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    • 专利摘要:
    Ultraviolet light absorbing polymer film, coating, or molded articleUV filter elements are described which comprise a polymer phase havingmolecularly dispersed therein a) a first ultraviolet absorbing dibenzoylmethanecompound of formula (I)where R1 through R5 are each independently hydrogen, halogen, nitro, orhydroyxl, or further substituted or unsubstituted alkyl, alkenyl, aryl, alkoxy,acyloxy, ester, carboxyl, alkyl thio, aryl thio, alkyl amine, aryl amine, alkylnitrile, aryl nitrile, arylsulfonyl, or 5-6 member heterocylce ring groups, and b) asecond ultraviolet light absorbing compound which absorbs ultraviolet light at awavelength for which the first compound is deficient at absorbing. In particularembodiments, the second ultraviolet light absorbing compound may comprise ahydroxyphenyl-s-triazine, hydroxyphenylbenzotriazole, formamidine,benzoxazinone, or benzophenone compound. In a specific embodiment of theinvention, the above UV absorbing compounds are employed in cellulose acetatefilm for the fabrication of a protective film for polarizers for use in displayapplications.
    公开号:EP1300700A1
    申请号:EP02078938
    申请日:2002-09-23
    公开日:2003-04-09
    发明作者:Timothy Charles Eastman Kodak Company Schunk；Kurt Michael Eastman Kodak Company Schroeder；Charles Howard Eastman Kodak Company Appell；Daniel Talbot Eastman Kodak Company Linehan
    申请人:Eastman Kodak Co；
    IPC主号:G02B5-00
    专利说明:
    [0001] The present invention relates to a UV filter element comprising apolymer phase containing at least two ultraviolet light absorbing compounds, oneof which is a derivative of dibenzoylmethane and one other of which absorbs UVlight at a wavelength at which the dibenzoylmethane compound is deficient atabsorbing UV light. In a particular embodiment, the invention relates to the useof particular UV absorbing compounds in cellulose acetate film for the fabricationof polarizers for use in display applications.
    [0002] An ultraviolet light (UV) filter element is employed as a sharp cutfilter to transmit visible light while blocking UV light in either an optical deviceor to protect an underlying element. Such applications include color correction ofan image during optical recording (e.g., in either silver halide or digitalphotography), color correction in a display device (e.g., backlit or reflective liquidcrystal displays or emissive displays, OLED), or maintenance of appearance andfunction of a multicomponent device. Protective functions of such an UV filterelement may be provided in the form of protective polymeric overcoats,interlayers, or cast or molded films or other articles used to stabilizeaccompanying materials against the degradation of optical and mechanicalproperties induced by UV light exposure (e.g., degradation of liquid crystalcomponents in an LCD display).
    [0003] An UV filter element is required to thoroughly transmit light oflonger than a specified wavelength, while thoroughly blocking light shorter thanthat wavelength. Optimum performance is provided by a very sharp transitionbetween these wavelengths (i.e., sharp cut). In addition, light transmitted in thevisible region should be of neutral hue as perceived by the human eye (e.g., asmeasured according to the CIE, International Commission on Illumination). Thefunctional performance of the UV filter element should remain as constant aspossible during the normal lifetime of the application and under the standardenvironment of use. That is, in addition to stable mechanical properties, the UVfilter element should not significantly lose its ability to transmit visible light(discolor) or block UV light (fade) under normal use in its intended application.
    [0004] Various classes of UV absorbing compounds are known, and manyhave been suggested for use in UV filter elements. US Pat. No. 4,043,639, e.g.,suggests the use of salicyclic acid esters, hydroxybenzophenone, benzotriazole and their derivatives as UV light-absorbing agents in cellulose triacetate filmsbonded to a polarizing film for the protection of the liquid crystal componentsfrom degradation in a LCD display. The disclosure includes the description ofimproved resistance to high temperature and humidity of the device. Manyclasses of UV absorbing compounds previously disclosed for use in polymeric UVfilter elements, however, have various problems associated therewith, especiallywith regard to providing a desired sharp cut at approximately 390 to 400 nmwhile also providing complete protection throughout the UV range. US Pat. No.5,806,834 discloses the use of aminobutadiene derivatives to provide a sharp cutUV filter in the 400 nm region with reduced yellow discoloration of the filter asresults from high loading levels of benzotriazole or benzophenone derivatives.The formulations described include a second UV absorbing compound added tothe polymer in order to absorb light of shorter wavelengths that cannot beabsorbed by the primary aminobutadiene compound. Compounds such asbenzotriazole, salicylate, benzophenone and their derivatives are described asfulfilling this function. Aminobutadiene compounds, however suffer fromthermal instability.
    [0005] Additionally, use of various compounds as suggested in the priorart still may not provide as sharp a cut-off of absorption between the ultravioletand visible spectrum as may be desired. It would accordingly be desirable toprovide an UV filter element that provides a very sharp cut in transmissionbetween the UV and visible light spectral regions, while also providing effectiveUV absorption throughout the UV range, as well as good thermal stability.
    [0006] In accordance with the invention, ultraviolet light absorbingpolymer film, coating, or molded article UV filter elements are described whichcomprise a polymer phase having molecularly dispersed therein a) a firstultraviolet absorbing dibenzoylmethane compound of formula (I)
    [0007] FIG. 1 is a graph showing transmittance curves of light in awavelength region of 350 to 450 nm of UV filter elements obtained in Examples1 and 2 and Comparison Example 1.
