CN101176019A - Light management films with zirconia particles - Google Patents

Light management films with zirconia particles Download PDF

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CN101176019A
CN101176019A CNA200680016313XA CN200680016313A CN101176019A CN 101176019 A CN101176019 A CN 101176019A CN A200680016313X A CNA200680016313X A CN A200680016313XA CN 200680016313 A CN200680016313 A CN 200680016313A CN 101176019 A CN101176019 A CN 101176019A
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zirconia particles
light management
management films
zirconia
methyl
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克林顿·L·琼斯
埃米莉·S·根纳
戴维·B·奥尔森
布兰特·U·科尔布
约翰·T·考赫
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3M Innovative Properties Co
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3M Innovative Properties Co
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Abstract

Light management films and methods of making light management films are described. The light management films contain an optical layer having a microstructured surface that contains polymeric material and zirconia particles. The zirconia particles are colloidal, crystalline, substantially non-associated, and have a narrow size distribution.

Description

Light management films with zirconia particles
Technical field
The present invention relates to the method that light management films and preparation contain the light management films of zirconia particles.
Background technology
The optical articles of some microstructure, as be described in the following United States Patent (USP) those:
5,175,030 (Lu etc.), 5,183,597 (Lu), 5,917,664 (O ' Neill etc.), 5,919,551 (Cobb, Jr. etc.), 6,111,696 (Allen etc.), 6,280,063 B1 (Fong etc.), 6,356,39 B1 (Gardiner etc.) can be called structurized optical thin film or light management films.Light management films can comprise, for example, brightness enhancement film, reflectance coating, turning film, or the like.These light management films have various uses.For example, brightness enhancement film can be used in the electronic product to improve the brightness of backlight type flat-panel monitor, as the LCD (LCD) that comprises in electroluminescent cell, portable computer display, word processor, desktop monitor, handheld device, TV, video camera and automobile and the aviation display.
Resulting luminance gain when the refractive index of material usually is used for the backlight type display with this film in the brightness enhancement film (, ＂ gain ＂) is relevant.Thereby the brightness that improves makes electronic product more effectively to operate with a bright display by using energy still less.More lower powered use usually can reduce power consumption, can reduce the thermal load on the electronic component, and can prolong the serviceable life of electronic product.Brightness enhancement film usually contains the polymeric material of high index of refraction (for example, at least 1.4).
The microstructure that is included in the light management films can be a various forms, as the form with a series of projectioies that replace and groove.In some instances, light management films have the projection of symmetry and the rule of groove, repetitive pattern.In other examples, light management films has asymmetric projection and groove.The size of projection and groove, orientation or between distance can be uniform or uneven.
The defective of some existing light management films is: the projection of microstructure is to the mechanical damage sensitivity.For example, the light scraping that causes with nail or hard, sharp-pointed relatively corner all can make the projection fracture or the fragmentation of microstructure.The condition of projection fracture can appear being enough to cause in the course of normal operation of light management films.For example, the projection of brightness enhancement film can rupture in manufacturing contains the process of LCD of such film.
If the projection of microstructure fracture, the reflection of affected projection and refractive properties reduce and transmitted light can be with the scattering of nearly all advancing angle direction.If described light management films is the brightness enhancement film on the display, and display is line-of-sighted observation, the zone of then containing scratch in the light management films is lower than the brightness of not affected area periphery, brightness enhancement film.But, if with near or greater than cutoff angle (that is) angle observation display, the no longer visible angle of the image on the display, the described zone of containing scratch look that basically the not affected area of the film of periphery is brighter.Under two kinds of situations, see that from viewpoint attractive in appearance scratch all is harmful to.For the occasion of in some displays such as LCD, using, comprise more than a little, the brightness enhancement film of a small amount of scratch may be unacceptable.
General introduction
The invention provides the method for the goods that goods with microstructure and preparation have microstructure.More particularly, described goods with microstructure contain zirconia particles.Described zirconia particles is colloidal state (for example, less than 100 nanometers), crystallization, and be non-association basically.Described goods with microstructure can be light management films as, for example, brightness enhancement film, reflectance coating, turning film, or the like.
In first aspect, a kind of light management films that contains optical layers is provided, described optical layers comprises the surface with microstructure.Described optical layers contains the zirconia particles of polymeric material and a plurality of surface modifications.Described zirconia particles contains 0.1 to 8wt% yttrium, based on the weight meter of inorganic oxide in the zirconia particles.In addition, described zirconia particles mean primary particle size is not more than 30 nanometers, and dispersion coefficient is 1 to 3, and the ratio of intensity particle mean size and volume average particle sizes is not more than 3.0, and at least 70% of crystal structure is a cubic system, tetragonal crystal system, or its combination.
In addition, the method for preparing light management films has been described.First method comprises: zirconia sol is provided, it contains the zirconia particles that is dispersed in aqueous phase, modification is carried out to form the zirconia particles of surface modification in the surface of zirconia particles, preparation contains the zirconia particles of described surface modification and the coating composition of organic substrate, make coating composition contact, and make the coating composition polymerization comprise the optical layers on surface with formation with microstructure with little facility that duplicate.The preparation method of zirconia sol is: preparation contains first raw material of zirconates, make first raw material contain zirconium intermediate and accessory substance with formation through first hydrothermal treatment consists, by removing at least a portion first hydrothermal treatment consists accessory substance forming second raw material, and make second raw material through second hydrothermal treatment consists.
The second method of preparation light management films comprises: the zirconia sol that contains the zirconia particles that is dispersed in aqueous phase is provided, modification is carried out to form the zirconia particles of surface modification in the surface of zirconia particles, preparation contains the zirconia particles of described surface modification and the coating composition of organic substrate, make coating composition contact, and make the coating composition polymerization comprise the optical layers on surface with formation with microstructure with little facility that duplicate.Described zirconia sol comprises such carboxylic acid, and it contains and is no more than four carbon atom and is substantially free of the polyether carboxylic acid.Described zirconia particles mean primary particle size is not more than 50 nanometers, and dispersion coefficient is 1 to 5, and the ratio of intensity particle mean size and volume average particle sizes is not more than 3.0, and at least 50% of crystal structure is cubic system tetragonal crystal system or its combination.In the embodiment of some zirconia sols, zirconia particles contains 0.1 to 8wt% yttrium, based on the weight meter of inorganic oxide in the zirconia particles, and has crystal structure, and wherein at least 70% is cubic system, tetragonal crystal system or its combination.
When being used for this paper, ＂ of term ＂ and the described ＂ of ＂ and at least one ＂ of ＂ are used interchangeably to represent one or more described elements.
When being used for this paper, term ＂ association ＂ refers to the group that two or more primary particles are assembled and/or are condensed into.Similarly, the non-associated ＂ of term ＂ refers to two or more groups that do not have the primary particle of gathering and/or agglomeration.
When being used for this paper, the ＂ that term ＂ gathering ＂ or ＂ assemble refers to the strong association between the primary particle.For example, primary particle may be chemical bonding to each other.The broken ring of aggregation become granule (for example, primary particle) more normally is difficult to realize.Similarly, the ＂ of the non-gathering of term ＂ refers to not and the strong primary particle that associates of other primary particles.
When being used for this paper, the ＂ of term ＂ agglomeration ＂ or ＂ agglomeration refers to the weak association of primary particle.For example, primary particle may combine by electric charge or polarization.The broken ring of agglomerate is become more granule (for example, primary particle) aggregation is broken to that more granule is more easy.Similarly, the ＂ of the non-agglomeration of term ＂ refer to not with other primary particles a little less than the primary particle that associates.
When being used for this paper, term ＂ light management films ＂ refers to have the goods of the micro-structure surface that the repetitive pattern by the projection of rule and groove constitutes, and described projection and groove can be symmetry or asymmetric.The size of described projection and groove, orientation or between distance can be uniform or uneven.Light management films is selected from brightness enhancement film, reflectance coating or turning film (turning film) usually.Light management films is further described in, in for example following United States Patent (USP): 5,175,030 (Lu etc.), 5,183,597 (Lu), 5,771,328 (Wortman etc.), 5,917,664 (O ' Neill etc.), 5,919,551 (Cobb, Jr. etc.), 6,111,696 (Allen etc.), 6,280,063 B1 (Fong etc.), 6,356,39 B1 (Gardiner etc.).
When being used for this paper, term ＂ fluid dynamics particle diameter ＂ refers to the volume average particle size that zirconia particles uses described method to measure by photon coherent light spectroscopy (PCS) herein in liquid phase.
When being used for this paper, the ＂ of term ＂ hydro-thermal refers to such method, and it is paramount in the temperature of described aqueous medium normal boiling point wherein to add the hot aqueous medium in closed container, and pressure is equal to or greater than and prevents the described aqueous medium needed pressure that seethes with excitement.
When being used for this paper, term ＂ refraction coefficient ＂ or ＂ refraction coefficient ＂ refer to that () absolute index of refraction for example, organic substrate or coating composition, it is the electromagnetic radiation speed in a vacuum and the ratio of electromagnetic radiation speed in the material of being concerned about to material.Described electromagnetic radiation is a white light.Use the Abbe refractometer to measure refractive index, can derive from, for example, Pittsburgh, the Fisher Instruments of PA.Being determined at of refraction coefficient may be depended on employed concrete refractometer in a way.
When being used for this paper, term ＂ (methyl) acrylate ＂ refers to acrylate and methacrylate compound simultaneously.
When being used for this paper, term ＂ has the ＂ of microstructure or the surface that ＂ microstructure ＂ refers to have uncontinuity, depart from the protrusion that passes the average centerline that microstructure draws and recessed as seeing from section, thereby the area sum that surface profile surrounded that is higher than described center line equal under the line area and, described line is arranged essentially parallel to the nominal surface (having microstructure) of described goods.The height that departs from is at least 0.005 micron usually, and at least 0.01 micron, or at least 0.1 micron.The height that departs from is no more than 750 microns usually, is no more than 500 microns, is no more than 400 microns, is no more than 200 microns, or is no more than 100 microns.Some surface structures have a plurality of parallel longitudinal ridges, and its length or Width that is prolonging film extends.The height of ridge disalignment about 0.1 is to about 100 microns.These ridges may form the projection alternately and the pattern of groove, and it can be symmetry or asymmetrical.The size of projection and groove, orientation or between distance can be uniform or uneven.Have in the surface of microstructure at some, ridge can form by a plurality of prisms are top.These are top can be sharp keen, and circle flattens, or truncation.
When being used for this paper, the little facility ＂ that duplicates of term ＂ refers to such facility, and it is used in the surface that generation has microstructure in the polymeric material.Described little facility that duplicate have microstructure, and it contacts simultaneously by little composition that duplicates facility and polymerisable composition, polymerization or both and is replicated.Little surface of duplicating facility is negativity for polymeric material for the surface with microstructure that forms in duplicating.
When being used for this paper, term ＂ organic substrate ＂ refers to each organic substance and comprises, for example, monomer, oligomer, polymkeric substance, solvent, crosslinking chemical, initiating agent, or the like.Described organic substrate can comprise the combination of these compositions.
When being used for this paper, the ＂ of term ＂ polymkeric substance ＂ or ＂ polymerization or ＂ polymeric material ＂ are meant the material of preparing by one or more monomer reactions.That is, this term can refer to homopolymer, multipolymer, and terpolymer.When being used for this paper, term ＂ polymerization ＂ refers to from one or more monomers, oligomer, or its potpourri forms the reaction of polymeric material.
When being used for this paper, term ＂ polymerisable composition ＂ refers to such composition, and it comprises can carry out polyreaction to form monomer, oligomer or its potpourri of polymeric material.Polymerisable composition is the subclass of organic substrate.
When being used for this paper, term ＂ primary particle particle diameter ＂ refers to the particle diameter of non-associated monocrystalline zirconia particles.X-ray diffraction (XRD) is commonly used to measure the primary particle particle diameter, and measuring method is as described herein.
When being used for this paper, term ＂ colloidal sol ＂ refers to dispersion or the suspending liquid of colloidal particles in liquid phase (for example, aqueous medium).Particle in the colloidal sol is non-agglomeration usually, non-gathering, or its combination.
When being used for this paper, term ＂ zirconia ＂ refers to zirconic various stechiometry, is typically referred to as ZrO most 2, also can be called as zirconia or zirconium dioxide.Zirconia may contain up to other chemicals part of 30wt% as, for example, yttria and organic substance.
The above-mentioned summary of the present invention does not plan to describe each disclosed embodiment or each embodiment of the present invention.Accompanying drawing subsequently, detailed Description Of The Invention and embodiment will more specifically illustrate these embodiments.
Description of drawings
With the detailed description of following each embodiment of the present invention, can understand the present invention more completely in conjunction with the accompanying drawings, wherein:
Fig. 1 is the representative X-ray diffractogram of exemplary zirconia particles;
Fig. 2 is the synoptic diagram of the exemplary light management films with microstructure on backlight liquid crystal displays;
Fig. 3 is the skeleton view with exemplary light management films of microstructure;
Fig. 4 is the cut-open view with exemplary light management films of microstructure, and its prism elements has different height;
Fig. 5 is the cut-open view with exemplary light management films of microstructure, and its prism elements has different height;
Fig. 6 is the cut-open view with exemplary light management films of microstructure;
Fig. 7 is the cut-open view with exemplary light management films of microstructure, and its prism elements has different height and its basis is in the different planes;
Fig. 8 is the cut-open view with exemplary light management films of microstructure;
Fig. 9 is the cut-open view with exemplary light management films of microstructure;
Figure 10 is the cut-open view with exemplary light management films of microstructure;
Figure 11 is the synoptic diagram that contains the lighting device of exemplary turning film;
Figure 12 is the cut-open view of exemplary turning film; And
Figure 13 is the cut-open view of another exemplary turning film.
The present invention can accept various modifications and alternative form, and mode is shown in the drawings and will describe in detail by way of example for its details.But, should be appreciated that its purpose is not that the present invention is limited to described specific embodiment.On the contrary, described purpose comprises all modifications, and as long as equivalent, and replacement scheme are its essence according to the invention and scope.
Detailed Description Of The Invention
The invention provides goods such as light management films with microstructure, it contains zirconia particles.Described zirconia particles is colloidal state (for example, less than 100 nanometers), crystallization, and non-associated basically.Described zirconia particles can improve the refraction coefficient of light management films, can improve the durability of light management films, or its combination.The canonical form of described light management films has brightness enhancement film, reflectance coating, turning film or the like.
In first aspect, the invention provides the light management films that contains optical layers, described optical layers comprises a surface with microstructure.Described optical layers contains the zirconia particles of polymeric material and a plurality of surface modifications.Described zirconia particles contains 0.1 to 8wt% yttrium, based on the weight meter of inorganic oxide in the zirconia particles.In addition, described zirconia particles mean primary particle size is not more than 50 nanometers, and dispersion coefficient is 1 to 3, and the ratio of intensity particle mean size and volume average particle sizes is not more than 3.0, and at least 70% of crystal structure is a cubic system, tetragonal crystal system, or its combination.
Have the light management films of zirconia particles and compare, have higher refraction coefficient usually with the light management films that only contains polymeric material.In some embodiments, light management films is a brightness enhancement film.In other embodiments, light management films is reflectance coating or turning film.
Described zirconia particles contains yttrium, and it usually exists with the yttria form.The scope of yttrium content is 0.1 to 8wt%, based on the weight meter of inorganic oxide in the zirconia particles.For example, the amount of yttrium can be within following scope: 0.5 to 8wt%, and 1 to 5wt%, or 1 to 4wt%, based on the weight meter of inorganic oxide in the zirconia particles.
Except that inorganic oxide, described zirconia particles usually contains some organic substances at least.Described organic substance can be attached to the surface of zirconia particles and usually derive from the negative ion of the precursor solution salt that is used for preparing zirconia particles.Described zirconia particles usually contains up to 15wt%, up to 12wt%, and up to 10wt%, up to 8wt%, or up to the organic substance of 6wt%, based on the weight meter of particle.
Described zirconia particles is a crystalline state.The more unbodied zirconia of the zirconia of crystallization is easy to have higher refraction coefficient.Since be difficult to when using X-ray diffraction to characterize fine texture respectively to cube and tetragonal crystal quantitatively (, the peak, (111) peak usually zirconic with tetragonal crystal system (101) of cubic zirconia overlaps), these two kinds of crystal structures are combined.For example, 2 θ that are combined in the X-ray diffractogram shown in Figure 1 at these two peaks appear at about 30.5 degree.At least 70% zirconia particles has cubic structure, tetragonal structure, or its combination, and all the other are monoclinic system.For example, in some zirconia samples, at least 75%, at least 80%, or at least 85% zirconia particles has cubic crystal structure, tetragonal structure, or its combination.Cube and tetragonal structure be easy to promote the formation of low aspect ratio primary particle, it presents the cuboid shape of class when observing under electron microscope.
