Luminescent gel coats and moldable resins

专利摘要:
Luminescent polymers are prepared from thermosetting unsaturated polyesters, suspending fillers and phosphorescent pigments and utilized to make gel coated articles and molded, cast and fiberglass reinforced plastic (FRP) articles. The preferred thermosetting unsaturated polyester resins are prepared by condensing mixtures of ethylenically unsaturated and aromatic dicarboxylic acids and anhydrides with dihydric alcohols and a polymerizable vinylidene monomer. Preferred suspending fillers and thixotropic modifiers include silica flakes (particularly precipitated and fumed silica and fine to coarse sand), microspheres, glass fibers and other short fibers, nepheline syenite, feldspar, mica, pumice, magnesium sulfate, calcium carbonate, bentonite and the various clays and thixotropic modifiers and mixtures thereof. Preferred phosphorescent pigments include alkaline earth aluminate phosphors, zinc sulfide phosphors and mixtures of these phosphors, particularly those phosphors activated by multiple metals and/or rare earths. The luminescent resins may be rendered fire retardant with halogenated polyester resins and/or additives and made flexible by the addition of flexible resins.
公开号:KR20020075437A
申请号:KR1020027010724
申请日:2000-02-18
公开日:2002-10-04
发明作者:버넬-존스피터
申请人:오리온 21 에이. 디. 피티와이 리미티드；
IPC主号:

专利说明:

Luminescent Gel Coatings and Moldable Resin {LUMINESCENT GEL COATS AND MOLDABLE RESINS}
[2] The term "luminescenz" was first used in 1888 by German physicist and historian Eilhardt Wiedemann for "all phenomena of light not controlled only by temperature rise". Wiedemann notes that the rise in temperature allows liquids and solids to emit more and more shorter wavelengths gradually as their temperature increases, and the material finally becomes red and then white and visible to the naked eye. This is incandescent or "hot light" as opposed to luminescence or "cold light".
[3] Examples of luminescence include faint luminescence (chemiluminescence) of phosphorus, phosphorescence of certain solids (phosphorus) exposed after exposure to sunlight, X-rays or electron beams, and many exposures when excited by various types of radiation Transient luminescence of materials, electroluminescence of aurora borealis and gases when current flows, triboluminescence of crystals when rubbed or broken, firefly, firefly larvae and "burning of the sea", trees Bioluminescence of organisms, including bacterial luminescence from the flesh of dead animals or dead bodies of fish or dead bodies of fish.
[4] For centuries incandescent has been a common method of artificial lighting: torches, candles, oil lamps, gas lamps and tungsten filaments have been used to light in this way. Useful, renewable cold light sources, in particular photoluminescent materials capable of absorbing light and emitting useful amounts of light for a long time, thermoluminescent materials that are activated by heat, and electrons There is a need for an electroluminescent material that emits light with respect to a current within the luminescent material.
[5] In phosphorescent pigments, excitation due to special wavelengths of visible or ultraviolet radiation continues to emit light after excitation due to electron excitation. After luminescence is stopped and exposure to light is resumed, the material again exhibits the property of absorbing light energy and glow-in-the-dark (absorption-accumulation-emission cycles). Most phosphorescent pigments have the problem of low luminescence and / or short afterglow.
[6] Various phosphorescent materials are known, including sulfides, metal aluminate oxides, silicates and various rare earth compounds (particularly rare earth oxides). The most common form of phosphorescent pigment is zinc sulfide structure, which is substituted with zinc and excited by an activator of various elements. It is known that many luminescent materials can be prepared by mixing metallic zinc sulfide (which emits green). In addition to zinc sulfide, substances or mixtures thereof which are variously referred to as activators, coactivators or compensators are generally used. Known activators include copper, aluminum, silver, gold, manganese, gallium, indium, scandium, lead (which forms ZnS: Cu, which may be the most common zinc sulfide phosphor), cerium, terbium, europium, gadolinium, samarium , Praseodymium or other rare earth elements and elements such as halogens. These activators can enter the crystal lattice of the host material, giving it a luminescent property. Other sulfide phosphors that emit light of various colors include ZnCdS: Cu and ZnCdS: Ag, CaS: Bi, CaSrS: Bi, alphabarium-zinc sulfide, barium-zinc-cadmium sulfide, strontium sulfide, and the like. The main types of long-lived phosphorescent pigments are metal aluminates, in particular alkaline earth metal aluminate oxides of the formula MAl ₂ O ₄ where M is a metal or a mixture of metals. Examples include strontium aluminum oxide (SrAl ₂ O ₄ ), calcium aluminum oxide (CaAl ₂ O ₄ ), barium aluminum oxide (BaAl ₂ O ₄ ), and mixtures. These magnesium or aluminate phosphors without magnesium can be further activated by other metals and rare earths.
[7] For example, US Pat. No. 5,558,817 (1996) to Bredol et al . Discloses a cube structure in which a high luminous efficacy as well as a high x-value of a color point is formed in a simple manner and activated by copper and aluminum. A method for producing luminescent zinc sulfide is described. US Pat. No. 3,595,804 (1971) to Martin Jr. describes a process for preparing zinc sulfide and zinc-cadmium sulfide phosphors containing aluminum and activated by silver or copper. US Pat. No. 3,597,678 (1976) to Dikhoff et al . Describes a process for preparing luminescent sulfides of zinc and / or cadmium. Luminescent sulfides may be activated by themselves, or may be activated by silver, copper and / or gold, and may be coactivated by aluminum, gallium, indium, scandium and / or rare earths. US Pat. No. 3,970,582 (1976) to Fan et al . Describes a phosphorescent material comprising alpha barium zinc sulfide or barium zinc cadmium sulfide activated by manganese, europium, cerium, lead or terbium and a process for the preparation thereof. have.
[8] Alkaline earth metal aluminate oxide phosphors and methods for their preparation are discussed in US Pat. No. 5,424,006 to Murayama et al . In alkaline earth metal aluminum oxide phosphors of formula MAl ₂ O ₄ , alkaline earth metal aluminum oxide phosphors have been prepared with M selected from calcium, strontium, barium or mixtures thereof, with or without added magnesium. These phosphorescent aluminates were activated by europium and were activated with lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium, erbium, tulium, ytterbium, lutetium, tin, bismuth or mixtures thereof. These metal aluminate phosphors have a bright and long-lasting phosphorescent afterglow when emitted by ultraviolet or visible light having a wavelength of 200 to 450 nm at room temperature, and thermoluminescent glow peaks at high temperatures of 50 ° C. or higher. (glow peak).
[9] Aluminate phosphors in the form of alkaline earth metals from Murayama et al . Have the problem that zinc sulfide phosphors decompose as a result of irradiation with ultraviolet (UV) radiation in the presence of moisture (thus, zinc sulfide phosphors are outdoors and are exposed to direct sunlight). Difficult to use) and problems with insufficient length of afterglow (for items such as luminous watches, self-luminescent paints that continually emit light by doping radioactive phosphors into phosphorescent phosphors and absorbing radiant energy). Was developed in response to Metal aluminate phosphors, such as activated alkaline earth metal aluminate oxides, exhibit UV sensitivity and bright, long-lasting afterglow luminescence. However, compared to zinc sulfide phosphors, metal aluminate phosphors are excited to achieve afterglow saturation, which is disadvantageous in that they require a very long time and / or strong roughness and are susceptible to moisture and moisture. can do. This indicates that it is necessary to apply special phosphors and mixtures of phosphors used to vary the excitation conditions, and that UV protection is required when water-resistant preparations and sulfides suitable for protecting phosphorescent particles are used.
[10] Phosphorescent materials have been used in a variety of commercial applications, including warning signs, machine signs, luminescent dials, direction signs, stairway edge signs, fire helmets, casualties, safety clothing, sporting goods and the like. Commercially applicable sheets of phosphorescent materials are usually phosphorescent pigments in transparent polyvinylchloride. In addition, thermoplastic materials (which may be softened by heating and hardened by cooling may be repeated) or materials close thereto, including elastic and rubbery materials, may be used.
[11] For example, US Pat. No. 4,211,813 (1980) to Gravisse et al . Describes photoluminescent textiles and other flexible sheet materials coated with a photoluminescent synthetic resin thin film. Textile raw materials were applied with synthetic resins containing phosphorescent metal sulfides and materials that absorb energy of short wavelengths and emit energy at wavelengths that lie within the absorption spectrum of the phosphorescent component. Preferred resins include polyurethane resins, polyvinyl chloride resins, polyacrylates and / or acrylates, elastic silicones and combinations of these resins. As sulfide, zinc sulfide is preferable, and zinc sulfide can be used together with calcium sulfide, cadmium sulfide, and strontium sulfide. US Patent 5,692,892 (1997) to Farzin-Nia et al . Describes luminescent orthodontic appliance applications. Preferred orthodontic materials are plastics, preferably polycarbonates, glass fiber reinforcements and luminescent pigments, preferably zinc sulfide doped with copper or zinc sulfide doped with copper and manganese. US Patent No. 5,605,734 (1997) to Yeh describes a method of making carpets with phosphorescent directional signals and directional markers. The carpet was labeled with a polymer filament and fiber containing a zinc sulfide activated pigment.
[12] Yonetani's US Pat. No. 5,698,301 (1997) discloses a phosphorescent composition comprising a transparent resin layer containing a UV light absorber, a phosphorescent layer using SrAl ₂ O ₄ as a phosphorescent dye, and a sequential layer of a reflective layer optionally having an adhesive layer on the back side of the reflective layer. Write about the article. This transparent resin layer may be a material such as polycarbonate, acrylic resin, polyvinyl chloride resin and polyester. This phosphorescent layer is obtained by dispersing a phosphorescent dye in a gloss agent prepared by dissolving one of the above resins (preferably an acrylic resin or a vinyl chloride-acrylic copolymer resin) in a solvent, and printing on a transparent layer or a reflective layer. Geisel's US Pat. No. 5,674,437 (1997) describes a method of making a luminescent fibrous material comprising bonding a metal aluminate oxide pigment with a thermoplastic polymer that is heated, mixed and then extruded into fibers. Such luminescent fiber materials include polypropylene, polyamide, polyester, polymethacrylic acid, polyacrylate, polycarbonate, polycyanoethylene, polyacrylonitrile, polyvinyl chloride, polyethylene, polystyrene, polyurethane, Thermoplastic polymers such as acrylate resins, halogenated polymers or mixtures thereof. The metal aluminate oxide pigments are selected from strontium, calcium or barium with or without magnesium, europium activators and lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium, erbium, tulium, ytterbium, lutetium, Tin or bismuth coactivators. In addition, a plasticizer is added. US Patent 5,607,621 (1997) to Ishihara et al . Describes a method of making a phosphorescent resin and the articles formed. The phosphorescent resins may include acrylic resins, ABS resins, acetal homopolymers or acetal copolymer resins, polyamides such as PET, nylon, vinyl chloride resins, polycarbonates, polyphenylene oxides, polyimides, polyethylene, polypropylene or Resinous materials such as polystyrene, SrAl ₂ O ₄ phosphorescent pigments and liquid paraffin lubricants. The phosphorescent resin mixture is mixed at a temperature above the melting point of the synthetic resin and extruded to produce pellets for injection molding or injection molding.
[13] US Pat. No. 5,716,723 (1998) to Van Cleef et al . Discloses rubber (styrene block copolymers or butadiene block copolymers) glowing in the dark, processed oils (plasticizers or extenders), stabilizers (ultraviolet stabilizers, antioxidants and / or preservatives) and Shoe soles of phosphorescent materials (preferably zinc sulfide copper mixtures) are described. This shoe sole optionally includes a flow modifier, a modified polymer and a filler. Goguen's US patent 4,629,583 (1986) describes phosphorescent compositions containing phosphorescent polymers used in footwear. The composition comprises an elastomeric polymer, a process oil, a stabilizer and a phosphorescent pigment (preferably a zinc sulfide copper mixture) and optionally a modified polymer, a dry blend flow modifier and a filler. The elastic polymer is preferably a styrene block copolymer, a monoalkenyl arene copolymer or a polystyrene polybutadiene block copolymer. Preferred modified polymers include high density polyethylene, ethylene vinyl acetate, polybutadiene resins, high stryrene resins, poly (alpha-methylstyrene) resins, crystalline polystyrene resins, impact resistant styrene resins, copolymers thereof and their There is a mixture.
[14] In addition, numerous other plastic articles containing phosphorescent materials are known. For example, Hodges, U.S. Patent 3,936,970 (1976) describes a fish bait that emits light. Luminescent materials include phosphorus such as zinc sulfide, extenders such as magnesium carbonate to increase luminescent lifetime, suspending agents such as silica and zinc palmitate and luminescent material carriers such as transparent plastics or translucent plastics. Bussiere's U.S. Patent 5,490,344 (1996) describes luminous lures prepared by mixing white powder with plastic resins and phosphorescent materials. Typical resins thereof are thermoplastic rubbers, styrenes, polyolefins and plastisols. Paetzold, U.S. Patent 4,759,453 (1988) describes a baby bottle labeled with a luminescent indicator band made from a synthetic plastic with an inorganic zinc sulfide phosphor with dual lubricants. Stone's U.S. Patent 4,210,953 (1980) describes a flashlight having a light emitting case, light emitting band or light emitting sleeve containing zinc sulfide or zinc-cadmium sulfide phosphorescent material.
[15] Epoxy polymers are available from Hunt's U.S. Used in patent 5,395,673 (1995), which describes a composition useful for leaking from the bottom surface where lighting conditions can be poor. The composition comprises an epoxy polymer (preferably a diglycidyl ether resin aliphatic amine adduct modified with amylethyl piperidine as stabilizer), a phosphorescent pigment (preferably zinc sulfide activated copper) and aluminum oxide Aggregates such as are preferred.
[16] While there are many others close to it, it is pointed out that there is a need for improved thermoset luminescent resins, which are described in Vockel, Jr. et al ., US Pat. Nos. 5,135,591 (1992) and 5,223,330 (1993). These patents describe a method of manufacture and a phosphorescent fiberglass reinforced plastic article in which the phosphorescent pigment is first applied to a reinforced fabric using a carrier resin and then cured. Suitable carrier resins include acrylic latex, epoxy, polyvinyl chloride, ethylene vinyl chloride, polyurethane, polyvinylacetate, acrylonitrile rubber, melamine and copolymers of these compounds. The coated phosphorescent fibers are thermoplastic resins (which can be melted to heat and reshape even after curing) and thermoplastics (which cannot be melted to heat after curing) to form a fiberglass reinforced plastic (FRP) product. Can be used with both thermosetting resins. This proximity using phosphorescent fibers is used for two reasons: 1) The first attempt to add phosphorescent material directly to the resin system was successful, usually due to the release of dense phosphorescent material off the surface of the final article. 2) due to the relative opacity of the resin mixture resulting from preventing luminescence from appearing, due to obstruction by fillers that prevent the phosphorescent material from being filled.
[17] Vockel, Jr. The method of coating the fibers used by et al . with a phosphor still requires a polyester thermoset resin system that does not settle the phosphorescent pigment during storage or use, and has adequate transparency and / or to make good use of the phosphorescent particles. Or a translucent polyester resin system. Such thermosetting luminescent resins may be very useful because they have the property of making the resin suitable for large items such as boats and spas, as well as for bulky articles. In addition to applications when thermosetting laminates are used with fiber reinforcements, improved luminescent thermosetting resins, manufacturing methods and products in both gel coating applications and molding and molding applications, even when no reinforcing fibers are used. There is a demand for
[18] Unsaturated polyesters are well known in the art and have been widely studied and described. Fiberglass reinforced plastics (FRP) combine fibrous materials (including fibers other than glass) with resinous materials, such as thermoset or thermoplastic polymer resins, to produce materials that are stronger than the resin itself. FRP manufacturing methods are used to produce many products such as furniture, swimming pools, baths and spas, boats, automotive goods, aerospace products, sporting goods and toys.
[19] Thermosetting resins include a wide variety of materials including, for example, polyesters, vinyl esters, and epoxies. In the manufacture of thermoset polyester FRP articles, the fiber reinforcements are saturated or wet with liquid thermoset resins and are made in the form of final articles, either manually or mechanically. Once formed, the form must be cured through the polymerisation of the thermosetting resin. The gel coating may optionally be applied in an open molding process prior to the FRP process. Thermoset molding and casting processes can generally be used to form non-fabric reinforced articles that use crushed and short fiber reinforcements or crushed and / or crushed short fiber reinforcements.
[20] When the thermoset polyester resin was first used with fiberglass or other fiber reinforcement, a gel coating was introduced. It is known that among the molded parts its surface exhibits a unique tertiary pattern due to shrinkage of the resin deviating from the glass fiber during curing. Some of these were initially used only on aircraft, so this resin could not be tolerated for aerodynamic and aesthetic reasons. Measures were soon developed in using gel coatings, which are used on the surface of thermoset polyester plastics today to produce decorative, protective, glossy surfaces that require little or no finishing. do. To produce plastics in which the gel coating coating is a complete part of the composite, resin and glass fiber reinforcements can be applied to the gel coating by using lay-up or spray-up techniques by hand. Apply. The gel coating suppresses the glass-fiber pattern, removes peeled paint and surface resin light emission, removes chalking by outdoor climate, pinholes, and the like, so that the gel coating can be easily cleaned or polished to give high gloss. It will impart filling and stiffness, stiffness, wear resistance and impact resistance (without sacrificing water resistance). In addition, the gel coating surface, on the one hand, acts as an obstacle to ultraviolet radiation, which degrades the glass fiber stack in the FRP and reduces or eliminates blistering of the substrate at high humidity, and the presence of moisture and the like. Eliminates the possibility of whipping the glass fibers under Gel coatings are used exclusively in items such as showers and tubs, outer surfaces of boats, camp cars, car bodies, swimming pools, and parts that require a smooth, hard, painted surface and the subject of the surface.
[21] As mentioned above, one problem with the use of phosphorescent pigments (which may have a specific gravity of 3.5 to 4 or more) in the polymer resin is that the phosphorescent pigments precipitate particles, especially large sizes, during blending operations and storage ( tends to settle). Generally known luminescent polymers must be blended and used immediately and are often blended and used with an air device to keep the phosphorescent particles suspended. The same also applies to thermosetting laminating resins and thermosetting molding resins, in which usually phosphorescent particles can be sprayed away from the suspension or act conveniently. Accordingly, there is a need for polyester thermosetting methods and products in which the phosphorescent particles remain suspended, particularly during storage and blending and application beyond the usable life of the luminescent polymer.
[22] Additional problems arise when using phosphorescent pigments with polyester gel coatings. If phosphorescent particles, such as excited zinc sulfide, are added to the gel coating, these phosphorescent particles are usually separated and overcoagulate the mixture (similar to the extent that the flour is too high to be added to water). Thus, not only the molding of resins not provided by the prior art is possible, but also an unmet need for phosphorescent polyester gel coatings remains.
[23] It would be more useful if the polyester base resin is easily applied to various molding applications such as gel coating applications, lamination applications, mold applications and injection or foam molding. Usually gel coatings are unsuitable as laminating or casting resins and easily crumble from hands if molded into a thick layer; Laminating and casting resins suffer from surface finish problems that require the use of a gel coating. Typical laminating resins cannot usually be used as mold applications because thick layers of 7-10 mm or more are overheated due to the accumulation of internal heat during curing. Phosphorescent thermosetting polyester base resins have been readily applied to both gel coating applications, and therefore various molding, laminating and molding processes will be particularly useful.
