CN101467074A

CN101467074A - Polarizing optical elements and method for preparing polyurethane-containing films

Info

Publication number: CN101467074A
Application number: CNA2007800213383A
Authority: CN
Inventors: V·J·纳格帕尔; A·库马尔; C·L·科诺克斯; 张迎潮; P·C·弗勒
Original assignee: PPG Industries Inc
Current assignee: PPG Industries Ohio Inc; PPG Industries Inc
Priority date: 2006-06-08
Filing date: 2007-06-07
Publication date: 2009-06-24

Abstract

Described is a method of preparing a cured, non-elastomeric polyurethane-containing film including: a) providing as a first component comprising a polyurethane material having isocyanate functional groups; b) providing as a second component a material having active hydrogen-containing functional groups that are reactive with isocyanate; c) combining the first and second components to form a reaction mixture; d) casting the reaction mixture onto a support substrate in a substantially uniform thickness to form a film thereon; e) heating the film on the support substrate to a temperature and for a time sufficient to yield a cured film; and f) removing the cured film from the support substrate to yield a non-elastomeric polyurethane-containing free film. The free film is non-birefringent. Optical elements and articles prepared from the films are also provided.

Description

Polarization optical element and preparation contain the method for the film of polyurethane

The cross reference of related application

[0001] the application requires the U.S. Provisional Patent Application No.60/811 of submission on June 8th, 2006,906 right of priority.

Invention field

[0002] method that the present invention relates to polarization optical element and goods and prepare the film that contains non-resilient polyurethane that solidifies.

Background of invention

[0003] multiple application need provides the polarization optical element that the acceptable image quality keeps permanance and wearing quality simultaneously, described application examples such as display, screen, wind shield, sunglasses, fashion lens (fashion lenses), OTC (over-the-counter) and prescription lens, motion face shield (sportmask), face guard (face shield) and safety goggles.

[0004] traditional Polarization filter by polymeric material for example the sheet material or the layer of polyvinyl alcohol (PVA) forms, described polymeric material has been stretched or has been orientated and floods with iodine chromophore or dichroic dye (iodine chromophore or dichroic dye).Usually these impregnated sheet materials by stratification between the support membrane of cellulose triacetate with favorable optical performance or polyethylene terephthalate.

[0005] because the character of their excellences for example low birefringence, rebound resilience and chemical-resistant and impact resistance, developed contain polyurethane material for example polyurethane-urea as the useful polymkeric substance in producing optical goods.They have been used in the molding of lens, windowpane (glazing) etc. usually.Owing to be difficult to prepare the polymer film that contains polyurethane, their purposes is confined to these application up to now.Described difficulty may comprise low gelation time and high viscosity, makes owing to the processibility difference is difficult to these materials are carried out traditional film casting.

[0006] birefringence in the polymer film (birefringence) or " birefringence (doublerefraction) " may cause owing to the orientation of polymkeric substance during the film production operation.The molecular orientation of polymkeric substance may cause visibly different refractive index in membrane plane.Birefringence is the difference between these refractive indexes on the vertical direction in membrane plane.Optical material with low or insignificant birefraction is desirable in some optical goods, particularly makes up with Polarization filter.

[0007] the desirable method that provides the material that contain polyurethane of a kind of preparation in no lining form, it is as the rete in optical element and other goods, to utilize its excellent optics and mechanical property.

Summary of the invention

[0008], provides a kind of method for preparing the no lining form that contains non-resilient polyurethane of curing according to the present invention.This method comprises:

A) provide first component, it comprises the polyurethane material with isocyanate functional group;

B) provide second component, it comprises the material with the functional group that contains reactive hydrogen, and described functional group is reactive to isocyanates;

C) merge first and second components, to form reaction mixture;

D) this reaction mixture is cast on the support base material (supportsubstrate) with homogeneous thickness basically, thereby forms film thereon;

E) film on the described support base material is heated to uniform temperature and reaches certain hour, so that be enough to produce cured film; With

F) take off cured film from described support base material, contain the no lining form of non-resilient polyurethane with generation, its right and wrong are birefringent.The no lining form that contains non-resilient polyurethane with the curing of the inventive method preparation provides excellent temperature and chemical-resistant; And be suitable for multiple polymers film and coating.

[0009] the present invention relates to a kind of polarization optical element in addition, it comprises in combination:

A) has two apparent surfaces' polarizing film; With

B) protection supporting layer, it comprises the film that contains non-resilient polyurethane of the curing of at least one among the apparent surface who is attached to described polarization layer.

[0010] in addition, the invention provides a kind of optical goods.These optical goods comprise in combination:

A) base material; With

B) be attached to polarization optical element on the described base material, it comprises in combination:

I) has two apparent surfaces' polarizing film; With

Ii) protect supporting layer, it comprises the no lining form that contains non-resilient polyurethane of the curing of at least one among the apparent surface who is attached to described polarization layer.Optical goods of the present invention can comprise display, screen, lens, wind shield, ophthalmology goods or windowpane, and this optical goods particularly suitable is made the element of LCD.

The accompanying drawing summary

[0011] Fig. 1 is the sectional view according to the polarization optical element of an embodiment of the invention.

[0012] Fig. 2 is the particular embodiment according to polarization optical element of the present invention.

[0013] Fig. 3 is the sectional view of optical goods of the present invention; Especially, it is the decomposition section of LCD.

Detailed Description Of The Invention

[0014] should be noted that ＂ of singulative ＂, the ＂＂ and the described ＂ of ＂ that use in this specification and the additional claims comprise plural object, unless clearly and clearly be defined as the odd number object.

[0015] for this specification, except as otherwise noted, all numerical value of expression group component amount, reaction condition and other parameter of using in specification and claims are understood to be modified by term " about " in all cases. Therefore, unless on the contrary explanation, the numerical parameter of listing in following specification and claims is approximation, the required character that it can obtain according to the present invention and changing. At least, and be not intended to attempt to limit range applications doctrine of equivalents to claim, each numerical parameter should be at least according to having the numerical value of the significant digits of reporting and understanding by using the common technology of rounding off.

[0016] herein all number ranges comprise all numerical value of being in the mentioned number range and the scope of all numerical value. Although describing number range and the parameter of wide region of the present invention is approximation, the numerical value of listing in the instantiation is as far as possible accurately reported. Yet any numerical value comprises some error that must be caused by the standard deviation of finding in the experimental measurement separately inherently.

[0017] numerous embodiments of the present invention that provides herein and embodiment are understood to respectively not to be for the restriction scope of the invention.

[0018] the following describes the implication of the following term of using in book and claims shown in having:

[0019] term " acrylic compounds (acrylic) " and " acrylate " commutative use (can change the expection implication unless make like this), and comprise acrylic acid, acid anhydrides and its derivative, for example its C₁-C ₅The acrylic acid that Arrcostab, low alkyl group replace, for example C₁-C ₅The acrylic acid that replaces, such as methacrylic acid, ethylacrylic acid etc., and its C₁-C ₅Unless Arrcostab is in addition clearly explanation. Acrylic acid/esters and the methacrylic/methacrylic acid ester-formin of material, for example (methyl) acrylate monomer shown in term " (methyl) acrylic compounds ((meth) acrylic) " or " (methyl) acrylate " are intended to contain.

[0020] as employed about the composition or the curable compositions that solidify, at least part of polymerizable and/or crosslinkable component that " composition of curing " during for example some specifies, term " curing ", " curing " or similar terms refer to form curable compositions are at least part of that be aggregated and/or crosslinked. For example employed about curable film-forming composition, composition was polymerizable or crosslinkable shown in term " curable " referred to, for example by including, but are not limited to heat, catalysis, electron beam, chemical free radical initiation and/or light-initiated, for example by being exposed to ultraviolet ray or other actinic radiation. In the context of the invention, depend on the availability of polymerizable or crosslinkable component, the composition of " curing " can continue and can further solidify.

[0021] term " non-resilient " relates to the material that does not show typical elastic behavior; That is, they are not easy at least twice that experiences reversible deformation or be stretched to original length.

[0022] material such as coating, film, base material etc. shown in the term of term " influence of light function (light influencing function) ", " influence of light character (light influencing property) " or similar meaning refers to can be by absorbing incident light radiation that (or filtration) shine this material for example visible light, ultraviolet ray (UV) and/or infrared ray (IR) radiation and modification. In the embodiment that substitutes, the influence of light function can be light polarization, for example, and by the polarizer and/or dichroic dye; By changing optical absorption property, for example utilize the chromophore (chromophore) of variable color when being exposed to actinic radiation, for example photochromic material; By only permeation parts incident light radiation, for example utilize fixed dye (fixed tint), for example conventional dyes; Or the combination by one or more described influence of light functions.

[0023] for example employed about the rigid optical base material, term " so that adapt to ground have at least a influence of light character " refers to that described object can have to be incorporated into or is additional to wherein influence of light character. For example, refer to that described matrix has enough internal freedom volumes so that have plastics or the polymeric matrix of influence of light character, to hold photochromic dyes or coloring agent (tint) in inside with adapting to. The surface of this plastic substrate can selectively can have photochromic or dyed layer, film or the coating that is attached on it, and/or can have the polarizing coating that is attached on it.

[0024] term " ... on ", " being attached to ", " being fixed to ", " being bonded to ", " adhering to " or similar terms refer to described object for example coating (coating), film or layer (layer) be directly connected to (being stacked in) target object or substrate surface (on), perhaps for example by one or more other coatings, film or interlayer receive in succession (being stacked in) target object or substrate surface (on).

[0025] term " ophthalmology " relates to element and the equipment relevant with eyes and vision, for example still is not limited to ophthalmic lens, for example correct and non-correcting lens, and amplifying lens.

[0026] for example about polymeric material for example " resin with optical quality " or " organic polymer materials with optical quality " employed, for example polymeric material, resin or resin combination are material shown in term " optical quality " refers to or formation can be used as optical goods for example base material, layer, film or the coating of eyeglass, or or form base material, layer, film or the coating that can be used in combination with optical goods, this is owing to due to its suitable optical property.

[0027] for example employed about optical element, term " rigidity " refer to described to as if self-supporting.

[0028] term " optical element " refers to when for example measuring under 550 nanometers with Haze Gard Plus Instrument, specific base material shows at least 4% printing opacity value (seeing through incident light), and show and be lower than 5%, for example be lower than 1% haze value, (thickness that depends on base material). Optical element includes, but are not limited to optical goods for example lens, optical layers, for example optical resin layer, blooming and optical coating, and the optical element with influence of light character.

[0029] object had enough free volumes shown in term " photochromic acceptance (photochromic receptive) " was meant, changed coloured form (being returned to its colorless form then) into to the required degree of commercial optical application with the photochromic material (one or more) that allows to introduce wherein from its colorless form.

[0030] for example employed about ophthalmic devices and optical element, object comprised fixing optical radiation absorbing agent shown in term " painted (tinted) " was meant, for example but be not limited to shown on the object or wherein conventional illuminating colour, infrared ray and/or ultraviolet absorption material.This painted object has the absorption spectrum for visible radiation, its not marked change when the response actinic radiation.

[0031] for example employed about ophthalmic devices and optical element, object was substantially free of fixing optical radiation absorbing agent shown in term " non-staining " was meant.The object of this non-staining has the absorption spectrum for visible radiation, its not marked change when the response actinic radiation.

[0032] term " actinic radiation " comprises having from ultraviolet ray (" UV ") scope, through visible-range and enter the light of the electromagnetic radiation wavelength of infra-red range.The actinic radiation that can be used for solidifying the coating composition that uses among the present invention has 150 to 2,000 nanometers (nm), 180 to 1 usually, 000nm or 200 to 500nm electromagnetic radiation wavelength.In one embodiment, can use ultraviolet radiation with wavelength of 10 to 390nm.The example of suitable ultraviolet light source comprise mercury arc, carbon arc, low, in or high-pressure sodium lamp, swirling flow plasma arcs and ultraviolet emitting diode.Suitable ultraviolet ray emission lamp is to cross the medium pressure mercury lamp that fluorescent tube length has the output power of 200 to 600 watts of per inchs (79 to 237 watts every centimetre).

[0033] for example employed about ophthalmic devices and optical element, object comprised fixing light absorber and photochromic material shown in term " painted is photochromic " was meant.Shown in object have absorption spectrum for visible radiation, it changes when the response actinic radiation, and is hot reversible when remove actinic radiation.For example, painted photochromic articles can have for example first feature of illuminating colour (coloring tint) of light absorber, and has light absorber and second color characteristic of the combination of the photochromic material that is activated when photochromic material is exposed to actinic radiation.

[0034] term " dichroic material ", " dichroic dye (dichroic dye) " or similar terms be meant absorb two vertical plane polarizations see through in the radiation component one than another stronger material/dyestuff.The non-limiting example of dichroic material comprises indigoid, thioindigo class, part cyanines, indane, azo and polyazo dye, benzoquinones, naphthoquinones, anthraquinone, (gathering) anthraquinone, anthra pyrimidone (anthrapyrimidinone), iodine and iodate.The word synonym of term " dichromatism " and " polarization (polarizing) " or similar meaning.

[0035] term " dichromatism is photochromic " is meant certain material or the goods that show dichromatism and photochromic property.In the indefiniteness embodiment that substitutes, described certain material can comprise photochromic dyes/compound and dichroic dye/compound simultaneously, or the homogencous dyes/compound with photochromism and dichromatism.

