WO2019079194A2 - Inherently flame retardant compound to diffuse visible light from fixtures containing light emitting diodes and panels made therefrom - Google Patents

Inherently flame retardant compound to diffuse visible light from fixtures containing light emitting diodes and panels made therefrom Download PDF

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Publication number
WO2019079194A2
WO2019079194A2 PCT/US2018/055906 US2018055906W WO2019079194A2 WO 2019079194 A2 WO2019079194 A2 WO 2019079194A2 US 2018055906 W US2018055906 W US 2018055906W WO 2019079194 A2 WO2019079194 A2 WO 2019079194A2
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Prior art keywords
panel
particles
mixture
visible light
led
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PCT/US2018/055906
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French (fr)
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WO2019079194A3 (en
Inventor
Tung TO
Shixiong Zhu
Jinping Wu
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Polyone Corporation
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Publication of WO2019079194A3 publication Critical patent/WO2019079194A3/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/22Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer

Definitions

  • This invention relates to a method to cause diffusion of visible light emanating from light emitting diodes via refraction without appreciable loss of light transmission, by use of a textured thermoplastic panel intermediate between the light emitting diodes and a viewer of light from such light emitting diodes.
  • LEDs Light emitting diodes
  • LEDs are produced in commercial quantities at a variety of color temperatures.
  • a typical display of LEDs on sale in a commercial retail store includes LEDs in the range of "Soft White” (2700 K); “Warm White” (3000 K); “Bright White” (35(30 K); and “Daylight” (500(3 K), where the color
  • a mixture of a particular polymer and particular type and size of particle can provide diffusion and hiding power via refraction of visible light without appreciable loss of light transmission through the mixture.
  • the mixture of the particular polymer and the particular type and size of particle with also a second particular type and a second size of particle, extruded in the shape of a lighting fixture panel can result in one or more textured or randomly uneven surfaces of the panel to minimize gloss on the surface of the panel, which in turn minimizes any manufacturing artefacts or imperfections caused by extrusion of the melted polymer mixture through a profile or other die.
  • One aspect of this disclosure is a mixture of a continuous phase of polyvinyl halide, a discontinuous phase of visible light refracting particles having a different refractive index from the polyvinyl halide, and a
  • discontinuous phase of surface altering particles having a different average particle size than average particle size of the visible light refracting particles.
  • Another aspect of this disclosure is a LED lighting fixture having a panel identified above. [00012] BRIEF DESCRIPTION OF THE DRAWING
  • Fig, 1 is a view of the surface of a panel of Comparison Example
  • Fig. 2 is a five times (5x) magnification of a portion of the surface of the panel seen in Fig. 1.
  • Fig. 4 is a view of the surface of a panel of Example 1.
  • Fig. 5 is a five times (5x) magnification of a portion of the surface of the panel seen in Fig. 4.
  • Fig. 6 is a 5x magnification of the edge of the panel seen in Fig.
  • Any polyvinyl halide capable of transiucency in the shape of panel is a candidate for use in this invention, because of their inherent transparency and suitability for compounding with other materials for affecting the degree of light transmission and translucency, as well as their inherent flame retardant properties arising from the presence of halide moieties which naturally retard onset and continuity of combustion in the presence of oxygen.
  • Polyvinyl chloride polymers are presently preferred.
  • vinyl chloride may be polymerized in the presence of said Tg enhancing agent, the agent having been formed prior to or during the vinyl chloride polymerization.
  • Tg enhancing agent the agent having been formed prior to or during the vinyl chloride polymerization.
  • polyvinyl chloride homopolymers or copolymers of polyvinyl chloride comprising one or more comonomers copolymerizable therewith.
  • Suitable comonomers for vinyl chloride include acrylic and methacrylic acids; esters of acrylic and methacrylic acid, wherein the ester portion has from 1 to 12 carbon atoms, for example methyl, ethyl, butyl and ethylhexyl acrylates and the like; methyl, ethyl and butyl meihacrvlaies and the like; hydroxyalkyl esters of acrylic and methacrylic acid, for example hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate and the like; glycidyl esters of acrylic and methacrylic acid, for example glycidyl acrylate, glycidyl methacrylate and the like; alpha, beta uns
  • maleimides for example, N-cyciohexyl maleimide; olefin, for example ethylene, propylene, isobutylene, hexene, and the like; vinylidene chloride, for example, vinylidene chloride; vinyl ester, for example vinyl acetate; vinyl ether, for example methyl vinyl ether, allyl glycidyl ether, n -butyl vinyl ether and the like; crosslinking monomers, for example diallyl phthalate, ethylene glycol dimethacrylate, methylene bis-acrylamide, tracrvlyl triazine, divinyl ether, allyl silanes and the like; and including mixtures of any of the above comonomers.
  • the present invention can also use chlorinated polyvinyl chloride
  • CPVC CPVC
  • PVC containing approximately 57% chlorine is further reacted with chlorine radicals produced from chlorine gas dispersed in water and irradiated to generate chlorine radicals dissolved in water to produce CPVC, a polymer with a higher glass transition temperature (Tg) and heat distortion temperature.
  • Commercial CPVC typically contains by weight from about 58% to about 70% and preferably from about 63% to about 68% chlorine.
  • CPVC copolymers can be obtained by chlorinating such PVC copolymers using conventional methods such as that described in U.S. Pat. No. 2,996,489, which is incorporated herein by reference.
  • Commercial sources of CPVC include Lubrizol Corporation.
  • the preferred composition is a polyvinyl chloride homopolymer, which has a refractive index ranging from about 1.52 to about 1.55 and preferably from about 1.53 to about 1.54.
