CN101151555A - Internal components of optical device comprising hardcoat - Google Patents

Abstract

A hard coating composition for use as a stain repellent single layer on an optical display. The coating composition adds a monomer of a mono or multi(methyl)acrylate bearing at least one monovalent hexafluoropolypropylene oxide derivative and a free radically reactive compatibilizer consisting of either a fluoroalkyl-group containing acrylate compatibilizer or a fluoroalkylene-group containing acrylate compatibilizer to a conventional hydrocarbon-based hard coat formulation. The resultant coating is substantially smooth and forms a durable surface layer that has low surface energy that is stain and ink repellent.

Description

Optical devices inner member with hard conating

Background technology

U.S. Patent No. 6,132,861 (people such as Kang), 6,238,798 B1 (people such as Kang), 6,245,833 B1 (people such as Kang), 6,299,799 (people such as Craig); The open No.WO 99/57185 of PCT application people such as () Huang; And people's such as Liu U.S. Patent No. 6,660,388,6,660,389 and 6,841,190 have described the hard coating composition that contains the blend that is made of colloidal inorganic oxide particle, curable adhesive precursor and some fluorochemicals.

Brief Description Of Drawings

Fig. 1 is the synoptic diagram of the exemplary assembling method of optical imaging device.

Fig. 2 is the cut-open view with exemplary optical devices inner member of surperficial hard conating.

Fig. 3 is the cut-open view of exemplary optical devices inner member (it comprises the diaphragm goods with surperficial hard conating).

Fig. 4 has the exemplary article that a plurality of and hard conating are protected membrane-bound inner member.

Fig. 5 is the cut-open view of exemplary optics imaging device.

Summary of the invention

In one embodiment, the invention describes goods with optical devices inner member.Described inner member has surperficial hard conating, this surface hard conating comprises the reaction product of polymerisable compound, wherein said polymerisable compound contains at least 0.2 weight % at least aly has the fluorochemicals composition of at least one polymerizable moiety and one or more crosslinking chemicals that can randomly fluoridize of at least 50 weight %.Usually, crosslinking chemical is a nonfluorinated.Have the embodiment of the crosslinking chemical of fluoridizing part for employing, hard coating composition can contain the crosslinking chemical up to 100 weight %.

In another embodiment, the invention describes the optical devices inner member, wherein said inner member has surperficial hard conating, and the static contact angle of this superficial layer and water is at least 70 degree.

In one aspect; described goods are the sheet material of the element of optical devices; this sheet material comprises the diaphragm of the surperficial hard conating with curing and the element of a plurality of optical devices; wherein said element has at least one distinguishable border, and this element combines with the surperficial hard conating of described curing.

In another aspect, described goods are the wavelength selectivity wave filter with absorption layer, and wherein said absorption layer contains the reaction product of following material: one or more of at least 50 weight % have the crosslinking chemical of two or more polymerizable moieties, at least a fluorochemicals composition or inorganic particle and the absorbability composition with at least one polymerizable moiety of at least 0.5 weight %.

In another aspect, described goods are the inner member (as imageing sensor or silicon wafer) with surperficial hard conating, and wherein said surperficial hard conating contains polymeric binder precursor, optional inorganic particle and optional fluorochemicals composition.

The method of protection optical devices inner members has been described in other embodiments.This method comprises by various technology described surperficial hard conating is arranged on the optical devices inner member.

The method of assembling optical devices has been described in another embodiment.This method comprises assembles the optical devices inner member, and wherein at least one inner member has one or more layers described surperficial hard conating.

Detailed description of the preferred embodiments

Known have multiple optical devices.These optical devices adopt multiple element to reach to utilize light to carry out sensing, imaging, projection and illumination purposes.

In the manufacture process of optical devices, a plurality of independent elements are assembled together, and the great majority of these elements all are inner members, that is, in the routine of optical devices was used, these elements were not exposed in the external environment condition.The optical devices inner member is easy to be damaged and is easy to be subjected to chips affect in the assembling process of optical devices.Fig. 1 has described an exemplary assemble method.This method comprises: usually by welding method with imageing sensor 550 attached on (for example, flexible) printed circuit board (PCB) 590.Make infrared (IR) wave filter 540 and imageing sensor 550 (for example, with bonding mode) combination then.Make pre-assembled one or more lens 520 and IR wave filter (for example, with bonding mode) combination in cylindrical shell 511 then.A plurality of suppliers (for example, Asia Opical, Flextronic, Lite-on Tech, SEMCO, Hicel, Samsung Techwin, Pixart, IC Media, West Electric, Sanshin, Panasonic and Sharp) produce the pre-assembling shooting module with aperture, lens, wave filter and cover glass.As the part of assembling process, can be with pre-assembled shooting module attached on the imageing sensor.Then, mobile-phone manufacturers (as Nokia, Motorola, Samsung, LG, SonyEriccson, Siemens, Panasonic and Sanyo) are assembled into final camera with this shooting module.

Each inner member of optical devices (for example, camera-type optical devices) has the defective threshold that depends on element function and Design of device situation.For example, the factor such as the resolution of the distance of element and focal plane and imager can be included in the defective threshold of digital camera.In assembling process, if any one independent element contains fragment or is damaged, then this defective can make whole camera defective.As a rule, up to whole device assembled finish and tested after just can detect defective element.In assembling process, following situation is not rare: the quantity of defective device arrives hundreds of dollar or more up to 10-20% thereby make the loss of manufacturer in each unit all can reach tens dollars.It is unpractiaca contaminated or impaired element being cleaned or reprocesses regularly, or spends high.

Therefore, advantageously, reducing the formation of defective parts before the assembling process or during the assembling process and advantageously making cleaning, reparation and the reprocessing of optical element become easy.As this type of way to solve the problem, the invention describes a kind of like this method: protect the optical devices inner member on inner member by surperficial hard conating is set.In addition, the invention describes inner member with surperficial hard conating and the method for assembling the optical devices inner member.Described hard conating is tough and tensile wearing layer, and its protection inner member is avoided the scraping and the wearing and tearing of pollutant (for example, solvent).As shown in Figure 2, inner member (for example, imageing sensor) 250 comprises the hard coating composition 210 on the surface (being preferably all surfaces that is arranged on inner member) that is arranged on inner member.It is outstanding that the electric contact 205 of imageing sensor (for example, solder bumps) passes surperficial hard conating, makes that imageing sensor can be electrically connected with printed circuit board (PCB) formation in assembling process.Hard conating comprises polymerisable binder precursor, and this binder precursor can randomly be mixed with inorganic particle.Hard coating composition is preferably hard coating easy to clean.

The surface hard conating is permanance preferably, this means that its surface surface distress is not taking place or optical property significantly (is not for example lost through showing as basically after the endurancing of carrying out according to the described method of embodiment part, kept 97% initial transmittance), wherein, in described endurancing, employing has the steel wool of 200g counterweight, carry out at least 50 times, be preferably at least 100, at least 500 times wiping more preferably sweeps.In addition, preferably, even through after the described endurancing, superficial layer and goods still show as and have low surface energy properties (for example, contact angle is higher, ink repellent and be pearl).

When the needs hard conating also was easy to clean, preferably, surperficial hard conating contains one or more fluoridized composition.Fluoridize composition generally include have one or more (entirely) fluoridize the part monomer, oligomer and polymkeric substance.Preferably, fluoridize composition also have one or more can with the part of binder precursor component generation copolymerization in the hard coating.In this article, but the hard coating of fluoridizing composition that will have a this copolymerization is called " hard coating easy to clean ".

Can adopt several different methods such as contact angle and ink repellent (as measuring) to characterize the surface energy of surperficial hard conating easy to clean according to the described test method of embodiment part.Preferably, the static contact angle of described superficial layer and water is at least 70 °.More preferably, the static contact angle of described superficial layer and water is at least 80 °, even more preferably, and the static contact angle of described superficial layer and water is at least 90 ° (for example, at least 95 °, be at least 100 °).

Can for other character of selecting for use or except above-mentioned character, the advancing contact angle of described superficial layer and hexadecane be at least 50 °, more preferably at least 60 °.Surface energy is low to signify that the surface has pollution resistance, and the surface is easy to clean.Another low indication is that the printing ink of the commercially available permanent marking pen that gets (commodity are called " no 30001 for Sanford Sharpie, Fine Pointpermanent marker ") is preferably pearl as surface energy.Furthermore, superficial layer as herein described and goods show " ink repellent ", this is meant the paper handkerchief wiping that can be called " SURPASS FACIAL TISSUE " available from the commodity of the Kimberly Clark company that is positioned at State of Georgia, US Roswell city by adopting, and can easily wipe above-mentioned printing ink.

The contact angle of considering described surperficial hard conating easy to clean and water is high like this, and then this surperficial hard conating easy to clean can also be protected the optical devices inner member to the barrier functionality of aqueous vapor by providing.

In some embodiments, hard conating is set to single one deck, as shown in Figure 2.In other embodiments, hard conating can have sandwich construction.For example, the superficial layer that contains hard coating easy to clean can prepare by the following method: to (for example, nonfluorinated) hard conating applies successively, dry and curing, then to the superficial layer of fluoridizing apply, dry and solidify, as described in the U.S. Patent application No.10/841159 that submits on May 7th, 2004; Or to hard coating easy to clean apply successively, dry and solidify, wherein, but the composition of fluoridizing of copolymerization directly is formulated in the hard coating, as described in the U.S. Patent application No.11/121456 that submits on May 4th, 2005.Be not intended to be limited by theory, but under above any situation, fluoridize composition and all be present on the coating surface, so that character easy to clean to be provided.By inference: can apply that this is two-layer by the mode on the hard conating of being set at superficial layer simultaneously, make this two-layer all dry and solidify the structure easy to clean that forms multilayer then.

The gross thickness of hard conating is generally about 1 micron to about 100 microns, about 2 microns to about 50 microns or about 3 microns to about 30 microns.When fluorinated surface layer easy to clean being applied on (for example, nonfluorinated) hard conating, the thickness of easy cleaning layer is at least about 10 nanometers, is preferably at least about 25 nanometers.Usually, the thickness of the layer of curing is less than about 200 nanometers, is preferably less than about 100 nanometers, more preferably less than about 75 nanometers.Therefore, permanance is mainly provided by following (for example, nonfluorinated) hard conating.

Can adopt several different methods that hard conating is arranged on the inner member.

In one aspect, form hard conating by the following method: polymerisable liquid (for example, ceramic condensate) hard coating composition is coated on the inner member, and this polymerisable hard coating composition is solidified, thereby form cured film.Can use the coating method of multiple routine that coating composition is applied on the inner member.Suitable coating method comprises (for example): spin coating, blade coating, die head coating, wire rod coating (wire coating), flow coat (flood coating), tamponing, spraying, roller coat, dip-coating, brushing, foaming coating, printing coating etc.After the coating, adopt methods such as heating, vacuum to flash away solvent (if containing).Usually use the forced draft baking oven to make the coating drying.Adopt the energy (for example, heat energy, visible light, ultraviolet light or electron beam irradiation) of appropriate format to make dried coating partly solidified at least, be generally full solidification.Usually adopt the radiotechnology of using ultraviolet light under environmental baseline, this is because the cost of this curing technology is low relatively and curing rate is fast.Preferred energy source comprises the ultraviolet light polymerization device, and the UV that this device provided " C " dosage is about 5-60 millijoule/square centimeter (mJ/cm ²).Preferably, under the environment of oxygen content low (for example, less than about 100 parts/1,000,000 parts), be cured.Nitrogen gas is preferred environmental gas.

In other embodiments, suitable method that can be by comprising (for example) heat lamination, thermoforming, bonding agent combination or be attached on the inner member by the diaphragm that ultra-sonic welded or radio frequency combination technology will have a hard conating of curing.Bonding agent can be applied on the inner member or in advance and be applied on the diaphragm.Diaphragm can comprise the curing hard conating on being arranged in the removable isolation liner simply, and perhaps diaphragm can also have the extra play such as light transmission substrate and/or adhesive phase.For example, Fig. 3 shows and the diaphragm goods 380 of inner member (for example, imageing sensor) 350 combinations.The diaphragm goods have through crosslinked surperficial hard conating 310 and are arranged at transparent substrates 370 between surperficial hard conating and the inner member.Adhesive phase 360 is attached on the inner member 350 diaphragm.The lower surface that can make adhesive phase 360 is micro-structural randomly, thereby makes air is overflowed.It is outstanding that the electric contact 205 of imageing sensor (for example, solder bumps) passes diaphragm, makes that imageing sensor can be electrically connected with printed circuit board (PCB) formation in assembling process.Perhaps, electric contact may reside in back to (for example, top) surface on.Can adopt mask technique or etching technique to form the electric contact that exposes.

A particularly advantageous purposes of protective coating is that the commitment in supply chain just is applied to it in substrate, and in this case, material is to be applied on the master slice of optical element or on the master mold of pre-converted.For example, protective coating can be applied directly to large polymer " master mold sheet material " and go up (or, the rete that has this coating on it is laminated on this sheet material), this master mold sheet material is enough big, makes a plurality of single elements to be transformed by it.Subsequently, can the master mold sheet material be changed into single parts by the several different methods such as delineation, cutting and machining.Second embodiment relates to wafer-level processes.At first columniform ingot bar is made diameter and made the sensor (for example, silicon photoelectric diode) of particular types for the LED reverse mounting type of about 3-10 inch.These wafers finally are cut the small pieces that (a kind of technology that is called as excision forming) becomes the discrete component size, and these small pieces can also be further packaged and be assembled in the optical element.Apply protective coating (precut moulding) in the mode of wafer scale and have such advantage: the starting stage in supply chain just can provide defencive function to single small pieces, can reduce the damage of parts thus during whole supply chain.Can make coating and other optical element (for example, wave filter) combination, thereby can also have other optical function.

The optical quality of surperficial hard conating of the present invention and diaphragm (for example, also can randomly have substrate and the bonding agent) inner member that can not detract.

The optional substrate and the bonding agent of superficial layer and diaphragm goods are light transmissions, and this is meant that light can see through substrate.The substrate of diaphragm goods can not change or damage the expectation function of the inner member that is applied with these diaphragm goods on it basically.Haze value at the bottom of superficial layer and optional substrate and the adhesive group is preferably less than 5%, more preferably less than 2% even more preferably less than 1% and most preferably be less than 0.5%.In addition, transmittance is preferably more than about 90%.

