (it is maintained at the pressure flowing through sample room of 3.5cfm) control 23+/- The temperature of 0.2 DEG C.

Test is to use simulation when be in set point of temperature or at the 6.7 watts/m2 (UVA) of 315-380nm integration and the family of 50Klux Time outer, the condition of the average photochromic lens response of wearer is carried out.Unactivated state is to activation or dimmed state The response measurement of optical density (OD) change (Δ OD) aspect determines as got off: sets up initial unactivated absorbance, opens xenon The optical gate (shutter) of lamp, and with the absorbance in selected time interval measurement sample activation process.According to formula: Δ OD=log (%Tb/%Ta) determines the change of optical density (OD), and wherein %Tb is the % absorbance of bleaching state, and %Ta is activation The % absorbance of state.Optical density (OD) is measured to respond according to concrete wavelength or photophile and is carried out.

Part 6B is (BWS) response test after windshield

In a similar manner, by these eyeglasses after windshield (BWS) test in, use above-mentioned A-BMP and condition be simulation In automobile, the photochromic lens response of wearer, tests.Determine and can be used for activating the light-induced variable on wearer in automobile The amount of the luminous energy of color eyeglass is 0.75 watt/m2 and 1.7Klux (kilolumen/rice 2) at 380-420nm integration.These conditions are Simply use what lamp 1 obtained, there is the direct irradiation paths to sample.In this irradiation paths, use The windshield of 3mmSchottKG-2 bandpass filter and simulation obtains irradiance spectrum curve.The windshield of this simulation It is that between the Solex97 glassy layer thick by coming from the 2.3mm of PPGIndustries, Inc at two, lamination comes from Prepared by the sheet of the poly-vinyl butyrate film that 0.73mm SolutiaInc. is thick.The gross thickness of the windshield of this simulation is 5.33mm.Test result record is in table 1 below.

Table 1 photochromic properties test result

Photochromic properties is tested, and measures including polarization efficiency and optic response

There is outdoor simulation (OSP) test of polarization

Before response test on optical bench, regulation that this substrate is such as got off: they are exposed with the distance from light source 14cm In 365nm ultraviolet light 10 minutes, carry out this photochromic molecules of pre-activate.UVA irradiance at sample is to use LicorModelLi-1800 spectroradiometric measurements, and it was found that be 22.2W/m2.Then by this sample with from lamp about The distance of 36cm is placed under high-intensity halogen lamps (500W, 120V) about 10 minutes, makes the photochromic compound in sample Bleaching or inactivation.Illumination at sample Licor spectroradiometric measurements, and it was found that be 21.9Klux.Will This sample is exposed to yellow fluorescence lamp provides further visible ray to bleach for 30 minutes.The most before test by this sample black Dark situation keeps at least 1 hour, and cool down and persistently fade back ground state.

Measure the optical property of coated substrate with optical bench, and derive two photochromic properties.By each test sample Be placed on 30 ° of-35 ° of angle of incidence in surface relative to test sample has activation light source (Newport/Oriel model 66485300-watt of xenon arc lamp, its be provided with VS-25 high-speed computer control optical gate, it temporarily closes in data-gathering process Closing, so that veiling glare not interference data collects process, 3mmKG-2 bandpass filter, it removes short wavelength radiation, for intensity The Midst density optical filter of decay and for the light-collecting lens of beam collimation) optical bench.Arc light is equipped with light intensity control Device (Newport/Oriel model 68950).

Position in the way of being perpendicular to test sample surface for monitoring broadband (broadband) light source of response measurement. The signal of the increase of shorter visible wavelength is (next by constant voltage source by collecting and combine the tungsten halogen lamp from 100 watts Control) the light individually filtered obtain with division end, the fibre-optic cable of bifurcated.Light from tungsten halogen lamp side is used KG1 optical filter filters, in order to absorbs heat and allows shorter wavelength to pass through with B-440 optical filter.The light of opposite side is used KG1 optical filter filters or does not filters.This light is such as got off collection: the light from the every side of lamp is focused on division end, bifurcated The single end of fibre-optic cable, be subsequently merged into a light source, it brings out from the single of cable.By 4 " or 6 " light pipe It is connected to the single end of cable, guarantees properly to mix.This wideband light source is provided with the optical gate that VS-25 high-speed computer controls, It is temporarily opened in data-gathering process.