  • Thermoplastic resin compounds typically contain a variety of additives selected according to the performance requirements of the article produced therefrom well within the understanding of one having ordinary skill in the art without the necessity of undue experimentation.
  • the PVC mixture not contain any additives which could appreciably decrease the light transmission properties of the PVC. Hiding power disguises the location of the point sources of LED when the PVC mixture is made into a panel for positioning between the LED lights and the viewer of such visible light.
  • thermoplastic compounds polyvinyl chloride polymer homopoiymers whose inherent viscosity ranges from 0.4 to 1.3, preferably 0.5 to 0.8 are presently preferred for use in making mixtures of this invention.
  • Visible Light Refracting Particles are presently preferred for use in making mixtures of this invention.
  • the particles can range in mean particle size from about 1 ⁇ to about 8 ⁇ and preferably from about 2 ⁇ to about 6 ⁇ .
  • the particles can be present in the polyvinyl halide can range in parts per hundred resin (PHR) from about 0.1 to about 10 and preferably from about 0.2 to about 2.5.
  • PHR parts per hundred resin
  • the PMMA particles can have a refractive index ranging from about 1.490 to about 1.497 and preferably from about 1.494 to about 1 .496.
  • the PMSQ particles can have a refractive index ranging from about 1.420 to about 1.425 and preferably from about 1.420 to about 1.422.
  • the PS particles can have a refractive index ranging from about
  • Such initially refracted light proceeds through the PVC until it encounters the spherical or spheroidal surface of one of the visible light refracting particles dispersed in the PVC, whereupon such light is refracted to the extent of the difference between the refractive index of PVC and the retractive index of the PMMA, PMSQ, or PS.
  • Such doubly refracted light then proceeds through the particle until it leaves the spherical or spheroidal surface and enters the PVC again, whereupon such light is refracted to the extent of the difference between the refractive index of PMMA, PMSQ, or PS and the refractive index of the PVC.
  • triply refracted light proceeds through the PVC until it leaves the panel and enters the air again, whereupon such light is refracted to the extent of the difference between the refractive index of PVC and the refractive index of the air. That triply refracted light emerges from the light transinissive panel in a different location than the point of source of LED visible light.
  • a panel of PVC and light refracting particles therein can have a light transmission ranging from about 70 % to about 85 % and preferably from about 75% to about 83%.
  • a panel of PVC of the same thickness had a light transmission of from about 75% to about 85% and preferably from about 80 % to about 85%.
  • light transmission without appreciable loss can range from about 1 % to about 6% and preferably from about 1 % to about 5%.
  • Any other additive which causes appreciable loss of light transmission from the light transmission percentage of the panel without such additive above is discouraged for use in the mixture of PVC and visible light refracting particles.
  • polyvinyl halide and particularly PVC homopolymer, can provide both the light transmission properties and the flame retardance for use in a LED lighting panel. Though both polyvinyl halide and PMMA particles have been known, they have not been combined to achieve the multiple advantages identified in this disclosure.
  • PMMA polymethyl methacrylate
  • PMSQ polymethylsilsesquioxane
  • PS polystyrene
  • the surface altering particles can range in average particle size from about 10 ⁇ to about 300 ⁇ and preferably from about 40 ⁇ to about 120 ⁇ .
  • the surface altering particles can be present in the polyvinyl halide can range in parts per hundred resin (PHR) from about 5 to about 30 and preferably from about 8 to about 12.
  • the surface altering PMMA particles can have a refractive index ranging from about 1.490 to about 1.497 and preferably from about 1.494 to about 1.496.
  • the PVC With surface altering particles of PMMA dispersed within a PVC homopolyrner, the PVC becomes a continuous polymer phase while the particles become a second dispersed or discontinuous polymeric phase separate from the first dispersed phase of the visible light refracting particles.
  • the large sized surface altering particles do not contribute much if any to the refractive light diffusion properties of the compound. Therefore, both small and large sizes of particles are required for the polymer compound to have solved both the light diffusion and surface appearance problems identified above.
  • any optional additive should not be wasteful of the additive or detrimental to the processing or performance of the compound.
  • Those skilled in the art of thermoplastics compounding without undue experimentation but with reference to such treatises as Plastics Additives Database (2004) from Plastics Design Library (www.elsevier.com), can select from many different types of additives for inclusion into the compounds of the present invention.
  • Non-limiting examples of optional additives include adhesion promoters; biocides (antibacterials, fungicides, and mildewcides), anti-fogging agents; anti-static agents; bonding, blowing and foaming agents; dispersants; fillers and extenders; fire and flame retardants and smoke suppresants; impact modifiers; initiators; lubricants; micas; pigments, colorants and dyes;
  • plasticizers processing aids; release agents; silanes, tilanates and zirconates; slip and anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; viscosity regulators; waxes; and combinations of them,
  • PVC compounds suitable for use in this disclosure can contain effective amounts of additives ranging from none at all, namely 0.00, to about 500 weight parts per 100 weight parts of PVC (parts per hundred resin or "phr").
  • various primary and/or secondary lubricants such as oxidized polyethylene, paraffin wax, fatty acids, and fatty esters and the like can be utilized.
  • diisooctylthioglycolate mixed metal stabilizers like Barium Zinc and Calcium Zinc, and lead stabilizers (tri-basic lead sulfate, di-basic lead phthalate, for example).
  • Secondary stabilizers may be included for example a metal salt of phosphoric acid, polyols, and epoxidized oils.
  • Specific examples of salts include water-soluble, alkali metal phosphate salts, di sodium hydrogen phosphate, orthophosphai.es such as mono-, di-, and tri-orthophosphates of said alkali metals, alkali metal polyphosphates, -tetrapolyphosphates and -metaphosphates and the like.