Can with various permanent be arranged on the opposite side (that is, the phase dorsal part of hard conating) of substrate with removable adhesive composition, thereby can easily these goods be installed on the inner member.The suitable bonding composition comprises: (for example, hydrogenation) segmented copolymer, and for example, the segmented copolymer of commodity " Kraton G-1657 " by name can be available from the Kraton Polymers company that is positioned at Texas, USA Westhollow city; And other (for example similar) thermoplastic elastomer.Other exemplary bonding agent comprises: acrylic compounds, polyurethanes, silicone based and epoxy adhesive.Preferred adhesive has sufficient optical property and light stability, thereby makes the bonding agent can be not in time or weathering and flavescence, so that reduce the viewing quality of optical display.Can adopt various known coating technologies (for example, shifting coating process, knife coating, spin-coating method, mould Tu Fa etc.) to come applying adhesive.U.S. Patent Application Publication No.2003/0012936 has described exemplary bonding agent.Several such bonding agents can be available from the 3M company that is positioned at the Saint Paul City, State of Minnesota, US, commodity by name 8141,8142 and 8161.

In one embodiment, the diaphragm that has (for example, easy to clean) hard conating comprises the UV curing adhesive.The UV curing adhesive is contacted with inner member, and carry out radiation, thereby make UV curing adhesive and inner member coupling mutually with UV.Can be light transmission in the isolation liner, be cured thereby make the UV bonding agent to see through in the isolation liner.Known have a multiple UV adhesive composition, for example, and UV curable coating (can derive from Mitsubishi Rayon company, commodity are called " UR6530 ").

In other embodiments, by the following method the diaphragm thermocouple is linked on the optical devices inner member: the mold with base plate and top board is provided; Introduce diaphragm, make described bonding agent closely be coupled on the inner member; Top board and base plate are heated; Close mold, thereby adhesive phase is adhered on the optical substrate; Open mold; Optical devices are taken out from mold.

Can be with diaphragm (for example by (for example); laser or punch die) (for example cut into small pieces that size is fit to discrete component; 5mm * 5mm) also uses automatic chip mounting disposal system (as is known in the art) to make diaphragm be placed and is attached on the single inner member, thereby diaphragm is applied on the single inner member.For the ease of handling; can be (for example; easy to clean) on protective film is arranged in the isolation liner; wherein; with surperficial hard conating (for example; if substrate and bonding agent are arranged, can make surperficial hard conating with substrate and bonding agent) cut into the suitable part of size, so that place it on the inner member.(that is, in the uncut isolation liner) played the effect of the carrying base-material of protective film small pieces in the isolation liner.

Perhaps, can diaphragm be arranged on a plurality of (that is, more than one) inner member simultaneously by the method such as spraying or dip-coating.

In one embodiment, can diaphragm be applied on the optical devices inner member by shifting process (in-mold transferprocess) in the mold.This technology can make molded inner member and the process that diaphragm is applied on the inner member is carried out simultaneously.Described technology can comprise: diaphragm is incorporated in the internal cavities of mould; Close mould; Inject a certain amount of molten polymer material, make it fill up described internal cavities basically; Make the polymeric material cooling of molten state; Taking-up has the inner member of the diaphragm material that is applied by mould; And separation layer removed on the element internally.For example, can be before injection be used for forming the molten polymer of a plurality of lens simultaneously, the sheet material of diaphragm is inserted in the lens injection molding apparatus.After the injection mo(u)lding, two or more single lens 420 can be connected with each other by hard conating diaphragm 410, as shown in Figure 4.Can make lens separately by (for example) cut or die cut tripping protection film subsequently.

Above-mentioned aspect is to help making and handling by the sheet material of a plurality of (for example, inside) element that optical devices are provided.Described element has at least one distinguishable border and can be the discrete element that only is connected by surperficial hard conating, and perhaps described element can be common border.Usually, described element is uneven, for example, and the state of the lens among Fig. 4.Can also form this sheet material of element by other method, described method for example has, and adopts suitable associated methods (associated methods as described herein) to make a plurality of combination of elements.

Various substrates can be used for protecting mechanograph.Suitable base material comprises: glass (for example, crown glass, flint glass, borosilicate glass) and thermosetting polymer or thermoplastic polymer, as polycarbonate, polynary (methyl) acrylate (for example, polymethacrylate or " PMMA "), polyolefin (for example, polypropylene or " PP "), polyurethane, polyester (for example, polyethylene terephthalate or " PET "), polyamide, polyimide, phenolics, cellulose diacetate, Triafol T, polystyrene, styrene-acrylonitrile copolymer, epoxy resin etc.Usually, partly use required optical property and mechanical property and select substrate according to expection.That described mechanical property generally includes is flexible, dimensional stability and impact resistance.The thickness of substrate also depends on the expection application usually.Great majority are used, and the thickness of substrate is preferred less than about 0.5mm; More preferably, the thickness of substrate is the about 0.2mm of about 0.02mm-.The polymer film of self support type is preferred.By polyester (as, PET) or polyolefin (as PP (polypropylene), PE (tygon) and PVC (Polyvinylchloride)) be particularly preferred.Can polymeric material be made film with conventional masking technique (for example, extruding and the film of extruding is carried out the technology of optional single shaft or biaxial orienting).Can handle (for example, chemical treatment, corona treatment (as air or nitrogen corona treatment), Cement Composite Treated by Plasma, flame treatment or actinic radiation) to substrate, to improve the adhesion between substrate and the hard conating.If desired, optional articulamentum or prime coat can be coated on substrate and/or the hard conating, to improve the adhesion between each layer.

The various inner members of optical devices can be benefited from the introducing of surperficial hard conating.In some embodiments, inner member can be the film of substantially flat, for example under the situation of blooming.In other embodiments, inner member can be that full-size is the small-sized discreet component of about 5cm to 20cm.In some cases, internal optical component can be a flexible film.Yet in other embodiments, inner member is a rigidity.

Though inner member can be made of the inorganic material such as glass, inner member contains polymeric material usually, for example, and thermoplasticity, thermosetting or through crosslinked polymer resin.

Under the situation of (for example) optical display, inner member can be a blooming, for example, multi-layer optical film, micro-structural film are (for example, brightness enhancement film), (for example, reflectivity or absorbability) polarizing coating, diffusion barrier and (for example, twin shaft) phase shift films and compensate film.Inner member can also comprise the basilar memebrane or the above-mentioned any material that is used as the substrate of diaphragm goods of monolithic.

Term " optical display " or " display panel " are meant not illuminated and especially illuminated any conventional optical display, it comprises that (but not being subject to) multiword (for example accords with multi-thread display, LCD (" LCD "), plasma scope, preceding throwing and rear projection display, cathode-ray tube (CRT) (" CRT "), sign) and monocase or binary displays (for example, light emitting diode (" LED "), signal lamp and switch).The exposed surface of this display panel can be called " lens ".

As described in U.S. Patent application 2003/0217806, multi-layer optical film is a kind of like this film, and this film obtains required transmission performance and/or reflecting properties by the arrangement of the different microbedding of refractive index at least in part.Each microbedding has different refractive index characteristics, thereby makes some light being reflected at the interface between adjacent microlayers.The thickness of microbedding is enough thin, between the light that makes place, a plurality of interface reflect constructive interference or destructive interference takes place, thereby makes film body have required reflecting properties or transmission performance.For the blooming of the light that is designed to be used for to reflect ultraviolet, visible or near-infrared wavelength place, the optical thickness of each microbedding (being that physical thickness multiply by refractive index) is generally less than about 1 μ m.Yet, wherein can also comprise thicker layer, for example, be positioned at the superficial layer of film outer surface, perhaps a plurality of microbedding assemblies are separated and be disposed in film with interior protective boundary layer.Multilayer optical film body can also contain one or more thick adhesive phases, so that two in the lamination or multi-disc multi-layer optical film are glued together.

The reflecting properties of multilayer optical film body and transmission performance are the functions of the refractive index of each microbedding.Each microbedding localized positions in film at least can be by refractive index n in the face _x, n _yAnd the refractive index n relevant with the thickness axis of film _zCharacterized.These refractive indexes represent that separately measured material is to the refractive index along the light of mutually orthogonal x axle, y axle and z axle polarization.In force, control refractive index by rational selection of material and treatment conditions.Can make film like this: will be generally two kinds of polymer A that replace, the coextrusion of B layer tens of or hundreds of layers, subsequently, can randomly make the multilayer extrudate by one or more multiplications mould (multiplication die), then extrudate is stretched or (otherwise) extrudate is orientated, to form final film.The film of gained is made up of tens of or hundreds of independent microbeddings usually, adjusts the thickness and the refractive index of microbedding, thereby forms one or more reflection bands of a spectrum in required SPECTRAL REGION (for example, visible region or near-infrared region).For the layer with right quantity obtains high reflectivity, preferably, adjacent microlayers is to poor (the Δ n along the refractive index of the light of x axle polarization _x) be at least 0.05.Polarized light to two kinds of quadratures shows high reflectivity if desired, and then further preferably, adjacent microlayers is to poor (the Δ n along the refractive index of the light of y axle polarization _y) be at least 0.05.In addition, the difference of refractive index can be less than 0.05, and be preferably about 0, so multi-stacked to form, the vertical incidence light of a certain polarization state of this multi-stacked reflection and the vertical incidence light of transmission orthogonal polarization state.If desired, can also adjust adjacent microlayers to poor (Δ n along the refractive index of the light of z axle polarization _z), thereby obtain required reflecting properties at the p polarized component of oblique incident ray.

Can in the open WO99/36248 of PCT people such as () Neavin, find the exemplary materials that can be used to make the polymer multi-layer blooming.What suit the requirements is that at least a material is the very big polymkeric substance of absolute value of stress optical coefficient.In other words, when this polymkeric substance is stretched, its tend to produce stronger birefringence (at least about 0.05, more preferably at least about 0.1 or even be 0.2).According to the application of multilayer film, can two orthogonal directionss in membrane plane between, produce birefringence in one or more interior directions and between perpendicular to the direction of membrane plane or between the direction of its array mode.In particular cases widely different between each isotropic refractive index that polymeric layer had that does not stretch, can weaken the back that stretches and at least a polymkeric substance, produce strong birefringent trend, but birefringence is still desirable usually.When selective polymer is used for mirror coating and be used for polarizing coating (this film adopts twin shaft technology to make, and this technology stretches to film on the direction in the face of two quadratures), can produce this special circumstances.In addition, desirable polymkeric substance can keep birefringence after stretching, thereby gives finished film with required optical property.Can select second polymkeric substance to be used for other layer of multilayer film, make that in finished film second polymkeric substance is obviously different with the refractive index of first polymkeric substance on this equidirectional in the refractive index at least one direction.For convenience, can make film like this: adopt only two kinds different polymeric material, and in extrusion, these materials are alternately placed, to form layer A, layer B, layer A, layer B etc. alternately.Yet, only alternately place two kinds different polymeric materials not necessarily.The substitute is, each in the multi-layer optical film can be made of the unique material of not using in other layer of this film or potpourri layer respectively.Preferably, all had identical or similar melt temperature by the polymkeric substance of coextrusion.

The combination that had not only had suitable refractive index difference but also had two kinds of exemplary polymkeric substance of suitable interlayer adhesion comprises: (1) for employing was mainly the polarization multi-layer optical film that the method for uniaxial tension makes, this was combined as PEN/coPEN, PET/coPET, PEN/sPS, PET/sPS, PEN/Easter ^TMAnd PET/Easter ^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 based on the multipolymer of terephthalic acid (TPA) or blend, " sPS " refers to syndiotactic polytyrene and derivant thereof, Easter ^TMBe can be available from the polyester or the copolyester (it is believed that it contains cyclohexanedimethanol unit and terephthalate unit) of Eastman Chemical company; (2) for the polarization multi-layer optical film that makes by the process conditions of controlling biaxial stretch-formed method, this is combined as PEN/coPEN, PEN/PET, PEN/PBT, PEN/PETG and PEN/PETcoPBT, wherein " PBT " refers to polybutylene terephthalate, " PETG " referred 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), this is combined as 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 available from the thermoplastic polyester or the copolyester (it is believed that it contains cyclohexanedicarboxyester ester unit, polytetramethylene ether diol unit and cyclohexanedimethanol unit) of Eastman Chemical company, THV ^TMBe can be available from the fluoropolymer of 3M company.

Can in people's such as open WO 95/17303 of people's such as people's such as Jonza U.S. Patent No. 5,882,774, Ouderkirk PCT and Ouderkirk the open WO 99/39224 of PCT, find the further details of suitable multi-layer optical film and dependency structure thereof.Polymer multi-layer blooming and film body can contain extra play and the coating of selecting for use in order to satisfy its optics, machinery and/or chemical property.U.S. Patent No. 6,368,699 referring to people such as Gilbert.Polymer film and film body can also contain inorganic layer, for example, and metal or coating of metal oxides or layer.

Under the situation of optical imaging device, surperficial hard conating can be applied on any one inner member of this type of device or be applied on any array configuration of inner member of this type of device.For example, referring to Fig. 5, digital camera has usually: the cover plate 510 that exposes, interior lens 520, optional internal low pass filter 530, inner infrared (IR) wave filter 540 and interior view image sensor 550 (that is imager).The digital camera assembly can also have the cover glass (not shown) between image sensor and IR wave filter.Usually use the cylindrical shape lens barrel to hold these elements, and they are remained on the relative position to each other according to the optical design of each particular camera.In addition, can use subassembly, in this case, some elements can be assembled in advance, in final step, they are grouped together then.