    [0008] The present invention describes the use of multiple UV absorbingagent compounds molecularly dispersed in a polymeric phase of a polymeric film,coating or molded article, where at least one of the UV absorbing compoundscomprises a dibenzoylmethane derivative. Dibenzoylmethane derivativecompounds of the type employed in the present invention are themselves known,and have been previously described primarily for use in oil emulsions to blockUV light in sunscreen compositions, e.g., in US Pat. Nos. 4,387,089; 5,783,173;5,849,273; 5,788,954; 5,993,789; and 6,129,909. Additionally, Wu et al. "AStudy of the Photo-stabilizing Behaviors of β-Diketones," Polym. Degrad. Stab.,16 (1986) 169-186, discloses the use of dibenzoylmethane derivatives as UVexposure stabilizers for viscosity retention of polybutadiene solutions. Further,Japanese Kokai JP 04213348 A2 discloses the use of a dibenzoylmethanederivative to improve the weatherability of an acrylic resin film by incorporatingthe UV absorber inside of cross-linked polymer particles that are dispersed in theresin film to reduce migration out of the film.
    [0009] In Formula I, each of R1 through R5 independently representshydrogen, halogen, nitro, or hydroyxl, or further substituted or unsubstitutedalkyl, alkenyl, aryl, alkoxy, acyloxy, ester, carboxy, alkyl thio, aryl thio, alkylamine, aryl amine, alkyl nitrile, aryl nitrile, arylsulfonyl, or 5-6 member heterocycle ring groups. Preferably, each of such groups comprises 20 or fewercarbon atoms. Further preferably, R1 through R5 of Formula I are positioned inaccordance with Formula I-A:
    [0010] Representative compounds of Formula (I) which may be employedin accordance with the invention include the following: (I-1): 4-(1,1-dimethylethyl)-4'-methoxydibenzoylmethane (PARSOL 1789) (I-2): 4-isopropyl dibenzoylmethane (EUSOLEX 8020) (I-3): dibenzoylmethane (RHODIASTAB 83)
    [0011] While the present inventors have observed that dibenzoylmethanederivatives of Formula I have been found to advantageously provide a sharp cutoff in absorption between the UV and visible light ranges, such compounds havealso been observed to provide less than desired absorption over substantialportions of the UV spectrum. In particular, while the ultraviolet absorber of theFormula I shows a steeply rising transmittance curve at a wavelength of approx.390 to 400 nm, the ultraviolet absorber cannot sufficiently absorb light in aportion of the ultraviolet region (i.e., in the region of not longer than 350 nm,generally approx. 250 nm to approx. 350 nm, especially in the region in thevicinity of 300 nm).
    [0012] In order to provide an UV filter element which is capable ofproviding both a sharp cut off in absorption between the UV and visible lightspectral regions, as well as increased protection across more of the UV spectrum,a second UV absorbing compound is employed in combination with the primarydibenzoylmethane compound, which second ultraviolet absorbing compound isselected to provide absorption of light in a portion of the ultraviolet region forwhich the first absorbing compound is deficient, while transmitting visible light(generally in a wavelength region of 400 to 750 nm). In accordance with theinvention, in order to provide good optical characteristics for the UV filter element, both the first and second compounds are molecularly dispersed in apolymeric phase of the element.
    [0013] In accordance with specific embodiments of the invention, thesecond ultraviolet light absorbing compound preferably comprises ahydroxyphenyl-s-triazine, hydroxyphenylbenzotriazole, formamidine,benzophenone, or benzoxazinone compound. Additional possible UV absorberswhich may be employed include salicylate compounds, such as 4-t-butylphenylsalicylate;and [2,2'thiobis-(4-t-octylphenolate)]n-butylaminenickel(II). Such ultraviolet light absorbing compounds are themselves known,and have been described for use in various polymeric elements. Preferred arehydroxyphenyl-s-triazine and hydroxyphenylbenzotriazole compounds.
    [0014] Hydroxyphenyl-s-triazine compounds which may be used as thesecond UV absorbing compound, e.g., may be a derivative of tris-aryl-s-triazinecompounds as described in USP 4,619,956. Such compounds may be representedby Formula II:
    [0015] Hydroxyphenylbenzotriazole compounds which may be used as thesecond UV absorbing compound, e.g., may be a derivative of compoundsrepresented by Formula III:
    [0016] Formamidine compounds which may be used as the second UVabsorbing compound, e.g., may be a formamidine compound as described in USP4,839,405. Such compounds may be represented by Formula IV or Formula V:
    [0017] Benzophenone compounds which may be used as the second UVabsorbing compound, e.g., may include 2,2'-dihydroxy-4,4'dimethoxybenzophenone,2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-dodecyloxybenzophenone.