  • Polyols such as sugar alcohols, and epoxides such as epoxidized soybean oil can be used.
  • Typical levels of secondary stabilizers range from about 0.1 wt. parts to about 10.0 wt. parts per 100 wt. parts PVC (phr).
  • antioxidants such as phenolics, BPA, BHT, BHA, various hindered phenols and various inhibitors like substituted benzophenones can be utilized.
  • processing aids can also be utilized in amounts up to about 20 or 30 phr.
  • exemplary processing aids are acrylic polymers such as poly methyl (meth)acrylate based materials.
  • Adjustment of melt viscosity can be achieved as well as increasing melt strength by employing 0.5 to 5 phr of commercial acrylic process aids such as those from Dow Chemical under the Paraloid* trademark. Paraloid®. K- 120ND, K--120N, K-175, and other processing aids are disclosed in The Plastics and Rubber Institute: International Conference on PVC
  • fillers include calcium carbonate, clay, silica and various silicates, talc, carbon black and the like.
  • Reinforcing materials include glass fibers, polymer fibers and cellulose fibers.
  • Such fillers are generally added in amounts of from about 0 to about 500 phr of PVC. Preferably from 0 to 300 phr of filler can be employed.
  • flame retardant fillers like ATH (Aluminum trihydrates),
  • AOM ammonium octamolybdate
  • antimony trioxides antimony trioxides
  • magnesium oxides and zinc borates are added to boost the flame retardancy of polyvinyl chloride which is already inherently flame retardant.
  • concentrations of these fillers could range from 0 phr to 200 phr.
  • the PVC it is possible, indeed desirable, for the PVC to have no additives which decrease the light transmission properties of the PVC and the visible light refracting particles.
  • Mixing in a continuous process typically occurs in an extruder that is elevated to a temperature that is sufficient to melt the polymer matrix with addition either at the head of the extruder or downstream in the extruder of the solid ingredient additives.
  • Extruder speeds can range from about 50 to about 500 revolutions per minute (rpm), and preferably from about 100 to about 300 rpm.
  • the output from the extruder is pelletized for later extrusion or molding into polymeric articles.
  • Mixing in a batch process typically occurs in a Banbury mixer that is also elevated to a temperature that is sufficient to melt the polymer matrix to permit addition of the solid ingredient additives.
  • the mixing speeds range from 60 to 1000 rpm and temperaiure of mixing can be ambient. Also, the output from the mixer is chopped into smaller sizes for later extrusion or molding into polymeric articles.
  • the panels of the present invention need to be appreciably light transmissive to permit efficient passage of light emitted from the LED through the entire thickness of the panel to be perceived by a viewer on a side of the panel distant from the LED,
  • a ceiling lighting fixture could have one or more LEDs within the frame of the fixture with one side of the fixture facing the floor being a panel of the present invention. That panel needs to be translucent for the passage of light but also needs to be sufficiently flame retardant to satisfy fire protection standards and to be sufficiently diffuse in order hide the point source location of the LEDs.
  • the panel can be any size to accommodate any number of LEDS, whether the panel is vertical as a lighted wall sign or horizontal as a ceiling fixture.
  • the length of a preferred panel can range from about 0.254 cm (0.1 inch) to about 3.04 m (10 feet) and preferably from about 2.54 (1 inch) to about 121 cm (4 feet).
  • the width of a preferred panel can range from about 12.7 cm (5 inches) to about 3.04 m (10 feet) and preferably from about 2.54 (1 inch) to about 182 cm (6 feet).
  • the thickness of a panel can affect its translucency. Again, one having ordinary skill in the art without undue experimentation can determine the appropriate thickness of the panel through which the LED light travels.
  • the thickness of a panel can range from about 0.5 mm to about 10 mm and preferably from about 1.5 mm to about 5 mm.
  • translucency or light transmission percent can range from about 30% to about 90 % and preferably from about 50% to about 85% as measured using ASTM D1003.
  • Panels can be made using any conventional polymer shaping technique, including without limitation, extrusion, molding, calendering, thermoforming, casting, etc.
  • Panels can be placed between any LED and a viewer of that LED and be diffusive enough to hide the point source of the LED. End uses for such panels include, without limitation, lighting fixtures of all types, backlit signage of all types, general illumination, display lighting, automotive, and mobile devices.
  • the cosmetic appearance of the surface of the panel is textured and not glossy compared with that panel without the surface altering particles present.
  • Example 1 The formulation of Example 1 with ingredients well dispersed in the molten PVC was extruded using a profile die to form a panel seen in surface view in Fig. 4, in 5x magnification of the surface view in Fig. 5, and in 5x magnification of the edge view of Fig. 6.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

Visible light actually emitted by a light emitting diode (LED) at a point source is perceived by a viewer of that LED to be sufficiently diffuse to hide the point source. A panel between the LED and the viewer is made from a mixture of polyvinyl halide polymer in a continuous phase and visible light refracting polymeric particles in a discontinuous phase. The polyvinyl halide has a refractive index different from the particles, and both have a different refractive index from air. Optical refraction causes the diffusion, providing "hiding power" to the panel, which is beneficially, inherently flame retardant because of the use of the polyvinyl halide as the continuous phase. Mixtures made with large visible light refracting polymeric particles can cause during profile extrusion randomly uneven surfaces to increase diffusion and reduce gloss.

Description

INHERENTLY FLAME RETARD ANT COMPOUND TO DIFFUSE VISIBLE LIGHT FROM FIXTURES CONTAINING LIGHT EMITTING DIODES AND PANELS MADE THEREFROM
CLAIM OF PRIORITY
[0001] This application claims priority from U.S. Provisional Patent
Application Serial Number 62/572,966 bearing Attorney Docket Number 12017023 and filed on October 16, 2017, which is incorporated by reference.
