CN101361011A - Optical films comprising high refractive index and antireflective coatings - Google Patents

Abstract

Provided are reflective polarizing films and brightness enhancing films, comprising a high refractive index and/or antireflective coating.

Description

The optical thin film that comprises high refractive index coating and antireflecting coating

CROSS-REFERENCE TO RELATED PATENT

The application require to be filed on June 13rd, 2006 U.S. Provisional Application No.60/804591, be filed in the right of priority of the U.S. Provisional Application No.60/806017 on June 28th, 2006; And the application also requires to be filed in the pending trial U.S. Patent application No.11/267790 on November 5th, 2005 and is filed on Dec 19th, 2005 and with the right of priority of the disclosed PCT patented claim of WO2006/073773 No.US2005/045876.

Background technology

People have described multiple anti-reflection polymer film (" AR film ").The physical principle that anti-reflection film and coating play a role is known by people.For example, some summaries can be from Optical Engineering, S.Muskiant Ed, and Vol.6., OpticalMaterials, Chap.7 finds among the p 161,1985, and as U.S. Patent No. 3,833, described in 368 (people such as Land).The AR film is made of (" RI ") polymeric layer of the high index of refraction that replaces with suitable optical thickness and low refractive index polymer layer usually.For visible light, the order of magnitude of this thickness is approximately 1/4th of light wavelength to be reflected.The light of human eye about for 550nm is the most responsive.Therefore, wish to design in such a way the thickness of high refractive index coating and low refractive index coating, this mode makes the interior catoptrical amount of above-mentioned optical range reach and minimizes (for example, 3% or following).

As at Groh and Zimmerman, described in the Macromolecules, Vol.24p.6660 (1991), well-known, fluorine material has lower refractive index, therefore can be used in the low-index layer of AR film.

People have also described the various AR coatings of using fluorine-containing (methyl) acrylate polymer and fluorine material.Although the increase of fluorine content can reduce the refractive index of low refractive index coating composition, the minimizing of produced simultaneously surface energy may cause the coating performance and the visual appearance of difference, and causes the interface adhesion of low-index layer and adjacent high refractive index layer to reduce.In addition, known to people, highly fluorinated material can reduce the hardness and the permanance of coating.

Summary of the invention

In one embodiment, a kind of polarization by reflection optics film has been described, this polarization by reflection optics film comprises such anti-reflection film, this anti-reflection film comprises high refractive index layer that is connected to described polarization by reflection optics film and the low-refraction superficial layer that is connected to this high refractive index layer, and the gain added value of wherein said polarization by reflection film is at least 0.01 (being preferably at least 0.02).Preferred anti-reflection film produces the film with identical or higher (for example polarization) transmissivity.This polarization by reflection film is preferably can be randomly and the multilayer film of microstructured film combination.

Preferred anti-reflection film comprises the low-refraction superficial layer, and according to the steel wool durability test under the condition of using the 400g counterweight, the cut that this superficial layer is presented after swiping through 10 times is less than 10 roads.

In another embodiment, described a kind of brightness enhancement film, this brightness enhancement film comprises anti-reflection film, and according to the steel wool durability test under the condition of using the 400g counterweight, the cut that this anti-reflection film is presented after swiping through 10 times is less than 10 roads.

In another embodiment, described a kind of polarization by reflection film, it comprises the high index of refraction superficial layer that can improve permanance.According to the steel wool durability test under the condition of using the 400g counterweight, the cut that this superficial layer is presented after swiping through 10 times preferably is less than 10 roads.

In one aspect, the low-index layer of anti-reflection film preferably comprises the reaction product of polymerisable compound, and this polymerisable compound comprises at least aly fluoridizes free radical polymerization section bar material and through the inorganic nanoparticles of surface modification.

High refractive index layer preferably comprises the inorganic nanoparticles through surface modification (for example, refractive index is at least 1.60 inorganic nanoparticles) that is dispersed in the crosslinked organic material.High refractive index layer preferably comprises the Zirconium oxide nano grain through surface modification of 5 volume % to about 40 volume %.Preferred high refractive index layer can not reduce gain.

Anti-reflection film and/or high refractive index layer can be set on the first type surface or be arranged on simultaneously on two first type surfaces.

Description of drawings

Fig. 1 is the skeleton view of the exemplary optical articles with microstructure of the present invention.

Embodiment

The numerical range of being described by end points comprises all numerical value (for example, from 1 to 10 scope comprises 1,1.5,3.33 and 10) that comprised in this scope.

Term " radical polymerization mould assembly " is meant to have monomer, oligomer and the polymkeric substance that participates in the functional group of cross-linking reaction when being exposed to suitable radical source.Radical polymerization mould assembly group comprises (for example): (methyl) acryloyl group ,-SH, allyl or vinyl.Radical polymerization mould assembly group can be by halogenation, for example by the fluorine halogenation, for example at-COCF=CH ₂Situation in.

Preferred radical polymerization mould assembly monomer and oligomer have one or more " (methyl) acryloyl group " group usually, and it comprises can be randomly by (methyl) acrylamide and (methyl) acrylate of (for example) fluorine and sulphur replacement.Preferably (methyl) acryloyl group is an acrylate group.Many (methyl) acrylate material comprises at least two polymerisable (methyl) acrylate groups; Single (methyl) acrylate material then has single (methyl) acrylate group.As selection, an end of many (methyl) acrylate monomer compound can comprise two or more (methyl) acrylate groups.Radical polymerization mould assembly fluoropolymer comprises the functional group with (methyl) acrylate group or the reaction of other (methyl) acryloyl group usually.

As used herein, " solid weight number percent " is meant and desolventizes outer component sum.In some cases, described is the solid weight number percent of polymerizable organic composite, this be meant desolventize with inorganic (for example particle) material outside the component sum.

This paper has described the optical thin film that only has high refractive index coating, thereby or the combination with high refractive index coating and low refractive index coating the optical thin film of anti-reflection film is provided.In a preferred embodiment, high refractive index coating and/or anti-reflection film coating can make gain improve and/or the permanance enhancing.

In general, optical thin film is the film of light-transmissive.Many optical thin films are designed to change wave vector, and change the opticpath of light by this film thus.This can introduce the surface of micro-structural, mute optical surface, minute surface and body diffusive property by (for example) and be achieved.

The optical thin film of various transmitted lights is known, these films include, but is not limited to: multilayer optical film, microstructured film (for example retrodirective reflection sheet material and brightness enhancement film), polarization film are (for example, reflectivity or absorbability polarization film), diffusion film and retardation films (for example, biaxial retardation film) and compensation film (for example those described in the U.S. Patent Application Publication No.2004/0184150 that submitted on January 29th, 2004).

As used herein, term " film " is meant that its thickness is significantly less than the substantitally planar structure of width and length (for example, little at least 10 times than width and length) usually.The thickness of optical thin film is generally at least 25 microns.Although its thickness can be up to (for example) 3cm, the thickness of film is usually less than 2mm, more generally less than 800 microns.

The optical thin film of preferred type comprises the surface (for example having a plurality of prisms on film surface) of micro-structural, makes this film can be used for changing by reflection and refraction the direction of light (for example, the light of diffused light source).This film is known as brightness enhancement film and light control film.

Typical brightness enhancement film comprises such microstructured surface, and this surface has the regular repeat patterns that is made of the top rib of symmetry and groove.Other example of groove pattern comprises the top rib and groove is asymmetric and the size of top rib and groove, orientation or the inconsistent pattern of distance.

Referring to Fig. 1, the optical thin film 30 of micro-structural can comprise basalis 2 and microstructured optical layer 4.As selection, microstructured optical films can be all-in-one-piece, and wherein bottom and optical layers are made of identical materials.All-in-one-piece microstructured optical films can prepare by known method, for example makes by the molten thermoplastic resin is extruded.Optical layers 4 comprises the linear array that is made of the rectangular prism of rule (being denoted as prismatic 6,8,12 and 14 among the figure).Prismatic height arrives in about 75 microns scope at about 1 micron usually.Each prism (for example prism 6) all has first faceted pebble 10 and second faceted pebble 11.Prismatic 6,8,12 and 14 are formed in the substrate 2, this substrate have first surface 18 (being formed with prism on it) and smooth basically or be the plane and with the opposing second surface 20 of first surface 18.So-called rectangular prism is meant that apex angle is generally about 90 ° prism.Yet this angle can be in 70 ° to 120 ° scope, and can be in 80 ° to 100 ° scope.In addition, the peak can be sharp, circle, smooth or cut flat.The prismatic drift angle of circle can intersect angulation by (as smooth) faceted pebble and come approximate representation.Prismatic face needn't be identical, and prism also can be tilted in relation to each other.The height of the prism during this is arranged can be basic identical or can be different.Relation between optical goods gross thickness 24 and the prism heights 22 can change.Yet, wish to use relatively thin optical layers usually with clear and definite faceted pebble.The typical ratio of prism heights 22 and gross thickness 24 is usually between 25/125 and 2/125.

The function of supposing optical thin film is the direction that changes light, and then surface structure can have different pitches, forms different cross recesses and/or have different prismatic angles.For example, surface structure can have pseudorandom prismatic the fluctuating, and for example U.S. Patent No. 6,322, described in 236 like that.Surface structure can have the face more than three, therefore can have other shape such as pyramid.In addition, these faces can be discs and/or have the shape of other non-triangle.According to described shape, surface structure can be non-prism-shaped.

Many polymeric materials can be used as base material and/or microstructured optical layer.Suitable material has enough optical transparences, and structure is enough solid, so that assembled or be used for specific optical articles.Preferably, select to make the performance of optical articles can As time goes on not descend to temperature and aging base material with enough tolerances.

The concrete chemical composition of base material and/or microstructured optical layer and thickness can depend on the requirement of the particular optical product that will construct.That is to say, between intensity, transparency, temperature tolerance, surface energy, requirements such as adhesiveness, carry out balance optical layers.The thickness of basalis is generally at least about 0.025 millimeter (mm), is more typically at least about 0.125mm.In addition, basalis generally has the thickness that is no more than about 1mm.

Available basalis and/or microstructured optical layer material comprise glass and various polymeric material, and these polymeric materials comprise cellulose acetate-butyrate, cellulose-acetate propionate, cellulose triacetate, polyethersulfone, polymethylmethacrylate, polyurethane, polyester, polycarbonate, Polyvinylchloride, syndiotactic polystyrene, PEN, norbornene polymer, based on the multipolymer or the blend of naphthalenedicarboxylic acid.Can randomly be that described base material can contain these mixtures of material or composition.For example, substrate can be a multilayer, perhaps can contain to suspend or be dispersed in disperse phase in the external phase.Exemplary base layer material comprises polyethylene terephthalate (PET) and polycarbonate.The example of available PET film comprises photographic-grade polyethylene terephthalate (PET) and can (Wilmington is Delaware) with the commercially available PET of trade name " Melinex " from DuPont Films company.

The film of being made by this base layer material has certain birefringence that the manufacturing process because of film produces usually.Though the microstructured optical films with this base layer material preparation also can have this birefringence, because this optical thin film can not be used as the polaroid in the band light source display (as LCD), so it is not named as polarization film usually.As used herein, the variation that " unpolarized basically optical thin film " is meant variation along with polarization state, its diffuse reflectance is less than 0.5 optical thin film.In addition, film (film that for example, is stretched in manufacture process) also has such feature usually: its a certain axially refractive index of (as machine direction) is higher than another axially refractive index of (as horizontal dimension direction).

Different therewith is, " polarization by reflection optics film " is meant at least 0.05 the optical thin film of being changed to of variation along with polarization state, its diffuse reflectance.Polarization by reflection optics film usually at the reflectivity under a certain polarization mode apparently higher than its reflectivity under another kind of polarization mode.Along with the variation of polarization mode, the variation of its diffuse reflectance is generally at least 0.1, is more typically at least 0.2.

The polarization by reflection optics film of micro-structural can be made by the base layer material that has optical activity and can play the polarized material effect.Known have multiple base layer material to can be used as the polarized material use.Also can be by introducing inorganic material (for example Ding Xiang mica wafer) or realizing light polarization by being dispersed in discontinuous phase in the continuous film (for example being dispersed in the optical modulation liquid crystal that one-tenth in the continuous film drips shape).As a kind of selection, can prepare film by the superthin layer of different materials.For example, can be by using such as oriented film, applying electric field or methods such as magnetic field and coating technology and make polarized material in the described film along the polarization direction orientation.