[24] The electroluminescent device was first proposed by Destrau in 1947. The lamp he proposed may include a sheet of glass or plastic, an electroluminescent layer containing phosphorus in a binder, and a conductive sheet acting as a secondary electrode on the other side of the electroluminescent layer together with a conductive layer serving as a primary electrode. When voltage is applied through these two electrodes, phosphorus emits light.
[25] For example, US Pat. No. 4,916,360 (1990) to Mikami et al . Discloses an insulating film sandwiched between a phosphorescent center, an electroluminescent (EL) film and a pair of electrodes on the outer surface of the insulating layer, BACKGROUND OF THE INVENTION An electroluminescent device is described that includes an electroluminescent film thin film made with zinc sulfide that acts as a subject material and doped with rare earth elements. This EL film preferably has a ratio of sulfur atoms to zinc atoms (S / Zn) of about 1.02 ≦ S / Zn ≦ 1.13, and is applied to obtain increased excitation efficiency at the emission center in order to exhibit improved emission luminance. Rare earth elements (Pr to Tm) having an atomic number of 56 to 69 are suitable for doping, of which terbium, samarium, europium and praseodymium are preferred, and are selected in relation to the emission color to be obtained. This film is doped with rare earth elements in an amount of 0.5 to 3 atomic percent. US Pat. No. 3,740,616 (1973) to Suzuki et al . Describes an electroluminescent display device that can be adjusted to display properties or display form. This display device utilizes a multilayer comprising a plurality of split electrodes and an electrically luminescent layer. This electrically luminescent layer comprises a composition of a plastic binder, such as zinc sulfide powder and urea resin activated with copper and aluminum in thin film form, zinc sulfide powder activated with copper or manganese, cadmium sulfide or silicon carbide luminescent material and ZnCdS: Ag Luminescent material. An insulating film such as a polyester film or barium titanate and a white plastic binder can be used, which reflects light emitted from the electrically luminescent film, thereby enhancing the emission of light. US Patent 4,665,342 (1987) to Topp et al . Describes a polymer light emitting display device formed by crosslinking of respective light emitting elements applied to excitation from a voltage supply. This light emitting display device can be manufactured using a printed circuit and a screen printing technique. The matrix is formed on a substrate, each of the light emitting elements being a primary electrical conductor located on the substrate, a dielectric having a relatively high dielectric constant located on the primary electrical conductor, a light emission embedded on the dielectric and embedded in the polymer. And secondary light conducting conductors such as indium oxide or indium oxide / silver polymers which are located above the phosphors and which characterize windows in which electrically excited phosphors can be seen. Polymer dielectrics having a relatively low dielectric constant separate each light emitting element from each other and reduce crosstalk between each light emitting element.
[1] The present invention relates to a luminescent synthetic polymer. In particular, the present invention relates to photoluminexcent, thermoluminescent and electroluminescent polymer blends useful as gel coatings and moldable resins.
[26] We have recognized the need for an improved luminescent polymer for the electroluminescent applications shown in the examples above.
[27] In particular, there remain unresolved problems that must be overcome before various demands and thermoset polyester resins can be effectively used with various phosphorescent particles. Effective thermoset resins must be water resistant, must protect UV-stimulating phosphorescent pigments, and provide a way for heavy phosphorescent particles to remain suspended even during storage and use. To be used with phosphorescent pigments, these thermosets must have acceptable optical properties. Ideally, thermoset phosphorescent polyester resins can be used, or they can be easily modified for use as gel coatings, laminating resins, molding resins or moldable resins, and photoluminescent, thermoluminescent and electroluminescent Will be excellent. In view of eliminating the disadvantages of luminescent materials of known type, the present invention provides an improved luminescent thermoplastic polyester blend.
[28] In one alternative, the present invention
[29] a) thermoplastic polyester;
[30] b) suspension fillers; And
[31] c) phosphorescent pigments
[32] It provides a light-emitting polymer comprising a.
[33] In another alternative, the invention
[34] a) thermosetting polyester resin;
[35] b) suspension fillers; And
[36] c) phosphorescent particles
[37] It provides a photoluminescent and thermoluminescent polymer comprising a.
[38] In addition, the present invention
[39] a) thermosetting polyester resin;
[40] b) vinylidene monomers;
[41] c) suspension fillers;
[42] d) thixotrop modifiers;
[43] e) UV stabilizers; And
[44] f) phosphorescent pigments
[45] It provides a method for producing a luminescent polymer comprising the step of mixing.
[46] In addition, the present invention
[47] a) mixing a thermosetting polyester gel coating resin with a thermosetting moldable resin selected from the group consisting of a thermosetting laminating resin, a thermosetting molding resin, and mixtures thereof, to produce a thermosetting polyester resin mixture;
[48] b) adding a suspending filler to the thermosetting polyester resin mixture in an amount sufficient to suspend the heavy phosphorescent pigment; And
[49] c) adding a phosphorescent pigment to the thermosetting polyester resin mixture
[50] It provides a method for producing a luminescent polymer comprising a.
[51] Photoluminescent, thermoluminescent and electroluminescent phosphorescent resins are provided that are useful as a base for gel coated articles, laminated articles, casted articles, and molded articles. The luminescent resin is a thermosetting polyester resin having an intermediate property between a general polyester gel coating, a laminating resin, and a molding resin. This luminescent polymer has improved luminescence and improved phosphorus-suspending properties for ease of storage and use.
[52] The luminescent polymer resin can be conveniently prepared by mixing various thermosetting polyester gel coating resins, laminating resins and molding resins, suspension fillers or mixtures of suspension fillers and phosphorescent pigments. UV stabilizers are preferably added to protect the phosphorescent pigments belonging to "greying" when polymers and phosphorescent pigments are used.
[53] Preferred unsaturated polyester resins in the present invention are unsaturated components of maleic acid and fumaric acid, orthophthalic and isophthalic acid aromatic components or substituted derivatives and (neopentyl glycol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol Styrene monomer or a mixture of glycols are mixed together. Useful suspension fillers include silica, glass microspheres and various flake, fiber and crystalline fillers. Preferred phosphorescent pigments include multiply activated zinc sulfide phosphors, polyvalent activated metal aluminate oxide phosphors such as alkaline earth metal aluminate oxides and mixtures of these phosphors. The luminescent polymer base resin can be flexibly prepared by adding orthophthalic acid flexible resin and / or isophthalic acid flexible resin and refractory material using halogen substituted derivatives and various adducts. The luminescent polymer base resin can be readily modified to use gel coatings, laminated resins for FRP products, mold resins or moldable resins.
[54] The improved luminescent polymer exhibits unexpected luminescent and polymeric properties. Such luminescent properties include a combination of brightness and prolonged luminescence, rapid recovery of luminescent properties after exposure to light and strong thermal luminescence that can be activated by heat sources such as body heat, automobile heat, braking heat and hot water. Special thermoset polymer properties include suitability, easy applicability and gel coating, laminating resins, molding resins, and molding, as well as the ability to keep heavy phosphorescent particles suspended during extended storage or use. Convenience to use as possible resin is mentioned.
[55] Throughout the specification and claims below, "comprise", "comprise" and "comprising" are used inclusively rather than exclusively, and the integers or groups of integers referred to herein may be one or It may include an integer or a group of integers not mentioned above.
[56] Prior to describing the preferred embodiments of the present invention in detail, the present invention is not limited to the particular details described. The limitations with respect to the particular embodiments described are not intended or are not inferred. Although the present invention has been described in connection with a preferred embodiment, it will be apparent that various modifications and changes are one of the techniques. Such modifications are possible but the results will appear within the scope of the present invention. The terminology used herein is for the purpose of description and not of limitation.
[57] In order to describe in more detail the luminescent gel coatings and moldable resins described herein, the following definitions will be used.
[58] The term "phosphorescence", as used publicly, means any kind of cold light, but here the permanent luminescence resulting from exposure of the material to visible or ultraviolet radiation--photoluminescence more appropriately specified Will be limited to adults. An important property of phosphorescent materials is that they are distinct from chemiluminescent, since they do not require constant chemical changes resulting from light exposure.
[59] Since "thermoluminescence" was initially discovered and used for a long time, it has survived the emission of light when heating the material to a relatively low temperature (lower than the temperature at which it begins to glow). The term implies that heat energy excites luminescence, and in practice the present invention acts as if heat energy excites luminescence, but in theory usually heat is released into a luminescent form, energy already absorbed from light and stored in the material. It is suggested. As a more modern term for excitation of electrons due to temperature rise and the transition of excited electrons to cause light emission, "thermostimulation" may be appropriate in more appropriate terms. In this specification, "thermoluminescence" and "thermostiumlation" will be used interchangeably.
[60] "Electroluminescence" is usually applied to light generated by the current flowing through a tube in which a gas is partially evacuated. However, the electroluminescence phenomena herein also includes, and will be used to describe, the excitation of a light emitting sheet of phosphorescent material by electric current.
[61] As used herein, "unsaturated polyester resin" and "unsaturated polyester gel coat resin" have unsaturated ethylenic dicarboxylic acids or mixtures of anhydrides or dihydric or dihydric alcohols. Thermoplastic polyesters prepared by condensation of these mixtures. As used herein, "polymaerizable vinylidene monomer" includes vinyl monomers that are polymerizable with the polyesters described above.
[62] The list of applications for the luminescent polymer blends of the present invention shows that a useful renewable light source is needed. A partial list of such applications may include signals (such as warning device signals, emergency exits, advertisements, buildings, directional signs, accident prevention signs and street signs); Emergency lights in basements or buildings (including buildings and basements, aircraft, tunnels, subway and metro stations, shelter and hangars); Pedestrian crossing marking, curve marking, passage marking; Electronic board; Steplights on stairwells and stairways (especially in case of fire emergency stairs, stair edges); transportation (including cars, trucks, aircraft, boats, bicycles, trailers, lifeboats, manual glider and helium gas balloons and warmth balloons) Organ markings; Hard hats and hard hats; Safety clothing; Oil spill barriers and nets; Outdoor clothing (of both towns and wastelands); Jumpsuit (preventing night escapes); Clock faces, gauges, dials and panels; Ski or skateboard; Water ski ropes and slopes; Parachutes and parasails; Marine buoys; Camping equipment; Fishing equipment (fishing rods, baits and nets); Address plate; Safety barricade; Agricultural fence and doorway markings; Collars, straps and indicators for dogs, cats and animals; Marking trails and ski routes; Telephone line and power line indication; Identification and marking of license panels and emergency vehicles; Military and protective applications; Bands and contours for ignition switches, locks and ignition switches; A smoke detector comprising a direction indicator; instrument; Night light; Dish; standing statue; Insect removers and traps; Artificial grass; Marine and outdoor carpets; Reflective indicators and reflective tape substitutes; toy; jewelry; Mannequins (which can combine fluorescent green pigments with fluorescent red pigments to give a pinkish tint to the skin of the mannequins); special effects; New products and the like.
[63] Emergency lights must be operated at any time in adverse conditions and harsh environments (power loss, fire, smoke, etc.), which makes it particularly difficult to apply to resilient cold light emitters.
[64] In addition, the luminescent polymers described herein are very useful for coating solar cells to increase cloudy day production.
[65] The present invention is novelly used to coat headlights and other reflectors with this luminescent gel coating (also with good reflecting properties). This coating helps to produce uniform and increased light without shadows. In a combined parking / headlamp, light is emitted from the entire reflector when only one light is activated. The taillight lens can include a luminous area to shine as the taillight is turned on.
[66] One of the newer uses of the luminescent materials of the present invention is to help control bacteria in hospitals. The best place to hide bacteria in the operating room is the darkened area behind the light reflector on the operating table (which can fall on the patient when the bacteria are disturbed by airflow), so coating the back of the reflector will brighten the area and fear the light. You will be able to pack more bacteria.
[67] "Black light" (safe UV light) is particularly suitable for activating the luminescent polyesters described herein. Black light bulbs coated with polyester are particularly useful because the luminescent gel coating will shine bright for extended periods of time even after a relatively short light action.
[68] In addition, this luminescent gel coating is particularly suitable for precision molding where the darker the thinner the area, the easier the thickness of the gel coating can be measured.
[69] Luminescent base materials for circuit boards and computer chips illuminate chips and elements for alignment, investigation and diagnostic purposes. "Hot spots" in these chips, parts or connections will cause the luminescent polyester to shine brighter, especially for design analysis, which will indicate failure factors.
[70] The luminescent polymers described herein are also useful in such applications due to their thermoluminescent properties. Thus, for example, clothing and helmets can be activated by body heat, wheels and wheel covers of an automatic vehicle can be activated by brake heat, motor covers of marine vehicles and hoods and fenders of automatic vehicles. ) Can be activated by engine heat, spas, showers, baths and hottubs can be activated by hydrothermal, and other objects can be activated by hot air or liquid.
[71] New special effect applications include "liquid writing" on luminescent polymers using laser beams or laser pointers. An interesting effect can be more useful by coating the fiber optic with a luminescent polymer, which follows. In addition, these luminescent polyesters coated with fiber optics are useful for signal or direction indication. Thermally activated thermal stimulation of the photoluminescent article causes the heated area to shine brighter in the selected design or recording; As with other hot liquids, gases or heating elements, hot water works well.
[72] Such luminescent polymers are useful for electroluminescent illumination, which are coated with metal conductors or transparent conductors. The signal can be powered by small cells in areas where current is not available or economical.
[73] Electroluminescent polymers (luminescent capacitors) can be prepared as follows: A conductive substrate (material, glass with conductive film, conductive polymer) is phosphorescent embedded in a binder having a high dielectric constant (such as a luminescent polymer described herein). It is coated with a thin film of color pigment. Lower percentages of luminescent phosphorus (less than 1% by weight) are usually used in electroluminescent embodiments as compared to photoluminescent embodiments. Low percent long-lived phosphorus is preferred for electroluminescent applications because light dims when the power is interrupted. Alternatively, short-lived phosphorus can be used in large quantities if desired. The layer may be applied by any known method, such as spraying, coating, curtain coating, screen printing or spread coating, or more exotic methods such as vacuum deposition. Plastic mixtures or ceramic mixtures having a high dielectric constant can be used as the binder. Suitability The layer thickness depends on the voltage and frequency when the light emitting element is in operation.
[74] The non-nucleophilic ratio of the polymer results in a relatively high quantum efficiency for radiation decay of singlet excitation (protons protruding for an excitation state, ie protons protruding for protons absorbed by photoluminescence and electroluminescence). Protons protruding to the electrons inserted into the structure). For example, U.S. by Holmes. Patent 5,401,827 (1995). However, neither the efficiency nor the efficacy of luminescent materials, especially polymers containing luminescent materials, can be explained by modern theoretical models. Therefore, the present specification does not explain in detail the reason why the present invention can exhibit high efficiency including the brightness of phosphorescence and the length of afterglow and heat emission compared to known light emitting materials.
[75] In general, long-lived phosphorus is preferred in the photoluminescent and thermoluminescent applications of the present invention. Otherwise, the plastic may have to be overloaded with additives, particularly in the case of mixtures of phosphorus with bright initial brightness and phosphorus with extended afterglow or mixtures of slow and fast filling phosphorus.
[76] Various considerations are taken into account when selecting phosphorus or mixtures of phosphorus when used in various applications. Alkaline earth metal aluminate oxides are suitable for outdoor applications and high intensity light applications due to their brighter initial brightness and long afterglow. Zinc sulfide phosphors are preferably carried out under low light conditions. Alkaline oxide aluminate phosphors are very expensive compared to zinc sulfide phosphors, so it is preferred that these zinc sulfide phosphors be used in many applications (such as low cost lines and new products). Mixtures of zinc sulfide and alkaline earth metal aluminate phosphors are most useful for objects such as bicycles that can receive outdoor and indoor lighting of varying intensity (such as bicycles, clothing, etc.). In addition, this mixture is most useful for short excited states because zinc sulfide can achieve brighter brightness and faster charge saturation compared to alkaline earth metal aluminate oxide phosphors. Sulphide phosphors that impart a variety of colors are useful for their particular color and also for blending with yellow-green copper activated zinc sulfide and alkaline earth aluminate, but tend to shorten the length of afterglow. Other forms of short-lived phosphors known in the art may be desirable as important or desirable applications for the electroluminescent application, in particular light turning off quickly after an electrical stimulus continues.