FIELD OF THE INVENTION
[0002] This invention relates to a method to cause diffusion of visible light emanating from light emitting diodes via refraction without appreciable loss of light transmission, by use of a textured thermoplastic panel intermediate between the light emitting diodes and a viewer of light from such light emitting diodes.
BACKGROUND OF THE INVENTION
[0003] Light emitting diodes ("LEDs") are rapidly becoming popular for interior and exterior lighting because of their lower energy consumption as compared with incandescent lamps.
[0004] LEDs are produced in commercial quantities at a variety of color temperatures. A typical display of LEDs on sale in a commercial retail store includes LEDs in the range of "Soft White" (2700 K); "Warm White" (3000 K); "Bright White" (35(30 K); and "Daylight" (500(3 K), where the color
temperature from 2700 - 5000 is measured in degrees Kelvin.
[0005] LEDs are point sources of light, intense in origin of their luminosity. Therefore, as with conventional lighting fixtures with incandescent light, the LEDs are visible as point sources of light unless the fixture is modified to provide a translucent or transmissive panel with "hiding power" to diffuse the transmitted light enough to hide the particular location(s) of the LEDs within the lighting fixture. [0006] Lighting fixtures and many other articles for interior spaces where human occupation is possible need materials which are flame retardant sufficiently to meet or exceed regulatory and industrially managed standards,
SUMMARY OF THE INVENTION
[0007] What the art needs is a material which can be inexpensively made and used in an extruded thermoplastic panel intermediate between the light emitting diodes and a viewer of light from such light emitting diodes to diffuse the point source(s) of LED generated light ("hiding power") without appreciable loss of transmitted light.
[0008] It has been found that a mixture of a particular polymer and particular type and size of particle can provide diffusion and hiding power via refraction of visible light without appreciable loss of light transmission through the mixture. Moreover, it has been found that the mixture of the particular polymer and the particular type and size of particle with also a second particular type and a second size of particle, extruded in the shape of a lighting fixture panel can result in one or more textured or randomly uneven surfaces of the panel to minimize gloss on the surface of the panel, which in turn minimizes any manufacturing artefacts or imperfections caused by extrusion of the melted polymer mixture through a profile or other die.
[0009] One aspect of this disclosure is a mixture of a continuous phase of polyvinyl halide, a discontinuous phase of visible light refracting particles having a different refractive index from the polyvinyl halide, and a
discontinuous phase of surface altering particles having a different average particle size than average particle size of the visible light refracting particles.
[00010] Another aspect of this disclosure is a light transmissive panel having hiding power for LED visible lights made from the mixture identified above.
[00011] Another aspect of this disclosure is a LED lighting fixture having a panel identified above. [00012] BRIEF DESCRIPTION OF THE DRAWING
[00013] Fig, 1 is a view of the surface of a panel of Comparison Example
A.
[00014] Fig. 2 is a five times (5x) magnification of a portion of the surface of the panel seen in Fig. 1.
[00015] Fig. 3 is a 5x magnification of the edge of the panel seen in Fig.
1.
[00016] Fig. 4 is a view of the surface of a panel of Example 1.
[00017] Fig. 5 is a five times (5x) magnification of a portion of the surface of the panel seen in Fig. 4.
[00018] Fig. 6 is a 5x magnification of the edge of the panel seen in Fig.
4.
EMBODIMENTS OF THE INVENTION
[00019] Polvvinyl Haiides
[00020] Any polyvinyl halide capable of transiucency in the shape of panel is a candidate for use in this invention, because of their inherent transparency and suitability for compounding with other materials for affecting the degree of light transmission and translucency, as well as their inherent flame retardant properties arising from the presence of halide moieties which naturally retard onset and continuity of combustion in the presence of oxygen. Polyvinyl chloride polymers are presently preferred.
[00021] Polyvinyl chloride polymers are widely available throughout the world. Polyvinyl chloride resin (PVC), as referred to herein, includes polyvinyl chloride homopolymers, vinyl chloride copolymers, graft copolymers, and vinyl chloride polymers polymerized in the presence of any other polymer such as a heat distortion temperature enhancing polymer, impact toughener, barrier polymer, chain transfer agent, stabilizer, plasticizer or flow modifier. [00022] For example a combination of modifications may be made with the PVC polymer by overpolymerizing a low viscosity, high glass transition temperature (Tg) enhancing agent such as SAN resin, or an imidized
polymethacfylate in the presence of a chain transfer agent.
[00023] In another alternative, vinyl chloride may be polymerized in the presence of said Tg enhancing agent, the agent having been formed prior to or during the vinyl chloride polymerization. However, only those resins possessing the specified average particle size and degree of friability exhibit the advantages applicable to the practice of the present invention.