The example of polarization film comprises as U.S. Patent No. 5,825,543 and 5,783, and those described in 120.(St.Paul MN) sells with trade name DBEF (reflecting type polarizing brightness enhancement film) the multilayer polarization film by 3M company.The use of this multilayer polarization optical film in brightness enhancement film be in U.S. Patent No. 5,828, describes to some extent in 488, and this patent documentation is incorporated this paper by reference into.U.S. Patent No. 5,882 has been described other example of polarization film in 774,5,965,247 and 6,025,897.As U.S. Patent No. 5,612,820 and 5,486, other polarization described in 949 and unpolarized film also can be used as the basalis of brightness enhancement film of the present invention.

In one embodiment, one or more coatings are set on the surface of polarization by reflection optics film (be the light of a kind of polarization state of transmission, and reflect the film of the light of another polarization state).Can realize that the material of required function and the example of structure are found in (for example) multilayer reflective polarizer, external phase/disperse phase reflecting polarizer, cholesteric reflective polarizers (it can be combined with quarter-wave plate) and wire grid polarizer.In general, multilayer reflective polarizer and cholesteric reflective polarizers are specular reflectors, and external phase/disperse phase reflecting polarizer is a diffuse reflector, but these qualitative neither be absolute (for example, referring to U.S. Patent No. 5,867, the diffusion type multilayer reflective polarizer described in 316).In addition, cited exemplary polarization by reflection element is not to be intended to exhaustive all polarization by reflection elements that can use in conjunction with the present invention more than.

The refractive index difference that multilayer reflective polarizer and external phase/disperse phase reflecting polarizer all depends between two kinds of different materials (being preferably polymkeric substance) at least optionally reflects the light on the polarization direction, and the transmission light on the polarization direction of quadrature with it.Exemplary multilayer reflective polarizer is described in (for example) PCT patented claim open No.WO95/17303, WO95/17691, WO95/17692, WO95/17699 and WO96/19347 to some extent.A kind of multilayer reflective polarizer form of commercially available acquisition is by 3M company (St.Paul, MN) the reflecting type polarizing brightness enhancement film (DBEF) of Xiao Shouing.

Can be included in (for example) U.S. Patent No. 5,825 in conjunction with the diffuse reflective polarizing sheet that the present invention uses, the external phase described in 543/disperse phase reflecting polarizer, and in U.S. Patent No. 5,867, the diffuse reflection type multilayer polaroid described in 316.Can in the open WO 96/31794 of PCT patented claim, describe to some extent in conjunction with other polarization by reflection element that the present invention uses.

Cholesteric reflective polarizers also can be used in conjunction with the present invention, and this polaroid is described in (for example) U.S. Patent No. 5,793,456 to some extent.A kind of cholesteric reflective polarizers by Merck company with trade name TRANSMAX ^TMSell.Also can use wire grid polarizer, and this polaroid is described to some extent in the open WO 94/11766 of (for example) PCT patented claim.

The polarization by reflection optics film that uses in conjunction with the present invention can comprise the direct reflection polaroid, and this polaroid makes the light generation direct reflection of some polarization directions.Alternatively, reflecting polarizer also can be the diffuse reflective polarizing sheet, and this polaroid makes the light generation diffuse reflection of some polarization directions.

Described in U.S. Patent application 2003/0217806, the multilayer optical film arrangement of the microbedding by having different refractivity at least in part provides desired transmissison characteristic and/or reflection characteristic.These microbeddings have different refractive index characteristics, so that some light being reflected at the interface between adjacent microlayers.The thickness of microbedding is enough thin, makes to produce constructive interference or destructive interference between a plurality of light that reflect at the interface, thereby makes film body have desired reflection characteristic or transmissison characteristic.Be used for reflecting the optical thin film of the light at ultraviolet, visible or near-infrared wavelength place for design, each microbedding generally has less than about 1 micron optical thickness (being that physical thickness multiply by refractive index).Yet, wherein also can comprise thicker layer, for example the top layer of film outside surface or the protectiveness boundary layer that is arranged on film inside, a plurality of microbedding assemblies are separated.Multilayer optical film body also can comprise one or more thick adhesive phases, so that with two in the lamination or more the multilayer optical film of multi-disc is bonding.

The reflection characteristic of multilayer optical film body and transmissison characteristic are the functions of the refractive index of each microbedding.Each microbedding at least can be by refractive index n in the face in the localized positions of film _x, n _yWith the refractive index n relevant with the thickness axis of film _zCharacterized.These refractive indexes represent that separately measured material is to the ray refraction rate along x, y and the z axle polarization of mutually orthogonal.In force, control refractive index by rational selection of material and processing conditions.The method for making of film is: will have tens or the alternately laminated two kinds of polymer A and the B coextrusion of hundreds of layer usually, then can be randomly with this multilayer extrudate by one or more multiplication moulds, then extrudate is stretched or otherwise extrudate is orientated, to form final film.The gained film usually by tens or a hundreds of independent microbedding forms, the thickness and the refractive index of adjustment microbedding, thus form one or more zones of reflections in desired SPECTRAL REGION (as visible region or near-infrared region).For the layer by right quantity obtains high reflectivity, preferably, adjacent microlayers is at refractive index difference (the δ n along the light of x axle polarization _x) be at least 0.05.If wish the polarized light of two kinds of quadratures is shown high reflectivity, so further preferably, adjacent microlayers is at refractive index difference (the δ n along the light of y axle polarization _y) be at least 0.05.In addition, refractive index difference can be less than 0.05 (being preferably about 0), so that form so multi-stackedly, this stacks the vertical incidence light of a certain polarization state of reflection, and the transmission vertical incidence light of the polarization state of quadrature with it.If desired, can also adjust between adjacent microlayers at refractive index difference (δ n along the light of z axle polarization _z), so that the reflection characteristic that obtains expecting at the p polarized component of oblique incidence light.

The examples material that can be used for making the multiple layer polymer optical thin film is found among the open WO 99/36248 of PCT patented claim people such as () Neavin.What suit the requirements is that wherein at least a material is the polymkeric substance that stress optical coefficient has big absolute value.In other words, when this polymkeric substance was stretched, it preferably produced bigger birefraction (at least about 0.05, more preferably at least about 0.1 or even 0.2).According to the application of these multilayer film, can two orthogonal directionss in this thin film planar between or between one or more interior directions and direction, produce birefringence perpendicular to thin film planar, perhaps be their array mode.Between each isotropic refractive index that polymeric layer had that does not stretch, differ greatly in particular cases, have birefringence although often still wish it, can relax the requirement that at least a polymkeric substance is had big this optimum condition of birefraction.When selecting polymkeric substance to be used for mirror film and polarization film (these films adopt twin shaft technology to make, and this technology stretches to film on the direction) in the face of two quadratures, this special circumstances can appear.In addition, desirable polymkeric substance should be able to keep birefringence after stretching, thereby gives finished film with desired optical characteristics.Can select second polymkeric substance be used for multilayer film other layer so that second polymkeric substance in the finished film can be obviously different with the refractive index of first polymkeric substance on same direction in the refractive index at least one direction.For convenience's sake, can make film like this: use only two kinds of different polymeric materials, and in extrusion, these two kinds of materials are arranged alternately, to form layer A, layer B, layer A, layer B etc. alternately.Yet only being arranged alternately, two kinds of different polymeric materials are not necessary.The substitute is, each of multilayer optical film layer all can be made of the unique material of not using in other layer of this film or blend.Preferably, had same or analogous melt temperature by the polymkeric substance of coextrusion.

Not only provided suitable refractive index difference but also provided the exemplary double focusing compound combination of suitable ply adhesion to comprise: (1) is mainly the multilayer polarization optical film that the method for uniaxial tension is made for employing, comprises PEN/coPEN, PET/coPET, PEN/sPS, PET/sPS, PEN/Eastar ^TMAnd PET/Eastar ^TMWherein, " PEN " refers to PEN, " coPEN " refers to based on the multipolymer of naphthalenedicarboxylic acid or blend, " PET " refers to polyethylene terephthalate, " coPET " refers to that based on the multipolymer of terephthalic acid (TPA) or blend, " sPS " refers to syndiotactic polystyrene and derivant thereof, Eastar ^TMBe can be from Eastman Chemical company commercially available polyester or copolyesters (it is believed that it comprises cyclohexanedimethanol unit and terephthalate units); (2) for the multilayer polarization optical film of making by the process conditions of controlling biaxial stretch-formed method, comprise PEN/coPEN, PEN/PET, PEN/PBT, PEN/PETG and PEN/PETcoPBT, wherein, " PBT " refers to polybutylene terephthalate, " PETG " refers to adopt the PET multipolymer of second kind of dibasic alcohol (being generally cyclohexanedimethanol), " PETcoPBT " refers to terephthalic acid (TPA) or its ester and ethylene glycol and 1, the copolyester that the potpourri of 4-butylene glycol forms; (3) for mirror coating (comprising coloured mirror coating), comprise PEN/PMMA, coPEN/PMMA, PET/PMMA, PEN/Ecdel ^TM, PET/Ecdel ^TM, PEN/sPS, PET/sPS, PEN/coPET, PEN/PETG and PEN/THV ^TM, wherein, " PMMA " refers to polymethylmethacrylate, Ecdel ^TMBe can be from Eastman Chemical company commercially available thermoplastic polyester or copolyesters (it is believed that it comprises cyclohexyl dicarboxylic acid's ester units, polytetramethylene ether diol unit and cyclohexanedimethanol unit), THV ^TMBe can be from the commercially available fluoropolymer of 3M company.

The relevant suitable multilayer optical film and the further details of relative configurations thereof are found in U.S. Patent No. 5, open WO 95/17303 of 882,774 people such as () Jonza and PCT patented claim people such as () Ouderkirk and WO 99/39224 people such as () Ouderkirk.Multiple layer polymer optical thin film and film body can comprise extra play and the coating of selecting in order to satisfy its optics, machinery and/or chemical characteristic.Referring to U.S. Patent No. 6,368,699 (people such as Gilbert).Thin polymer film and film body also can comprise inorganic layer, for example metal or coating of metal oxides or layer.

Polarization by reflection optics film also can comprise gain diffuser (gain diffuser).One type gain diffuser is described in the U.S. Patent application No.11/427948 that is filed on June 30th, 2006 to some extent, and this patent documentation is incorporated this paper by reference into.In cementing agent, add globule (this cementing agent is in the light path of light of the polarizer institute polarization that is reflected) and can produce some favourable optics or mechanical properties.These characteristics comprise that (for example) improve gain, enhancing contrast ratio, reduce or eliminate to soak with Newton ring, diffusion and color and shelter or equalization.Preferably, globule and cementing agent have low birefraction, and contain the pearl layer and can keep polarization.

Usually, to contain the globule that is comprised in the pearl layer be substantial transparent and be preferably transparent solid articles.These globules can be made by any suitable transparent material known to those of ordinary skill in the art, and described material for example is organic (for example polymkeric substance) or inorganic material.Some examples material include, but is not limited to: inorganic material, as silicon dioxide (as 3M company (St.Paul, Zeeospheres MN) ^TM), the alloy of sodium silicoaluminate, aluminium oxide, glass, talcum, aluminium oxide and silicon dioxide; And polymeric material, as liquid crystal polymer (Eastman ChemicalProducts company (Kingsport, liquid crystal polymer Vectram Tenn.) for example ^TM), amorphous polystyrene, styrene acrylonitrile copolymer, crosslinked granules of polystyrene or polystyrene copolymer, dimethyl silicone polymer, crosslinked dimethyl silicone polymer, poly methyl silsesquioxane and polymethylmethacrylate (PMMA), any suitable combination of preferably crosslinked PMMA or these materials.Other suitable material comprises such inorganic oxide and polymkeric substance, these inorganic oxides and polymkeric substance are gone up substantially can not be miscible, in the process of particle-containing layer, can not cause the bad reaction (degraded) of layers of material, thermal degradation can not take place, and can not absorb wavelength or the interior light of being paid close attention to of wavelength coverage basically under processing temperature.