Because imageing sensor is generally element the most expensive in the digital camera, therefore infer: it is particularly advantageous that surperficial hard conating is set on imageing sensor, shown in above Fig. 2 and 3.The imageing sensor that most of digital camera and other optical imaging device adopted is generally charge-coupled device (CCD) or complementary metal oxide semiconductor (CMOS) (CMOS).CCD and cmos image sensor all are to be electronics with phototransformation, by the Circuits System of element formed electronics are handled then.In case sensor is converted to electronics with light, then this sensor just can detect the value (charges accumulated) of each unit in the image.The mode of these sensor convert light is different.CCD is delivered charge on entire chip, and in one jiao of reading electric charges of array.Then, analog to digital converter is by the quantity of electric charge measuring each sensitization site (photosite) and locate and convert the measured value of gained to binary mode and convert the value of each pixel to numerical value.The CMOS device uses several transistors at each pixel place, so that use more conventional circuit just electric charge can be amplified and make its migration.Cmos signal is a digital signal, so do not need analog to digital converter.Various imageing sensors can derive from following company, comprise (for example) Primax company, Toshiba company, Agilent company, Micron company, Omnivision company, ST Micro company, Hynix company and Sony company.

Imageing sensor can be packed in the packing box, or provide with the form of exposed die.Imageing sensor can randomly can be layered between two sheet glass, and be encapsulated in the epoxy resin.Electric contact is arranged in the dorsal part of silicon chip, thereby the front side (may optionally be photosensitive side) of silicon chip is exposed, thereby be used for sensitization.Such imageing sensor can be available from Shellcase company, and commodity are called " ShellOP ".For the present embodiment, can be imageing sensor is stacked or be arranged on and surperficial hard conating be arranged on this imageing sensor before on glass.Yet, preferably, use (for example, easy to clean) hard conating or diaphragm to replace glass and epoxy resin, shown in Fig. 2 and 3.

In another embodiment, surperficial hard conating is arranged on the interior lens that is used to focus an image to detecting device.For mobile phone camera, these type of lens are made by polycarbonate or polymethylmethacrylate (that is acryl resin) usually.Yet for large-scale optical package, lens can be prepared from by multiple glass (for example, borosilicate).A plurality of lens package can be contained in single one the shooting module.For the embodiment that not only adopts lens, usually lens are assembled in the sub-assemblies in advance, and then this sub-assemblies is offered final shooting module assembler.Known have multiple lens and lens subassembly, and they can comprise (for example) Leica company, Sharp company, Konica company, Enplas company, Largan company, Ricoh company, Sekonix company and Canon company available from a plurality of suppliers.

In another embodiment, can use hard conating easy to clean (that is, contain can with the composition of fluoridizing of cementing agent generation copolymerization in the hard coating) that infrared filter is provided.Infrared (IR) cut-off filter is used with colored CCD or cmos imager, so that form true color image.The IR cut-off filter stops infrared light to be propagated, but visible light is passed through.Usually, the IR wave filter that is used for electronic camera stops that wavelength coverage is the light of about 650nm to about 1100nm, thereby makes visible light propagate sensor, however this IR wave filter also stop detecting device responsive near infrared light.This can realize by two kinds of optical technologies: absorb or reflection.The absorption-type wave filter has used and can absorb the special optical glass of near-infrared radiation and make.Reflection bandstop filter is to lead to interference filter with the weak point of efficient reflects infrared light substantially.These wave filters can be made by multilayer film, and this multilayer film comprises the layer with high index of refraction and low-refraction alternately.The IR wave filter can derive from 3M company, and commodity are called " DEA ".Other supplier of IR wave filter comprises Hoya company, Ashai Techno Glass company, KeihinKomaku company, Matsunami Glass company, Isuzu Glass company, Sunex company and Lifetime company.

The open No.US 2005/0041292 of laid-open U.S. Patents application on February 24 in 2005 has described a kind of like this blooming, this blooming (for example has the reflection-type interference element, constituted by multi-layer optical film) and the absorption-type element is (for example, be made of one or more colorants, described colorant is included in pigment or the dyestuff that visible region absorbs unevenly).Pigment is dispersed in the matrix that can form film.As the form of Gong selecting for use of multilayer film, interference element can optionally comprise cholesteric (Chinrally nematic) liquid crystal film, as is known in the art.Can be for the another kind of mode of selecting for use, interference element comprises and has metal/inorganic oxide and (for example stack, U.S. Patent No. 4,799, described in 745 (people such as Meyer) those) polymer-backed or comprise has by in U.S. Patent No. 5,440,446 (people such as Shaw), U.S. Patent No. 5,725,909 (people such as Shaw), U.S. Patent No. 6,010,751 (people such as Shaw) and U.S. Patent No. 6, the polymer-backed that the polymer/inorganic oxide that replaces of the method preparation described in 045,864 people such as () Lyons stacks.

In one embodiment, can be by absorbability dyestuff or absorptive pigment (that is, having absorbability in visible spectrum) being joined the absorber element that absorption-type IR wave filter or reflection-type IR wave filter are provided in the hard coating composition easy to clean as herein described.The function of the hard conating performance IR wave filter that solidifies.On absorbability hard coating composition easy to clean can being coated in substrate or the isolation liner; thereby form the absorption-type diaphragm; maybe absorption component directly can be coated on the interference element in (for example, multilayer film), the effective coverage on the inside surface of detecting device or cover on the forms or lens element of effective coverage.

Interference element reflects the vertical incidence light of the band that mainly is arranged near infrared region basically, and the most of or all basically vertical incidence light that is positioned at visible wavelength region of transmission basically.The average transmittance of interference element in the visible region be preferably at least about 50%, more preferably at least about 70%, and the transmittance in the entire emission band of interference element in extending near infrared region for less than about 5%, more preferably less than about 2% or 1%.For the detector system that adopts silicon photoelectric diode, 5%, 2% and 1% transmissivity limited range has preferably been contained about 800nm arrives about 1200nm to about 1100nm or about 700nm wavelength coverage.As a rule, the absorption of interference element is insignificant, thereby makes that its percentage transmission at the setted wavelength place is about 100% with reflection percent sum.

For the optical sensor that needs resemble human eye response (photopic response), green pigment, yellow pigment or the combination pigment that is preferably the two are dispersed in the absorbability hard coating composition easy to clean.Preferred green pigment comprises phthalocyanine green and phthalocyanine green 6Y; And preferred yellow pigment comprises PY-150, PY-138, PY-139, PY-185, PY-180 and PY-110.

Infrared absorbing dye that uses in absorbing filter and pigment (for example, referring to U.S. Patent No. 6,049,419) are known.Suitable dyestuff comprises (for example) phthalocyanine dye, for example, can be called those (for example, " Project 830NP ", " Project 860 NP " and " Project 900 NP ") of " Project Series " available from the commodity of Zeneca company.Suitable infrared absorption pigment comprises cyanines indigo plant, metal oxide and square cyanines (squaraine).Suitable pigment is included in U.S. Patent No. 5,215, those described in 838, for example, metal phthalocyanine salt (for example, phthalocyanine oxygen alum, phthalocyanine chlorine indium, TiOPc, phthalocyanine chlorine aluminium, CuPc, magnesium phthalocyanine etc.), Fang Jing (for example, hydroxyl Fang Jing etc.) and their potpourri.Exemplary CuPc pigment comprises can be available from the pigment of BASF AG, commodity " 6912 " by name.Other exemplary infrared pigment comprises metal oxide pigment, can be available from HeubachLangelsheim company, and commodity are called " Heucodor ".

The consumption of dyestuff or pigment changes with the kind of dyestuff or pigment and/or the change of final use in the optical body.Usually, when being applied to dyestuff or pigment on the film surface, it is present on the surface with the infrared absorption effect that is suitable for reaching required and the concentration and the coating thickness of visual appearance.Usually, if dyestuff or pigment are contained in the extra play or the multilayer optical body in, then its concentration be account for the optical body general assembly (TW) about 0.05 weight % to about 0.5 weight %.In addition, when using pigment, need its particle diameter less usually, for example, less than light wavelength.

The inner member of multiple optical imagery, sensing, projection and illuminator is benefited from (for example, easy to clean) as herein described surperficial hard conating.

For example, hard conating can be arranged on the optical sensor.Optical sensor be detect whether visible light exists, the electronic component of infrared (IR) transmittance and/or ultraviolet (UV) energy.Most optical sensor is made of the semiconductor with so-called photoconductivity, and wherein, electrical conductance changes with the change of the radiation intensity that incides material.The optical sensor of general type is photodiode, bipolarity phototransistor and light PET (photosensitive field-effect transistor).These devices are originally identical with conventional diode, bipolar transistor and field-effect-transistor-based, and difference is that described package has transparent forms, thereby makes emittance can arrive the junction between the internal semiconductor material.Bipolarity and field-effect photo electric transistor also have amplification except having the sensing ability.Silicon photoelectric diode is the example that is used for the sensor of non-imaging detection system (non-imaging photodection system), in described non-imaging detection system, visible light or near infrared light are converted into electric signal, for use in (for example) light intensity in the sensed luminance sensor.Optical sensor is used in multiple electronic installation, circuit and the system (comprising fibre system, optical scanner, WLAN, automatic control system for lighting, Vision Builder for Automated Inspection, electronic eyes, CD drive, optical memory chip and telechiric device).

Described optics inner member can comprise the inner member in the multiple imaging system (for example, camera, telescope, binocular, microscope and medical image system).Optical projection system comprises that liquid crystal on silicon (LCOS), digital light are handled (DLP) system and high temperature gathers silicon (HTPS).Display comprises CRT, plasma, Organic Light Emitting Diode (OLED), LCD (LCD) and Field Emission Display.Sensor-based system comprises barcode scanner, CD-DVD, guidance system and telechirics.The disposal system of energy and light comprises photoconductive tube, luminophor and solar-energy collecting device.Lighting source comprises light emitting diode, fluorescent light, arc lamp, incandescent lamp, Halogen lamp LED, OLED and electroluminescent cell.

Internal optical component (for example can comprise (for example) filter wheel, those that in digital light projection (DLP) system, use), cube polarization spectroscope (for example, those that in digital projection system, use, described digital projection system has used liquid crystal on silicon (LCOS) technology to carry out the separation/recombination of color) and multiple other type be used to make light separately and the prism that changes direction (for example, the TIR prism is used to change the direction of the light path in the digital projection system), catoptron (for example, the front of using in digital projection is coated with the catoptron of silver, thereby light is redirected to or is diverted to the target area).In addition, polarizer is the ordinary optical element in (for example) LCOS system, and it comprises absorptive polarizers, wiregrating formula polarizer and birefringent polarizer.Other internal optical component comprises forms, grating, diffusing globe, delayer, liquid crystal panel, photoconductive tube and has prism array or the structured surface film of microlens array.Prism, spectroscope, wave filter and various catoptron can derive from such as Schott Glass company and Bausch﹠amp; The company of Lomb company and so on.Silicon photoelectric diode can be obtained by Hamamatsu company.Polarizer can derive from following company, comprises SumitomoChemical company and 3M company.Prism film such as brightness enhancement film also can derive from 3M company.

The inner member that can use any (for example, shown in Figure 1 schematic assemble method) in the multiple known assemble method will have (for example, easy to clean) hard conating is assembled in the optical devices.Owing to exist by the surface protection that hard conating provided, therefore infer: compare with the identical assemble method of surperficial hard conating after wherein one or more inner members lack curing, said method can provide the flawless imaging device of higher yield.

Described hard conating comprises polymerisable binder precursor, and this binder precursor randomly (and preferably) and inorganic particle is used in combination.Described hard conating easy to clean also comprises the composition of fluoridizing at least a and the cementing agent copolymerization.

Multiple cementing agent can be used for hard conating.Binder precursor and the optional composition of fluoridizing have at least one polymerizable moiety,, have the end group part or the side group part of stretching out from monomer, oligomer or main polymer chain that is, and this part by being exposed to suitable radiation source cross-linking reaction takes place.As used herein, term " monomer " is meant and can combines with itself or combine with other monomer and form the single unit molecule of oligomer or polymkeric substance.Term " oligomer " is meant the compound of 2 to 20 monomeric unit combinations.Term " polymer " " be meant the compound of 21 or more monomer combination.Suitable curing comprises electron beam, heat (heat energy), ultraviolet light, visible light, microwave, infrared energy etc. with energy source.

Bonding agent is preferably derived from radical polymerization mould assembly binder precursor, wherein, in case hard coating composition is applied in inner member, the isolation liner or in the substrate of diaphragm, then described radical polymerization mould assembly binder precursor just photocuring can take place.The representative example of radical-curable part comprises carbon-to-carbon double bond, allyloxy, α-Jia Jibenyixi group, (methyl) acrylamide group, vinyl and the vinyl ether group of (methyl) acrylate group, alkene, the combination of these groups etc.

Yet available alternate manner is that the polymerizable moiety such as epoxide and vinyl ether can be a cationic polymerization.The third polymerizable groups reacts by condensation polymerization and carries out polymerization, and the most conventional be to drive by heat to finish described polyreaction.For example, material can have with silica-type, silsesquioxane type and silicone-type coating surface on the silane group (particularly alkoxysilane groups) of surface group (for example, silanol) condensation.The condensation of alkoxysilane groups is the example of sol-gel type chemistry.Binder precursor, optionally fluoridize composition and optional inorganic particle can contain the multiple polymerizable groups that adopts one or more curing mechanisms.Preferably, the polymerizable groups with cementing agent is identical substantially to fluoridize the polymerizable groups of composition.For example, cementing agent and fluoridize composition and can contain (methyl) acrylate polymerizable moiety, perhaps cementing agent and fluoridize composition and can contain (for example, hydrolyzable) silane moiety.The acrylate part is preferred often.

Can adopt multiple known hard coating composition, it is included in those that describe in the following patent documentation: U.S. Patent No. 6,132,861 (people such as Kang, ' 861), 6,238,798B1 (people such as Kang, ' 798), 6,245,833 B1 (people such as Kang, ' 833) and 6,299,799 (people such as Craig, ' 799); WO 99/57185 (people such as Huang), 5,677050 (Bilkadi), 4,885,332 (Bilkadi) and 5,104,929 (Bilkadi); U.S. Patent No. 6,660,388,6,660,389 and 6,841,190 (people such as Liu); The U.S. Patent application No.11/026573 that on Dec 30th, 2004 submitted to; The U.S. Patent application No.11/009181 that on Dec 10th, 2004 submitted to; The U.S. Patent application No.11/121742 that on May 4th, 2005 submitted to; The U.S. Patent application No.11/087413 that on March 23rd, 2005 submitted to; And the U.S. Patent application No.11/121456 of submission on May 4th, 2005.