[00024] In the practice of the invention, there may be used polyvinyl chloride homopolymers or copolymers of polyvinyl chloride comprising one or more comonomers copolymerizable therewith. Suitable comonomers for vinyl chloride include acrylic and methacrylic acids; esters of acrylic and methacrylic acid, wherein the ester portion has from 1 to 12 carbon atoms, for example methyl, ethyl, butyl and ethylhexyl acrylates and the like; methyl, ethyl and butyl meihacrvlaies and the like; hydroxyalkyl esters of acrylic and methacrylic acid, for example hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate and the like; glycidyl esters of acrylic and methacrylic acid, for example glycidyl acrylate, glycidyl methacrylate and the like; alpha, beta unsaturated dicarboxylic acids and their anhydrides, for example maleic acid, f umaric acid, itaconic acid and acid anhydrides of these, and the like;
acrylamide and methacrylamide; acrylonitriie and methacrylonitrile;
maleimides, for example, N-cyciohexyl maleimide; olefin, for example ethylene, propylene, isobutylene, hexene, and the like; vinylidene chloride, for example, vinylidene chloride; vinyl ester, for example vinyl acetate; vinyl ether, for example methyl vinyl ether, allyl glycidyl ether, n -butyl vinyl ether and the like; crosslinking monomers, for example diallyl phthalate, ethylene glycol dimethacrylate, methylene bis-acrylamide, tracrvlyl triazine, divinyl ether, allyl silanes and the like; and including mixtures of any of the above comonomers. [00025] The present invention can also use chlorinated polyvinyl chloride
(CPVC), wherein PVC containing approximately 57% chlorine is further reacted with chlorine radicals produced from chlorine gas dispersed in water and irradiated to generate chlorine radicals dissolved in water to produce CPVC, a polymer with a higher glass transition temperature (Tg) and heat distortion temperature. Commercial CPVC typically contains by weight from about 58% to about 70% and preferably from about 63% to about 68% chlorine. CPVC copolymers can be obtained by chlorinating such PVC copolymers using conventional methods such as that described in U.S. Pat. No. 2,996,489, which is incorporated herein by reference. Commercial sources of CPVC include Lubrizol Corporation.
[00026] The preferred composition is a polyvinyl chloride homopolymer, which has a refractive index ranging from about 1.52 to about 1.55 and preferably from about 1.53 to about 1.54.
[00027] Commercially available sources of polyvinyl chloride polymers include Oxy Vinyls LP of Dallas, TX and Shintech USA of Freeport, TX.
[00028] Compounds of Resins
[00029] Thermoplastic resin compounds typically contain a variety of additives selected according to the performance requirements of the article produced therefrom well within the understanding of one having ordinary skill in the art without the necessity of undue experimentation.
[00030] But it is significant for this disclosure that the PVC mixture not contain any additives which could appreciably decrease the light transmission properties of the PVC. Hiding power disguises the location of the point sources of LED when the PVC mixture is made into a panel for positioning between the LED lights and the viewer of such visible light.
[00031] Of all possible thermoplastic compounds, polyvinyl chloride polymer homopoiymers whose inherent viscosity ranges from 0.4 to 1.3, preferably 0.5 to 0.8 are presently preferred for use in making mixtures of this invention. [00032] Visible Light Refracting Particles
[00033] It has been found that polymethyl methacrylate (PMM A) or polymethyisilsesqmoxane (PMSQ) or polystyrene (PS) have refractive indices different enough from PVC that particles of them, usually spheres or spheroids, can refract point sources of light to cause diffusion of such light.
[00034] The particles can range in mean particle size from about 1 μιη to about 8 μηι and preferably from about 2 μηι to about 6 μηι.
[00035] The particles can range in average particle size from about 1 μπ\ to about 8 μπι and preferably from about 2 μπι to about 6 μιη.
[00036] The particles can be present in the polyvinyl halide can range in parts per hundred resin (PHR) from about 0.1 to about 10 and preferably from about 0.2 to about 2.5.
[00037] The PMMA particles can have a refractive index ranging from about 1.490 to about 1.497 and preferably from about 1.494 to about 1 .496.
[00038] The PMSQ particles can have a refractive index ranging from about 1.420 to about 1.425 and preferably from about 1.420 to about 1.422.
[00039] The PS particles can have a refractive index ranging from about
1.590 to about 1.597 and preferably from about 1.593 to about 1.595.
[00040] With particles of either PMMA or PMSQ or PS or any two or three of them dispersed within a PVC homopolymer, the PVC becomes a continuous polymer phase while the particles become a dispersed or discontinuous polymeric phase.
[00041] Applying the laws of optics, in its most basic occurrence, visible light from a point source such as a LED reaches a light transrnissive panel made from visible light refracting particles in PVC whereupon such light is refracted to the extent of the difference between the refractive index of air and the refractive index of the PVC.
[00042] Such initially refracted light proceeds through the PVC until it encounters the spherical or spheroidal surface of one of the visible light refracting particles dispersed in the PVC, whereupon such light is refracted to the extent of the difference between the refractive index of PVC and the retractive index of the PMMA, PMSQ, or PS.
[00043] Such doubly refracted light then proceeds through the particle until it leaves the spherical or spheroidal surface and enters the PVC again, whereupon such light is refracted to the extent of the difference between the refractive index of PMMA, PMSQ, or PS and the refractive index of the PVC.
[00044] Such triply refracted light proceeds through the PVC until it leaves the panel and enters the air again, whereupon such light is refracted to the extent of the difference between the refractive index of PVC and the refractive index of the air. That triply refracted light emerges from the light transinissive panel in a different location than the point of source of LED visible light.
[00045] It is possible and likely that doubly refracted light identified above encounters another spherical or spheroidal particle in the PVC before completely transiting the thickness of the panel. Thus, the complexity of the predictable refractions of visible light further diffuse the incident original LED light quadruply, quintuply, or more times.
[00046] Multiplied by the number of particles in the PVC continuous phase, as well as the PVC itself, the array of point sources of LED light diffuse without appreciable loss of transmission, causing the desired hiding power for the LED lighting fixture.
[00047] It has been found that a panel of PVC and light refracting particles therein, the panel having a thickness ranging from about 1 .5 mm to about 3.0 mm and preferably from about 1.5 mm to about 2.0 mm, can have a light transmission ranging from about 70 % to about 85 % and preferably from about 75% to about 83%. By comparison a panel of PVC of the same thickness had a light transmission of from about 75% to about 85% and preferably from about 80 % to about 85%. Thus, light transmission without appreciable loss can range from about 1 % to about 6% and preferably from about 1 % to about 5%. [00048] Any other additive which causes appreciable loss of light transmission from the light transmission percentage of the panel without such additive above is discouraged for use in the mixture of PVC and visible light refracting particles.
