CN108822606A - A kind of coating - Google Patents

Abstract

The invention belongs to the field of coatings. A coating, the coating comprises conventional components of the coating and blue long-lasting phosphor powder, the blue long-lasting phosphor powder is uniformly distributed in the conventional components of the coating, and the addition amount of the blue long-lasting phosphor powder is 1 to 30%; The general formula of the chemical composition of the blue long-lasting phosphor is Ca _{1-x- y} AlO ₂ Cl: x Eu ²⁺ , y Re ³⁺ , wherein Re is one or more combinations of Tm, Gd and La , the value ranges of x and y are respectively: 0.01≤x≤0.1, 0.01≤y≤0.1. The luminescent center of the phosphor is Eu ²⁺ ions, and the long afterglow effect can be effectively enhanced by introducing rare earth impurity ions such as Tm ³⁺ , Gd ³⁺ and La ³⁺ . The paint provided by the invention has high afterglow brightness and long afterglow time, and can be used in the fields of building materials, home appliances, image storage and the like.

Description

a paint

This application is a divisional application, the filing date of the original application: 2017-11-02, the original application number: 2017110616282,

Invention title of the original application: a blue long-lasting phosphor and its preparation method.

technical field

The invention belongs to the field of coatings.

Background technique

Long afterglow material is a material that can still emit fluorescent afterglow for a long time (several seconds to more than ten hours) after the external excitation source (ultraviolet-visible light, X-ray, β-ray, etc.) stops. Long afterglow phenomenon It was discovered in Chinese paintings thousands of years ago, and the scientific description of the long afterglow phenomenon can be traced back to the 17th century. However, until the 20th century, there were few scientific reports on the long afterglow. There are two main reasons. The intensity of afterglow luminescence is low, and the weak light detection technology at that time was difficult to detect afterglow with very low intensity; second, the afterglow intensity of the long afterglow materials at that time was not high, and the practical significance was not great. A milestone report on the research of long afterglow materials Originated from an article published by Matszuzawa in August 1996, they found that by co-doping Dy ³⁺ in the long afterglow material SrAl ₂ O ₄ : Eu ²⁺ , the afterglow intensity can be greatly enhanced. At the same time, Takasaki et al. : It is also found that co-doping Co in Cu can greatly improve the afterglow intensity. Since then, the research on long afterglow materials has entered a new stage. At present, long afterglow materials have been widely used in passive night signs and various warnings and tracers device.

At present, the research on long-lasting luminescent materials mainly focuses on blue-green luminescent materials, and the research systems mainly include sulfides, aluminates, and silicates. Early studies on sulfide systems found that sulfides activated by rare earth ions Dy ³⁺ and Tm ³⁺ can emit blue light. Most of the long afterglow materials in the aluminate matrix system emit light in the blue-green light region, among which the better blue long afterglow luminescent material is CaAl ₂ O ₄ : Eu ²⁺ , Nd ³⁺ , and its emission spectrum peak wavelength is 446nm. Afterglow time can reach 1000min. In addition, among the silicate-based long-lasting luminescent materials, the research on 2MO·MgO·2SiO ₂ : Eu, Dy (M is an alkaline earth metal element) is the most widely studied. , and its luminous range can cover from blue-violet light to yellow-green light. Among them, Sr ₂ MgSi ₂ O ₇ : Eu ²⁺ , Dy ^{3 +} , which emits blue light with long afterglow performance, has better performance. Its main emission peak is located at 469nm, and its afterglow time can exceed 10h. Its luminescence performance is better than that of CaAl ₂ O ₄ : Eu ²⁺ , Nd ^{3 +} , and Sr ₂ MgSi ₂ O ₇ : Eu ²⁺ , Dy ³⁺ have good chemical stability and thermal stability, high-purity silica raw materials are cheap and easy to get, so they have been attention by people.

Contents of the invention

In order to overcome a series of problems such as weak luminous intensity and short afterglow time of blue long afterglow materials in the prior art, the present invention provides a blue long afterglow phosphor and a preparation method thereof. The phosphor has chemically stable Good performance, high afterglow brightness, long afterglow time, etc., can be used in decoration, emergency display and other fields.