[77] Although the luminescent polyesters described herein may contain 50% or more phosphorescent pigments, it is generally preferred for phosphorescent and thermoluminescent applications to be included in amounts of less than 1% to 20%, It is preferably included in the luminescent application in an amount of less than 1% to 2%. A preferred embodiment of the phosphorescent pigment LUMILUX ^(R), ZnS: Cu (Hoechst or AlliedSignal of Australia), UMC phosphorescent pigment (a mixture of the zinc sulfide and other cargo Chemistry) (United Mineral & Chemical Corp., USA, Ltd.) the multi-activated zinc sulfide (multiply activated zinc sulfide), LUMILUX (R) ( commercially available from AlliedSignal of Australia) a rare earth activated alkaline earth aluminate oxides, such as the Green-SN and LUMINOVA ^(R) strontium aluminate oxide pigments (United Mineral and Chemical Corp., commercially available in the United States) and mixtures thereof.
[78] Suitable sources of excitation for the phosphorescent polymers described herein include daylight, UV light and most forms of artificial light. In general, the wider the spectrum of energized light, the longer the afterglow of the phosphorescent plastic. Abundant white light in UV light is very suitable. Since the filament bulb is usually an alkaline earth metal aluminate, the red or yellow light from the sodium vapor lamp is generally less suitable. In addition, the luminescent polymers described herein can be energized or stimulated by electromagnetic fields and friction (electrostatic charges).
[79] Unsaturated polyesters used in the present invention are reaction products of polycarboxylic acids or anhydrides and at least one polyhydric alcohol dissolved in a curing monomer containing an inhibitor to prevent the resin from curing until used by the manufacturer. This unsaturated polyester is a condensation product of at least one unsaturated dicarboxylic acid and anhydride, at least one aromatic dicarboxylic acid or anhydride, at least one polyhydric alcohol and a polymerizable vinylidene monomer. At least one of the components of the polyesters described above should be unsaturated with ethylene and is preferably a component of the polycarboxylic acid.
[80] Typical unsaturated acids include maleic anhydride, maleic acid, fumaric acid, methacrylic acid, acrylic acid, carboxylic acid and anhydrides such as itaconic acid and citraconic acid. Although maleic anhydride can be replaced by fumaric acid, it is mostly an economical derivative, producing resins with the same properties, but with some subtle structural differences. In addition, acrylic acid and methacrylic acid with modified polyester resins are used.
[81] The degree of unsaturation is phthalic anhydride, isophthalic acid, phthalic acid, chloric acid anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, adipic acid, succinic acid, suveric acid, sebacic acid, azelaic acid, terephthalic acid And saturated dibasic acids (including aromatic acids, as far as polyester is concerned), and the like. In particular, orthophthalic acid (derived from phthalic anhydride or phthalic acid) and isophthalic acid based polyester resin (derived from isophthalic acid) and substituted and halogenated derivatives thereof are preferred for practicing the present invention. In addition, DCPD modified phthalic acid and / or isophthalic acid resins may be used.
[82] Typical polyhydric alcohols include propylene glycol, ethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, dibromoneopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol Glycols such as 1,3-butanediol, 1,5-pentanediol, 1,3-propanediol, hexylene glycol, triethylene glycol, tetraethylene glycol, dicyclopentadiene hydroxy adduct and the like; Propylene oxide; Triols such as trimethylol ethane, trimethylol propane, trimethylol hexane and hexane triol; Bisphenol A ether and bisphenol A adducts (such as bisphenol dipropoxy ether and adducts of ethylene oxide and bisphenol A), hydrogenated bisphenol A and brominated bisphenols and the like. Generally glycols or mixtures of glycols are preferred in the present invention, and in particular (neopentyl glycol and at least one propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, dibromoneopentyl glycol, bisphenol dipropoxy ether, Neo) such as 2,2,4-trimethylpentane-1,3-diol, tetrabromobisphenol dipropoxy ether, 1,4-butanediol, bisphenol A adduct, hydrogenated bisphenol A and DCPD hydroxy adduct Preference is given to glycol-based polyesters based on mixtures containing pentyl glycol or neopentyl glycol.
[83] Although the above mixtures may be used with hard polyesters, ethylenically unsaturated polyesters are generally semi-rigid polyesters or flexible polyesters. Preferred polyesters form copolymerizates with vinylidene monomers. Preferred vinyl monomers are styrene. Compared to other commercial monomers, styrene offers equivalent properties at a much lower cost. In general, the monomers improve specificity, for example diallyl phthalate and triallyl cyanurate, which extend the heat resistance required for the corresponding electrical elements. Other monomers include vinyl toluene, α-methylstyrene, divinylbenzene, p - t -butylstyrene, aromatic vinyls such as o -chlorostyrene and dichlorostyrene, methyl methacrylate, ethyl acrylate and 2-ethylhexyl acrylate Ethylene unsaturated α-monocarboxylic acids, alkyl esters of β-carboxylic acids and vinyl esters such as vinyl acetate and vinyl propionate. These generally show utility in combination with styrene. In the practice of the invention said vinyl esters are usually less suitable. Preferably the ethylenically unsaturated polyester comprises from about 30 to 80% of the polymerizable resin forming elements, the remaining 20 to 70% being composed of cured vinylidene monomer. In particular, the amount of styrene adjustment is useful to include a brightener on a high brightness surface.
[84] Exposure to heat or light can lead to uncontrolled curing and increase in viscosity. Thus, in general, inhibitors (free radical inhibitors) such as hydroquinone, toluhydroquinone, parabenzoquinone and / or tertiary butyl catechol are used to inhibit the formation of oxygen-initialized free radicals and to prevent the reaction prior to the addition of the catalyst. It is included in the resin formulation.
[85] Weatherability is obtained using neopentylglycol, methylmethacrylate and UV stabilizers (discussed below). Diol aromatic derivatives such as isophthalic acid, terephthalic acid and diols derived from bisphenol A further increase the hardness, hardness and improve the thermal properties. Aliphatic components such as adipic acid, 1,4-butanediol and diethylene glycol produce flexible, flexible products. Property modifications are affected by the number of methylene or oxyethylene units that separate the reaction functionality. Monofunctional chain terminators such as benzoic acid or dicyclopentadiene (DCPD) can be used to enhance their properties. Other properties are derived from reactive halogenated compounds that impart heat resistance.
[86] Highly branched aliphatic or substituted aromatic derivatives cause steric effects that reduce the ability to cure with styrene or other monomers around the double bond (in particular, in this respect 2,2,4-trimethyl-1,3 Pentanediol is notable). Similarly, α-methylstyrene is affected by methyl groups suspended on double bond carbons, which slows down the reaction rate during curing with fumarate groups.
[87] In general, the longer the chain length of the glycol or unsaturated dicarboxylic acid component constituting the polyester, the more flexible the polyester is. Aromatic components, in particular phthalic acid, are not as useful as saturated aliphatics with long chains to lower the modulus of the copolymer. It is also confirmed that synthetic elastomers are used for flexible polyesters.
[88] Gel coatings and similar formulations include gelcoats, flow coats, flowcoats, and glazes (glazes are generally resistant to deformation, gloss, and coatings when applied to sculpted marble or mold products). Variously called transparent gel coats used to enhance depth. Gel coatings used in swimming pools are usually nonporous gel coatings. Flow coatings usually contain wax additives and styrene and are good at correcting properties to hide defects in the fiberglass portion of the molded article. Pore gel coatings, especially neopentyl glycol-based gel coatings, are designed to meet exactly the requirements for gel coatings used in the manufacture of moldings. Gel coatings (and other polymer resins) can often be used in two steps, the summer phase for high temperatures and the winter phase using accelerating materials to increase the temperature of the cured material after adding the targeted catalyst. Neopentyl glycol or a mixture of other glycols and neopentyl glycol is preferred for the practice of the present invention.
[89] Typical gel coatings are polyester resins, often filled with mineral fillers (and pigments, if any), which shows little shrinkage due to the high ratio of filler to resin. In general, the formulation includes various additives and the catalyst is added just before the formulation is applied. Gel coatings usually produce a hard or smooth coating with a thickness of 250 to 750 μm when properly applied and cured. Since the gel coating does not contain glass fiber reinforcement, its surface maintains a glossy shape and does not break down to expose the glass fiber as an uncoated FRP product.
[90] Typical polyester gel coating formulations may contain the following component materials.
[91] Resins: Low viscosity (500-1000 cps) resins are used because they can be easily filled and let out trapped air. In general, high impact ratings are preferred to ensure that they are free from chipping due to impact or thermal stress. The concentration in the complete formulation is usually 25 to 95% by weight.
[92] Fillers: Depending on the desired physical, chemical or battery properties, the most widely used fillers are calcium carbonate (high purity fine synthetic fillers are used for high purity, nonsag coatings), hydrated aluminum silicates and other silicates, four Pellin cyanite, feldspar, carbide, oxide, metal powder and carbon. These fillers are first used to reduce resin shrinkage, lower heat generation, increase hardness, increase thermal conductivity and dimensional stability, increase fire resistance, or change the volume and opacity of the resin. The filler concentration can be 5 to 75 weight percent.
[93] Thixotropes: Colloidal silica or fumed silica and magnesium aluminum silicate clay (such as bentonite) are applied to prevent sagging and running of gel coatings when applied to vertical surfaces and dense surfaces without voids. Used as thixotrop modifier. In addition, they are used to minimize the movement of the filler and to increase the pigment efficiency. This filler is used at a concentration of 2 to 15% by weight. Other known thixotropes include hydrogenated castor oil and aliphatic acidamides. As is well known in the art, the thixotropy properties of gel coatings need to be controlled first, in terms of the thickness of the film being deposited and the tendency of such films to warp. This gel coating should be uniformly thixotropic to remove dripping when applied to dense surfaces without vertical planes and voids. Since the extension of gel time impairs the cure of the coating in the allotted time, the gel coating formulation usually contains an accelerator. Particular attention should be paid to the delay of gel time due to the absorption and deactivation of the cobalt accelerator by pigment and by thixotropic agents such as fumed silica.
[94] Pigmentation: The pigment is dispersed into a resin which acts as a color developer. This pigment is used at a concentration of 0 to 10% by weight.
[95] Solvent: A solvent, such as acetone, is added to the formulation to dilute the material to the spray concentration. Since the use of a solvent penetrates during mold release, it leads to sticky parts, bad parts and the like, so a minimum amount of molding (or preferably no solvent) is used.
[96] Other usable ingredients include inhibitors, cure accelerators, leveling agents and defoamers.
[97] Gel coatings comprising the luminescent gel coatings of the present invention are generally formulated to minimize drainage on vertical surfaces when applied to wet films (surfaces) with a thickness of about 0.50 to 0.76 mm. In wet films, shrinkage of about 30% may occur to the thickness of the cured film.
[98] Generally the catalyzed gel coating is applied to a release-coated molding surface or other surface by spraying (the most common method), brush, roller coating or forced slush. This coating is applied to the gel and the reinforcement fiber and the laminating resin are applied while the gel coating is still viscous. If done correctly, the bond between the gel coating and the fiber reinforced laminate will be excellent.
[99] Gel coatings are usually fed and accelerated first, with a gel time of 5 to 25 minutes depending on temperature and the type and concentration of catalyst. A sufficient amount of catalyst to cure the composition at room temperature is added to such an extent that curing is moderate (usually 0.5 to 2.5% by weight).
[100] Since the gel coating used alone is a material that breaks and breaks under stress, the gel coating should be used as a laminating resin. The luminescent polymers of the present invention are somewhat unique; Combined with blending, laminating and casting resins, suspension fillers of gel coatings, metal phosphors can be used as gel coating resins, laminating resins, molding resins or moldable resins, or are easily modified for such use. Produces a base formulation that can be.
[101] Fillers comprising reinforcing fillers and suspending fillers useful in the present invention (in addition to short and long fiber reinforcements) include silicon dioxide, glass flakes, glass spears and microspheres, nephelin cyanite, feldspar, mica, pumice, calcium carbonate , Alumina trihydrate, flaky talc, bentonite, magnesium sulfate and other sulfur oxides, titanium oxide, synthetic sodium aluminum silicate (SSAS), calcium silicate, quartz, silicon carbide, alumina and tungsten carbide . Using fillers increases strength and stiffness, reduces and prevents plating defects (fiber protruding on the surface), reduces cost, reduces shrinkage, reduces heat generation, reduces thermal expansion coefficient, increases thermal resistance, slightly increases thermal conductivity, surface morphology There are many advantages such as improvement, reduced porosity, increased wet strength, reduced crazing, improved fabrication mobility, increased viscosity, improved wear resistance and improved impact strength. In addition, the fillers have disadvantages including limiting the manufacturing method and adversely affecting the curing and pot life of the resin in question. Mineral surface treatment should proceed to conditions that can be tailored for proper performance and uniformity and shape of silanes, stearates or other moisture / coupling additives.
[102] Suspension fillers with suitable optical properties are needed as a component of the present invention. There is a need for any filler that can be balanced in a way that helps keep the phosphor particles suspended. The heavy phosphorescent particles used in the present invention will not remain suspended in common gel coat resins or moldable resins. Given that the viscosity properties of the luminescent polymers are to be used for a particular use, sufficient suspending fillers should be added to keep the phosphorescent pigments in suspension.
[103] In general, most useful suspension fillers are various forms of silica (silicon dioxide). In the present invention, the flake form or the amorphous form of the silica suspension filler is preferable to the powder form or the microcrystalline form. Given the rheology and thixotropy effects, grades ranging from coarse to fine can be used. In the fine form, the sand acts like a sponge to absorb the resin. As a result, by producing a resin that is very strong and hard enough to absorb shocks without breaking, it is possible to lower the level of chips against impacts. Coarse particle size affects heavy loads, good dimensional stability and predictable packing. Coarse materials may help to control luminescence in molding the mixture and may be used where coarse, highly abrasive glazes are desired. Silica will add weight as well as strength, and thus are useful for items such as fishing baits. Colored sand or large rocks can be added to the luminescent thermoset polyester for use in fish ponds or aquariums.
[104] Other preferred suspending fillers include microspheres, crushed fiberglass and other crushed fibers and short fibers (usually in a ratio of 1: 1 to 20: 1 or more, or in a ratio of length to particle diameter), Nephelin signite, feldspar, glass flakes, pumice and mica. Calcium carbonate is known for use as a suspension filler, in particular in crystalline form such as calcite. Magnesium sulfate, calcium sulfate and other sulfates are also known for use in crystalline form. ATH (alumina trihydrate, in fact crystalline aluminum hydroxide) is also known as a suspending filler in addition to its use as a refractory material or flame retardant. Just as talc, carbon black and other powdered fillers are not usually suspension fillers, great care must be taken in using them in connection with the present invention (although talc also tends to solidify when used excessively, and carbon black is luminescent. May interfere). Principle guidance and specific applications are mentioned below.
[105] Flakes comprising silica, glass and mica represent a special class of discontinuous reinforcing fillers. Flake reinforcements are advantageous for fibers in that they provide reinforcement in plane instead of along the uniaxial direction. In flake reinforced composites, properties such as modulus, strength, thermal expansion and shrinkage are considered to be planarly identical.
[106] Crystalline silica is a low oil-absorbent product with high Mohs hardness that occurs naturally, such as sand, quartz, tripoly and novaculite. This low oil absorption makes it easy to disperse the filler and lower the viscosity of the resin-filler mixture. Precipitated fumed silica is a high quality product that is synthesized and is extremely useful for improving suspension properties, changing thixotropy properties and strengthening properties. Silica has additional benefits like flow agents and helps to prevent vibration for phosphorescent particles.
[107] Nephelin cyneite and feldspar can provide particular benefits to gel coatings and the present invention by helping to improve weather resistant, polished surfaces and stress-cracking resistance. They make it easy to wet and disperse in hard, transparent polymers, make them transparent and translucent, exhibit chemical resistance, weather resistance and abrasion resistance and are applicable for good quality contact applications. These particle surfaces are smooth, glassy, and have almost no color, thus exhibiting a full massstone effect of color and luminescent pigments. For all fillers in the gel coating, they reduce shrinkage upon curing and thus prevent stress of warpage or lamination and peeling of the gel coating. In addition, since fillers reduce elongation and impact resistance in hard thermosets, it is essential that elastic polyester or more flexible forms be used when feldspar or nephelin cinite is used.
[108] Hollow solid glass microspheres are widely used in resin systems because their spherical shape, controlled particle size and density and other unique properties can improve performance and / or reduce coatings. The size of the solid glass spheres is 5 to 5000 μm. Solid and hollow microspheres have been arbitrarily defined as a product having a large number of particles having a particle diameter of less than 200 μm. The most frequently used size in plastics is less than 44 μm. These may be glass, ceramic, carbon, organic or polymer (microspheres are usually preferred in the present invention). Solid and hollow spears act as small bearings because they have a minimum ratio of surface to volume that reduces viscous drag and improves flowability. Because microspheres are directional and have no sharp edges, they provide a smoother surface with more uniform shrinkage in plastic than can be obtained with fiber or many unspecified fillers. Solid spheres are usually used when considering strength. Solid spheres modify the properties of the resin, in particular flexural modulus and compressive strength, improve wear resistance and corrosion resistance, and reduce mold shrinkage and cycle time. Initial features of hollow spheres include volume reduction, improved hardness and impact resistance, modification of physical properties including reduced crazing compared to non-spherical fillers (especially in flexible applications) and the ability to fill large volumes of more expensive polymers. have. The surface of the hollow and solid microspheres can be applied with special coatings to enhance the sphere-resin bonds. Solid glass spheres or beads are known to be used in 30% increments in step scaffolding and other similar applications for special applications such as pedestrian crossings, curve signs or numbers.