The polarization of light source is maintained at computer drives, Mobile rotating stage by being passed through from the single end of cable by light (motorizedrotationstage) Moxtek, polariser (model M-061-PD, from Polytech, PI or equivalent) Realize.Set monitoring light beam, so that a plane of polarization (0 °) is perpendicular to optical bench platform (opticalbenchtable) Plane and the second plane of polarization (90 °) be parallel to the plane of optical bench platform.Sample is in atmosphere, by temperature controlled air room (aircell) 23 DEG C kept ± 0.1 DEG C run.

In order to make each sample be orientated, the second polariser is joined in optical line.This second polariser is set as relatively It it is 90 ° in the first polariser.This sample is placed in the air chamber in the self centering retainer being arranged on rotation platform.Will Laser beam (Coherent ULN635 diode laser) is directed through crossed-polarizer and sample.By this rotary sample (with 3 ° Step is done thick mobile and does with 0.1 ° of step fine mobile) find minimum transmittance.When this, by sample parallel or hang down Directly it is orientated in Moxtek polariser, and the second polariser and diode laser bundle are removed from optical line.Any Before activation, this sample is orientated in ± 0.5 °.

In order to carry out this measurement, each test sample is exposed to UVA10-20 minute of 6.7W/m2 of self-activation light source, comes Activate this photochromic compound.Use has detector system (model SED033 detector, B optical filter, and bubbler) The exposure when every day starts identified by InternationalLightResearch radiometer (model IL-1700).Then will Light (it is polarized in 0 ° of plane of polarization) from the source of supervision passes through this coated sample, and is gathered into 1 " integrating sphere, use list Functional fibre optical cable is connected on OCEANS2000 spectrophotometer or equivalent.Use OCEANOOIBase32 and OOIColor software and PPG proprietary software be collected in by sample after spectral information.When this photochromic material activates, partially Shake and rotate from light polarization to the 90 ° plane of polarization of supervision light source and return before and after the position of sheet.With 5 in activation process The data of about 600-1200 second are collected at the interval of second.For each test, the rotation adjusting polariser to put down with following polarization The order in face collects data: 0 °, 90 °, 90 °, 0 ° etc..

Obtain absorption spectrum, and use IgorPro software (available from WaveMetrics) to analyze each test sample.Each The change of test sample absorbance on each polarization direction is to deduct sample (that is, not live in 0 time of each test wavelength Change) absorptiometry value calculates.For each sample, mean absorbance values is at activation curve (activationprofile) (wherein the photochromic response of this photochromic compound is saturated or close to full in region (that is, such region, absorbance measured among these changes over time and do not increases or do not dramatically increase) of sum) in, Obtained by the absorbance equalization making each time interval in this region.Right

Determine from bleached state to the optical density (OD) of dimmed state change (Δ OD) as above-mentioned.

Polarization efficiency (PE) such as calculating of getting off: take from 0 and 90 degree of polarization orientation 90 degree of maximum λ (absorption position, 90 degree of peaks) Those Δ absorbances are changed into absorbance (1/10^ (Δ OD)), then carry out following calculating by activation Δ OD value completely:

PE=100* ((T0 T90)/(T0+T90))

In this calculates, perfect polarization will be 100%, no polarization=0%, and partial polarization scope is > 0 arrive 100%.Optics, EugeneHecht, the 4 editions, AddisonWesley, the 2002, the 8th is come from for this foundation calculated Chapter.Absorbance replaces intensity in this calculates.

Fade half (T1/2) is in room temperature, is removing activation light source such as by closing after optical gate, is activating in test sample The photochromic compound of form over the course of 15 mins or realize saturated or the most saturated after reach the one of measured Δ OD The time interval (in seconds) of the Δ OD of half.

(BWSP) response test after there is the windshield of polarization

There is the mode that the outdoor simulation (OSP) of polarization is tested, carried out the windshield with polarization efficiency and optic response Rear response test, has following change: the temperature of temperature controlled air room is set in 27+/-0.2 DEG C.It is exposed to UV-VIS and radiates it Front temperature residence time is 2-3 minute.Relative humidity in air chamber is 20-28%, and has one due to room humidity A little changes.Soak time is 15 minutes.Activation exposure (irradiance level) in the integration wave-length coverage of 380-420nm is set in 1.00+-0.02W/m2, it uses WG295, KG-2 (3mm), SolarGreen/PVB windshield optical filter, and different Neutral-density filter and lamp power obtain described exposure levels.Visible light illumination (380-780nm) be 4800+/- 200lux measures, although this level is not controlled.Irradiance is to use to come from InternationalLight ILT950 spectral radiometer is measured.By the output data post-treatment from this spectral radiometer, for wavelength calibration, so that Wavelength accuracy < +/-1nm of this spectral radiometer.Test result record is in table 2 below.