The mean diameter of globule is generally in the scope of (for example) 5 to 50 μ m.Usually, the mean diameter of particle is in the scope of 12 to 30 μ m, perhaps in certain embodiments in the scope of 12 to 25 μ m.In at least some cases, preferentially select less globule for use,, and tend to form more coarse or more uniform rough surface or more light is dispersed the center because can in the coating of per unit volume, add more globule like this.In certain embodiments, bead size distribution can be+/-50%, and can be in other embodiments+/-40%.Other embodiment can comprise the bead size distribution less than 40%, and it comprises that distribute single the dispersion.

Though can use the globule of Any shape, general in some cases preferred spherical bead, make color shelter and gain especially like this when reaching at utmost.For surface diffusion, spheric grain is compared with the particle of other shape, the surface undulation degree that each spheric grain produced is bigger, this be because aspherical particle often along the thin film planar orientation, thereby make the shortest main shaft of particle be positioned on the thickness direction of film.

Usually, the cementing agent that contains the pearl layer also is a substantial transparent, and preferably transparent.In most of exemplary embodiments, binder material is a polymkeric substance.According to desired use, cementing agent can be polymeric material, thermoplastic, polymeric materials or the adhesive material of ionizing radiation curing type (for example, UV curing type).A kind of exemplary UV curing type cementing agent can comprise urethane acrylate oligomer, for example can derive from the Photomer of Cognis company ^TM6010.

Polarization by reflection optics film (blooming that does not promptly contain antireflection or high refractive index coating) has at least 1.65 monolithic relative gain usually.This monolithic relative gain is usually less than 1.80.

Go up additional anti-reflection film at optical thin film (as brightness enhancement film) and can improve gain.In conjunction with the gain test method described in the example, can be obtained up to few 0.01 to 0.02 or bigger improving gain.

The permanent seal cooling anti-reflective film comprises thicker relatively high refractive index layer and relatively thin low-index layer.

With regard to purpose of the present invention, when term " low-refraction " referred to be applied to substrate in the form of layer certain material, it is about 1.5 that the refractive index of the formed coating of this material is lower than, and more preferably less than about 1.45, and most preferably is lower than about 1.42.The lowest refractive index of low-index layer is generally at least about 1.35.

With regard to purpose of the present invention, when term " high index of refraction " referred to be applied to substrate in the form of layer certain material, the refractive index of the formed coating of this material was higher than about 1.5.The largest refractive index of high refractive index layer is not more than about 1.80 usually.Refractive index difference between high refractive index layer and the low-index layer is generally at least 0.15, is more typically 0.2 or bigger.

The thickness of high refractive index layer is generally at least 0.5 micron, is preferably at least 1 micron, and more preferably at least 2 microns, and be not more than 10 microns usually.The optical thickness of low-index layer is the odd-multiple of about 1/4 wavelength or 1/4 wavelength.This thickness more generally less than about 0.2 micron, and is generally about 90nm to 110nm usually less than 0.5 micron.When permanent seal cooling high refractive index layer and permanent seal cooling low-index layer are used in combination, can under the situation that does not have additional hard conating, provide (for example double-deck) anti-reflection film of permanance.

Low-index layer comprises the reaction product of free radical polymerization section bar material.Therein high refractive index layer comprise be dispersed in the crosslinked organic material, in the preferred embodiment of the nano particle of surface modification, this high refractive index layer also comprises the reaction product of free radical polymerization section bar material.This paper is described free radical polymerization section bar material at (methyl) acrylate material.Yet, also can obtain similar result by using other radical polymerization mould assembly group known in the art.

The low-refraction superficial layer comprises the reaction product of polymerisable low refractive index composition, and described composition comprises at least aly fluoridizes free radical polymerization section bar material and through the inorganic nanoparticles of surface modification.Particle dispersion the fluoridizing in the organic material that preferably has low-refraction (for example, being lower than 1.50) in free radical polymerization as herein described through surface modification.Multiple low-refraction inorganic oxide particles is known, described inorganic oxide such as metal oxide, metal nitride and metal halide (for example metal fluoride).Preferred low-refraction particle comprises colloidal silica, magnesium fluoride and lithium fluoride.Be used for low refractive index composition silicon dioxide can from Nalco Chemical company (Naperville, IL) commercially available with trade name " Nalco Collodial Silicas " (as product 1040,1042,1050,1060,2327 and 2329).Suitable pyrogenic silica comprises that (for example) can (Hanau be Germany) with trade name " Aerosilseries OX-50 " and production code member-130 ,-150 and-200 commercially available products from DeGussa AG company.Pyrogenic silica also can from Cabot company (Tuscola, I) commercially available with trade name " CAB-O-SPERSE2095 ", " CAB-O-SPERSE A105 " and " CAB-O-SILM5 ".

The fluorinated component of low-index layer produces low-surface-energy.The surface energy of low refractive index coating composition can characterize by the whole bag of tricks, described method such as contact angle and ink repellent.The low-index layer that solidifies and the static contact angle of water are generally at least 80 °.More preferably, this contact angle is at least 90 °, and most preferably is at least 100 °.Alternatively or in addition, the advancing contact angle of itself and hexadecane is at least 50 °, and more preferably at least 60 °.Low-surface-energy is given the performance of low-index layer antiscale decontamination, and makes expose surperficial easy to clean.

In certain embodiments, anti-reflection film as herein described has permanance.In one aspect, the permanent seal cooling anti-reflection film can prevent to be spoilt when contacting repeatedly such as abrasive materials such as steel wools.The obvious cut that the anti-reflection film surface exists can increase its mist degree.In one embodiment, according in example with the steel wool durability test that further describes, wipe with steel wool under the condition of using diameter heavy counterweight as the footstalk of 3.2cm and 400g and sweep after 5,10,15,20 or 25 times, the mist degree of anti-reflection film is less than 1.0%.

The superficial layer of anti-scratches visible not necessarily keeps lower surface energy.In a preferred embodiment, anti-reflection film with also keep low-surface-energy after abrasive material (for example steel wool) contacts repeatedly.In a preferred embodiment, according to the steel wool durability test, sweep after 5,10,15,20 or 25 times using diameter to wipe with steel wool under as the condition of the footstalk of 3.2cm and 400g counterweight, the advancing contact angle of anti-reflection film and hexadecane is preferably at least 45 °, 50 ° or 60 °.Use diameter as the condition of the footstalk of 3.2cm and 400g counterweight under with steel wool wipe sweep 10,50,100,200 or even after 300 times, the static contact angle of anti-reflection film and water also is at least 90 °, 95 ° or 100 ° usually.

In certain embodiments, the permanent seal cooling anti-reflection film comprises low-index layer as herein described and the high refractive index layer that is made of inorganic material (as metal or metal oxide) thin layer (as individual layer).This high refractive index coating generally forms with thermal evaporation, sputtering method or other evaporating deposition technique deposition.The example of concrete metal oxide comprises the oxide of (for example) aluminium, silicon, tin, titanium, niobium, zinc, zirconium, tantalum, yttrium, cerium, tungsten, bismuth, indium, mixed oxide, and their potpourri.

The high refractive index layer of permanent seal cooling anti-reflection film preferably comprises the nano particle through surface modification that is dispersed in the crosslinked organic material (nano particle that preferably has at least 1.60 high index of refraction).In the organic material of high refractive index layer, can use monomer, oligomer, polymkeric substance and their potpourri of multiple (for example nonfluorinated) radical polymerization mould assembly.Preferably, the organic material of high refractive index layer only comprises the nonfluorinated free radical polymerization section bar material with three or more (methyl) acrylate groups, or comprise the simple function and/or the dual-functional materials of nonfluorinated simultaneously, as hereinafter at described those materials of low-index layer.Multiple suitable high index of refraction composition is known, for example be filed in the unexamined U. S. application No.11/026573,11/026674 and 11/026702 on Dec 30th, 2004 simultaneously, and PCT applies for described in No.US2005/045764, No.US2005/046526 and the No.US2005/045876 those; These patent documentations are incorporated this paper by reference into.Though fluorine atom is not preferred for high refractive index layer, can adopt other halogen (as bromine and iodine), for example bromination (methyl) acrylate.

Multiple high refractive index particle is known, and these particles comprise (for example): the zirconia (" ZrO of Cun Zaiing alone or in combination ₂"), titania (" TiO ₂"), antimony oxide, aluminium oxide and tin oxide.The zirconia that uses in the high refractive index layer can obtain with trade name " Nalco OOSSOO8 " from Nalco Chemical company, or obtains with trade name " Buhler zirconia Z-WO sol " from Buhler AG Uzwil company (Switzerland).Zirconium oxide nano grain also can be filed in the U.S. Patent application No.11/027426 and the U.S. Patent No. 6,376 on Dec 30th, 2004 according to (for example), and method is prepared described in 590.

The concentration of (for example inorganic) nano particle in low-index layer and/or the high refractive index layer is generally at least 5 volume %, and is preferably at least 15 volume %.The concentration of inorganic particle is not more than about 50 volume % usually, and more preferably no more than 40 volume %.

Inorganic nanoparticles is preferably handled through surface conditioning agent.Nano particle is carried out surface treatment the stable dispersion that is in the polymerism resin can be provided.Preferably, come stable nanoparticles, make these particles be dispersed in well in the polymerisable resin, and obtain the composition of homogeneous basically by surface treatment.In addition, can carry out modification at least a portion surface of nano particle with surface conditioning agent, make stable particle during curing can with polymerisable resin copolymerization or reaction.Interpolation helps to make particle and radical polymerization mould assembly organic component generation covalent bonding through the inorganic particle of surface modification, thereby forms more tough and tensile, the polymkeric substance/particle network of homogeneous more.

In general, surface conditioning agent has: first end group, and it will be connected (realizing by covalent bond, ionic link or by strong physisorption) with particle surface; With second end group, it makes particle and resin have compatibility, and/or in solidification process with resin reaction.The example of surface conditioning agent comprises: alcohol, amine, carboxylic acid, sulfonic acid, phosphonic acids, silane and titanate esters.Preferred treating agent type is partly determined by the chemical property of metal oxide surface.Silane is preferred for silicon dioxide and other siliceous filler.Silane and carboxylic acid are preferred for metal oxide (for example zirconium dioxide).Can particle with carry out surface modification after monomer mixes immediately or mixing a period of time after carry out surface modification.With regard to silane, preferably before particle or nano particle are incorporated in the resin, make silane and particle or react with the surface of nano particle.The amount of required surface modifier depends on Several Factors, for example the type of the molecular weight of granularity, grain type, modifier and modifier.In general, preferably, making substantially, the modifier of individual layer is connected with particle surface.Required method of attachment or required reaction conditions also depend on employed surface modifier.For silane, preferably under acid or alkaline condition, carry out about 1-24 hour high temperature surface treatment.Surface conditioning agent (for example carboxylic acid) may not need high temperature or long period.

The representative embodiment that is suitable for the surface conditioning agent of composition comprises (for example) following compounds: as isooctyltrimethoxysi,ane, N-(3-triethoxysilylpropyltetrasulfide) carbamic acid methoxy ethoxy ethoxy ethyl ester, N-(3-triethoxysilylpropyltetrasulfide) carbamic acid methoxy ethoxy ethoxy ethyl ester, 3-(methacryloxy) propyl trimethoxy silicane, 3-acryloxy propyl trimethoxy silicane, 3-(methacryloxy) propyl-triethoxysilicane, 3-(methacryloxy) propyl group methyl dimethoxysilane, 3-(acryloxy propyl group) methyl dimethoxysilane, 3-(methacryloxy) propyl-dimethyl Ethoxysilane, 3-(methacryloxy) propyl-dimethyl Ethoxysilane, vinyl-dimethyl base oxethyl silane, phenyltrimethoxysila,e, the n-octyl trimethoxy silane, the dodecyl trimethoxy silane, the octadecyl trimethoxy silane, propyl trimethoxy silicane, the hexyl trimethoxy silane, vinyl methyl diacetoxy silane, the vinyl methyldiethoxysilane, vinyltriacetoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide, vinyltrimethoxy silane, vinyl triple phenoxyl silane, vinyl three tert-butoxy silane, vinyl three isobutoxy silane, vinyl silane triisopropoxide, vinyl three (2-methoxy ethoxy) silane, the styryl ethyl trimethoxy silane, mercaptopropyl trimethoxysilane, the 3-glycidoxypropyltrimewasxysilane, acrylic acid, methacrylic acid, oleic acid, stearic acid, dodecylic acid, 2-[2-(2-methoxy ethoxy) ethoxy] acetate (MEEAA), propenoic acid beta-carboxylic ethyl ester (BCEA), 2-(2-methoxy ethoxy) acetate, methoxybenzene guanidine-acetic acid, and their potpourri.