[109] Magnesium sulfate is useful for improving the brightness of luminescent polymers. As with other fillers, crystalline or flake forms are preferred over powdered forms. Calcium sulfate and barium sulfate are similarly useful.
[110] In order to improve the weather resistance of the polymer composition and to prevent the zinc sulfide phosphors from being "overloading" and "burning out", it is desirable to add a mixture of ultraviolet stabilizers. When acted upon by ionization energy, many phosphorescent mixtures degrade gradually with the resulting loss of luminescence. For polymers, UV energy is a chemical known as chromophores such as double bonds, residual monomers or catalysts in polymer structures that cause thermal oxidation during processing, aromatics or other double bonded contaminants, peroxides or carbonyl groups in the form of certain elements. Absorbed by the group. When the zinc sulfide compound is exposed to UV light in the presence of moisture, a photochemical "greying" of the zinc sulfide compound occurs. This is thought to be due to the reduced light emission due to the deposition of zinc on the crystal surface.
[111] "Graying" can be prevented by removing one of these causes: moisture or UV radiation in the atmosphere. In addition, moisture and UV radiation in the atmosphere can advance a time dependent decrease in brightness while using the electroluminescent polymers mentioned herein. Therefore, when phosphorus containing zinc sulfide is used, it is important that sufficient UV stabilizer or stabilizer is present in the photoluminescent and electroluminescent polymers. If phosphorus is used that is not sensitive to UV light, such as alkaline earth metal oxides, then UV stabilizers need only be present in an amount sufficient to protect the polymer.
[112] In the polyester thermosetting polymers of the present invention, if the absorbed UV energy is quickly consumed, the chemical bonds in the polymer molecular chain will begin to break slowly (lower molecular weight chain structures will no longer exhibit the original polymer properties). . It also generates free radicals to initiate and propagate chain decomposition reactions. These results include embrittlement, discoloration, chalking and loss of physical properties. UV stabilizers are also prepared by mixing additives (screeners) to mask UV energy, additives (absorbers) that preferentially absorb UV energy, or additives (quenchers) that suppress the excitation state, as soon as they are formed. Mechanisms including inhibiting sequence initialization by mixing additives that will react chemically with free radicals and peroxides (including free radical scavengers), antioxidants and peroxide degradants that cause harm by agitation To break the order of these events.
[113] Common sunscreen agents include pigments that render the polymer translucent or opaque and absorb or reflect UV light. Useful blocking agents include titanium dioxide and zinc dioxide, including organic synergists such as zinc dialkyl dithiocarbamates (methyl and ethyl jimate), titanium-organic salts and phosphites. Care should be taken when using these pigments in the present invention to prevent excessive occlusion of the phosphorescent pigments.
[114] UV absorbers inhibit the initialization of the decomposition process. The materials at this stage compete with the polymer chromophores for UV energy and win because their absorption is higher than the chromophore's absorption. Once they absorb UV energy, it converts this UV energy into an infrared energy that is harmlessly consumed as an indestructible form, heat. UV absorbers include sulfuric acid groups such as 2,4-dihydroxy benzophenone, substituted 2-hydroxy-4-alkoxy benzophenone (such as 2-hydroxy-4-methoxy benzophenone), and hydroxy bentophenone; Benzophenones, including higher alkyl substituents with reduced volatility and increased compatibility (such as octyl, decyl and dodecyl); Benzoates including dibenzoate of diphenylol propane, tertiary butyl benzoate of diphenylol propane, salicylate, resorcinol monobenzoate and aryl or alkyl hydroxy benzoate and the like; 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine, sulfur containing derivatives of dialkyl-4-hydroxy phenyl triazine, hydroxyphenyl-1,3,5-triazine and the like; Substituted benzotriazoles and 2 (2′-hydroxy) such as 2-phenyl-4- (2,2-dihydroxy benzoyl) -triazole, hydroxy-phenyltriazole and substituted hydroxy-benzotriazole Triazoles such as derivatives of phenyl) benzotriazole and the like; Oxanilides and substituted oxanilides; Acrylic esters; Formamidine and mixtures of those described above. Absorbents are more effective in the thicker cross section than in the dilute, and they may not provide sufficient protection for their surface.
[115] In addition, UV inhibitors (excitation state inhibitors) inhibit initialization, even if they act a little later in sequence than the absorbers. They absorb UV energy and receive excess energy from the polymer chromophore in the excited state, returning the chromophore to the ground state, and bringing the inhibitor into the excited state. The inhibitor then harmlessly consumes the received energy as heat. Inhibitors include organic nickel compounds such as [2,2'thiobis (4-octylphenolato) -n-butylamine nickel II, nickel salts such as thiocarbamates and complexes of alkylated phenol phosphonates with nickel. It includes.
[116] UV scavengers and disintegrators act free radicals later in the sequence and inhibit propagation rather than initialization. This is similar to the action of antioxidants. In fact, (secondary) indirect antioxidants, organic nickel inhibitors and carbon blacks have been called as decomposers, but their initial function is to the extent that they are consumed in peroxide reactions. In combination with absorbents and inhibitors, free radicals are almost always produced, whereby the scavenging and termination mechanism of the free radicals is important when the stabilizer acts with the radicals formed at the initial stage of the degradation sequence. UV scavengers and disintegrators include bis (1,2,2,6,6-pentamethyl-4-piperidinyl sebacate), di [4 (2,2,6,6-tetramethyl piperidinyl)] Hindered amines, such as sebacate and other tetramethyl piperidine mixtures and the like, which may act as excitation state inhibitors and peroxide degradants in addition to their primary functions of free radical scavenging and termination. The nature of the hindered amine form is the tetramethyl piperidine structure; The nitrooxy radicals act as R. and ROO. Radicals and are reproduced in the process (cyclic reproduction used in excess for UV stabilization). Unlike this absorbent, hindered amines show that the surface is protected and is effective for thin areas. Unlike inhibitors, they do not show color. Hindered amines can be used in combination with absorbents and / or inhibitors to maximize UV protection.
[117] To obtain the refractory material, polyesters are usually used (chloroated and / or brominated) halogenated / halogenated or high grade alumina trihydrate (ATH) or higher alumina trihydrate or refractory materials. In addition, the refractory resins described herein are particularly useful for those that tend to protect other polymer resins and phosphorus from UV light.
[118] Refractory polyester resins are obtained by using reactive intermediates chlorenic anhydride, tetrabromophthalic anhydride, dibromoneopentyl glycol, tetrachlorophthalic anhydride and / or other halogen acids and glycols. It is also known that decabromodiphenyl oxide (DBDPO) (ether), bromobisphenol-A and pentabromodiphenyl oxide blends are used. Bromine ions containing phosphonium bromide are used for synergistic coordination. The dispersibility and compatibility of bromine-containing additives along with polymer crosslinking are important for obtaining good equity between fire protection and fairness. Many halogen-containing refractory materials also include stabilizers to increase shelf life, improve thermal stability, and protect process equipment from corrosion.
[119] ATH is a dry, light powder that works by absorbing heat, releasing steam to dilute the combustible gas produced, and by producing a flame retardant char barrier between heat and the material. ATH also acts as extenders and smoke inhibitors. The load rating is usually relatively high. In order to improve properties such as flex strength, flex-whitening, filler control, wetout, viscosity and molding flow, various surface treatments are used for stearate coatings, silanes and titanates. And treating with phosphate can be used to enhance various properties of the polymer filled with ATH.
[120] In general, ATH materials have been devised for sprayup. In a wet-layup system in which the glass is placed in the molding and the filled resin system is distributed thereon, the ATH particle size distribution should be optimized to prevent filtration of the filler and provide good coloration. Due to other indices of pure white reflectance, they are generally preferred over calcium carbonate as filler, since they provide a translucency that is not possible with calcium carbonate together.
[121] Other retardants known for their use include phosphorus-based materials such as magnesium, hydroxide and phosphate esters, vinylphosphonates such as bis (hydrocarbyl) vinylphosphonate and their condensation products, antimony oxide, zinc borate And barium methaborate and molybdenum compounds. Calcium carbonate is an excellent smoke inhibitor. Mixtures of compounds are often used, and complementary flame retardants are sometimes preferred.
[122] Foaming agents or blowing agents and initiators may be useful in the molding process and are preferably used in the present invention. Suitable physical blowing agents include compressed gases and low boiling hydrocarbons and halogenated derivatives. Chemical blowing agents useful in the present invention include sulfone hydrazide blowing agents, isocyanate based reagents, nitrogen based reagents and other reagents known in the art. The blowing agent brings additional benefits that keep the phosphorescent particles in suspension and tend to push the phosphorescent particles onto the surface of the molded article. Since some blowing agents can generally be dissolved in the resins used in the present invention, the luminescent polymer will contain the same proportion of blowing agent if such reagents are used.
[123] Another useful component of unsaturated polyester resins is flow control agents such as polyacrylic acid, polyalkylacrylates, polyether modified dimethyl polysiloxane copolymers and polyester modified polydimethyl siloxanes. Flow regulators are generally used in amounts of about 0.1 to 5 weight percent. Other useful additives may include lubricants, processing aids and primary antioxidants.
[124] Peroxides consist of one class and a major group of initiators (catalysts) having diacyl peroxides (such as benzoyl peroxide). Organic peroxides are a source of free radicals, free radicals comprising: 1) initiators for free radical polymerization and / or copolymerization of vinyl monomers and diene monomers; 2) curing agent of thermosetting resin; And 3) crosslinking agents of elastomers. The choice of catalyst is generally governed by the temperature during processing and curing. The most useful peroxides in the present invention are generally used with accelerators (curing accelerators) present in the resin. Common accelerators include cobalt naphthenate, cobalt octoate, cobalt 2-ethylhexanoate, divalent and trivalent acetylacetoneatocobalt, potassium hexanoate, zirconium naphthenate, vanadium naphthenate, cupric naphthenate, manganese Acetyl of cobalt, potassium, copper, vanadium, zirconium, manganese and lead, and transition metal salts such as octoate, ferric naphthenate, potassium hexanoate, acetylacetoneatozirconium, acetylacetoneatovanadium, acetylacetone atrium and mixtures thereof Acetonate. The resin can be further promoted with amine accelerators such as dimethylamine, diethyl aniline and dimethyl- p -toluidine and other substituted anilines. Other known accelerators include phosphorus containing compounds and β-diketones.
[125] The temperature at which the organic peroxide catalyst initiator decomposes at a moderate rate usually determines the application. Other important factors are cost, solubility, safety, efficiency and type of radicals produced, the need for freezing storage and shipping, compatibility with the product system, any effect of the final product, and the ability to be activated. In the luminescent polymers described herein, preferred initiators are generally ketone peroxides, in particular methylethylketone peroxide (MEKP in 40% solution). Commercially available products are usually made by reacting ketones with hydrogen peroxide to produce a mixture of peroxy structure and hydrogen peroxide.
[126] Reinforced plastics are composites in which a resin is combined with a reinforcing agent in order to enhance at least one or more properties of the plastic matrix. This reinforcing agent is a strong inert substance bound to plastics to improve its physical properties (such as strength, hardness or impact resistance), or to provide special chemical or thermal properties. The reinforcing agent may be fibrous, powder spherical, crystals, or whiskers, and may be made of organic, inorganic, metal or ceramic materials. The ratio of strength to weight of reinforced plastic is usually due to the nature of the reinforcement, with crosslinking materials or resins that bind the reinforcement to each other and transfer the load to the reinforcing fibers or other materials.
[127] Microfibers and short fibers will perform reinforcement operations that would not be possible with either continuous fibers or continuous fillers in injection molding, extrusion and transfer molding. This class includes whiskers, microfibers, mineral fibers, chopped and milled fibers, short metal fibers and cut metal-coated fibers. Whiskers are high-quality crystal perfection and small, and therefore are short-lasting fiber reinforcements. Microfibers are usually polycrystalline fiber collections and do not have the purity and crystal integrity of genuine whiskers with the resulting effect on mechanical properties. Mineral fibers are naturally found short fibers that are processed for use. With changes from asbestos, wollastonite (calcium metasilicate, CaSiO ₃ ) is a mineral fiber of primary importance. This has the advantage of a pure white, pointed form all over. Cut and ground fibers are made from continuous fibers such as glass fibers, carbon, boron and aramid fibers, as well as metal fibers. The nature of this cut and ground fiber is related to its structure, size and manufacturing method. Resilient thermoplastic ad fabrics can be processed, in particular, to embrittle thermosets and to provide the necessary permanentity for properties such as non-wear and crush resistance. Metallic fibers, especially stainless steel fibers, produce excellent conductive reinforcements, but because of their high price, most applications come with the manufacture of rather expensive conductive fibers and fillers, including aluminum coated glass fibers, sculpted aluminum foil ribbons and melted aluminum fibers. Excluded from Ceramic fibers have high temperature resistance, high modulus, compressive strength and excellent chemical resistance. Resilient thermoplastic fibers have been processed to provide the required lifetime, especially for fragile thermosets.
[128] Any fibrous reinforcement must meet the needs of a particular end use of strength and price. For many chucks of low strength requirements, paper is an excellent reinforcement. Preferred fibrous reinforcements in the present invention are usually fiberglass. Some forms of glass fiber products can be used to reinforce thermoset plastics. These include woven fabrics, continuous strand rovings, chopped strands, woven strands, nonwovens, mats (both continuous and chopped strands), yarns, crushed fibers, and the like. Surface mats or bales (open-weave up to 0.25 mm thick, flexible type glass fiber cloth and synthetic nonwovens or mats) are resin-rich surfaces in matched-die molding and other processes It can be used to support it. In general, for open molded and press molded laminates, woven fabrics are more useful and more common. Nonwoven forms may be desirable when considering prices. If high strength is particularly essential at high temperatures, regardless of price, graphite, carbon fibers, metal oxide fibers, ceramics, aramids (aromatic polyamides), hybrid aramids / carbons, carbon / glass hybrids, (reflective ceramic fibers, alumina fibers Non-metallic inorganic fibrous materials, such as boron fibers and silicon carbide monofilaments, ceramic fibers (defined in whiskers and fibers), alumina boria-silica or alumina chromia-silica ⁽ such as Nextel ^(R) ) May be required.
[129] Glass fiber reinforcements usually improve the properties of the polymer composite, such as high strength, dimensional stability, resistance to temperature zones, corrosion resistance, desirable electrical properties, and ease of manufacture. Several factors determine the physical properties of the reinforced molded part. The amount of fiber used-the ratio of glass to resin-is the most important. Strength increases the direct proportion to glass content. Fiber length and orientation affect the load-bearing potential and the continuity of stress transitions. One-way orientation provides optimum strength in one direction and makes it possible to obtain a glass content of at least 80%. Bidirectional orientation with glass of 75% or more content usually places fibers at each exact angle to provide strength in both directions. Optimum Strength Multiple directions or random orientations are similar but provide lower strength in all directions, resulting in at least 65% glass content.
[130] Silicate base fiberglass is made from a melt of SiO ₂ and other oxides cooled in fiber form without crystallization (amorphous form). Various compositions, filament particle diameters, and shaped glass reinforcements are useful in the present invention.
[131] Various fiber silicon oxide materials can be used. Examples in glass form include Form A glass (standard soda lime silica window or bottle glass composition); Form E (electrical) glass, which may be the most widely used form of reinforcement (with good water resistance and high resistance to alkalis and weak resistance to acids); Form C glass (calcium aluminosilicate); Form S and Form R glass (glass in high strength, high modulus form for improved compositions); And Form D glass (enhanced electrical driveability and lower density) alkali glass.
[132] The diameter of the glass fiber is preferably less than 20 μm, but may vary from approximately 3 μm to 30 μm. Glass fiber diameters are usually given in letter designations between A and Z. Although fibers of more than P-filament (about 18 μm) are often used, the most common diameters used in glass reinforced thermoplastics are G-filaments (about 9 μm) and K-filaments (about 13 μm). Continuous filament standards are generally used in lengths of 1/8, 3/16, 1/4, 1/2, 3/4 and 1 inch or larger for compound efficacy in various processes and products.
[133] Commercial glass fiber reinforcement products are usually sold with materials that have already been sorted and combined (organic carrier media), divided into specific sizes during or before the fiber forming process. The sizing amount for the glass fiber product is usually from about 0.2% to about 1.5% by weight, although at least 10% dropping may be added to the mat product. Sizing compositions used to treat glass fibers typically include glass fiber strands, polishes that protect the glass fiber strands (typically amine-type varnishes; forming agents or binders that impart integrity and operability to the film on the glass fiber strands; glass fibers Coupling agents that improve adhesion between the strands and polymeric materials reinforced with glass fiber strands, and other additives such as emulsifiers, wetting agents, nucleating agents, and the like. It has been developed for glass fiber reinforcement to improve the adhesion between the glass fiber and the brightener, film former and coupling agent may be a single compound or a mixture of two or more compounds.