Can be according to the required performance of final ceramic polymer composition or compound substance, the radical-curable monomer of multiple content monofunctional, two senses, trifunctional, four senses, face energy and six senses is mixed in (for example, free radical) aggretion type binder precursor.

Can in hard coating, use multiple cementing agent.Cementing agent can be derived from radical polymerization mould assembly precursor, and wherein, in case hard coating composition is applied in the substrate, then described radical polymerization mould assembly precursor just photocuring can take place.Binder precursor the acrylic acid ester that replaces such as the proton group of describing in ' 799 or acrylic acid acid amides or the ethylenically unsaturated monomers described in ' 799 etc. is normally preferred.Suitable binder precursor comprises many acrylate or many methacrylates of polyvalent alcohol, for example: the diacrylate of dibasic alcohol or two (methyl) acrylate (wherein, described dibasic alcohol comprises ethylene glycol, triethylene glycol, 2,2-dimethyl-1, ammediol, 1,3-encircles pentanediol, 1-ethoxy-2, ammediol, 2-methyl-2, the 4-pentanediol, 1, the 4-cyclohexanediol, 1,6-hexylidene glycol, 1, the 2-cyclohexanediol, 1, the 6-cyclohexanedimethanol, resorcinol, catechol, bisphenol-A and phthalic acid two (2-hydroxy methacrylate)), the triacrylate of trihydroxy alcohol or trimethyl acrylic ester are (wherein, described trihydroxy alcohol comprises glycerine, 1,2,3-propane three methyl alcohol, 1,2, the 4-butantriol, 1,2,5-penta triol, 1,3, the 6-hexanetriol, 1,5,10-triol in the last of the ten Heavenly stems, 1,2,3,-thrihydroxy-benzene, phloroglucin and 2-phenyl-2,2-methylol ethanol), (wherein, described tetra-atomic alcohol comprises 1 for the tetraacrylate of tetra-atomic alcohol or tetramethyl acrylate, 2,3, the 4-butantetraol, 1,1,2,2-tetra methylol ethane, 1,1,3,3-tetra methylol propane and tetramethylol methane tetraacrylate), five acrylate of pentabasis alcohol and pentamethyl acrylate (wherein, described pentabasis alcohol comprises ribitol); Six acrylate of hexahydroxylic alcohols and hexamethyl acrylate (wherein, described hexahydroxylic alcohols comprises sorbierite and bipentaerythrite, dihydroxy ethyl hydantoins) and their potpourri.Cementing agent can also be derived from one or more monofunctional monomers described in ' 798 that exist as people such as Kang.Cementing agent comprises described one or more N as people such as Bilkadi, the dibasic acrylamide of N-and/or N-replacement-N-vinyl-amide monomer.Hard coating can be derived from ceramic polymer composition, this pottery polymer composition contains about 20% to about 80% the ethylenically unsaturated monomers that accounts for ceramic polymer composition total weight of solids and about 5% to about 40% N, the dibasic acrylamide monomer of N-or N-replacement-N-vinyl-amide monomer.

Preferably, the cementing agent in the hard coating is derived from least a polyfunctional (for example, free radical) aggretion type monomer (this paper is also referred to as crosslinking chemical).Fluoridize crosslinking chemical though also can use,, usually preferably use the crosslinking chemical of nonfluorinated separately, or with the nonfluorinated crosslinking chemical with fluoridize crosslinking chemical and be used in combination.Though for some application, content only is that the crosslinking chemical of 5 weight % just can produce suitable permanance,, preferably make the concentration of crosslinking chemical reach maximum usually.Therefore, coating composition as herein described contains the crosslinking chemical of at least 20 weight % usually.The total amount of crosslinking chemical can account for 50 weight % of polymerizable coating composition, and can account for (for example) at least 60 weight %, at least 70 weight %, at least 80 weight %, at least 90 weight % even about 95 weight % of polymerizable coating composition.

Useful radical polymerization mould assembly crosslinking chemical comprises (for example) polynary (methyl) acryl monomer, wherein said polynary (methyl) acryl monomer is selected from: the compound that (a) contains two (methyl) acryloyl group, as, diacrylate 1, the 3-butanediol ester, diacrylate 1, the 4-butanediol ester, diacrylate 1,6-hexanediol ester, single acrylic acid monomethyl acrylic acid 1,6-hexanediol ester, ethylene glycol diacrylate, the alkoxy fatty alcohols diacrylate, the alkoxylate cyclohexane dimethanol diacrylate, the alkoxylate hexanediyl ester, the alkoxylate neopentylglycol diacrylate, caprolactone modification neopentyl glycol hydroxyl trimethylace tonitric ester diacrylate (caprolactonemodified neopentylglycol hydroxypivalate diacrylate), caprolactone modification neopentyl glycol hydroxyl trimethylace tonitric ester diacrylate, cyclohexane dimethanol diacrylate, the diacrylate binaryglycol ester, dipropylene glycol diacrylate, ethoxylation (10) bisphenol a diacrylate, ethoxylation (3) bisphenol a diacrylate, ethoxylation (30) bisphenol a diacrylate, ethoxylation (4) bisphenol a diacrylate, hydroxy pivalin aldehyde modification trimethylolpropane diacrylate, diacrylic acid pentyl diol ester, polyglycol (200) diacrylate, polyglycol (400) diacrylate, polyglycol (600) diacrylate, ethoxylated neopentylglycol diacrylate, diacrylate tetraethylene glycol ester, diacrylate tristane diformazan alcohol ester, triethylene-glycol diacrylate and tri (propylene glycol) diacrylate; (b) contain the compound of three (methyl) acryloyl group, for example, three acrylic acid glyceride, trimethylolpropane triacrylate, the ethoxylation triacrylate (for example, ethoxylation (3) trimethylolpropane triacrylate, ethoxylation (6) trimethylolpropane triacrylate, ethoxylation (9) trimethylolpropane triacrylate, ethoxylation (20) trimethylolpropane triacrylate), pentaerythritol triacrylate, propoxylation triacrylate (for example, propoxylation (3) glycerol tri-acrylate, propoxylation (5.5) glycerol tri-acrylate, propoxylation (3) trimethylolpropane triacrylate, propoxylation (6) trimethylolpropane triacrylate), trimethylolpropane triacrylate and ethoxylation cyamelide triacrylate (tris (2-hydroxyethyl) isocyanurate triacrylate); (c) contain the compound of higher functionality (methyl) acryloyl group, for example, two (trimethylolpropane) tetraacrylate, dipentaerythritol five acrylate, ethoxylation (4) tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate and caprolactone modification dipentaerythritol acrylate; (d) compound of oligomeric (methyl) acryloyl group, such as for example, urethane acrylate, polyester acrylate and epoxy acrylate; The similar thing of polynary acrylamide of above-claimed cpd; And combination.This compounds can derive from supplier widely, such as for example, be positioned at the Sartomer company in Pennsylvania, America Exton city, be positioned at the UCBChemicals company in State of Georgia, US Smyrna city, and the AldrichChemical company that is positioned at Wisconsin, USA Milwaukee city.Other available (methyl) esters of acrylic acid material comprises polynary (methyl) acrylate of containing hydantoins part (for example, as United States Patent (USP) 4,262, described in 072 people such as () Wendling).

Preferred cross-linking agents contains at least three (methyl) acrylate-functional groups.The preferred commercially available crosslinking chemical that gets comprises the crosslinking chemical that derives from the Sartomer company that is positioned at Pennsylvania, America Exton city, for example, ethoxylation (4) pentaerythritol triacrylate of ethoxylation (3) trimethylolpropane triacrylate of dipentaerythritol five acrylate of the pentaerythritol triacrylate of the trimethylolpropane triacrylate of commodity " SR351 " by name, commodity " SR444 " by name, commodity " SR399LV " by name, commodity " SR454 " by name and commodity " SR494 " by name.

Multiple inorganic oxide particles can be used in the hard coating.It is spherical that described particle is essentially usually, and have particle diameter relatively uniformly.Described particle can have the size distribution of basic monodispersity or the size distribution of polydispersity, and the size distribution of described polydispersity is by two or more basic single particle mixing that disperse to distribute are obtained.Inorganic oxide particles is generally non-gathering (dispersing substantially), because gathering can cause inorganic oxide particles precipitation or hard coating gelling.The particle diameter of inorganic oxide particles is generally colloid, its mean grain size be about 0.001 micron-Yue 0.2 micron, less than about 0.05 micron, less than about 0.03 micron.Such particle size range helps inorganic oxide particles is distributed in the resin glue, and makes ceramic condensate have required surface nature and optical transparence.Can measure the mean grain size of inorganic oxide particles thus by the quantity of using transmission electron microscope to measure inorganic oxide particles with given diameter.Inorganic oxide particles comprises: cataloid, colloidal titania, colloidal alumina, colloidal zirconia, colloid vanadium oxide, colloidal chromia, colloidal iron oxide, colloidal antimony, colloid tin oxide and composition thereof.Inorganic oxide particles can (substantially) be made up of single oxide (for example silicon dioxide); Perhaps can contain oxide composition (for example silicon dioxide and aluminium oxide); Perhaps can be a kind of like this particle: on a kind of core (the perhaps core of the material except that metal oxide) of oxide, deposit another kind of oxide.Silicon dioxide is the inorganic particle of using always.Usually with colloidal sol (it comprises the aqueous colloidal dispersion of inorganic oxide particles in liquid medium) form, provide inorganic oxide particles.Can adopt multiple technologies to prepare colloidal sol, and colloidal sol is made various ways, these forms comprise that the hydrosol (wherein, water plays the effect of liquid medium), (wherein, liquid medium had both contained water for organosol (wherein, organic liquid plays the effect of liquid medium) and mixed type colloidal sol, also contain organic liquid), for example, as U.S. Patent No. 5,648,407 (people such as Goetz), 5,677,050 (people such as Bilkadi) and 6,299,799 (people such as Craig) are described.Can adopt the hydrosol (for example hydrosol of amorphous silica).Colloidal sol contains at least 2 weight %, at least 10 weight % that account for the colloidal sol general assembly (TW), at least 15 weight %, at least 25 weight % usually, often is the colloidal inorganic oxide particle of at least 35 weight %.The amount of colloidal inorganic oxide particle is generally and is not more than 50 weight % (for example 45 weight %).As described in people such as Bilkadi, the surface of inorganic particle can be by " acrylate functional ".Colloidal sol can also be complementary with the pH of cementing agent, and can contain counterion or water soluble compound (for example sodium aluminate), and all these are all as described in people's such as Kang patent documentation ' 798.

By (for example with the hydrosol of inorganic oxide particles and radical-curable binder precursor, one or more radical-curable monomers, oligomer or polymkeric substance, described monomer, oligomer or polymkeric substance are after being exposed to suitable curing energy source, can participate in cross-linking reaction) mix, can make hard coating easily.The composition of gained is dried before coated usually, to remove all moisture substantially.This drying steps is called as " processed (stripping) " sometimes.Before coated, organic solvent can be added in the ceramic polymer composition of gained, thereby make it have improved viscosity characteristics, and help ceramic polymer composition is coated in the substrate.After the coating, but the drying of ceramic polymer composition, to remove the solvent of any interpolation, then, in order to make the radical-curable binder precursor partly solidified at least, the composition of drying can be exposed to appropriate energy source, thereby make said composition partially hardened at least.

Inorganic particle in the hard coating, cementing agent and other any composition are selected, made the refractive index of the hard conating after solidifying approach the refractive index of substrate.Help to reduce the possibility that produces moire pattern or other visible interference fringe like this.

As mentioned above, hard conating can be formed by such water-based paint compositions: before coating, described water-based paint compositions is carried out processed, thereby remove moisture, and can randomly dilute with solvent, thereby help to apply said composition.Those skilled in the art will appreciate that and to depend on the character of single composition in the hard coating, required substrate and coating condition the selection of required solvent and quantity of solvent.In people such as Kang exist ' 798 several available solvents, quantity of solvent and coating viscosity have been described.

If mix with binder precursor by the hydrosol with the colloidal inorganic oxide particle and to prepare hard coating, then colloidal sol can have the pH that makes the negative surface charge of particle band.For example, if inorganic particle mainly is a silica dioxide granule, colloidal sol is pH greater than 7, greater than 8 or greater than 9 alkaline state so.Colloidal sol can comprise ammonium hydroxide etc., thereby makes NH ₄ ⁺Can be used as the counter cation of the particle that has negative surface charge.If desired the colloidal inorganic oxide particle is carried out surface treatment, suitable surface conditioning agent can be blended in the colloidal sol so, for example, exist described in ' 833 as people such as Kang.Then the radical-curable binder precursor is joined in the ceramic polymer composition.This pottery polymer composition is carried out processed, thereby remove all moisture basically.For example, have been found that it is suitable removing about 98% water and about 2% water is remained in the ceramic polymer composition.In case all basically moisture are removed, usually just can be added in the organic solvent of kind described in people's such as Kang ' 798 by following consumption, described consumption makes ceramic polymer composition comprise the solid of about 5 weight % to about 99 weight % (be preferably about 10 weight % and arrive about 79 weight %).

Hard coating composition can comprise fluoridizing composition, polyfunctionally fluoridizing composition and their combination of multiple simple function.In at least some embodiments, have been found that with at least a simple function fluoridize composition and at least a polyfunctional to fluoridize that composition is used in combination be preferred.

The total amount of fluoridizing composition in the hard coating composition precursor is generally at least 0.5 weight % (for example, at least about 1 weight %, 2 weight %, 3 weight % and 4 weight %).Preferably, hard coating precursor composition comprises the composition of fluoridizing at least about 5 weight %.Particularly for adopting multifunctional embodiment of fluoridizing composition, hard coating precursor composition can contain the nearly multifunctional composition of fluoridizing of 95 weight %.Yet as mentioned above, the cost effective method typically uses the composition of fluoridizing of the Cmin that is used to produce required low surface energy more.Therefore, the total amount of fluoridizing composition is no more than 30 weight % usually, and is preferably and is no more than about 15 weight % (for example, being lower than about 14 weight %, 13 weight %, 12 weight % and 11 weight %).