[00049] Stated another way, if 85% is the theoretically possible light transmission percentage for the inherently flame retardant polyvinyl halide in the panel, then 80% is the practically possible light transmission percentage for the polyvinyl halide panel with the visible light refracting particles, and any lower percentage caused by any other additive is discouraged or even refused.
[00050] The manufacturer of the PMMA particles sells such particles for light refraction diffusion for use in a variety of polymers. But the problem in the art is that the polymeric continuous phase of LED light diffusing panels have not been the inherently flame retardant polyvinyl halide candidates identified above. For that reason, to comply with regulatory and industrially established standards, such LED light diffusing panels have also required the presence of flame retardants which cause an unacceptable decrease in visible light transmission through the panel.
[00051] Use of polyvinyl halide, and particularly PVC homopolymer, can provide both the light transmission properties and the flame retardance for use in a LED lighting panel. Though both polyvinyl halide and PMMA particles have been known, they have not been combined to achieve the multiple advantages identified in this disclosure.
[00052] Surface Altering Particles
[00053] It has been found that polymethyl methacrylate (PMMA) beads or particles are available in sufficiently large average particle size to have capacity to alter the surface of extruded polyvinyl chloride compounds. If polymethylsilsesquioxane (PMSQ) or polystyrene (PS) particles are available in large average particle sizes, they are candidates also for surface altering effects. [00054] The surface altering particles can range in average particle size from about 10 μιη to about 300 μπ\ and preferably from about 40 μιη to about 120 μηι.
[00055] The surface altering particles can be present in the polyvinyl halide can range in parts per hundred resin (PHR) from about 5 to about 30 and preferably from about 8 to about 12.
[00056] As with the PMMA particles for visible light refracting effect, the surface altering PMMA particles can have a refractive index ranging from about 1.490 to about 1.497 and preferably from about 1.494 to about 1.496.
[00057] With surface altering particles of PMMA dispersed within a PVC homopolyrner, the PVC becomes a continuous polymer phase while the particles become a second dispersed or discontinuous polymeric phase separate from the first dispersed phase of the visible light refracting particles.
[00058] Unlike the visible light refracting particles, the large sized surface altering particles do not contribute much if any to the refractive light diffusion properties of the compound. Therefore, both small and large sizes of particles are required for the polymer compound to have solved both the light diffusion and surface appearance problems identified above.
[00059] Optional Additives
[00060] The compound of the present invention can include conventional plastics additives in an amount that is sufficient to obtain a desired processing or performance property for the compound, so long as there is resulting no light transmission percentage in the panel lower than the light transmission percentage of the polyvinyl halide and the visible light refracting particles.
[00061] The amount of any optional additive should not be wasteful of the additive or detrimental to the processing or performance of the compound. Those skilled in the art of thermoplastics compounding, without undue experimentation but with reference to such treatises as Plastics Additives Database (2004) from Plastics Design Library (www.elsevier.com), can select from many different types of additives for inclusion into the compounds of the present invention.
[00062] Non-limiting examples of optional additives include adhesion promoters; biocides (antibacterials, fungicides, and mildewcides), anti-fogging agents; anti-static agents; bonding, blowing and foaming agents; dispersants; fillers and extenders; fire and flame retardants and smoke suppresants; impact modifiers; initiators; lubricants; micas; pigments, colorants and dyes;
plasticizers; processing aids; release agents; silanes, tilanates and zirconates; slip and anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; viscosity regulators; waxes; and combinations of them,
[00063] If there is no appreciable loss of light transmission, using PVC as only one possible embodiment, PVC compounds suitable for use in this disclosure can contain effective amounts of additives ranging from none at all, namely 0.00, to about 500 weight parts per 100 weight parts of PVC (parts per hundred resin or "phr").
[00064] For example, various primary and/or secondary lubricants such as oxidized polyethylene, paraffin wax, fatty acids, and fatty esters and the like can be utilized.
[00065] Thermal and ultra-violet light (UV) stabilizers can be utilized such as various organo tins, for example dibutyl tin, dibutyltin-S-S'-bi- (isooctylmercaptoacetate), dibutyl tin dilaurate, dimethyl tin
diisooctylthioglycolate, mixed metal stabilizers like Barium Zinc and Calcium Zinc, and lead stabilizers (tri-basic lead sulfate, di-basic lead phthalate, for example). Secondary stabilizers may be included for example a metal salt of phosphoric acid, polyols, and epoxidized oils. Specific examples of salts include water-soluble, alkali metal phosphate salts, di sodium hydrogen phosphate, orthophosphai.es such as mono-, di-, and tri-orthophosphates of said alkali metals, alkali metal polyphosphates, -tetrapolyphosphates and -metaphosphates and the like. Polyols such as sugar alcohols, and epoxides such as epoxidized soybean oil can be used. Typical levels of secondary stabilizers range from about 0.1 wt. parts to about 10.0 wt. parts per 100 wt. parts PVC (phr).
[00066] In addition, antioxidants such as phenolics, BPA, BHT, BHA, various hindered phenols and various inhibitors like substituted benzophenones can be utilized.
[00067] Various processing aids, fillers, flame retardants and reinforcing materials can also be utilized in amounts up to about 20 or 30 phr. Exemplary processing aids are acrylic polymers such as poly methyl (meth)acrylate based materials.