The operation of particle in the colloidal dispersion being carried out surface modification can realize by multiple known way, U.S. Patent application No.11/027426 that described mode such as preamble are quoted (being filed on Dec 30th, 2004) and U.S. Patent No. 6, mode described in 376,590; These patent documentations are all incorporated this paper by reference into.Zirconium oxide nano grain also can be commercially available from Nalco company and Buhler company.

Can use the combination of surface modifier, at least a in the wherein said modifier have can with the functional group of curable resin copolymerization.The combination of surface modifier can produce low viscosity.For example, described polymerizable groups can be ethylenic unsaturated functional group or the ring-type functional group that is easy to ring-opening polymerization.The unsaturated polymerization group of ethylenic can be (for example) acrylate or methacrylate or vinyl groups.Heteroatoms (for example oxygen, sulphur or nitrogen) in general contained in the ring-type functional group that ring-opening polymerization takes place easily, and be preferably oxygen containing three-membered ring (for example epoxy radicals).

The preferred compositions of surface modifier comprises: at least a first surface modifier and be different from the second surface modifier of first surface modifier, wherein said first surface modifier have can with the functional group of the organic component copolymerization of polymerizing resin.Second surface modifier is preferably the modifier that contains polyoxygenated alkene, optionally be, this modifier can with the organic component copolymerization of polymerisable compound.

Colloid nano particle through surface modification can condense basically fully.The not silica containing crystallinity of the nano particle of cohesion fully (form with the metal oxide particle that separates is measured) usually greater than 55%, is preferably greater than 60%, and more preferably greater than 70%.For example, crystallinity can reach about 86% or more than.Crystallinity can adopt the X-ray diffractive technology to measure.Crystallization (as the zirconia) nano particle of cohesion has high index of refraction, and unbodied nano particle has low-refraction usually.

Inorganic particle preferably has monodispersed substantially size-grade distribution, perhaps has by two or more monodispersed substantially distributions to mix the multimodal distribution that obtains mutually.Alternatively, can introduce such inorganic particle, this inorganic particle has the certain particle scope that obtains by the particle size range that particle is ground to expectation.Inorganic oxide particles is non-gathering (discrete basically) usually, can cause inorganic oxide particles generation optical scattering (atomizing) or precipitation because assemble, or gelation.Inorganic oxide particles is generally colloid, its mean grain size in 5 nanometers between 100 nanometers.The granularity of high index of refraction inorganic particle is preferably less than about 50nm, to have the sufficient transparency.Utilize transmission electron microscope to calculate the quantity of the inorganic oxide particles of given diameter, can record the particle mean size of inorganic oxide particles.In order to have the transparency, preferably adopt the unimodality distribution of particles.

Anti-reflection film can have the surface of gloss or mute light.Mute light anti-reflection film is compared with typical gloss film, has lower transmissivity and higher mist degree usually.For example, measure according to ASTM D1003, its haze value is generally at least 5%, 6%, 7%, 8%, 9% or 10%.And measure under 60 ° condition according to ASTM D2457-03, the glossiness of glossy surface is generally at least 130, and the glossiness of mute optical surface is less than 120.

Can make surface roughening or veining, to form mute optical surface.This can realize by multiple mode known in the art, described mode comprises that use impresses the low-refraction surface by the suitable tools of shot blast or alternate manner roughening, and, realizes composition by being solidified on suitable coarse master mold, as U.S. Patent No. 5,175,030 people such as () Lu and No.5, described in 183,597 (Lu) like that.

In yet another aspect, by high refractive index layer and low-index layer (as superficial layer) are placed in the mute optical thin film substrate, can be made into mute light anti-reflection film.Exemplary mute optical thin film can from U.S.A.Kimoto Tech company (Cedartown, GA) commercially available with trade name " N4D2A ".

The low refractive index coating of mute light and high refractive index coating also can prepare by add particles with suitable particle filler (as silica sand or beaded glass) in composition.This mute light particle is far longer than the low-refraction particle through surface modification usually.For example, its particle mean size is usually between about 1 to 10 micron.The concentration of this type of mute light particle can be at least 2 weight % in about 10 weight % or above scope.When its concentration less than 2 weight % (for example, 1.8 weight %, 1.6 weight %, 1.4 weight %, 1.2 weight %, 1.0 weight %, 0.8 weight %, 0.6 weight %) time, the common deficiency of this concentration is so that gloss reduces to the degree (this also can increase mist degree) of expectation.Yet, also can under the situation that does not have this mute light particle, provide the permanent seal cooling anti-reflection film.

Low-refraction polymerisable compound and organic high refractive index polymerizable compositions comprise at least a crosslinking chemical with at least three radical polymerization mould assembly groups usually.This component often is many (methyl) acrylate monomer of nonfluorinated.Introduce the hardness that this material helps to increase hardening composition.

Low-refraction polymerisable compound and organic high refractive index polymerizable compositions comprise the crosslinking chemical of at least 5 weight %, 10 weight % or 15 weight % usually.The concentration of crosslinking chemical in low refractive index composition generally is not more than about 40 weight %.For the preferred embodiment that adopts the high concentration inorganic particle, the concentration of crosslinking chemical in the high index of refraction composition generally is not more than about 25 weight %.

Suitable monomers comprises (for example): trimethylolpropane triacrylate (can be from (the Exton of Sartomer company, PA) commercially available with trade name " SR351 "), ethoxylated trimethylolpropane triacrylate (can be from Sartomer company (Exton, PA) commercially available with trade name " SR454 "), pentaerythritol tetracrylate, pentaerythritol triacrylate (can be commercially available with trade name " SR444 ") from Sartomer company, five acrylic acid dipentaerythritol ester (can be commercially available with trade name " SR399 ") from Sartomer company, the ethoxylation tetramethylol methane tetraacrylate, ethoxylation pentaerythritol triacrylate (can be commercially available with trade name " SR494 ") from Sartomer company, six acrylic acid dipentaerythritol ester and three (2-hydroxyethyl) isocyanuric acid ester triacrylate (can be commercially available with trade name " SR368 ") from Sartomer company.In some respects, can use many (methyl) acrylate compounds that comprises hydantoins part, as U.S. Patent No. 4,262, those described in 072 people such as () Wendling.

The polymerizable coating composition of low-refraction and high index of refraction also can comprise at least a dual functional (methyl) acrylate monomer.Multiple difunctionality (methyl) acrylate monomer is known in the art, it comprises (for example): 1, the 3-butanediol diacrylate, 1, the 4-butanediol diacrylate, diacrylate 1,6-hexanediol ester, 1,6-hexanediol acrylate acrylate, glycol diacrylate, the alkoxylated alphatic diacrylate, the alkoxylate cyclohexane dimethanol diacrylate, the alkoxylate hexanediyl ester, the alkoxylate neopentylglycol diacrylate, the neopentyl glycol hydroxyl trimethylace tonitric ester diacrylate of caprolactone modification, the neopentyl glycol hydroxyl trimethylace tonitric ester diacrylate of caprolactone modification, cyclohexane dimethanol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, ethoxylated bisphenol a diacrylate, neopentylglycol diacrylate, polyethyleneglycol diacrylate (Mn=200 gram/mole, the 400g/ mole, 600 gram/moles), ethoxylated neopentylglycol diacrylate, tetraethylene glycol diacrylate, tristane dimethanol diacrylate, triethylene glycol diacrylate and tripropylene glycol diacrylate.

Low-index layer preferably comprises the free radical polymerization section bar material of one or more fluorine content at least 25 weight %.Highly fluorinated monomer, oligomer and polymkeric substance are characterised in that to have low-refraction.Multiple fluorine content is at least about many (methyl) acrylate of fluoridizing of 25 weight % and single (methyl) acrylate material is known.In certain embodiments, the fluorine content of low-refraction polymerisable compound is at least 30 weight %, at least 35 weight %, at least 40 weight %, at least 45 weight % or at least 50 weight %.Usually, the highly fluorinated material of the overwhelming majority is multifunctional free radical polymerization section bar material.Yet this class material can use with the simple function combination of materials of fluoridizing.

The multiple list of fluoridizing (methyl) acrylate and many (methyl) acrylate compounds can be used for preparing polymerisable low refractive index coating composition.This class material generally comprises radical polymerization mould assembly part and (entirely) perfluoroalkyl polyether part, (entirely) fluoroalkyl part and (entirely) fluorine alkylene moiety.Each material in the material of these classifications all has high fluorine content (for example at least 25 weight %).Other material that the interior fluorine content of various types of materials is less than 25 weight % can be used as helper component.

In certain embodiments, this complementary fluoridizing (methyl) acrylate monomer can help the low-index material of existence in the intensified response potpourri or the compatibility of other fluorinated material.For example, have been found that, the PFPE carbamate compounds is particularly useful for strengthening the compatibility of high fluorine content material, as the U.S. Patent application No.11/087413 that is filed on March 23rd, 2005, be filed in the U.S. Patent application No.11/277162 on March 22nd, 2006 and the files No.62060US002 that submits to simultaneously described in.This perfluoropolyethers carbamate compounds generally comprises at least one polymerisable (as end) (methyl) acrylate part and (can the randomly repeat) unit at least one, and this unit comprises (entirely) perfluoroalkyl polyether group that closes at least two linking group and amino-formate bond or urea bond by quantivalency.Amino-formate bond and urea key are generally-NHC (O) X-, and wherein X is O, S or NR, and R is H or the alkyl that contains 1 to 4 carbon.As previously mentioned, PFPE partly is preferably the HFPO-part.A kind of PFPE carbamate (methyl) acrylate of exemplary high fluorine content is: HFPO-C (O) NHC ₂H ₄OC (O) NHC ₂H ₄OC (O) C (CH ₃)=CH ₂, wherein HFPO is F (CF (CF ₃) CF ₂O) aCF (CF ₃)-, " a " average out to 2 to 15.

In a preferred embodiment, the low-refraction polymerisable compound comprises at least a radical polymerization mould assembly fluoropolymer.The generality of this class fluoropolymer is described and the preparation method is found in Encyclopedia Chemical Technology, Fluorocarbon Elastomers, Kirk-Othmer (1993), perhaps see Modern Fluoropolymers, J.Scheirs Ed, (1997), J Wiley Science, Chapters 2,13,32 (ISBN 0-471-97055-7).

Preferred fluoropolymer is made of the constituent monomers that is called as tetrafluoroethene (" TFE "), hexafluoropropylene (" HFP ") and vinylidene fluoride (" VDF ", " VF2 ").The monomer structure of these components is as follows:

TFE:CF ₂＝CF ₂ (1)

VDF:CH ₂＝CF ₂ (2)

HFP:CF ₂＝CF-CF ₃ (3)

Fluoropolymer preferably comprises at least two kinds of above-mentioned constituent monomers (HFP and VDF), more preferably comprises all three kinds of constituent monomers with various molar weights.Not explanation but same other useful monomer comprises the perfluorovinyl sulfide ether monomer in (1), (2) or (3), its general structure is CF ₂=CF-OR _f, R wherein _fCan be side chain or straight chain perfluoroalkyl, and itself can comprise other heteroatoms, as oxygen atom with 1-8 carbon.Concrete example has perfluoro methyl vinyl ether, perfluoro propyl vinyl ether and perfluor (3-methoxyl-propyl group) vinyl ether.Other example is found in the WO00/12574 (Worm) that transfers 3M company, and U.S. Patent No. 5,214,100 (Carlson).

To be called the FKM that is named as ASTM D 1418 by the amorphous copolymer that VDF-HFP and optional TFE constitute hereinafter, or the FKM elastic body.The FKM elastic body has following general formula:

Wherein x, y and z represent with molar percentage.In certain embodiments, x can be zero, as long as the enough height (usually greater than about 18 moles of %) of the molar percentage of y gets final product to such an extent as to its microstructure is an amorphous form.Also exist wherein x that the present invention can use greater than other fluoroelastomer composition of zero.