Table 2 is photochromic and polarization property test result

The chemical durability of the polaroid manufactured is assessed by polarized lenses is immersed in boiling water 3 hours.Boiling test it Before and afterwards by with standard viscose band attempt release coating assess adhesion level.

Test result is shown in Table 3.

Example	Polarization efficiency before durability test	Durability test rear polarizer efficiency	Peelable degree after durability test
Example	Polarization efficiency before durability test	Durability test rear polarizer efficiency	Peelable degree after durability test	Embodiment 1	85%	70%	It is easily peeled
Embodiment 2	80%	66%	It is easily peeled	Embodiment 1	85%	70%	It is easily peeled
Embodiment 2	80%	66%	It is easily peeled	Embodiment 3	77%	60%	It is easily peeled
Embodiment 4	90%	82%	It is easily peeled	Embodiment 3	77%	60%	It is easily peeled
Embodiment 4	90%	82%	It is easily peeled	Embodiment 5	91%	84%	It is easily peeled
Embodiment 6	93%	88%	It is easily peeled	Embodiment 5	91%	84%	It is easily peeled
Embodiment 6	93%	88%	It is easily peeled	Embodiment 7	95%	90%	It is easily peeled
Embodiment 8	98%	95%	Difficult stripping	Embodiment 7	95%	90%	It is easily peeled
Embodiment 8	98%	95%	Difficult stripping	Embodiment 9	98%	46%	Difficult stripping
Embodiment 10	98%	98%	The most peelable	Embodiment 9	98%	46%	Difficult stripping

Data above is it can be seen that by using specific allochroic paint and esters of acrylic acid adhesive, the light polarizing products obtained There is more preferable weatherability and longer service life, be thus provided that the Advantageous Effects of the present invention.

Aforesaid example is merely illustrative, for explaining some features of the feature of the disclosure.Appended claim is intended to Require the widest scope that it is contemplated that, and embodiments as presented herein is only the group according to all possible embodiment The explanation of the embodiment of the selection closed.Therefore, the purpose of applicant is that appended claim is not by the spy of the explanation present invention The selectional restriction of the example levied.And the progress in science and technology will be formed due to language performance inaccurate reason and not by mesh Possible equivalent or the son of front consideration are replaced, and these changes also should be interpreted in the conceived case by appended right Require to cover.

Claims

1. photochromic optical article, including:

(a) upper base material；

Base material under (b)；

2. the photochromic optical article of claim 1, wherein, described upper base material can be identical or different with lower base material, and respectively From copolymer, acetylbutyrylcellulose and three independently selected from polyethylene terephthalate, norborene and ethylene At least one in cellulose acetate.

3. the photochromic optical article of claim 1, wherein, described first photochromic coating and the second photochromic coating Being obtained by coating photochromic coating, the raw material of preparing of described photochromic coating includes:

Base resin 100 weight portion；

Photochromic compound 0.1-30 weight portion；With

Organic solvent 10-1000 weight portion.

4. the photochromic optical article of claim 3, wherein, described base resin is selected from polyurethane polymer, amino tree At least one in lipid aggregate thing and acrylic polymer.

5. the photochromic optical article of claim 3, wherein, described organic solvent selected from ether solvents, alcoholic solvent, ester solvent, At least one in sulfoxide solvent, alkane solvent and ketone solvent.

6. the photochromic optical article of claim 1, wherein, described adhesive selected from (methyl) esters of acrylic acid adhesive, At least one in epoxy resin tackifier, polyurethane tackifier and polyimide adhesive.

7. the method preparing photochromic optical article, including:

Base material and lower base material in offer；

8. the photochromic optical article of claim 1, wherein, described photochromic optical article is selected from ophthalmic articles, display One in device goods, window, mirror and active liquid crystal wafer goods and passive liquid crystal wafer goods.

9. the photochromic article of claim 8, wherein said ophthalmic articles is selected from correcting lens, non-correcting lens, contact thoroughly One in mirror, intraocular lens, amplifying lens, protection lens and protective eye lens.

10. the photochromic article of claim 8, wherein said display goods are in screen, monitor and safety element One.