The average primary particle diameter of described zirconia particles is no more than 50 nanometers usually, is no more than 40 nanometers, is no more than 30 nanometers, is no more than 25 nanometers, or is no more than 20 nanometers.The primary particle particle diameter refers to the non-associated particle diameter of zirconia particles, can measure by X-ray diffraction, as described in the example part.
Described zirconia particles tends in being present in colloidal sol the time have (, non-gathering with non-agglomeration) with uncombined basically form.The degree of associating between the primary particle can be determined by the fluid dynamics particle diameter.The PCS technology is used in the measurement of fluid dynamics particle diameter, and it will be described in the example part in more detail.Term ＂ fluid dynamics particle diameter ＂ and ＂ volume average particle size ＂ are used interchangeably herein.If zirconia particles associates, then the fluid dynamics particle diameter becomes measuring of primary particle size that assemble in the zirconia sol and/or agglomeration.If zirconia particles is non-association, then the fluid dynamics particle diameter becomes measuring of primary particle size.
The quantitative criterion of degree of association is a dispersion coefficient between the colloidal sol internal oxidation zirconium primary particle.When being used for this paper, ＂ dispersion coefficient ＂ is defined as the fluid dynamics particle diameter divided by the primary particle particle diameter.Primary particle particle diameter (for example, average weighted crystallite dimension) uses the X-ray diffraction technical measurement, and fluid dynamics particle diameter (for example, volume average particle size) uses the PCS method to measure.With the reduction of associating intensity between primary particle in the colloidal sol, the value of dispersion coefficient approaches 1.The dispersion coefficient of zirconia particles normally 1 to 5,1 to 4,1 to 3,1 to 2.5 or 1 to 2.
The PCS method can be used for further characterizing the zirconia particles in the colloidal sol.For example, six powers of the intensity of grain optical scattering and particle diameter are proportional.Therefore, and compare than granule, light intensity distributions is tended to larger particles more responsive.In fact, intensity mean grain size (for example, by the nanometer metering) is the pairing particle size of light intensity distributions mean value of Instrument measuring.The intensity mean grain size of zirconia particles is tended to be no more than 70 nanometers, is no more than 60 nanometers, is no more than 50 nanometers, is no more than 40 nanometers, is no more than 35 nanometers or is no more than 30 nanometers.
Use the light intensity distributions that obtains in the PCS analytic process to combine to calculate the volume distributed median of spherical particle with the refraction coefficient of particle and the refraction coefficient of suspending medium.Volume distributed median provides in the given size scope particle with respect to the number percent of total particle volume.Volume average particle size is the particle size corresponding with volume distributed median mean value.Because the volume of particle is directly proportional with the cube of diameter, this distribution is more insensitive to larger particles than the intensity mean grain size.That is, compare with the intensity mean grain size usually can be littler for volume average particle size.Usually the volume average particle size of zirconia sol is no more than 50 nanometers, is no more than 40 nanometers, is no more than 30 nanometers, is no more than 25 nanometers, is no more than 20 nanometers or is no more than 15 nanometers.Volume average particle size is used to calculate dispersion coefficient.
For the particulate samples that only has single particle size, the intensity mean grain size should be identical with volume average particle size.Therefore, the ratio of intensity mean grain size and volume average particle size provides measuring of size distribution in the particle.Big ratio is corresponding to wide size distribution.Usually zirconia particles intensity mean grain size (that is, with nanometer metering) is no more than 3.0 with the ratio of volume average particle size (that is, with the nanometer metering), is no more than 2.5, is no more than 2.0, is no more than 1.8, is no more than 1.7 or be no more than 1.6.
Zirconia sol usually has high transmittance, this be since in little particle diameter and the colloidal sol the non-associated form of zirconia primary granule cause.The high transmission rate of colloidal sol may be wished in the preparation of transparent or semitransparent goods.When being used for this paper, ＂ transmittance ＂ refers to also can use following formula to calculate by the amount of the light of sample (for example, zirconia sol) divided by the total amount that incides the sample glazing:
% transmittance=100 (I/I 0)
Wherein: I is the light intensity by sample, I 0It is the light intensity that incides on the sample.Transmittance can use ultraviolet light/visible spectrophotometer to measure, and its wavelength set is 600 nanometers and path-length is 1cm.
Transmittance is the culvert number of zirconia amount in the colloidal sol.For having the zirconic zirconia sol of about 1wt%, transmittance is 70%, at least 80% usually at least, or at least 90%.For containing the 10wt% zirconia oxidation zirconium colloidal sol of having an appointment, transmittance is 20%, at least 50% usually at least, or at least 70%.
Zirconia particles is through surface modification.Surface modification comprises makes zirconia particles and surface modification reagent or the reaction of surface modification combination of agents thing, and wherein surface modification reagent is attached to the surface of zirconia particles and the surface characteristics of zirconia particles is carried out modification.
Usually to carry out surface modification to improve the compatibility of itself and organic substrate material to zirconia particles.The zirconia particles of surface modification usually is non-association in the organic substrate material, non-agglomeration, or its combination.The light management films that gained contains the zirconia particles of these surface modifications can have high transmittance and low light turbidity.Compare with the film that only contains polymeric material, add the gain that the zirconia particles of these surface modifications can improve brightness enhancement film.
Surface modification reagent can be represented that wherein group A can be attached on the surface of zirconia particles by formula A-B, and wherein B is compatible group.The A group can be attached on the surface by suction-operated, forms ionic link, forms covalent bond, or its combination.The A group example that is fit to comprises, for example, carboxylic acid or its salt, sulfonic acid or its salt, phosphoric acid or its salt, phosphonic acids and salt thereof, silane, or the like.The compatibility group B can be activity or inactive, and can be polarity or nonpolar.
Can comprise for zirconia particles provides the compatible group B of polar character, for example, polyethers.Representative example with polarity modifier of carboxylic acid functional comprises the polyether carboxylic acid, as 2-[2 (2-methoxy ethoxy) ethoxy] acetate (MEEAA), 2-(2-methoxy ethoxy) acetate (MEAA), and single (polyglycol) succinate.
The compatibility group B that can make zirconia particles have nonpolar feature comprises, for example, and the fragrance of linearity or side chain or aliphatic hydrocarbon.That the representative example that comprises the nonpolar modifier of carboxylic acid functional comprises is sad, dodecylic acid, stearic acid, oleic acid, and combination.
In some embodiments, carboxylic acid can react with polymerisable organic substrate (carboxylic acid that for example, has polymerizable groups).In another embodiment, carboxylic acid contains carboxylic acid with polymerizable groups and the carboxylic acid that does not contain polymerizable groups simultaneously.Active carboxylic acid surface modifier (for example, having the carboxylic acid of polymerizable groups) comprises, for example, and acrylic acid, methacrylic acid, β-propyloic acrylic ester, list-2-(methylacryoyloxyethyl) succinate, and make up.A kind of useful can be single (methacryloxypropyl polyglycol) succinate for zirconia particles provides polar character and active surface modification reagent simultaneously.This material is specially adapted to be added in the acrylate and/or methacrylate organic substrate material of radiation-hardenable.
Exemplary silane comprises, but be not limited to alkyltrialkoxysilaneand such as n-octyl trimethoxy silane, n-octyl triethoxysilane, isooctyltrimethoxysi,ane, dodecyl trimethoxy silane, octadecyl trimethoxy silane, propyl trimethoxy silicane and hexyl trimethoxy silane; Methacryloxypropyl alkyltrialkoxysilaneand or propylene oxyalkyl trialkoxy silane, as 3-methacryloxypropyl triethoxysilane, 3-acryloyl-oxy propyl trimethoxy silicane, and 3-(methacryloxypropyl) propyl-triethoxysilicane; Methacryloxypropyl alkyl-alkyl bis-alkoxy or acryloyloxyalkyl alkyl bis-alkoxysilane, as 3-(methacryloxypropyl) propyl group methyl bi-methoxy silane, and 3-(acryloyl-oxy propyl group) methyl bi-methoxy silane, two alkylalkoxy silanes of methacryl oxyalkyl or the two alkylalkoxy silanes of acryloyloxyalkyl are as the two methyl ethoxy silane of 3-(methacryloxy) propyl group; The mercaptoalkyl trialkoxy silane, as 3-sulfydryl propyl trimethoxy silicane, the aryl trialkoxy silane is as styryl ethyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane and right-tolyl triethoxysilane; Vinyl silanes, as vinyl methyl diacetoxyl silane, the two methyl ethoxy silane of vinyl, the two Ethoxysilanes of vinyl methyl, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl triacetic acid base silane, vinyl silane triisopropoxide, vinyltrimethoxy silane, vinyl triple phenoxyl silane, vinyl three tert-butoxy silane, vinyl three (isobutoxy) silane, vinyl three iso-propenyloxysilanes and vinyl three (2-methoxy ethoxy) silane; 3-glycidoxypropyl trialkoxy silane is as glycidoxypropyltrimewasxysilane; Polyether silane is as (3-triethoxysilylpropyltetrasulfide) methoxy (ethoxy) ethoxyethyl carbamate PEG3TES just), just (3-triethoxysilylpropyltetrasulfide) methoxy (ethoxy) ethoxyethyl carbamate (PEG2TES) and SILQUEST A-1230); And combination.
The optical layers of this light management films also contains polymeric material except that the zirconia particles of surface modification.Optical layers contains the zirconia particles up to the surface modification of 80wt% usually.In some embodiments, optical layers contains up to 75wt%, up to 70wt%, up to 65wt%, up to 60wt%, up to 55wt%, up to 50wt%, up to 45wt% or up to the zirconia of the surface modification of 40wt%.This optical layers contains at least 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, the 35wt% or the zirconia particles of the surface modification of 40wt% at least at least at least at least at least at least at least at least usually.In some embodiments, optical layers contains the zirconia particles of 1 to 80wt%, 1 to 70wt%, 1 to 60wt%, 5 to 60wt%, 10 to 60wt%, 20 to 60wt%, 30 to 60wt% or 40 to 60wt% surface modification.
Polymeric material in the optical layers can be the material that is fit to arbitrarily, as long as it has sufficiently high refraction coefficient.The refraction coefficient of polymeric material normally at least 1.40, at least 1.45 or at least 1.50.Polymeric material can, for example, form by the polymerisable composition reaction that contains one or more monomers (for example, ethylenically unsaturated monomer), one or more oligomer (for example, olefinic unsaturated oligomers) or its combination.Polymerisable composition can also contain optional crosslinking chemical and optional light trigger.
Some exemplary polymeric materials are to be prepared by the polymerisable compound that contains the oligomeric materials that has hard segment and soft segment simultaneously.Hard segment usually is a polyurethane, and soft segment usually is a polyester.In addition, polymerisable composition usually contain monomer with provide the viscosity that is suitable for preparing goods with microstructure (for example, 1,000 to 5,000cps).For example, oligomeric resin usually is acrylate-based, and monomer is ethylenically unsaturated monomer such as alkyl (methyl) acrylate, aromatics (methyl) acrylate, or its combination.Polymerisable composition usually is solvent-free, crosslinkable and can be by ultraviolet curing in the presence of light trigger.Such polymerisable composition is further described in, and for example, United States Patent (USP) 5,183 is among 597 (Lu) and 5,175,030 (Lu etc.).
Other exemplary polymeric materials are prepared by polymerisable composition, and described composition contains the oligomeric materials with high index of refraction, reactive diluent, and crosslinking chemical (that is, crosslinking chemical or cross-linking monomer).Polymerisable composition usually contains initiating agent.Oligomeric materials provides main optical characteristic and permanance for polymeric material.Reactive diluent is a kind of monomer, adds to regulate the viscosity of polymerisable composition.Viscosity be adjusted to usually enough become flowable so that the bubble that is mingled with in the composition minimizes and can form the geometric configuration that has microstructure completely.Add the glass temperature (for example, the glass temperature of polymeric material usually is higher than 45 ℃) that polyfunctional crosslinking chemical is used to improve the permanance of optical layers and can improves polymkeric substance.These exemplary polymeric materials are further described in the following U.S. Patent application: 10/938006 of the submission of submitting to 10,10/662085,2004 on September of application on September 12nd, 2003 in 10,10/939184 and 2004 on September.
The oligomeric materials that is used for these exemplary polymer usually is a urethane acrylate, epoxy acrylate or its combination.Typical oligomer comprises, but be not limited to, the aromatic polyurethane acrylate (for example, can be available from Surface Specialties, Smyrna, the commercial goods EBECRYL 6700-20T of GA), the aromatic polyurethane diacrylate (for example, can be available from commercially available product EBECRYL 4849 and the EBECRYL 4827 of SurfaceSpecialties), aromatic polyurethane triacrylate (can available from the commercial goods EBECRYL 6602 of Surface Specialties), urethane acrylate (for example, commercial goods CN972 available from Sartomer), the urethane acrylate potpourri (for example, commercial goods CN970A60 and CN973A80 available from Sartomer, promptly with the potpourri of tripropylene glycol diacrylate), hexafunctional aliphatic urethane acrylates (for example, available from the commercial goods CN975 of Sartomer with available from the EBECRYL 220 of Surface Specialties), the bisphenol-A epoxy diacrylate (for example, commercial goods EBECRYL 608 available from Surface Specialties, EBECRYL 1608, with EBECRYL 3700), modified bisphenol A epoxy thing diacrylate (for example, EBECRYL 3701 available from Surface Specialties), the bisphenol-A epoxy diacrylate of part acrylic acid esterification (for example, commercial goods EBECRYL3605), epoxy acrylate (for example, available from Sartomer, Exton, the commercial goods CN120 of PA and CN104 and available from the EBECRYL 3200 of Surface Specialties), the modified epoxy acrylate (for example, commercial goods CN115 available from Sartomer, CN116, CN117, CN118, and CN119), aliphatic/aromatic epoxy acrylate is (for example, commercial goods EBECRYL 3201 available from SurfaceSpecialties), and rubber modified epoxy resin diacrylate (for example, available from Surface Specialties commercial goods EBECRYL 3302).
The typical reactive diluent monomer that is used for these exemplary polymer comprises, but be not limited to, mono acrylic ester, as (methyl) acrylic acid phenyl thio-ethyl ester, the isooctyl acrylate ester (for example, available from Sartomer, Exton, the commercial goods SR-440 of PA), isodecyl acrylate (for example, available from Sartomer commercial goods SR-395), isobornyl acrylate (for example, commercial goods SR-506 available from Sartomer), acrylic acid 2-phenoxy group ethyl ester (for example, available from sartomer commercial goods SR-339), acrylic acid alcoxyl base tetrahydrofurfuryl ester (for example, and acrylic acid 2 (2-ethoxy ethoxy) ethyl ester (for example, available from sartomer commercial goods SR-256) commercial goods CD-611 available from sartomer); Diacrylate, as diacrylate 1,3-butanediol ester (for example) available from the commercial goods SR-212 of Sartomer, diacrylate 1,6-hexanediol ester (for example, commercial goods SR-238 available from Sartomer), diacrylic acid pentyl diol ester (for example, available from Sartomer commercial goods SR-247), and diacrylate diglycol ester (for example, available from Sartomer commercial goods SR-230).Other reactive diluent monomer comprises, for example, methyl styrene, styrene, divinylbenzene, or the like.
The typical multi-group crosslink agent who is used for these exemplary polymer is a triacrylate, tetraacrylate, and five acrylate.This crosslinking chemical comprises, but be not limited to, trimethyol propane triacrylate (for example, available from Surface Specialties, Smyrna, the commercial goods TMPTA-N of GA and available from Sartomer, Exton, the SR-351 of PA), the potpourri of pentaerythritol triacrylate and pentaerythritol tetracrylate (for example, commercial goods PETIA available from SurfaceSpecialties, wherein the ratio of tetraacrylate and triacrylate is about 1: 1, and PETA-K, wherein the ratio of tetraacrylate and triacrylate is approximately 3: 1), pentaerythritol tetracrylate (for example, commercial goods SR-295 available from Sartomer), pentaerythritol triacrylate (for example, commercial goods SR-444 available from Sartomer), the isocyanuric acid ester triacrylate (for example for three (2-hydroxyethyls), commercial goods SR-368 available from Sartomer), tetrapropylene acid double trimethylolpropane ester (for example, available from Sartomer commercial goods SR-355), and the two penta ertythritol esters of five acrylic acid (for example, available from Sartomer commercial goods SR-399).