[134] Film formers are usually water soluble during the process or may be suspended in water and need not necessarily be water sensitive after curing. Examples of film formers include, but are not limited to, polyesters, epoxy resins, polyurethanes, polyacrylates, polyvinyl acetates, polyvinyl alcohols, styrene-butadiene latexes, starches, and the like.
[135] The coupling agent is a silane coupling agent having a reactive organic moiety that is compatible with polymer materials reinforced with glass fibers and hydrolyzable moieties that normally bind to glass. Chromium complexes and titanate crosslinkers or coupling agents may also be used.
[136] Carbon fibers are used in areas such as automotive, aviation and sporting goods applications. Carbon fibers provide high modulus and high strength, low density, low coefficient of thermal expansion, low coefficient of friction and excellent resistance to conditions and chemicals exposed to most environments. Ceramic fibers are continuous fibers of metal oxides. Many benefits of this fiber are high temperature resistance, high modulus and compressive strength. In addition, this ceramic fiber is resistant to foreign compounds and can be woven into a woven fabric.
[137] It is known that some types of conductive fillers and conductive fibers are useful in lowering the natural electrical resistivity of plastics, i.e., imparting partial conductivity. This includes three levels of conduction—antistatic or electrostatic losses; It is implemented in semiconducting and almost conductive enough to shield electromagnetic interference (EMI) in electronic packages and cabinets to protect the wires. In particular, the addition of conductive fillers and fibers may prove useful in electroluminescent applications where current is used to activate luminescence.
[138] In addition, other classes of materials that are known to be useful in relation to improving the reflective properties associated with the present invention include luminescence such as optical brighteners, fluorescent whiteners, color brighteners and spectral enhancers. It is an enhancer. Fluorescent sun pigments are particularly effective in UV defense with regard to UV stabilizers.
[139] Other materials that may prove useful in the present invention include UV protection, sun fluorescence pigments, pearlescent pigments, metal flake pigments, thermochromic (which produces thermally activated color changes), (photoactivated colors) Photochromic, diamond-like materials made from a solution of polyphenylcarbine, coral extracts, coral isolates and derivatives for color concentrates and the like.
[140] Examples of materials that can be used to practice the invention are as follows. These substances are to be regarded as examples only and are not to be considered unduly limiting.
[141] AQUAGUARD 83279 Clear Gel Coating (FGI Product Code No. 12217) (manufactured by fiber glassinternational (FGI)) is an orthophthalate, neopentyl glycol and propylene glycol based gel coating containing alumina trihydrate as a refractory material. This AQUAGUARD gel coating is an accelerated thixotropic spray grade that was first developed for use as a sanitaryware application, which has been used for applications such as swimming pools. This AQUAGUARD gel coating has excellent flow / calibration, quick release of air, excellent anti-bending, anti-wrinkle and weather resistance, which is excellent in durability. Gel time of AQUAGUARD is 10 to 15 minutes (2% v / w NR20 MEKP).
[142] JS AQUAGUARD Culture Finish / Clear Gelcoat is a transparent polyester / styrene gel used as a topcoat for swimming pools containing fumed silica, benzophenone and / or phenolic UV inhibitors, and metal naphthenates and octoates as lubricants Coating.
[143] ESCON EX80 (61-286) (FGI, Australia) is a low viscosity, high transparency, acrylic modified polyester resin designed for embellishment with decorative moldings and excellent color and transparency. The ESCON EX80 is first accelerated and stabilized to minimize discoloration and degradation by UV light. When adding 1% MEKP at 25 ℃ gel time can be expected to 45 to 60 minutes. Curing proceeds relatively slowly once this resin has gelled; Very low exothermic (approximately 40-50 ° C.) properties allow it to cure slowly over several hours, ensuring that cracks and discolorations due to overheating in large molds are avoided. The low viscosity ESCON EX80 is beneficial for the rapid release of bubbles before gelation occurs. Post curing of the processed article is very important.
[144] ESCON CR64 (61-283) (FGI, Australia) is a medium viscosity, low reactivity, unsaturated fumaric and phthalic acid (orthophthalate) based resin. This ESCON CR64 61-283 can be interchangeably replaced in place of the ESCON EX80 61-286 described above in this embodiment. ESCON CR64 is a highly transparent polyester designed for the manufacture of decorative molds where outstanding color and transparency are important. It is pre-accelerated at room temperature, cured with 1% MEKP at 25 ° C. for a gel time of 20-30 minutes, and contains a stabilizer to minimize discoloration by UV light. It may be desirable to use the slower curing mold resin ESCON EX80 for very large molds and laminations.
[145] POLYLITE ^(R) 33-101--01 (formerly Koppers 1061-5 West Coast, Reichhold Chmicals, Inc.) is a wax-containing resin for orthophthalic acid having 40% to 50% styrene monomer.
[146] NORPOL 62-303 is a product of Jotun Polymer AS (Norway, now Reichhold AS Norway) (manufactured by FGI, Australia). This NORPOL 62-303 orthophthalic acid polyester resin is suitable for 3-7 mm thick laminations applied to wet-on-wet coatings for manual or spray lay-up applications, and is a universal objective of medium reactivity. Low styrene emmision (LSE) resin used for the purpose. The resin is thixotropy and has a built-in accelerator system that forms a low exothermic temperature combined with relatively long gel times and fast cure. The resin has a gel time of 30 to 45 minutes in summer (2% MEKP) and 20 to 30 minutes in winter.
[147] DION ^(R) ISO 33-434-00 (formerly DION ^(R) Iso 6631T, now ReicholdChemicals, Inc.) is an unsaturated polyester resin that is wax-free, has a high molecular weight, and contains up to 55% styrene monomer. As resin for isophthalic acid lamination, it is excellent in mechanical property and heat resistance.
[148] POLYLITE ^(R) 61-358 and POLYLITE ^(R) 61-359 (Reichold Chemicals Inc.) are thixotropic, first activated, have a viscosity suitable for spray-up, easy to roll out, and low heat in thick areas It is a wax-free polyester resin having a high chemical resistance. POLYLITE ^(R) 61-358 is wax free. POLYLITE ^(R) 61-359 is a wax that includes a low styrene emission (LSE) grade. The gel time when using 1% MEKP at 25 ° C. is approximately 15 minutes.
[149] POLYLITE ^(R) 61-340 and POLYLITE ^(R) 61-341 (manufactured by Reichld Chemicals Inc.) are tick-roft activated ore for the production of rigid, reinforced plastic parts by spray-up or manual layup techniques. It is resin for the sophthalic acid lamination. POLYLITE ^(R) 61-340 is wax free and POLYLITE ^(R) 61-341 contains wax. The gel time when using 1% MEKP at 25 ° C. is approximately 15 minutes. The color change, which appears as a low color during curing, allows for the observation of catalysis, gels and curing.
[150] ESCON EX663P 61-627 (FGI, Australia) is a self-extinguishing orthophthalate (phthalic acid) based lamination resin used for general purposes when halogenated compounds, especially transparent laminates, are required. The resin is formulated with a spray application and a manual application containing 30-40% styrene monomer, the tickstrip is activated first, and has a gel time of 20-30 minutes at a temperature of 25 ° C. (1% MEKP). do. This fully cured resin will be made to the following standard. Class 2-BS 476-Part 7, self-extinguishing to ASTMD 635, grade for AS1530-Part 3 1982 with flammability index 16, spread of flame index 9, heat release index 10 and smoke development index 9 Having Improved refractory materials can be obtained through the addition of additives such as antimony trioxide or alumina hydrate.
[151] POLYLITE ^(R) 61-428 from Reichold Chemicals, Inc. is a flexible isophthalic acid molding resin containing 35% to 37% monomer which provides a low color and highly flexible mold. It is used with fillers to rebuild molds and as blends with other resins when adding flexibility and reducing heat generation during curing.
[152] ESCON 400 (61-440) (Hatrick Chemicals Pty. Ltd., Australia) is a low reactivity, medium viscosity, 30% monomer content, fully flexible isophthalic acid resin, gel time at room temperature is approximately 20-30 Minutes. ESCON 400 is used in hard resins to improve resistance and minimize stress and shrinkage, and is used to make filled patching putties that are characterized by good adhesion and storage stability.
[153] POLYLITE ^(R) 61-801 wax solution (Reichold Chemicals Inc.) is a 5% solution of paraffin wax in styrene monomer. POLYLITE ^(R) 61-801 shows that the film-forming properties of paraffin wax reduce styrene monomer release from polyester resins, which reduces or eliminates surface adhesion due to air blockage during curing, and also enhances surface gloss. Let's do it. It is also suitable for improving the smoothness and gloss of the surface and reducing the need for mold release agents.
[154] AEROSOL R202 fumed silica (FGI, Australia) has more than 99.8% SiO ₂ having a BET surface area of v100 ± 20 m 2 / g, an average particle size of 14 nm and a tap density of approximately 50 g / l.
[155] Q-CEL "5 Series" Grade 570 hollow microspheres (product of PQ Australia Pty. Ltd.) are high strength, highly functional surface-molded organosilicon sodium borosilicates. It has a bulk density of 0.34 g / dl, an effective density of 0.70 g / dl and a particle size of 1 to 50 microns with an average particle size of 20 microns. This microsphere is easy to disperse into the liquid system and leaves free flow. The viscosity of the thermoset polyester base material will increase less with respect to the volume allocated when Q-CEL is added in place of other suspending fillers and is useful for adjusting the final viscosity. High shear and energy mixing is not necessary and can harm or break the sphere.
[156] CAB-O-SIL ^(R) M-5U untreated fumed silica (Cabot Corp., Australia) is a high purity silica that provides rheology control and reinforcement and / or free flow. It has an amorphous form, a surface area of 200 ± 25 m 2 / g, a bulk density of 40 g / l (2.5 lb / ft ³ ), a refractive index of 1.46 and an average particle (agglomerate) length of 0.2 to 0.3 microns.
[157] HIGHLITE H320 (E1000F) alumina trihydrate (Showa Aluminum Industries KK, Australia) is a fine aluminum hydroxide with excellent bleaching and optical properties (index of refraction 1.57). HIGILITE is 99.9% Al (OH) ₃ with an average particle size of 10 μm, a bulk density of 0.6 g / cm 3, a tap density of 1.0 g / cm 3, a bleaching degree of 98 and a BET specific surface area of 2.0 m 2 / g.
[158] UCAR ^(R) Thermoset microballoons (Phenolic microballoons) from Union Carbide Chemicals (Australia) Pty. Ltd., Australia, are hollow spheres of phenolformaldehyde resins.
[159] Talc TM (Commercial Minerals Limited of Australia, Australia) is a hydrated magnesium silicate mineral that is significantly finer than 75 microns (residue> 75 microns 1.5% maximum). This talc has a refractive index of 1.59 and a reflectance of 84 (457 mu m).
[160] BEKI-SHIELD ^(R) conductive fiber (Bekaert Fiber Technologies, Australia) is an 8 micron diameter stainless steel wire that is applied in both continuous and cut fiber forms with various polymer binders.
[161] Calcium carbonate (from APS Ajax Finechem of Australia, Australia) was obtained from FGI in Australia.
[162] Dry magnesium sulfate (approximately MgSO ₄ 3H ₂ O) from APS Ajax Finechem of Australia was obtained from FGI of Australia.
[163] LUMILUX ^(R) Green N-PM 50090 The long afterglow ZnS: Cu (zinc sulfide: copper) pigment is from Riedel-de Haen GmbH of AlliedSignal Inc. obtained from Hoechst Australia Ltd. LUMILUX ^(R) Green N-PM 50090 has an emission spectral peak of 530 nm and a broad excitation spectrum of approximately 380-400 nm. Afterglow brightness according to DIN 67510 Part 4 (mcd / m2) is 47 after 5 minutes, 25.4 after 10 minutes, 8.8 after 30 minutes, 4.5 after 60 minutes and 2.3 after 120 minutes. Natural collapse (= 0.3 mcd / m2) for the 100 x threshold of cognition occurs after 960 minutes. In addition, LUMILUX ^(R) Green N-PM 50090 ZnS: Cu contains some selenium, and silicon contains gallium, indium, magnesium, gold, silver, calcium, magnesium and iron, and many elements added to copper Activated multiplely by The volume of this pigment is 4.1 g / ml. Frequent excitation of this phosphorescent pigment does not impair luminescence.
[164] LUMILUX ^(R) Green SN-pigment (Riedel-de Haen, Germany) is a luminescent alkaline earth metal aluminate with a long afterglow lifetime and doped with rare earths. The LUMILUX ^(R) Green SN-pigment has a maximum excitation of 380-400 nm, an emission maximum of 520 nm and a density of about 3.5 g / ml. The afterglow effect is about 10 times brighter than classic zinc sulfides such as the LUMILUX ^(R) Green N-PM 50090 described above, with an afterglow duration of more than 3600 minutes. The emission intensity of this afterglow can be increased by up to 30% or more when excitation is carried out with light emission of 3000 to 5000 lux levels instead of 1000 lux. LUMILUX ^(R) Green SN-pigment is stable to graing but sensitive to water. This pigment is sensitive to the extension of spectra into the starting and long-wave UV wavelengths in the blue portion of visible light. If the emission level applied at the time of excitation is low (less than 300 lux) or only the filament bulb is applied, the afterglow effect is greatly reduced in the level as charging is carried out for a long time. The maximum afterglow effect is obtained by excitation due to daylight or high intensity, cold white lamp. LUMILUX ^(R) Green SN-FO 50069 has a density of 3.4 g / cm 3, screen discharge size of less than 80 μm (less than 1% of oversized particles) and a particle size distribution d ₅₀ of 40 μm ± 4 μm. While having a phosphorescent spectra maximum at about 520 nm, this excitation spectrum has a maximum at about 370 nm. LUMILUX ^(R) Green SN-FOG 50089 has properties similar to screen discharge sizes of less than 125 μm (less than 1% of oversized particles) and a particle size distribution d ₅₀ of 50 μm ± 5 μm.
[165] LUMILUX ^(R) Effect N-series pigments (Riedel-de Haen) include green, blue, yellow, yellowgreen, orange and red afterglow pigments based on activated zinc sulfide. LUMILUX ^(R) Effect Blue N 50050 has a density of about 3.2 g / cm 3 and an average particle size of 15 μm. LUMILUX ^(R) Effect Red N 100 50031 is zinc calcium sulfide having a density of about 2.5 g / cm 3 and an average particle size of 17 μm.
[166] Phosphorescent pigments ^of LUMINOVA ^(R) Green (G) and Blue Green (BG) strontium oxide aluminate long afterglow are manufactured by Nemoto & Co. Ltd., Japan, and described in US Pat. No. 5,424,006, supra. Commercially available from Chemical Corp. (United States). The initial afterglow brightness and the afterglow time are at least ten times those of conventional zinc sulfide based on phosphorus. They can be excited by a broad wavelength range (200-450 nm), but the best results can be obtained at wavelengths below 365 nm with the most effective energy saturation obtained from UV-rich light sources. Afterglow brightness increases with increasing light source intensity; Afterglow brightness is also proportional to the intensity of UV contained in the excitation light. LUMINOVA ^(R) Green (G) has an emission peak of 520 nm, whereas LUMINOVA ^(R) Blue Green (BG) has an emission peak of 480 nm. Afterglow disappearance (time taken for afterglow brightness to reduce to 0.32 mcd / m 2) exceeds 2000 minutes. LUMINOVA ^(R) pigments can be applied with varying particle sizes with D ₅₀ particle sizes varying from 1.45 μm to 42.00 μm. The coarser the particles, the better the brightness and afterglow will be. LUMINOVA ^(R) Green (G) has a density of 3.6, and LUMINOVA ^(R) Blue Green (BG) has a density of 3.9.
[167] UMC phosphorescent pigments (commercially available from United MIneral & Chemical Corp.) are sulfide-based pigments used for various color emission and diversification of daylight luminescent colors. UMC 6SSU is ZnS: Cu phosphorus with emission peak at 529 ± 4, specific gravity of 4.1 and average particle size of 22. UMC GSR is a ZnS: Cu, Mn phosphor that emits yellow with an emission peak at 520 and 570, specific gravity of 4.1 and average particle size of 22. UMC BAS is a (Ca, Sr) S: Bi phosphor that emits blue with an emission peak at 450 and 480, specific gravity of 3.2 and average particle size of 35.
[168] TINUVIN ^(R) 292 (Ciba-Geigy Australia Ltd., Australia) has bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl- (1,2,2,6 It is a UV stabilizer and a spectrum enhancer (color brightener) containing 6-pentamethyl-4-piperidyl) sebacate. It is recommended to use it at a concentration of 0.5 to 2% with respect to the solid binder.
[169] TINUVIN ^(R) 171 (Ciba-Geigy Australia Ltd., Australia) is a UV stabilizer of 2- (2-hydroxy-benzotriazol-2-yl) -4-methyl-6-dodecyl phenol.
[170] TINUVIN ^(R) 384-2 (manufactured by Ciba Specialty Chemicals) is a coating (benzenepropanoic acid, 3-2 (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4- Hydroxy-, C7-9 branched alkyl esters and linear alkyl esters 95% and 1-methoxy-2-propyl acetate 5%) developed UV absorbers of hydroxyphenylbenzotriazole. This absorbent is suitable for extremely environmental conditions with high operability and permanence. The broad UV absorption of this absorbent makes the properties of the base coating or substrate effective. The action of TINUVIN ^(R) 384-2 may be enhanced when used in combination with HALS stabilizers such as TINUVIN ^(R) 292 or 123. These mixtures improve durability by preventing or delaying failure occurrences such as gloss reduction, cracking, color change, blistering and desorption. TINUVIN ^(R) 384-2 is preferably used at a concentration of 1.0 to 3.0% with 0.5 to 2.0% of TINUVIN ^(R) 123, 144 or 292.
[171] UVITEX ^(R) OB is a Ciba Specialty Chemicals fluorescent brightener. This fluorescent brightener is a high molecular weight low volatility optical brightener of thiophendiyl benzoxazoles (2,5-thiophendiylbis (5-tert-butyl-1,3-benzoxazole)). UVITEX OB has exceptional brightening properties, good light resistance and bluish glowing template (with absorption peak at 380 nm and emission peak at 430 nm). The grade of use of this UVITEX OB depends on the performance requirements of the final application and is between about 0.005 and 0.1%. Basically, the luminous effect is not light stable. Can be used in a variety of blends and crude mixtures with other UV stabilizers and optical brighteners; The concentration of UVITEX OB can be increased when mixed with the TINUVIN UV stabilizer described herein.
[172] GAFSORB UV Absorber 2H4M (A GAF Europe of Surrey) is 2-hydroxy-4-methoxy-benzophenone and has a K value (absorption index) of at least 64.0 at 286 nm in methanol.
[173] CHIMASSORB 90 (Ciba Specialty Chemical, Australia) is a 2-hydroxy-4-methoxybenzophenone UV stabilizer.
[174] BYK-A 501 (BYK-Chemie GmbH, Germany) is a silicone-free air release additive for unsaturated polyesters. BYK-A 501 is a combination of bubble breaking polymers used to prevent air confinement and voids in filled and unfilled unsaturated polyester, epoxy and vinyl ester resins. BYK-A 501 is preferably added prior to the filler or reinforcement, but can be added to the final composition with no difficulty.
[175] Common fiberglass products used to manufacture FRP items can be used. For example, BTI C-24 (manufactured by Brunswick Technologies Inc.) is a PPG Choped Strand Mat (CSM) (PPG Industries Inc.) applied from high strength, rigid and reinforced surface hardened plastics (fiber content 55% by weight) one PPG. of Pittsburgh, Pennsylvania) is ≧ 93.0% fiber glass and amorphous glass The surface binder (polyester) is ≦ 6.0%. There are no fibers smaller than 6 μ in diameter in a mat product that is usually cut PPG and braided into strands.
[176] CELOGEN ^(R) XP-100 (Uniroyal Chemicals, AC Hatrick Chemicals of Botany, NSW, Australia) is a sulfonyl developed for isophthalic acid resins, orthophthalic acid resins and other resins for diversified thermoset polyester applications Hydrazide (sulfonylhydrazide) is a chemical blowing agent. CELOGEN ^(R) XP-100 is foamed at ambient temperature and easily incorporated into polyester resin. It is usually added to the polyester at a concentration of 2% by weight before adding the filler. This foaming action helps the phosphorescent particles to have the surface of the moldable article and also helps to surround the glass fiber (if used), thereby reducing the demand for rounded resins or other resins in the glass.