[00068] Adjustment of melt viscosity can be achieved as well as increasing melt strength by employing 0.5 to 5 phr of commercial acrylic process aids such as those from Dow Chemical under the Paraloid* trademark. Paraloid®. K- 120ND, K--120N, K-175, and other processing aids are disclosed in The Plastics and Rubber Institute: International Conference on PVC
Processing, Apr. 26-28 (1983), Paper No. 17.
[00069] Examples of fillers include calcium carbonate, clay, silica and various silicates, talc, carbon black and the like. Reinforcing materials include glass fibers, polymer fibers and cellulose fibers. Such fillers are generally added in amounts of from about 0 to about 500 phr of PVC. Preferably from 0 to 300 phr of filler can be employed.
[00070] Also, flame retardant fillers like ATH (Aluminum trihydrates),
AOM (ammonium octamolybdate), antimony trioxides, magnesium oxides and zinc borates are added to boost the flame retardancy of polyvinyl chloride which is already inherently flame retardant.
[00071] The concentrations of these fillers could range from 0 phr to 200 phr. In other words, it is possible, indeed desirable, for the PVC to have no additives which decrease the light transmission properties of the PVC and the visible light refracting particles.
[00072] Processing [00073] The preparation of compounds of the present invention is uncomplicated. The compound of the present invention can be made in batch or continuous operations.
[00074] Mixing in a continuous process typically occurs in an extruder that is elevated to a temperature that is sufficient to melt the polymer matrix with addition either at the head of the extruder or downstream in the extruder of the solid ingredient additives. Extruder speeds can range from about 50 to about 500 revolutions per minute (rpm), and preferably from about 100 to about 300 rpm. Typically, the output from the extruder is pelletized for later extrusion or molding into polymeric articles.
[00075] Mixing in a batch process typically occurs in a Banbury mixer that is also elevated to a temperature that is sufficient to melt the polymer matrix to permit addition of the solid ingredient additives. The mixing speeds range from 60 to 1000 rpm and temperaiure of mixing can be ambient. Also, the output from the mixer is chopped into smaller sizes for later extrusion or molding into polymeric articles.
[00076] Subsequent extrusion or molding techniques are well known to those skilled in the art of thermoplastics polymer engineering. Without undue experimentation but with such references as "Extrusion, The Definitive Processing Guide and Handbook"; "Handbook of Molded Part Shrinkage and Warpage"; "Specialized Molding Techniques"; "Rotational Molding
Technology"; and "Handbook of Mold, Tool and Die Repair Welding", all published by Plastics Design Library (elsevier.com), one can make articles of any conceivable shape and appearance using compounds of the present invention.
[00077] Panel of Thermoplastic Compounds
[00078] Regardless of the selection of ingredients identified above, the panels of the present invention need to be appreciably light transmissive to permit efficient passage of light emitted from the LED through the entire thickness of the panel to be perceived by a viewer on a side of the panel distant from the LED, For example, a ceiling lighting fixture could have one or more LEDs within the frame of the fixture with one side of the fixture facing the floor being a panel of the present invention. That panel needs to be translucent for the passage of light but also needs to be sufficiently flame retardant to satisfy fire protection standards and to be sufficiently diffuse in order hide the point source location of the LEDs.
[00079] The panel can be any size to accommodate any number of LEDS, whether the panel is vertical as a lighted wall sign or horizontal as a ceiling fixture. The length of a preferred panel can range from about 0.254 cm (0.1 inch) to about 3.04 m (10 feet) and preferably from about 2.54 (1 inch) to about 121 cm (4 feet). The width of a preferred panel can range from about 12.7 cm (5 inches) to about 3.04 m (10 feet) and preferably from about 2.54 (1 inch) to about 182 cm (6 feet).
[00080] The thickness of a panel can affect its translucency. Again, one having ordinary skill in the art without undue experimentation can determine the appropriate thickness of the panel through which the LED light travels. For example, the thickness of a panel can range from about 0.5 mm to about 10 mm and preferably from about 1.5 mm to about 5 mm. For panels of such thicknesses, translucency or light transmission percent can range from about 30% to about 90 % and preferably from about 50% to about 85% as measured using ASTM D1003.
[00081] Panels can be made using any conventional polymer shaping technique, including without limitation, extrusion, molding, calendering, thermoforming, casting, etc.
[00082] When the panels are made using extrusion through a profile die as final shaping, it has been found that the size and quantity of the light refracting particles affect the surface appearance of the extruded panel by providing a randomly uneven surface or texturing which increases the diffusion of the panel as well as hiding any anomalies, artefacts, or imperfections caused by the profile die during the exit of the molten polymer mixture from the die. USEFULNESS OF THE INVENTION
[00083] Panels can be placed between any LED and a viewer of that LED and be diffusive enough to hide the point source of the LED. End uses for such panels include, without limitation, lighting fixtures of all types, backlit signage of all types, general illumination, display lighting, automotive, and mobile devices.
[00084] These panels improve the appearance of luminosity uniformity for LED light point sources such that the point sources may not be identifiable when viewing the light through the lighting fixture.
[00085] Moreover, with the surface altering particles present, the cosmetic appearance of the surface of the panel is textured and not glossy compared with that panel without the surface altering particles present.
EXAMPLE
[00086] Diffusion and Flame Testing of Panels
[00087] 100 phr polyvinyl chloride polymer made by Shintech was melt- mixed with 1 phr of PMMA particles made by Sekisui having a mean particle size of 5 μιη, an average particle size of 5 μπι , and a refractive index of 1.495, well dispersed in the PVC.
[00088] A panel of that mixture was made for testing using a Haze Gard plus from BYK following ASTM D1003.