These polymerisable compositions are used the free radical polymerisation process polymerization usually.Usually contain initiating agent in the polymerisable composition.Initiating agent can be a thermal initiator, light trigger, or the both has.The example of initiating agent comprises organic peroxide, azo-compound, quinine, nitro compound, carboxylic acid halides, hydrazone, sulfhydryl compound, pyrylium compound, imidazoles, chlorotriazine, styrax, styrax alkyl ether, diketone, phenyl ketone, or the like.Commercially available light trigger comprises; but be not limited to; methyl isophthalic acid-phenyl-propane-1-ketone (for example for 2-hydroxyl 2-; commercial goods DAROCUR 1173 available from Ciba Specialty Chemicals); 2; 4; the potpourri of 6-trimethylbenzoyl-diphenyl-phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone (for example; commercial goods DARACUR 4265 available from Ciba SpecialtyChemicals); 2; 2-dimethoxy-1; 2-diphenyl second-1-ketone (for example; commercial goods IRGACURE 651 available from Ciba Specialty Chemicals); two (2; 6-dimethoxy benzoyl)-2; 4; the potpourri of 4-trimethyl-amyl group phosphine oxide and 1-hydroxy-cyclohexyl-phenyl ketone (for example; commercial goods IRGACURE 1800 available from Ciba Specialty Chemicals); two (2; 6-dimethoxy benzoyl)-2; 4; the 4-trimethyl-the amyl group phosphine oxide (for example; commercial goods IRGACURE 1700 available from Ciba Specialty Chemicals), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone (for example, available from Ciba SpecialtyChemicals commercial goods IRGACURE 907); with two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide (for example, available from Ciba Specialty Chemicals commercial goods IRGACURE819); 2; 4,6-trimethylbenzene formyl diphenyl phosphonous acid ethyl ester is (for example, available from BASF; Charlotte; the commercial goods LUCIRIN TPO-L of NC) and 2,4; 6-trimethylbenzene formyl diphenyl phosphine oxide (for example; available from BASF, Charlotte, the commercial goods LUCIRINTPO of NC).The working concentration of light trigger usually is about 0.1 to 10wt% or 0.1 to 5wt%, based on the weight meter of oligomeric in the polymerisable composition and monomeric substance.
Reduce the monomer of viscosity and the polymeric material of light trigger prepared in reaction is described in United States Patent (USP) 6,844 by oligomeric materials, optional being used to, among 950 B2 (Chisholm etc.).The oligomer that is fit to is polyurethane many (methyl) acrylate.Exemplary polymeric material is by 2,2, the prepared in reaction of 4-two isocyanic acid trimethyl hexene esters, poly-(caprolactone) glycol and methacrylic acid 2-hydroxyl ethyl ester.The optional monomers that is fit to comprises, for example, alkyl (methyl) acrylate, (methyl) acrylamide that N-replaces, N, N '-dibasic (methyl) acrylamide, distyryl compound, or the like.
Other exemplary polymer are the reaction product that contain the polymerisable composition of formula I monomer.
Figure S200680016313XD00161
Among the formula I, R aBe hydrogen or methyl; Q is oxygen or sulfenyl; R cBe C 2-C 12Alkylidene, it is for unsubstituted or replaced by hydroxyl; N is 0 to 6 integer; M is 0 to 6 integer; Each X is hydrogen independently, bromine, or chlorine; Y is a divalent linking group, is selected from-C (CH 3) 2-,-CH 2-,-S-,-S (O)-, or-S (O) 2-.The polymerisable composition that contains formula I monomer is further described in United States Patent (USP) 6,541,591 B2 (Olson etc.) and 6,833,391 B1 (Chisholm etc.); And among U.S. Patent Publication 2004/0249100 A1 (Chisholm etc.) and 2004/0242720 A1 (Chisholm etc.).Can in polymerisable composition, add other monomer or oligomer.These polymerisable compositions can further contain crosslinking chemical and initiating agent such as light trigger.
In the embodiment of some formula I, R cBe C 2-C 3Alkylidene, it is for unsubstituted or replaced by hydroxyl; N equals 0 or 1; M equals 0 or 1.For example, R cCan be selected from-CH 2CH 2-,-CH (CH 3) CH 2-, or-CH 2CH (OH) CH 2-.
Formula I monomer can be by the prepared in reaction of (methyl) acrylic acid and di-epoxide, described di-epoxide as, for example, bisphenol A diglycidyl ether; The bisphenol-f diglycidyl ether; The tetrabromobisphenol A diglycidyl ether; 1,3-pair 4-[1-methyl 1-(4-epoxy radicals methoxyl-phenyl)-ethyl]-phenoxy group }-propane-2 alcohol; 1,3-pair 2,6-two bromo-4-[1-(3,5-two bromo-4-epoxy radicals methoxyl-phenyl)-1 methyl-ethyl]-phenoxy group }-propane-2 alcohol, or the like.
The exemplary monomer of formula I includes, but not limited to 2, two (4-(2-(methyl) acryloyl-oxy ethoxy) phenyl) propane of 2-; 2, two ((4-(methyl) acryloyl-oxy) phenyl) propane of 2-; Acrylic acid 3-(4-{1-[4-(3-acryloxy oxygen-2-hydroxyl propoxyl group)-3,5-two bromo-phenyl]-the 1-Methylethyl }-2,6-two bromo-phenoxy groups)-the 2-hydroxy propyl ester; Acrylic acid 3-[4-(1-{4-(3-acryloxy oxygen-2-hydroxyl propoxyl group)-3,5-two bromo-phenyl }-1-methyl-ethyl)-2,6-two bromo-phenoxy groups]-2-hydroxyl-propyl ester; Acrylic acid 3-[4-(1-{4-[3-(4-{1-4-(3 acryloxies oxygen-2-hydroxyl propoxyl group)-3,5-two bromo-phenyl }-the 1-Methylethyl)-2,6-two bromo-phenoxy groups]-2-hydroxyl propoxyl group }-3,5-two bromo-phenyl)-1 methyl-ethyl]-2,6-two bromo-phenoxy groups)-the 2-hydroxy propyl ester; Or the like.In some polymerisable compositions, formula I monomer comprises that bromine bisphenol A diglycidyl ether and acrylic acid reaction product are to form 2-propionic acid, (inferior second two bases of 1-methyl) two [2,6-two bromo-4,1-penylene] oxygen (2-hydroxyl-3,1-propane two bases) } ester four.
The cross-linking monomer that is used for combining with formula I monomer or is used for other polymer compositions as herein described usually comprises three or more (methyl) acryloyl group.This crosslinking group includes, but not limited to trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, isocyanuric acid ester triacrylate, two (trimethylolpropane) tetraacrylate, dipentaerythritol five acrylate, or the like.Can use the potpourri of crosslinking chemical.
The polymerisable composition that contains formula I monomer can also comprise simple function group (methyl) acrylate.In some such polymerisable compounds, simple function group (methyl) acrylate has formula II.
Figure S200680016313XD00181
Among the formula II, Ar is a phenyl or naphthyl, and it is for unsubstituted or replaced by one or more substituting groups, and substituting group is selected from halogen, alkyl, aryl, aralkyl or its combination; Q is oxygen or sulfenyl; R cBe C 2-C 12Alkylidene, it is for unsubstituted or replaced by hydroxyl; P is 0 to 6 integer; And R aBe hydrogen or methyl.
Exemplary formula II monomer comprises, but be not limited to, phenoxy group ethyl (methyl) acrylate, phenoxy group-2-first and second bases (methyl) acrylate, phenoxy group ethoxyethyl (methyl) acrylate, 3-phenoxy group 2-hydroxypropyl (methyl) acrylate, 2,4-dibromo-phenoxy ethyl (methyl) acrylate, 2,4,6-tribromo-benzene oxygen ethyl (methyl) acrylate, 4,6-two bromo-2-alkyl phenyl (methyl) acrylate, 2,6-two bromo-4-alkyl phenyl (methyl) acrylate, 2-(1-naphthoxy) ethyl (methyl) acrylate, 2-(2-naphthoxy) ethyl (methyl) acrylate, 2-(1-naphthalene sulfenyl) ethyl (methyl) acrylate, 2-(2-naphthalene sulfenyl) ethyl (methyl) acrylate, or the like.
In first example, polymerisable composition may comprise formula I monomer, 2,4, and 6-tribromo-benzene oxyalkyl (methyl) acrylate and fragrant polyurethane six acrylate.Such polymerisable composition is further described in United States Patent (USP) 5,908, among 875 (Fong etc.).
In second example, polymerisable composition can comprise formula I monomer, 4 of alkyl replacement, 6-dibromo phenyl acrylate, methyl styrene and fragrant polyurethane six acrylate.Such polymerisable composition is further described in United States Patent (USP) 6,280, among 063 B1 (Fong etc.).
In the 3rd example, polymerisable composition comprises first monomer of formula I, comprises 2,4,6-tribromo-benzene oxyalkyl (methyl) acrylate (for example, 2,4,6-tribromo-benzene oxygen ethyl (methyl) acrylate) second monomer, and crosslinking chemical (for example, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, or its potpourri).Polymerisable composition can also comprise light trigger and simple function group reactive diluent monomer (for example, (methyl) acrylic acid phenoxy ethyl, (methyl) benzyl acrylate, and composition thereof).These polymerisable compositions are further described in the United States Patent (USP) of submitting on Dec 30th, 2,003 10/78049.
In another specific example, polymerisable composition comprises first monomer of formula I, comprise that simple function group reactive diluent monomer as (methyl) acrylic acid benzene oxyalkyl ester (for example, the acrylic acid phenoxy ethyl) second monomer, and crosslinking chemical (for example, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, or its potpourri), and light trigger.These polymerisable compositions are further described in the United States Patent (USP) of submitting on Dec 30th, 2,003 10/747985.
Other polymeric materials comprise by containing formula II monomer but do not contain the material of prepared in reaction gained of the polymerisable compound of formula I monomer.Formula II monomer can with, for example, optional cross-linking monomer and optional initiating agent such as light trigger make up.
For example, the prepared in reaction of the polymerisable compound that this polymeric material can be by containing alkyl (methyl) phenyl acrylate (that is, variable p equals zero among the formula II) that replace, bromination.Such polymerisable compound is further described in following United States Patent (USP): 5,932,626 (Fong etc.), and 6,107,364 (Fong etc.), and among 6,355,854 (Olson etc.).Exemplary alkyl replaces, the monomer of bromination comprises, for example, (methyl) acrylic acid 4,6-two bromo-2-alkyl phenyl esters are as (methyl) acrylic acid 4,6-two bromo-2-secondary butyl phenenyl esters, (methyl) acrylic acid 4,6-two bromo-2-tert-butyl-phenyl esters and (methyl) acrylic acid 4,6-two bromo-2-isopropyl phenyl esters; (methyl) acrylic acid 2,6-two bromo-4-alkyl phenyl esters is as (methyl) acrylic acid 2,6-two bromo-4-nonyl phenylesters and (methyl) acrylic acid 2,6-two bromo-4-dodecylphenyl esters.
Some comprise that the polymerisable compound of alkyl (methyl) phenyl acrylate that replace, bromination can also comprise the comonomer with high index of refraction, as methyl styrene; The aromatic monomer of bromination such as tribromo phenyl (methyl) acrylate or penta-bromophenyl (methyl) acrylate; Or another kind of formula II monomer, wherein Ar is unsubstituted phenyl or the phenyl that replaced by alkyl, aryl, aralkyl or its combination.For example, polymerisable composition can comprise alkyl phenyl (methyl) acrylate that replace, bromination, methyl styrene, the epoxide diacrylate of bromination, 2-phenoxyethyl acrylate and fragrant polyurethane six acrylate are as United States Patent (USP) 6,355,754 (Olson etc.) are described.
Other contain formula II monomer but the polymerisable compound that do not contain formula I monomer is further described in United States Patent (USP) 6,663, among 978 B1 (Olson etc.).These monomers comprise, but be not limited to, acrylic acid 6-(4,6-two bromo-2-isopropyl-phenoxy groups) hexyl ester, acrylic acid 6-(4,6-two bromo-2-sec-butyl phenoxy groups) hexyl ester, acrylic acid 2-(1-naphthoxy) ethyl ester, acrylic acid 2-(2-naphthoxy) ethyl ester, acrylic acid 6-(1-naphthoxy) hexyl ester, acrylic acid 6-(2 naphthoxy) hexyl ester, acrylic acid 8-(1-naphthoxy) octyl group ester, acrylic acid 8-(2-naphthoxy) octyl group ester, acrylic acid 2-thiophenyl ethyl ester, acrylic acid phenoxy group ethyl ester, and combination.
Other polymkeric substance also can be formed by aromatics sulfur-bearing diacrylate, as the United States Patent (USP) submitted on Dec 30th, 2,004 11/026573 described those.Aromatics sulfur-bearing diacrylate can have formula III or formula IV.
Figure S200680016313XD00201
Among formula I and the formula II, each R 1Be independently selected from following formula:
Or
Figure S200680016313XD00211
R wherein 3Be (CH 2) xX is 2 to 8 integer; R 4Be hydrogen or methyl.Polymerisable material can also contain cross-linking monomer.The formula III monomer that is fit to includes, but not limited to acrylic acid 2-[7-(2-acryloyl group oxygen-ethyl sulfane base)-naphthalene-2-base sulfane base]-ethyl ester.The monomer of the formula IV that is fit to includes, but not limited to acrylic acid 2-{4-[4-(2-acryloyl group oxygen-ethyl sulfane base)-phenyl sulfane base]-phenyl sulfane base }-ethyl ester.
Other polymeric materials can be formed by the aromatics sulfur-bearing diacrylate of formula V.
Figure S200680016313XD00212
Among the formula V, R 2Be hydrogen or methyl, Ar is aryl (for example a, phenyl or naphthyl); M is 1 to 6 integer, and n is 1 to 6 integer, and p is 1 to 6 integer, and q is 1 to 6 integer.Suitable monomer according to formula V comprises, but be not limited to acrylic acid 2-acryloyl-oxy ylmethyl-3-(naphthalene-2-base sulfane base)-2-(naphthalene-2-base sulfane ylmethyl-propyl ester and acrylic acid 2-acryloyl-oxy ylmethyl-3-phenyl sulfane base-2-phenyl sulfane ylmethyl-propyl ester.
Other polymeric materials that are fit to are described among the United States Patent (USP) 2004/0131826A1 (Chisholm etc.).This polymeric material is the reaction product of following material: (a) at least a simple function group acrylic monomers that is selected from the following stated: (1) (methyl) acrylic acid tertiary alkyl ester, (2) N-replace or N, N-dibasic (methyl) acrylamide, or (3) (methyl) acrylic acid C 1-C 8Uncle or secondary Arrcostab; (b) at least a polyfunctional (methyl) acrylate; (c) optional at least a oligomeric materials; And (d) at least a light trigger.
The tertiary alkyl (methacrylate) that is fit in the component (a) has 4 to 8 carbon atoms usually, as (methyl) tert-butyl acrylate.That the N-that is fit in the component (a) replaces or N, N dibasic (methyl) acrylamide comprises for example, having the alkyl substituent of 1 to 4 carbon atom, as N-N-isopropylacrylamide, N tert butyl acrylamide, N, N-DMAA, and N, N-diethyl acrylamide.The C that is fit in the component (a) 1-C 8Uncle or secondary alkyl (methyl) acrylate comprise, for example, (methyl) methyl acrylate, ethyl acrylate, and 2-(N-butyl carbamyl) ethyl propylene acid esters.
Multifunctional (methyl) acrylate that is used for component (b) comprises, for example, and ethylene glycol diacrylate, 1, the 6-hexanediyl ester, trimethylolpropane triacrylate, two (trimethylolpropane) tetraacrylate, tetramethylol methane tetraacrylate, and N, N '-methylene diacrylamine.
Although the polymeric material that is included in the light management films optical layers usually is crosslinked (that is, this polymeric material is a thermosetting material), also can use thermoplastic, as described in U.S. Patent Publication 2004/0233526 A1 (Kaminsky etc.).The thermoplastics that is fit to comprises acrylic acid, polyolefin, polyester (for example, by aromatic series with 4 to 40 carbon atoms, aliphatics, or the cycloaliphatic dicarboxylic acid and have the aliphatics of 2 to 24 carbon atoms or polyester that the alicyclic diol reaction forms), polyamide (for example, nylon 6 and nylon 66), polycarbonate (for example, bisphenol-a polycarbonate), cellulose esters (for example, cellulose nitrate, Triafol T, the diacetate cellulose propionate, and acetylbutyrylcellulose), polystyrene, polyvinyl resin (for example, Polyvinylchloride and polyvinyl acetate (PVA)), polysulfonamide, polyethers, polyimide, the polyvinylene fluoride, polyurethane, polyphenylene sulfide, teflon, polyacetal, polysulfonate, polyester ionomer and polyolefin ionomer.Also can use the multipolymer (for example, plastic of poly vinyl acetate) or the potpourri of these thermoplastics.
Polymerisable compound described herein can also contain one or more other useful constituents.For example, polymerisable compound can comprise one or more surfactants, pigment, filling agent, polymerization inhibitor, antioxidant, antistatic agent, or the like.Effective addition of this component is known.Can in polymerisable compound, add surfactant, as the number of fluorochemical surfactant with reduction surface tension, raising wetting state, the slickness that improves coating or reduction coating defect.