In order to solve the above-mentioned deficiencies in the prior art, the technical scheme adopted in the present invention is as follows:

A kind of blue long afterglow fluorescent powder, the chemical composition general formula of described fluorescent powder is Ca _1-xy AlO ₂ Cl: x Eu ²⁺ , y Re ³⁺ , wherein Re is one of Tm, Gd and La or Several combinations, the value ranges of x and y are: 0.01≤x≤0.1, 0.01≤y≤0.1. Preferably, the luminescent center of the phosphor is Eu ²⁺ ions, and trap energy levels are provided by introducing one or more combinations of rare earth ions Tm ³⁺ , Gd ³⁺ and La ³⁺ , effectively enhancing the long-lasting luminous effect .

A kind of preparation method of blue long-lasting phosphor, is characterized in that comprising the following steps:

(1) Ingredients: Using high-purity CaCO ₃ , CaCl2, Al ₂ O ₃ , Eu ₂ O ₃ , Tm ₂ O ₃ , Gd ₂ O ₃ and La ₂ O ₃ as raw materials, according to the chemical composition formula Ca _1-xy The ratio of each element in AlO ₂ Cl: x Eu ²⁺ , y Re ³⁺ , accurately weigh each raw material;

(2) Mixing: Put the above raw materials into an agate mortar and grind them evenly. When grinding, add absolute ethanol as the grinding medium according to the total mass ratio of 1:1, and the grinding time is 0.5~1 hour;

(3) Drying: Place the slurry-like mixture obtained above in an oven, heat-preserve and dry at 80°C for 4 hours, take out the sample after drying, and grind and disperse to obtain evenly mixed raw materials;

(4) Sintering: put the uniformly mixed raw materials into a high-temperature tube furnace for pre-sintering, the sintering temperature is 1000-1300°C, the sintering time is 4-6 hours, the heating rate is 7.5°C/min, and the sintering atmosphere is 5%H ₂ /95%N ₂ mixed gas of hydrogen and nitrogen, after the sintering is completed, it is cooled to room temperature with the furnace to obtain a sintered body;

(5) Powder selection: the sintered body obtained in step (4) is ball milled, and the pulverized powder is classified according to the particle size by an airflow classifier to obtain the blue long afterglow phosphor.

Compared with prior art, the beneficial effect of the present invention is:

(1) The present invention provides a new type of blue long-lasting phosphor, whose matrix composition is CaAlO ₂ Cl, and the blue light emission is obtained by doping rare earth ions Eu ²⁺ , and by introducing rare earth ions Tm ³⁺ , Gd ³⁺ and One or several combinations of La ³⁺ provide trap energy levels, effectively enhancing the afterglow brightness and time of the phosphor;

(2) The blue long afterglow phosphor provided by the present invention has the advantages of good chemical stability, high afterglow brightness and long afterglow time.

The invention also discloses a blue long afterglow light-emitting element, which adopts the substrate made of the above-mentioned blue long afterglow fluorescent powder.

The invention also discloses a blue long-lasting light-emitting element, which includes a base and a long-lasting light-emitting film attached to the base, and the long-lasting light-emitting film is the above-mentioned blue long-lasting phosphor powder or blue long-lasting phosphor powder flakes.

The invention also discloses a blue long-lasting light-emitting element including a base and a long-lasting light-emitting film attached to the base, and the long-lasting light-emitting film is a blue long-lasting phosphor powder or a blue long-lasting phosphor sheet.

Preferably, the thickness of the long afterglow luminescent film is 1-10 mm.

The substrate of the present invention may be a rigid substrate or a flexible substrate. Preferably, the rigid substrate can be selected from glass, silicon, steel, ceramics, cement, wood and stone, and the flexible substrate can be selected from PDMS (polydimethylsiloxane) film, PET (polyterephthalate Ethylene glycol ester) film, PS (polystyrene) film, PU (polyurethane) film, PI (polyimide) film and PVA (polyvinyl alcohol) film.

The above-mentioned preparation method of the blue long-lasting light-emitting element includes: coating the above-mentioned suspension of blue long-lasting phosphor powder particles on the above-mentioned substrate.

Although the above-mentioned blue long-lasting phosphor powder particle suspension is prepared into a suspension, and then coated on the substrate, the light-emitting element meeting the requirements of the present invention can be prepared, but when the suspension is When polymer substances are also included, the sensitivity and precision of the final light-emitting element prepared will be further improved.