In coating composition of the present invention, can use the multiple polymerizable compound of fluoridizing.This compounds can be represented by following formula I:

(R _f)-[(W)-(R _A)] _w(formula I)

R wherein _fComprise (entirely) fluoroalkyl, (entirely) fluorine alkylidene or (entirely) perfluoroalkyl polyether group.(entirely) perfluoroalkyl polyether group comprises (entirely) fluorinated groups, for example, and-(C _pF _2p)-,-(C _pF _2pO)-,-(CF (Z))-,-(CF (Z) O)-,-(CF (Z) C _pF _2pO)-,-(C _pF _2pCF (Z) O)-,-(CF ₂CF (Z) O)-or its combination; W is a linking group; R _AComprise polymerizable groups, for example, (methyl) acryloyl group or polymerisable (for example, hydrolyzable) silane group; And w is 1 or 2.

Multiple polymerizable silane group is known in the art.Silane atom common and at least one halogen atom and/or at least one oxygen atom bonding, wherein, described oxygen atom is preferably the component part of acyloxy and/or alkoxy.

Fluoridize composition and can be straight chain, side chain, ring-type or its combination, and can be saturated or unsaturated.

Linking group W comprises the divalent group that is selected from alkylidene, arlydene, assorted alkylidene or its combination, and the optional divalent group that is selected from carbonyl, ketonic oxygen base, carbonyl imino group, sulfonamido or its combination.W can be unsubstituted group or the group that is replaced by alkyl, aryl, halogen or its combination.The W group has 30 carbon atoms at the most usually.In some compounds, the W group has at the most 20 carbon atoms, 10 carbon atoms, 6 carbon atoms or 4 carbon atoms at the most at the most at the most.For example, W can be an alkylidene, the alkylidene that replaced by aryl or the combination of arlydene and alkylidene.W can also be carbamate linking group (that is, (OCONH-)).

In (entirely) perfluoroalkyl polyether radicals R _fIn the repetitive, p is generally 1 to 10 integer.In some embodiments, p is 1 to 8,1 to 6,1 to 4 or 1 to 3 integer.Group Z is perfluoroalkyl, perfluor ether, holo-fluorine polyester or perfluoro alkoxy, and they can be straight chain, side chain or ring-type.Group Z has at the most 12 carbon atoms, 10 carbon atoms or 9 carbon atoms, 4 carbon atoms, 3 carbon atoms, 2 carbon atoms or 1 carbon atom at the most at the most at the most at the most at the most at the most usually.In some embodiments, group Z can have at the most 4 oxygen atoms, 3 oxygen atoms, 2 oxygen atoms, 1 oxygen atom or do not have oxygen atom at the most at the most at the most.

R _fCan be monovalence or divalence.At R _fIn some compounds for monovalence, end group can be (C _pF _2p+1)-, (C _pF _2p+1O)-, (X ' C _pF _2pO)-or (X ' C _pF _2p+1)-, wherein X ' is hydrogen, chlorine or bromine, and p is 1 to 10 integer.At R _fGroup is in some embodiments of monovalence, and end group is fluoridized, and p is 1 to 10,1 to 8,1 to 6,1 to 4 or 1 to 3 integer.

(entirely) perfluoroalkyl polyether compound can be represented by following formula I, wherein R _fIt is (perfluor) polyether group; R _ABe (methyl) acryl group or-COCF=CH ₂W is 1 or 2.Exemplary monovalence R _fGroup comprises CF ₃O (C ₂F ₄O) _nCF ₂-and C ₃F ₇O (CF (CF ₃) CF ₂O) _nCF (CF ₃)-, the wherein mean value of n is 0 to 50,1 to 50,3 to 30,3 to 15 or 3 to 10.Divalence R _fThe suitable construction of (entirely) perfluoroalkyl polyether group includes, but is not limited to-CF ₂O (CF ₂O) _q(C ₂F ₄O) _nCF ₂-,-(CF ₂) ₃O (C ₄F ₈O) _n(CF ₂) ₃-,-CF ₂O (C ₂F ₄O) _nCF ₂-and-CF (CF ₃) (OCF ₂CF (CF ₃)) _sOC _tF _2tO (CF (CF ₃) CF ₂O) _nCF (CF ₃)-, the wherein mean value of q is 0 to 50,1 to 50,3 to 30,3 to 15 or 3 to 10; The mean value of n is 0 to 50,3 to 30,3 to 15 or 3 to 10; The mean value of s is 0 to 50,1 to 50,3 to 30,3 to 15 or 3 to 10; (n+s) mean value of sum is 0 to 50 or 4 to 40; (q+n) sum is greater than 0; And t is 2 to 6 integer.

When synthetic, the represented compound of formula I comprises multiple R usually _fThe potpourri of group.Average structure is in addition average to this ingredients of a mixture and structure that obtain.The value of q in these average structures, n and s can change, as long as the number-average molecular weight of this compound is at least about 400.The represented compound of formula I has 400 to 5000,800 to 4000 or 1000 to 3000 molecular weight (number-average molecular weight) usually.

Can be (for example by known technology, U.S. Patent No. 3,553,179 and 3,544,537 and U.S. Patent Application Publication No.2004/0077775 (title is " FluorochemicalComposition Comprising a Fluorinated polymer and Treatment of aFibrous Substrate Therewith ") described in technology) synthesize perfluoropolyether acrylate compound (for example, the represented compound of formula I).

In some embodiments, polyfunctional perfluoropolyether acrylate contains end group HFPO-group.As used herein, " HFPO-" is meant F (CF (CF ₃) CF ₂O) _aCF (CF ₃) C (O) OCH ₃F in (methyl esters) (CF (CF ₃) CF ₂O) _aCF (CF ₃)-, wherein " a " average out to is about 6.2, and the mean molecular weight of this methyl esters is 1, the 211g/ mole, and it can be according to U.S. Patent No. 3,250, and 808 (Moore etc.) institute reported method is prepared and adopts fractionating process to purify.Some these compounds are further described in the U.S. Patent application No.11/121742 that submitted on May 4th, 2005.

Exemplary compound comprises (for example):

HFPO-C(O)N(H)C(CH ₂OC(O)CH＝CH ₂) ₂CH ₂CH ₃、

HFPO-CO-NHCH(CH ₂OCOCH＝CH ₂) ₂、

HFPO-C(O)N(H)CH ₂CH(OC(O)CH＝CH ₂)CH ₂OC(O)CH＝CH ₂、

HFPO-C(O)NH(CH ₂) ₃N(CH ₂CH ₂OCOCH＝CH ₂) ₂、

HFPO-CO-NHCH ₂CH ₂N (CO-CH=CH ₂) (CH ₂CH ₂OCOCH=CH ₂) and mol ratio be about 1: 1 HFPO-C (=O) NHCH ₂CH ₂CH ₂NHCH ₃Addition product with TMPTA.

In another embodiment, can be with (entirely) perfluoroalkyl polyether acrylate compounds (for example, HFPO-C (O) N (H) CH that can prepare by the wheat Kerr-type addition reaction of reactive (entirely) perfluoroalkyl polyether and polynary (methyl) acrylate ₂CH ₂CH ₂N (H) CH ₃Addition product with trimethylolpropane triacrylate (TMPTA)) fluoridizes composition as polymerizable.This type of (entirely) perfluoroalkyl polyether acrylate compounds is further described in the U.S. Patent application No.11/009181 (exercise question is " Polymerizable Compositions; Methods Of Making the Same, andComposite Articles Therefrom ") that submitted on Dec 10th, 2004.

In another embodiment, can use aggretion type PFPE polyurethane (for example, those described in the U.S. Patent application No.11/087413 that submits on March 23rd, 2005).The exemplary configuration (2) of PFPE polyurethane with the many acrylate end groups shown in the formula (1) is as follows:

(formula 2)

This compound is the biuret of HDI and the oligomeric amidol of the HFPO (F (CF (CF of 1 equivalent ₃) CF ₂O) _6.5CF (CF ₃) C (O) NHCH ₂CH ₂OH) and the reaction product of the pentaerythritol triacrylate of 2 equivalents.

In addition, can use by formula R _i-(NHC (O) XQR _f) _m,-(NHC (O) OQA) _nRepresented PFPE polyurethane with mono acrylic ester end group.

In another embodiment, can use the urethane acrylate of representing by formula (3A) by the PFPE replacement with monovalence PFPE part:

R _r-Q-(XC (O) NHQOC (O) C (R)=CH ₂) _f(formula 3A)

Wherein, R _fBe monovalence PFPE part, this part is by comprising formula F (R _FcO) _xC _dF _2d-group constitute, in described formula, R _FcRepresentative independently of one another has the alkylidene of fluoridizing of 1 to 6 carbon atom, and x represents the integer more than or equal to 2 independently of one another, and wherein, d is 1 to 6 integer, and a is 2-15; Q represents the linking group that is at least divalent independently, and be selected from covalent bond, alkylidene, arlydene, inferior aralkyl, alkarylene, optionally (for example contain heteroatoms, O, N and S) the linking group with straight or branched or ring and optionally contain heteroatomic functional group (for example, carbonyl or sulfonyl) and their combination; X represents O, S or NR independently, and wherein, R is H or the low alkyl group with 1 to 4 carbon atom; And f is 1-5.

Meeting polyurethane (methyl) acrylate that a preferred PFPE to formula (3A) illustration replaces has in formula (3B) more specifically and describes:

HFPO-Q-(XC (O) NHQOC (O) C (R)=CH ₂) _f(formula 3B)

Wherein, HFPO is F (CF (CF ₃) CF ₂O) _aCF (CF ₃)-, a is 2-15; Q represents the linking group that is at least divalent independently, and be selected from covalent bond, alkylidene, arlydene, inferior aralkyl, alkarylene, can (for example randomly contain heteroatoms, O, N and S) the linking group with straight or branched or ring and optionally contain heteroatomic functional group (for example, carbonyl or sulfonyl) and their combination; X represents O, S or NR independently, and wherein, R is H or the low alkyl group with 1 to 4 carbon atom; And f is 1-5.The urethane acrylate that operable two preferred HFPO replace comprises:

HFPO-C (O) NHC ₂H ₄OC (O) NHC ₂H ₄OC (O) C (CH ₃)=CH ₂With

HFPO-C(O)NHC(C ₂H ₅)(CH ₂OC(O)NHC ₂H ₄OC(O)C(CH ₃)＝CH ₂) ₂。

In another embodiment of the present invention, use by represented one or more PFPE polyurethane of formula (4) with monovalence PFPE part:

R _i-(NHC(O)XQR _f) _m，-(NHC(O)OQ(A) _p) _n，-(NHC(O)XQG) _o，-(NCO) _q

(formula 4)

Wherein, R _iResidue for multicomponent isocyanate; X represents O, S or NR independently, and wherein R is H or the low alkyl group with 1 to 4 carbon atom; R _fBe monovalence PFPE part, this part is by comprising formula F (R _FcO) _xC _dF _2d-group constitute, in described formula, R _FcRepresentative independently of one another has the alkylidene of fluoridizing of 1 to 6 carbon atom, and x represents the integer more than or equal to 2 independently of one another, and wherein, d is 1 to 6 integer; Q represents the linking group that is at least divalent independently, and be selected from covalent bond, alkylidene, arlydene, inferior aralkyl, alkarylene, can (for example randomly contain heteroatoms, O, N and S) the linking group with straight or branched or ring and optionally contain heteroatomic functional group (for example, carbonyl or sulfonyl) and their combination; A is (methyl) acryloyl group functional group-XC (O) C (R ₂)=CH ₂, wherein, R ₂For low alkyl group or be H or F with 1 to 4 carbon atom; G is selected from alkyl, aryl, alkaryl and aralkyl; wherein; G can (for example randomly contain heteroatoms; O, N and S) and can randomly contain and (for example have heteroatomic functional group; carbonyl and sulfonyl) and heteroatoms and contain the combination of heteroatomic functional group, and G can randomly contain be selected from (methyl) acryloyl group, vinyl, allyl and-Si (OR ₃) ₃The side group of group or end group reactive group, wherein, R ₃For having the low alkyl group of 1 to 4 carbon atom, wherein G also can randomly have fluoroalkyl or perfluoroalkyl; M is at least 1; N is at least 1; O is 0 or bigger; P is 2 to 6; Q is 0 or bigger; (m+n+o+q)=N _NCO, wherein, N _NCOBe to be connected in R at first _iOn the number of isocyanate groups; And (m+n+o)/N _NCONumerical value more than or equal to 0.67, and wherein, by each unit and the R of subscript m, n, o and q mark _iThe unit connects.Preferably, R _FcFor-CF (CF ₃) CF ₂-.

Employed single alcohol, single mercaptan or monoamine HXQG can comprise such as C in the material shown in the manufacturing formula (4) ₄F ₉SO ₂N (CH ₃) CH ₂CH ₂OH, H ₂NCH ₂CH ₂CH ₂(SiOCH ₃) ₃, HSCH ₂CH ₂CH ₂Si (OCH ₃) ₃And the material of HEA (" hydroxy ethyl methacrylate ") and so on.