Optical layers can the surface tool structuringization or that have microstructure, and it can have any amount of useful pattern as described below and shown in the drawings.Surface with microstructure can be a plurality of parallel longitudinal ridges, and its length or Width along film extends.These burrs can form by a plurality of prisms are top.These are top can be sharp keen, and circle flattens, or truncation.Prismatic pattern can be regular or irregular.Prismatic pattern can be the microstructure of prismatic pattern, cube corner pattern or any other lens of annular.Useful microstructure is the prismatic pattern of rule, and it provides the light management films that can play complete internal reflection membrane interaction.Another useful microstructure is the prismatic pattern of cube corner, the element that it can be used as the back reflection film or is used as reflectance coating.Another useful microstructure is prismatic pattern, and it can be used as the optical element that is used for optical display.Another useful microstructure is prismatic pattern, and it can be used as turning film or the element that is used for optical display.
Except that optical layers, many light management films further comprise basalis.Optical layers can directly contact with basalis or optional and basalis optics on be coupled together (that is, between optical layers and the basalis one or more middle layers can be arranged).The size that basalis can have, profile and thickness should make optical layers lead or assemble light stream.The character of this basalis and composition should be suitable in the optics product, are about to this product and are designed for the control light stream.Almost any material can be used as its bottom, as long as enough firm in to be assembled into or to be used among the specific optics finished product on the optically sufficiently transparent and structure of this material.Preferably, the selection of base layer material requires it to temperature with aging have enough tolerances, so that the performance of optical articles is not in time and undermined.
Be used for the particular chemical composition of basalis of any optical articles and the needs that thickness depends on the particular optical product that will constitute.Promptly for example, the selection of material need balance strength, transparency, thermotolerance, surface energy, to the needs of the each side such as adhesiveness of optical layers.
Useful base layer material comprises, for example, styrene-acrylonitrile, acetylbutyrylcellulose, cellulose acetate propionate, Triafol T, polyethersulfone, polymethylmethacrylate, polyurethane, polyester, polycarbonate, Polyvinylchloride, polystyrene, polyethylene terephthalate, naphthalenedicarboxylic acid polyvinyl ester, based on multipolymer or potpourri, polycyclic olefin, polyimide and the glass of naphthalene dicarboxylic acids.Optional, described base material can contain these mixtures of material or combination.Basalis can contain the one layer or more material.In some embodiments, basalis comprises and suspends or be dispersed in disperse phase in the external phase.
To some light management films, the exemplary substrate layer is selected from polyethylene terephthalate (PET) and polycarbonate.The example of useful PET film comprises sensitization level polyethylene terephthalate and MELINEX TMPET derives from DuPont Films, Wilmington, Del.
Some base layer material can be optically active, and can be used as polarization material.Many basalises are also referred to as film or matrix herein, knownly in the optical articles field can be used as polarization material.By for example, in film forming matter, comprise and optionally to absorb the light polarization that can realize passing film by the dichroic polarizer of light.Light polarization can also as the scrap mica of aligning (aligned) or by disperseing to introduce the discontinuous phase realization in continuous film inside, be dispersed in continuous film inside as the drop of light being regulated liquid crystal by introducing dead matter.As alternatives, can prepare polarizing coating with the fine layer of different materials.The polarization material of film inside can, for example,, use the electric or magnetic field, and coating technique is aligned to polarization orientation by making with the following method as stretched film.
The example of polarizing coating comprises described in the following patent: United States Patent (USP) 5,825,543 (Ouderkirk etc.) and 5,783,120 (Ouderkirk etc.).Polarizing coating is described in United States Patent (USP) 6,111 with being used in combination of brightness enhancement film, among 696 (Allen etc.).
Can be used as other case descriptions of basalis polarizing coating in United States Patent (USP) 5,882, in the middle of 774 (Jonza etc.).The example of the commercially available this film that gets is the multilayer film of selling with trade name DBEF (Dual Brightness Enhancement Film), derives from 3M, SaintPaul, MN.In brightness enhancement film, use such multilayer polarization light management films to be described in United States Patent (USP) 5,828, among 488 (Ouderkirk etc.).
These base layer material and other polarizations or unpolarized film also can be used for above-mentioned optical layers.These basalises can combine with any amount of other films, for example comprise polarizing coating, to form sandwich construction.The short list of other matrix material can comprise, as be described in United States Patent (USP) 5,612, those films among 820 (Schrenk etc.) and 5,486,949 (Schrenk etc.).The thickness of particular substrate also can depend on the above-mentioned needs of optical articles.
Another aspect of the present invention provides the method for preparing light management films.First method comprises: zirconia sol is provided, it contains the zirconia particles that is dispersed in aqueous phase, the surface of modified zirconia particle is to form the zirconia particles of surface modification, preparation contains the zirconia particles of described surface modification and the coating composition of organic substrate, make coating composition contact, and make the coating composition polymerization have the optical layers of micro-structure surface with formation with little facility that duplicate.The preparation method of zirconia sol is: preparation contains first raw material of zirconates, make first raw material contain zirconium intermediate and accessory substance with formation through first hydrothermal treatment consists, by removing at least a portion first hydrothermal treatment consists accessory substance forming second raw material, and make second raw material through second hydrothermal treatment consists.
Zirconia particles can prepare with hydrothermal technique.More particularly, first raw material that will contain zirconates carries out first hydrothermal treatment consists and contains zirconium intermediate and accessory substance with formation.Second raw material is to prepare by removing the accessory substance that forms at least a portion first hydrothermal treatment consists process.Then, second raw material is carried out second hydrothermal treatment consists contains zirconia particles with formation zirconia sol.
First raw material is the aqueous solution precursor solution preparation that contains zirconates by formation.The anionic selection of zirconates need make it can remove in the subsequent step of preparation zirconia sol technology usually.In addition, negative ion usually is chosen to be non-corrosive, thereby when selecting the material type of process equipment such as hydrothermal reactor higher dirigibility can be arranged.
The zirconates negative ion is carboxylate normally.At least the contained carbon atom of the carboxylate anion of 50mol% is no more than 4.For example, in some precursor solutions, at least 60mol%, at least 70mol%, at least 80mol%, at least 90mol%, at least 95mol%, at least 98mol% or at least the carboxylate anion of 99mol% have and be no more than 4 carbon atoms.
The carboxylate that is no more than 4 carbon atoms that has that is fit to comprises formates, second hydrochloric acid, propionate, butyrate or its combination.These carboxylate anions are usually removed by being converted into corresponding volatile acid in technological process.In addition, these carboxylate anions and other negative ion such as chloride or nitrate radical are compared easier to be compatible with the organic substrate material.
In some precursor solutions, negative ion is to have carboxylate and the anionic potpourri of polyether carboxylic acid's root that is no more than 4 carbon atoms.The polyether carboxylic acid's root negative ion that is fit to is the corresponding weak base of water-soluble monocarboxylic acid (that is carboxyl of per molecule) and has the polyethers afterbody.The polyethers afterbody contains the difunctionality ether group of repetition, and it has general formula-O-R-, wherein-R-be alkylidene group as, for example, methylene, ethylidene and propylidene (comprising positive propylidene and isopropylidene) or its combination.The polyether carboxylation who is fit to have more than 4 carbon atoms and include, but not limited to form by the polyether carboxylic acid those, as 2-[2-(2-methoxy ethoxy) ethoxy] acetate (MEEAA) and 2-(2-methoxy ethoxy) acetate (MEAA).The polyether carboxylation, if be included in the precursor solution, amount is no more than 50mol% usually, based on the molal quantity of carboxylate anion in the precursor solution.For example, polyether carboxylation's amount can be to be no more than 40mol%, to be no more than 30mol%, to be no more than 20mol%, to be no more than 10mol%, to be no more than 5mol%, to be no more than 2mol% or to be no more than the amount of the carboxylate anion in the precursor solution of 1mol%.
Some precursor solutions are substantially free of the polyether carboxylation, are substantially free of the carboxylate that has more than 4 carbon atoms, or its combination.When being used for this paper, term ＂ is substantially free of the amount that the polyether carboxylation ＂ meaning refers in the precursor solution polyether carboxylation in the carboxylate or corresponding polyether carboxylic acid and is less than 1mol%.For example, polyether carboxylation or corresponding polyether carboxylic acid's content are less than 0.5mol%, are less than 0.2mol% or are less than 0.1mol% in the carboxylate in the precursor solution.When being used for this paper, term ＂ is substantially free of to have more than 4 carbon atom carboxylic acid's salt ＂ meanings and refers to that the carboxylate or the corresponding carboxylic acid that are less than 1mol% in the precursor solution have more than 4 carbon atoms.For example, the carboxylate or the corresponding carboxylic acid that be less than 0.5mol%, are less than 0.2mol% or are less than 0.1mol% have more than 4 carbon atoms.
Some precursor solutions are substantially free of halogenide such as chloride.When being used for this paper, term ＂ is substantially free of the halogenide ＂ meaning and refers to that halogenide is less than 10 in the precursor solution -2Mol is less than 10 -3Mol is less than 10 -4Mol, or be less than 10 -5Mol.
Zirconates usually is a zirconium acetate.Zirconium acetate can be represented by general formula, as, ZrO ((4-n)/2) N+(CH 3COO -) n, wherein n is within 1 to 2 scope.According to for example, the pH value of precursor solution, zirconium ion can exist with various structures.The method for preparing zirconium acetate is described in, for example, W.B.Blumenthal, ＂ The Chemical Behavior of Zirconium, ＂ 311-338 page or leaf, D.VanNostrand Company, Princeton is among the NJ (1958).The aqueous zirconium acetate solution that is fit to is commercially available getting, and for example, derives from Magnesium Elektron, Inc. (Flemington, NJ), it contains the zirconium up to 17%, the zirconium up to 18%, the zirconium up to 20%, or up to 22% zirconium.
Some precursor solutions contain yttrium salt except that zirconates.As zirconates, the yttrium salt anionic selects those can remove in the following process process and non-corrosive ion usually.The yttrium salt anionic usually is to have the carboxylate that is no more than 4 carbon atoms, and for example, negative ion can be an acetate.Yttrium salt amount usually up to 0.12 gram yttrium every gram zirconium, up to the every gram zirconium of 0.10 gram yttrium, up to the every gram zirconium of 0.08 gram yttrium, up to the 0.06 gram every gram zirconium of yttrium or up to the every gram zirconium of 0.04 gram yttrium.
The liquid phase of precursor solution mainly is water usually.But other mixable cosolvent also can be included in the liquid phase, and based on liquid phase weight meter, its amount may be up to 20%.The cosolvent that is fit to includes, but not limited to 1-methoxyl 2-propyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, N,N-dimethylacetamide and N-Methyl pyrrolidone.
In some embodiments, the preparation process of first raw material is: form the water precursor solution of the yttrium salt that contains zirconates and choose wantonly, remove at least a portion negative ion then from precursor solution.Can use any anionic suitable method of a part that can be used for removing as known in the art.Removal methods include, but not limited to evaporation, saturating dialysis, ion-exchange, precipitation, filtration, or the like.In some removal methods, negative ion is removed with the form of acid.Although do not wish to be limited by theory, part removes the formation that negative ion may reduce agglomeration and gathering in one or more hydrothermal treatment step processes subsequently from precursor solution.
In remove anionic a kind of method at least in part from precursor solution, precursor solution can be heated to the negative ion that can evaporate sour form.For example, having the carboxylate anion that is no more than 4 carbon atoms can be used as corresponding carboxylic acid and removes.More particularly, the acetate negative ion can be used as acetate and removes.Except that carboxylic acid, the liquid phase (for example, aqueous medium) that heating also can be removed precursor solution to small part.The part of liquid phase removes and causes forming concentrated precursor.In certain methods, solid can be increased to up to 25wt%, up to 50wt%, up to 75wt% or up to 100wt%.The precursor that concentrates usually contains at least 10wt% zirconium, 15wt% zirconium, 20wt% zirconium, 25wt% zirconium, 30wt% zirconium, 35wt% zirconium or 40wt% zirconium at least at least at least at least at least at least.For example, the precursor of Nong Suoing can contain 11 to 43wt% zirconiums or 21 to 43wt% zirconiums.
All or part of liquid phase removes to form concentrated precursor and can be substituted into before first hydrothermal treatment consists.Can dilute concentrated precursor so that first raw material to be provided for water (for example, deionized water).The solid load of first raw material can be lower than the solid load of precursor solution, equals the solid load of precursor solution, or greater than the solid load of precursor solution.
The solid of first raw material is usually in 0.5 to 20wt% or 2 to 15wt% scope.First raw material usually contains the zirconium of 0.2wt% at least, zirconium, zirconium or the zirconium of 2wt% at least of 1wt% at least of 0.5wt% at least.In some embodiments, first raw material contain zirconium up to 6wt%, up to the zirconium of 8wt% or up to the zirconium of 9wt%.For example, first raw material usually contains 0.2 to 9wt% zirconium or 1 to 6wt% zirconium.
The pH value of first raw material is usually at acid range.For example, the pH value usually less than 6, less than 5, less than 4 or less than 3.
First raw material is carried out first hydrothermal treatment consists.Zirconium material generation partial hydrolysis in first raw material contains zirconium intermediate and accessory substance with formation.Equally, be present in that partial hydrolysis can take place any optional yttrium salt in first raw material.When negative ion was carboxylate, hydrolysis reaction was usually followed the release of acidic by-products.For example, if negative ion is formates, acetate, propionate or butyrate, then can discharge corresponding acid (that is, respectively being formic acid, acetate, propionic acid or butyric acid successively) in the hydrolysis reaction.
Hydrothermal treatment consists can be carried out in batch reactor or flow reactor.Flow reactor is compared the common residence time with batch reactor shorter and temperature is higher.The time of hydrothermal treatment consists can change according to the temperature of reactor and the concentration of raw material.Pressure in the reactor can be spontaneous (that is, the water vapor pressure under the temperature of reactor), can be (that is, the pressure that pumping fluid produced by the antagonism fluid resistance) of hydraulic pressure, or can produce by adding inert gas such as nitrogen or argon gas.The batch (-type) hydrothermal reactor that is fit to can, for example, available from Parr InstrumentsCo. (Moline, IL).The continous way hydrothermal reactor that is fit to is described in, and for example, United States Patent (USP) 5,453 is among 262 (Dawson etc.) and 5,652,192 (Matson etc.); And people such as Adschiri, J.Am.Ceram.Soc.75,1019-1022 (1992); And Dawson, Ceramic Bulletin.67 (10) are among the 1673-1678 (1988).
In certain methods, at least one hydrothermal treatment consists is carried out in flow reactor.For example, first hydrothermal treatment consists can be carried out in flow reactor and second hydrothermal treatment consists is carried out in batch reactor.In another example, first hydrothermal treatment consists can be carried out in batch reactor and second hydrothermal treatment consists is carried out in flow reactor.In another example, first and second hydrothermal treatment consists are all carried out in flow reactor.
First hydrothermal treatment consists can be carried out in batch reactor, and its temperature is in 150 ℃ to 300 ℃ scopes, in 155 to 250 ℃ of scopes or in 160 to 200 ℃ of scopes.In first hydrothermal treatment consists that some carry out in batch reactor, reactor is heated to the temperature cooling immediately then of requirement.May need, for example, meet the requirements of temperature in about 1 hour.In first hydrothermal treatment consists of carrying out in other batch reactors, temperature of reaction kept 0.5 hour, 0.75 hour, 1 hour or 2 hours at least at least at least at least.The time that keeps under the temperature of reaction in the batch reactor can be up to 3 hours, up to 3.5 hours, up to 4 hours, up to 5 hours, up to 6 hours or up to 8 hours.For example, the time of temperature of reaction maintenance can be 0.25 to 8 hour, 0.5 to 6 hour or 0.75 to 3.5 hour.
Perhaps, first hydrothermal treatment consists can be carried out in flow reactor, temperature in 150 to 300 ℃ of scopes, in 160 to 250 ℃ of scopes, in 170 to 220 ℃ of scopes or in 180 to 215 ℃ of scopes, at least 1 minute time.In some flow reactors, the residence time is 2 minutes, at least 3 minutes, at least 3.5 minutes or at least 4 minutes at least.The residence time in the flow reactor can be up to 8 minutes, up to 10 minutes, up to 12 minutes, up to 15 minutes or up to 20 minutes.For example, the residence time in the flow reactor can be 1 to 20 minute, 2 to 15 minutes or 3 to 10 minutes.