[0036] for example employed about base material, film, material and/or coating, base material, coating, film and/or material had the character of printing opacity shown in term " transparent " was meant, and did not have the obvious scattering effect, so that the object that is positioned at the back fully as seen.

[0037] phrase " to the small part film " is meant the film amount of the part of covering substrates at least until all surfaces." film " is defined as thin continuous layer of material basically, and it can be formed by sheet type material or coating type material." no lining form " used herein comprises the goods of independent structures integrality; That is, needn't contact and not need the thin slice of support base material.

[0038] term " photochromic amount " is meant that the photochromic material of q.s is used to produce the discernible photochromic effect of naked eyes when activation.Desirable color intensity and the method that is used to introduce described photochromic material when concrete use amount depends on its irradiation usually.Usually, in another indefiniteness embodiment, what be introduced into is photochromic many more, and color intensity is big more until a certain limit.There is a point, will can not have a significant effect adding more materials thereafter,, can add more materials although if desired.

[0039] term " stacked " is described in the layered articles on another specified layer or coating that applies afterwards or film.

[0040] as mentioned before, the present invention relates to a kind of method for preparing the no lining form that contains non-resilient polyurethane of curing.This method comprises:

C) merge first and second components, to form reaction mixture;

D) this reaction mixture is cast on the support base material with homogeneous thickness basically, thereby forms film thereon;

F) take off cured film from described support base material, contain the no lining form of non-resilient polyurethane with generation.These no lining form right and wrong are birefringent.In some embodiments, depend on to be used to prepare the described material that contains the material of polyurethane that no lining form can show the faulting stress of at least 9000 pounds/square inches (psi) and at least 70% breaking strain.

[0041] be used for the suitable polyurethane material that first component has the isocyanate functional group and can comprise polyurethane prepolymer, the material that it derives from (a) polyisocyanate and (b) has the group that contains reactive hydrogen, described group is reactive to isocyanates.

[0042] polyisocyanate that is used in the polyurethane material for preparing in first component has a lot, and difference is very big.Non-limiting example can comprise that aliphatic polymeric isocyanate, wherein one or more isocyanate groups (isocyanato) are connected directly to the cycloaliphatic polyisocyanates of cyclic aliphatic ring, and wherein one or more isocyanate groups are not connected directly to the cycloaliphatic polyisocyanates of cyclic aliphatic ring, the aromatic polyisocyanate that wherein one or more isocyanate groups are connected directly to aromatic ring, aromatic polyisocyanate and its potpourri that wherein one or more isocyanate groups are not connected directly to aromatic ring.Use for some, should carefully select not cause to contain the material of the material painted (for example yellow) of polyurethane.

[0043] described polyisocyanate can include, but are not limited to aliphatic series or cycloaliphatic diisocyanates, aromatic diisocyanates, its cyclic dimer and cyclic trimer, with and composition thereof.The non-limiting example of suitable polyisocyanate can comprise the DESMODURN3300 (hexylidene diisocyanate trimer) that can be purchased from Bayer; DESMODUR N 3400 (60% hexylidene diisocyanate dipolymer and 40% hexylidene diisocyanate trimer).In an indefiniteness embodiment, described polyisocyanate can comprise dicyclohexyl methane diisocyanate and its isomeric mixtures.The term that uses in this paper and claims " isomeric mixtures " is meant suitable-suitable, anti--the anti-and/or cis-trans isomer potpourri of polyisocyanate.The non-limiting example that is used for the present invention's isomeric mixtures can comprise 4,4 '-anti--trans isomer of di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), hereinafter to be referred as ＂ PICM ＂ (to isocyanate group cyclohexyl methane), suitable-suitable isomeride and its potpourri of the cis-trans isomer of PICM, PICM.

[0044] the suitable isomeride that is used for the present invention include, but are not limited to following 4,4 '-three kinds of isomeride of di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate).

Suitable, suitable

[0045] can use method well known in the art, for example United States Patent (USP) 2,644, and 007; Disclosed method in 2,680,127 and 2,908,703 (incorporating this paper by reference into), by phosgenation 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl amine) (PACM) and preparation PICM.During phosgenation, the PACM isomer mixture can at room temperature produce the PICM of liquid phase, Partial Liquid Phase or solid phase.As selection, can by the hydrogenation methylene dianiline (MDA) and/or by water and alcohol for example methyl alcohol and ethanol in the presence of to PACM isomer mixture fractional crystallization, obtain the PACM isomer mixture.

[0046] operable other aliphatic series and cycloaliphatic diisocyanates comprise the 3-isocyanate group-methyl-3 that can be purchased from ArcoChemical, 5,5-trimethyl cyclohexyl isocyanate (" IPDI ") and can be from Cytec Industries Inc with trade name TMXDI

(Meta) Aliphatic Isocyanate be purchased between tetramethylxylene diisocyanate (1,3-two (1-isocyanate group-1-Methylethyl) benzene).

[0047] term " aliphatic series and cycloaliphatic diisocyanates " that uses in this paper and claims relates to 6 to 100 carbon atoms with two di-isocyanate reaction end groups that be connected with straight chain or cyclisation.In an indefiniteness embodiment of the present invention, be used for aliphatic series of the present invention and cycloaliphatic diisocyanates and can comprise TMXDI and formula R-(NCO) ₂Compound, wherein R represents aliphatic group or cycloaliphatic groups.

[0048] material with the group that contains reactive hydrogen (b) that is used to prepare the polyurethane material of first component can be to comprise hydroxyl (OH) group and if desired, comprises other and isocyanates is reactive active hydrogen group (for example amino) and/or any compound of mercapto or the potpourri of compound.Material (b) can comprise having at least two compounds that contain the group of reactive hydrogen, and the described group that contains reactive hydrogen comprises OH base and primary amine groups, secondary amine, mercapto and/or its combination.Can use single polyfunctional compound with OH base; Maybe can use to have the single polyfunctional compound who mixes functional group, maybe can use potpourri.Can mix and use some different compounds with identical or different functional group; For example can use two kinds of different polyamines, can use the polythiol that mixes with polyamines, or the polyamines that for example mixes with the polythiol of hydroxyl-functional is suitable.

[0049] is used for the suitable material that contains OH that the present invention prepares the polyurethane material of first component and can includes, but are not limited to polyether glycol, polyester polyol, polycaprolactone polyol, polycarbonate polyol and its potpourri.

[0050] example of polyether glycol is the polyalkylene ethoxylated polyhydric alcohol, and it can comprise those with following structural:

Or

Wherein substituent R 1 is hydrogen or the low alkyl group that comprises 1 to 5 carbon atom, and it comprises the substituting group of mixing, and n normally 2 to 6, and m is 8 to 100 or higher.Comprise poly-(oxidation tetramethylene) glycol, poly-(oxidation four ethylidene) glycol, poly-(oxidation-1,2-propylidene) two pure and mild poly-(oxidation-1,2-butylidene) glycol.The non-limiting example of oxyalkylene can comprise oxirane, epoxypropane, epoxy butane, oxinane, the inferior aralkyl (aralkylene oxide) of oxidation, for example still is not limited to styrene oxide, the potpourri of oxirane and epoxypropane.In another indefiniteness embodiment, can by random or progressively alkoxylate prepare polyoxyalkylene polyols with oxyalkylene intermixture.

[0051] in addition usefully by the multiple polyvalent alcohol of alkoxylate, glycol for example, ethylene glycol, 1 for example, 6-hexylene glycol, bisphenol-A etc., or other higher polyol polyether glycol of forming such as trimethylolpropane, pentaerythrite for example.Can be for example by for example sucrose or sorbierite alkoxylate produce the polyvalent alcohol of the higher functionality that can use as indication with compound.A kind of normally used alkoxylating method is in the presence of acidity or base catalyst, with polyvalent alcohol and oxyalkylene (alkylene oxide) for example epoxypropane or reacting ethylene oxide.Concrete polyethers comprises can be from E.I.Du Pont de Nemours and Company, Inc. sell those that obtain with title TERATHANE and TERACOL, with can be from the Great Lakes Chemical Corp. Q O Chemicals of subsidiary company, those that Inc. obtains with title POLYMEG.

[0052] is used for polyether glycol of the present invention and can includes, but are not limited to polytetramethylene ether diol.

[0053] polyvalent alcohol that contains polyethers can comprise segmented copolymer, comprises the block of epoxy ethane-epoxy propane and/or oxirane-epoxy butane.Can be used as the polyvalent alcohol material that contains polyethers the present invention from PLURONIC R, PLURONIC L62D, TETRONIC R and the TETRONIC that BASF is purchased.

[0054] suitable polyester-diol can include, but are not limited to one or more dicarboxylic acid with 4 to 10 carbon atoms and one or more have the esterification products of the low molecular weight diols of 2 to 10 carbon atoms, wherein said dicarboxylic acid for example is hexane diacid, succinic acid or decanedioic acid, described low molecular weight diols for example is ethylene glycol, propylene glycol, diethylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,6-hexylene glycol and 1, the 10-decanediol.In an indefiniteness embodiment, polyester-diol can be the esterification products of the glycol of hexane diacid and 2 to 10 carbon atoms.

[0055] the suitable pla-pcl glycol that is used for the present invention can comprise the reaction product of E-caprolactone and one or more above-mentioned low molecular weight diols of listing.Can by two functional activity hydrogen compounds for example water or at least a above-mentioned low molecular weight diols of listing in the presence of the condensation caprolactone prepare polycaprolactone.The particular instance of pla-pcl glycol comprises can CAPA

2047 and CAPA

The 2077 polycaprolactone polyesters glycol that obtain from Solvay Corp..

[0056] polycarbonate polyol is known in the art, and can be purchased for example Ravecarb ^TM107 (Enichem S.p.A.).In an indefiniteness embodiment, can by make organic diol for example the reaction of glycol (diol) and dialkyl carbonate produces polycarbonate polyol, for example United States Patent (USP) 4,160, description in 853.In an indefiniteness embodiment, described polyvalent alcohol can comprise the poly-hexamethyl carbonic ester with different polymerization degree.

[0057] described glycol material can comprise low molecular weight polyols, for example has the polyvalent alcohol and its compatible blend that are lower than 500 molecular weight.The term of Shi Yonging " compatible " is meant that glycol is solvable each other to form single phase herein.The non-limiting example of these polyvalent alcohols can comprise low molecular weight diols and triol.If use, select the amount of triol so that avoid high level of crosslinking in the polyurethane.High level of crosslinking may cause curable polyurethane, and it can not be by appropriate heating and pressure forming.Organic diol comprises 2 to 16 or 2 to 6 or 2 to 10 carbon atoms usually.The non-limiting example of this glycol can comprise ethylene glycol, propylene glycol, diglycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-, 1,3-and 1, the 4-butylene glycol, 2,2,4-trimethyl-1,3-pentanediol, the 2-methyl isophthalic acid, the 3-pentanediol, 1,3-, 2,4-and 1,5-pentanediol, 2,5-and 1, the 6-hexylene glycol, 2, the 4-heptandiol, 2-ethyl-1, the 3-hexylene glycol, 2,2-dimethyl-1, ammediol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 1, the 10-decanediol, 1, the 4-cyclohexanediol, 1,4 cyclohexane dimethanol, 1, two (the hydroxyethyl)-thiacyclohexanes of 2-, glycerine, tetramethylol methane, for example still be not limited to pentaerythrite, trimethylolethane and trimethylolpropane; With its isomeride.

[0058] material that contains OH can have for example at least 60, for example at least 90 or at least 200 weight-average molecular weight.In addition, the material that contains OH can have and for example is lower than 10,000, for example is lower than 7000 or be lower than 5000 or be lower than 2000 weight-average molecular weight.

[0059] material that is used for the OH of containing of the present invention can comprise from least a low-molecular-weight dicarboxylic acid terester that produces of hexane diacid for example.

[0060] can utilize known esterification process or ester exchange method, D.M.Young for example, people's such as F.Hostettler paper, ＂ Polyesters from Lactone ＂ (UnionCarbide F-40,147 pages) describe, preparation is used for polyester-diol of the present invention and pla-pcl glycol.

[0061] in addition can be from 1, the reaction of 6-hexylene glycol and hexane diacid; 1, the reaction of 10-decanediol and hexane diacid; Or 1, the reaction of 10-decanediol and caprolactone, preparation polyester-diol.

[0062] in an alternative indefiniteness embodiment, the material that is used for the OH of containing of the present invention can be selected from: (a) hexane diacid be selected from 1,4-butylene glycol, 1,6-hexylene glycol, neopentyl glycol or 1, the esterification products of at least a glycol of 10-decanediol; (b) the E-caprolactone be selected from 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol or 1, the reaction product of at least a glycol of 10-decanediol; (c) polytetramethylene glycol; (d) aliphatic polycarbonate glycol and (e) its potpourri.

[0063] material that contains mercaptan can be used to produce for example polyurethane of the isocyanates-sense of sulfur-bearing of prepolymer, and it is used to prepare the film that contains polyurethane of high index; That is the film that, has relative high index.Please note that in these embodiments owing to be used for the polythiol of polyurethane preformed polymer and/or the disulfide bond that the polythiol oligomer comprises, the polyurethane prepolymer that is used as first component may comprise disulfide bond.