In yet another embodiment, use one or more PFPE polyurethane of representing suc as formula (5):

(R _i) _c-(NHC(O)XQR _f) _m，-(NHC(O)OQ(A) _p) _n，-(NHC(O)XQG) _o，

(R _f(Q)(XC(O)NH) _y) _z-，-NHC(O)XQD(QXC(O)NH) _u) _s-，

D ₁(QXC(O)NH) _y) _zz-NHC(O)OQ(A) _tQ ₁Q(A) _tOC(O)NH)) _v-，-(NCO) _w

(formula 5)

Wherein, R _iResidue for multicomponent isocyanate; C is 1 to 50; X represents O, S or NR independently, and wherein R is H or low alkyl group; R _fBe monovalence PFPE part, this part is by comprising formula F (R _FcO) _xC _dF _2d-group constitute, in described formula, R _FcRepresentative independently of one another has the alkylidene of fluoridizing of 1 to 6 carbon atom, and x represents the integer more than or equal to 2 independently of one another, and wherein, d is 1 to 6 integer; Q represents the linking group that is at least divalent independently, and be selected from covalent bond, alkylidene, arlydene, inferior aralkyl, alkarylene, can (for example randomly contain heteroatoms, O, N and S) the linking group with straight or branched or ring and optionally contain heteroatomic functional group (for example, carbonyl or sulfonyl) and their combination; A is that chemical formula is (XC (O) C (R ₂)=CH ₂) (methyl) acryloyl group functional group, wherein, R ₂For low alkyl group or be H or F with 1 to 4 carbon atom; G is selected from alkyl, aryl, alkaryl and aralkyl; wherein; G is optional (for example to contain heteroatoms; O, N and S) and can randomly contain and (for example have heteroatomic functional group; carbonyl and sulfonyl) and heteroatoms and contain the combination of heteroatomic functional group, and G can randomly contain be selected from (methyl) acryloyl group, vinyl, allyl and-Si (OR ₃) ₃The side group of group or end group reactive group, wherein, R ₃For having the low alkyl group of 1 to 4 carbon atom, wherein G also can randomly have fluoroalkyl or perfluoroalkyl; D is selected from alkylidene, arlydene, alkarylene, fluorine alkylidene, perfluorinated alkylidene and inferior aralkyl, and can randomly contain the heteroatoms such as O, N and S; D1 is selected from alkyl, aryl, alkaryl, fluoroalkyl, perfluoroalkyl and aralkyl, and can randomly contain the heteroatoms such as O, N and S; Q1 is the limiting mode linking group identical with Q; M or z are at least 1; N or v are at least 1; Y is 2 or bigger independently; O, s, v, w, z and zz are 0 or bigger; (m+n+o+[(u+1) s]+2v+w+yz+y (zz))=cN _NCO, wherein, N _NCOBe to be connected in R at first _iOn the number of isocyanate groups; And (m+n+o+ ([(u+1) s]+2v+yz+y (zz))/(cN _NCO) numerical value more than or equal at least 0.75; P is 2 to 6; T is 1 to 6; And u is 1 to 3 independently; Wherein, by each unit and the R of subscript m, n, o, s, v, w, z and zz mark _iThe unit connects, and preferably, R _FcFor-CF (CF ₃) CF ₂-.

As have (entirely) perfluoroalkyl polyether part fluoridize composition for other form of selecting for use, can use (methyl) acrylic acid (entirely) fluothane alcohol ester.Preferably (methyl) acrylic acid (entirely) fluothane alcohol ester comprise have at least 2 carbon atoms, the fluoroalkyl group of at least 3 carbon atoms more preferably.Though the number of carbon atom can reach 12 or higher,, the carbon atom number of fluoroalkyl is preferably about at the most 6.

As can be, fluoridize composition and can comprise a kind of in the multiple fluorine containing silane composition (for example, described in the patent documentation US2003/0168783 those) for the another kind of form selected for use.In one aspect, fluoridize composition and can comprise as U.S. Patent No. 5,851, the fluorinated siloxane described in 674, this fluorinated siloxane are to prepare by the coating composition that use contains the fluorinated silane that is shown below:

R _f-R ₁-SiX _3-xR _2x

Wherein:

R _fFor can randomly containing one or more heteroatomic fully-fluorinated groups;

R ₁Be divalent alkyl, arlydene or its potpourri, these groups are replaced by one or more heteroatomss or functional group, and contain and have an appointment 2 to about 16 carbon atoms;

R ₂Be low alkyl group;

X is halogen, lower alkoxy or acyloxy; And

X is 0 or 1.

Hard coating composition can contain fluoridizes compatilizer, so that improve the compatibility between conventional hydro carbons hard coating composition or ceramic condensate and the fluorinated compound (for example, HFPO derivant).Compatilizer can be with 2 weight % of dry state solid amount to 15 weight %, more preferably about 2 weight % add to the amount of 10 weight %.Compatilizer can be preferably at least 5 times at least 3 times of the amount of the monobasic of HFPO or polynary (methyl) acryl compound.

The chemical formula that contains the free radical reaction compatilizer of fluoroalkyl or fluorine alkylidene is respectively done for oneself: (R _f) Q (X) _n(X) _nXQ (R _F2) Q (X) _n, R wherein _fIt is fluoroalkyl; R _F2It is the fluorine alkylidene; Q is a linking group, and it comprises alkylidene, arlydene, arlydene-alkylidene or alkylidene-arlydene, and can comprise the linking group of straight or branched, and the linking group of this straight or branched can contain heteroatoms (for example O, N and S); X be selected from (methyl) acryloyl group ,-free radical reaction group in SH, allyl or the vinyl; N is 1-3.Typical Q group comprises :-SO ₂N (R) CH ₂CH ₂-,-SO ₂N (CH ₂CH ₂) ₂-,-(CH ₂) _m-,-CH ₂O (CH ₂) ₃-and-C (O) N (R) CH ₂CH ₂-, wherein R is H or the low alkyl group that contains 1-4 carbon atom, m is 1-6.Preferably, fluoroalkyl or fluorine alkylidene are perfluoroalkyl or perfluorinated alkylidene.

In a preferred embodiment, compatilizer is the compatilizer that perfluoroalkyl or perfluorinated alkylidene replace, and this compatilizer contains and is connected in acrylate carbochain part, that have at least five carbon atoms, and this compatilizer contains the fluorine of at least 30 weight %.The compatilizer requirement when satisfying the above-mentioned composition that is used for hard conating 18, that the preferred fluoroalkyl of a class or fluorine alkylidene replace is the acrylate compatilizer that perfluoro butyl replaces.Satisfy above-mentioned requirements and can be used for acrylate compatilizer that the exemplary and nonrestrictive perfluoro butyl among the present invention replaces and comprise in the following compounds one or more, described compound is:

C ₄F ₉SO ₂N(CH ₃)CH ₂CH ₂OC(O)CH＝CH ₂、

C ₄F ₉SO ₂N (CH ₂CH ₂OC (O) CH=CH ₂) ₂, or

C ₄F ₉SO ₂N(CH ₃)CH ₂CH ₂OC(O)C(CH ₃)＝CH ₂。

Other nonrestrictive example of the compatilizer that operable preferred fluoroalkyl replaces comprises: acrylic acid 1H, and 1H, 2H, 2H-perfluor ester in the last of the ten Heavenly stems can derive from the Lancaster Synthesis company that is positioned at Windham city, New Hampshire.People's such as Hulme-Lowe U.S. Patent No. 4; 968; 116 and people's such as Babirad U.S. Patent No. 5; mention multiple other (methyl) acryl compound that has perfluoroalkyl moieties of the composition that also can be used for hard conating 239,026 (comprising methacrylic acid perfluor cyclohexyl methyl esters).Other fluorochemicals (methyl) acrylate that satisfies above-mentioned requirements and can be used comprises (for example): diacrylate 2,2,3,3,4,4,5,5-octafluorohexane diol ester and acrylic acid ω-hydrogen 2,2,3,3,4,4,5,5-octafluoro pentyl ester (H-C ₄F ₈-CH ₂O-C (O)-CH=CH ₂).People's such as Kang U.S. Patent No. 6,238,798 has been described other fluorochemicals (methyl) acrylate that can use separately or use as potpourri.

In order to promote to solidify, can also contain at least a free radical thermal initiator and/or light trigger according to polymerisable compound of the present invention.Usually, if having this initiating agent and/or light trigger, then its content is the about 10 weight % less than the polymerisable compound general assembly (TW), is more typically the about 5 weight % less than the polymerisable compound general assembly (TW).The radically curing technology is well-known in the art, and it comprises (for example): thermal curing methods and the radiation-curing method such as electron beam or ultraviolet radiation.Can be at for example U.S. Patent No. 4,654,233 (people such as Grant), No.4,855,184 (people such as Klun) and No.6 among 224,949 (people such as Wright), find the further details about free radical thermal polymerization and light polymerization technique.

Available free radical photo-initiation comprises (for example): those in the known ultraviolet curing that can be used for acrylic polymer.This class initiating agent comprises: benzophenone and derivant thereof; Diphenylhydroxyethanone, Alpha-Methyl diphenylhydroxyethanone, α-phenyl diphenylhydroxyethanone, α-allyl diphenylhydroxyethanone and α-benzyl diphenylhydroxyethanone; Benzoin ether, for example, benzoin dimethylether dimethyl ketal (can be available from the Ciba Specialty Chemicals company that is positioned at New York, United States Tarrytown city, commodity are called " IRGACURE 651 "), benzoin methyl ether, benzoin ethyl ether and styrax n-butyl ether; Acetophenone and derivant thereof, for example, 2-hydroxy-2-methyl-1-phenyl-1-acetone (can be available from Ciba Specialty Chemicals company, commodity are called " DAROCUR 1173 ") and 1-hydroxycyclohexylphenylketone (also can be available from Ciba Specialty Chemicals company, commodity are called " IRGACURE 184 "); 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-(4-morpholinyl)-1-acetone (also can be, commodity are called " IRGACURE907 ") available from Ciba Specialty Chemicals company; 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone (also can be, commodity are called " IRGACURE 369 ") available from Ciba Specialty Chemicals company; The aromatic series ketone, for example, benzophenone and derivant thereof, anthraquinone and derivant thereof;  salt, for example, diazo salt, iodine  salt, sulfonium salt; Titanium complex for example, also can be called the titanium complex of " CGI 784DC " available from the commodity of Ciba SpecialtyChemicals company; Halogenated methyl nitrobenzene; And monoacyl phosphine and two acylphosphanes; for example, the compound of by name " IRGACURE 1700 ", " IRGACURE 1800 " of commodity, " IRGACURE 1850 ", " IRGACURE 819 ", " IRGACURE 2005 ", " IRGACURE 2010 ", " IRGACURE 2020 " and " DAROCUR 4265 " (all can available from Ciba Specialty Chemicals company).Can use the combination of two or more light triggers.Furthermore, one or more light triggers (for example, " IRGACURE 369 ") and emulsion (for example, the 2-isopropyl thioxanthone can be available from the FirstChemical company that is positioned at Mississippi, America Pascagoula city) can be used together.

It will be appreciated by those skilled in the art that: coating composition of the present invention can contain other optional auxiliary material, for example, surfactant, antistatic agent (for example, conducting polymer), levelling agent, photosensitizer, ultraviolet ray (" UV ") absorbing agent, stabilizing agent, antioxidant, lubricant, pigment, dyestuff, plastifier, suspending agent etc.Have anlistatig performance if desired, then antistatic agent can be mixed in the coating of any functionality, perhaps antistatic agent is applied as independent layer.

Preferably, described hard coating composition contains and helps the solvent that applies.Though can randomly use fluorated solvent separately or itself and organic solvent are used in combination,, preferably, the composition in the hard coating can be dissolved in the nonfluorinated solvent fully.Therefore, advantageously, hard coating composition is the fluorinated solvent not.Preferred solvent comprises ketone (for example, MEK (MEK), methyl isobutyl ketenes (MIBK) and methyl propyl ketone (MPK)) and the acetic acid esters (for example, ethyl acetate) can obtain to expect that the concentration (for example, solid content is 2% to 3%) of coating thickness is used.Usually adding again after aforesaid auxiliary material is dissolved in the solvent arbitrarily.

Hard coating composition easy to clean does not contain hydrophilic composition (for example, monomer) usually, and this is to tend to reduce pollution resistance and can pollute certain class medium (for example, substrate) because contain specific examples of such components.In addition, hydrophilic composition also degraded easily after being exposed to water-based cleaner.

Following examples will further specify objects and advantages of the present invention, but described in these embodiments certain material and consumption thereof, and other condition and details should not be regarded as and be used for excessively limiting the present invention.

Embodiment

Test method

1. contact angle-before the contact angle of testing coating and water and hexadecane, elder generation stirs coating cleaning 1 minute with hand in IPA.(this deionized water passes through filtration system filters to adopt direct SILVER REAGENT hexadecane (Aldrich company) that uses and deionized water, wherein said filtering system derives from the Millipore company that is positioned at Massachusetts, United States Billerica city), on video contact angle analyser, test, this video contact angle analyser can be available from the AST Products company that is positioned at Massachusetts, United States Billerica city, and production number is VCA-2500XE.The numerical value of record is the mean value of test data that at least three samples are measured in its left and right sides separately, and this value is shown in Table 2.During the tested static contact angle, the volume of every sample is 5 μ L; When test advancing contact angle and receding angle, the volume of every sample is 1-3 μ L.For hexadecane, only write down advancing contact angle and receding contact angle, this is because of having been found that its static contact angle value and advancing contact angle value are almost equal.

2. endurancing-with respect to the coating direction the coated film tablet in a lateral direction, mechanical hook-up with the steel wool that can swing back and forth, in the wearing quality of whole film surface test cured film of the present invention, wherein steel wool is fixed together by rubber sheet gasket and contact.Contact is swept in the width in the wide wiping of 10cm with the speed of wiping 3.5 p.s. and is swung back and forth, and wherein " wiping is swept " once is meant one way 10cm.Contact is flat, columniform geometry, and its diameter is 6mm.Described device is equipped with platform, is placed with counterweight on this platform, to increase the power that contact applies perpendicular to the film surface.Steel wool derives from the Rhodes-American branch that is positioned at Washington state Bellingham city HomaxProducts company, and commodity are called " #0000-Super-Fine ", and can directly use.All a single sample is tested among each embodiment, and be recorded in the counterweight grammes per square metre that puts on contact in the process of the test and the wiping of being carried out and sweep number of times.

3. mist degree and transmittance-employing BYK Gardner mist degree-transparency-transmittance tester is measured the mist degree and the light transmittance values of coated film.With measured value with percentile form record.

Composition

F (CF (CF ₃) CF ₂O) _aCF (CF ₃) COOCH ₃, wherein a average out to is about 6.3, and mean molecular weight is 1, and 211g/ mole, this compound can be according to U.S. Patent No.s 3,250, and 808 people such as () Moore reported method is prepared, and adopts fractionating process to purify.

Trimethylolpropane triacrylate (" TMPTA ") derives from the Sartomer company that is positioned at Pennsylvania, America Exton city, and commodity " SR351 " by name (AC-1).

Acrylic acid ω-hydrogen 2,2,3,3,4,4,5,5-octafluoro pentyl ester (H-C ₄F ₈-CH ₂O-C (O)-CH=CH ₂), derive from the Oakwood Products company that is positioned at South Carolina, United States WestColumbia city.

The N-methyl isophthalic acid, 3-propane diamine, 2-amino-2-ethyl-1, ammediol and 2-amino-1, ammediol all derives from the Sigma-Aldrich company that is positioned at Wisconsin, USA Milwaukee city.

Acryloyl chloride derives from Sigma-Aldrich company.