In the first hydrothermal treatment consists process, partial hydrolysis only takes place in zirconates in first raw material and optional yttrium salt.The product of first hydrothermal treatment consists comprises that containing the zirconium intermediate adds various accessory substances in the liquid phase.If comprise optional yttrium salt in first raw material, then contain the zirconium intermediate and also contain yttrium.Contain the only partial hydrolysis and be not the zirconia of crystallization of zirconium intermediate.According to X-ray diffraction analysis, containing the zirconium intermediate is unbodied basically.That is, the X-ray diffractogram that contains the zirconium intermediate tends to have the narrow relatively peak of broad peak rather than expression crystalline material.
Conversion ratio (that is, hydrolysis degree) can, for example, calculate with thermogravimetry (TGA).The computing method of conversion ratio are particularly suitable for carboxylate anion in first raw material and do not contain the polyether carboxylation, do not contain and have more than the carboxylate of 4 carbon atoms or the situation of its combination.The conversion ratio that contains the zirconium intermediate can be represented with following formula:
% conversion ratio=100 (A-B)/(A-C)
Wherein A is the loss in weight number percent of first raw material, and B is the number percent that contains the zirconium intermediate loss in weight, and C is the loss in weight number percent of zirconia sol.The number percent of first raw material, intermediate and the zirconia sol loss in weight by measuring at 120 ℃ of down dry each samples before analyzing in 30 minutes.In the thermogravimetric analyzer after 85 ℃ of balances, each sample with 20 ℃/minute speed be heated to 200 ℃.Temperature kept 20 minutes at 200 ℃, increased to 900 ℃ with 20 ℃/minute speed, and kept 20 minutes at 900 ℃.Loss in weight number percent can be calculated by following formula:
Loss in weight %=100 (weight 200 ℃-weight 900 ℃)/weight 900 ℃
For first raw material, contain zirconium intermediate and zirconia sol.It is not the part of inorganic oxide that loss in weight number percent is equivalent in each dry sample.
The conversion ratio that contains the zirconium intermediate normally 40 to 75%.In certain methods, the conversion ratio that contains the zirconium intermediate is 45 to 70%, 50 to 70%, 55 to 70% or 55 to 65%.Conversion ratio can be used for selecting the suitable condition of first hydrothermal treatment consists.
If can proceeding to the conversion ratio generation greater than about 75%, the hydrolysis reaction in the first hydrothermal treatment consists process contains the zirconium intermediate, then final zirconia sol tends to contain association (for example, gathering and/or agglomeration) rather than non-associated zirconia primary particle.Although do not wish to be entangled in theory, the accessory substance of removing at least a portion hydrolysis reaction in course of reaction is favourable.Therefore, it is favourable before second hydrothermal treatment consists first raw material being carried out first hydrothermal treatment consists and removes a part of accessory substance.
Second raw material promptly will carry out the material of second hydrothermal treatment consists, by the preparation of product of first hydrothermal treatment consists.The preparation of second raw material generally includes removes the accessory substance that generates to the small part first hydrothermal treatment consists process.Acid, it can be formed by zirconates and optional yttrium salt anionic, is one of first common hydrothermal treatment consists accessory substance.If acidic by-products is to have to be no more than 4 carbon atom carboxylic acids, then can by the whole bag of tricks as evaporation, saturating dialysis, ion-exchange, precipitation, filtration, or the like remove disacidify.
The accessory substance that is removed to small part first hydrothermal treatment consists also can cause removing of Partial Liquid Phase (for example, aqueous medium) at least,, may form the concentrate of intermediate that is.In some embodiments, only remove a part of liquid phase (that is, the intermediate concentrate has liquid phase).For example, some of first hydrothermal treatment consists products of containing solid phase can separate (for example, solid phase can be precipitated out) from liquid phase from Partial Liquid Phase.At least a portion liquid phase can be removed by methods such as siphon, decant or centrifuge method.In other embodiments, the product of first hydrothermal treatment consists is dried to form residue (that is, the intermediate concentrate contains seldom or do not have a liquid phase).The solid phase of intermediate concentrate is usually in 10 to 100wt% scopes.
The intermediate concentrate contains the zirconium of 5wt% at least, zirconium, zirconium, zirconium or the zirconium of 30wt% at least of 20wt% at least of 10wt% at least of 8wt% at least usually.The intermediate concentrate can contain zirconium up to 30wt%, up to the zirconium of 40wt%, up to the zirconium of 50wt% or up to the zirconium of 52wt%.For example, the intermediate concentrate can contain 5 to 52wt% zirconium or 8 to 52wt% zirconium.
The intermediate concentrate if solid phase is no more than 50wt%, can be used as second raw material and uses.Perhaps, the intermediate concentrate can dilute to form second raw material by water (for example, deionized water).When second hydrothermal reactor was batch reactor, second raw material usually contained 0.5 to 50wt% solid phase or 3 to 40wt% solid phase.When second hydrothermal reactor was flow reactor, second raw material usually contained 0.5 to 25wt% solid phase or 7 to 22wt% solid phase.
Second raw material contains the zirconium of 0.3wt% at least usually.If second reactor is a batch reactor, second raw material usually contains the zirconium of 0.5wt% at least, zirconium or the zirconium of 2wt% at least of 1wt% at least.Second raw material that is used for batch reactor can contain zirconium up to 15wt%, up to the zirconium of 20wt%, up to the zirconium of 21wt%, up to the zirconium of 25wt% or up to the zirconium of 26wt%.For example, second raw material that is used for batch reactor can contain 0.3 to 26wt% zirconium or 2 to 21wt% zirconium.If second reactor is a flow reactor, second raw material usually contains the zirconium of 1wt% at least, zirconium, zirconium or the zirconium of 8wt% at least of 4wt% at least of 2wt% at least.Be used for flow reactor second raw material usually contain zirconium up to 11wt%, up to the zirconium of 12wt% or up to the zirconium of 13wt%.For example, second raw material that is used for flow reactor can contain 0.3 to 13wt% zirconium or 8 to 11wt% zirconium.
The pH value of second raw material is usually less than 7.For example, the pH value of second raw material can be no more than 6 or be no more than 5.
Second raw material carries out second hydrothermal treatment consists to form zirconia sol.If batch reactor is used for second hydrothermal treatment consists, temperature of reaction usually in 150 ℃ to 300 ℃ scopes, in 160 ℃ to 250 ℃ scopes or in 175 ℃ to 200 ℃ scopes, at least 30 minutes time.In some batch reactors, the residence time is at least 1 hour, at least 2 hours or at least 4 hours.The residence time in batch reactor can be up to 8 hours, up to 10 hours, up to 12 hours, up to 14 hours, up to 16 hours, up to 18 hours or up to 24 hours.For example, the residence time in batch reactor can be 0.5 to 24 hour, 1 to 18 hour or 1 to 14 hour.Perhaps, second hydrothermal treatment consists can be carried out in flow reactor, temperature in 150 to 300 ℃ of scopes, in 160 to 250 ℃ of scopes, in 180 to 220 ℃ of scopes or in 200 to 215 ℃ of scopes, at least 1 minute time.In some flow reactors, the residence time is at least 1 minute, at least 2 minutes, at least 5 minutes or at least 10 minutes.The residence time in flow reactor can be up to 60 minutes, up to 80 minutes, up to 90 minutes, up to 100 minutes or up to 120 minutes.For example, the residence time in the flow reactor can be 1 to 120 minute, 5 to 100 minutes or 10 to 90 minutes.
In the second hydrothermal treatment consists process, contain the zirconium intermediate and carry out further hydrolysis.The product of second hydrothermal treatment consists is the zirconia sol that contains the crystallization zirconia particles.Zirconia sol can be dry so that zirconia particles to be provided under 120 ℃ of temperature, and it contains 75 to 95% inorganic oxide usually.Zirconia particles removes outside the zirconia (that is zirconium dioxide) can also contain yttria (that is Y, 2O 3).Zirconia particles also can contain some organic substances.
In some embodiments, zirconia sol is further handled so that small part is removed the accessory substance that forms in the second hydrothermal treatment consists process.Accessory substance usually is the acid that is formed by zirconates or optional yttrium salt anionic.If the zirconia particles in the zirconia sol will combine with organic substrate to form compound substance, then usually wish to remove acidic by-products.For example, acidic by-products may be a carboxylic acid, and it can be removed by evaporation, ion-exchange, precipitation or saturating dialysis.Zirconia sol usually contains 0.5 to 55% solid phase or 2 to 51% solid phase.
Zirconia sol contains at least 0.3% zirconium usually.For example, zirconia sol may contain at least 1% zirconium, at least 2% zirconium, at least 5% zirconium or at least 10% zirconium.Zirconia sol usually contains zirconium up to 34%, the zirconium up to 35% or up to 37% zirconium.For example, zirconia sol may contain zirconium, 0.5 to 35% zirconium or 1 to 34% the zirconium of 0.3 to 37% oxidation.
The method for preparing zirconia sol comprises at least twice hydrothermal treatment consists.In some embodiments, use more than twice hydrothermal treatment consists.Between each hydrothermal treatment consists, to be removed at least partially in the acidic by-products that forms in the hydrothermal treatment consists before.
After making the zirconia sol that zirconia particles is dispersed in aqueous phase, zirconia particles is carried out surface modification.Surface modification comprises that the adding surface modifier is to form the zirconia particles of surface modification.In the method for zirconia particles of some preparation surface modifications, can remove to the small part water before or after adding surface modifier.The zirconia particles of surface modification combines with organic substrate to form coating composition.In certain methods, before or after adding organic substrate, can remove to the small part water.
Usually, surface modification can be achieved by add surface modifier in zirconia sol simply.Optional, can improve the dissolubility of surface modifier with the cosolvent of water miscibility and/or through the zirconia particles of surface modification compatibility at aqueous phase.The cosolvent that is fit to comprise can with the miscible organic compound of water as, for example, 1-methoxyl-2-propyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, N,N-dimethylacetamide, N-Methyl pyrrolidone, or the like.Cosolvent can improve the dissolubility of surface modifier and the dissolubility of surface modified granules.
Surface modification reaction can be carried out in room temperature (for example, 20 ℃ to 25 ℃) or under high temperature (for example, up to about 95 ℃).If surface modification reagent is sour as carboxylic acid, zirconia particles typically usually at room temperature carries out surface modification.If surface modification reagent is silane, zirconia particles typically at high temperature carries out surface modification.
Surface modification reaction can be carried out under acid or alkaline condition, and this depends on specific surface modifier.For example, silane can heat under acid condition with zirconia sol.Can add alkali such as ammoniacal liquor with the precipitation zirconia particles.The zirconia particles of precipitation can separate (for example, filtering out) with the surface modifier that adheres to from liquid phase.Then the zirconia particles of Fen Liing just can be dispersed in the solvent of water miscibility.
Can in all sorts of ways zirconia sol of the present invention is combined with the organic substrate material to form coating composition.In one embodiment, can use solvent exchange process.In solvent exchange process, the zirconia particles in the zirconia sol is by surface modification, and then, the organic substrate material at first joins in the zirconia sol of surface modification.Optional, before adding the organic substrate material, cosolvent such as 1-methoxyl-2-propyl alcohol or N-Methyl pyrrolidone can be joined in the zirconia sol to improve the miscibility of organic substrate material in water.Add after the organic substrate material, water and optional cosolvent can be removed by evaporation, and stay the zirconia particles that is dispersed in the organic substrate material.The method of evaporating that is fit to comprises, for example, and distillation, rotary evaporation, oven dry, or the like.
Perhaps, the method that another kind is used to prepare coating composition comprises the zirconia sol drying and then zirconia particles to be dispersed in the organic substrate to generate pulverous zirconia particles.Zirconia particles in the colloidal sol can carry out surface modification or can carry out surface modification in the presence of organic substrate before the drying.Zirconia sol can use classic method such as oven dry or spray drying process and dry be powder.For example, zirconia sol can be in traditional baking oven, drying under at least 70 ℃ temperature.Some zirconia sols can be under 70 ℃ to 90 ℃ temperature dry about 2 to 4 hours.
Prepare in the method for coating composition at another, the nonpolar carboxylic acid of the zirconia particles in the zirconia sol, for example oleic acid carries out surface modification.Nonpolar acid makes its flocculation be filterable agglomerate the zirconia particles surface modification.The zirconia particles of surface modification can pass through isolated by filtration from the liquid phase of zirconia sol then, optionally drying, and combine to form coating composition with the organic substrate material.
Prepare in the method for coating composition at another, the zirconia particles in the zirconia sol carries out surface modification with the surface modifier with nonpolar B group.The zirconia particles of surface modification can be extracted in water-immiscible solvent or the monomer, for example, toluene, hexane, ethyl acetate, styrene, or the like in, then, the zirconia particles of the surface modification that extracts can combine with oligomer, monomer or polymkeric substance.
Coating composition contains the zirconia particles and the polymerisable composition of surface modification.The polymerizable composition that is fit to as mentioned above.Polymerisable composition can contain solvent or can not contain solvent.Coating composition contacts with the little facility (that is, little surface of duplicating facility has microstructure) that duplicate with a plurality of burrs then.The coating composition polymerization contains the optical layers on the surface with microstructure with formation.
The surface with microstructure of brightness enhancement film optical layers can be configured to various forms, comprises the form that those contain a series of projectioies that replace and groove and are enough to generate complete internal reflection film.A this example with surface of microstructure is one and has the projection of regular symmetry and the repetitive pattern of groove.Other have in the pattern on surface of microstructure, and projection and groove are asymmetric.Be used for the suitable microstructure of brightness enhancement film and be further described in following United States Patent (USP): 5,175,030 (Lu etc.), 5,183,597 (Lu), 5,771,328 (Wortman etc.), 5,917,664 (O ' Neill etc.), 5,919,551 (Cobb, Jr. etc.), 6,111,696 (Allen etc.), 6,280,063 B1 (Fong etc.), 6,356,39 B1 (Gardiner etc.).
Optical layers with microstructure can be passed through, for example, and the method preparation that may further comprise the steps: (a) prepare polymerisable composition; (b) polymerisable composition is deposited to little duplicating on the facility, this machine is a negativity for the molded surface with microstructure, and deposition only is enough to fill little recess that duplicates facility; (c) by filling recess in prefabricated matrix and little pearl of duplicating (wherein at least one is flexible) mobile polymerizable composition between the facility; (d) cure component.Little facility that duplicate can be metals, as the copper or the brass of nickel, nickel plating, maybe can be that thermoplastic stable under polymerizing condition and surface energy that preferably it had make polymeric material to remove up hill and dale from little duplicating on the facility.Ad hoc approach and the United States Patent (USP) 5,691 that is used to produce configuration described herein with microstructure, resemble process described in 846.Have microstructure goods can by continuous process form with the length of any hope as, for example, 5,10,100,1000 meters or longer.
The second method of preparation light management films comprises: the zirconia sol that contains the zirconia particles that is dispersed in aqueous phase is provided, the surface of modified zirconia particle is to form the zirconia particles of surface modification, preparation contains the zirconia particles of described surface modification and the coating composition of organic substrate, make coating composition contact, and make the coating composition polymerization comprise the optical layers on surface with formation with microstructure with little facility that duplicate.Before the zirconia particles surface modification, zirconia sol comprises those carbon numbers and is not more than 4 carboxylic acid and is substantially free of the polyether carboxylic acid.Described zirconia particles mean primary particle size is not more than 50 nanometers, and dispersion coefficient is 1 to 5, and the ratio of intensity particle mean size specific volume particle mean size is not more than 3.0, and crystal structure at least 50% is cubic system, tetragonal crystal system, or its combination.In the embodiment of some zirconia sols, zirconia particles contains 0.1 to 8% yttrium, based on the weight of inorganic oxide in the zirconia particles, and has crystal structure, and wherein at least 70% is cubic system, tetragonal crystal system, or its combination.
For this method, zirconia particles can be a surface modification, and the preparation of coating composition can be as mentioned above.In addition, can, as mentioned above, by coating composition is contacted the surface that also polymer coated composition formation has microstructure with little facility that duplicate.The gained light management films can be, for example, and brightness enhancement film, reflectance coating, turning film, or the like.
Light management films can be used in combination with display such as panel of LCD.Mark as position among Fig. 2 10, backlight liquid crystal displays generally includes light management films (for example, brightness enhancement film) 11, and it can be placed between fan diffuser 12 and the panel of LCD 14.Backlight liquid crystal displays can also comprise light source 16 as fluorescent light, is used to transmit the light photoconductive tube 18 of (it is used for to panel of LCD 14 reflections), and is used for equally to the catoptrical white reflection mirror 20 of panel of LCD.Thereby the brightness that the optical alignment that light management films 11 sends photoconductive tube 18 improves panel of LCD 14.Brightness improves makes panel of LCD can generate distincter image, and the power reduction of light source 16 when making the selected brightness of generation.Light management films 11 in the backlight liquid crystal displays can be used in the following equipment: as the instrument display board of graphoscope (kneetop computer display and computer monitor), TV, video recorder, mobile communication equipment, hand portable equipment (for example mobile phone and PDA(Personal Digital Assistant)), automobile and aircraft electrical subset, or the like, by reference marker 21 expressions.