Fluoropolymer comprises radical polymerization mould assembly group.This can realize that these halogen-containing cure site monomer (" CSM ") and halogenation end group can utilize multinomial technology known in the art to be copolymerized in the polymkeric substance by introducing halogen-containing cure site monomer (" CSM ") and/or halogenation end group.These halogen groups provide the reactivity at other component of coating mix, and help forming polymer network.Available halogen containing monomer is known in the art, and representative example is found in U.S. Patent No. 4,214, among 060 (people such as Apotheker), European patent No.EP398241 (Moore) and the European patent No.EP407937B1 (people such as Vincenzo).

Optionally be, can the halogen cure sites be incorporated in the polymer architecture that this halogenation chain-transferring agent can produce the fluoropolymer end of the chain that contains the reactive halogen end group by using a kind of like this halogenation chain-transferring agent.This class chain-transferring agent (" CTA ") is known by the people in the literature, and its representative instance is: Br-CF ₂CF ₂-Br, CF ₂Br ₂, CF ₂I ₂And CH ₂I ₂Other representative instance is found in U.S. Patent No. 4,000, among 356 (Weisgerber).Be by cure site monomer, or by chain-transferring agent, or by this dual mode halogen to be introduced in the polymer micro-structural be not particular importance, crosslinked and have more active fluoropolymer with the coreaction of other component (as acrylate) in the network at UV because this dual mode all can produce.Different with the dehydrofluorination method of hereinafter discussing is, using cure site monomer to form the co-crosslinking network has the following advantages: the light transmission of formed polymeric layer does not suffer damage, and this is because the reaction of acrylate and fluoropolymer does not rely on the degree of unsaturation that has for reaction in the main polymer chain in this case.Therefore, brominated fluoroelastomer is (as deriving from Dyneon LLC company (St.Paul, Dyneon Minnesota) ^TME-15742, E-18905 or E-18402) can be used in combination with FKM or replace FKM as fluoropolymer.

In another embodiment, can be by coming dehydrofluorination with any method that can make fluoropolymer have enough carbon-to-carbon degrees of unsaturation, so that fluoropolymer has reactivity, thus the bond strength between increase fluoropolymer and hydrocarbon substrate or the layer.The dehydrofluorination method is a kind of method of knowing that can produce unsaturation, and this method is most commonly used to make fluoroelastomer carry out ionomer by nucleopilic reagent (as xenol and diamines).This reaction is the elastomeric feature that contains VDF.Associated description is found in document The Chemistry of Fluorocarbon Elastomer, A.L.Logothetis, Prog.Polymer Science (1989), 14,251.In addition, simple function fat primary amine and simple function fatty primary secondary amine also may be realized this class reaction, and can produce the DHF-fluoropolymer that has pendant amine groups.Yet this DHF reaction can not take place in the polymkeric substance that does not contain the VDF unit, because this polymkeric substance does not take off the ability of HF under the effect of this class reagent.

Can adopt by introducing the combination that cure site monomer produces reactive fluoropolymer and produces reactive fluoropolymer by the dehydrofluorination method.The low refractive index composition that contains fluoropolymer as herein described preferably comprises at least a amino-organosilanes ester coupling agent or its condensation product, as being filed in described in the U.S. Patent application No.11/026640 on Dec 30th, 2004 those, this patent documentation is incorporated this paper by reference into.Preferred amino-organosilanes ester coupling agent comprises: the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, (aminoethylamino methyl) phenethyl trimethoxy silane, (aminoethylamino methyl) phenethyl triethoxysilane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-aminopropyl methyldiethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyltriethoxywerene werene, the amino butyl trimethoxy silane of 4-, the amino butyl triethoxysilane of 4-, 3-aminopropyl methyldiethoxysilane, 3-aminopropyl methyl dimethoxysilane, 3-aminopropyl dimethyl methyl TMOS, 3-aminopropyl dimethylethoxysilane, 2,2-dimethoxy-1-azepine-2-silicon is for cyclopentane-1-ethamine, 2,2-diethoxy-1-azepine-2-silicon is for cyclopentane-1-ethamine, 2,2-diethoxy-1-azepine-2-silicon is for cyclopentane, 2,2-dimethoxy-1-azepine-2-silicon is for cyclopentane, 4-aminophenyl trimethoxy silane, and 3-phenyl amino propyl trimethoxy silicane.

In another embodiment, low-index layer comprises the reaction product of following material: A) fluorine-containing (methyl) acrylate polymer intermediate and B) at least a fluoridizing (methyl) acrylate monomer (those described in the files No.61846US002 that submits to simultaneously, this patent documentation is incorporated this paper by reference into).A) and potpourri B) preferably be cured by being exposed under the radiation (as ultraviolet light).The low refractive index polymer composition that solidifies can comprise A) and copolyreaction product B).By inference, the low refractive index polymer composition of curing also comprises B) polymerizate.Fluorine-containing (methyl) acrylate polymer intermediate can combine with other component of low refractive index coating composition by covalent bond.In addition, but fluorine-containing (methyl) acrylate polymer intermediate polymerization that other optional components of low refractive index coating (as the nonfluorinated crosslinking chemical) can make physics twine, thus form interpenetrating networks.

Fluorine-containing (methyl) acrylate polymer intermediate A) comprise the reaction product of following material: i) at least a many (methyl) acrylate monomers or the oligomer of fluoridizing, its fluorine content is at least about 25 weight %; Ii) optional one or more are fluoridized or many (methyl) acrylate material of nonfluorinated.This optional many (methyl) acrylate material can comprise monomer with many (methyl) acrylate part, oligomer, polymkeric substance, through the inorganic nanoparticles of surface modification, and the various combinations of these materials.The total amount of many (methyl) acrylate material is generally at least 25 weight % of polymerizable organic composite solid (weight %).The total amount of many (methyl) acrylate material can for about 30 weight % of the composition that contains nano particle to 70 weight %.

Low refractive index composition can comprise various simple functions and/or polyfunctional HFPO-per-fluoro polyether compound.Introducing can produce such low-surface-energy surface at least about 5 weight % to simple function and/or the polyfunctional HFPO-per-fluoro polyether compound of about 10 weight %, and the initial static contact angle of this surface and water is at least 110 °.

Single (methyl) acrylate compounds of multiple PFPE is known.A kind of this type of exemplary low-index material is HFPO-C (O) NHCH ₂CH ₂OC (O) CH=CH ₂, it contains the fluorine of 62.5 weight % as calculated.Other can be by single (methyl) acrylate compounds of the low-refraction PFPE of similar fashion preparation: HFPO-C (O) NHCH ₂CH ₂OCH ₂CH ₂OCH ₂CH ₂OC (O) CH=CH ₂, it contains the fluorine of 59.1 weight % as calculated; HFPO-C (O) NH (CH ₂) ₆OC (O) CH=CH ₂, it contains the fluorine of 60.2 weight % as calculated; And HFPOC (O) NHCH ₂CH ₂OCH ₂CH ₂OCH ₂CH ₂OCH ₂CH ₂OC (O) CH=CH ₂, it contains the fluorine of 57.3 weight % as calculated.This compounds is at the U.S. Patent application No.11/277 that is filed on March 22nd, 2006, describes (referring to preparation part 31a-31d) to some extent in 162.

Exemplary low-refraction PFPE many (methyl) acrylate monomer is HFPO-C (O) N (H) CH ₂CH (OC (O) CH=CH ₂) CH ₂OC (O) CH=CH ₂, it contains 53.4% fluorine as calculated.This monomer can be prepared according to the method (referring to FC-4) described in the U.S. Patent Application Publication No.2005/0249940-A1.Other low-refraction PFPE many (methyl) acrylate compounds comprises: H ₂C=CHC (O) OCH ₂CH ₂N (H) is C-HFPO-C (O) N (H) CH (O) ₂CH ₂OC (O) CH=CH ₂(it contains 58.1% fluorine) and (H ₂C=CHC (O) OCH ₂) ₂CH ₃CH ₂CN (H) is C-HFPOC (O) N (H) CCH (O) ₂CH ₃(CH ₂OC (O) CH=CH ₂) ₂(it contains 50.1% fluorine).These compounds can be prepared according to U.S. Patent application No.11/087413 that is filed on March 23rd, 2005 and the described method (referring to preparation process No.28 and No.30) that is filed among the pending trial U.S. Patent application No.11/277162 on March 22nd, 2006.

Usually use at least a radical initiator to prepare polymerisable low-refraction and high refractive index coating composition.Available free radical thermal initiator comprises (for example): azo-compound, superoxide, persulfate and redox initiator, and their combination.Available free radical photo-initiation comprises (for example): knownly can be used for making acrylate polymer to carry out those free radical photo-initiations that UV solidifies.In addition, can in final composition, add other adjuvant.These adjuvants comprise (but being not limited to): resinousness flow promortor, light stabilizer, high boiling solvent and other compatilizer well-known to those having ordinary skill in the art.

By free radical polymerization section bar material is dissolved in the compatible organic solvent with about solid concentration of 1% to 10%, can form polymerisable compound.Can use the blend of single a kind of organic solvent or multiple solvent.According to the difference of employed free radical polymerization section bar material, suitable solvent comprises: alcohol, as isopropyl alcohol (IPA) or ethanol; Ketone is as MEK (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), cyclohexanone or acetone; Aromatic hydrocarbons is as toluene; Isophorone; Butyrolactone; N-Methyl pyrrolidone; Tetrahydrofuran; Ester is as lactate, acetate (comprises propylene glycol monomethyl ether acetate (as can be commercially available with trade name " 3M Scotchcal Thinner CGS10 " (" CGS10 ") from 3M company), acetic acid 2-butoxy ethyl ester (as can be commercially available with trade name " 3M Scotchcal Thinner CGS50 " (" CGS50 ")) from 3M company, diethylene glycol ether acetate (DE acetate), 2-Butoxyethyl acetate (EB acetate), dipropylene glycol monomethyl ether acetate (DPMA)), the isoalkyl ester is (as acetic acid dissident ester, the acetic acid isocyanate, isooctyl acetate, acetic acid ester in the different ninth of the ten Heavenly Stems, acetic acid isodecyl ester, acetic acid dodecane ester, the different tridecane ester of acetic acid or other isoalkyl ester); And the combination of above-mentioned substance etc.

Although can use multiple fluorated solvent, in one aspect, prepared compatibility low refractive index coating composition is the fluorinated solvent not.Compatible coating composition is transparent, and non-fuzzy.Compatible coating does not have visible defects basically.When using incompatible coating, can include, but is not limited to by observed visual defects: haze, pit, flake, spot, agglomerate or significant ripple, or other known visual indicator of the those of ordinary skill of optics and coatings art.

The method that forms the antireflecting coating on the optical display or be formed for the anti-reflection film of optical display can comprise: provide the light transmission basalis, as the polarization by reflection film; High-index material is set on basalis; And provide the low-index layer that is connected with high refractive index layer as herein described.Low-index layer can be set by the following method: the described low-index material of one deck is coated on the described high-index material layer (as cured layer), fully shines to carry out crosslinked with UV radiation then.Alternatively, low refractive index coating can be coated on the release liner, make it partly solidified at least, carry out transfer coated then.In addition, antireflection material can be applied directly in the substrate, perhaps it be coated on the separation layer of transfer printing type anti-reflection film, by heat transfer or optical radiation it be transferred in the substrate from separation layer then.

Thin film cladding technology that can be by routine is coated to this low refractive index composition and high index of refraction composition on the high refractive index layer with single one or more layers form, or is applied directly in the substrate (as display surface or film).Alternatively, low refractive index coating can be coated in release liner or the substrate, make it partly solidified at least, adopt heat transfer or optical radiation technology to carry out transfer coated then.Although substrate can be the form of the continuous tablet of rolling usually easily, coating can be coated on the independent thin slice.Advantageously, by being set, single one deck low-index layer can obtain antiradar reflectivity and favorable durability simultaneously on single one deck high refractive index layer.

Can use multiple technologies that film is applied, described technology comprises dip coating, forward rolling method and inverse roller coating method, the excellent rubbing method of coiling and mould rubbing method.Mould is coated with machine and comprises: knife type coater, slit coater, slidingtype coating machine, fluid bearing coating machine, the curtain formula of a sliding coating machine, fall mould curtain formula coating machine and extrusion coated machine etc.Multiple mould is coated with machine and describes to some extent in following document, described document for example is " the Modern Coating andDrying Technology " that Edward Cohen and Edgar Gutoff are shown, VCH Publishers, NY 1992, ISBN 3-527-28246-7, and " Coating and Drying Defects:Troubleshooting Operating Problems " that Gutoff and Cohen showed, Wiley Interscience, NYISBN 0-471-59810-0.