[0064] material that contains mercaptan can have at least two thiol functionalities, and can comprise two mercaptan (dithiol), have compound, or two mercaptan and have the potpourri of compound (senior polythiol) more than two thiol functionalities more than two thiol functionalities.This potpourri can comprise the potpourri of two mercaptan and/or the potpourri of senior polythiol.Thiol functionalities is end group normally, but smaller portions (promptly being lower than 50% whole groups) can be hung along the chain side.Compound (a) can comprise other reactive hydrogen functional group (promptly being different from mercaptan) of smaller portions, for example hydroxy functional group in addition.The material that contains mercaptan can be line style or branching, and can comprise ring-type, alkyl, aryl, aralkyl or alkylaryl group.

[0065] can select to contain the material of mercaptan, to produce the oligomeric polythiols of line style basically.Therefore, when this material comprises two mercaptan and have potpourri more than the compound of two thiol functionalities, have more than the compound of two thiol functionalities at the most the amount of 10 weight % be present in the described potpourri.

[0066] suitable two mercaptan can comprise aliphatic series, cyclic aliphatic, aromatics, heterocycle, polymerization, oligomeric two mercaptan and its potpourri of line style or branching.Two mercaptan can comprise multiple key, include, but are not limited to ehter bond (O-), thioether bond (S-), the combination of polysulfide bond (Sx-, wherein x is at least 2, or 2 to 4) and described key.

[0067] non-limiting example that is used for suitable two mercaptan of the present invention can include, but are not limited to 2,5-dimercapto methyl-1,4-dithiane, dimercapto diethyl thioether (DMDS), dithioglycol, 3,6-two oxa-s-1, hot two mercaptan of 8-, ethylene glycol bisthioglycolate (2-thioglycollate), ethylene glycol bisthioglycolate (3-mercaptopropionic acid ester), poly-(ethylene glycol) two (2-thioglycollate) and poly-(ethylene glycol) two (3-mercaptopropionic acid ester), dimercaptobenzene, the 4-tert-butyl group-1,2-dimercaptobenzene, 4,4 '-dimercapto diphenyl sulfide and its potpourri.

[0068] two mercaptan can comprise two mercaptan oligomer with disulfide bond, for example the material of representing with following formula:

Wherein n can represent 1 to 21 integer.

[0069] as known in the art, for example can by in the presence of base catalyst with 2,5-dimercapto methyl-1, the reaction of 4-dithiane and sulphur, two mercaptan oligomer that the preparation general formula I is represented.

[0070] character of SH base makes and can oxidative coupling take place easily in the polythiol, causes forming disulfide bond.Multiple oxygenant can cause this oxidative coupling.In some cases, between the storage life, airborne oxygen can cause this oxidative coupling at polythiol.The a kind of of oxidative coupling who it is believed that mercapto may mechanism relate to formation sulphur center free radical (thiyl), subsequently by the described sulphur of coupling center free radical, forms disulfide bond.It is believed that in addition can causing to form under the condition of sulphur center free radical, include, but are not limited to the reaction conditions that comprises that free radical causes, can form disulfide bond.Polythiol as the compound (a) in the preparation polythiol of the present invention can comprise the species that contain the disulfide bond that forms between the storage life.

[0071] polythiol of material (b) that is used for preparing the polyurethane material of first component can comprise the species that contain the disulfide bond that forms during synthetic polythiol in addition.

[0072] in some embodiments, be used for two mercaptan of the present invention and can comprise at least a two mercaptan of representing by following structural:

[0073] can be by unsym.-dichloroacetone and two mercaptan (dimercaptan) be reacted, then with reaction product and dimercapto alkyl thioether, two mercaptan (dimercaptan) or the reaction of its potpourri, thereby preparation comprises 1, the 3-dithiolane (for example, formula II and III) or 1, two mercaptan that contain thioether of 3-dithiane (for example formula IV and V) are as United States Patent (USP) 7,009, described in the 032B2.

[0074] be used for non-limiting example with suitable two mercaptan (dimercaptan) of unsym.-dichloroacetone reaction and can include, but are not limited to material by the following formula representative:

VI

Wherein Y can represent CH ₂Or (CH ₂-S-CH ₂), n can be 0 to 5 integer.Among the present invention, be used for to be selected from for example dithioglycol, dimercaptopropane and its potpourri with two mercaptan of unsym.-dichloroacetone reaction.

[0075] is applicable to that the unsym.-dichloroacetone that carries out above-mentioned reaction and the amount of two mercaptan can change.For example, unsym.-dichloroacetone and two mercaptan can a certain amount ofly be present in the reaction mixture, and this amount makes the mol ratio of described dichloroacetone and two mercaptan can be 1:1 to 1:10.

[0076] suitable temperature that is used for unsym.-dichloroacetone and two thiol reactants can change, and is generally 0 to 100 ℃.

[0077] is used for non-limiting example with suitable two mercaptan (dimercaptan) of the reaction of unsym.-dichloroacetone and two mercaptan and can includes, but are not limited to material, aromatics two mercaptan (aromatic dimercaptans), naphthenic base two mercaptan (cycloalkyl dimercaptans), heterocycle two mercaptan (heterocyclicdimercaptans), branching two mercaptan (branched dimercaptans) and its potpourri by above-mentioned general formula VI representative.

[0078] be used for non-limiting example with the suitable dimercapto alkyl thioether (dimercaptoalkylsulfide) of the reaction of unsym.-dichloroacetone and two mercaptan and can comprise material by following general formula representative:

VII

Wherein X can represent O, S or Se, and n can be 0 to 10 integer, and m can be 0 to 10 integer, and p can be 1 to 10 integer, and q can be 0 to 3 integer, and condition is 1 to 20 integer for (m+n).

[0079] non-limiting example that is used for suitable dimercapto alkyl thioether of the present invention can comprise branching dimercapto alkyl thioether.

[0080] is applicable to that the amount with two mercaptan, dimercapto alkyl thioether or its potpourri of the reaction of unsym.-dichloroacetone and two mercaptan can change.Usually, two mercaptan, dimercapto alkyl thioether or its potpourri can a certain amount ofly be present in the reaction mixture, and this amount makes the equivalent proportion of reaction product and two mercaptan, dimercapto alkyl thioether or its potpourri can be 1:1.01 to 1:2.In addition, the suitable temperature that carries out this reaction can change in 0 to 100 ℃ of scope.

[0081] can in the presence of acid catalyst, carry out the reaction of unsym.-dichloroacetone and two mercaptan.Described acid catalyst can be selected from multiple material known in the art, for example still is not limited to lewis acid and Bronsted acid.The non-limiting example of suitable acid catalyst can comprise Ullmann ' s Encyclopedia of Industrial Chemistry, the 5th edition, and 1992, A21 volume, those that describe in 673 to 674 pages.Described acid catalyst is selected from boron trifluoride diethyl etherate, hydrogen chloride, toluenesulfonic acid and its potpourri usually.The amount of acid catalyst can be 0.01 to 10 weight % of described reaction mixture.

[0082] reaction product of unsym.-dichloroacetone and two mercaptan can be used as selectively and reacts in the presence of alkali with dimercapto alkyl thioether, two mercaptan or its potpourri.Described alkali can be selected from multiple material known in the art, for example still is not limited to lewis base and brnsted base.The non-limiting example of appropriate base can comprise Ullmann ' s Encyclopedia of IndustrialChemistry, the 5th edition, and 1992, A21 volume, those that describe in 673 to 674 pages.Described alkali is generally NaOH.The amount of alkali can change.Usually, the suitable equivalent ratio of the alkali and the first reaction response product can be 1:1 to 10:1.

[0083] can in the presence of solvent, carry out the reaction of unsym.-dichloroacetone and two mercaptan.But described solvent can be selected from and be not limited to organic solvent.The non-limiting example of suitable solvent can include, but are not limited to chloroform, methylene chloride, 1,2-ethylene dichloride, diethyl ether, benzene, toluene, acetate and its potpourri.

[0084] in another embodiment, the reaction product of unsym.-dichloroacetone and two mercaptan can be reacted under the situation that has or do not have solvent to exist with dimercapto alkyl thioether, two mercaptan or its potpourri, but wherein said solvent can be selected from and is not limited to organic solvent.The non-limiting example of appropriate organic solvent can comprise alcohol, for example still is not limited to methyl alcohol, ethanol and propyl alcohol; Aromatic solvent for example still is not limited to benzene,toluene,xylene; Ketone for example still is not limited to methyl ethyl ketone; Water; With its potpourri.

[0085] also can in the presence of dehydrated reagent, carry out the reaction of unsym.-dichloroacetone and two mercaptan.Described dehydrated reagent can be selected from multiple material known in the art.The suitable dehydrated reagent that is used for this reaction can include, but are not limited to magnesium sulphate.The amount of dehydrated reagent can change on a large scale according to the Chemical Measurement of dehydration.

[0086] in some indefiniteness embodiment, can pass through 2-methyl-2-dichloromethyl-1,3-dithiolane and the reaction of dimercapto diethyl thioether, to produce the dimercapto-1 of formula III, 3-dithiolan derivatives thing, preparation are used for preparing the polythiol of material (b) of the polyurethane material of first component.As selection, 2-methyl-2-dichloromethyl-1, the 3-dithiolane can be with 1, the reaction of 2-dithioglycol, with the dimercapto-1 of production II, 3-dithiolan derivatives thing.2-methyl-2-dichloromethyl-1, the 3-dithiane can react with dimercapto diethyl thioether, with the dimercapto-1 of production V, 3-dithiane derivant.In addition, 2-methyl-2-dichloromethyl-1, the 3-dithiane can be with 1, the reaction of 2-dithioglycol, with the dimercapto-1 of production IV, 3-dithiane derivant.

[0087] non-limiting example of two mercaptan of another applicable crops matter (b) can comprise at least a two mercaptan oligomer, and it prepares dichloro-derivatives and the reaction of dimercapto alkyl thioether by as follows:

Wherein R can represent CH ₃, CH ₃CO, C ₁To C ₁₀Alkyl, naphthenic base, aryl alkyl or alkyl-CO; Y can represent C ₁-C ₁₀Alkyl, naphthenic base, C ₆-C ₁₄Aryl, (CH ₂) _p(S) _m(CH ₂) _q, (CH ₂) _p(Se) _m(CH ₂) _q, (CH ₂) _p(Te) _m(CH ₂) _q, wherein m can be 1 to 5 integer, p and q can be 1 to 10 integer separately; N can be 1 to 20 integer; X can be 0 to 10 integer.

[0088] can in the presence of alkali, carry out the reaction of dichloro-derivatives and dimercapto alkyl thioether.Except above-mentioned those disclosed, suitable alkali comprises any material that those skilled in the art are known.

[0089] can in the presence of phase transfer catalyst, carry out the reaction of dichloro-derivatives and dimercapto alkyl thioether.It is known being used for suitable phase transfer catalyst of the present invention, and has multiple.Non-limiting example can include, but are not limited to tetraalkylammonium salt and Si Wan Ji phosphonium salt.Usually in the presence of Si butyl phosphonium bromide, carry out this reaction as phase transfer catalyst.The amount of phase transfer catalyst can change on a large scale, and from 0 to 50 equivalent %, or from 0 to 10 equivalent %, or from 0 to 5 equivalent % are with respect to the dimercapto sulfide reactant.

[0090] polythiol that is used for material (b) can further comprise hydroxy functional group.Non-limiting example with suitable substance of two hydroxyls and a plurality of (more than one) mercapto can include, but are not limited to glycerine two (2-mercaptoacetate), glycerine two (3-mercaptopropionic acid ester), 1,3-dimercapto-2-propyl alcohol, 2,3-dimercapto-1-propyl alcohol, trimethylolpropane two (2-mercaptoacetate), trimethylolpropane two (3-mercaptopropionic acid ester), pentaerythrite two (2-mercaptoacetate), pentaerythrites three (2-mercaptoacetate), pentaerythrite two (3-mercaptopropionic acid ester), pentaerythrite three (3-mercaptopropionic acid ester) and its potpourri.

[0091] except disclosed two mercaptan (dithiol) above, the instantiation of two suitable mercaptan can comprise 1, the 2-dithioglycol, 1, the 2-dimercaptopropane, 1, the 3-dimercaptopropane, 1, the 3-succinimide mercaptans, 1, the 4-succinimide mercaptans, 2, the 3-succinimide mercaptans, 1, the 3-pentane disulfide thioalcohol, 1, the 5-pentane disulfide thioalcohol, 1, the 6-ethanthiol, 1,3-dimercapto-3-methylbutane, cinene two mercaptan (dipentenedimercaptan), ethyl cyclohexyl two mercaptan (ECHDT), dimercapto diethyl thioether (DMDS), methyl substituted dimercapto diethyl thioether, dimethyl replaces dimercapto diethyl thioether, 3,6-two oxa-s-1, hot two mercaptan of 8-, 1,5-dimercapto-3-oxa-pentane, 2,5-dimercapto methyl-1,4-dithiane (DMMD), ethylene glycol bisthioglycolate (2-mercaptoacetate), ethylene glycol bisthioglycolate (3-mercaptopropionic acid ester) and its potpourri.

[0092] be used for the suitable trifunctional of material (b) or more the polythiol of higher functional can be selected from multiple material known in the art.Non-limiting example can comprise pentaerythrite four (2-mercaptoacetate), pentaerythrite four (3-mercaptopropionic acid ester), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionic acid ester) and/or sulfo-glycerine two (2-mercaptoacetate).