Light management films 11 contains prismatic array, by prismatic 22,24,26 and 28 expressions, as shown in Figure 3.Each prism for example, as prism 22, has first facet 30 and second facet 32. Prismatic 22,24,26 and 28 can form on main part 34, main part 34 has first surface 36, prismatic being formed on the first surface 36, main part 34 also has second surface 38, and this surface is smooth or flat and relative with first surface basically.
The linear array of rule right prism can provide the simplification of optical property and manufacturing simultaneously.Described right prism is meant that vertex angle theta is approximately 90 degree, but also can spend to 120 degree about 70, or spends in the scopes of 100 degree from about 80.Prismatic facet needs not be identical, and prism can relative to each other tilt.In addition, the thickness 40 and the relation between the prism heights 42 of film are not critical, but wish to use the thin film and the prismatic facet of sharp outline.If the facet angle facet is protruded, facet can be 45 degree with the angle that surface 38 forms.But this angle can change with the inclination angle or the vertex angle theta of facet.
Fig. 4 to 10 shows the representative embodiment that is used for light management films (for example, brightness enhancement film) structure.What should be noted that is, these accompanying drawings be not proportional and, especially, the size of body structure surface is greatly amplified to reach exemplary purpose.The structure of light management films can comprise the combination of two or more embodiments hereinafter described.
With reference to figure 4, it shows the part of the representative xsect of a light management films embodiment.Light management films 130 (for example, brightness enhancement film) comprises first surface 132 with relative structurized surperficial 134, and the latter is contained the prism elements 136 that a plurality of substantial linear are extended.Each prism elements 136 have first side 138 and second side 138 ', its top margin intersects the peak point that has defined prism elements 136, or top 142.The side 138,138 of contiguous prism elements 136 ' the base intersect the groove 144 that forms linear extension between the prism elements.In embodiment shown in Figure 4, prismatic top 142 dihedral angles that define are determined as about 90 degree, but the accurate measurement that is to be understood that dihedral angle in this and other embodiment may be according to the optical parameter of hope and difference.
The patterned surface 134 of light management films 130 can be described as having the graded area of a plurality of prism elements, and described prism elements has the peak point that is configured in apart from the common reference face different distance.Common reference field can be selected arbitrarily.A simple example of common reference field is the plane of containing first surface 132; Another is the plane that minimum bottom portion of groove defined by structurized surface, shown in dotted line 139.In embodiment shown in Figure 4, shorter prism elements is of a size of about 50 microns wide and about 25 microns high, measure from dotted line 139, and higher prism elements size is approximately wide 50 microns and high about 26 microns.The zone that comprises higher prism elements, its width dimensions is between about 1 micron and 300 microns.The zone that comprises shorter prism elements, its width are not critical, and size can be between 200 microns and 4000 microns.In any given embodiment, the zone of shorter prism elements at least can be wide equally with the zone of higher prism elements.Should be appreciated that to those skilled in the art optical layers described in Fig. 4 only is exemplary and does not plan to limit the scope of the invention.For example, the height of prism elements or width can change (for example, machining go out to stretch out about 1 micron be feasible to about 200 microns accurate prism) in feasible limited field.In addition, dihedral angle can change or prism axis can tilt with the optical effect that obtains wishing.
The width of first area can be less than about 200 to 300 microns.Under normal observation condition, human eye is difficult to tell the little variation of the light intensity that takes place in about 200 to 300 microns width regions.Therefore, if the width of first area is reduced to less than about 200 to 300 microns, any being optically coupled under the normal observation condition of taking place in should the zone can't be detected with human eye.
Can also realize the structurized surface of alterable height by the height that changes one or more prisms along the range of linearity, contain with generation and be higher than the zone that replaces that common reference field and peak point are configured in the part prism elements on the differing heights.
Fig. 5 illustrates another embodiment that is similar to Fig. 4 light management films, difference (for example is light management films 150, brightness enhancement film) contain structurized surperficially 152, it has the zone of the relative shorter prism elements 154 of the zone of being contained single higher prism elements 156 separating.Be very similar to the embodiment described in Fig. 4, higher prism elements defines second thin slice and structurized surperficial 152 the physical proximity of film, thereby has reduced the possibility of visible wet-out condition.Determine that human eye has susceptibility to the variation of light guiding film facet height, and the wide relatively zone of higher prism elements can show as the lip-deep visible lines of film.Although this can not have substantial influence to the optical property of film, described lines may be undesirable in some industrial situations.The width regions that reduces higher prism elements can correspondingly reduce human eye detection ability by lines that higher prism elements causes in the film.
Fig. 6 is the representative example of another embodiment of light management films (for example, brightness enhancement film), wherein prismatic element approximately be identical size but by the step that repeats or the arranged in patterns of inclination.Light management films 160 described in Fig. 6 contains the patterned surface 164 of first surface 162 and the relative prismatic element 166 that contains a plurality of substantial linear.Each prismatic element have relative side 168,168 ', it intersects to define prism peak point 170 at upper limb.The dihedral angle metering of opposite flank 168,168 ' define is approximately 90 degree.The highest prism can be considered to the first area and contiguous prism can be considered to second area in this embodiment.Equally, the metering of first area can be less than about 200 to 300 microns.
Fig. 7 illustrates another embodiment of light management films (for example, brightness enhancement film).The disclosed light management films 180 of Fig. 7 comprises first surface 182 and relative structurized surperficial 184.The light management films feature can be to comprise relatively and contain the prism elements with differing heights in the second area than short prismatic element.The described structurized surface of Fig. 7 has extra advantage, promptly reduced basically because prismatic element heights changes on the optical layers surface that causes lines to the observability of human eye.
Fig. 8 has shown another embodiment of light management films (for example, brightness enhancement film), and it provides flexible by (soft cutoff).The light management films that Fig. 8 shows is usually as 240 marks.Light management films 240 contains basalis 242 and has the optical layers 244 of microstructure.The outside surface of basalis 242 is preferably smooth, but can be structurized equally.In addition, can use other matrix.
Optical layers 244 with microstructure has a plurality of prisms of formation thereon as prismatic 246,248 and 250.Prismatic 246,248 and 250 have peak point 252,254 and 256 respectively.All peak points 252,254 and 256 peak point or prism angle are preferably 90 degree, are the angles of 60 degree to 120 degree although comprise scope.Between prismatic 246 and 248 is paddy portion 258.Between prismatic 248 and 250 is paddy portion 260.Paddy portion 258 can be considered to have the paddy portion relevant with prismatic 246 and paddy portion angle is 70 degree, and it is 110 degree that paddy portion 260 can be considered to paddy portion and the paddy portion angle relevant with prismatic 248, although can use other values.In fact, brightness enhancement film 240 improves by reflection and recirculation portion light splitter and with all the other light refractions and axially goes up apparent brightness backlight, and this is similar to the brightness enhancement film of prior art, but prismatic direction by checker cuts corner angle.The effect of prismatic corner cut has been to improve the size of output light cone.
Fig. 9 has shown another embodiment of light management films (for example, brightness enhancement film), and it is top that it has the roundel prism.That light management films 330 is characterised in that is flexible, with the integrally formed basalis 332 of optical layers.This light management films has a pair of facing surfaces 334,336, and both and basalis 332 integrally form.Surface 334 is characterised in that the light scatter element 338 of a series of protrusions.The ＂ projection ＂ form of these elements in can the surface is by making with layer 332 identical materials.The spy on surface 336 is loaded in a series of linear prism, and it has peak blunt or roundel point 340, integrally forms with basalis 332.These peak points are characterised in that string 342, the inclination angle width 344 in cross section, and radius-of-curvature 346, and root angle 348, wherein the string width equals about 20-40% of inclination angle, cross section width, and radius-of-curvature equals about 20-50% of inclination angle, cross section width.The root angle scope is about 70-110 degree, or about 85-95 degree, about 90 degree of wherein preferred root angle.Select the feasible optical property maximization of wishing of the inner prismatic placement of array.
Goods (for example, light management films) with circular prismatic top microstructure can make gain reduce usually.But the surface modification colloid nano particle that adds high index of refraction of the present invention can compensate the gain that goods lost with circular prismatic top microstructure.
Figure 10 has shown another embodiment of light management films (for example, brightness enhancement film), and it has smooth or flat prismatic top.That light management films 430 is characterised in that is flexible, with the integrally formed basalis 432 of optical layers.This brightness enhancement film has a pair of facing surfaces 434,436, and both and basalis 432 integrally form.Surface 434 is characterised in that the light scatter element 438 of a series of protrusions.The ＂ smooth projection ＂ form of these elements in can the surface is by making with layer 432 identical materials.Surface 436 is characterised in that the linear prism array with peak pressing or flat point 440, and itself and basalis 432 integrally form.These peak points are characterised in that the inclination angle width 444 that flattens width 442 and cross section, wherein flatten about 0-30% that width equals the inclination angle width in cross section.
Another method of extracting light from photoconduction is to use frustrated total internal reflection (TIR).Be subjected to press down among the TIR a kind of, photoconduction has wedge shape, light incide on the webbing of photoconduction and by internal reflection fully up to the critical angle that reaches with respect to photoconduction top and lower surface.These subcritical angle light are extracted then, or refract to output surface with glancing angle more easily from photoconduction.In order to can be used for illuminating display device, these light must be diverted to observation or the output shaft that is arranged essentially parallel to display device.This turning to usually by using relay lens or turning film to realize.
Figure 11-13 illustrates the lighting device that contains turning film.Turning film can comprise the material of the present invention that is used to form durable turning film disclosed herein.Relay lens or turning film typically are included in the input surface and go up the prism structure that forms, and the input surface configuration is at the adjacent light guides place.Light withdraws from photoconduction with glancing angle, and common and output surface angle is spent less than 30, runs into prism structure.Light is by the first surface of prism structure refraction and by the reflection of the second surface of prism structure, thereby it is diverted the direction that lens or turning film are directed to hope, for example, is arranged essentially parallel to display and observes axle.
With reference to Figure 11, illuminator 510 comprises the light source 512 of coupling on the optics; Light source reflector 514; Photoconduction 516 and output surface 518, the back side 520, input surface 521 and end face 522; The catoptron 524 contiguous back sides 520; First light is redirected element 526 and input surface 528 and output surface 530; Second light is redirected element 532; And reflective polarizer 534.Photoconduction 516 can be wedge shape or its remodeling.As everyone knows, the purposes of photoconduction be on big a lot of zones than light source 512 for the light from light source 512 provides even distribution, more particularly, be basically on the Zone Full that output surface 518 forms.Photoconduction 516 further preferably in compactness, is finished this task in the thin assembly.
Light source 512 can be CCFL, and 521 limits, input surface of itself and photoconduction 516 are coupled together, and light source reflector 514 can be a reflectance coating, and it is wrapped in light source 512 peripheries and forms the light source die cavitys.Catoptron 524 supports photoconduction 516 and can be effective backreflection mirror, for example, and lambert or specular film or its combination.
The light of limit coupling is propagated to end face 522 from importing surface 521, is limited by TIR.Light is subjected to press down TIR and is extracted from photoconduction 516.Be limited in the light in photoconduction 516 scopes, because the existence of the angle of wedge is beated with each TIR, its incident angle with respect to top and base wall plane improves.Therefore, light finally reflects from each output surface 518 and back of the body surface 520, because it is no longer limited by TIR.Be reflected mirror 524 dorsad or direct reflection or diffuse reflection from the light of carrying on the back surface 520 refractions, and mainly pass photoconduction 516.The arrangement that first light is redirected element 526 is redirected light to withdraw from output surface 518 along the direction that is arranged essentially parallel to the preferred view direction.The preferred view direction can be perpendicular to output surface 518, but more typically angled with output surface 518.
As shown in figure 12, it is light management films of light transmission that first light is redirected element 526, its output surface 530 be basically the plane and input surface 528 has formed prismatic 538,540 and 542 array 536.It also can be the film of light transmission that second light is redirected element 532, brightness enhancement film for example, as 3M Brightness Enhancement Film product (sell with trade name ＂ BEFIII ＂, from 3M Company, St.Paul, MN).Reflective polarizer 534 can be inorganic, polymerization, cholesteryl liquid crystal reflective polarizer or film.The film that is fit to is 3M Diffuse ReflectivePolarizer film product (being sold with the trade name of ＂ DRPF ＂ by 3M Company) or SpecularReflective Polarizer film product (being sold with the trade name of ＂ DREF ＂ by 3M Company).
In array 536 inside, each prism 538,540 with 542 can with contiguous prismatic form different side angles with respect to each.That is, prismatic 538 (the angle A and B) of prismatic 540 (angle C and D), and prismatic 542 (angle E and F) can form different side angles.As shown, prismatic 538 prism angle, that is, interior angle equals angle A and B sum.Similarly, prismatic 540 prism angle equals angle C and D sum, and prismatic 542 prism angle equals angle E and F sum.Although array 536 comprises three prism structures based on different prism angles among the figure, it should be understood that and to use almost any amount of different prism.
Prism 538,540 also can form common prism angle with 542 but have different prism orientation.The prism axis ＂ l ＂ of prism 538 is shown among Figure 12.Prism axis l can be set to perpendicular to output surface 530, shown in prism 53 8, or angled with output surface, perhaps towards or leave light source, as respectively for the video axle ＂ l+ ＂ and the ＂ l-＂ of prism 540 and 542.
Prism 538,540 and 542 can be arranged on array 536 inside as shown in figure 12, is arranged as bunches 543 of the repetitive pattern of rule or prism, if the contiguous place of alike prism does not have alike prism among array 536 figure, also can use such structure.In addition, array 536 inside, prism 538,540 and 542 can as prism structure 538, change to second prism structure continuously from first prism structure, as prism structure 540, or the like.For example, prism structure can be changed into second prism structure from first prism structure in the gradient mode.Perhaps, prism can change in mode progressively, is similar to structure shown in Figure 12.Each bunch 543 inside, prism has the prism inclination angle, selects its feasible ripple frequency less than the space.Equally, bunch bunch inclination angle that can have rule.Prism array can be symmetrical, and as shown in figure 12, or prism array can be asymmetric.
If the array 536 that is shown in Figure 12 has the prism of balanced configuration, can use such prism array, as be shown among Figure 13 array 536 in light-redirecting element 526 ' middle formation '.Then with reference to Figure 13, array 536 ' in, prism 538 ' the have angle A ' that is not equal to angle B ' for example.Similarly, for prism 540 ' and 542 ', angle C is not equal to angle A ' and angle D ', and angle E ' is not equal to angle A ', angle C ' or angle F ' any one.Array 536 ' can advantageously use single diamond cut facility to form predetermined angle has different prism angles and symmetric prism to each cutting inclination facility with generation.But, should be appreciated that by means of single cutting implement, prism angle should be identical, that is, i.e. and A+B=C+D=E+F.
Use in expection array 536 inner tuft and different prism structures are set may be as few as two, although can use abundant prism dimensions the distribution plan of output from photoconduction 516 to be retrofited realizing as required.The purpose that the prism side angle changes is that first light is redirected the amount that variable light intensity is expanded and added to element 526.Prism 538,540 and 542 different structure are used to provide sampling uniformly basically on the photoconduction input aperture, and the heterogeneity of the light that this will extract from photoconduction 516 drops to minimum.Last net result is that the general minimizes near the ripple effect of photoconduction 516 entrance points 521 especially effectively.
The present invention should not be regarded as being limited to specific embodiment described here, should be appreciated that, it has covered whole aspect of the present invention, in claims clear define.Various modification, equivalent processes, and numerous structures that the present invention can be suitable for just should be conspicuous with reference to this instructions directly for the technology people in field involved in the present invention.
Embodiment
Test method
Photon correlation spectroscopy (PCS)
(derive from Malvern InstrumentsInc., Southborough MA), measures volume average particle size with photon correlation spectroscopy (PCS) to use Malvern Series 4700 particle size analyzers.Use the syringe applied pressure with the zirconia sol sample filtering of dilution by 0.2 μ m filtrator, be filled in the hyaloid cup and with its covering.The sample chamber temperature balance is 25 ℃ before the beginning data acquisition.Application institute joins software and carries out the CONTIN analysis with an angle of 90 degrees.CONTIN is widely used mathematical method, is used to analyze general inverse transformation problem, and it is further described in S.W.Provencher, Comput.Phys.Commun., in 27,229 (1982).Analysis is carried out with 24 bit data.Use following numerical value in the calculating: the refraction coefficient of water equals 1.333, and the viscosity of water equals 0.890 centipoise, and the refraction coefficient of zirconia particles equals 1.9.