Low-refraction and high refractive index coating composition are put into oven drying, desolvate to remove, (for example) makes it to solidify carrying out ultraviolet irradiation (preferably carrying out) under the required wavelength in oxygen concentration is lower than the inert atmosphere of 50ppm by adopting H lamp or other lamp then.It is crosslinked that free radical polymerization section bar material takes place this reaction mechanism.

Although invention has been described by preferred embodiment, should be appreciated that the present invention is not limited only to these embodiment, because those skilled in the art also can carry out various modifications to it, especially make amendment according to above-mentioned instruction content.

Method of testing

The steel wool durability test

On the horizontal dimension direction of coating direction, test the wearing quality of cured film across film surface attached to the mechanical hook-up of the steel wool sheet on the contact with swinging back and forth.Contact swings back and forth in the scope that width is 60mm is swept in wiping with the speed of 210mm/ second (3.5 wipings are swept/second), and wherein " wiping is swept " once is meant one way 60mm.Contact has the smooth cylindrical base structure that diameter is 3.2cm.Contact is designed to counterweight attached, to increase by steel wool applied force on perpendicular to the direction of film surface.#0000 steel wool sheet is to derive from Hut Products company (Fulton, " Magic Sand-Sanding Sheets " MO).It is the suitable designated size of sand paper of 600-1200 that #0000 steel wool sheet has with granularity.Downcut the steel wool dish of 3.2cm from the polishing sheet upper punch, and it is adhered on the contact pedestal of 3.22cm with 3M Brand Scotch Permanent Adhesive Transfer Tape.At sample of each example test, the wiping of adopting in the test process is swept number of times shown in record under the condition of using the 400g counterweight.The cut of visual examination sample then.Also to estimate ink repellent and contact angle simultaneously.

The gain test method

With deriving from Photo Research company (Chatsworth, the SpectraScan that the MS-75 lens are housed CA) ^TMThe PR-650 spectrocolorimeter is measured the optical property of film.Film is placed the top of the hollow light box of diffuse transmission.The diffuse transmission of light box and diffuse reflection can be depicted as lambertian pattern.Light box is six a hollow cube, is of a size of about 12.5cm * 12.5cm * 11.5cm (length * wide * height), and it is that the PTFE diffusing panel of about 6mm is made by thickness.The one side of selecting this light box is as sample surfaces.The diffuse reflectance measured value at the sample surfaces place of hollow light box is about 0.83 (for example average out to is about 83% in the 400-700nm wavelength coverage, adopts following method to measure).In the gain test process, the circular hole of the about 1cm of this light box by being positioned at light box bottom throw light on internally (bottom of this light box is relative with sample surfaces, and light is internally according to sample surfaces).Provide this illumination with stable band incandescent light sources, wherein this light source is connected with fibre bundle (the Fostec DCR-II that has the fibre bundle extended line of the about 1cm of diameter that is used for conducting light, can derive from Schott-Fostec LLC company (Marlborough MA and Auburn, NY)).Between sales kit (SK) and camera, place the linear absorption polaroid (as Melles Griot 03 FPG 007) of standard.Camera focus on the light box sample surfaces of camera lens apart from about 34cm, and is placed the about 2.5cm of camera distance camera lens place with absorptive polarizer.Do not have being placed with polaroid under the situation of sample thin film, record the brightness＞150cd/m of illuminated light box ²When sample thin film is parallel to the light box sample surfaces and places (sample thin film contacts with light box usually), incide the sample brightness on the sample surfaces plane of light box with the PR-650 measuring vertical.By being compared with the brightness of the independent light box that records in the same manner, sample brightness calculates relative gain.Whole mensuration process is all carried out in the darkroom, to eliminate source of stray light.When the film assembly that contains reflecting polarizer being carried out the relative gain test, the light transmission shaft of reflecting polarizer is aimed at the light transmission shaft of the absorptive polarizer of test macro.The relative gain value of the prismatic films of being reported generally obtains under the following conditions: from the prismatic groove of the nearest film of the absorptive polarizer light transmission shaft homeotropic alignment with respect to absorptive polarizer.

Be the integrating sphere that scribbles Spectralon, the stable broadband halogen light source of 15.25cm (6 inches) and be the power supply of light source power supply that with diameter measure the diffuse reflectance of light box, (Sutton NH) provides by Labsphere company for integrating sphere, light source and power supply.Integrating sphere has three openings, an opening is light inlet (diameter is 2.5cm), one is the detecting device mouth (diameter is 2.5cm) that is 90 degree along second, and the 3rd opening is the sample port (diameter is 5cm) that is 90 degree along the 3rd (promptly with all vertical axle of preceding two axles).PR-650 spectrocolorimeter (the same) focuses on the detecting device mouth of its about 38cm.The reflection efficiency of integrating sphere adopts the calibration that is provided by Labsphere company to calculate with reflectance standard (SRT-99-050), and this standard film has about 99% diffuse reflectance.This standard film is calibrated by Labsphere company, and can consult NIST standard (SRS-99-020-REFL-51).The reflection efficiency of integrating sphere is calculated as follows:

Spheroid brightness ratio=1/ (1-R _Spheroid* R _{Standard film})

In this case, the spheroid brightness ratio is the ratio that covers the brightness gained that the brightness that records at detecting device mouth place after the sample port records at detecting device mouth place when not covering sample port with reference sample.Reflection efficiency (R when this brightness ratio and calibration standard sheet _{Standard film}) when known, can try to achieve the reflection efficiency R of integrating sphere _SpheroidAnd then this value is used for similar formula, with the reflection efficiency of measuring samples (being the PTFE light box in this case):

Spheroid brightness ratio=1/ (1-R _Spheroid* R _Sample)

At this moment, the measured spheroid brightness ratio resulting ratio of brightness that to be the detecting device brightness of sample when being positioned at sample port record when not having sample.Owing to learnt R from above experiment _Spheroid, therefore can calculate R _SamplePress these reflectivity of wavelength distance computation of 4nm, and write down the mean value of these reflectivity in the 400-700nm wavelength coverage.

The transmissivity test:

(BYK-Gardner USA company, Columbia Maryland) collect the transmissivity measured value with the BYK-Gardner haze meter.Polarization film is contained on glass, makes polaroid directly contact the light source of haze meter, and the light transmission shaft of polarization by reflection film is aimed at the light transmission shaft of test macro polaroid.Then with the data that record transmittance values, with the amount of the polarized light of determining to see through coated optical thin film sample divided by polaroid itself.

The composition that adopts in the example

Unless otherwise indicated, otherwise employed in the example " HFPO-" is meant methyl esters F (CF (CF ₃) CF ₂O) _aCF (CF ₃) C (O) OCH ₃End group F (CF (CF ₃) CF ₂O) _aCF (CF ₃)-, wherein a average out to is about 6.22, and mean molecular weight is 1,211g/mol.This material is according to U.S. Patent No. 3,250, and the disclosed method of 808 (people such as Moore) is prepared (the content disclosed in this patent is incorporated this paper by reference into), and carries out purifying with fractionating process.

HFPO-C (O) N (H) CH ₂CH ₂CH ₂N (H) CH ₃Preparation process according to the FC1/AM1 among the U.S. Patent Application Publication No.2005/0250921A1 is prepared.

The multifunctional free radical polymerization section bar material of high fluorine content

1.HFPO-TMPTA be meant HFPO-C (O) N (H) CH ₂CH ₂CH ₂N (H) CH ₃(FC1/AM1) and the Michael type adduct of trimethylolpropane triacrylate (TMPTA).This adduct is prepared according to the method described in the example 1 of U.S. Patent Application Publication No.2005/0250921A1, that is, it is that mol ratio or the FC1/AM1/AC-1 mol ratio of FC1/AM1 and AC-1 (TMPTA) are about 1: 1 adduction product.The fluorine content of this adduct is 52.02 weight %, and nominal Mn is 1563 gram/moles.

2.C6DIACRY be 2,2,3,3,4,4,5, the trade name of 5-octafluoro-1,6 hexanediol diacrylate (being commonly referred to 8F-HDDA), its molecular weight is 370.2 gram/moles, and contains the fluorine of 40 weight % at least, derive from Exfluor Research company (Round Rock, Texas).

3.CN 4000 derive from Sartomer company (Exton, PA).

4.Br-FKM (E18402) be the amorphous terpolymer of radical polymerization mould assembly of tetrafluoroethene (TFE), vinylidene fluoride (VDF) and hexafluoropropylene (HFP) and halogen-containing cure site monomer (fluorine content is 70 weight %), can derive from Dyneon LLC company (Oakdale, MN).

A1106 is the trade name of 3-TSL 8330, and (Paris France) makes by OsiSpecialties company (GE Silicones) for it.

BYK-411 is a kind of trade name of solution of modified urea, its can derive from BYK Chemie company (Wesel, Germany).

Darocur 4265 be a kind of UV light trigger (the 2-hydroxy-2-methyl by 50%-1-phenyl-1-acetone and 50% 2; 4; the potpourri that 6-trimethylbenzoyl-diphenyl-phosphine oxide constitutes) trade name; its derive from Ciba Specialty Products company (Tarrytown, NewYork).

Darocur 1173 is trade names (it is a kind of UV light trigger) of 2-hydroxy-2-methyl-1-phenyl-1-acetone, can derive from Ciba Specialty Products company (Tarrytown, New York).

Esacure ONE is the trade name of difunctionality alpha-alcohol ketone photoinitiator, its derive from Lamberti Spa company (Gallarate, Italy).

Irgacure 184 is trade names of 1-hydroxyl-cyclohexyl phenyl ketone light trigger, can derive from CIBA Specialty Chemicals company (Tarrytown, New York).

HMDS is the trade name of hexamethyldisilazane, and it can derive from Aldrich company.

KB-1 is 2, the trade name of 2-dimethoxy-2-phenyl acetophenone (benzyl dimethyl ketal) UV light trigger, and it can derive from Sartomer company, and (Exton Pennsylvania), can directly use.

MBX-20 is the trade name of the globule made by the multipolymer of methyl methacrylate and ethylene glycol dimethacrylate, its can derive from Sekisui Chemical company (Osaka, Japan).

Nalco 2327 is trade names of the aqueous dispersion (solids content is 41% in the water, and stable with ammonia) of the nano SiO 2 particle of 20 nanometers, and can derive from Nalco Chem. company (Naperville, Illinois).

Prostab 5198 is 4-hydroxyls-2,2,6, and 6-tetramethyl-1-piperidine NO free radical (is commonly referred to the trade name of 4-hydroxyl-TEMPO), can derives from CIBA Specialty Chemicals company (Tarrytown, New York).

Perenol F-45 is the trade name of acrylate copolymer levelling agent, its can derive from Cognis company (Dusseldorf, Germany).

Photomer 6010 is trade names of aliphatic urethane acrylate oligomer, its can derive from Cognis company (Dusseldorf, Germany).

The 3-methyl allyl acyloxypropyl trimethoxysilane can derive from Alfa Aesar company (WardHill, MA) (goods 30505), and can directly use.

SR295 is the trade name of pentaerythritol tetracrylate, its can derive from Sartomer company (Exton, Pennsylvania).

SR351 is the trade name of trimethylolpropane triacrylate (TMPTA), can derive from Sartomer company (Exton, Pennsylvania).

SR399 is the trade name of five acrylic acid dipentaerythritol ester (molecular weight is 525 gram/moles), and it is to derive from Sartomer company (Exton, multifunctional (methyl) acrylate monomer of nonfluorinated Pennsylvania).

SR444C is the trade name of pentaerythritol triacrylate (PET3A), and it is to derive from Sartomer company (Exton, multifunctional (methyl) acrylate monomer of nonfluorinated Pennsylvania).

SR494 is the trade name of ethoxylation tetramethylol methane tetraacrylate and ethoxylation pentaerythritol triacrylate, its can derive from Sartomer company (Exton, Pennsylvania).

Vazo 52 is 2, the trade name of 2 '-azo two (2, the 4-methyl pentane nitrile), and it is to derive from DuPont company (Wilmington, free radical thermal initiator Delaware).