[0093] for example, polythiol can be selected from the material by following general formula representative,

R wherein ₁And R ₂Can be independently selected from straight or branched alkylidene, cyclic alkylidene, phenylene and C separately ₁-C ₉The phenylene that alkyl replaces.The non-limiting example of straight or branched alkylidene can comprise methylene, ethylidene, 1,3-propylidene, 1,2-propylidene, 1,4-butylidene, 1,2-butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, inferior nonyl, inferior decyl, inferior undecyl, inferior octadecyl and inferior eicosyl (icosylene).The non-limiting example of cyclic alkylidene can comprise cyclopentylene, inferior cyclohexyl, inferior suberyl, inferior ring octyl group and its alkyl-substituted derivatives.Divalent linker R ₁And R ₂Can be selected from methylene, ethylidene, phenylene and alkyl substituted phenylene, for example methyl, ethyl, propyl group, isopropyl and nonyl substituted phenylene.

[0094] in specific implementations, can prepare polythiol by compound (for example diene) reaction that (1) any above-mentioned two mercaptan (dithiol) and (2) is had at least two two keys.

[0095] compound (2) with at least two two keys can be selected from the non-annularity diene, comprise straight chain and/or side chain aliphatic series non-annularity diene, the diene that does not contain aromatic ring, comprise that wherein two keys can be included in the ring or are not included in the diene that does not contain aromatic ring in the ring, or its any combination, and the diene that does not wherein contain aromatic ring can comprise non-aromatic monocyclic group or the many cyclic groups of non-aromatics or its combination; The diene that contains aromatic ring; Or contain the diene of heterocycle; Or comprise the diene of any combination of described non-annularity and/or cyclic group.Described diene can be chosen wantonly and comprise thioether bond, disulfide bond, polysulfide bond, sulfone key, ester bond, thio-acid ester bond, carbonic acid ester bond, thiocarbonic acid ester bond, amino-formate bond or thiocarbamate key, or halogenic substituent, or its combination; Condition be described diene comprise can with two keys of the SH radical reaction of polythiol, and form covalency C-S key.Usually the compound (2) that has at least two two keys comprises the potpourri of the diene that differs from one another.

[0096] compound (2) with at least two two keys can comprise two (methyl) acrylate of acyclic non-conjugated diene, acyclic polyvinylether, (methyl) acrylic acid allyl ester, (methyl) acrylic acid vinyl esters, glycol, two (methyl) acrylate of two mercaptan, poly-(aklylene glycol) glycol two (methyl) acrylate, the non-aromatic diene of monocycle, encircle non-aromatic diene more, contain the diene of aromatic ring, the diallyl ester of aromatic ring dicarboxylic acid, the divinyl ester of aromatic ring dicarboxylic acid, and/or its potpourri.

[0097] non-limiting example of acyclic non-conjugated diene can comprise those that represented by following general formula:

Wherein R can represent C ₁-C ₃₀Line style or the saturated alkylidene of branching divalence, or C ₂-C ₃₀Divalent organic base, comprise group for example but be not limited to contain those of ether, thioether, ester, thioester, ketone, many sulphur, sulfone and its combination.Acyclic non-conjugated diene can be selected from 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene and its potpourri.

[0098] non-limiting example of suitable acyclic polyvinylether can comprise those that represented by following structural:

CH ₂＝CH--O--(--R ²--O--) _m--CH＝CH ₂

Middle R ²Can be C ₂-C ₆Positive alkylidene, C ₃-C ₆Sub-branched alkyl or--[(CH ₂--) _p--O--] _q-(--CH ₂--) _r--, m can be 0 to 10 rational number, is generally 2; P can be 2 to 6 integer, and q can be 1 to 5 integer, and r can be 2 to 10 integer.

[0099] non-limiting example of the polyvinylether monomer of Shi Yonging can comprise the divinyl ether monomer, for example ethylene glycol bisthioglycolate vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether and its potpourri.

[00100] two of the line style glycol (methyl) acrylate can comprise ethylene glycol bisthioglycolate (methyl) acrylate, 1, ammediol dimethylacrylate, 1,2-propylene glycol two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, 1,3-butylene glycol two (methyl) acrylate, 1,2-butylene glycol two (methyl) acrylate and its potpourri.

Two (methyl) acrylate of [00101] two mercaptan (dithiol) can comprise and for example comprises 1 of its oligomer, two (methyl) acrylate of 2-dithioglycol, two (methyl) acrylate (promptly 2 that comprises the dimercapto diethyl thioether of its oligomer, 2 '-sulfo-dithioglycol two (methyl) acrylate (2,2 '-thioethanedithiol di (meth) acrylate)), comprise 3 of its oligomer, 6-two oxa-s-1, two (methyl) acrylate of hot two mercaptan of 8-, two (methyl) acrylate that comprises the 2-mercaptoethyl ether of its oligomer, 4, two (methyl) acrylate of 4 '-dimercapto diphenyl sulfide, with its potpourri.

[00102] other non-limiting example of suitable diene can comprise the monocycle aliphatic diolefine, for example by those of following structural representative:

Wherein X and Y can represent C separately independently _1-10The saturated alkylidene of divalence; Or C _1-5The saturated alkylidene of divalence, it also comprises at least a element that is selected from sulphur, oxygen and silicon except carbon and hydrogen atom; R ₁Can represent H or C ₁-C ₁₀Alkyl; With

Wherein X and R ₁Can be as defined above, R ₂Can represent C ₂-C ₁₀Thiazolinyl.Described monocycle aliphatic diolefine can comprise 1,4-cyclohexadiene, 4-vinyl-1-cyclohexene, cinene and terpinene.

[00103] non-limiting example of many cyclic aliphatics diene can comprise 5-vinyl-2-norborene; 2, the 5-norbornadiene; Bicyclopentadiene and its potpourri.

[00104] non-limiting example that contains the diene of aromatic ring can comprise by those of following structural representative:

R wherein ₄Can represent hydrogen or methyl.The diene that contains aromatic ring can comprise monomer for example di isopropenylbenzene, divinylbenzene and its potpourri.

[00105] example of the diallyl ester of aromatic ring dicarboxylic acid can include, but are not limited to by those of following structural representative:

Wherein m and n can be 0 to 5 integer separately independently.The diallyl ester of aromatic ring dicarboxylic acid can comprise diallyl phthalate, properties of diallyl isophathalate, diallyl terephthalate and its potpourri.

[00106] compound (2) with at least two two keys can comprise 5-vinyl-2-norborene, the ethylene glycol bisthioglycolate vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, the butylene glycol divinyl ether, vinyl cyclohexene, 4-vinyl-1-cyclohexene, cinene, terpinene, bicyclopentadiene, encircle 12 carbon diene, cyclo-octadiene, 2-cyclopentene-1-base-ether, 2, the 5-norbornadiene, divinylbenzene, comprise 1, the 3-divinylbenzene, 1,2-divinylbenzene and 1, the 4-divinylbenzene, di isopropenylbenzene, comprise 1, the 3-di isopropenylbenzene, 1,2-di isopropenylbenzene and 1, the 4-di isopropenylbenzene, (methyl) acrylic acid allyl ester, two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid 1, the ammediol ester, two (methyl) acrylic acid 1, the 2-propylene glycol ester, two (methyl) acrylic acid 1, the 3-butanediol ester, two (methyl) acrylic acid 1, the 2-butanediol ester, two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid diglycol ester, dimercapto diethyl thioether two (methyl) acrylate, 1,2-dithioglycol two (methyl) acrylate, and/or its potpourri.

[00107] other non-limiting example of suitable two (methyl) acrylate monomer can comprise two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid 1, the 3-butanediol ester, two (methyl) acrylic acid 1, the 4-butanediol ester, 2,3-dimethyl-1, ammediol two (methyl) acrylate, two (methyl) acrylic acid 1,6-hexylene glycol ester, two (methyl) acrylic acid propylene glycol ester, two (methyl) acrylic acid dipropylene glycol ester, two (methyl) acrylic acid tripropylene glycol ester, two (methyl) acrylic acid, four propylene glycol esters, ethoxylation hexylene glycol two (methyl) acrylate, propoxylation hexylene glycol two (methyl) acrylate, two (methyl) acrylic acid DOPCP, alkoxylate neopentyl glycol two (methyl) acrylate, two (methyl) acrylic acid hexylene glycol ester, two (methyl) acrylic acid diglycol ester, polyglycol two (methyl) acrylate, thiodiglycol two (methyl) acrylate, two (methyl) acrylic acid trimethylene ester, two (methyl) acrylic acid triethyleneglycol ester, alkoxylate hexylene glycol two (methyl) acrylate, alkoxylate neopentyl glycol two (methyl) acrylate, two (methyl) acrylic acid pentadiol ester, cyclohexane dimethyl carbinol two (methyl) acrylate, with ethoxylation bisphenol-A two (methyl) acrylate.

[00108] can to produce refractive index when react with polyisocyanate (a) be at least 1.50, for example at least 1.52 or at least 1.55 or at least 1.60 or at least 1.65 or at least 1.67 polymkeric substance to the polythiol that is used for material (b) in the polyurethane material of preparation in first component.In addition, can to produce Abbe number when react with polyisocyanate (a) be at least 30, for example at least 35 or at least 38 or at least 39 or at least 40 or at least 44 polymkeric substance to the polythiol that is used for material (b) in the polyurethane material of preparation in first component.Can by methods known in the art for example Unite States Standard (USS) test method (ASTM) numbering D542-00 use multiple known equipment, measure described refractive index and Abbe number.Can also measure refractive index and Abbe number according to ASTM D 542-00, but except that following: (i) test minimum three samples of stipulating among one or two specimen/sample rather than the Section 7.3; (ii) test unregulated sample, rather than before according to such test of Section 8.1 regulations, regulate described specimen/sample.In addition, can use the refractive index and the Abbe number of Atago model DR-M2 Multi-Wavelength Digital AbbeRefractometer measuring samples/sample.

[00109] suitable polythiol can also comprise U.S. Patent application No.11/744, and 247 in [0025]-[0092] and [0093]-0094] in the oligomeric polythiols of disclosed thioether functional, the document is incorporated this paper by reference into.

[00110] polythiol that is used for material (b) in the polyurethane material of preparation in first component can produce Martens hardness and is at least 20 or usually at least 50 or more generally 70～200 newton/square millimeter (N/mm when reacting with polyisocyanate (a) ²) polymkeric substance.Described polymkeric substance is not flexible usually; That is because its rigidity, they be not basically can reversible deformation (for example stretchable), and do not show the nature and characteristic of rubber and other elastomeric polymer usually.

[00111] polyamines (comprising diamines) also is applicable to the material (b) in the polyurethane material of preparation in first component.

[00112] suitable substance with amine functional group that is used for material (b) in the polyurethane material of preparation in first component can have at least two primary amine and/or secondary amine group (polyamines).The non-limiting example of suitable polyamines comprises uncle or secondary diamine or polyamines, the group that wherein is connected to nitrogen-atoms can be saturated or undersaturated, aliphatic, alicyclic, aromatics, aromatics replace aliphatic series, aliphatic series replaces aromatics and heterocycle.The suitable aliphatic series and the non-limiting example of alicyclic diamine comprise 1,2-ethylenediamine, 1,2-propane diamine, 1,8-octamethylenediamine, different fluorine that ketone diamines, propane-2,2-cyclohexyl amine etc.The non-limiting example of suitable aromatic diamine comprises phenylenediamine and toluene diamine, for example o-phenylenediamine and to toluene diamine (p-tolyene diamine).Polynuclear aromatic diamines for example 4,4 '-benzidine, 4,4 '-methylene dianiline (MDA) and 4, the monochloro of 4 '-methylene dianiline (MDA) and dichloro-derivatives also are suitable.

[00113] be applicable to that polyamines of the present invention can include, but are not limited to have the material of following chemical formula:

R wherein ₁And R ₂Can be independently selected from methyl, ethyl, propyl group and isopropyl, R separately ₃Can be selected from hydrogen and chlorine.The non-limiting example that is used for polyamines of the present invention comprises the following compound of being produced by Lonza Ltd. (Basel, Switzerland)

LONZACURE

M-DIPA：R ₁＝C ₃H ₇；R ₂＝C ₃H ₇；R ₃＝H

LONZACURE

M-DMA：R ₁＝CH ₃；R ₂＝CH ₃；R ₃＝H

LONZACURE

M-MEA：R ₁＝CH ₃；R ₂＝C ₂H ₅；R ₃＝H

LONZACURE

M-DEA：R ₁＝C ₂H ₅；R ₂＝C ₂H ₅；R ₃＝H

LONZACURE

M-MIPA：R ₁＝CH ₃；R ₂＝C ₃H ₇；R ₃＝H

LONZACURE

M-CDEA：R ₁＝C ₂H ₅；R ₂＝C ₂H ₅；R ₃＝Cl

R wherein ₁, R ₂And R ₃Corresponding to above-mentioned chemical formula.