Measure according to two kinds of particle diameters of PCS data computation.The intensity mean grain size is a unit with the nanometer, equals the size corresponding to the particle of scattered light intensity distribution average.Six powers of scattered light intensity and particle diameter are in direct ratio.Volume average particle size is a unit with the nanometer also, stems from the volume distributed median that is obtained by the scattered light intensity Distribution calculation, has considered the refraction coefficient of zirconia particles and the refraction coefficient of dispersion medium (that is water) in the calculating simultaneously.Volume average particle size equals the particle diameter corresponding to volume distributed median mean value.
The intensity mean grain size can be represented size distribution divided by the ratio that volume average particle size obtains.
Crystal structure and size (XRD analysis)
With the zirconia samples of agate mortar and pestle hand lapping drying to reduce particle diameter.The sample of q.s is coated on the glass slide with scraper, has adhered to the band of a part of double spread on it.By with wing sample being pressed to band and sample being pressed in the cementing agent in the band.Excess sample scrapes sample area to be removed with the blade of wing, stays skim and is attached to particle on the cementing agent.Remove the remaining loose material of scraping after removing that adheres to by microslide being forced pat on crust.In a similar manner, and preparation emery (Linde 1.0 μ m aluminum oxide polishing powders, lot number C062, Union Carbide, Indianapolis is IN) and in order to the diffractometer of calibration instrument broadening.
Use the vertical diffractometer of Philips to obtain X-ray diffraction scanning, it has reflection geometry, copper K αThe ratio detector of radiant rays and record scattered radiation.Diffractometer has variable incident wave beam slit, fixing diffracted beam slit and graphite diffracted beam monochromator.Scanning is comprehensively observed at from 25 to 55 degree 2 θ angles, uses 0.04 degree step-length, 8 seconds residence time.X ray generator is set to 45kV and 35mA.The data acquisition of emery standard is carried out in three separate areas of several separate emery slide glass.On three separate areas of thin-layer sample slide glass, collect data.
Observed diffraction peak and International Center for Diffraction Data (ICDD) powder diffraction data storehouse (serial 1-47, ICDD, Newton Square, PA) the reference diffractogram in is compared differentiating, and belongs to cube/zirconia of tetragonal crystal system (C/T) or monoclinic (M).(111) peak of cube phase and (101) peak of tetragonal crystal system phase can't separate, so these records together mutually.According to the amount of each zirconia form of relative basic evaluation, its relative intensity numerical value of zirconia form that diffraction peak is the strongest is designated as 100.The strongest line of the zirconia form of all the other crystallizations is graded with respect to intense line and is obtained numerical value between 1 and 100.
Measure the peak width of observe by the distribution plan match by the diffraction peak of emery generation.For measuring the relation between emery peak width mean value and the emery peak position (2 θ angle), these data can be carried out fitting of a polynomial to generate a continuous function, so that the instrument width at any peak position place in the assessment emery trial stretch.The zirconia diffraction peak peak width that observes is carried out match by the diffraction peak distribution plan that will observe and is measured.Assess following peak width mutually according to the zirconia of finding to exist.
Cube/tetragonal crystal system (C/T): (111)
Monoclinic system (M): (111) and (111)
All use K under all situations α 1And K α 2Pearson VII peak shape model under the wavelength component, and linear background model.Width is defined as the halfwidth (FWHM) at peak, and unit is degree.The distribution plan match is achieved by the function of using JADE diffraction package software.Carry out the assessment of sample peak width for three mask datas collections that obtain on the same thin-layer sample slide glass.
By the width numerical value of emery instrument calibration gained instrument, use the instrument broadening at interpolation method calibration sample peak, the peak width of calibration is converted into Rad.The Scherrer formula is used to calculate the size of primary crystal.
Crystallite dimension (D)=K λ/β (cos θ)
In the Scherrer formula,
K=waveform factor (getting 0.9 herein);
λ=wavelength (1.540598 );
Peak width (unit is a radian)=[width of the FWHM-instrument at the peak of calculating] (being converted into radian) of calculating after β=instrument broadening calibration, wherein FWHM is a halfwidth;
θ=1/2 peak position (scattering angle).
Cube/measurement of tetragonal crystal system crystallite dimension uses the average of three measured values at (111) peak.
Cube/tetragonal crystal system average grain size=[D (111) Area 1+ D (111) Area 2+ D (111) Area 3]/3
Monoclinic crystallite dimension uses the average of three measured values at three measured values at (111) peak and (111) peak to measure.
Monoclinic mean value crystallite dimension=
[D (111) Area 1+ D (111) Area 2+ D (111) Area 3+
D (111) Area 1+ D (111) Area 2+ D (111) Area 3]/6
Calculate cube/tetragonal crystal system (C/T) and monoclinic system (M) weighted mean mutually.
Weighted mean=[(%C/T) (C/T Size(the M of)+(%M) Size)]/100,
In this formula,
In the %C/T=zirconia particles cube and the percent crvstallinity of tetragonal crystal system crystallite composition contribution;
C/T Size=cube and the size of tetragonal crystal system crystallite;
The percent crvstallinity of monoclinic crystallite component content contribution in the %M=zirconia particles;
M SizeThe size of=monoclinic system crystallite.
Dispersion coefficient
Dispersion coefficient equals the crystallite dimension weighted mean that volume average particle size that the PCS method records records divided by XRD.
The solid phase percent by weight
The measurement of solid phase percent by weight is that the sample that heavy 3-6 restrains was obtained down at 120 ℃ in dry 30 minutes.Percent solids can use wet sample weight (that is, the weight of weighing before the drying, weight in wet base) and dry sample weight (that is, the weight of weighing after the drying, dry weight) to calculate by following formula:
Solid phase wt%=100 (dry weight)/weight in wet base
Thermogravimetric analysis (TGA)
Contain the conversion ratio of zirconium intermediate and the percent by weight of inorganic oxide and measure by thermogravimetric analysis, and the 2950 TGA type instruments of use TA Instruments (New Castle, DE).
For mensuration contains the conversion ratio of zirconium intermediate, sample (for example, 3-6 gram) earlier in 120 ℃ of baking ovens heating 30 minutes with drying.Dry sample (as, 30-60 milligram) in TGA in 85 ℃ of following balances.Temperature is brought up to 200 ℃ with 20 ℃/minute speed then, keeps 20 minutes at 200 ℃, brings up to 900 ℃ with 20 ℃/minute speed, and keeps 20 minutes at 900 ℃.Organic substance volatilizees between 200 ℃ and 900 ℃ and only stays inorganic oxide such as ZrO 2And Y 2O 3Use following formula calculated weight percent loss.
Loss in weight %=100 (%200 ℃ of weight-%900 ℃ of weight)/%900 ℃ weight
The weight (dry weight) of example weight when wherein, %200 ℃ of weight is by 200 ℃ (200 ℃ of weight) and the dry sample that is used to analyze (for example, analyze before at the sample of 120 ℃ of dryings) is calculated.
%200 ℃ of weight=100 (200 ℃ of weight)/dry weight
The weight (dry weight) of %900 ℃ of weight example weight (900 ℃ of weight) and dry sample of being used to analyze during by 900 ℃ (for example, analyze before at the sample of 120 ℃ of dryings) is calculated.
%900 ℃ of weight=100 (900 ℃ of weight)/dry weight
The conversion ratio that contains the zirconium intermediate can be represented with following formula
% conversion ratio=100 (A-B)/(A-C)
Wherein: A is the loss in weight number percent of first raw material, and B is the number percent that contains the zirconium intermediate loss in weight, and C is the number percent of the zirconia sol loss in weight.
The percent by weight of inorganic oxide is calculated by solid phase percent by weight and 900 ℃ of following oxide weight percentages.That is, the inorganic oxide percent by weight can use following formula to calculate:
Inorganic oxide weight %=(solid phase weight %) (900 ℃ of weight %)/100
Refraction coefficient
Refraction coefficient uses the Abbe refractometer to measure, and (Ivyland, commercial goods PA) available from Milton Roy Co. are counted in refraction.
Term
Except as otherwise noted, all chemical reagent derive from or can derive from Aldrich ChemicalCo., Milwaukee, WI.
When being used for this paper,
" or ＂ TMPA ＂ refers to trimethylolpropane triacrylate to ＂ SR-351, derives from SartomerCo., Inc., Exton, PA;
＂ BR-31 ＂ refers to tribromo-benzene oxygen ethyl propylene acid esters, derives from Dai-Ichi Kogyo SeiyakuCo., Ltd., Kyoto, Japan;
＂ SR-339 ＂ refers to phenoxyethyl acrylate, derives from Sartomer Co., Inc., Exton, PA;
＂ SILQUEST A-174 ＂ refers to the trimethoxy silylpropyl methacrylate, derives from OSi Specialties North America, South Charleston, WV;
＂ SILQUEST A-1230 ＂ refers to derive from OSi Specialties North America, SouthCharleston, the special silane of WV;
＂ SR-238 ＂ refers to hexanediol diacrylate, derives from Sartomer Co., Inc., Exton, PA;
＂ BCEA ＂ refers to propenoic acid beta-carboxyl ethyl ester, derives from Cytec Surface Specialties, Smyrna, GA;
＂ NOEA ＂ refers to 1-naphthalene oxygen ethyl propylene acid esters, according to United States Patent (USP) 6,541, and 591 preparations;
＂ NSEA ＂ refers to 2-naphthalene sulphur ethyl propylene acid esters, according to common unsettled U.S. Patent application 11/026573 described preparation;
＂ RDX-51027 ＂ refers to the tetrabromobisphenol A diacrylate, derives from Surface Specialties, Inc., Smyrna, GA;
＂ MEEAA ＂ nail oxygen ethoxyacetic acid derives from Aldrich Chemical Co., Milwaukee, WI;
＂ HDDA ＂ refers to hexanediol diacrylate, derives from Aldrich Chemical Co., Milwaukee, WI;
＂ TMPTA ＂ refers to trimethylolpropane triacrylate;
＂ TPO-L ＂ refers to 2,4,6-trimethyl benzoyl diphenyl phosphinate, according to trade name ＂ LUCIRIN TPO L ＂ available from BASF Corp., Florham Park, NJ; And
＂ PROSTAB 5198 ＂ refer to polymerization inhibitor, derive from Ciba Specialty Chemicals, Tarrytown, NY.
The preparation of brightness enhancement film
Using little facility that duplicate that the preparation of polymerisable resinous principle is become brightness enhancement film, is 90 degree by the defined drift angle of prism sides slope in the facility.
In a series of experiments, use-case 1-5,7 and 8 resin, about 50 microns of mean distance between the contiguous pinnacle, the pinnacle of prism is sharp keen, prism changes along the height of its length direction, is similar to the brightness enhancement film that 3M Company sells with trade name ＂ VIKUITI BEF III90/50 FILM ＂.Polymerisable resinous principle is heated to about 50 ℃ temperature and impouring is little duplicates in the facility, inject volume and be enough to produce continuous film.The polyethylene terephthalate film (PET) of 5mil is contacted with polymerisable resin.PET, polymerisable resin, and littlely duplicate the pulling of the coated carrying device of facility, thus make polymerisable resin expand at PET and little duplicating between the facility.Applying band makes the thickness of polymerizing resin be approximately 25 microns with respect to little position of duplicating facility.Little duplicate between facility and the PET film form polymerisable resin bed after, polymerisable resin bed solidifies with ultraviolet curing equipment, during curing polymerisable resin is exposed to about 3000 millijoules/cm 2Ultraviolet light under.After the curing, polymer resin and PET film are peeled off from little facility that duplicate.
In the second series experiment, use the resin that derives from example 4, about 24 microns of the mean distance (＂ HTBEF ＂) between the contiguous pinnacle, the pinnacle of prism vertex angle is sharp keen.Polymerisable resinous principle is heated to about 50 ℃ temperature and impouring is little duplicates in the facility, inject volume and be enough to produce continuous film.The polyethylene terephthalate film (PET) of 2mil is contacted with polymerisable resin.PET, polymerisable resin, and littlely duplicate the pulling of the coated carrying device of facility, thus polymerisable resin is expanded at PET and little duplicating between the facility.Applying band makes polymerisable resin thickness be approximately 13 microns with respect to little position of duplicating facility.Little duplicate between facility and the PET film form polymerisable resin bed after, polymerisable resin bed solidifies with the ultraviolet spotter, during curing polymerisable resin is exposed to about 3000 millijoules/cm 2Ultraviolet light under.After the curing, polymer resin and PET film are peeled off from little facility that duplicate.
In the experiment of tertiary system row, use the resin that derives from example 6, it is coated to that brightness enhancement film (deriving from the commercial goods of the trade name ＂ VIKUITI DBEF-P ＂ of 3M) goes up rather than the PET film on, about 24 microns of mean distance between the contiguous pinnacle, the pinnacle of prism vertex angle is sharp keen.Polymerisable resinous principle is heated to about 50 ℃ temperature and impouring is little duplicates in the facility, inject volume and be enough to produce continuous film.VIKUITI DBEF-P film is placed into and polymerisable resin position contacting.VIKUITI DBEF-P film, polymerisable resin, and littlely duplicate the pulling of the coated carrying device of facility, thus make polymerisable resin expand at VIKUITI DBEF-P film and little duplicating between the facility.Applying band makes polymerisable resin thickness be approximately 13 microns with respect to little position of duplicating facility.Little duplicate between facility and the VIKUITI DBEF-P film form polymerisable resin bed after, polymerisable resin bed solidifies with the ultraviolet spotter, during curing polymerisable resin is exposed to about 3000 millijoules/cm 2Ultraviolet light under.After the curing, polymer resin and VIKUITI DBEF-P film are peeled off from little facility that duplicate.
The gain of gained brightness enhancement film is with deriving from Photo Research, Inc, Chatsworth, the SpectraScan of CA TMPR-650 SpectraColorimeter measures.The gain of embodiment brightness enhancement film is shown in table 1.With brightness enhancement film sample cutting and be positioned in the Teflon lamp box, this lamp box uses Foster DCR II light source to illuminate by photoconductive tube, and makes the groove of prism be parallel to the front of Teflon lamp box.A polarizing coating is placed on brightness enhancement film top, thus polarizing coating pass through a front perpendicular to the Teflon lamp box.For some samples, second identical brightness enhancement film be placed under first thin slice and directed, thereby make the groove of second thin slice perpendicular to the front of Teflon lamp box.
The structure of reflection reducting coating that is used for gain measurement is called the ＂ HBEF III ＂ (film that first serial experiment prepares, promptly be similar to the brightness enhancement film that 3M Company sells with trade name ＂ VIKUITI BEF III90/50 FILM ＂), " HXBEF III ＂ (piling up of two HBEF III films that derive from first serial experiment; it places and makes each film burr pinnacle vertical mutually with another film on the Teflon lamp box; and distance is 50 microns between the contiguous pinnacle); ＂ HTBEF ＂ (film of second series Experiment Preparation; wherein the distance on contiguous pinnacle is 24 microns); ＂ HXTBEF ＂ (piling up of two HTBEF films that derive from the second series experiment, wherein those of each film burr pinnacle and another film are vertical mutually), the ＂ HDBEF ＂ (film of tertiary system row Experiment Preparation, wherein the distance on contiguous pinnacle is 24 microns), ＂ HDBEF/T-BEF ＂ (piling up of two films, one of them film is by tertiary system row Experiment Preparation, another film is to derive from 3M Company, with the commercial goods of trade name ＂ VIKUITI T-BEF ＂ sale).
Preparation embodiment 1: the preparation of zirconia sol 1
With hydration yttrium acetate (38.58 grams; Derive from Aldrich Chemical Co., Milwaukee WI) is dissolved in zirconium acetate solution (1500.0 grams; Derive from Nyacol Nano Technologies, Inc.Ashland, MA) in.Potpourri is dried overnight at room temperature, then further in the forced draft case in 90 ℃ of dryings 4 hours.The solid that obtains is dissolved in enough deionized waters to obtain the solution of 12.5wt%.This solution (that is, first raw material) passes the stainless-steel tube of 100 feet 0.25 inch of external diameter with the speed pumping of 80 milliliters of per minutes, and pipe is dipped in the oil bath that is heated to 206 ℃.Fluid passes other one section 40 feet long pipe that are dipped in the ice-water bath then.Back pressure regulator is placed so that top hole pressure remains on 260 to 290psig in the pipeline end.This step products is the suspending liquid of white solid particulate.Liquid suspension uses rotary evaporator to be concentrated into the solid that contains 14.5wt%.The suspending liquid (that is, second raw material) that should concentrate passes the stainless-steel tube of 100 feet 0.25 inch of external diameter with the speed pumping of 10 milliliters of per minutes, and pipe is dipped in the oil bath that is heated to 206 ℃.Fluid passes other one section 40 feet long pipe that are dipped in the ice-water bath then.Back pressure regulator is placed so that top hole pressure remains on 260 to 270psig in the pipeline end.This step products is colloidal sol (that is, zirconia sol), and recording its solid is 10.5wt%.The characterization data of this preparation embodiment is listed in table 2 and 3.