The content of the blue long-lasting phosphor powder particles can also be changed within a wide range, preferably, based on 100 parts by weight of the suspension, the content of the blue long-lasting phosphor powder particles is 0.5 - 10 parts by weight, preferably 1-5 parts by weight.

Preferably, the macromolecular substance is selected from PVA, EVA (ethylene-vinyl acetate copolymer), PDMS, PU, PMMA (polymethyl methacrylate), PAM (polyacrylamide), PVP (polyvinylpyrrolidone), One or more of starch, cellulose, vegetable gum, animal glue, carboxymethyl starch, acetate starch, hydroxymethyl cellulose and carboxymethyl cellulose.

According to the present invention, the content of the polymer substance can also be changed within a wide range, preferably, based on 100 parts by weight of the suspension, the content of the polymer substance is 1-10 parts by weight, preferably 3-8 parts by weight.

According to the present invention, the solvent can be various solvents conventionally used in the art, preferably selected from water, methanol, ethanol, acetone, ethylene glycol, isopropanol, diethylene glycol, ethylene glycol methyl ether, ethylene glycol Ethyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, conol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, diacetone alcohol, Tridecyl Alcohol, Tetradecyl Alcohol, Dioctyl Phthalate, Ethyl Acetate, Butyl Acetate, Cyclohexanone, Xylene, Dicyclohexyl, Cyclohexane, n-Butanol, Butanone, O-Phenyl One or more of dimethyl diformate and sorbitol.

According to the present invention, the method of coating the suspension of the blue long-lasting phosphor powder particles on the surface of the substrate can be a conventional choice in the art, for example, coating methods such as spray coating and spin coating can be used, or Printing technology can be used. The preferred printing technology of the present invention is to print the suspension of blue long-lasting phosphor powder particles on the surface of the substrate, so that the sensitivity and accuracy of the prepared sensor are further improved. Wherein, the printing technology may be selected from one of dispensing, inkjet printing, water transfer printing, screen printing and roll-to-roll printing. When printing technology is used to print the suspension of the blue long-lasting phosphor powder particles on the surface of the substrate, the suspension is preferably prepared into an ink, and the ink is prepared by co- Obtained by mixing or blending by ultrasonic dispersion.

The present invention also discloses a blue long afterglow luminescent element, which comprises a polymer material and the blue long afterglow phosphor powder, the blue long afterglow phosphor powder is uniformly distributed on the polymer material Among them, the addition amount of the blue long-lasting phosphor powder is 1-90%; preferably 10-80%. The polymer material can be selected from PDMS (polydimethylsiloxane), PET (polyethylene terephthalate), PS (polystyrene), PU (polyurethane), PI (polyimide) and PVA (polyvinyl alcohol) is thin. Moderately, in order to improve the processing performance, the film material can also be added with coupling agent, lubricant, plasticizer and so on.

The present invention also discloses an ink, which comprises conventional components of the ink and the blue long-lasting phosphor powder, the blue long-lasting phosphor powder is evenly distributed in the conventional components of the ink, and the blue long-lasting phosphor powder is The amount added is 1~30%; preferably 5~10%. The ink resin system can be polyamide, chlorinated polypropylene, polyurethane or acrylic. It can be either oil-based ink or water-based ink.

The invention also discloses a coating, which comprises conventional components of the coating and the blue long-lasting phosphor powder, the blue long-lasting phosphor powder is evenly distributed in the conventional components of the coating, and the blue long-lasting phosphor powder is The amount added is 1~30%; preferably 5~10%. Coating resin systems can be polyamide, chlorinated polypropylene, polyurethane or acrylic. It can be both oil-based paint and water-based paint.

In addition, by forming blue long-lasting phosphors on ordinary paper, synthetic paper, or polymers such as epoxy resin, polyethylene, polyethylene terephthalate, polyester, polypropylene, and polyvinyl chloride, etc. Exterior surfaces of raw materials, natural or synthetic rubber, glass, ceramics, metal, wood, artificial or natural fibers, concrete, or combinations thereof and their processed products, or by containing blue long-lasting phosphors inside .