[00114] polyamines can comprise the diamine reactant compound for example 4,4 '-di-2-ethylhexylphosphine oxide (3-chloro-2,6-diethylaniline), (Lonzacure

M-CDEA), it can be from AirProducts and Chemical in the U.S., and (Allentown Pa.) obtains Inc; 2,4-diamido-3,5-diethyl-toluene, 2,6-diamido-3,5-diethyl toluene and its potpourri (" diethyl toluene diamine " or " DETDA " on the whole), it can be purchased with trade name Ethacure 100 from Albemarle Corporation; Diformazan sulfenyl toluene diamine (DMTDA), it can be purchased with trade name Ethacure 300 from Albemarle Corporation; 4,4 '-methylene-two (2-chloroaniline), it can be purchased with MOCA from Kingyorker Chemicals.DETDA at room temperature can be a liquid, and its viscosity under 25 ℃ is 156 cPs.DETDA can be isomeric, wherein 2, and 4-isomeride scope is 75 to 81%, and 2,6-isomeride scope can be 18 to 24%.Can use the colour stable form (that is, comprising adjuvant to reduce yellow prescription) of Ethacure 100 in the present invention, it can obtain by title Ethacure 100S.

[00115] other example of polyamines can comprise ethylene-amines.Suitable ethylene-amines can include, but are not limited to morpholine, the piperidines of ethylenediamine (EDA), diethylene triamine (DETA), trien (TETA), tetren (TEPA), penten (PEHA), piperazine, morpholine, replacement, piperidines, two ethylenediamines (DEDA) and the 2-amino-1-ethyl piperazidine of replacement.In specific implementations, polyamines can be selected from C ₁-C ₃One or more isomeride of dialkyl group toluene diamine for example still are not limited to 3,5-dimethyl-2,4-toluene diamine, 3,5-dimethyl-2,6-toluene diamine, 3,5-diethyl-2,4-toluene diamine, 3,5-diethyl-2,6-toluene diamine, 3,5-diisopropyl-2,4-toluene diamine, 3,5-diisopropyl-2,6-toluene diamine and its potpourri.Methylene dianiline (MDA) and propylene glycol two p-aminobenzoic acid esters also are suitable.

[00116] other example of suitable polyamines comprises methylene dianiline (MDA), aniline sulfide and diphenyl amine, and wherein any can be assorted the replacement, and condition is any reaction that substituting group takes place between can the disturbance reponse thing.Instantiation comprises 4,4 '-methylene-two (2,4,4 the 6-xylidin), '-methylene-two (2, the 6-diethylaniline), 4,4 '-methylene-two (2-ethyls-6-methylaniline), 4,4 '-methylene-two (2, the 6-diisopropyl aniline), 4,4 '-methylene-two (2-isopropyls-6-methylaniline) and 4,4 '-methylene-two (2,6-diethyl-3-chloroaniline).

[00117] normally used suitable substance with amine functional group comprises the diethylene toluene diamine, methylene dianiline (MDA), the methyl diisopropyl aniline, the isomeride of methyl diethylaniline, propylene glycol two p-aminobenzoic acid esters, 4,4 '-methylene-two (2, the 6-diisopropyl aniline), 4,4 '-methylene-two (2, the 6-xylidin), 4,4 '-methylene-two (2-ethyl-6-methylaniline), 4,4 '-methylene-two (2, the 6-diethylaniline), 4,4 '-methylene-two (2-isopropyl-6-methylaniline), and/or 4,4 '-methylene-two (2,6-diethyl-3-chloroaniline).United States Patent (USP) 5,811,506,3 hurdles, 44 walk to 5 hurdles, and 25 row are also described suitable diamines in detail, and it incorporates this paper by reference into.

[00118] In some embodiments of the present invention, the isocyanate functional group on the material described in first component can be partially end-blocked at least (partially capped).If isocyanate group is closed or end-blocking, any suitable aliphatic series, cyclic aliphatic or aromatic alkyl monohydroxy alcohol that those skilled in the art are known or phenolic compound can be used as capping reagent.The example of suitable end-capping reagent comprises those materials of separating end-blocking at elevated temperatures, and for example rudimentary aliphatic alcohol comprises methyl alcohol, ethanol and normal butyl alcohol; Cycloaliphatic alcohol, for example cyclohexanol; Aromatic alkyl alcohol, for example phenmethylol and methyl phenyl carbinol; And phenolic compound, for example phenol itself and substituted phenol, wherein substituting group can not influence coating operation, for example cresols and nitrophenols.Glycol ethers also can be used as capping reagent.Suitable glycol ethers comprises ethylene glycol butyl ether, diethylene glycol butyl ether, Ethylene Glycol Methyl ether and methyl proxitol.Other suitable capping reagent comprises oximes, for example methyl ethyl ketone oxime, acetoxime and cyclohexanone-oxime, and lactams is epsilon-caprolactams for example, and pyrazoles is dimethyl pyrazole and amine diisopropylamine for example for example.

[00119] in some embodiment of the present invention, as utilize polystyrene standards to measure by gel permeation chromatography, the material that has the isocyanate functional group in first component can have 1000 or at the most 500 or at the most 300 number-average molecular weight at the most.

[00120] in independent indefiniteness embodiment of the present invention, as utilize polystyrene standards to measure by gel permeation chromatography, the material with isocyanate functional group can have the number-average molecular weight greater than 1000 or at least 1500 or at least 2500.

[00121] first component can further comprise solvent.Suitable solvent can comprise any organic solvent that those skilled in the art are known, and condition is that they are not reactive with the isocyanate functional group.Possible solvent can include, but are not limited to following: the dialkyl ether of acetone, amyl propionate, methyl phenyl ethers anisole, benzene, butyl acetate, thiacyclohexane, ethylene glycol, for example diethylene glycol dimethyl ether and its derivant are (with CELLOSOLVE

Industrial solvent is sold), dibenzoic diglycol laurate, dimethyl sulfoxide, dimethyl formamide, dimethoxy benzene, ethyl acetate, methyl cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, methyl propionate, propylene carbonate, tetrahydrofuran, toluene, dimethylbenzene, 2-methyl ethyl ether, ammediol monomethyl ether and its potpourri.Except or replace above-mentioned organic solvent, can use halogenated solvent, for example alkyl halide methylene chloride for example.Solvent can 0 to 95 weight % or the amount of 20 to 80 weight % or 40 to 60 weight % be present in first component, based on the general assembly (TW) of first component.

[00122] second component of using in the inventive method comprises and has the material that isocyanates is reactive reactive hydrogen functional group.

[00123] the suitable material with reactive hydrogen functional group can comprise in any above-mentioned polyurethane material that has the isocyanate functional group in preparation first component as material (b) those disclosed.

[00124] second component can further comprise solvent.Suitable solvent can comprise any above-mentioned those disclosed.Described solvent can 0 to 95 weight % or the amount of 20 to 80 weight % or 40 to 60 weight % be present in second component, based on the general assembly (TW) of second component.

[00125] in the step (c) of the inventive method, merges first and second components, to form reaction mixture.Described reaction mixture can further comprise solvent, except or replace solvent in described single component one or two.Described solvent can be any above-mentioned those disclosed.Described solvent can 0 to 95 weight % or the amount of 20 to 80 weight % or 40 to 60 weight % be present in the reaction mixture, based on the general assembly (TW) of reaction mixture.

[00126] in some embodiment of the present invention, described reaction mixture can further comprise surfactant, any known those in for example any this area.Suitable surfactant can include, but are not limited to can be from Solutia, and Inc is with title MEDAFLOW

Those that obtain; The BYK-307 that can obtain from BYK-Chemie

And BYK-377

, and/or the MULTIFLOW that can obtain from CytecSurface Specialties

Described surfactant at the most 0.2 weight %, for example at the most 0.1 weight % or at the most the amount of 0.07 weight % be present in the reaction mixture, based on the general assembly (TW) of the resin solid in the reaction mixture.

[00127] In some embodiments of the present invention, described reaction mixture can further include and helps isocyanate functional group and amine functional group catalyst for reaction.Appropriate catalyst can be selected from known in the art those.Non-limiting example can comprise tertiary amine catalyst, for example still is not limited to triethylamine, triisopropylamine, dimethylcyclohexylam,ne, N, N-dimethyl benzylamine and its potpourri.Described suitable tertiary amine is disclosed in United States Patent (USP) 5,693,738 the 10th hurdles, and 6-38 is capable, and wherein disclosure is incorporated this paper by reference into.The character that depends on multiple reactive component, other appropriate catalyst comprise for example dibutyl tin laurate of phosphine class, tertiary amine salt, organic phosphorus compound, tin compound, or its potpourri.

[00128] after merging first and second components formation reaction mixture, can reaction mixture be cast on the support base material according to conventional solvent cast method.Described base material has smooth surface usually, and can comprise for example glass, stainless steel etc., and condition is that the material of the described base material of preparation can stand solidification temperature subsequently.

[00129] described reaction mixture is cast on the support base material with homogeneous thickness basically, after curing, to produce 0.5 to 20 mil (12.7 to 508 microns), the build of 1 to 10 mil (25.4 to 254 microns) or 2 to 4 mils (50.8 to 101.6 microns) for example.

[00130] after described reaction mixture is applied to base material, drive that solvent leaves film or by the air-dry cycle by mild heat, generally include and be exposed to environmental baseline about 1 to 20 minute, thereby on described substrate surface, form film.Then the film on the base material is heated to uniform temperature and reaches certain hour, so that be enough to produce cured film.In curing operation, drive away solvent, and the continuation of the reactive functional groups in reaction mixture reaction or reacts.In the preparation of polyurethane-urea film, for example, can under 100-210 ℃ temperature, carry out described heating or curing operation 10 to 100 minutes.In the embodiment that substitutes, can to 100 ℃ temperature range, be cured the long period environment temperature (for example, 23-27 ℃), for example 100 minutes to 5 days.The solidification temperature and the residence time will be depended on the character of reactant, comprise the type of reactive group, the existence of any catalyzer and type etc.Behind effective curing operation, can take off cured film from described support base material, to produce no lining form.The composition that is used for preparing the no lining form that contains polyurethane can comprise that release agent is as component.The variety of release agents that can introduce the composition that is used to prepare the no lining form that contains polyurethane can include, but are not limited to alkyl release agent, fatty acid-based release agent, fatty acid acyl amido release agent, alcohol radical release agent, fatty acid ester group release agent, organic silica-based release agent, phosphoric acid C8 to C16 alkyl ester group release agent and its potpourri or combination.The suitable example of alkyl release agent comprises synthetic paraffin, Tissuemat E and fluorocarbon.Operable fatty acid-based release agent comprises for example stearic acid and hydroxy stearic acid.Operable fatty acid acyl amido release agent can comprise for example stearic amide, ethylenebisstearamide and alkylene bis-fatty acid amides.The example of alcohol radical release agent can comprise stearyl alcohol, cetanol and polyvalent alcohol, for example polyglycol and polyglycerol.The example of the fatty acid ester group release agent that can comprise is a butyl stearate.The example of phosphoric acid C8 to C16 alkyl ester group release agent is the ZELEC that is produced by S tepan Company

UN.

[00131] the no lining form right and wrong that contain non-resilient polyurethane of the curing of gained are birefringent.Described no lining form is planar with all right and wrong are birefringent outside the plane.Described no lining form can be on three dimensions right and wrong birefringent.Measure birefraction according to the mode of describing among the embodiment hereinafter.In some embodiment, use Instron model 5543 stretching testing machines to measure, described film can show at least 9000 pounds/square inches faulting stress and at least 70% breaking tension.

[00132] the no lining form that contains non-resilient polyurethane according to the curing of method for preparing can be used to form polarization optical element of the present invention.

[00133] as mentioned before, the invention still further relates to a kind of polarization optical element, it comprises that (a) has two apparent surfaces' polarizing film; (b) protection supporting layer is comprising the no lining form that contains non-resilient polyurethane of any above-mentioned curing of at least one among the apparent surface who is attached to described polarizing film.Illustrate an embodiment of described optical element among Fig. 1.As shown in Figure 1, polarization optical element 10 of the present invention comprises following combination:

A) has the polarizing film 11 of two

apparent surfaces

12 and 13; With

B) be attached to each apparent surface 12 of described polarization layer and 13

protection supporting layer

21A and 21B, make polarizing film 11 place between two supporting layer 21A and the 21B, wherein at least one protection supporting layer comprises the no lining form that contains non-resilient polyurethane of curing.

[00134] as mentioned above, at least one protection supporting layer comprises the no lining form that contains non-resilient polyurethane of curing.In a specific embodiment, two protection supporting layers comprise the film that contains non-resilient polyurethane of curing.

[00135] described layer comprises that another protection supporting layer can comprise the different materials that is selected from any multiple material well known in the art in the embodiment of the film that contains non-resilient polyurethane of curing therein.For example, the protection supporting layer (is a coating; film or do not have lining form) can comprise polycarbonate; many cyclenes (polycyclic alkene); polyurethane; poly-(urea) carbamate (poly (urea) urethane); polythiourethane (polythiourethane); poly-sulfo-(urea) carbamate (polythio (urea) urethane); polyvalent alcohol (propylene carbonate); cellulose acetate; cellulose diacetate; Triafol T; cellulose acetate propionate; acetylbutyrylcellulose; polyvinyl acetate (PVA); polyvinyl alcohol (PVA); Polyvinylchloride; poly-asymmetric dichloroethylene; polyethylene terephthalate; polyester; polysulfones; polyolefin; its multipolymer; and/or its potpourri.In a specific implementations of the present invention, the protection supporting layer that is different from the protection supporting layer of the film that contains non-resilient polyurethane that comprises curing can comprise cellulose acetate, cellulose diacetate, Triafol T, cellulose acetate propionate and/or acetylbutyrylcellulose.Polarizing film can by any known Polarization filter for example polymeric material sheet material or layer form, wherein said polymeric material has been stretched or has been orientated and floods with for example iodine chromophore or dichroic dye (iodine chromohoreor dichroic dye).For example, a kind of method that is formed for traditional Polarization filter of ocular devices is heating polyvinyl alcohol (PVA) (" PVA ") sheet material or layer, and with softening PVA, the described sheet material that stretches then is so that PVA polymer chain orientation.Then, iodine chromophore or dichroic dye are impregnated into described sheet material,, and present specific order or arrangement mode so that iodine or dye molecule are connected to the polymer chain of arrangement.As selection, can at first iodine chromophore or dichroic dye dipping be entered the PVA sheet material, the described sheet material that can heat as mentioned above and stretch thereafter is with orientation PVA polymer chain and relevant chromophore or dyestuff.Polyethylene terephthalate (PET) polarizing coating also is suitable in addition.