    [0018] The present invention provides an ultraviolet-absorbing polymerfilm, coating or molded article that is capable of transmitting thoroughly light in awavelength region of longer than 400 nm, and absorbing thoroughly light in awavelength region of not longer than 400 nm. In preferred embodiments of theinvention, the first and second UV absorbing compounds are selected andemployed in a polymer film to provide a transmittance at a wavelength of 380 nmof not more than 10% (more preferably not more than 5%) and at 390 nm of notmore than 25% (more preferably not more than 20%), and a transmittance at awavelength of 400 nm of not less than 55% (more preferably not less than 60%)and at 420 nm of not less than 85% (more preferably not less than 90%, and mostpreferably not less than 90% throughout the visible wavelength range of 420-750nm).Further, the polymer film preferably shows transmittance at 370 nm of not more than 3%, especially not more than 1%. In more detail, the use of acompound of formula (I) provides a transmittance curve having a steeply risingposition (point) at wavelengths between approx. 390 to 400 nm, while the use of asecond ultraviolet absorbing compound provides absorption of light in a portionof the ultraviolet region in which the compound of the formula (I) is relativelydeficient in absorption.
    [0019] The UV filter element is advantageously employed as a protectivefilm of a polarizing sheet, the polarizing sheet comprising a polarizing plate andthe protective film provided on one side or both sides of the polarizing plate.Further, the filter element can be suitably employed for a sharp cut filter forultraviolet (e.g., polarizing glasses, UV-cut filter). Further, the filter element ofthe invention can be utilized, in combination with other optical filters, for a sharpcut filter, a color correction filter for taking color photography, a color correctionfilter for color print or a filter for special use (e.g., separation filter, masking filterfor photomechanical process, visual sensitivity filter).
    [0020] Examples of polymers employable for the polymer phase of thefilter elements of the invention include polyesters (e.g., polyethylene terephthalateand polyethylene-2,6-naphthalate); cellulose esters (e.g., cellulose diacetate,cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate);polyolefins (e.g., polypropylene and polyethylene); polymers derived from vinylchloride (e.g., polyvinyl chloride and vinyl chloride/vinyl acetate copolymer);acrylic resins (e.g., polymethyl methacrylate); polycarbonate esters (e.g.,polycarbonate); norbornene resins; and water soluble resins (e.g., polyvinylalcohol, gelatin).
    [0021] In a particularly preferred embodiment, the UV filter element ofthe invention is in the form of a polymer film wherein the polymer is a celluloseester such as a cellulose acetate, particularly cellulose triacetate. The UV filterelement in such embodiment may be advantageously employed as a protectivefilm of a polarizing sheet, the polarizing sheet comprising a polarizing plate andthe protective film provided on one side or both sides of the polarizing plate.Further, as cellulose triacetate, the known materials can be employed. The acetylvalue of cellulose triacetate preferably is in the range of 35% to 70%, especiallyin the range of 55% to 65%. The weight average molecular weight of celluloseacetate preferably is in the range of 70,000 to 200,000, especially 80,000 to190,000. The polydispersity index (weight average divided by number averagemolecular weight) of cellulose acetate is in the range of 2 to 7, especially 2.5 to 4. Cellulose acetate may be obtained from cellulose starting materials derived fromeither wood pulp or cotton linters. Cellulose acetate may be esterified using a fattyacid such as propionic acid or butyric acid so long as the acetyl value satisfies thedesired range.
    [0022] Cellulose acetate film generally contains a plasticizer. Examples ofthe plasticizers include phosphate esters such as triphenyl phosphate, biphenylyldiphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyldiphenyl phosphate, trioctyl phosphate, and tributyl phosphate; and phthalateesters such as diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, anddioctyl phthalate. Preferable examples of glycolic acid esters are triacetin,tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, andmethyl phthalyl ethyl glycolate. Two or more plasticizers shown above may becombined. The plasticizer is preferably contained in the film in an amount of notmore than 20 weight %, especially of 5% to 15 weight %. Films prepared frompolymers other than cellulose triacetate may also contain appropriately the aboveplasticizer.
    [0023] Both of the ultraviolet absorber of the formula (I) and otherultraviolet absorber (the other of two or more ultraviolet absorbers) is generallycontained in the polymer in an amount of 0.01 to 20 weight parts based on 100weight parts of the polymer containing no ultraviolet absorber, and preferablycontained in an amount of 0.01 to 10 weight parts, especially in an amount of 0.05to 2 weight parts.
    [0024] A ratio of the ultraviolet absorber of the formula (I) and otherultraviolet absorber (the other of two or more ultraviolet absorbers) generally is inthe range of 1: 30 to 5:1 by weight (absorber of the formula (I): other absorber),and preferably in the range of 1:20 to 2:1. The sharp cut position (wavelengthvalue) in the transmittance curve can be shifted by variation of the amount of theultraviolet absorber added.
    [0025] The filter elements of the invention may contain particles of aninorganic or organic compound to provide surface lubrication. Examples of theinorganic compound include silicon dioxide, titanium dioxide, aluminum oxide,zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calciumsilicate, hydrate calcium silicate, aluminum silicate, magnesium silicate, andcalcium phosphate. Preferred are silicon dioxide, titanium dioxide, and zirconiumoxide, and especially silicon dioxide. Examples of the organic compound (polymer) include silicone resin, fluororesin and acrylic resin. Preferred is acrylicresin.
    [0026] UV filter elements in accordance with the invention preferably arein the form of a polymer film. The polymer film is preferably prepared byutilizing a solvent casting method. In more detail, the solvent casting methodcomprises the steps of: casting the polymer solution fed from a slit of a solutionfeeding device (die) on a support and drying the cast layer to form a film. In alarge-scale production, the method can be conducted, for example, by the steps ofcasting a polymer solution (e.g., a dope of cellulose triacetate) on a continuouslymoving band conveyor (e.g., endless belt) or a continuously rotating drum, andthen vaporizing the solvent of the cast layer. In a small-scale production, themethod can be conducted, for example, by the steps of casting a polymer solutionfed from a slit of a solution feeding device on a fixed support having a regularsize such as a metal plate or glass plate by moving the device, and then vaporizingthe solvent of the cast layer.