The blue long-lasting light-emitting element of the present invention can be used as illumination and safety display. For example: device vibration lights, wind lights and other lighting appliances; emergency, abnormal notification, emergency tools, danger display, emergency lights, emergency signs, signs, signboards, and display devices for life-saving tools; safety bars, hanging on factory buildings Tension ropes around objects, animal guardrails; step steps, handrails, and liners for destinations installed in a state half-buried in roads, etc.; health appliances, walking aids (walking aid walking sticks, light-emitting notification antennas) etc.); earrings, necklaces and other jewelry; pillars supporting flags, cutting sticks for road cutters such as railways, exterior or internal parts of bicycles, automobiles, trams, boats, airplanes, etc., fishing gear (dummy bait, Fishing rods, fishing nets, etc.; luminous fiber structures, luminous fishing gear, fishing lines, fishing nets, etc.), buoys (floats, buoys); pets such as humans, dogs, and cats, livestock such as cattle, pigs, sheep, and chickens, etc. location display; fans (wind power generation, fan blades, etc.), clothing (shoes, sportswear, artificial luminous cloth, artificial luminous silk, artificial luminous fiber, etc.); packaging (boxes, brackets, containers, envelopes, thick paper , outer skin packaging, external coating), medical products (respiratory aids, experimental research equipment), robots (artificial luminous hair structure, artificial luminous skin, artificial luminous body), etc. Examples of applications in which blue long-lasting phosphors are contained in coating compositions, ink compositions, adhesives, and surface coating agents include: those used in financial organizations, public organizations, credit card companies, distribution industries, etc., and those used for pasting Postal items such as crimped postcard sheets containing blue long-lasting phosphor in the adhesive; chairs, beds and other furniture; floor materials, ceramic tiles, wall materials, prefabricated panel materials, paving materials, wood, steel, concrete and other building materials; Automatic navigation system devices installed in vehicles; operating devices for operating audio devices and air conditioners; input devices such as home appliances, portable devices, and electronic computers; image storage means such as digital cameras, CCD cameras, films, photos, and videos, etc.

Since a new appearance can be produced by making blue long-lasting phosphor emit light, it is also considered to expand to entertainment products such as toys and event products, and daily necessities. Examples include: dynamic toys, kites, carp-shaped flags and other wind flags, swings, scooters, merry-go-rounds, bows and arrows, etc.; non-power-sourced light emitting devices (wind chimes, etc.) that simultaneously generate sound and light through wind power. Luminous balls (golf balls, baseball balls, table tennis balls, billiard balls, etc.), windmills with light-emitting mechanisms; balloons; Picture books; sporting goods (long objects such as pole vault poles, fencing, bows and arrows, etc.); pressure-sensitive seals for golf club score confirmation, circuit testers for tennis courts, dynamic decorations, dynamic engravings, dynamic souvenirs ;Dynamic display device; Luminous decoration device; Loudspeaker and other audio devices, musical instruments (violin, guitar and other stringed instruments, xylophone, drum and other percussion instruments, trumpet, flute and other wind instruments, glass and other diaphragms), tuning forks, etc.; entertainment products such as event products Water plants and containers for ornamental water tanks in aquariums; luminous watches, luminous sand timers or sand timer-type luminous devices; luminous analog candle devices; artificial plants capable of luminescence; artificial eyes; cosmetics containing adhesive polymers Compositions, printed matter and securities that can be visually discriminated against forgery, printing inks containing long-lasting luminescent particles, bills, checks, stocks, bonds, various securities, commodity certificates, book certificates, tickets for transportation organizations, Fee-charging facilities, admission tickets for events, lottery tickets, winning tickets for public sports competitions, banknotes, ID cards, tickets, passes, etc., passports, printed matter with confidential documents, or sealed seals, etc.

The long-lasting luminous body-photocatalyst complex obtained by activating the photocatalyst attached to the surface of the blue long-lasting phosphor with the luminescence of the long-lasting phosphor can be used for: antibacterial, sterilizing, and non-human animal protection Treatment, decontamination of antibacterial articles such as handrails and handles of vehicles, and decontamination of flow energy using internal wall surfaces such as piping in dark places. The long-lasting luminescent substance activates the photocrosslinking agent in the polymer resin by emitting light, and can also promote crosslinking.