[00136] iodine chromophore and dichroic dye are dichroic material, and promptly they absorb the stronger than another through in the component of radiation of two vertical plane polarizations.Although dichroic material if suitably do not place or arrange the molecule of dichroic material, will can not get seeing through the clean polarization of radiation with in the component of radiation one of seeing through of two vertical plane polarizations of preferential absorption.Promptly owing to the molecule of random arrangement dichroic material, the selectivity of individual molecule absorbs and will cancel each other, and makes to obtain clean polarization or overall polarization effect.Yet,, can obtain clean polarization by in the orientated polymer chain of PVA sheet material, suitably placing or arrange the molecule of dichroic material.That is, can make PVA sheet material polarization see through radiation, or in other words, can form Polarization filter.

[00137] method of using liquid crystal material to form polarization sheet material or layer also is known, and this sheet material can be as the polarizing film in the optical element of the present invention.For example, be suitable by the film formed polarization sheet material of the orientation thermotropic liquid crystal that comprises dichroic dye.As selection, can use by extruding the polarization sheet material that liquid crystal polymer forms, wherein liquid crystal polymer comprises by the dichroic dye of a covalently bound part as the host polymer chain.

[00138] in optical element of the present invention, the thickness of polarizing film can be 0.1 to 10 mil (2.54 to 254 microns), or 0.3 to 2 mil (7.62 to 50.8 microns), or 0.4 to 0.7 mil (10.16 to 17.78 microns).

[00139] refer again to Fig. 1, the no lining form that contains non-resilient polyurethane of curing is affixed at least one among the

apparent surface

12 and 13 of described polarization layer 11.Therefore described polarizing film 11 " is clipped in " between two supporting layer 21A and the 21B effectively.

[00140] in described sandwich construction, can for example use contact adhesive so that polarizing film 11 adheres to mutually with supporting layer 21A and 21B.As selection, can make each layer adhere to mutually by before assembling optical element, polarizing film and/or supporting layer being carried out surface treatment.This surface treatment can comprise chemistry or mechanical treatment, for example etching or by friction roughening, physics or chemical cleaning, Cement Composite Treated by Plasma, corona treatment and/or to apply coating bonding to promote.Can adopt laminating method known in the art equally.In addition, any above-mentioned layer/film can comprise one or more tackifier, adheres to one or more other layers to promote one deck.

[00141] polarization optical element of the present invention can have extra influence of light character, for example painted tone (colored tint) or photochromy sex change.For example, protection supporting layer (one or more) can comprise colorant to give color.Same protection supporting layer (one or more) can comprise one or more photochromic materials, for example any those that describe hereinafter.For example, photochromic material can be applied to the no lining form of curing, as the coating on it; Introduce the no lining form that solidifies by inhalation method; Be included as the component that is used to form film composition before the film forming.In addition, except described dichroic material, polarizing film can comprise colorant and/or photochromic material.Described polarizing film can also comprise dichromatism photochromic compound/material of giving described film photochromism and polarization.

[00142] as graphic among Fig. 2 for example, polarization optical element 10 of the present invention may further include the extra play that is stacked among supporting layer 21A and the 21B one or two.Non-limiting example can comprise removable diaphragm 24; during transportation be not scratched with protecting component and not damaged by other; can also comprise contact adhesive 22, apply described element to the multilayer optical goods with help with removable stripping film 23, or the like.Can also comprise photochromic coating or film, for example those disclosed hereinafter.

[00143] as mentioned above, polarization optical element of the present invention can be as the assembly in the multilayer optical goods.For example, according to the present invention, provide a kind of polarization optics goods, it comprises in combination:

A) base material; With

B) polarization optical element, for example any aforesaid those.

[00144] optical goods of the present invention can comprise the ophthalmology goods, and for example zero diopter lens (not having light intensity) and correcting vision (prescription) lens (finished product and semi-manufacture) comprise multi-focus lens (bifocus, three focuses and progressive lens); With ophthalmic device for example contact lens and intraocular lens, solar lens, fashion lens, motion face shield, face guard and safety goggles.Described optical goods can also be selected from display, screen (for example touch-screen), windowpane for example window and vehicles transparency, for example automobile or aircraft wind shield and side window.In a specific implementations of the present invention, described optical goods are assemblies of LCD.

[00145] can be so that optical goods of the present invention has influence of light character, for example color or tone and/or photochromy sex change with adapting to.This character can have more than one type, and can give any assembly of optical goods, comprises base material, polarization optical element and/or has been applied to base material and/or any any stacked coating or film that comprises the layer of described polarization optical element.

[00146] base material that uses in the polarization optical element of the present invention a) comprises optical element, and can be selected from especially mineral glass, pottery, for example collosol and gel and polymerization organic material.Described base material can be a rigidity, promptly can keep its shape, and supports the curable film-forming composition that applies.Can have at least a influence of light character as discussed above so that comprise optical element to its any coating that applies or processing with adapting to.In an embodiment of the invention, described base material is the polymerization organic material, and for example optically transparent polymkeric substance for example is suitable for for example material of ophthalmology goods of optical application.This optically transparent polymkeric substance has the refractive index that can change on a large scale.Example comprises the polymkeric substance of optical resin, and described optical resin is thermoplastic polycarbonate and by PPG Industries for example, and Inc is with TRIVEX

Monomer composition and CR-name for example CR-39

Monomer composition is sold.In addition can be from Mitsui Chemicals Co., Ltd. also is suitable with the high index polythiourethane base material that title MR-6, MR-7, MR-8 and MR-10 obtain.The non-limiting example of other suitable substrates is disclosed in paragraph in the U.S. Patent Publication 2004/0096666 [0061] and [0064] to [0081], and it incorporates this paper by reference into.

[00147] base material that uses in the optical goods of the present invention can comprise the polymerization organic material that is selected from thermoplastic, thermosets and its potpourri.The suitable example of this material is disclosed in Kirk-Othmer Encyclopedia of Chemical Technology, and the 4th edition, 6 volumes, 669 to 760 pages.Can pass through the known suitable chemical modification of those skilled in the art, make thermoplastic be thermoplasticity or thermosetting basically.

[00148] can comprise the resin that is used to form hard and soft contact lens as other example of the optical resin of base material among the present invention, for example U.S. Patent No. 5,166,345,11 hurdles, 52 walk to those disclosed in 12 hurdles, 52 row, and U.S. Patent No. 5,965, disclosing in 630 has the soft-contact lens of high moisture content, U.S. Patent No. 5, disclosed prolongation wearing and tearing contact lens wherein relates to contact lens and incorporates this paper by reference into the disclosure of optical resin in 965,631.

[00149] base material itself can comprise display, screen, lens, wind shield, ophthalmology goods or windowpane.

[00150] in some embodiments, described base material can be included in its lip-deep coating or film, and its floating coat or film are given influence of light character and/or provided the protection base material not rubbed or other damages.The example of suitable wear-resistant coating comprises asks No.2004/0207809 in the United States Patent (USP), those disclosed in paragraph [0205]-[0249], and it incorporates this paper by reference into.Design comprises U.S. Patent No. 5,316 with the suitable coating that impact resistance is provided, those disclosed in 7 row-7 hurdles, 791,3 hurdles, 35 row.Discuss other suitable coating compounds and film hereinafter in more detail.

[00151] described polarization optical element is affixed at least one surface of base material.Here randomly, between base material and polarization optical element, there are one or more middle layers, aforesaid.A kind of suitable middle layer can comprise delay compensation layer (retardat ion compensationlayer), as being used as the assembly in the LCD usually, the delay that causes when being used to compensate light by display unit changes, to improve visual angle characteristic.Can have the coating or the film that are stacked on the polarization optical element in addition, for example above-described those.

[00152] Fig. 3 illustrates a specific implementations of the present invention, the cross section of LCD 50.Form liquid crystal layer between two glass substrates 53, it comprises liquid crystal 54, cell isolation body (cell spacer) 55 and encapsulant 56.Be stacked on the glass substrate 53 is retardation compensation film 52 and polarization optical element 10.Lens sheet 51 is stacked on the top polarization optical element 10, forms the outmost surface of LCD.The internal layer of LCD 50 comprises polarization separating film (polarized separation film) 57, optically focused sheet material (condensing sheet) 58, scatterer 62, optical plate 60 and reverberator 61.Light source 59 can be a cold-cathode fluorescence lamp for example.

[00153] numerous photochromic materials can be used for optical goods of the present invention, so that influence of light character to be provided.At any time material can be inhaled in the base material, or is introduced in as known in the art the coating and is applied to base material then.In addition, photochromic material can constitute base material and be attached to the optical element of base material, and/or photochromic material can constitute base material and optical element simultaneously.Photochromic material can be provided in a variety of forms.Example comprises: single photochromic compound; The potpourri of photochromic compound; The material that comprises photochromic compound, for example solution of the not gelling of monomer or polymerization; Chemical bond has the material of photochromic compound, for example monomer or polymkeric substance; Comprise and/or have a material that chemical bond has photochromic compound, the outside surface of described material is sealed (being encapsulated as a kind of coating form) by for example polymer resin or protective finish, protective finish metal oxide for example wherein, thereby prevent photochromic material contact exterior materials for example oxygen, wet branch and/or chemicals, these materials can have a negative impact to photochromic material; Before applying protective finish, described material can be shaped as particle, as United States Patent (USP) 4,166, and 043 and 4,367, described in 170; Photochromic polymer for example, comprises the photochromic polymer that is combined with photochromic compound; Or its potpourri.

[00154] inorganic photochromic material can comprise silver halide, halogenation cadmium and/or copper halide crystallite.Can prepare other inorganic photochromic material by europium (II) and/or cerium (III) are added for example soda quartz glass of mineral glass.In another non-limiting embodiment, inorganic photochromic material is added in the melten glass, and be configured as particle, described particle is introduced may be applied in the film-forming composition of base material.This inorganic photochromic material is at Kirk OthmerEncyclopedia of Chemical Technology, and the 4th edition, 6 volumes are stated in the 322-325 page or leaf.

[00155] this photochromic material can be organic photochromic material, and it has the absorption maximal value of the activation in 300 to 1000 nanometer range.In the embodiment, organic photochromic material comprises having 400 to the peaked organic photochromic material of visible λ (a) that is lower than 550 nanometers with have the potpourri of the peaked organic photochromic material of visible λ (b) of 550 to 700 nanometers.

[00156] photochromic material can be used as and selectively comprises organic photochromic material, and it can be selected from pyrans class, oxazine class, fulgides, pyrroles's fulgides (fulgimide), two fragrant alkene class (diarylethenes) and its potpourris.

[00157] non-limiting example of the operable photochromic pyrans class of this paper comprises benzo pyran and aphthopyrans class, for example naphtho-[1,2-b] pyrans, naphtho-[2,1-b] pyrans, indeno-fused aphthopyrans and heterocyclic fused aphthopyrans, spiral shell-9-fluorenes also [1,2-b] pyrans, phenanthro-pyrans, quino pyrans; Fluoranthene and pyrans (fluoroantheno) and spiro-pyrans, for example spiral shell (benzo indoline) aphthopyrans, spiral shell (indoline) chromene, spiral shell (indoline) aphthopyrans, spiral shell (indoline) quino pyrans and spiral shell (indoline) pyrans and its potpourri.The non-limiting example of benzo pyran and aphthopyrans class is disclosed in United States Patent (USP) 5,645,767 2 hurdles, and 16 walk to 12 hurdles, 57 row; United States Patent (USP) 5,723,072 2 hurdles, 27 walk to 15 hurdles, 55 row; United States Patent (USP) 5,698,141 2 hurdles, 11 walk to 19 hurdles, 45 row; United States Patent (USP) 6,022,497 2 hurdles, 21 walk to 11 hurdles, 46 row; United States Patent (USP) 6,080,338 2 hurdles, 21 walk to 14 hurdles, 43 row; United States Patent (USP) 6,136,968 2 hurdles, 43 walk to 20 hurdles, 67 row; United States Patent (USP) 6,153,126 2 hurdles, 26 walk to 8 hurdles, 60 row; United States Patent (USP) 6,296,785 2 hurdles, 47 walk to 31 hurdles, 5 row; United States Patent (USP) 6,348,604 3 hurdles, 26 walk to 17 hurdles, 15 row; United States Patent (USP) 6,353,102 1 hurdle, 62 walk to 11 hurdles, 64 row; United States Patent (USP) 6,630,597 2 hurdles, 16 walk to 16 hurdles, 23 row; With United States Patent (USP) 6,736,998 2 hurdles, 53 walk to 19 hurdles, 7 row, its disclosure is incorporated this paper by reference into.The aphthopyrans class is disclosed in patent 5,658 with other non-limiting example of the organic photochromic material that replenishes, 501 1 hurdle, and 64 walk to 13 hurdles, 17 row, wherein disclosure is incorporated this paper by reference into.Spiral shell (indoline) pyrans is at Techniquesin Chemistry in addition, and III rolls up, and " Photochromism ", the 3rd chapter, Glenn H.Brown, editor, John Wiley and Sons, Inc, New York was stated in 1971.