ZrO ₂Colloidal sol is (in water, solids content is 40.8%) be according to being filed in the method preparation described in the U.S. Patent application No.11/079832 on March 14th, 2005, described patented claim has required to be filed in the right of priority of the U.S. Patent application No.11/078468 on March 11st, 2005.According to the ZrO of photon correlation spectroscopy method (PCS), x-ray diffraction method and the thermogravimetry described in U.S. Patent application No.11/079832 and 11/078468 to gained ₂Colloidal sol is estimated.The ZrO that uses in the example ₂Colloidal sol has the characteristic in the following scope:

Zirconium oxide nano grain formulation 1 through surface modification

The aqueous dispersion (solids content in the water is 40.8%) that in 10 gallons reactor, adds 20.4 pounds of 10nm Zirconium oxide nano grains.Under agitation in reactor, add 12.9 pounds of additional water and 33.3 pounds of 1-methoxyl-2-propyl alcohol.Under agitation in reactor, slowly add 2.5 pounds of 3-methacryloxypropyl trimethoxy silane.Prostab 5198 aqueous solution that under agitation in reactor, add 0.021 pound 5%.Potpourri was stirred 18 hours down at 80 ℃.

Under vacuum state (24-40 holder), reaction mixture is heated, and distill out 1-methoxyl-2-propanol/water azeotropic mixture,, add 70.5 pounds of 1-methoxyl-2-propyl alcohol simultaneously more lentamente to remove all water basically.Add 0.4 pound 30% ammonium hydroxide in reaction mixture, by distilling out 1-methoxyl-2-propyl alcohol reactant being concentrated into solids content then is 59.2%.Surface modification reaction can be created in 1-methoxyl-2-propyl alcohol, contain the zirconia (ZrO of 59.2% (by weight) through surface modification ₂-SM) potpourri.With 0.5 micron filter final mixture is filtered.

Zirconium oxide nano grain formulation 2 through surface modification

With ZrO ₂Colloidal sol (207.4g) bag filter of packing into, and in the 3500g deionized water 6 hours (MWCO of used Sigma diagnostic tube＞1200) of dialysis.Colloidal sol is separated (solids content is 34.03%), and be used for silane treatment.

With the ZrO after the dialysis ₂(80g, solids content is 34.03% to colloidal sol, ZrO ₂Content is 30.8%) in 16 ounces the wide-necked bottle of packing into.Under agitation add 80g water.Under agitation methoxypropanol (160g) and methyl allyl acyloxypropyl trimethoxysilane (8.59g) are added in the beaker of 500ml.Under agitation the methoxy propyl alcohol mixture of gained is added ZrO then ₂In the colloidal sol.With the wide-necked bottle sealing, and be heated to 90 ℃, kept 3 hours 15 minutes.After the heating, potpourri is evaporated to 170g, and obtains white slurries by rotary evaporation.

With deionized water (258g) and concentrated NH ₃In the beaker that (5.7g, 29 weight %) adding is 1 liter.Under gentle agitation, in gains, add above-mentioned concentrated colloidal sol.By vacuum filtration solids separation is obtained wet cake.The solid (82g) that will wet is distributed in the methoxypropanol (200g).By rotary evaporation the gained potpourri is concentrated (97g) then.Add methoxypropanol (204g), and the gained potpourri is concentrated (85.5g) by rotary evaporation.Add methoxypropanol (205g), and the gained potpourri is concentrated by rotary evaporation.It is 27.4% that final product (91.46g) is separated into solids content.Filtrator with 1 μ m filters the gained potpourri.

The nano SiO 2 particle that is used for low-refraction formulation 1 through surface modification

In the reaction flask with 1 liter of 305 gram Nalco, 2327 adding.Under agitation 486 gram 1-methoxyl-2-propyl alcohol are added in the reactor.Under agitation 19.38 gram 3-methyl allyl acyloxypropyl trimethoxysilanes are slowly added in the reactor.Under agitation Prostab 5198 aqueous solution with 0.15 gram 5% add in the reactor.The gained potpourri was stirred 18 hours down at 90 ℃.

Reaction mixture is heated under vacuum state, and distill out 1-methoxyl-2-propanol/water azeotropic mixture (, adding 1-methoxyl-2-propyl alcohol again), so that remove all water basically if any necessity is arranged.Surface modification reaction can be created in 1-methoxyl-2-propyl alcohol, contain the potpourri of 40% (by weight) through the silicon dioxide (Silica 20) of surface modification.

The nano SiO 2 particle that is used for low-refraction formulation 2 through surface modification

(with the stable 20nm colloidal silica sol of ammonium, its solids content is 41%, and (Naperville Ill.) puts into the glass jar of 200ml to derive from Nalco company with 15g 2327.1-methoxyl-2-propyl alcohol (Aldrich) solution of preparation 10g in flask independently, wherein contain 0.47g methacrylic acid 3-(trimethoxysilyl) propyl ester (Gelest company, Tullytown, PA).Methacrylic acid 3-(trimethoxysilyl) propyl ester solution with gained under the condition that stirs silicon dioxide gel adds in the glass jar.Use extra 5ml solvent cleaning flask then, and in the solution under the adding stirring condition.After adding fully, cover wide-necked bottle, and be put in 90 ℃ the baking oven about 20 hours.In soft air-flow, carry out drying by at room temperature colloidal sol being exposed to the open air then.Collect the white powder solid of gained, and be distributed in 50ml tetrahydrofuran (THF) solvent.2.05g HMDS (excessive) is slowly added in the THF silicon dioxide gel, cover wide-necked bottle then, and placed the ultrasound wave bath about 10 hours.Remove organic solvent with rotary evaporator subsequently, and with residual white solid 100 ℃ of following heated overnight, further to react and to remove volatile matter.

Fluorinated acrylate polymer intermediate 1

Prepare hyper branched copolymer according to following method.With 17.01 gram C6DIACRY, 8.51 gram CN4000,2.84 gram SR399,1.70 gram HFPO-TMPTA, 241.02 gram ethyl acetate, 25.52 gram MEKs be dissolved in 3.40 in MEK gram Vazo 52 in advance and add in the reaction vessel.Preferably, at first HFPO-TMPTA is added among the CN4000, and then add residue reagent.

Under nitrogen environment, the content in the reaction vessel is outgased, in 80 ℃ air-tight bottle, heated about 1 to 1.5 hour then.Answer SC, to avoid the excessive and reaction content generation gelation of molecular weight.Concentration of reactants in the reaction mixture, temperature of reaction and reaction time are all selected,, when using different reactants, needed to adjust above-mentioned one or more parameters to guarantee to reach above-mentioned effect.

According to aforementioned method of testing, analyze resulting fluorinated acrylate polymer midbody solution with gel phase chromatography/size exclusion chromatography (SEC).Fig. 4 shows resulting chromatogram.

The fluorinated acrylic ester monomer

The monomer mixture solution that contains the fluorinated acrylic ester monomer by following method preparation.39.79 gram C6DIACRY, 13.14 gram CN4000,22.52 gram SR399, the silica dispersion through surface modification (this silica dispersion is being removed the solid that contains 35-55% behind the azeotropic mixture usually) and the 4.50 gram Darocur 1173 (light trigger) that are enough to produce 45.05 gram solids are dissolved in respectively in the MEK individually, with solution or the dispersion that forms 10 weight %.Then, first three is planted solution mix, make and fully mixed before monomer is in adding nano SiO 2 particle to, add Darocur 1173 at last again according to specified order.

Low-refraction formulation 1

1250 gram fluorate acrylic acid ester monomer compositions are placed container, and to add 300 gram solid concentrations carefully be 10% fluorinated acrylate polymer midbody composite, and in the interpolation process, will fully stir, to avoid silica aggregate.Behind this low-refraction formulation of preparation, in the week it is coated with.

Low-refraction formulation 2

Br-FKM(E 18402)	Nano SiO 2 particle through surface modification	SR 399	A1106	KB-1	The weight % of fluorine in the coating
						50	15	30	5	1.5	34.5

Low-refraction formulation 3

Br-FKM(E 18402)	Nano SiO 2 particle through surface modification	SR 399	A1106	Darocur 1173
					55	10	30	5	2.0

High index of refraction formulation 1

By the following material of weighing and place wide-necked bottle to prepare high refractive index coating solution: 6.94gSR494 (ethoxylation tetramethylol methane tetraacrylate), 5.60g 10% Darocur 1173 solution and 23.86g IPA at IPA.Sample is carried out jolting, till solid all dissolves.Then, in same wide-necked bottle, add 33.60g and contain 61% (ZrO ₂-SM) and the zirconia formulation 1 through surface modification of 39%2-methoxyl-1-propyl alcohol.Solution is stirred, till evenly.The solution of gained contains 40% the solid in IPA and 2-methoxyl-1-propyl alcohol.

High index of refraction formulation 2

Be dissolved in by solid and prepare high refractive index coating solution in the ethyl acetate following umber.Solution is stirred, till evenly.

Zirconia formulation 2 through surface modification	SR295	Darocur 4265 ％
			60	40	2

High index of refraction formulation 3

By the following material of weighing and place wide-necked bottle to prepare high refractive index coating solution: 2.98gSR494 (ethoxylation tetramethylol methane tetraacrylate), 0.24g Darocur 1173 and 11.79gIPA.Sample is carried out jolting, till solid all dissolves.Then, will contain 58.6% (ZrO ₂-SM) 15.0g with 41.4%2-methoxyl-1-propyl alcohol adds in the same wide-necked bottle through the zirconia formulation 1 of surface modification.With solution stirring till evenly.

Be positioned at high refractive index coating or antireflecting coating on the reflection multilayer polarization film

With the polarization by reflection substrate (except thickness is 94 microns, its with from 3M company with trade name " Vikuiti ^TMDBEF E " commercially available product is identical) cut into 7 inches * 10 inches size, and remove the original frisket of a slice (being printed on the 3M logo), to expose the surface that is used to apply.The two ends of DBEF film are pasted on the glass plate, and purge, to remove the chip of sample with pressurized air.The excellent applicator (BYK-Gardner:AR4112) that will wind the line places on the film.(about 1mL) high refractive index coating solution is expelled to the position in the coiling rod dead ahead on the DBEF film surface through syringe-type filtrator (PALL:0.45m GHPPN4560T) on a small quantity.Immediately solution evenly is coated with along the film length direction with the excellent applicator of coiling.After most of solvent all evaporates, take off coated film from glass plate, and be attached in the aluminium dish.With sample retention the band guard shield the aluminium dish in, till being coated with all other solution.Sample is put into baking oven, and drying is 2 minutes under 100 ℃.(Fusion UV Systems company: MC6RQN) make the coating polymerization reaction take place of oven dry with the speed of 30 feet per minute clocks (fpm), polymerizing condition is to use H lamp (Fusion UV:525632H) irradiation sample once with uviol lamp under nitrogen environment.The measurement result of the UV output power that coating sample received (EIT company: UV Power Puck, S/N2001) as follows:

UV-A	UV-B	UV-C	UV-V	Unit
					1.693	1.794	0.200	1.201	W/cm 2
0.525	0.492	0.059	0.370	J/cm 2

Prepare other sample according to above-mentioned same way as, reverse side (back side) the high index of refraction composition of the same race that also applied thickness is identical that different is at the DBEF film (that is, remove second original frisket then apply).This can obtain the DBEF film that the two sides all scribbles high refractive index layer.

The average thickness of high index of refraction hard conating is 4 microns.The estimation refractive index (estimating RI) that obtains through estimation is 1.62.The refractive index that percent by volume and refractive index calculated that this estimated value is based on by each component draws.The formula that is used for calculating the cured film refractive index is as follows:

Coating RI=∑ [RI * volume fraction]

The refractive index of calculating according to the percent by volume and the refractive index of each component is 1.62.

Example for adopting antireflecting coating at first should apply and solidify high refractive index coating in the manner described above.Then, with MEK specified low refractive index coating (promptly 1 or 2) being diluted to solids content is 3.5%, to use it for coating.The two ends that scribble the DBEF of high refractive index coating are pasted on the glass plate, and sweep, to remove the chip of sample with the pressurized air spray.The excellent applicator (BYK-Gardner:AR4104) that will wind the line places on the film.A small amount of (about 0.5mL) low refractive index coating solution is inhaled the position that moves to the excellent dead ahead of the lip-deep coiling of HIHC.Immediately solution evenly is coated with along the film length direction with the excellent applicator of coiling.After solvent evaporation, take off coating from glass plate, and be attached in the aluminium dish.Coating protection is existed in the aluminium dish of band guard shield, till being coated with all other solution.Coating is put into baking oven, and drying is 1 minute under 100 ℃.(Fusion UV Systems company: MC6RQN) make the coating polymerization reaction take place of oven dry with the speed of 30 feet per minute clocks, polymerizing condition is to use H lamp (Fusion UV:525632H) irradiation twice in sample (UV output power data as above provide) with uviol lamp under nitrogen environment.The average thickness of low-index layer is 95 microns.