    [0027] Any support can be employed in the solvent casting method, solong as the support has property that a film formed thereon can be peeledtherefrom. Supports other than metal and glass plates (e.g., plastic film) areemployable, so long as the supports have the above property. Any die can beemployed, so long as it can feed a solution at a uniform rate. Further, as methodsfor feeding the solution to the die, a method using a pump to feed the solution at auniform rate can be employed. In a small-scale production, a die capable ofholding the solution in an appropriate amount can be utilized.
    [0028] Polymer employed in the solvent casting method is required to becapable of dissolving in a solvent. Further a film formed of the polymer isgenerally required to have high transparency and to have little optical anisotropyfor application in optical products. Furthermore, the polymer preferably hascompatibility with the absorbers. As the polymer employed in the solvent castingmethod, preferred is cellulose triacetate. However, other polymers can beemployed so long as they satisfy the above conditions.
    [0029] As a method for the formation of polymer UV filter elements otherthan the solvent casting method, there can be mentioned the known extrusionmolding method comprising the steps of mixing the polymer and the absorberswith melting, and extruding the mixture. The method is generally applied topolymers that cannot utilize the solvent casting method.
    [0030] A process for the preparation of an UV filter element in the formof an optical polymer film in accordance with preferred embodiments of theinvention is explained in detail referring to a cellulose triacetate film. In a mixingvessel, a solvent, cellulose triacetate and a plasticizer are placed, and celluloseacetate is dissolved by stirring (under heating, if desired under pressure) toprepare a dope. In another mixing vessel, a solvent and two ultraviolet absorbersare placed, and the absorbers are dissolved by stirring. In the case that particles toimprove surface lubrication are added, the particles may be placed in the resultantabsorber containing solution and the mixture is dispersed using a dispersingmachine to prepare a dispersion. An appropriate amount of the absorbercontaining solution is fed to the vessel holding the dope, and they are mixed. Themixture (dope) is fed to a casting head appropriately through a filter for dope, andis cast from the casting head on a drum or continuous belt of metal (support). Thecast film is dried during one rotation of the support to form a film having self-bearingproperties, and the dried film is separated from the support, and then thefilm is sufficiently dried to be wound.
    [0031] The dope and the absorber containing solution can be mixed by theuse of a static mixer which is mounted in the piping before the casting head, fedto the casting head and cast from the casting head on a metal drum (support).Any solvent can be employed in the solvent casting method so long as thepolymer used (e.g., cellulose triacetate) can be dissolved. The solvent may besingle solvent or a combination of solvents. Examples of solvents employed inthe solvent casting method include aliphatic hydrocarbons such as pentane,hexane, heptane, octane, isooctane and cyclohexane; aromatic hydrocarbons suchas benzene, toluene and xylene; chlorinated hydrocarbons such as chloromethane,dichloromethane, carbon tetrachloride and trichloroethane; alcohols such asmethanol, ethanol, isopropyl alcohol and n-butyl alcohol; ketones such as acetone,methyl ethyl ketone, and cyclohexanone, and esters such as methyl formate, ethylformate, methyl acetate and ethyl acetate, or dioxalane.
    [0032] In the case of employing cellulose triacetate as the polymer, amixed solvent of dichloromethane and methanol is generally employed. Othersolvents such as isopropyl alcohol and n-butyl alcohol can be employed so long ascellulose triacetate is not deposited (e.g., during the procedure of preparing thedope or adding the particles to the dope). A ratio of cellulose triacetate andsolvent in the dope is preferably 10:90 to 30:70 by weight (cellulosetriacetate: solvent).
    [0033] In the procedure of preparing the dope or the dispersion, variousadditives such as a dispersing agent, a fluorescent dye, an antifoamant, alubricant, an antioxidant, a radical scavenger, an acid scavenger, an inhibitor offade, and a preservative can be added to the dope or the dispersion. In addition,enhanced durability of the polymer UV filter element to the action of light, heat,moisture, and oxygen in terms of LV light blockage, visible spectrum color, anddimensional stability may be imparted by the addition of chemical stabilizers fromthe list of hindered amine light stabilizers, hindered phenols, acid scavengers, andUV stabilizers. Combinations of stabilizer technologies may be employed.