Used UV light trigger derives from the CibaSpecialty Products company that is positioned at New York, United States Terrytown city, and commodity are called " Darocur 1173 ".

" hard coating composition of nonfluorinated " that use among the embodiment is according to U.S. Patent No. 5,677, and the 10th hurdle 25-29 is capable and embodiment 1 described method preparation among 050 people such as () Bilkaldi.

Hereinafter described the preparation method of the diaphragm with double-deck hard conating, described double-deck hard conating comprises the hard conating easy to clean that is arranged on the nonfluorinated hard conating, and wherein, described nonfluorinated hard conating is set on the lower transparent substrates of mist degree.

1. prepare initiation material HFPOC (O)-NH-CH ₂CH ₂-OH (that is, HFPO-AE-OH)

(the Mw=1211g/ mole 50.0g) places the 200ml round-bottomed flask with HFPO-C (O) OCH3.Use the nitrogen purging flask, and flask is placed in the water-bath, thereby make its temperature remain 50 ℃ or lower.The 2-ethylaminoethanol (deriving from Aldrich company) that in this flask, adds 3.0g (0.045 mole).With reaction mixture stir about 1 hour, the infrared spectrum of the reaction mixture of Ce Lianging showed after this: 1790cm ^-1The methyl esters bands of a spectrum at place thoroughly disappear, and at 1710cm ^-1There is the strong flexible peak of the carbonyl of acid amides in the place.(MTBE 200ml) be added in the potpourri of reaction gained, and water/HCl (about 5%) carries out twice extraction to organic phase, and then removes unreacted amine and methyl alcohol with methyl tert-butyl ether.Use MgSO ₄Dry MTBE layer.Under reduced pressure, remove MTBE, the viscous liquid that obtains clarifying. ¹H nuclear magnetic resoance spectrum (NMR) and infrared spectrum (IR) confirm that titled reference compound generates.

Preparation simple function perfluoropolyether acrylate (FC-1)

HFPO-C(O)N(H)CH ₂CH ₂OC(O)CH＝CH ₂(HFPO-AEA)

HFPO-AE-OH (600g) is mixed in the three neck round-bottomed flasks that are equipped with mechanical stirrer, reflux condenser, charging hopper and hose adapter (being connected with source nitrogen) with triethylamine (57.9g) with ethyl acetate (600g).Under nitrogen atmosphere, stir the gained potpourri, and be heated to 40 ℃.Acryloyl chloride (51.75g) was added drop-wise to the described flask from charging hopper in about 30 minutes.The stirring under 40 ℃ of gained potpourri is spent the night.Then, this potpourri is cooled to room temperature, dilutes this potpourri with the 2N HCl aqueous solution of 300ml, and it is moved in the separating funnel.Remove the water-bearing zone, the 2N HCl with another part 300ml extracts ethyl acetate layer again.Then, with the NaHCO of 5 weight % ₃The aqueous solution extraction organic phase is once separated this organic phase, uses MgSO ₄Drying, and filter.Remove volatile ingredient with Rotary Evaporators, obtain 596g product (productive rate is 93%). ¹H NMR and IR spectrum confirm that titled reference compound generates.

2. prepare initiation material HFPOC (O)-NH-CH ₂CH ₂-O-CH ₂CH ₂-OH (that is, HFPO-AEE-OH)

With HFPO-C (O) OCH ₃(the Mw=1211g/ mole 51.0g) places the 200ml round-bottomed flask.Use the nitrogen purging flask, and flask is placed in the water-bath, thereby make its temperature remain 50 ℃ or lower.The 2-amino ethoxy ethanol (deriving from Aldrich company) that in this flask, adds 5.35g (0.045 mole).With reaction mixture stir about 1 hour, the infrared spectrum of the reaction mixture of Ce Lianging showed after this: 1790cm ^-1The methyl esters bands of a spectrum at place thoroughly disappear, and at 1710cm ^-1There is the strong flexible peak of the carbonyl of acid amides in the place.Methyl tert-butyl ether (200ml) is added in the reaction mixture, and water/HCl (about 15%) carries out twice extraction to organic phase, to remove unreacted amine and methyl alcohol.MTBE is also laminated, and use MgSO ₄Dry.Under reduced pressure, remove MTBE, the viscous liquid that obtains clarifying.Under room temperature and 0.1mmHg pressure,, obtain 48g product (productive rate is 90%) with gained liquid further dry 16 hours.

¹H NMR and IR spectrum confirm that titled reference compound generates.

Preparation simple function perfluoropolyether acrylate (FC-2)

HFPO-C(O)N(H)CH ₂CH ₂OCH ₂CH ₂OC(O)CH＝CH ₂

HFPO-AEE-OH (25g) is mixed in the three neck round-bottomed flasks that are equipped with mechanical stirrer, reflux condenser, charging hopper and hose adapter (being connected with source nitrogen) with triethylamine (5g) with ethyl acetate (200g).Under nitrogen atmosphere, stir the gained potpourri, and be heated to 40 ℃.Acryloyl chloride (5.5g) was added drop-wise to the described flask from tap funnel in about 30 minutes.The stirring under 40 ℃ of gained potpourri is spent the night.Then, this potpourri is cooled to room temperature, dilutes this potpourri with the 2N HCl aqueous solution of 300ml, and it is moved to charging hopper.Remove the water-bearing zone, use the 2N hcl as extraction agent ethyl acetate layer of another part 300ml again.Then, with the NaHCO of 5 weight % ₃The aqueous solution extraction organic phase is once separated this organic phase, uses MgSO ₄Drying, and filter.Remove volatile ingredient with Rotary Evaporators, obtain product. ¹H NMR and IR spectrum confirm that titled reference compound generates.

3. prepare initiation material Perfluoropolyether amide-amine

HFPO-C(O)N(H)CH ₂CH ₂CH ₂N(H)CH ₃

In 1 liter round-bottomed flask, add 291.24g (0.2405 mole) HFPO-C (O) OCH that all is under the room temperature ₃(that is, Mw 1211g/ mole) and 21.2g (0.2405 mole) N-methyl isophthalic acid, the 3-propane diamine obtains turbid solution.Rotate flask, the temperature of solution is increased to 45 ℃, obtains water white liquid, with this liquid 55 ℃ of following heated overnight.Then this solution is placed on the Rotary Evaporators, remove methyl alcohol under the condition of 75 ℃ and 28 inches Hg vacuum, generate the light yellow viscous liquid of 301.88g (99%), it is 98% titled reference compound that this liquid is characterized as being purity by the NMR method.

Preparation multifunctional perfluoro-polyether acrylate (FC-3)

Mol ratio is 1: 1 HFPO-C (O) N (H) CH ₂CH ₂CH ₂N (H) CH ₃Mike's that addition compound product with TMPTA

In the round-bottomed flask of 250mL, add 4.48g (15.2 mMs are 294 nominal MW based on value) TMPTA, 4.45g tetrahydrofuran (THF) and 1.6mg phenothiazine (deriving from Sigma-Aldrich company), and this flask is placed 55 ℃ oil bath.Then, in the bottle of 100mL, with 20g (15.78 mMs, Mw are 1267.15) HFPO-C (O) N (H) CH ₂CH ₂CH ₂N (H) CH ₃Be dissolved among the 32g THF.This solution is placed on 60mL to have in the tap funnel of the side arm that equalized pressure uses, clean this bottle (washing lotion also joins in the tap funnel) with about 3ml THF, then, under air atmosphere, the material in the funnel was joined in the potpourri of TMPTA/THF/ phenothiazine in 38 minutes.Reactant is muddy at first, but becomes clarification after about 30 minutes.After 20 minutes after finishing dropwise operation, it is on 28 inches the Rotary Evaporators that reaction flask is placed 45-55 ℃, vacuum tightness, generates the viscosity yellow liquid of 24.38g clarification, and this liquid can be characterized by titled reference compound by NMR and HPLC/ mass spectrum.

4. prepare initiation material HFPO-C (O) N (H) C (CH ₂OH) ₂CH ₂CH ₃

The H that in 500ml is equipped with the three-neck flask of stirring rod, reflux condenser and heating bath, adds 11.91g (0.1 mole) ₂NC (CH ₂OH) ₂CH ₂CH ₃(deriving from Sigma-Aldrich company) and 60g THF.Then, under the heating bath temperature is about 85 ℃ condition, in about 80 minutes, add HFPO-C (O) OCH of 121.1g (0.1 mole) through tap funnel ₃Reactant is muddy at first, but after about 1 hour of reaction, reactant becomes clarification.Behind reinforced the end, close heating bath, and make reactant cooling 3 days.Under 55 ℃, forming by aspirator under the condition of vacuum, concentrate above-mentioned material, generate 130.03g light color slurry.NMR the analysis showed that this product is works I: the mixing ratio of works II is 87: 13 a potpourri, and described works I and works II are as follows:

Preparation multifunctional perfluoro-polyether acrylate

HFPO-C(O)N(H)C(CH ₂OC(O)CH＝CH ₂) ₂CH ₂CH ₃(FC-4)

In being equipped with three neck round-bottomed flasks of cantilevered stirrer, 250ml adds 65g (0.05 mole) HFPO-C (O) N (H) C (CH ₂OH) ₂CH ₂CH ₃(product mixtures of above generation), 12.65g (0.125 mole) triethylamine and 65g ethyl acetate.At room temperature, working pressure balanced type tap funnel added 11.31g (0.125 mole) acryloyl chloride in the described flask in 12 minutes, and temperature of reaction rises to 40 ℃ of maximum temperatures from 25 ℃.Clean described tap funnel with the extra ethyl acetate of 5g again, and washing lotion is joined in the described reactant, place 40 ℃ heating bath then, it was reacted 2 hours 10 minutes again.Subsequently, organic layer is used 65g 2% aqueous sulfuric acid, 65g 2% sodium bicarbonate aqueous solution and 65g water washing successively, use anhydrous magnesium sulfate drying, filter, handle, concentrate down at 45 ℃ with Rotary Evaporators again with 16mg methoxyl quinhydrones (MEHQ); Obtain the 62.8g crude product at last.Then, use ethyl acetate: heptane be 25: 75 potpourri as eluent, (SX0143U-3,62 grades, the 60-200 order, EM Science company produces) goes up the 35g above-mentioned material carried out chromatographic resolution at 600ml silica gel.The volume of two initial fractions is 250ml, and the volume of all the other fractions is 125ml.Fraction 4-10 is mixed, 8mg MEHQ is added in this fraction potpourri, gains are concentrated under 55 ℃ with Rotary Evaporators then, obtain the 25.36g product, NMR analyzes and finds that products therefrom is works III: works IV is 88: 12 a potpourri.

5. prepare initiation material HFPO-C (O) N (H) C (CH ₂OH) ₂H

Adopt (CH with preparation HFPO-C (O) N (H) C ₂OH) ₂CH ₂CH ₃Identical method makes 106.74g (0.088 mole) HFPO-C (O) CH ₃And 8.03g (0.088 mole) 2-amino-1, ammediol reacts in 51g THF, and generate amide diol: the ester amino alcohol is 93: 7 a product.

Preparation multifunctional perfluoro-polyether acrylate (FC-5)

HFPO-C(O)N(H)C(CH ₂OC(O)CH＝CH ₂) ₂H

Adopt (CH with preparation HFPO-C (O) N (H) C ₂OC (O) CH=CH ₂) ₂CH ₂CH ₃Identical method makes 50g (0.3936 mole) HFPO-C (O) N (H) C (CH ₂OH) ₂H and 8.55g (0.0945 mole) acryloyl chloride and 9.56g (0.946 mole) triethylamine react in 100g ethyl acetate, and in the reaction end and through after the chromatographic resolution, obtain diacrylate: the acrylamide and acrylic acid ester is 93: 7 a potpourri.

The preparation of coating solution:

Use the polymerisable compound coated substrates, this polymerisable compound has used table 1A and listed material and the weight percent of 1B.All polymerizable components are diluted to the solution that solid amount is 10 weight % in MEK.By using solid content is the methyl ethyl ketone solution of 10% light trigger, is that the light trigger Darocure 1173 of 2 weight % adds in the described polymerisable compound with solid content.Before mixture diluted is become the coating solution of ultimate density, add above-mentioned light trigger.Use methyl isobutyl ketone, mixture diluted is become described solid concentration (that is, 2 weight % or 2.5 weight %).The final solid concentration that is used for the coating solution of each embodiment is listed among table 1A and the 1B.

Coating, drying and solidification process

Substrate is polyethylene terephthalate (PET) hyaline membrane (derive from the E.I.DuPontde Nemours and Company company that is positioned at Delaware, USA Wilmington city, commodity are called " the Melinex 618 ") preparation on 5.0 mils and the surface with process primary coat by thickness.The hard coating composition of nonfluorinated is coated in described, and it is lower than in the 50 parts/UV chamber of per 1,000,000 parts (ppm) at oxygen content solidify through on the surface of primary coat.600 watts of H type lamps of working are equipped with in this UV chamber under full power, this lamp derives from the Fusion UV systems company that is positioned at Maryland, USA Gaithersburg city.

Adopt gageable accurate die head coated technique with hard applying coating easy to clean on Melinex 618 films.Hard coating easy to clean is diluted to solid content in IPA be 30 weight %, and it is coated on the PET backing of 5 mil thick, and obtaining dry state thickness is 5 microns.The flow velocity by the material that flows out in the pressure vessel is monitored and set to the use traffic meter.Regulate flow velocity by the air pressure that changes in the sealing container, the air pressure in the wherein said airtight container orders about liquid and flows out the back by pipeline, filtrator, flowmeter, passes through die head then.The cured film of dry state is wound on the take up roll, and used as the charging backing of coating solution described below.