[177] To specifically illustrate the present invention, working examples of embodying luminescent gel coatings and moldable resins are set forth below.
[178] Example 1
[179] Sample weight part POLYLITE ^(R) 61-358 H / P resin without isophthalic acid wax 30 kg to 10.7% FGI 29-652 A271 / 77 BW fire-resistant resin ^* W / G30 kg to 10.7% FGI 32CL 1-N Marbleglaze s / g 369-000244 kg to 15.7% POLYLITE ^(R) 61-341 waxed orthophthalic acid resin 30 kg to 10.7% POLYLITE ^(R) 61-340 waxless orthophthalic acid resin 30 kg to 10.7% Talc TM25 kg to 8.9% AEROSOL R202 fumed silica 26 kg-9.3% Q-CEL 570 Cavity microsphere 30 kg-10.7% LUMILUX ^(R) Green N-PM 50090 ZnS: Cu 35 kg-12.5% Total: 280 kg 100%
[180] 30 kg of FGI 29-652 A271 / 77 BW fire resistant resin ^* W / G was mixed with 30 kg of POLYLITE ^(R) 61-340 waxless orthophthalic acid resin and 25 kg of Talc ™ was blended into the resins . To this mixture is added a thermosetting polyester / suspend filler base material by adding 30 kg POLYLITE ^(R) 61-358 isophthalic acid wax-free H / P resin, 26 kg AEROSOL R202 fumed silica and 30 kg Q-CEL 570 cavity microspheres. Formed. In a separating drum, 35 kg of LUMILUX ^(R) Green N-PM 50090 ZnS: Cu are blended into 40 kg of FGI 32CL 1-N Marbleglaze s / g 369-0002 and added to the thermoset polyester / suspension filler base material And mixed. 30 kg of POLYLITE ^(R) 61-341 waxed the orthophthalic acid resin and, to form a thermoset luminescent polyester, the final 4 kg of 1-N Marbleglaze s / g 369-0002 was added and mixed. Some more Q-CEL 570 hollow microspheres were preferred over separation of phosphorescent pigments. As a result, a product of a closed porous surface was produced by using appropriate additives respectively for spraying, buffering, rolling and resin transfer molding.
[181] This base material was modified as follows according to the final intended use. Wax was added to the casting gel coating. Aeration material (BYK) was added to the spray gel coating to accelerate luminescence. Wax and styrene monomers were added for brushing, rolling or decoration.
[182] Example 2
[183] Sample weight part AQUAGUARD 83279 Orthophthalic acid neopentyl glycol / propylene glycol Transparent gel coating 420 g 42.0% ESCON EX80 61-286 Transparent molding resin (or ESCON CR64 61-283 transparent orthophthalic acid / fumaric acid resin) 230 g23. 0% POLYLITE ^(R) 61-627 Orthophthalic acid laminated refractory resin 230 g23.0% HIGHLITE H320 (E1000F) alumina trihydrate 92.5 g9.25% AEROSOL R202 fumed silica 21 g2.1% POLYLITE ^(R) 61- in styrene 801 Wax solution 6.5 g 0.65% Total: 1000 g100%
[184] For use in the examples below, a thermoset polyester / suspension filler base material was first prepared. POLYLITE ^(R) 61-627 fire resistant resin was first mixed with ESCON 61-286 mold resin. AEROSOL R202 fumed silica was mixed in the mixture with slow stirring. When all R202 fumed silica was added, the mixture was dispersed at high speed of 40-50 μ (Hegman gauge). When properly dispersed, the AQUAGUARD83279 clear gel coating base and POLYLITE ^(R) 60-801 wax solution were added with reduced stirring speed and continued stirring until mixing was uniform. If necessary, HIGILITE E1000F alumina trihydrate was added little by little while increasing the stirring speed. As a result, Brookfield viscosity measured by LVF 4/60 is 5000-5500 cP, Brookfield viscosity measured by LVF 4/6 is 26000-32000 cP, and gel time is 20-30 at 25 ° C (1.5% NR20 MEKP). The polyester base which is powder was obtained.
[185] By blending in order of parts by weight, as described below (Examples below), the final components can be easily added to the concentrated thermoplastic polyester / suspension filler base material prepared for the addition of phosphorescent particles.
[186] Sample weight part Thermosetting polyester / suspension filler base material 1000 g39.2% ESCON EX80 61-286 resin for transparent casting (or 500 g 19.6% ESCON CR64 orthophthalic acid / fumaric acid transparent molding resin) AQUAGUARD 83279 orthophthalic acid neopentyl glycol 500 g 19.6% glycol transparent gel coating CAB-O-SIL ^(R) M-5 unsaturated fumed silica 20 g.78% magnesium sulfate 20 g.78% LUMILUX ^(R) Green N-PM 50090 ZnS: Cu 510 g20.0% total: 2550 g100%
[187] 10-15 ml of wax and styrene (POLYLITE ^(R) 61-801 wax solution) are added to this to improve the moisturizing cloth and surface gloss of this luminescent polyester. This luminescent polyester resin can be used for gel coating and molding, or can be produced flexibly as in the examples below. The following examples are likely to be made to the dimensions of the drum size or more.
[188] UV stabilizers, spectral flavoring agents, fluorescent brighteners and / or optical brighteners are added before or after LUMILUX ^(R) . If this mixture is somewhat powdery, it is preferred to add it before the phosphorescent pigment. Otherwise, it is added in pieces before or after phosphorus. UV stabilizers and fluorescence enhancers can be used with low area alkaline earth metal aluminate oxide phosphors and used with zinc sulfide phosphors (and mixtures of phosphors containing ZnS) and luminescent enhancers.
[189] Example 3
[190] Sample weight part Luminescent polyester resin 7.50 kg 75% POLYLITE ^(R) 61-428 Resin for isophthalic acid flexible molding 1.25 kg 12.5% ESCON 400 (61-440) Fully flexible isophthalic acid resin 1.25 kg 12.5% Total: 10 kg 100%
[191] By mixing 7.5 kg of the luminescent polyester resin of Example 2, 1.25 kg of POLYLITE ^(R) 61-428 asophthalic acid flexible template resin and 1.25 kg of ESCON 400 (61-440) fully flexible asophthalic acid resin, Semi-flexible luminescent polyester resins were prepared. The semi-flexible resin is used for items of toys, signs, numbers, letters, baits, bobbers and the like.
[192] Example 4
[193] Sample weight part Luminescent polyester resin 6.0 kg 60% POLYLITE ^(R) 61-428 Resin for isophthalic acid flexible casting 1.0 kg 10% ESCON 400 (61-440) Totally flexible isophthalic acid resin 3.0 kg 30% Total: 10 kg 100%
[194] By mixing 6 kg of the luminescent polyester resin of Example 2, 1.0 kg of POLYLITE ^(R) 61-428 isophthalic acid flexible mold resin and 3.0 kg of ESCON 400 (61-440) with a fully flexible isophthalic acid resin, Luminescent Polyester Resin Fully flexible luminescent polyester was prepared. These fully flexible objects include cloth, curtains, fishing rods, fishing nets, yacht sails, carved structures and advertisements, and the like.
[195] Example 5
[196] Thermoset polyester / suspension filler base materials were prepared as in Example 2. To prepare a luminescent polyester resin containing 10% of a phosphorescent pigment (comprising 70% zinc sulfide phosphor and 30% alkaline earth metal aluminate phosphor), the following ingredients were added to the base material.
[197] Sample weight part Thermosetting polyester / suspension filler base material 130 g26% NORPOL 62-303 orthophthalic acid waxed resin 90 g18% ESCON EX80 61-286 Transparent molding resin (or 110 g22% ESCON CR64 orthophthalic acid / fumaric acid transparent molding Resin) JS AQUAGUARD culture finish / transparence gel coating 110 g22% magnesium sulfate 2.5 g. 5% calcium carbonate 2.5 g. 5% CAB-O-SIL ^(R) M-5 untreated fumed silica 5 g 1% LUMILUX ^(R) Green N-PM 50090 ZnS: Cu 35 g7% LUMILUX ^(R) Green N-PM 50090 alkaline earth metal aluminate 15 g3% Aluminate Total: 500 g100%
[198] Example 6
[199] Thermoset polyester / suspension filler base materials were prepared as in Example 2. To prepare a luminescent polyester resin containing 15% of a phosphorescent pigment (80% zinc sulfide phosphor and 20% alkaline earth metal aluminate phosphor), the following ingredients were added to the base material.
[200] Sample weight part Thermosetting polyester / suspension filler base material 123.5 g24.7% NORPOL 62-303 orthophthalic acid waxed resin 85 g17% ESCON EX80 61-286 transparent molding resin (or ESCON CR64 orthophthalic acid / fumaric acid transparent molding resin) 103.5 g 20.7% JS AQUAGUARD culture finish / clear gelcoat 103.5 g 20.7% magnesium sulfate 2.375 g 0.475% calcium carbonate 2.375 g 0.475% CAB-O-SIL ^(R) M-5 untreated fumed silica 4.75 g 0.95 % LUMILUX ^(R) Green N-PM 50090 ZnS: Cu 60 g12% LUMILUX ^(R) Green N-PM 50090 alkaline earth metal aluminate 15 g3% Aluminate total: 500 g100%
[201] Example 7
[202] Thermoset polyester / suspension filler base materials were prepared as in Example 2. To prepare a luminescent polyester resin containing 20% of a phosphorescent pigment (comprising 90% zinc sulfide phosphor and 10% alkaline earth metal aluminate phosphor), the following ingredients were added to the base material.
[203] Sample weight part Thermosetting polyester / suspension filler base material 140 g28% NORPOL 62-303 orthophthalic acid waxed resin 50 g10% ESCON EX80 61-286 Transparent molding resin (or 100 g20% ESCON CR64 orthophthalic acid / fumaric acid for transparent molding Resin) JS AQUAGUARD culture finish / transparent gel coating product 100 g 20% magnesium sulfate 2.5 g 0.5% calcium carbonate 2.5 g 0.5% CAB-O-SIL ^(R) M-5 untreated fumed silica 5 g 1% LUMILUX ^(R) Green N-PM 50090 ZnS: Cu 90 g18% LUMILUX ^(R) Green N-PM 50090 Alkaline Earth Metal Aluminate 10 g2% Aluminate Total: 500 g100%
[204] Example 8
[205] Thermoset polyester / suspension filler base materials were prepared as in Example 2. To prepare a luminescent polyester resin containing 20% of a phosphorescent pigment (composed of 80% zinc sulfide phosphor and 20% alkaline earth metal aluminate phosphor), the following ingredients were added to the base material.
[206] Sample weight part Thermosetting polyester / suspension filler base material 140 g28% NORPOL 62-303 orthophthalic acid waxed resin 50 g10% ESCON EX80 61-286 transparent molding resin (or ESCON CR64 orthophthalic acid / fumaric acid transparent molding resin) 100 g20% JS AQUAGUARD culture finish / clear gelcoat 100 g20% magnesium sulfate 2.5 g 0.5% calcium carbonate 2.5 g 0.5% CAB-O-SIL ^(R) M-5 untreated fumed silica 5 g 1% LUMILUX ^(R) Green N- PM 50090 ZnS: Cu 80 g16% LUMILUX ^(R) Green N-PM 50090 Alkaline Earth Metal Aluminate 20 g4% Aluminate Total: 500 g100%
[207] Example 9
[208] Thermoset polyester / suspension filler base materials were prepared as in Example 2. To prepare a luminescent polyester resin containing 10% of a phosphorescent pigment (60% zinc sulfide phosphor and 40% alkaline earth metal aluminate phosphor), the following ingredients were added to the base material.
[209] Sample weight part Thermosetting polyester / suspension filler base material 130 g26% NORPOL 62-303 orthophthalic acid waxed resin 90 g18% ESCON EX80 61-286 clear molding resin (or ESCON CR64 orthophthalic acid / fumaric acid transparent molding resin) 110 g22% JS AQUAGUARD culture finish / clear gelcoat 110 g22% magnesium sulfate 2.5 g 0.5% calcium carbonate 2.5 g 0.5% CAB-O-SIL ^(R) M-5 untreated fumed silica 5 g 1% LUMILUX ^(R) Green N- PM 50090 ZnS: Cu 30 g6% LUMILUX ^(R) Green N-PM 50090 Alkaline Earth Metal Aluminate 20 g4% Aluminate Total: 500 g100%
[210] Example 10
[211] Thermoset polyester / suspension filler base materials were prepared as in Example 2. To prepare a luminescent polyester resin containing 10% of alkaline earth metal aluminate phosphorescent pigments, the following components were added to the base material.
[212] Sample weight part Thermosetting polyester / suspension filler base material 130 g26% NORPOL 62-303 orthophthalic acid waxed resin 90 g18% ESCON EX80 61-286 clear molding resin (or ESCON CR64 orthophthalic acid / fumaric acid transparent molding resin) 110 g22% JS AQUAGUARD culture finish / clear gelcoat 110 g22% magnesium sulfate 2.5 g 0.5% calcium carbonate 2.5 g 0.5% CAB-O-SIL ^(R) M-5 untreated fumed silica 5 g 1% LUMILUX ^(R) Green N- PM 50090 ZnS: Cu 50 g10% Aluminate Total: 500 g100%
[213] Example 11
[214] Thermoset polyester / suspension filler base materials were prepared as in Example 2. To prepare a high viscosity luminescent polyester resin containing 5.5% of alkaline earth metal aluminate phosphorescent pigments suitable for pressurized resin transfer molding, the components as described below were added to the base material.
[215] Sample weight part Thermoset Polyester / Suspension Filler Base Material 229.5 g45.9% Talc TM168.5 g33.69% UCAR ^(R) Thermoset Microbulun 7.2 g1.46% BYK-A 501 Air Release Additive (or Calcium Carbonate) 67.3 g13 .45% LUMILUX ^(R) Green N-PM 50090 ZnS: Cu 27.5 g5.5% Total: 500 g100%
[216] In the above examples, the 40% methylethylketone peroxide catalyst is preferably at least 1.0% and at most 2.0% and was used to cure suitably. It is recommended that the luminescent gel coating be used within the range of 15 to 30 ° C. When operating at temperatures other than room temperature, the gel time change with the polyester must be adjusted. Since the temperature of the gelcoat, molding or application surface must also be taken into account (cold molding or surface leads to undercure of the gelcoat), air temperature measurement alone is not sufficient to determine the concentration of the catalyst used. When 40% methylethylketone peroxide (MEKP) is used as the catalyst, the temperature range / catalyst percent for the luminescent gel coating described herein is recommended as follows.
[217] Temperature range catalyst percent Less than 15 ° C Not Recommended 15 ° C-20 ° C 2.0% 21 ° C-25 ° C 1.5% 26 ° C-30 ° C 1.0% 30 ° C Not recommended
[218] When the luminescent gel coat sample is 100 gm at the catalyst concentration, the gel time is about 10 minutes to 15 or about 20 minutes to 30 minutes in the molding. Curing problems may occur if the concentration of the catalyst is less than 1% or greater than 2%. In the present invention, undercure can be caused by using a diluted catalyst and a plasticizer adduct (such as dimethylphthalate), such as by using a diluting solvent with a solvent such as ethyl acetate. Various catalysts are known in the art that can be used outside the desired temperature range with MEKP in applications where molding is carried out at other temperatures.
[219] The transparent molding resin is an adduct useful as both a flow agent and a suspension adduct. In addition, isophthalic acid polyester resins and orthophthalic acid polyester resins are useful as suspension adducts for base gel coatings.
[220] In order to change the viscosity prior to the addition of the phosphorescent pigment, it is important that suspension fillers and other fillers are added to the polymer.
[221] When mixing the LUMILUX ^(R) or other phosphorescent materials into the base resin, the observation of the "skin" of this resin is very useful for adding the ideal amount. These phosphorus gaps will be filled and an iridescent or gloss can be observed on the surface (and on the surface of the spatula digging into the mixture), and this surface is observed tightly and densely. Adding too much phosphorous causes the mixture surface to become powdery and lose its gloss, resulting in an overly dry and brittle material with a damaged structure and degraded luminescence properties, and the mixture surface becomes thick.
[222] When mixing, air mixers are generally suitable because the impact force acts downward and affects the properties on the opposite side. Preferred mixers are jet type mixers 15244 or 15245 (manufactured by United States Plastic Corp.). Since the light emission of zinc sulfide phosphorescent pigments is closely related to the crystal structure, attention should be paid to all steps of the process in order not to destroy the crystals by mechanical force. In general, smaller phosphorescent particles are useful for increasing compactness on a surface.
[223] This luminescent gel coating can be used to cover fibers and laminating resins exposed to both the inner and outer surfaces. In particular, waxes and styrene monomers can be added for a smooth and decorative surface.
[224] The luminescent gel coating formulations shown above are applied to the molding surface in a suitable manner such as spraying or rolling. After partial curing, the gel coated film is opened with fiberglass, and the preferred laminating resin (whether luminescent or not) is applied so that the part is cured and demolded to form a molded article having a luminescent gel coating as the surface layer. is demolded. Similarly, luminescent gel coatings can be applied last to form a processed inner film of a high article (eg, inside a boat). Preferred non-luminescent laminate resins for use as hidden layers for interior use are POLYLITE ^(R) 61-358.
[225] The release agent may be applied to surface shaping prior to manufacture in order to facilitate the release of the cured laminate product. In order for this release agent to work well, it is insoluble in styrene and must not pass through styrene. Polyvinyl alcohol (PVA) solutions form excellent release films as copies of the molding surface (natural polished waxes containing high carnauba content are suitable for molding less complex).
[226] The blowing agent tends to push the phosphorescent particles onto the surface of the finished molded article, giving them excellent luminescent properties. Similarly, when the luminescent polymers described herein are used, injection molding tends to push these luminescent particles to the surface. Usually, the higher the viscosity, the more preferably it is used for injection molding rather than the gel coating.
[227] Conductive fibers, such as BEKI-SHIELD ^(R) stainless steel conductive fibers, can be incorporated into thermoset polyester blends (through increased electrical conductivity using metal aluminate oxide phosphors that are slower to respond to electrical stimulation than zinc sulfide). ) Useful for electroluminescent applications and thermoluminescent applications (via increased thermal conductivity).
[228] Excess trim from moldings are suitable for recycling or reuse in the luminescent polymers described herein.
[229] It will be evident how the embodiments are designed in the spray process, the open molding process and the injection in the technique of the present invention, the blowing molding being press laminated, resin transfer molding (RTM) and Structural reaction injection molding (S-RIM), compression or matched die molding, filament winding, spin or rotational molding, continuous panel processing, premixed or bulk molded mixtures, preforms and prepregs Can be modified when applied to processes such as vacuum-bag molding, pressure bag molding, autoclave molding, thermosetting, pultrusion and extrusion. Will be obvious. In addition, it is evident in the context of the invention described above that the coating or molding process techniques are varied with respect to the factors necessary to determine the optimum mixture and the optimum conditions.
[230] Embodiments of the invention described above have been made and tested, and it has been found that the described advantages are manifested. The luminescent polymer of the present invention has been used as a gel coating in articles including automobiles, automobile wheel caps, bicycles (frames and rims), signs, boats (exteriors), trailers, outboard motor covers, glossy plates and billboards. In addition, this luminescent polymer can be used for hard hats and bicycle helmets, dinghy runabout boats, address marking numbers and letters, keyboards on instrument keyboards, skateboards, other scratchboards, light switches and door handles, doors, smoke detector covers, etc. , Knife and extension handles, telephones, floor tiles, ceiling and wall panels, stair treads, seat inserts and table surfaces, printed circuit boards, headlights and light reflectors, solar cells, spa baths, vanity basins, wrist watches and Watch face, night reflector road sign, mousetrap, beetle catcher, cane, pamp stand, remote control body, truck battery cover, fishing bait, molded items including fiberglass rock used in spas Has been used in. Flexible items manufactured and tested include fishing nets, clothing and pennants of ships.
[231] The foregoing detailed description is intended to illustrate rather than limit the scope of rights in accordance with the scope of protection of the present invention, and therefore the description is to be regarded as illustrative and not exclusive. Although the invention has been described in connection with preferred embodiments, the invention should not be limited to these embodiments. On the contrary, it will be understood by those skilled in the art that all alternatives, modifications, and equivalents of the preferred embodiments of the present invention are encompassed as long as they do not depart from the basic principles of the present invention. The scope of the patent rights should be as broad as the invention allows. Therefore, it should be evaluated in the scope of the present invention or the appended claims and equivalents within the spirit and scope of the present invention.