    [0034] Hindered amine light stabilizers (HALS compounds) useful in thepolymer UV filter elements of this invention are known compounds and include,e.g., 2,2,6,6-tetraalkylpiperidine compounds, or the acid addition salts orcomplexes with metal compounds thereof, as described in US Pat. No. 4,619,956,columns 5-11, and US Pat. No. 4,839,405, columns 3-5. Such compounds includethose of the following Formula VI:
    [0035] Hindered phenols antioxidant compounds useful in the polymerUV filter elements of this invention are also known compounds, and include, e.g.,2,6-dialkylphenol derivative compounds such as described in US Pat. No.4,839,405 columns 12-14. Such compounds include those of the followingFormula VII:
    [0036] Acid scavengers useful in the polymer UV filter elements of thisinvention, e.g., include epoxy compounds such as those acid accepting epoxycompounds described in US Pat. No. 4,137,201. Such acid accepting epoxycompounds are known to the art and include diglycidyl ethers of variouspolyglycols, particularly those polyglycols that are derived from condensation ofsay 8 to 40 moles of ethylene oxide or the like per mole of polyglycol product;diglycidyl ethers of glycerol and the like; metallic epoxy compounds (such asthose conventionally utilized in and with vinylchloride polymer compositions);epoxidized ether condensation products; diglycidyl ethers of bisphenol A (i.e.,4,4'-dihydroxy diphenyl dimethyl methane); epoxidized unsaturated fatty acidesters, particularly 4 to 2 carbon atom or so alkyl esters of 2 to 22 carbon atomfatty acids such as butyl epoxy stearate and the like; and various epoxidized longchain fatty acid triglycerides and the like, such as the epoxidized vegetable andother unsaturated natural oils (which are sometimes referred to as beingepoxidized natural glycerides or unsaturated fatty acids, which fatty acidsgenerally contain between 12 and 22 carbon atoms) that may be specifically typified and particularized by such compositions as epoxidized soya bean oil.Particularly preferred is commercially available epoxy group containing epoxideresin compound EPON 815c, and other epoxidized ether oligomeric condensationproducts of Formula VIII
    [0037] A ratio of the acid scavenger to the total concentration of hinderedamine compound and hindered phenol compound is preferably 10:1 to 1:10 byweight, preferably 4:1 to 1:5 and especially in the range of 2:1 to 1:2. The ratio ofhindered amine light stabilizer (HALS) to hindered phenol (HP) preferably lies inthe range of 1:20 to 20:1 (HALS:HP) by weight, more preferably in the range of1:10 to 10:1, and especially in the range of 1:5 to 5:1.
    [0038] Additional stabilizers disclosed for use in combination withdibenzoylmethane derivatives are suggested, e.g., in US Pat. Nos. 5,783,173;5,849,273; 5,788,954; 5,993,789; and 6,129,909, which compounds mayadditionally be employed in the elements of the invention.
    [0039] In a particularly preferred embodiment, a UV filter element inaccordance with the invention comprises a cellulose triacetate film containingfrom 0.01 to 5 wt% (based on total weight) of a first ultraviolet absorbingdibenzoylmethane compound of formula (I) such as compound I-1 (Parsol 1789)(UV-1), from 0.01 to 5 wt% Tinuvin 326 (UV-3) and from 0.01 to 5 wt% Tinuvin328 (UV-2) as second UV absorbing compounds, from 0.01 to 10 wt% of ahindered amine light stabilizer compound such as Tinuvin 622 (HALS-1), from0.01 to 10 wt% of a hindered phenol compound such as Irganox 1010 (HP-1), andfrom 0.01 to 10 wt% of an epoxy containing acid scavenger compound such asEpon 815c (epoxy group containing oligomeric epoxide resin obtained from monomers of formula E-1), with 0.1 - 20 wt% of a plasticizer such astriphenylphosphate.
    [0040] Test procedure: The effectiveness of the UV filter elements asdescribed in the examples below were evaluated under initial conditions afterpreparation of the films. Transmission spectra of the example films wereobtained versus an air reference over the wavelength range 220 nm to 800 nm byusual procedures. Determination of the CIE human perception color parametersL*, a*, and b* were made using the D65 illumination standard. Example 1:
    [0041] In a mixing vessel for a polymer dope, 100 weight parts ofcellulose acetate (CTA) (combined acetic acid value: 60.8%), 11.8 weight parts oftriphenyl phosphate (TPP), 399 weight parts of dichloromethane and 33.4 weightparts of methanol and 9.3 weight parts of n-butanol were placed, and the celluloseacetate was dissolved by stirring under heating to prepare a dope.
    [0042] In another mixing vessel, 3.3 weight parts of an ultravioletabsorber (compound of formula UV-1), 27.3 weight parts UV-2, 5.2 weight partsUV-3, 145 weight parts of dichloromethane, 12 weight parts of methanol, and 3.4weight parts of n-butanol were placed, and the UV absorbers were dissolved bystirring to prepare a solution.
    [0043] To the CTA dope (302 weight parts), 10 weight parts of theultraviolet absorber containing solution was added, and they were sufficientlymixed to prepare a uniform solution (dope). The mixed dope was fed to anextrusion die and cast on a moving metal support. After the cast film wasseparated from the casting surface, the film was dried by passing through aheating zone to prepare a cellulose acetate film having a thickness of 80 µmproviding a polymer film suitable for the protective component of a polarizingplate. Comparison Example 1:
    [0044] The same procedure as in Example 1 was used with the exceptionthat ultraviolet absorber UV-1 was not added. A CTA film was prepared in thesame manner. Example 2:
    [0045] In another mixing vessel, 10.3 weight parts of an ultravioletabsorber (UV-1), 4.6 weight parts UV-4, 5.1 weight parts of HALS-2, having thefollowing structures, 145 weight parts of dichloromethane, 12 weight parts ofmethanol, and 3.4 weight parts of n-butanol were placed, and the UV absorberswere dissolved by stirring to prepare a solution. The same procedure as inExample 1 for mixing with CTA dope was then used and a CTA film wasprepared in the same manner.