The coating and the drying parameter of coating easy to clean are as follows:

Application width: 6 inches (15cm)

Web speed: 30 feet (9.1m)/minute

Solution solid content %:30.2%

Filtrator: 2.5 microns (absolute value)

Head tank: capacity is 1.5 gallons (5.7 liters)

Flow velocity: 35g/ minute

The thickness of wet coating: 24.9 microns

The thickness of dry coating: 4.9 microns

Conventional oven temperature: 1 district, 140  (60 ℃)

2 districts, 160  (53 ℃)

3 districts, 180  (82 ℃)

Baking oven length: 10 feet (3m)

Table 1A-contains the coating formulation that PFPE (methyl) acrylate is fluoridized composition (solid weight %)

Embodiment	Coating solution (solid weight %)	AC-1	FC-1	FC-3	FC-6	Substrate
							1a	2	90	2		8	S-1
2a	2	85	5		10	S-1
							4a	2.5	85		10	5	S-1
7a	2.5	85	5	5	5	S-1
							8a	2.5	90		10		S-1
9a	2.5	95	5			S-1

Table 1B-contains the coating formulation that PFPE (methyl) acrylate is fluoridized composition (solid weight %)

Embodiment	Coating solution (solid weight %)	AC-1	FC-1	FC-2	FC-5	FC-4
							16a	2.5	95				5
19a	2.5	95			5
							20a	2	85		5	10FC-6 (replacing FC-5)

The test of table 2-contact angle

Embodiment	Contact angle (degree) with water			Contact angle with hexadecane		Mist degree before the test	Transmissivity before the test
									Static contact angle	Advancing contact angle	Receding contact angle	Advancing contact angle	Receding contact angle
1a	98	108	76	51	39	0.22	93.1
								2a	106	119	92	63	55	0.53	92.5
4a	102	115	74	63	53	0.69	96
								7a	107	119	86	67	58	0.55	99.6
8a	103	115	75	64	54	0.94	99.4
								9a	104	115	88	60	51	0.56	99.6
16a	108	118	97	65	59	0.54	99.6
								19a	106	119	96	65	57	0.46	99.6
20a	105	118	91	63	54	0.28	93.2

Table 3-steel wool endurancing result

		Initially		After the endurancing
						Embodiment	Number of times is swept in wiping	Ink repellent has/does not have	The printing ink beading is/denys	Ink repellent has/does not have	The printing ink beading is/denys
2a	500	Have	Be	Have	Be
						4a	500	Have	Be	Have	Be
7a	50	Have	Be	Have	Be
						8a	100	Have	Be	Have	Be
9a	500	Have	Be	Have	Be
						16a	500	Have	Be	Have	Be
19a	500	Have	Be	Have	Be
						20a	500	Have	Be	Have	Be

All use the counterweight of 200g for all steel wool endurancings

Test findings shows that the diaphragm goods have the enough low mist degree that is adapted at using on the multiple inner member.

Use the PFPE urethane acrylate to become to assign to repeat the identical general process that preparation has the diaphragm of nonfluorinated hard conating (being set in the substrate) and hard conating (being set on the hard conating of nonfluorinated) easy to clean as fluoridizing.

Preparation PFPE polyurethane (methyl) acrylate

In being equipped with two neck round-bottomed flasks of magnetic stirring bar, 500ml adds 25.00g (0.131 equivalent, 191EW) Des N100,26.39g (0.0196 equivalent, 1344EW) F (CF (CF ₃) CF ₂O) _6.85CF (CF ₃) C (O) NHCH ₂CH ₂OH and 109.62g MEK, and rotate this flask, thus produce uniform solution.Flask is placed 80 degrees centigrade heating bath, add two dibutyltin dilaurate catalysts, and condenser is installed.Reactant is muddy at first, but becomes clarification in two minutes.In the time of about 1.75 hours, flask is taken out from heating bath, and add the solvent of 2.42g MEK with replenish lost.In flask, take out the 2.0g sample, the reactant of residue 1-(2.0/161.01) or 0.9876 weight portion, and 57.51g (58.23g 98.76%) (0.116 mole, 494.3 equivalents) PET3A joined in the reactant in the heating bath that is placed on 63 degrees centigrade.In the time of about 5.25 hours, FTIR measures and shows at 2273cm ^-1Place's isocyanate-free absorption peak, and add 0.56g MEK, with the solvent of replenish lost, be 50% thereby make the solid content of material.

HFPO AEA (HFPO-C (O) NHCH ₂CH ₂OC (O) CH=CH ₂) prepare in the method described in " preparing simple function perfluoropolyether acrylate (FC-1) " part according to the U.S. Patent application No.10/841159 (submission number) (files No.57927US002) that submitted on May 7th, 2004.

The TMPTA trimethylolpropane acrylates

The die head coating machine of employing accurate measurement is coated to the coating composition of superficial layer on the hard conating.In this step, use syringe pump that the solution metering is transported in the die head.With the concentration of MEK with solution dilution to 1%, and it is coated on the hard conating, the dry state thickness that obtains film is 60nm.Described material after the drying, under condition of nitrogen gas, is made its curing with 600 watts of Fusion systems lamps in the air-flotation type baking oven of routine, condition of cure is as follows:

Application width: 4 inches (10cm)

Web speed: 20 feet per minute clocks

Solution solid content %:10.0%

Pump: 60cc syringe pump

Flow velocity: 1.2cc/ minute

The thickness of wet coating: 4.1 microns

The thickness of dry coating: 60nm

Conventional oven temperature: 1 district-65 ℃

2 districts-65 ℃

The length in two districts is 10 feet (3m).

Table 5-contains the coating formulation that PFPE polyurethane (methyl) acrylate is fluoridized composition (solid weight %)

TMPTA (％)	PFPE polyurethane (methyl) acrylate (%)	HFPO AEA	Darocure 1173	Static contact angle (degree) with water
					95	3.75	1.25	4	100-101
90	7.5	2.5	4
					85	11.25	3.75	4	110-111
80	15	5	4
					90	10		4	93-94
80	20		4	103-104

The result shows that the hard conating that contains the PFPE urethane acrylate shows high contact angle.Though do not measure, think that these hard coating compositions have the enough low mist degree that can use on the optical devices inner member.

Be that 3 inches * 4 inches the polycarbonate of 1mm (can derive from GE company with hard coating composition (solid content the is 47%) flow coat of above-mentioned nonfluorinated to the thickness that is suitable for use as bluff piece by the following method, commodity are called " Lexan ") on the sheet, described method applies for drips of solution is traversed described POLYCARBONATE SHEET, the amount of drop enough makes it cover POLYCARBONATE SHEET, makes composition dries (estimation thickness is about 4 microns) then.Hard coating composition is solidified: use Fusion UV MC6RQN type, H lamp, move and 100% nitrogen protection with the speed of 15 feet per minute clocks.With hard coating composition easy to clean the hard conating of nonfluorinated is carried out flow coat then, described hard coating easy to clean is made of PFPE polyurethane (methyl) acrylate of TMPTA, the 9.6 weight % of 83.7 weight %, the HFPO-AEA of 2.9 weight % and 3.8% Darocure 1173, and should hard coating to be diluted to solid content with IPA be 2.5%.The whole nonfluorinated hard coating surface that again drips of solution is traversed POLYCARBONATE SHEET applies.Make composition dries, composition solidified: use Fusion UVMC6RQN type, H lamp, with the speed of 15 feet per minute clocks move, 100% nitrogen protection and 2 times are by the UV chamber; And then formation estimation thickness is the coating of about 10nm.

Use identical nonfluorinated hard coating used and hard coating easy to clean to apply glass sheet in an identical manner with applying polycarbonate.

From digital camera, take out the photographic lens of camera, and use with the used identical nonfluorinated hard coating composition of polycarbonate and glass sheet and apply.Remove excessive hard coating with brush, carry out dry and solidify under the following conditions then: use Fusion UV MC6RQN type, H lamp, move and 100% nitrogen protection with the speed of 15 feet per minute clocks.Then with in the photographic lens dip-coating with coating polycarbonate used identical hard coating easy to clean; remove excessive coating solution with brush, make coating dry and solidify under the following conditions: use Fusion UV MC6RQN type, H lamp, with the speed of 15 feet per minute clocks move, 100% nitrogen protection and 2 times are by the UV chamber.

Below listed energy (J/cm ²) and power (W/cm ²), these are worth from the A of ultraviolet spectrum portion, B portion, C portion and V portion zone, and be on the Fusion UV system travelling belt that is 15 feet per minute clocks the time with UV energy meter (making) speed of being placed on, write down with this UV energy meter by the EIT company that is positioned at Virginia, USA Sterling city.

The UV Fusion H of system lamp MC6RQN type
	J/cm 2					W/cm 2
A										B	C	V	A	B	C	V
	0.8557	0.7637	0.1007	0.6887		1.378	1.342	0.1573	0.9873

Polycarbonate sheet, glass sheet and lens with surperficial hard conating are tested, found that they have ink repellent.

Claims (37)

1. goods that comprise the optical devices inner member, wherein, described inner member has surperficial hard conating, and this surface hard conating comprises the reaction product of polymerisable compound, and described polymerisable compound contains:

I) at least 0.2 weight % at least a have at least one polymerizable moiety the fluorochemicals composition and

Ii) one or more crosslinking chemicals that can randomly fluoridize of at least 50 weight %.

2. described goods of claim 1, wherein, described inner member is not exposed in the external environment condition after in being assembled into described optical devices.

3. described goods of claim 1, wherein, described crosslinking chemical is a nonfluorinated.

4. described goods of claim 1, wherein, described crosslinking chemical has the part of fluoridizing, and described composition can contain high crosslinking chemical to 100 weight %.

5. described goods of claim 1, these goods also have second hard conating and described surperficial hard conating, and wherein said second hard conating is set between the polymerisable compound and described inner member of described curing.

6. described goods of claim 1, wherein said fluorochemicals composition are selected from simple function and fluoridize composition, multifunctionally fluoridize composition and fluoridize composition and at least a multifunctional potpourri that becomes to be grouped into of fluoridizing by at least a simple function.

7. described goods of claim 1, wherein, described fluorochemicals composition is selected from (entirely) perfluoroalkyl polyether (methyl) acrylate, (methyl) acrylic acid (entirely) fluothane alcohol ester, (methyl) acrylic acid (entirely) fluorohydrocarbon diol ester and their potpourri.

8. described goods of claim 7, wherein, described fluorochemicals composition has at least one acrylate polymerizable moiety.

9. described goods of claim 7, wherein, described fluorochemicals composition comprises PFPE polyurethane (many) acrylate.

10. described goods of claim 7, wherein, described fluorochemicals composition has-the HFPO group.

11. the described goods of claim 1, wherein, described inner member is a blooming, and this blooming is selected from multi-layer optical film, micro-structural film, polarizing coating, diffusion barrier, phase shift films, compensate film, monolithic hyaline membrane.

12. the described goods of claim 11, wherein, described inner member is the wave filter with multilayer film.

13. the described goods of claim 1, wherein, described optical devices are selected from display device, sensing device, imaging device and projection arrangement.

14. the described goods of claim 1, wherein, described inner member is selected from imageing sensor, optical sensor, silicon wafer, interior lens, prism, spectroscope, wave filter, catoptron, polarizer, fan diffuser and compensator.

15. goods that comprise the optical devices inner member, wherein, described inner member has surperficial hard conating, and should the surface hard conating and the static contact angle of water be at least 70 degree.

16. a method of protecting the optical devices inner member, this method comprises:

Surperficial hard conating is set on the optical devices inner member, and wherein, described surperficial hard conating comprises the reaction product of polymerisable compound, and described polymerisable compound contains:

I) at least 0.2 weight % at least a have at least one polymerizable moiety the fluorochemicals composition and

Ii) one or more of at least 50 weight % have the crosslinking chemical of two or more polymerizable moieties.

17. the described method of claim 16, wherein, described method comprises: described polymerisable compound is coated at least one surface of described inner member, and said composition is solidified.

18. the described method of claim 17, wherein, described polymerizable moiety is (methyl) acryloyl group part, and described polymerisable compound is cured by UV radiation.

19. the described method of claim 16 wherein, is coated in described polymerisable compound in the light transmission substrate, and it is solidified, and this coated substrate is combined with described inner member.

20. the described method of claim 1, wherein, be coated in described polymerisable compound in the isolation liner on, and make it partly solidified at least, and this partly solidified at least composition combined with described inner member.

21. the described method of claim 16, wherein, be arranged on described surperficial hard conating in the isolation liner on, and should cut into part by the surface hard conating, so that place it on the described inner member with suitable dimension.

22. a method of assembling optical devices, this method comprises:

The optical devices inner member is assembled, and wherein, at least one inner member has the surperficial hard conating of the reaction product that comprises polymerisable compound, and described polymerisable compound contains:

I) at least 0.2 weight % at least a have at least one polymerizable moiety the fluorochemicals composition and

Ii) one or more of at least 50 weight % have the crosslinking chemical of two or more polymerizable moieties.

23. the sheet material of the element of optical devices; this sheet material comprises diaphragm and a plurality of optical devices element, and described diaphragm has the surperficial hard conating of curing, wherein; described element has at least one distinguishable border, and this element combines with the surperficial hard conating of described curing.

24. the described sheet material of claim 23, wherein, described element disperses.

25. the described sheet material of claim 23, wherein, described element is uneven.

26. the described sheet material of claim 23, wherein, described element is lens.

27. the described sheet material of claim 23, wherein, described element is continuous.

28. the described sheet material of claim 23, wherein, described element is connected to each other by hard conating at least.

29. the described sheet material of claim 23, wherein, described a plurality of elements are to combine with the hard conating of described curing with bonding agent.

30. the described sheet material of claim 23, wherein, described element is an inner member.

31. a method for preparing the described sheet material of claim 19 wherein, by add the described element of thermosetting in the mold of arranging with described diaphragm, makes described a plurality of element combine with the hard conating of described curing.

32. a wavelength selectivity wave filter, this wave filter has:

Absorption layer, this absorption layer comprises the reaction product of following material:

One or more of at least 50 weight % have the crosslinking chemical of two or more polymerizable moieties,

At least 0.5 weight % at least a have the fluorochemicals composition of at least one polymerizable moiety or inorganic particle and

The absorbability composition.

33. the described wave filter of claim 32, wherein, described absorbability composition is colorant or dyestuff.

34. the described wave filter of claim 32, wherein, described absorption layer is set on the reflectivity interference element.

35. an optical devices inner member, this inner member is selected from imageing sensor or silicon wafer, and wherein, described inner member has the surperficial hard conating of the reaction product that comprises the polymerizable binder precursor.

36. the described inner member of claim 35, wherein, described reaction product also comprises inorganic particle.

37. the described inner member of claim 35, wherein, described reaction product also comprises the fluorochemicals composition.