The resin composition of the present invention can be formed by compounding the blue long-lasting phosphor of the present invention into a resin.

In addition, by further adding other inorganic materials or organic materials into the resin composition of the present invention to form a composite material, the long-lasting luminous body of the present invention can also be formed.

For example, when the resin is epoxy resin, acrylic resin, etc., 1 to 200 parts of the above-mentioned blue long-lasting phosphor are blended with respect to 100 parts by mass of the resin, and when the resin is polyethylene resin, soft vinyl chloride resin, etc. Next, 30 to 300 parts by mass of the blue long-lasting phosphor was blended with respect to 100 parts by mass of the resin. The compounded material can be prepared as a resin composition by using a mixer such as a cone mixer, a V-type mixer, a ribbon mixer, a Henschel mixer, a Banbury mixer, or a three-roll mill.

In addition, in the case of forming a long-lasting illuminant from the resin composition, for example, to obtain a sheet-shaped long-lasting illuminant, for example, 50 to 200 parts by weight of the above-mentioned blue long-lasting phosphor is compounded with respect to 100 parts by weight of polyvinyl chloride resin. Parts by mass, 3 to 5 parts by mass of calcium-zinc stabilizer, 30 to 100 parts by mass of dioctyl phthalate as a plasticizer, kneading at 150 to 200°C with a two-roll mill to obtain Flexible sheet-shaped long-lasting illuminant.

When obtaining a film-like long-lasting luminous body, for example, with respect to 100 parts by mass of polyethylene terephthalate resin, 20 to 50 parts by mass of the above-mentioned blue long-lasting phosphor is blended, and a twin-screw extruder, blower, etc. Kneading and molding are performed at 250-300°C in the expansion processing machine, so that a film-like long-lasting luminous body can be obtained.

To obtain long-lasting light emitters of other shapes, for example, 5 to 100 parts by mass of blue long-lasting phosphors are blended with 100 parts by mass of polypropylene resin, and kneaded at 170 to 200° C. with a twin-screw extruder. Forming, so as to obtain strip-shaped, plate-shaped, rod-shaped, and pellet-shaped long-lasting luminous bodies. In addition, by processing and molding the pellet-shaped long-lasting illuminant at 170-200° C. using an injection molding machine, a three-dimensional long-lasting illuminant can be obtained.

Examples of the aforementioned resin and other organic materials include resins such as thermoplastic resins and thermosetting resins. Examples of thermoplastic resins include polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polyvinyl chloride, etc. Vinylidene chloride, styrene polymers or copolymers such as acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as 6-nylon, 66-nylon, and 12-nylon, polyamideimide, Polyimide, polyetherimide, polyurethane, polymethyl methacrylate and other acrylic resins, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinylidene fluoride, polytetrafluoroethylene and other fluororesins , alkenyl aromatic resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polylactic acid and other polyesters, bisphenol A polycarbonate, etc. Polyacrylic acid such as polycarbonate, polyacetal, polyphenylene sulfide, polymethylpentene, cellulose, polyvinyl alcohol, polyvinyl acetate, polyacrylonitrile, styrene-acrylonitrile copolymer (AS resin), Polyphenylene ether (PPE), modified PPE, polyarylate, polyphenylene sulfide, polysulfone, polyether sulfone, polyether nitrile, polyether ketone, polyketone, liquid crystal polymer ethylene and propylene copolymer, ethylene or Copolymers of propylene and other α-olefins (1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, etc.), ethylene and other ethylenically unsaturated monomers (vinyl acetate , acrylic acid, acrylate, methacrylic acid, methacrylate, vinyl alcohol, etc.) copolymers, etc.

A thermoplastic resin can be used individually or in combination of 2 or more types. In addition, when a thermoplastic resin is a copolymer, it may be a copolymer of arbitrary forms, such as a random copolymer and a block copolymer. Examples of thermosetting resins include phenolic resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, epoxy resins, silicone resins, alkyd resins, polyimides, Polyaminobismaleimide, casein resin, furan resin, polyurethane resin, etc. In addition, resins cured by ultraviolet rays and radiation are also mentioned.