    [0046] The transmittance spectra of each of the films from Examples 1and 2 and Comparison Example 1 are shown in FIG. 1. The transmittance curvesfor Examples 1 and 2 rise steeply in the vicinity of 395 nm and demonstratetransmittance of less than 1% at 380 nm, less than 20% at 390 nm, and greaterthan 90% at 420 nm. In contrast, the spectrum of Comparison Example 1 shows amore shallow rise with a transmittance of greater than 4% at 380 nm, greater than30% at 390nm, while maintaining greater than 90% at 420 nm. The performance of Comparison Example 1 therefore, does not cut off UV light as sharply and isthus inferior to the films of Examples 1 and 2 as a UV filter element, thusdemonstrating the improved performance of dibenzoylmethane (Formula I)containing UV filter elements. As shown for Example 2, addition of a radicalscavenger stabilizer (HALS-2) does not impair the transmission spectral response.
    [0047] The spectral response parameters of the example films are shownin TABLE 1. Spectral properties of 80 µm film UV filters. Sample ID %T @ 380 nm %T @ 550 nm Cutoff range between 5% and 72% T [nm] L* a* b* Example 1 0.81 92.1 16.7 96.8 -0.15 0.56 Comparison Example 1 4.6 92.6 20.2 96.9 -0.13 0.52 Example 2 0.27 92.2 11.6 96.9 -0.07 0.41 Clearly as seen in TABLE 1, the performance of both Example films containingdibenzoylmethane compounds are superior to Comparison Example 1 in bothreduced transmittance at 380 nm and reduced transmittance cutoff range, whilemaintaining %T at 550 nm and L*a*b* color.
    权利要求:
    Claims (10)
    [1]
    An ultraviolet light absorbing polymer film, coating, or moldedarticle UV filter element comprising a polymer phase having molecularlydispersed therein
    a) a first ultraviolet absorbing dibenzoylmethane compound of formula (I)
    [2]
    An element according to claim 1, wherein the second ultravioletlight absorbing compound comprises a hydroxyphenyl-s-triazine,hydroxyphenylbenzotriazole, formamidine, benzoxazinone, or benzophenonecompound.
    [3]
    An element according to claim 1, wherein the second ultravioletlight absorbing compound comprises a hydroxyphenyl-s-triazine compound.
    [4]
    An element according to claim 1, wherein the second ultravioletlight absorbing compound comprises a hydroxyphenylbenzotriazole compound.
    [5]
    An element according to claim 1 providing a transmittance at awavelength of 380 nm of not more than 10% and at 390 nm of not more than25%, and a transmittance at a wavelength of 400 nm of not less than 55% and at420 nm of not less than 85%.
    [6]
    An element according to claim 5, which provides atransmittance at 370 nm of not more than 1%.
    [7]
    An element according to claim 6 providing a transmittance at awavelength of 380 nm of not more than 5% and at 390 nm of not more than 20%,and a transmittance at a wavelength of 400 nm of not less than 60% and at 420nm of not less than 90%.
    [8]
    An element according to claim 1, wherein the first ultravioletabsorbing dibenzoylmethane compound is of Formula I-A:
    [9]
    An element according to any one of claims 1-8 comprising acellulose ester film.
    [10]
    A liquid crystal display polarizer comprising a protective filmcomprising a cellulose ester film element according to claim 9.
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    JP2006195407A|2006-07-27|Optical film, method for manufacturing optical film, polarizing plate protective film, retardation film, and polarizing plate and liquid crystal display using those
    JP4788207B2|2011-10-05|Method for producing cellulose ester optical film
    JP4552593B2|2010-09-29|Method for producing optical film for display
    JP2006058825A|2006-03-02|Retardation film, polarizing plate and liquid crystal display device
    JPH0730318B2|1995-04-05|Photochromic composition
    JP2007007987A|2007-01-18|Cellulose ester optical film and its manufacturing method
    JP2004323607A|2004-11-18|Cellulose ester film
    JP2006341434A|2006-12-21|Optical film, its manufacturing method, polarizing plate and liquid crystal display device
    同族专利:
    公开号 | 公开日
    CN1409134A|2003-04-09|
    US20030080326A1|2003-05-01|
    KR20030029478A|2003-04-14|
    TWI308967B|2009-04-21|
    US6872766B2|2005-03-29|
    JP2003177235A|2003-06-27|
    CN100480746C|2009-04-22|
    KR100841856B1|2008-06-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4043639A|1975-07-07|1977-08-23|Hitachi, Ltd.|Field effect type liquid crystal display elements provided with polarizing plates|
    US4387089A|1978-11-13|1983-06-07|Givaudan Corporation|4--4'-methoxydibenzoylmethane|
    US4619956A|1985-05-03|1986-10-28|American Cyanamid Co.|Stabilization of high solids coatings with synergistic combinations|