[00089] When fully lit, the panel was viewed at approximately a 25.4 cm
(10 inch) distance. Because of the complexity of optical refractions of the visible light from the LEDs, caused at the several interfaces of air and PVC and PVC and PMMA, the viewer could not identify the point sources of the LED- generated light. This panel was found to have "hiding power" without appreciable loss of light transmission in a mixture which was inherently flame retardant. [00090] The polymeric mixture in a plaque having a 0.75 mm thickness passed V-0 and 2.0 mm thickness passed 5VA flame test measured using UL94 rest procedure without the presence of any flame retardant additive such as brominated flame retardants, non-halogenated flame retardants, or the like.
[00091] Surface Testing of Comparison Example A and Example 1
[00092] Having established the premise of diffusion of light and flame retardancy, the surface testing commenced in a direct comparison. Table 1 identifies the ingredients used, all the same except for the surface altering particles added.
Figure imgf000016_0001
Figure imgf000017_0001
[00093] The formulation of Comparative Example A with ingredients well dispersed in the molten PVC was extruded using a profile die to form a panel seen in surface view in Fig 1 ., in 5x magnification of the surface view in Fig. 2, and in 5x magnification of the edge view of Fig. 3.
[00094] The formulation of Example 1 with ingredients well dispersed in the molten PVC was extruded using a profile die to form a panel seen in surface view in Fig. 4, in 5x magnification of the surface view in Fig. 5, and in 5x magnification of the edge view of Fig. 6.
[00095] The unmelted 60 micrometer sized particles in Example 1, much larger in size than the 2 micrometer sized particles in both the Comparative Example A and the Example 1 formulations, protrude at the surface of the profile extruded panel as seen in Fig. 4 compared with Fig. 1. The five times magnification of the surface views of Figs. 1 and 4, now seen in Figs. 2 and 5, further identify the advantage of the mixture of Example 1 over the mixture of Comparative Example A.
[00096] The striations and die lines in Fig. 2 are unacceptable in commercial lighting fixtures and the overall glossier surface of Fig. 1 is less desired. By comparison, the randomly uneven surface of Fig. 4, magnified in Fig. 5 is acceptable for use in commercial lighting fixtures.
[00097] The comparison of Fig. 3 with Fig. 6 further proves the advantage of the mixture of Example 1. The 60 micrometer sized particles are less prevalent in the bulk of the panel, per unit surface area, than they are at the surface, a comparison of Fig. 6 with Fig. 5, at the same magnification. [00098] With Example 1 , an acceptable panel is possible, one with diffusion of light source, flame retardancv without flame retardant additives, and a randomly uneven surface to minimize appearance of profile extrusion abnormalities.
[00099] The formulation of Example 1 was also tested for UL 94 5VA at a 2.0 mm thickness and passed, showing flame retardance performance was retained without any additional flame retardants even with the presence of the surface altering particles.
[000100] The invention is not limited to the above embodiments. The claims follow.

Claims

What is claimed is:
1. A mixture of polymers, comprising:
(a) a continuous phase of polyvinyl halide
(b) a discontinuous phase of visible light refracting particles having a different refractive index from the polyvinyl halide, and
(c) a discontinuous phase of surface altering particles having a larger average particle size than average particle size of the visible light refracting particles.
2. The mixture of Claim 1, wherein the visible light refracting particles comprise poly methyl methacrylate (PMMA) or polymethylsilsesquioxane (PMSQ) or polystyrene (PS) or combinations of them, and wherein the surface altering particles comprise polymethyl methacrylate (PMMA) or
polymethylsilsesquioxane (PMSQ) or polystyrene (PS) or combinations of them.
3. The mixture of Claim 1 or Claim 2, wherein the surface altering particles have an average particle size from about 10 μηι to about 300 μηι and preferably from about 40 μιη to about 120 μιη.
4. The mixture of any one of Claims 1-3, wherein the surface altering particles are present in the polyvinyl halide in parts per hundred resin (PHR) from about 5 to about 30.
5. The mixture of Claim 4 wherein the surface altering particles are present in the polyvinyl halide in PHR from about 8 to about 12.
6. The mixture of any one of Claims 2-5, wherein the PMMA particles have a refractive index ranging from about 1 .490 to about 1.497.
7. The mixture of any one of Claims 2-5, wherein the PMSQ particles have a refractive index ranging from about 1.420 to about 1.425.
8. The mixture of any one of Claims 2-5, wherein the PS particles can have a refractive index ranging from about 1.590 to about 1.597.
9. The mixture of any one of Claims 1-8, wherein the polyvinyl halide is polyvinyl chloride, and wherein the mixture is sufficiently inherently flame retardant as to pass UL 5VA at 2.0 mm without the presence of flame retardant additives.
10. The mixture of Claim 9, wherein the polyvinyl chloride is polyvinyl chloride homopolymer having a refractive index ranging from about 1.52 to about 1.55.
11. A light transmissive panel for visible light spectrum LED light, comprising the mixture of any one of Claims 1-10, wherein light from the LED is sufficiently diffused to hide the point source location of the LED.
12. The panel of Claim 1 1 , wherein the panel has a thickness of from about 0.5 mm to about 10 mm.
13. The panel of Claim 12, wherein when the panel has a thickness ranging from about 1.5 mm to about 3.0 mm, the loss of light transmission can range from about 1% to about 6% as compared with a panel of the same thickness having the same polyvinyl halide but no visible light refracting particles.
14. The panel of Claim 12 or Claim 13, wherein the panel, having a thickness ranging from about 1.5 mm to about 3.0 mm, has a light transmission ranging from about 70 % to about 85 %.
15. A LED lighting fixture, comprising (a) at least one LED and (b) a panel of any one of Claims 11-14.
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