Furthermore, natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene-diene rubber, butyl rubber, neoprene rubber, acrylonitrile butadiene rubber, silicon Rubber-based materials such as rubber.

In addition, pigments, dyes, lubricants, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, flame retardants, fungicides, antibacterial agents, catalysts for curing, photopolymerization initiators, etc. Invented blue long-lasting phosphors are mixed together and formed into rods, plates, films, fibers, films, needles, spheres, foils, granules, sand, scales, flakes, liquids, gels, etc. Any shape such as colloid, sol, suspension, aggregate, capsule, etc.

Examples of pigments include inorganic pigments and organic pigments.

Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, carmine (red iron oxide (III)), cadmium red, ultramarine blue, dark blue, chromium oxide green, Cobalt green, ochre, titanium black, synthetic iron black, carbon black, mica, aluminum oxide covered by titanium oxide, iron oxide, mica covered by titanium oxide, iron oxide, glass flakes, holographic pigments, etc. In addition, as metal powder pigments, aluminum powder, copper powder, stainless steel powder, metal colloid, transparent pearl mica with interference effect, colored mica, interference mica, interference alumina, interference silica ( interference glass), etc.

Examples of organic pigments include: azo pigments (monoazo yellow, condensed azo yellow, azomethine yellow, etc.), yellow iron oxide, titanium yellow, bismuth vanadate, benzimidazolone, isoindole Yellow pigments such as phenone, isoindoline, quinophthalone, benzidine yellow, permanent yellow, etc.; orange pigments such as permanent orange; red iron oxide, naphthol AS series azo red, anthraquinone, anthraquinone red, pyrene Red-brown, quinacridone red, diketopyrrolopyrrole red, permanent red and other red pigments; cobalt violet, quinacridone purple, dioxazine violet and other purple pigments; cobalt blue, phthalocyanine pigments (phthalocyanine blue, etc.), blue pigments such as anthracene blue; green pigments such as phthalocyanine green, organic dyes such as azo-based disperse dyes, anthraquinone-based disperse dyes, etc.

Examples of dyes include azo dyes, anthraquinone dyes, indigo dyes, sulfur dyes, triphenylmethane dyes, pyrazolone dyes, stilbene dyes, diphenylmethane dyes, xanthene dyes, and alizarin dyes. , acridine dyes, quinoneimine dyes (oxazine dyes, oxazine dyes, thiazine dyes), thiazole dyes, methine dyes, nitro dyes, and nitroso dyes.

Examples of antioxidants include hindered phenol compounds, phosphite compounds, phosphonite compounds, and thioether compounds.

Examples of hindered phenolic compounds include: α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butyl phenyl) propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6- Di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 2,2'-methylene Bis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2, 6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl- Benzyl-p-cresol) 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis(4-methyl-6-tert-butyl phenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5- Methylphenyl) propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4 -Methyl 6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl -4-Hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-dithiobis(2,6-di-tert butylphenol), 4,4'-trithiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl -4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5 -Triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), N,N'-bis[3-(3,5-di-tert-butyl Base-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl -2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tri (3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) Isocyanurate, 1,3,5-tris-2[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethylisocyanurate and tetra [Methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane, etc.

Examples of phosphite-based compounds include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tris(octadecyl) phosphite, and trioctyl phosphite. ester, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite Mono-octyldiphenyl phosphite, tris(diethylphenyl) phosphite, tris(diisopropylphenyl) phosphite, tris(di-n-butylphenyl) phosphite , tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4 -di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4 -Ethylphenyl)pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite ester, bis(nonylphenyl)pentaerythritol diphosphite and dicyclohexylpentaerythritol diphosphite, etc. Examples of other phosphite-based compounds include phosphite-based compounds that react with dihydric phenols to have a cyclic structure.

Examples of phosphonite-based compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butyl phenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene Diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl )-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite and bis(2,6-di-tert-butyl Phenyl)-3-phenyl-phenylphosphonite, etc.

Examples of thioether-based compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, and dilauryl thiodipropionate. Distearyl ester, pentaerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3-dodecylthiopropionate), pentaerythritol-tetrakis(3-octadecylthiopropionate) propionate), pentaerythritol tetrakis (3-myristyl thiopropionate) and pentaerythritol-tetrakis (3-stearyl thiopropionate), etc. Examples of light stabilizers including ultraviolet absorbers include: benzophenone-based compounds, benzotriazole-based compounds, aromatic benzoate-based compounds, oxalanilide-based compounds, cyanoacrylate-based compounds, and Hindered amine compounds, etc.