According to above-mentioned same way as, use both sides that the two-sided AR sample of DBEF specimen preparation of high refractive index layer is all arranged.On this two-sided DBEF sample, apply low-refraction formulation 1 according to above-mentioned same way as.This can be created in the DBEF film that both sides all scribble anti-reflection film, and described anti-reflection film has high refractive index layer and the low-index layer that links to each other with this high refractive index layer.

Be positioned at the antireflecting coating that has on the reflection multilayer polarization film (gain diffuser DBEF) that contains the pearl layer

Provide the polarization by reflection substrate of removing original frisket layer (except thickness is 94 microns, its with can be from 3M company with trade name " Vikuiti ^TMDBEF E " commercially available product is identical).

Use slit-type mold injects pump that the above-mentioned pearl layer potpourri that contain is applied in the substrate.The coating width is 4 inches, and advances the substrate tablet with the speed of 15fpm.Come the weight of control coating by the amount (representing) of the material of syringe pump discharge with flow velocity by control.Determine the weight of coating by direct measurement.To have the weight of the sample that contains the pearl layer and the weight of the same a collection of substrate of size equally compares.The weight of coating is 19.1g/m ²

The two ends that to contain the DBEF film of globule paste on the glass plate, and make the one side that contains globule towards glass plate, purge with pressurized air simultaneously, to remove the chip of sample.The excellent applicator (BYK-Gardner:AR4112) that will wind the line places on the film.(about 1mL) high refractive index coating solution is expelled to the position in the coiling rod dead ahead on the DBEF film surface through syringe-type filtrator (PALL:0.45 μ m GHP PN4560T) on a small quantity.Immediately solution evenly is coated with along the film length direction with the excellent applicator of coiling.After most of solvent all evaporates, take off coated film from glass plate, and be attached in the aluminium dish.With sample retention the band guard shield the aluminium dish in, till being coated with all other solution.Sample is put into baking oven, and drying is 2 minutes under 100 ℃.(Fusion UV Systems company: MC6RQN) make the coating polymerization reaction take place of oven dry with the speed of 30 feet per minute clocks (fpm), polymerizing condition is to use H lamp (Fusion UV:525632H) irradiation sample once with uviol lamp under nitrogen environment.The measurement result of the UV output power that coating sample received (EIT company: UVPower Puck, S/N2001) as follows:

UV-A	UV-B	UV-C	UV-V	Unit
					1.693	1.794	0.200	1.201	W/cm 2
0.525	0.492	0.059	0.370	J/cm 2

The average thickness of high index of refraction hard conating is 4 microns.The estimation refractive index (estimating RI) that obtains through estimation is 1.62.

With MEK low refractive index coating formulation 3 being diluted to solids content is 5.0%, to use it for coating.The two ends that scribble the DBEF of high refractive index layer are pasted on the glass plate, and make high index of refraction surface exposed, purge with pressurized air simultaneously, to remove the chip of sample.The excellent applicator (BYK-Gardner:AR4104) that will wind the line places on the film.(about 0.5mL) low refractive index coating solution is inhaled the position in the coiling rod dead ahead that moves to the HIHC surface on a small quantity.Immediately solution evenly is coated with along the film length direction with the excellent applicator of coiling.After solvent evaporation, take off coating from glass plate, and be attached in the aluminium dish.Coating protection is existed in the aluminium dish of band guard shield, till being coated with all other solution.Coating is put into baking oven, and drying is 1 minute under 100 ℃.(Fusion UV Systems company: MC6RQN) make the coating polymerization reaction take place of oven dry with the speed of 30 feet per minute clocks, polymerizing condition is to use H lamp (Fusion UV:525632H) irradiation twice in sample (data of UV output power as above provide) with uviol lamp under nitrogen environment.The average thickness of low-index layer is 95 microns.

Each AR coating is carried out gain test and the steel wool durability test that uses the 400g counterweight, and test result is as follows.

The DBEF that has high refractive index coating 2					0 road cut, 0 road cut
							The gain diffuser DBEF that has high refractive index coating 3	1.852	1.854	1.854	1.853	The local cut in 1 road
The gain diffuser DBEF that has AR coating 3	1.888	1.884	1.888	1.887	The local cut in 2 roads
							Contrast gain diffuser DBEF	1.855	1.857	1.861	1.858	＞50 road cuts,＞50 road cuts
Contrast DBEF	1.709	1.709	1.710	1.709	＞50 road cuts,＞50 road cuts

Estimate that thickness is 132 microns " Vikuiti ^TMDBEF E " can produce essentially identical result.

After being arranged on AR coating 1,2 or 3 on the brightness enhancement film, estimate that it can produce essentially identical durability test result.

The polarization by reflection film that scribbles the anti-reflection film that contains low-refraction formulation 1 is carried out the transmissivity test.The result shows that transmissivity increases to some extent, and this result is as follows:

Claims (39)

1. optical thin film, it comprises:

Polarization by reflection optics film, this polarization by reflection optics film comprises anti-reflection film, described anti-reflection film comprises high refractive index layer that is connected on the described polarization by reflection optics film and the low-refraction superficial layer that is connected on the described high refractive index layer, and the gain added value of wherein said polarization by reflection film is at least 0.01.

2. optical thin film according to claim 1, wherein according to the steel wool durability test under the condition of using the 400g counterweight, described low-refraction superficial layer is being less than 10 roads through 10 shown cuts in scraping back.

3. optical thin film according to claim 1, wherein said low-refraction superficial layer comprises the reaction product of polymerisable compound, and described polymerisable compound comprises:

At least a free radical polymerization section bar material of fluoridizing, and

Inorganic nanoparticles through surface modification.

4. optical thin film according to claim 3, the wherein said fluorine content of fluoridizing free radical polymerization section bar material is at least 25 weight %.

5. optical thin film according to claim 4, wherein said to fluoridize free radical polymerization section bar material be polyfunctional.

6. optical thin film according to claim 5, the wherein said free radical polymerization section bar material package of fluoridizing contains radical polymerization mould assembly fluoropolymer.

7. optical thin film according to claim 3, wherein said low-index layer comprises the crosslinking chemical of at least a nonfluorinated, and the crosslinking chemical of described nonfluorinated has at least three radical polymerization mould assembly groups.

8. optical thin film according to claim 3, wherein said low-refraction superficial layer comprises the reaction product of following material:

A) radical polymerization mould assembly fluorinated polymer intermediate, it comprises the reaction product of following material:

I) at least a fluorine content is the multifunctional free radical polymerization section bar material of at least 25 weight %, and

Ii) optional at least a fluorine content is 0 to the multifunctional free radical polymerization section bar material that is lower than between the 25 weight %,

Wherein, the total amount of described multifunctional material is at least about 25 weight % of the solid weight percentage composition of described polymerizable organic composite; And

B) at least a free radical polymerization section bar material of fluoridizing.

9. optical thin film according to claim 1, the thickness of wherein said high refractive index layer is at least 2 microns.

10. optical thin film according to claim 3, wherein said low-refraction superficial layer comprises the reaction product of polymerisable compound, and described polymerisable compound comprises:

At least a radical polymerization mould assembly fluoropolymer,

At least a amino-organosilanes ester coupling agent or its condensation product, and

At least a nonfluorinated crosslinking chemical that has at least three radical polymerization mould assembly groups.

11. optical thin film according to claim 1, wherein said high refractive index layer comprise the inorganic particle through surface modification that is dispersed in the crosslinked organic substrate, the refractive index of described inorganic particle through surface modification is at least 1.60.

12. optical thin film according to claim 1, wherein said polarization by reflection optics film is multilayer film.

13. optical thin film according to claim 1, wherein said polarization by reflection optics film comprises two first type surfaces, and described anti-reflection film is set on the first type surface.

14. optical thin film according to claim 1, wherein said polarization by reflection optics film comprises two first type surfaces, and described anti-reflection film is set on these two first type surfaces.

15. optical thin film according to claim 14, wherein said gain added value is at least 0.02.

16. optical thin film according to claim 1, it also comprises the microstructured optical films of contiguous described polarization by reflection optics film.

17. optical thin film according to claim 16, the optical thin film of wherein said micro-structural comprises the repeat patterns of being made up of linear prism.

18. optical thin film according to claim 16, wherein said prism is set in the substrate.

19. optical thin film according to claim 18, wherein said substrate also comprises the anti-reflection film layer, this anti-reflection film layer be positioned at described substrate with described prismatic facing surfaces on.

20. optical thin film according to claim 1, wherein said anti-reflection film are the multi-layer anti-reflection films, described multi-layer anti-reflection film comprises two or more layers that replace that are made of high refractive index layer and low-index layer.

21. an optical thin film, it comprises:

The blast optical thin film, this blast blooming has substrate, described substrate has the repeat patterns of being made up of linear prism in its surface, and described substrate has the anti-reflection film superficial layer with above-mentioned surperficial facing surfaces, according to the steel wool durability test under the condition of using the 400g counterweight, this anti-reflection film superficial layer is being less than 10 roads through 10 shown cuts in scraping back.

22. an optical thin film, it comprises:

Polarization by reflection optics film, described polarization by reflection optics film has the high index of refraction hard conating that is connected on the described polarization by reflection optics film, wherein according to the steel wool durability test under the condition of using the 400g counterweight, described high index of refraction superficial layer is being less than 10 roads through 10 shown cuts in scraping back.

23. optical thin film according to claim 22, wherein said high refractive index layer comprise the inorganic particle through surface modification that is dispersed in the crosslinked organic substrate, the refractive index of described inorganic particle through surface modification is at least 1.60.

24. optical thin film according to claim 22, wherein said inorganic particle through surface modification comprise the zirconia of 5 volume % to about 40 volume %.

Form 25. optical thin film according to claim 22, wherein said high index of refraction hard conating are the reaction product by polymerisable compound, described polymerisable compound comprises the nonfluorinated crosslinking chemical that has at least three (methyl) acrylate groups.

26. optical thin film according to claim 22, wherein said polarization by reflection optics film is multilayer film.

27. optical thin film according to claim 22, wherein said polarization by reflection optics film comprises two first type surfaces, and described high index of refraction hard conating is set on these two first type surfaces of described polarization by reflection optics film.

28. optical thin film according to claim 22, it also comprises the microstructured optical films of contiguous described polarization by reflection optics film.

29. optical thin film according to claim 28, wherein said microstructured optical films comprises the repeat patterns of being made up of linear prism.

30. optical thin film according to claim 28, wherein said prism is set in the substrate.

31. optical thin film according to claim 30, wherein said substrate also has the high index of refraction hard conating, this high index of refraction hard conating be positioned at described substrate with described prismatic facing surfaces on.

32. according to the described optical thin film of claim 22-31, wherein said polarization by reflection optics film provides substantially the same gain with the described polarization by reflection film with described high index of refraction hard conating.

33. according to claim 1 or 21 described optical thin films, wherein said anti-reflection film increases transmissivity.

34. according to claim 1 or 21 described optical thin films, wherein said high refractive index layer and described low-refraction superficial layer comprise the organic material of radiation curing, this organic material contains the inorganic nanoparticles through surface modification.

35. an optical thin film, it comprises polarization by reflection optics film, and described polarization by reflection optics film comprises two first type surfaces, wherein on described first first type surface anti-reflection film is set, and on described second first type surface gain diffuser is set.

36. optical thin film according to claim 35, the gain added value of wherein said polarization by reflection optics film is at least 0.01.

37. optical thin film according to claim 35, wherein said gain diffuser comprises the globule that is positioned at binder matrix.

38. an optical thin film, it comprises polarization by reflection optics film, and described polarization by reflection optics film comprises two first type surfaces, wherein on described first first type surface high index of refraction hard conating is set, and on described second first type surface gain diffuser is set.

39. according to the described optical thin film of claim 38, wherein according to the steel wool durability test under the condition of using the 400g counterweight, described high refractive index layer is being less than 10 roads through 10 shown cuts in scraping back.

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