    US4839405A|1986-07-08|1989-06-13|Plasticolors, Inc.|Ultraviolet stabilizer compositions, stabilized organic materials, and methods|
    US5806834A|1995-03-06|1998-09-15|Fuji Photo Film Co., Ltd.|Ultraviolet-asborbing polymer film|
    EP0843996A2|1996-11-26|1998-05-27|3V SIGMA S.p.A|Sun protecting cosmetic compositions comprising derivatives of dibenzoylmethane and of benzophenone|WO2006104732A1|2005-03-31|2006-10-05|3M Innovative Properties Company|Stabilized polarizing beam splitter assembly|
    US7315418B2|2005-03-31|2008-01-01|3M Innovative Properties Company|Polarizing beam splitter assembly having reduced stress|
    EP2116585A1|2007-02-20|2009-11-11|Fujifilm Corporation|Ultraviolet absorber composition|
    EP2527404A4|2010-01-19|2017-09-13|Sumitomo Seika Chemicals CO. LTD.|Composition for ultraviolet ray-absorbable member, and ultraviolet ray-absorbable member comprising same|
    EP3265899A4|2015-07-31|2018-10-24|Hewlett-Packard Development Company, L.P.|Touch screen light absorption layer|
    US10520744B2|2006-09-29|2019-12-31|3M Innovative Properties Company|Adhesives inhibiting formation of artifacts in polymer based optical elements|US3981884A|1974-09-03|1976-09-21|Eastman Kodak Company|Multichromophoric benzotriazole ultraviolet stabilizers|
    JPH04213348A|1990-06-14|1992-08-04|Mitsubishi Rayon Co Ltd|Film and sheet both having improved weatherability|
    US6123928A|1992-12-21|2000-09-26|Biophysica, Inc.|Sunblocking polymers and their novel formulations|
    JPH0741660A|1993-07-28|1995-02-10|Mitsubishi Gas Chem Co Inc|Photoresistant polyphenylene ether type resin composition|
    IT1284525B1|1996-09-13|1998-05-21|3V Sigma Spa| Benzoxazole derivatives use them as stabilizers against UV radiation |
    US5783173A|1996-11-21|1998-07-21|The C. P. Hall Company|Stable sunscreen composition containing dibenzoylmethane derivative, E. G., PARSOL 1789, and C12, C16, C18, branched chain hydroxybenzoate and/or C12, C16, branched chain benzoate stabilizers/solubilizers|
    US5849273A|1996-11-21|1998-12-15|The C. P. Hall Company|Skin care and sunscreen composition containing dibenzoylmethane derivative, e.g., parsol® 1789, and C12, C16, C18 branched chain hydroxybenzoate and/or C12, C16 branched chain benzoate stabilizers/solubilizers|
    US5993789A|1999-03-25|1999-11-30|The C.P. Hall Company|Photostable sunscreen compositions containing dibenzoylmethane derivative, E.G., parsol® 1789, and diesters or polyesters of naphthalene dicarboxylic acid photostabilizers and enhancers of the sun protection factor |
    JP3547662B2|1999-09-20|2004-07-28|Ｈｏｙａ株式会社|Plastic spectacle lens excellent in ultraviolet absorption and method of manufacturing the same|
    AT479419T|2000-02-17|2010-09-15|Basf Se|Aqueous dispersion of water-insoluble organic UV filter compounds|
    CA2422865C|2000-08-16|2012-10-16|The General Hospital Corporation D/B/A Massachusetts General Hospital|Aminolevulinic acid photodynamic therapy for treating sebaceous gland disorders|US6773104B2|2000-07-24|2004-08-10|Optical Technologies Corp.|Ultraviolet filter coating|
    MXPA05011124A|2002-02-06|2006-05-25|Roehm Gmbh|Polymethylmethacrylate compositions of enhanced optics and low temperature impact strength.|
    US7097789B2|2001-08-21|2006-08-29|Milliken & Company|Thermoplastic containers exhibiting excellent protection to various ultraviolet susceptible compounds|
    US7936338B2|2002-10-01|2011-05-03|Sony Corporation|Display unit and its manufacturing method|
    JP2004192969A|2002-12-12|2004-07-08|Hitachi Displays Ltd|Organic el display device|
    TWI245130B|2003-05-02|2005-12-11|Optimax Tech Corp|Color compensational layer's structure and manufacturing method thereof|
    KR101060829B1|2003-08-08|2011-08-30|코닌클리즈케 필립스 일렉트로닉스 엔.브이.|Alignment layer with reactive mesogens to align the liquid crystal molecules|
    EP1557891A3|2004-01-20|2006-10-04|LG Electronics Inc.|Organic electroluminescent device and fabrication method thereof|
    KR101030012B1|2004-05-07|2011-04-20|삼성모바일디스플레이주식회사|Organic electroluminescent display using the same|
    JP2005338343A|2004-05-26|2005-12-08|Sumitomo Chemical Co Ltd|Polarizing plate and adhesive for polarizing plate|
    TWI352105B|2004-07-26|2011-11-11|Eternal Chemical Co Ltd|Optical film resistant to uv light|
    KR101110071B1|2005-04-29|2012-02-24|삼성전자주식회사|Photo-Luminescenct Liquid Crystal Display|
    US7101659B1|2005-07-01|2006-09-05|Eastman Kodak Company|Color photographic element with UV absorber|
    JP2007119505A|2005-10-24|2007-05-17|Fujifilm Corp|Cellulose compound composition and cellulose compound film|
    US7732007B2|2005-12-19|2010-06-08|Eastman Kodak Company|Method of making a polarizer plate|
    US7911699B2|2005-12-22|2011-03-22|Guardian Industries Corp.|Optical diffuser with UV blocking coating|