Examples of benzophenone-based compounds include: benzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2,2',4,4'- Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy -4,4'-dimethoxy-5-sulfonylbenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-Hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonylbenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4 -octyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and 2-hydroxy-4-(2-hydroxy-3-methyl-acryloyloxyisopropyl Oxygen) Benzophenone etc.

Examples of benzotriazole-based compounds include: 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzene Triazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-4'-methyl-2'- hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(5-tert-butyl-2-hydroxyphenyl ) benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]benzotriazole, 2-[2'-hydroxy-3' , 5'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole and 2-(4'-octyloxy-2'-hydroxyphenyl)benzotriazole, etc.

Examples of the aromatic benzoate-based compound include salicylic acid alkylphenyl esters such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate.

Examples of oxalanilide compounds include 2-ethoxy-2'-ethyl oxanilide, 2-ethoxy-5-tert-butyl-2'-ethyl oxanilide and 2 -Ethoxy-3'-dodecyl oxanilide, etc.

Examples of cyanoacrylate compounds include: ethyl-2-cyano-3,3'-diphenylacrylate, 2-ethylhexyl-cyano-3,3'-diphenylacrylate Wait.

Examples of hindered amine compounds include: 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine Pyridine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylacetoxy)-2,2,6,6-tetramethylpiperidine, 4-benzene Formyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-octadecyloxy-2, 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethyl Basepiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine Pyridine, bis(2,2,6,6-tetramethyl-4-piperidinyl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) oxalate, bis (2,2,6,6-tetramethyl-4-piperidinyl)malonate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl)adipate, bis(2,2,6,6-tetramethyl-4-piperidinyl)terephthalate , 1,2-bis(2,2,6,6-tetramethyl-4-piperidinyloxy)-ethane, α,α'-bis(2,2,6,6-tetramethyl- 4-piperidinyloxy)-p-xylene, bis(2,2,6,6-tetramethyl-4-piperidinyl)-tolylphenylene-2,4-dicarbamate, Bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylene-1,6-dicarbamate, tris(2,2,6,6-tetramethyl- 4-piperidinyl)-benzene-1,3,5-tricarboxylate, tris(2,2,6,6-tetramethyl-4-piperidinyl)-benzene-1,3,4-tri Carboxylate, 1,2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}-2,2,6,6-tetramethylpiperidine and 1,2 ,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine and β,β,β',β'-tetramethyl-3,9-[ 2,4,8,10-tetraoxaspiro(5,5)undecane]dimethanol condensation products, etc.

Examples of antistatic agents include carbon powders such as carbon black and graphite, tin-antimony composite oxides, antimony-indium-tin composite oxides, indium-tin composite oxides, doped with Sn, F, Cl, etc. Conductive indium oxide, tin oxide, zinc oxide and other metal oxides, copper, nickel, silver, gold, aluminum and other metal particles (powder) or inorganic antistatic agents such as metal fibers, and (β-lauroylamide Organic antistatic agents such as quaternary ammonium salts such as propionyl)trimethylammonium sulfate and sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds.

Examples of the flame retardant include bromine-based flame retardants, phosphorus-based flame retardants, chlorine-based flame retardants, triazine-based flame retardants, and other inorganic flame retardants such as salts of phosphoric acid and piperazine.

Examples of brominated flame retardants include brominated polystyrene, brominated polyacrylate, brominated polyphenylene ether, brominated bisphenol A epoxy resin, molecules of brominated bisphenol A epoxy resin Modified products in which part or all of the glycidyl groups at the chain ends are capped, polycarbonate oligomers synthesized from brominated bisphenol A, brominated diphthalimide compounds, brominated biphenyls Compounds such as ethers and brominated diphenylalkanes such as 1,2-bis(pentabromophenyl)ethane. Among them, brominated polystyrenes such as polytribromostyrene, poly(dibromophenylene ether), decabromodiphenyl ether, bis(tribromophenoxy)ethane, 1,2-bis( Brominated polystyrenes such as pentabromophenyl)ethane, ethylene-bis-(tetrabromophthalimide), tetrabromobisphenol A, brominated polycarbonate oligomers, and polytribromostyrene , 1,2-bis(pentabromophenyl)ethane, etc.