[00158] example of operable Guang Zhi Bian Se oxazine class comprises benzoxazine, Nai Bing oxazine He Luo oxazine, for example spiral shell (indoline) Nai Bing oxazine, spiral shell (indoline) pyrido-benzoxazine, spiral shell (benzo indoline) pyrido-benzoxazine, spiral shell (benzo indoline) Nai Bing oxazine, spiral shell (indoline) benzoxazine, spiral shell (indoline) fluoranthene Bing oxazine, spiral shell (indoline) Kui Lin Bing oxazine and its potpourri.

[00159] example of operable photochromic fulgide or pyrroles's fulgide comprises: fulgide and pyrroles's fulgide, it is disclosed in United States Patent (USP) 4,685,783 1 hurdle, 57 walk to 5 hurdles, 27 row, United States Patent (USP) 4,931,220 1 hurdle, 39 walk to 22 hurdles, 41 row, and the disclosure of described fulgide and pyrroles's fulgide is incorporated this paper by reference into.The non-limiting example of two fragrant alkene classes is disclosed in the paragraph [0025] of U.S. Patent application 2003/0174560 to [0086].

[00160] can use the polymerizable organic photochromic material, for example United States Patent (USP) 5,166, and 345 on 3 hurdles, and 36 walk to 14 hurdles, the disclosed polymerisable Nai Bing oxazine of 3 row; United States Patent (USP) 5,236,958 on 1 hurdle, and 45 walk to 6 hurdles, the disclosed polymerisable spirobenzopyran of 65 row; United States Patent (USP) 5,252,742 on 1 hurdle, and 45 walk to 6 hurdles, 65 disclosed polymerisable spirobenzopyran of row and spiral shell benzothiopyran derivatives; United States Patent (USP) 5,359,085 on 5 hurdles, and 25 walk to 19 hurdles, the disclosed polymerisable fulgide of 55 row; Patent 5,488,119 on 1 hurdle, and 29 walk to 7 hurdles, the disclosed polymerisable naphthonaphthalene diketone of 65 row; United States Patent (USP) 5,821,287 on 3 hurdles, and 5 walk to 11 hurdles, the disclosed polymerisable Luo oxazine of 39 row; United States Patent (USP) 6,113,814 on 2 hurdles, and 23 walk to 23 hurdles, the disclosed polymerisable poly-alkoxylation aphthopyrans of 29 row; United States Patent (USP) 6,555,028 on 2 hurdles, 40 walk to 24 hurdles, 56 row with the aphthopyrans of polymeric matrix compatibilized.Above-mentioned patent is incorporated this paper into by reference about the disclosure of polymerisable organic photochromic material.

[00161] photochromic material is present in the optical goods with photochromic amount usually; That is produce the amount of the discernible variable color of naked eyes when, being exposed to radiation.

[00162] in the specific implementations of the present invention, the polarized optical goods comprise the element of LCD.In typical liquid crystal, liquid crystal is sealed between two glass baseplates.Re-tardation films is stacked on the glass baseplate, with layer for example lens, scatterer, the protective seam etc. of after-applied polarizer membrane and any other needs.The polarizer membrane of LCD can comprise polarized optical goods of the present invention.

[00163] conventional polarizer membrane utilizes the carrier of cellulose triacetate (TAC) film as Polarization filter in the LCD.The present invention utilizes the polarized optical goods of the curable no lining form that contains non-resilient polyurethane that comparable optical transmittance and low birefringence are provided, the higher refractive index, temperature, chemistry and solvent resistance, and elongation strengths, lower water retting does not need plastifier.In addition, described no lining form and the multiple film that contains non-resilient polyurethane is compatible with coating, and acceptant they.

[00164] other is applicable to that the coating of optical goods of the present invention or film can comprise particularly colored coating (tint coating) and/or wear-resisting or other protective finish.The coating that can directly be applied to base material is discussed before any can be used as stacked coating additionally or alternati.Similarly, any following coating of discussing as stacked coating can directly be applied to base material additionally or alternati.

[00165] material type that is used for this film or coating can extensively change, and is selected from the polymerization organic material and the diaphragm described below of base material.The film thickness of polymerization organic material can change to a great extent.Thickness range can for example be 0.1 mil to 40 mil, and these the value between any thickness range, comprise enumerator.Yet if desired, can use bigger thickness.

[00166] described polymerization organic material can be selected from thermosets, thermoplastic and its potpourri.This material comprises the polymerization organic material of selecting to be used for base material and diaphragm.Other example of polymerization organic material film is disclosed in paragraph in the U.S. Patent Publication 2004/0096666 [0082] to [0098], and the disclosure of this polymeric membrane is incorporated this paper by reference into.

[00167] in some embodiments, described film or coating comprise thermoplasticity polymerization organic material, and it is selected from nylon, poly-(vinyl acetate), vinyl chloride-vinyl acetate copolymer, poly-(C ₁-C ₈Alkyl) acrylate, poly-(C ₁-C ₈Alkyl) methacrylate, Styrene-Butadiene resin, poly-(urea-carbamate), polyurethane, polyester terephthalate, polycarbonate, polycarbonate-Organosiliconcopolymere and its potpourri.

[00168] randomly, compatible (chemically and on the color editing (color-wise)) fixed dye can be added or be applied to base material and/or stacked film, to obtain result more attractive in appearance.For example, can select dyestuff,, obtaining neutral more color, or absorb the incident light of specific wavelength, as in the photochromic lens with the complementary colors that for example produces with the photochromic material of activation.In another embodiment, can select dyestuff, think that material of main part or base material provide required tone.

[00169] in another embodiment, the said fixing dyestuff can be combined with the diaphragm that is used for optical goods of the present invention described below, known as those skilled in the art.For example referring to United States Patent (USP) 6,042,737 4 hurdles, 43 walk to 5 hurdles, 8 row, its disclosure that relates to the colored film base material is incorporated this paper by reference into.

[00170] diaphragm can be applied to base material, with the scuffing that prevents to cause owing to friction and wear.Described diaphragm can also be used as stacked film or coating.In a specific implementations, the diaphragm that is connected to optical goods of the present invention is a wear-resistant membrane at least in part.Phrase " wear-resistant membrane at least in part " be meant protection partly solidified at least coating of polymeric material or sheet material to the small part film; it shows the wearing quality of overgauge reference substance; described standard reference material is generally by can be from PPGIndustries, the CR-39 that Inc. obtains

The plastics that monomer is made are as according to the method test of the ASTM F-735 standard method of test of transparent plastic that is equivalent to utilize vibration sand method and coating abrasion performance.

[00171] diaphragm can be selected from protection sheet material, protection gradient film (it also provides hardness gradient for the film that they are inserted into therebetween), protective finish and its combination.Protective finish for example hard conating can be applied on polymeric membrane, base material and/or any surface that applies film, for example covers on the protection transition film.

[00172] be selected from protection during sheet material when diaphragm, it for example can be selected from disclosed protection polymeric sheet in U.S. Patent Publication 2004/0096666 paragraph [0118] to [0126].

[00173] protection gradient film provides wear-resistant membrane at least in part, and it can appliedly have other diaphragm subsequently.Before applying extra diaphragm, the transportation or with aftertreatment during, described protection gradient film can be used to protect goods.After applying extra diaphragm, protection gradient film provides the hardness gradient that applies film to another film from.Can measure the hardness of this film with the procedure known to those skilled in the art.In another indefiniteness embodiment, the protection membrane cover is on protection gradient film.Provide the non-limiting example of the diaphragm of described gradient character to comprise (methyl) acrylate-based coating of radiation curing of describing in U.S. Patent Application Publication 2003/0165686 paragraph [0010] to [0023] and [0079] to [0173].

[00174] described diaphragm can also comprise protective finish.The example of the protective finish known in the art that provides wear-resistant and scratch can be selected from multifunctional acrylic compounds hard conating, melamine based hard coating, polyurethane-base hard conating, alkyd resin base coating and/or organosilane types of coatings.The non-limiting example of described wear-resistant coating is disclosed in the paragraph [0205] of the paragraph [0128] to [0149] of U.S. Patent application 2004/0096666 and U.S. Patent application 2004/0207809 to [0249], and both disclosures are incorporated this paper by reference into.

[00175] in another embodiment, optical goods comprise that further anti-reflecting surface is handled at least in part.Phrase " anti-reflecting surface at least in part " is meant the antireflection character of improving the optical goods that applied to small part.In the indefiniteness embodiment, to compare with untreated optical goods, the dazzle amount of the optical goods surface reflection of handling reduces and/or the percent transmission increase by the optical goods handled.

[00176] in another indefiniteness embodiment, by vacuum evaporation, sputter or other method, anti-reflecting surface at least in part can be handled (for example single or multiple lift metal oxide, metal fluoride or other this material) material and be connected to for example surface of lens of optical goods of the present invention.

[00177] optical goods of the present invention may further include hydrophobic surface processing at least in part.Phrase " hydrophobic surface at least in part " is a kind of film, and it is compared with untreated base material, by reducing the water yield from the surface that may adhere to base material, improves the hydrophobic property of the base material that is applied to small part.

[00178] at the following embodiment that only is used for illustrating the present invention is described in more detail, because many conversion wherein and variation are conspicuous for those skilled in the art.

Embodiment

Embodiment 1

[00179] although above describing specific implementations of the present invention for illustration purpose, under the situation of the present invention that limits in not departing from the accessory claim book, many variations of details of the present invention are conspicuous for those skilled in the art.

Embodiment 1 preparation TRIVEX

AH resin cast solution

Charging 1 is mixed the suitable glasses container that mixer is equipped with in adding as indicated in proper order.Charging 2 is mixed another suitable glasses container that mixer is equipped with in adding as indicated in proper order.In different glass containers, mix and add 3.8 parts of chargings 1 and 1 part of charging 2.

Charging 1

Substance weight (gram)

TRIVEX AH resin (1) 106.70

Methyl ethyl ketone (MEK) 120.78

EXALITE

Blue 7813 1.32

Dye solution (2)

Solution (3) 0.85

(1) before the use, can be from PPG Industries, Inc is purchased

Resin remain on 65 ℃ following 2 hours.

(2) by 0.1241 gram is derived from Exciton's

Blue 7813 dyestuffs join 11.6852 gram MEK, and mix preparation Blue 7813 dye solutions.

(3) by 1.0 grams are derived from BYK-Chemie's Polyether-modified dimethione joins 9.0 gram MEK, and mixes preparation

Solution.

Charging 2

Substance weight (gram)

Diethyl toluene diamine 24.29

Methyl ethyl ketone (MEK) 35.53

(3) 0.22

Embodiment 2 preparations

AY resin cast solution

According to the process of embodiment 1, except the material in charging 1 and 2 as described below:

Charging 1

Substance weight (gram)

Resin (4) 5.60

Methyl ethyl ketone (MEK) 6.34

Solution (5) 0.089

(4) before the use, can be from PPG Industries, Inc is purchased

Resin

Remain on 65 ℃ following 2 hours.

(5) by 1.0 grams are derived from BYK-Chemie's

Polyether-modified dimethione joins 9.0 gram MEK, and mixes preparation

Solution.

Charging 2

Substance weight (gram)

Diethyl toluene diamine 1.19

Methyl ethyl ketone (MEK) 1.86

(5) 0.023

Embodiment 3 preparations

AH resin cast solution

Charging 1

Substance weight (gram)

TRIVEX

Resin (1) 5.00

Methylene chloride 9.32

Solution (6) 0.0398

(6) by 3.0 grams are derived from BYK-Chemie's

Polyether-modified dimethione joins 27.0 gram methylene chloride, and mixes preparation Solution.

Charging 2

Substance weight (gram)

Diethyl toluene diamine 1.30

Methylene chloride 3.12

(7) 0.0102

UN solution (7) 0.0630

(7) by restraining with 0.94

The UN release agent is added to 17.86 gram methylene chloride and mixes, preparation

UN solution.

The casting and the test of embodiment 4 films

The casting of step 1 film

Use GARDCO Automatic Drawdown Machine (Gardner Co.Inc.).It has Microfilm Applicator and 30 inches * 45 inches (glass plates of 76.2 centimetres (cm) * 114.3cm).The gauge of Microfilm Applicator is set to 11 microns.The 3.8 parts of chargings 1 of about 10 to 15 grams and the combination of 1 part of charging 2 being poured on the glass plate, opening machine in embodiment 1 and 2, is 3.2 parts of charging 1:1 parts charging 2 in embodiment 3.For embodiment 1 and 2 and embodiment 3, the coated glass plate that produces to be put into 70 ℃ of baking ovens, and in 20 to 25 minute time interval, temperature is elevated to 190 ℃, initial oven temperature is 45 ℃, other condition is identical.Temperature remains on 190 ℃ and descended 20 to 25 minutes.Remove the coated glass plate, and be cooled to environment temperature, and take off film from this plate.