    US7901778B2|2006-01-13|2011-03-08|Saint-Gobain Performance Plastics Corporation|Weatherable multilayer film|
    WO2007121049A1|2006-04-11|2007-10-25|Polyone Corporation|Weatherable polyolefin nanocomposites|
    US20070262695A1|2006-05-11|2007-11-15|Reisman Juliana P|UV and near visible lamp filter|
    JPWO2007145090A1|2006-06-13|2009-10-29|コニカミノルタオプト株式会社|Cellulose ester film, method for producing cellulose ester film, polarizing plate, and liquid crystal display device|
    US8153782B2|2007-02-14|2012-04-10|Eastman Chemical Company|Reformation of ionic liquids|
    US10174129B2|2007-02-14|2019-01-08|Eastman Chemical Company|Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom|
    US9834516B2|2007-02-14|2017-12-05|Eastman Chemical Company|Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom|
    WO2008102822A1|2007-02-20|2008-08-28|Fujifilm Corporation|Polymer material containing ultraviolet absorbent|
    JP5236297B2|2007-03-30|2013-07-17|富士フイルム株式会社|Heterocyclic compounds|
    WO2008123504A1|2007-03-30|2008-10-16|Fujifilm Corporation|Ultraviolet ray absorber composition|
    JP5181558B2|2007-07-13|2013-04-10|コニカミノルタアドバンストレイヤー株式会社|Optical film, polarizing plate, and liquid crystal display device|
    KR101569220B1|2007-08-16|2015-11-13|후지필름 가부시키가이샤|Heterocyclic compound, ultraviolet ray absorbent, and composition comprising the ultraviolet ray absorbent|
    US9777074B2|2008-02-13|2017-10-03|Eastman Chemical Company|Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom|
    US20090203900A1|2008-02-13|2009-08-13|Eastman Chemical Comapany|Production of cellulose esters in the presence of a cosolvent|
    US8354525B2|2008-02-13|2013-01-15|Eastman Chemical Company|Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom|
    US8188267B2|2008-02-13|2012-05-29|Eastman Chemical Company|Treatment of cellulose esters|
    US8158777B2|2008-02-13|2012-04-17|Eastman Chemical Company|Cellulose esters and their production in halogenated ionic liquids|
    JP5244437B2|2008-03-31|2013-07-24|富士フイルム株式会社|UV absorber composition|
    JP5250289B2|2008-03-31|2013-07-31|富士フイルム株式会社|UV absorber composition|
    JP2009270062A|2008-05-09|2009-11-19|Fujifilm Corp|Ultraviolet absorbent composition|
    KR101414450B1|2008-08-08|2014-07-04|주식회사 동진쎄미켐|Method of preparing dye sensitized solar cell|
    JP2010059235A|2008-09-01|2010-03-18|Fujifilm Corp|Ultraviolet absorbent composition|
    JP5261319B2|2008-09-10|2013-08-14|富士フイルム株式会社|Lighting cover|
    US8524887B2|2009-04-15|2013-09-03|Eastman Chemical Company|Regioselectively substituted cellulose esters produced in a tetraalkylammonium alkylphosphate ionic liquid process and products produced therefrom|
    CN101565378B|2009-05-26|2012-01-04|华中师范大学|Preparation of derivative of dibenzoyl methane and application thereof|
    FR2947174B1|2009-06-24|2011-07-15|Oreal|COSMETIC COMPOSITION COMPRISING A SUPERABSORBENT POLYMER AND AN ORGANIC UV FILTER|
    JP5647872B2|2010-01-19|2015-01-07|富士フイルム株式会社|Polyester resin composition|
    US9273195B2|2010-06-29|2016-03-01|Eastman Chemical Company|Tires comprising cellulose ester/elastomer compositions|
    US9068063B2|2010-06-29|2015-06-30|Eastman Chemical Company|Cellulose ester/elastomer compositions|
    US8729253B2|2011-04-13|2014-05-20|Eastman Chemical Company|Cellulose ester optical films|
    US9417360B2|2011-11-15|2016-08-16|Adeka Corporation|Stretched optical compensation film|
    US9708472B2|2011-12-07|2017-07-18|Eastman Chemical Company|Cellulose esters in highly-filled elastomeric systems|
    JP6054233B2|2013-04-15|2016-12-27|株式会社Adeka|Resin composition and optical film using the same|
    JP6054242B2|2013-05-09|2016-12-27|株式会社Adeka|Cellulosic resin composition and optical film formed by molding the same|
    TWI648163B|2014-02-06|2019-01-21|日商住友化學股份有限公司|Polarizer protective film and polarizer|
    CN104049416A|2014-06-23|2014-09-17|京东方科技集团股份有限公司|Liquid crystal display screen, manufacturing method of liquid crystal display screen and display device|
    JP6622464B2|2015-02-16|2019-12-18|大成化工株式会社|Resin sheet for pharmaceutical packaging|
    US10077342B2|2016-01-21|2018-09-18|Eastman Chemical Company|Elastomeric compositions comprising cellulose ester additives|
    KR20190109519A|2017-01-31|2019-09-25|다이니폰 인사츠 가부시키가이샤|Optical film, polarizing plate, and image display device|
    US20200136094A1|2017-07-10|2020-04-30|Lg Chem, Ltd.|Circularly polarizing plate|
    CN109585512A|2018-12-06|2019-04-05|京东方科技集团股份有限公司|A kind of display base plate and preparation method thereof, display device|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    US32685301P| true| 2001-10-03|2001-10-03||
    US326853P||2001-10-03||
    US10/150,634|US6872766B2|2001-10-03|2002-05-17|Ultraviolet light filter element|
    US150634||2002-05-17||
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