权利要求:
Claims (86)
[1" claim-type="Currently amended] a) thermosetting polyester;
b) suspension fillers; And
c) phosphorescent pigments
Luminescent polymer comprising a.
[2" claim-type="Currently amended] The method of claim 1,
The thermosetting polyester is phthalic anhydride, isophthalic acid, phthalic acid, chloric acid anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, adipic acid, succinic acid, suberic acid, sebacic acid A luminescent polymer comprising an aromatic dicarboxylic acid or anhydride component selected from the group consisting of azelaic acid, terephthalic acid and mixtures thereof.
[3" claim-type="Currently amended] The method of claim 1,
Wherein said thermosetting polyester is selected from the group consisting of orthophthalic acid modified thermosetting polyesters, isophthalic acid modified thermosetting polyesters, and mixtures of orthophthalic acid modified thermosetting polyesters and isophthalic acid modified thermosetting polyesters.
[4" claim-type="Currently amended] The method of claim 1,
Wherein said thermosetting polyester further comprises an ethylene unsaturated dicarboxylic acid or anhydride component selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, methacrylic acid, acrylic acid, itaconic acid and citraconic acid.
[5" claim-type="Currently amended] The method of claim 1,
Wherein said thermosetting polyester is selected from the group consisting of a maleate thermosetting polyester, a fumarate thermosetting polyester and a maleate thermosetting polyester resin and a mixture of a fumarate thermosetting polyester resin.
[6" claim-type="Currently amended] The method of claim 1,
A light emitting polymer wherein said thermosetting polyester is a glycol-based thermosetting polyester.
[7" claim-type="Currently amended] The method of claim 6,
The glycol is propylene glycol, ethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, dibromoneopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, 1 A luminous polymer selected from the group consisting of, 3-butanediol, 1,5-pentanediol, 1,3-propanediol, hexylene glycol, triethylene glycol, tetraethylene glycol and mixtures thereof.
[8" claim-type="Currently amended] The method of claim 1,
The thermosetting polyester is neopentyl glycol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, dibromoneopentyl glycol, bisphenol dipropoxy ether, 2,2,4-trimethylpentane-1,3-diol , A light emitting polymer selected from the group of polyhydric alcohols consisting of tetrabromobisphenol dipropoxy ether, 1,4-butanediol, bisphenol A adduct, hydrogenated bisphenol A, DCPD hydroxy addition mole and mixtures thereof.
[9" claim-type="Currently amended] The method of claim 1,
The suspension filler is in the group consisting of silica, microspheres, glass fibers and other short fibers, nephelin cyanite, feldspar, glass flakes, pumice, mica, calcium carbonate, magnesium sulfate, calcium sulfate, alumina trihydrate and mixtures thereof Luminescent polymer selected.
[10" claim-type="Currently amended] The method of claim 1,
Wherein said phosphorescent pigment is selected from the group consisting of zinc sulfide phosphors, metal aluminate oxide phosphors, and mixtures thereof.
[11" claim-type="Currently amended] The method of claim 10,
The luminescent polymer wherein said zinc sulfide phosphor further contains selenium and silicon.
[12" claim-type="Currently amended] The method of claim 10,
The luminescent polymer wherein said zinc sulfide phosphor is an electroluminescent phosphor.
[13" claim-type="Currently amended] The method of claim 10,
The luminescent polymer wherein the zinc sulfide phosphor further comprises calcium sulfide.
[14" claim-type="Currently amended] The method of claim 10,
A luminescent polymer wherein said zinc sulfide phosphor is activated by copper.
[15" claim-type="Currently amended] The method of claim 14,
The zinc sulfide phosphor is an element selected from the group consisting of copper and aluminum, silver, gold, manganese, gallium, indium, scandium, lead, cerium, terbium, europium, gadolinium, samarium, praseodymium, rare earths, halogens, and mixtures thereof Luminescent polymer activated by.
[16" claim-type="Currently amended] The method of claim 14,
Wherein said zinc sulfide phosphor is further activated by a metal selected from the group consisting of gallium, indium, magnesium, gold, silver, calcium, manganese, iron and mixtures thereof.
[17" claim-type="Currently amended] The method of claim 10,
And the metal aluminate phosphor further comprises an alkaline earth aluminate oxide phosphor activated by at least one rare earth.
[18" claim-type="Currently amended] The method of claim 10,
The phosphorescent pigment is activated by a plurality of elements selected from the group consisting of metals and rare earths.
[19" claim-type="Currently amended] The method of claim 10,
The metal aluminate oxide phosphor is an alkaline earth aluminate oxide selected from the group consisting of strontium aluminum oxide, calcium aluminum oxide, barium aluminum oxide, and mixtures thereof, wherein the alkaline earth aluminate oxide is activated by europium, and lanthanum A luminescent polymer co-activated by an element selected from the group consisting of cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium, erbium, tulium, ytterbium, lutetium, tin, bismuth and mixtures thereof.
[20" claim-type="Currently amended] The method of claim 19,
The light emitting polymer, wherein the alkaline earth aluminate oxide further comprises magnesium aluminum oxide.
[21" claim-type="Currently amended] The method of claim 1,
The thermosetting polyester further comprises a polymerizable monomer component selected from the group consisting of aromatic vinyl, ethylene unsaturated alpha, beta alkyl ester of monocarboxylic acid and vinyl ester.
[22" claim-type="Currently amended] The method of claim 1,
The thermosetting polyester is styrene, diallyl phthalate, triallyl cyanurate, vinyl toluene, α-methylstyrene, divinylbenzene, p - t -butylstyrene, o -chlorostyrene, dichlorostyrene, methyl methacrylate, methyl A light emitting polymer further comprising a polymerizable monomer selected from the group consisting of acrylate, ethyl acrylate, 2-ethylhexyl acrylate and mixtures thereof.
[23" claim-type="Currently amended] The method of claim 1,
A luminescent polymer wherein said thermosetting polyester further comprises styrene.
[24" claim-type="Currently amended] The method of claim 1,
The luminescent polymer further comprises a UV stabilizer.
[25" claim-type="Currently amended] The method of claim 24,
Wherein said UV stabilizer is selected from the group consisting of UV screeners, UV absorbers, UV blockers, free-radical scavengers, antioxidants, peroxide degradants and mixtures thereof.
[26" claim-type="Currently amended] The method of claim 25,
The luminescent polymer further comprises a luminescent enhancer selected from the group consisting of an optical brightener, a fluorescent whitener, a color brightener and a spectrum enhancer.
[27" claim-type="Currently amended] The method of claim 1,
The luminescent polymer further comprises a refractory polyester resin.
[28" claim-type="Currently amended] The method of claim 1,
The luminescent polymer further comprises a flexible polyester resin.
[29" claim-type="Currently amended] The method of claim 1,
The luminescent polymer further comprises a thixotrop modifier.
[30" claim-type="Currently amended] The method of claim 29,
Wherein said thixotrop modifier is selected from the group consisting of colloidal silica, fumed silica, bentonite magnesium aluminum silicate clay, hydrogenated castor oil and aliphatic acidamides.
[31" claim-type="Currently amended] The method of claim 1,
The luminescent polymer further comprises a polymerization catalyst.
[32" claim-type="Currently amended] The method of claim 31, wherein
A light emitting polymer wherein said polymerization catalyst is methyl ethyl ketone peroxide.
[33" claim-type="Currently amended] The method of claim 31, wherein
The luminescent polymer further comprises a reinforcing material selected from the group consisting of reinforcing fillers and reinforced fabrics.
[34" claim-type="Currently amended] The method of claim 33, wherein
The reinforcing fibers are fiberglass fibers.
[35" claim-type="Currently amended] The method of claim 1,
The luminescent polymer further comprises a blowing agent.
[36" claim-type="Currently amended] a) thermosetting polyester resin;
b) suspension fillers; And
c) phosphorescent particles
Photoluminescent and thermoluminescent polymer comprising a.
[37" claim-type="Currently amended] The method of claim 36,
The thermosetting polyester resin is photoluminescent and thermoluminescent selected from the group consisting of orthophthalic acid polyester resin, isophthalic acid polyester resin, maleic acid polyester resin, fumaric acid polyester resin, glycol polyester resin and mixtures thereof Polymer.
[38" claim-type="Currently amended] The method of claim 36,
The suspension filler is a group consisting of silica, microspheres, glass fibers and other short fibers, nephelin cyanite, feldspar, glass plaque, pumice, mica, calcium carbonate, magnesium sulfate, calcium sulfate, alumina trihydrate and mixtures thereof Photoluminescent and thermoluminescent polymers selected from.
[39" claim-type="Currently amended] The method of claim 36,
A photoluminescent and thermoluminescent polymer wherein said phosphorescent particles are selected from the group consisting of activated zinc sulfide phosphors, activated alkaline earth aluminate oxide phosphors and mixtures thereof.
[40" claim-type="Currently amended] The method of claim 36,
A photoluminescent and thermoluminescent polymer wherein said phosphorescent particles are electroluminescent zinc sulfide phosphors.
[41" claim-type="Currently amended] The method of claim 36,
A photoluminescent and thermoluminescent polymer comprising a polymerizable monomer wherein the thermosetting polyester is selected from the group consisting of aromatic vinyls, alkyl esters of alpha and beta monocarboxylic acids unsaturated with ethylene and vinyl esters.
[42" claim-type="Currently amended] The method of claim 36,
A photoluminescent and thermoluminescent polymer comprising a polymerizable monomer wherein said thermosetting polyester is selected from the group consisting of styrene, aromatic vinyl, alkyl esters of alpha and beta monocarboxylic acids unsaturated with ethylene and mixtures thereof.
[43" claim-type="Currently amended] The method of claim 36,
A photoluminescent and thermoluminescent polymer wherein said polymerization catalyst is added to a photoluminescent and thermoluminescent polymer and said polymer is cured to form a molded article.
[44" claim-type="Currently amended] The method of claim 43,
A photoluminescent and thermoluminescent polymer wherein said molded article is a helmet.
[45" claim-type="Currently amended] The method of claim 43,
A photoluminescent and thermoluminescent polymer wherein said molded article is a component of a vehicle selected from the group consisting of automobile wheels, automobile wheel caps, hoods and fenders.
[46" claim-type="Currently amended] The method of claim 43,
A photoluminescent and thermoluminescent polymer wherein said shaped article is selected from the group consisting of spas, showers, baths and hottubs.
[47" claim-type="Currently amended] The method of claim 36,
A photoluminescent and thermoluminescent polymer wherein a polymerization catalyst is added and the photoluminescent and thermoluminescent polymers are applied as a gel coating to the surface of the article.
[48" claim-type="Currently amended] The method of claim 36,
A photoluminescent and thermoluminescent polymer added with a polymerization catalyst and used as a gel coating to form a coated article selected from the group consisting of laminated articles, moldable articles and molded articles.
[49" claim-type="Currently amended] The method of claim 36,
A photoluminescent and thermoluminescent polymer wherein a polymerization catalyst is added and the photoluminescent and thermoluminescent polymer is applied to a preexisting article to form the photoluminescent and thermoluminescent articles.
[50" claim-type="Currently amended] The method of claim 49,
A photoluminescent and thermoluminescent polymer wherein the preprocess is a fiber optic material.
[51" claim-type="Currently amended] The method of claim 49,
A photoluminescent and thermoluminescent polymer wherein said preprocessed product is a UV bulb.
[52" claim-type="Currently amended] The method of claim 49,
Wherein said photoluminescent and thermoluminescent polymers further comprise flexible polyesters, wherein said photoluminescent and thermoluminescent polymers are applied to fibers to form photoluminescent and thermoluminescent fibers and apparel articles.
[53" claim-type="Currently amended] The method of claim 49,
The photoluminescent and thermoluminescent polymer further comprising a refractory material selected from the group consisting of refractory resins and additives.
[54" claim-type="Currently amended] The method of claim 53,
The refractory resins include chloric anhydride, tetrabromophthalic anhydride, dibromoneopentyl glycol, tetrachlorophthalic anhydride, decabromodiphenyl oxide (DBDPO) (ether), bromobisphenol-A and pentabromodiphenyl oxide A photoluminescent and thermoluminescent polymer further comprising a reactive intermediate selected from the group consisting of:
[55" claim-type="Currently amended] The method of claim 53,
The refractory additives include bromine ions, phosphonium bromide, alumina trihydrate, magnesium hydroxide, phosphate esters, vinylphosphonates, bis (hydrocarbyl) vinylphosphonates and their condensates, antimony oxides, zinc borates, A photoluminescent and thermoluminescent polymer selected from the group consisting of barium metaborate, molybdenum compounds, magnesium carbonate and mixtures of these additives.
[56" claim-type="Currently amended] The method of claim 53,
The photoluminescent and thermoluminescent polymers are applied to fibers and used to form articles such as clothing and hot air balloons.
[57" claim-type="Currently amended] a) thermosetting polyester resin;
b) vinylidene monomers;
c) suspension fillers;
d) thixotrop modifiers;
e) UV stabilizers; And
f) phosphorescent pigments
Method of producing a luminescent polymer comprising the step of mixing.
[58" claim-type="Currently amended] The method of claim 57,
The thermosetting polyester resin,
a) an ethylenically unsaturated dicarboxylic acid or anhydride component selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, methacrylic acid, acrylic acid, itaconic acid and citraconic acid;
b) phthalic anhydride, isophthalic acid, phthalic acid, chloric anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, adipic acid, succinic acid, suberic acid, sebacic acid, azelaic acid Aromatic dicarboxylic acid or anhydride components selected from the group consisting of terephthalic acid and mixtures thereof; And
c) neopentyl glycol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, dibromoneopentyl glycol, bisphenol dipropoxy ether, 2,2,4-trimethylpentane-1,3-diol, tetrabro Dibis alcohols selected from the group consisting of mobisphenol dipropoxy ether, 1,4-butanediol, bisphenol A adduct, hydrogenated bisphenol A, DCPD hydroxy adduct and mixtures thereof
Method for producing a light-emitting polymer further comprising.
[59" claim-type="Currently amended] The method of claim 57,
The thermosetting polyester resin
a) an unsaturated component selected from the group consisting of maleic anhydride, fumaric acid, maleic acid and mixtures thereof;
b) an aromatic component selected from the group consisting of phthalic anhydride, isophthalic acid and phthalic acid; And
c) neopentyl glycol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, dibromoneopentyl glycol, bisphenol dipropoxy ether, 2,2,4-trimethylpentane-1,3-diol, tetrabro Glycol selected from the group consisting of mobisphenol dipropoxy ether, 1,4-butanediol, bisphenol A adduct, hydrogenated bisphenol A, DCPD hydroxy adduct and mixtures thereof
Method for producing a light-emitting polymer further comprising.
[60" claim-type="Currently amended] The method of claim 57,
Wherein said vinylidene monomer is selected from the group consisting of aromatic vinyl, ethylene unsaturated alpha, beta alkyl ester of monocarboxylic acid and vinyl ester.
[61" claim-type="Currently amended] The method of claim 57,
The vinylidene monomers are styrene, vinyltoluene, α-methylstyrene, divinylbenzene, p - t -butylstyrene, o -chlorostyrene, dichlorostyrene, methyl methacrylate, methyl acrylate, ethyl acrylate, 2-ethyl A method for producing a luminescent polymer selected from the group consisting of hexyl acrylate, diallyl phthalate, triallyl cyanurate and mixtures thereof.
[62" claim-type="Currently amended] The method of claim 57,
A method for producing a light emitting polymer wherein the vinylidene monomer is styrene.
[63" claim-type="Currently amended] The method of claim 57,
And the thixotrop modifier is selected from the group consisting of colloidal silica, fumed silica, bentonite magnesium aluminum silicate clay, hydrogenated castor oil and aliphatic acidamide.
[64" claim-type="Currently amended] The method of claim 57,
The phosphorescent dye is a method of producing a luminescent polymer selected from the group consisting of activated zinc sulfide phosphorescent dye, activated alkaline earth aluminate oxide phosphorescent dye and mixtures thereof.
[65" claim-type="Currently amended] 65. The method of claim 64,
The activated zinc sulfide phosphorescent pigment further comprises a calcium sulfide.
[66" claim-type="Currently amended] 65. The method of claim 64,
The phosphorescent dye is a method for producing a luminescent polymer is activated by a plurality of metals and rare earths.
[67" claim-type="Currently amended] The method of claim 66,
And the metal is selected from the group consisting of copper, gallium, indium, magnesium, gold, silver, calcium, manganese, iron, tin, bismuth and mixtures thereof.
[68" claim-type="Currently amended] 65. The method of claim 64,
The activated zinc sulfide phosphorescent pigment is a luminescent polymer activated by elements selected from the group consisting of copper, gallium, indium, silicon, magnesium, gold, silver, calcium, manganese, iron, rare earths, halogens and mixtures thereof. Manufacturing method.
[69" claim-type="Currently amended] The method of claim 57,
The method of manufacturing a light-emitting polymer wherein the light-emitting polymer further comprises a flexible polyester resin.
[70" claim-type="Currently amended] The method of claim 57,
The method of manufacturing a light emitting polymer wherein the light emitting polymer further comprises a refractory polyester resin.
[71" claim-type="Currently amended] The method of claim 57,
And the luminescent polymer further comprises a luminescent enhancer selected from the group consisting of an optical brightener, a fluorescent whitener, a color brightener, and a spectral enhancer.
[72" claim-type="Currently amended] The method of claim 57,
The method of manufacturing a light-emitting polymer wherein the light-emitting polymer further comprises a blowing agent.
[73" claim-type="Currently amended] The method of claim 57,
A method of producing a luminescent polymer further comprising the step of adding a polymerization catalyst.
[74" claim-type="Currently amended] The method of claim 73,
A method of making a luminescent polymer further comprising applying the luminescent polymer to a surface.
[75" claim-type="Currently amended] The method of claim 73,
A method for producing a luminescent polymer further comprising the step of forming a molded article from the luminescent polymer.
[76" claim-type="Currently amended] A luminescent polymer product comprising a molded article prepared by the method of claim 75.
[77" claim-type="Currently amended] A luminescent polymer product comprising a surface to which a luminescent polymer prepared by the method of claim 73 is applied.
[78" claim-type="Currently amended] a) mixing the thermosetting polyester gel coating resin with a thermosetting moldable resin selected from the group consisting of a thermosetting laminated resin, a thermosetting mold resin and mixtures thereof to form a thermoplastic polyester resin mixture;
b) adding a suspending filler to said thermoplastic polyester resin mixture in an amount sufficient to suspend heavy phosphorescent pigments; And
c) adding a phosphorescent pigment to the thermoplastic polyester resin mixture
Method for producing a light-emitting polymer comprising a.
[79" claim-type="Currently amended] The method of claim 78,
The thermosetting polyester resin is an orthophthalic acid polyester resin, isophthalic acid polyester resin, maleate polyester resin, fumarate polyester resin, glycol polyester resin, and a mixture thereof. .
[80" claim-type="Currently amended] The method of claim 78,
A method of producing a luminescent polymer further comprising the step of mixing the thermosetting refractory polyester resin into a resin mixture.
[81" claim-type="Currently amended] The method of claim 78,
A method of producing a luminescent polymer further comprising the step of mixing the thermosetting flexible polyester resin into a resin mixture.
[82" claim-type="Currently amended] The method of claim 78,
A method for producing a luminescent polymer wherein a catalyst is added to the luminescent polymer and the luminescent polymer is formed into a molded article.
[83" claim-type="Currently amended] A molded article produced by the method of claim 82.
[84" claim-type="Currently amended] 83. The method of claim 82,
A method for producing a luminescent polymer wherein the molded article is reinforced with fiberglass fibers.
[85" claim-type="Currently amended] The method of claim 78,
A polymerization initiator is added to the luminescent polymer, and the luminescent polymer is applied to the surface as a gel coating to prepare a luminescent gel coated product.
[86" claim-type="Currently amended] 85. A luminescent gel coated article prepared by the method of claim 85.

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同族专利:

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公开号 | 公开日

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KR100708808B1|2007-04-17|

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EP1265972A4|2006-12-20|

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AU767819B2|2003-11-27|

---

NZ521237A|2003-05-30|

---

CA2399829A1|2001-08-23|

---

AU2784300A|2001-08-27|

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JP2003523445A|2003-08-05|

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US6207077B1|2001-03-27|

---

BR0017127A|2003-03-05|

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WO2001060943A1|2001-08-23|

---

CN100344725C|2007-10-24|

---

AU767819C|2005-07-28|

---

CN1434848A|2003-08-06|

---

EP1265972A1|2002-12-18|

---

MXPA02008046A|2004-04-05|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-02-18|Application filed by 오리온 21 에이. 디. 피티와이 리미티드

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2000-02-18|Priority to PCT/AU2000/000116

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2002-10-04|Publication of KR20020075437A

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2007-04-17|Application granted

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2007-04-17|Publication of KR100708808B1

优先权:

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申请号 | 申请日 | 专利标题

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PCT/AU2000/000116|WO2001060943A1|2000-02-18|2000-02-18|Luminescent gel coats and moldable resins|