Preparation embodiment 2: the preparation of zirconia sol 2
With hydration yttrium acetate (79.5 grams; Derive from Aldrich Chemical Co., Milwaukee WI) is dissolved in zirconium acetate solution (3000.0 grams; Derive from Nyacol Nano Technologies, Inc.Ashland, MA) in.Potpourri is dried overnight at room temperature, then further in the forced draft case in 90 ℃ of dryings 4 hours.The solid that obtains is dissolved in enough deionized waters to obtain the solution of 12.5wt%.This solution (that is, first raw material) is crossed 100 feet long stainless steel pipeline of 0.25 inch of external diameter with the speed pump of 80 milliliters of per minutes, and described pipeline is dipped in the oil bath that is heated to 206 ℃.Other 40 feet long lines that are dipped in the ice-water bath are passed in logistics then.Back pressure regulator is placed so that top hole pressure remains on 250 to 310psig in the pipeline end.This step products is the suspending liquid of white solid particulate.Liquid suspension uses rotary evaporator to be concentrated into the solid that contains 14.5wt%.This concentrated suspension liquid (that is, second raw material) is crossed 100 feet long stainless steel pipeline of 0.25 inch of external diameter with the speed pump of 10 milliliters of per minutes, and described pipeline is dipped in the oil bath that is heated to 206 ℃.Other 40 feet long lines that are dipped in the ice-water bath are passed in logistics then.Back pressure regulator is placed so that top hole pressure remains on 230 to 340psig in the pipeline end.This step products is colloidal sol (that is, zirconia sol), and it uses rotary evaporator to concentrate so that the colloidal sol of concentration 40.5wt% to be provided.The characterization data of this preparation embodiment is listed in table 2 and 3.
Preparation embodiment 3: the preparation of zirconia sol 3
Preparation and the identical potpourri of preparation embodiment 2 compositions.Use is similar to preparation embodiment 2 described processes, the another kind of zirconia sol of preparation in having the hydrothermal reactor of bigger caliber.The characterization data of this preparation embodiment is listed in table 2 and 3.
Embodiment 1
With the zirconia sol of preparation embodiment 1 use MWCO greater than 12,000 dialysis membrane (derive from Sigma-Aldrich Corp., St.Louis, MO) dialysis is about 12 hours, to obtain containing the stable sol of 10.93wt% solid.The zirconia sol (435.01 gram) and the MEEAA (9.85 gram) of dialysis are joined in 1 liter of round-bottomed flask, and potpourri is concentrated by rotary evaporation.Then isopropyl alcohol (30 gram) and NSEA (35.00 gram) are joined in the concentrated colloidal sol to form dispersion.Concentrate dispersion to obtain curable resin with rotary evaporator afterwards, it contains the zirconia of 48.83wt%, and refraction coefficient is 1.674.Prepare potpourri by in 40.09 these curable resins of gram, adding 0.39 gram TPO-L.Then, in 10.03 these potpourris of gram, add 0.98 gram SR-351.
Embodiment 2
With the zirconia sol of preparation embodiment 1 use MWCO greater than 12,000 dialysis membrane (derive from Sigma-Aldrich Corp., St.Louis, MO) dialysis is about 12 hours, obtains having the stable sol of 10.93wt% solid.The zirconia sol of dialysis (437.02 gram) and MEEAA (10 restrain) joined in 1 liter the round-bottomed flask, this potpourri is concentrated into drying with rotary evaporator then.The powder that obtains like this is dispersed in the deionized water to obtain containing the zirconic potpourri of 21.45wt%.This dispersion (206.5 gram) is added in the wide-necked bottle also under agitation to wherein adding 1-methoxyl-2-propyl alcohol (300 gram), SILQUEST A-174 (9.89 gram), and SILQUESTA-1230 (6.64 gram).Then in the band nut jar with 1 liter of this potpourri impouring, sealing and 90 ℃ of heating 3 hours.Potpourri is transferred in the round-bottomed flask and is concentrated potpourri (that is the zirconia of Nong Suoing) to obtain the about 25.4wt% of zirconia content with rotary evaporator then.
The ammoniacal liquor (solution of 13.9 gram 29wt%) that in the 1L beaker, adds deionized water (450 gram) and concentrate.Adding the zirconia dispersion that concentrates at leisure in this beaker stirs simultaneously.With the white precipitate that obtains like this by isolated by vacuum filtration and use deionized water wash.The solid product of humidity is dispersed in round-bottomed flask in 1-methoxyl-2-propyl alcohol to obtain the potpourri of solids content 20.53wt%.With potpourri (117.03 gram), SR-339 (15.12 gram), HDDA (1.68 gram) and 5wt%PROSTAB 5198 solution (0.13 gram) in water joins in the round-bottomed flask.With rotary evaporator remove anhydrate and 1-methoxyl-2-propyl alcohol to obtain curable resin, its refraction coefficient is 1.584, zirconia content is 47.0wt%.
Embodiment 3
The zirconia sol MWCO of preparation embodiment 2 is 12,000 to 14,000 (derive from VWR International, West Chester, about 4.5 hours of SPECTRAPOR dialysis membrane dialysis PA) is to obtain the stable sol that solids content is 33.85wt%.With the zirconia sol (53.13 gram) of dialysis, MEEAA (1.59 gram), BCEA (1.14 gram), 1-methoxyl-2-propyl alcohol (133 gram), NSEA (7.09 gram) and TMPTA (0.97 gram) join in the round-bottomed flask and by rotary evaporation and concentrate.Contain the zirconia that zirconic resin contains 58.57wt%, its refraction coefficient is 1.682.To contain zirconic resin (21.94 gram) and TPO-L (0.09 restrains) mixes.
Embodiment 4
The zirconia sol MWCO of preparation embodiment 2 is 12,000 to 14,000 (derive from VWR International, West Chester, about 4.5 hours of SPECTRAPOR dialysis membrane dialysis PA) is to obtain the stable sol that solids content is 33.85wt%.With the zirconia sol (109.90 gram) of dialysis, MEEAA (3.28 gram), BCEA (2.36 gram), 1-methoxyl-2-propyl alcohol (200 gram), NOEA (14.68 gram) and TMPTA (2.00 gram) join in the round-bottomed flask and by rotary evaporation and concentrate.Contain the zirconia that zirconic resin contains 57.22wt%, its refraction coefficient is 1.661.To contain zirconic resin (29.47 gram) and TPO-L (0.13 restrains) mixes.
Embodiment 5
The zirconia sol MWCO of preparation embodiment 2 is 12,000 to 14,000 (derive from VWR International, West Chester, about 4.5 hours of SPECTRAPOR dialysis membrane dialysis PA) is to obtain the stable sol that solids content is 33.85wt%.Zirconia sol (144.02 gram) with dialysis, MEEAA (4.30 gram), BCEA (3.09 gram), 1-methoxyl-2-propyl alcohol (300 gram), NOEA (10.22 gram), TMPTA (4.38 gram), the PROSTAB 5198 of BR31 (21.89 gram) and the 5wt% solution (0.3 gram) in water joins in the round-bottomed flask.Remove alcohol and water by rotary evaporation.Gained contains the zirconia that zirconic resin contains 46.97wt%, and its refraction coefficient is 1.636.To contain zirconic resin (49.03 gram) and TPO-L (0.26 restrains) mixes.
Embodiment 6
Zirconia sol (100.00 gram) with preparation embodiment 3, MEEAA (4.44 gram), BCEA (2.13 gram), 1-methoxyl-2-propyl alcohol (115 gram), the PROSTAB 5198 of 50/50 SR-339/BR31 that mixes (29.78 gram) and the 5wt% solution (0.12 gram) in water joins in the round-bottomed flask.Remove alcohol and water by rotary evaporation.Gained contains that zirconia content is approximately 53.3wt% in the zirconic resin, and its refraction coefficient is 1.642.TPO-L is joined in the potpourri to obtain containing the composition of 0.47wt%TPO-L.
Embodiment 7
With the zirconia sol (50.0 gram) of embodiment 3 preparation, MEEAA (2.22 gram), BCEA (1.06 gram), 1-methoxyl-2-propyl alcohol (75.0 gram), and wait in the SR-339 of weight portion and the potpourri of RDX-51207 (17.60 gram) the adding round-bottomed flask.Potpourri concentrates to obtain curable resin with rotary evaporator, and its zirconia content is 49.59wt%, refraction coefficient 1.639.The TPO-L that adds q.s is to obtain containing the composition of 0.5wt%TPO-L.
Embodiment 8
Zirconia sol (200 gram) with preparation embodiment 3, MEEAA (8.81 gram), BCEA (4.22 gram), 1-methoxyl-2-propyl alcohol (230 gram), with the BR31/SR-339/TMPTA (59.1 gram) of ratio 38/50/12 mixing, and the solution (0.24 gram) of the PROSTAB 5198 of 5wt% in water joins in the round-bottomed flask.Remove alcohol and water by rotary evaporation.Contain the zirconia that zirconic resin contains 52.3 1wt%, its refraction coefficient is 1.638.To contain zirconic resin (116 gram) and TPO-L (0.55 restrains) mixes.
Embodiment 9-19
Measure with the gain of each brightness enhancement film of the resins of embodiment 1-8 and be shown in table 1.In the table 1, symbol ＂---＂ represents not prepare this sample.The preparation process of these films as mentioned above.
The gain of table 1, brightness enhancement film
Film embodiment Resin embodiment HBEF III HXBEF III HTBEF HXTBEF HDBEF HDBEF/T-BEF
9 1 1.799 2.361 --- --- --- ---
10 2 1.766 2.434 --- --- --- ---
11 3 1.955 2.606 --- --- --- ---
12 4 1.901 2.568 1.89 2.595 --- ---
13 5 1.854 2.573 --- --- --- ---
14 6 --- --- --- --- 2.159 3.143
15 7 1.881 2.687 --- --- --- ---
16 8 1.889 2.684 --- --- --- ----
The size distribution of table 2, zirconia particles
Intensity mean grain size (nm) Volume average particle size (nm) The ratio of intensity mean grain size and volume average particle size
ZrO 2Colloidal sol 1 21.0 12.9 1.62
ZrO 2Colloidal sol 2 33.8 16.4 2.06
ZrO 2Colloidal sol 3 42.1 17.5 2.41
The X-ray diffraction data of table 3, zirconia particles
M intensity M particle diameter (nm) C/T intensity C/T particle diameter (nm) ％C/T XRD mean grain size (nm) Dispersion coefficient
ZrO 2Colloidal sol 1 18 4.0 100 8.0 85 7.4 1.74
ZrO 2Colloidal sol 2 NA NA NA NA NA NA NA
ZrO 2Colloidal sol 3 9 6.5 100 8.0 92 7.9 2.21

Claims (21)

1. light management films that comprises optical layers, described optical layers has the surface with microstructure, and this optical layers comprises:
(a) polymeric material; With
(b) zirconia particles of a plurality of surface modifications, wherein said zirconia particles contains the yttrium based on the weight meter 0.1 to 8wt% of inorganic oxide in the zirconia particles, and wherein the average primary particle diameter of zirconia particles is no more than 30 nanometers, dispersion coefficient is 1-3, the ratio of intensity mean grain size and volume average particle size is no more than 3.0, and the 70wt% at least of crystal structure is cubic system, tetragonal crystal system or its combination.
2. the light management films of claim 1 wherein selects light management films to form brightness enhancement film, reflectance coating or turning film.
3. the light management films of claim 1, wherein light management films is a brightness enhancement film.
4. the light management films of claim 1 further comprises the basalis near optical layers.
5. the light management films of claim 1, wherein optical layers contains based on the weight of the optical layers zirconia particles up to 80wt%.
6. the light management films of claim 1, wherein polymeric material is the reaction product of following material: contain the polymerisable composition of the oligomeric materials with high index of refraction, reactive diluent and polyfunctional cross-linking monomer.
7. the light management films of claim 1, wherein said polymeric material is the reaction product that contains the polymerisable compound and the formula I monomer of crosslinking chemical:
Figure S200680016313XC00021
Wherein:
R aBe hydrogen or methyl;
Q is oxygen or sulfenyl;
R cBe C 2-C 12Alkylidene, it is for unsubstituted or replaced by hydroxyl;
N is 0 to 6 integer;
M is 0 to 6 integer;
Each X is hydrogen independently, bromine, or chlorine;
Y is the connection base of divalence, is selected from-C (CH 3) 2-,-CH 2-,-S-,-S (O)-, or-S (O) 2-.
8. the light management films of claim 7, described polymerisable compound further contains formula II monomer:
Wherein:
Ar is a phenyl or naphthyl, and it is for unsubstituted or replaced by one or more substituting groups, and described substituting group is selected from halogen, alkyl, aryl, aralkyl or its combination;
Q is oxygen or sulfenyl;
R cBe C 2-C 12Alkylidene, it is for unsubstituted or replaced by hydroxyl;
P is 0 to 6 integer;
R aBe hydrogen or methyl.
9. the light management films of claim 1, wherein said polymerisable compound further contains formula II monomer:
Figure S200680016313XC00023
Wherein:
Ar is a phenyl or naphthyl, and it is for unsubstituted or replaced by one or more substituting groups, and described substituting group is selected from halogen, alkyl, aryl, aralkyl or its combination;
Q is oxygen or sulfenyl;
R cBe C 2-C 12Alkylidene, it is for unsubstituted or replaced by hydroxyl;
P is 0 to 6 integer;
R aBe hydrogen or methyl.
10. the light management films of claim 1, wherein polymeric material is the reaction product that contains the polymerisable compound of phenyl (methyl) acrylate bromination, that alkyl replaces.
11. the light management films of claim 1, wherein polymerisable compound contains formula III monomer, formula IV monomer or its combination:
Figure S200680016313XC00031
Wherein: each R 1Be independently selected from following formula:
Or
Wherein:
R 3Be (CH 2) x
X is 2 to 8 integer; With
R 4Be hydrogen or methyl.
12. the light management films of claim 1, wherein polymerisable compound contains formula V monomer
Figure S200680016313XC00041
Wherein:
R 2Be hydrogen or methyl,
Ar is an aryl;
M is 1 to 6 integer,
N is 1 to 6 integer,
P is 1 to 6 integer,
Q is 1 to 6 integer.
13. the light management films of claim 1, wherein said polymeric material is a thermoplastic.
14. the light management films of claim 1 wherein carries out surface modification with carboxylic acid to described zirconia particles.
15. the light management films of claim 14 wherein carries out surface treatment with second carboxylic acid that does not contain first carboxylic acid of polymerizable groups and contain polymerizable groups to described zirconia particles.
16. the light management films of claim 1 wherein carries out surface modification with silane to described zirconia particles.
17. prepare the method for light management films, described method comprises:
The zirconia sol that contains the zirconia particles that is dispersed in aqueous phase is provided, and the preparation method of this zirconia sol comprises:
First raw material that preparation contains zirconates carries out first hydrothermal treatment consists to first raw material and contains zirconium intermediate and accessory substance with formation;
Accessory substance by removing at least a portion first hydrothermal treatment consists is to form second raw material; With
Second raw material is carried out second hydrothermal treatment consists;
Modification is carried out to form the zirconia particles of surface modification in the surface of zirconia particles;
Preparation comprises the zirconia particles of surface modification and the coating composition of organic substrate;
Coating composition is contacted with little facility that duplicate; With
Make described coating composition polymerization have optical layers with formation with micro-structure surface.
18. the method for claim 17, wherein said light management films is a brightness enhancement film.
19. prepare the method for light management films, described method comprises:
The zirconia sol that comprises the zirconia particles that is dispersed in aqueous phase is provided, described zirconia sol further comprises carboxylic acid, its carbon atom that contains is no more than 4 and be substantially free of the polyether carboxylic acid, wherein said zirconia particles primary particle mean grain size is no more than 50 nanometers, dispersion coefficient is 1 to 5, intensity mean grain size and volume average particle size ratio are no more than 3.0, and the 50wt% at least of crystal structure is cubic system, tetragonal crystal system, or its combination;
Modification is carried out to form the zirconia particles of surface modification in the surface of zirconia particles;
Preparation comprises the zirconia particles of described surface modification and the coating composition of organic substrate;
Described coating composition is contacted with little facility that duplicate;
Make the coating composition polymerization have optical layers with formation with micro-structure surface.
20. the method for claim 19, wherein said zirconia particles contain the yttrium based on the weight meter 0.1 to 8wt% of inorganic oxide in the zirconia particles, and have crystal structure, wherein 70wt% is cubic system, tetragonal crystal system or its combination at least.
21. the method for claim 19, wherein light management films is a brightness enhancement film.
CNA200680016313XA 2005-03-11 2006-03-03 Light management films with zirconia particles Pending CN101176019A (en)

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