The test of step 2 film

For the multiple character of listing in the table 1, the film of preparation in test implementation example 1 and 2 steps 1.Comparative Examples is the Triafol T (TAC) that derives from Fujifilm Corp..The density result of the Comparative Examples of listing derives from publication, other character of measurement Comparative Examples as described below.List the test result of embodiment 3 in the table 2.

Table 1-embodiment 1 and 2 and the physical property of Comparative Examples

Character	Embodiment 1 Trivex AH 107A	Embodiment 2 Trivex AY 064A	Comparative Examples TAC
Character	Embodiment 1 Trivex AH 107A	Embodiment 2 Trivex AY 064A	Comparative Examples TAC	Birefraction (6)	0(XY)，0(Z)	0(XY)4.65×10 ^-4(Z)	0(XY)， 5.31×10 ^-4(Z)
Mean refractive index (7)	-	1.52628	1.48763	Birefraction (6)	0(XY)，0(Z)	0(XY)4.65×10 ^-4(Z)	0(XY)， 5.31×10 ^-4(Z)
Mean refractive index (7)	-	1.52628	1.48763	Pulling strengrth (MPa) (8)	73	66	173

Breaking elongation, % (8)	44	109	11
Breaking elongation, % (8)	44	109	11	Young modulus (GPa) (8)	2.4	1.8	6.6
Density (g/cm3) (9)	1.11	1.11	1.27-1.29	Young modulus (GPa) (8)	2.4	1.8	6.6
Density (g/cm3) (9)	1.11	1.11	1.27-1.29	Transmissivity (%) (10)	93.1	92.9-93.5	94.0
Mist degree (10)	0.-0.2	0.24-0.70	0.38-0.67	Transmissivity (%) (10)	93.1	92.9-93.5	94.0
Mist degree (10)	0.-0.2	0.24-0.70	0.38-0.67	Thickness (mil) (11)	～3	～3	～3
Tg(℃)(12)	192	211	106	Thickness (mil) (11)	～3	～3	～3
Tg(℃)(12)	192	211	106	Scratch-proofness (steel timber, (mist degree) (13)	10.7％	28.3％	43.8％
Scratch-proofness (Bayer, Δ mist degree) (14)	41.3％	34.4％	66.7％	Scratch-proofness (steel timber, (mist degree) (13)	10.7％	28.3％	43.8％
Scratch-proofness (Bayer, Δ mist degree) (14)	41.3％	34.4％	66.7％	L ab(15)	90.39，-0.13， 0.42	91.15，-0.08， 0.58	92.45， -0.19， 0.57
Chemical-resistant (acetone) (16)	0	0	20	L ab(15)	90.39，-0.13， 0.42	91.15，-0.08， 0.58	92.45， -0.19， 0.57
Chemical-resistant (acetone) (16)	0	0	20	Thermal expansivity 25-70C (17)	93	138	30
Thermal expansivity 100-140C (17)	194	1220	75	Thermal expansivity 25-70C (17)	93	138	30
Thermal expansivity 100-140C (17)	194	1220	75	Moisture-penetrability (18)	-	35 gram water vapours/square metre/day	470 gram water vapours/square metre/day

(6) utilize and to be fixed with universal stage and 7-order crust than receiving the Optical Bench (deriving from the Model L305 of GaertnerScientific Co) of complementary color device (deriving from the Mode l617-F of Gaer tnerScientific Co), the mensuration birefringence value.

Use TD perpendicular to light path (casting laterally) axle and be parallel to ND (normal direction of film or the thickness direction) axle of light path, directly obtain with the interior birefraction (Δ n12) of the face of (XY) report.Utilize flow equation, from opticpath, around vertical TD birefraction (Δ n13) outside a plurality of rotations of MD (machine casting direction) axle are calculated with the face of (Z) report.

Wherein:

λ 0: lambda1-wavelength

D0: thickness of sample

The mean refractive index of material

The inclination angle

R0: derive from not the film of inclination measurement and delay

The pitch angle

Film delay

With the general micrometer measuring samples of accurate Fouler electronics thickness.

(7) use Epic Abbe 60 refractometers to measure the mean refractive index of the film of embodiment 2 and Comparative Examples.

(8) by using little stretching sample, according to ASTM D1708-06a standard method of test, at Instron 5543 electromechanical testing airborne measurements length growth rates, modulus and stress.The result who lists is the mean value of 5 tests.

(9) TRIVEX AH ﹠amp; The density value of AY is identical.

Reported TRIVEX AH result in the G2 lens material product bulletin, and as reporting by ASTM D792 Standard Test Method forDensity and Specific Gravity (Relative Density) of Plastics byDisplacemen test.The result that Comparative Examples is listed derives from people such as H.Sata " Properties and Applications of Cellulose Triacetate Film ", Macromo l.Symp.2004,208,323-333.

(10) according to manufacturer's indication, on Garder Hazegard Plus equipment, measure transmissivity and mist degree.

(11) with the general micrometer measuring samples of accurate Fouler electronics thickness.The result who lists is 5 mean values of measuring.

(12),, in covering the alumiseal jar, analyze whole samples with 25 ℃ minutes to 300 ℃ with TA Instruments 2920 DSC.Nitrogen purging speed is 50mL/ minute.With indium and tin reference material calibration DSC.Utilize the contrary flexure baseline to calculate peak area.Be generally by differential scanning calorimetry the ASTM D3419-03 standard method of test of polymer melted and crystalline transition temperature and heat content after this process.

(13) according to Steel Wool Abrasion-

The Steel Wool Test of breadboard SOP#-L-11-12-05 is except the report result represents initial % mist degree of specimen and final % mist degree.The result who lists is the mean value of 2 tests.

(14) basis

The Bayer scratch-proofness of laboratory Bayer test SOP#_L-11-10-06.The result who lists is the mean value of 2 tests.

(15) utilize Hunter Lab model D25P-9 calorimeter, use the LumenC light source, measure percent transmission (L), a* (redness-green) and b* (yellow-blueness) value according to ASTM D 1925-70.Positive a* value shows redness, and negative a* value shows green, and positive b* value shows yellow, and negative b* value shows blueness.

(16) use 2 inches * 2 inches (the sample determination chemical-resistants of 5.08cm * 5.08cm)." before " haze value of measuring samples on Hazegard Plus equipment.At room temperature sample was immersed in the solvent 10 minutes.After removing from solvent, use the rinsed with deionized water sample, and at room temperature dry.Measure " afterwards " haze value.Difference in the table between report " before " and " afterwards " haze value.

(17) use the about 20.5mm of measurement to take advantage of 6 millimeters rectangular strips that are fixed on the TA Instruments DMA model 2980, measure thermal expansivity with the control pattern.With 5 ℃/minute and 0.2N power, sample is heated to 180 ℃ from 0 ℃.Collected data in per 4 seconds, and base measuring temperature correspondingly.

(18) use the programmable moisture-penetrability tester of MOCON Permatran W-6 to measure moisture-penetrability, and under 37.8 ℃, test.General type method of testing is described in ASTM F1249-06 ＂ Standard Test Method for Water Vapor Transmission Rate ThroughPlastic Film and Sheeting Using a Modulated Infrared Sensor ＂, except using MOCON Permatran W-6.

Table 1 presentation of results embodiment 1 and 2 films show the character of improving that is better than the Comparative Examples film.Embodiment 1 and 2 film have lower birefraction; The low explanation better mechanical property of higher length growth rate and Young modulus; Scratch-proofness shows as the low difference of % mist degree; And thermal expansivity and glass transition temperature are higher.The film of embodiment 2 has anti-preferably acetone chemistry moral character, the low difference of Comparative Examples % mist degree as shown; And the test value of moisture-penetrability is lower.

The physical property of table 2-embodiment 3

Character	Embodiment 3 Trivex AH 0410
Character	Embodiment 3 Trivex AH 0410	Pulling strengrth (MPa) (8)	65.4
Breaking elongation, % (8)	39	Pulling strengrth (MPa) (8)	65.4
Breaking elongation, % (8)	39	Young modulus (GPa) (8)	1.1
Transmissivity (%) (10)	91.4	Young modulus (GPa) (8)	1.1
Transmissivity (%) (10)	91.4	Mist degree (10)	0.0
Thickness (mil) (11)	3.26-4.45	Mist degree (10)	0.0
Thickness (mil) (11)	3.26-4.45	L ab(15)	96.62，-0.08， 0.41

The present invention is described with reference to the details of its specific implementations.These details are not to be considered to limit protection scope of the present invention, unless be included in the appended claims to a certain extent.

Claims

1. method for preparing the film that contains non-resilient polyurethane of curing, it comprises:

B) provide second component, it comprises the material with the functional group that contains reactive hydrogen, and wherein said functional group is reactive to isocyanates;

C) merge first and second components, to form reaction mixture;

F) take off cured film from described support base material, contain the no lining form of non-resilient polyurethane with generation, its right and wrong are birefringent.

2. method according to claim 1, wherein said first component further comprises solvent.

3. method according to claim 2, wherein based on the general assembly (TW) of first component, described solvent is present in first component with the amount of 20 to 80 weight %.

4. method according to claim 1, wherein said second component further comprises solvent.

5. method according to claim 4, wherein based on the general assembly (TW) of second component, described solvent is present in second component with the amount of 20 to 80 weight %.

6. method according to claim 1, wherein said reaction mixture further comprises surfactant.

7. method according to claim 1, wherein said reaction mixture further comprises catalyzer.

8. method according to claim 1, wherein the isocyanate functional group on the material described in first component is partially end-blocked at least.

9. method according to claim 1, the material that wherein has the isocyanate functional group described in first component has 1000 number-average molecular weight at the most.

10. method according to claim 1, the material that wherein has the isocyanate functional group described in first component has the number-average molecular weight greater than 1000.

11. method according to claim 1, the material that wherein has the functional group that contains reactive hydrogen in second component comprises diethyl toluene diamine, methylene dianiline (MDA), the methyl diisopropyl aniline, the methyl diethylaniline, propylene glycol two p-aminobenzoic acid esters, 4,4 '-methylene-two (2, the 6-diisopropyl aniline), 4,4 '-methylene-two (2, the 6-xylidin), 4,4 '-methylene-two (2-ethyl-6-methylaniline), 4,4 '-methylene-two (2, the 6-diethylaniline), 4,4 '-methylene-two (2-isopropyl-6-methylaniline) and/or 4,4 '-methylene-two (2,6-diethyl-3-chloroaniline).

12. method according to claim 1, wherein the build of the no lining form of the curing that forms in the step (f) is 0.5 to 20 mil (12.7 to 508 microns).

13. method according to claim 1, wherein the temperature of heating described film to 100～210 ℃ reaches 10～100 minutes in the step (e).

14. method according to claim 1, wherein the temperature of heating described film to 25～100 ℃ reaches 100 minutes to 5 days in the step (e).

15. a polarization optical element, it comprises in combination:

A) has two apparent surfaces' polarizing film; With

B) protection supporting layer, it comprises the film that contains non-resilient polyurethane of the curing of at least one among the apparent surface who is attached to described polarizing film.

16. optical element according to claim 15, wherein said polarizing film comprise and are stretched and with the polymeric material of iodine chromophore or dichroic dye dipping.

17. optical element according to claim 16, wherein said polymeric material comprises polyvinyl alcohol (PVA).

18. optical element according to claim 15, the film right and wrong that contain non-resilient polyurethane of wherein said curing are birefringent.

19. optical element according to claim 15 is wherein adhered to one another with described polarizing film and described supporting layer with contact adhesive.

20. optical element according to claim 15, wherein the assembling described optical element before by described polarizing film and/or described supporting layer are carried out surface treatment, make that described polarizing film and described supporting layer are adhered to one another.

21. optical element according to claim 15, the thickness of the polarizing film in the wherein said element are 0.1 to 10 mil (2.54 to 254 microns).

22. optical element according to claim 15 wherein is disposed in described polarizing film between two protection supporting layers, described protection supporting layer comprises the film that contains non-resilient polyurethane of curing.

23. optical element according to claim 15, it further comprises the removable protective seam that is stacked at least one supporting layer.

24. optical element according to claim 15, the wherein film that contains non-resilient polyurethane that solidifies by the described method preparation of claim 1.

25. optical goods, it comprises in combination:

A) base material; With

B) be attached at least one lip-deep polarization optical element of described base material, described polarization optical element comprises in combination:

I) has two apparent surfaces' polarizing film; With

Ii) protect supporting layer, it comprises the film that contains non-resilient polyurethane of the curing of at least one among the apparent surface who is attached to described polarizing film.

26. optical goods according to claim 25, wherein said polarization optical element are stacked at least one surface of described base material.

27. optical goods according to claim 25 wherein are placed in described polarizing film between two protection supporting layers, described protection supporting layer comprises the film that contains non-resilient polyurethane of curing.

28. optical goods according to claim 25, wherein said base material comprise mineral glass, stupalith and/or polymerization organic material.

29. optical goods according to claim 25, wherein said base material comprise display, screen, lens, wind shield, ophthalmology goods or windowpane.

30. optical goods according to claim 25, it further comprises as the middle layer and places at least one film or coating between described base material and the described polarization optical element.

31. optical goods according to claim 27, wherein said middle layer comprises phase shift films.

32. optical goods according to claim 25, it further comprises at least one film and/or at least one coating that is stacked on the described polarization optical element.

33. optical goods according to claim 32, wherein said stacked film or coating comprise wear-resistant coating.

34. optical goods according to claim 25, wherein said optical goods comprise the assembly of LCD.