Examples of phosphorus-based flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, Tricresyl phosphate, tris(xylyl) phosphate, tris(isopropylphenyl) phosphate, tris(phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, Dicresyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di(isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl Acid Phosphate, 2-Methacryloyloxyethyl Acid Phosphate, Diphenyl-2-Acryloyloxyethyl Phosphate, Diphenyl-2-Methacryloyloxyethyl Phosphate Esters, melamine phosphate, di(melamine) phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methane phosphonate, diethyl phenyl phosphonate and other phosphates, m-phenyl Diphenol polyphenyl phosphate, 1,3-phenylene bis(2,6-dimethylphenyl phosphate), resorcinol poly(di-2,6-xylyl) phosphate, bis Condensed phosphoric acid esters such as aromatic condensed phosphoric acid esters such as phenol A polycresyl phosphate, bisphenol A polyphenyl phosphate, hydroquinone poly(2,6-xylyl) phosphate, and their condensates.

Examples of the chlorine-based flame retardant include pentachloropentacyclodecane, hexachlorobenzene, pentachlorotoluene, tetrachlorobisphenol A, polychlorostyrene, and the like. Examples of triazine-based flame retardants include melamine, methylguanamine, benzoguanamine, acryloylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methanol Oxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3 ,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine and 2 -Amino-4,6-dimercapto-1,3,5-triazine, etc.

Examples of salts of phosphoric acid and piperazine include piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate.

Examples of the inorganic flame retardant include antimony compounds such as antimony trioxide and antimony pentachloride, zinc borate, sodium borate, aluminum hydroxide, magnesium hydroxide, red phosphorus, and the like.

Examples of the fungicide include copper fungicides such as quinoline copper, organosulfur fungicides such as Zineb and Maneb, organochlorine fungicides such as captan and chlorothalonil, formazan, etc. Benzimidazole-based fungicides such as thiophanate, benlaide, carbendazim, and thiabendazole, dicarboximide-based fungicides such as iprodione, vinclozolin, and procymidone, and furamet Amide-based fungicides such as fludioxonil, phenylpyrrole-based fungicides such as fludioxonil, morpholine-based fungicides such as dimethomorph, azoxystrobin, kresoxim-methyl, ORIBRIGHT and other methoxyacrylate-based fungicides, azoxystrobin , cyprodinil, pyrimethanil and other anilinopyrimidine fungicides, triadimefon, flubuconazole and other ergosterol biosynthesis inhibitors, chloropicrin, PCNB and other soil fungicides, and fluazinam, ortho Phenylphenol (OPP), diphenyl, chlorodiphenyl, cresol, 1,2-bis(bromoacetoxy)ethane, cinnamaldehyde, phenyl acetate, allyl isothiocyanate, alpha- Methylacetophenone, thymol, perchlorocyclopentadiene, bromoacetic acid, 2,2-dibromo-3-cyanopropionamide, ethyl chloroacetate, butyl chloroacetate, methyl chloroacetate, 5 -Chloro-2-methylisothiazolin-3-one, glutaraldehyde, hinokitirol, etc.

Examples of the antimicrobial agent include inorganic powders obtained by supporting one or two or more antimicrobial metals of silver, zinc, and copper on an inorganic compound. Examples of the carrier include zeolite, apatite, zirconium phosphate, titanium oxide, silica gel, aluminum sulfate hydroxide, calcium phosphate, calcium silicate, and the like. In addition, it can also be mentioned: one or more than two kinds of silver, zinc, and copper are contained in the glass that uses one or more than two kinds of glasses of phosphoric acid, boric acid, and silicic acid as glass-forming components. Antibacterial glass powder obtained from non-toxic metals.

Examples of lubricants include fatty acids, fatty acid metal salts, oxo fatty acids, paraffin, low molecular weight polyolefins, fatty amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partially saponified esters, fatty acid lower alcohol esters, Fatty acid polyol ester, fatty acid polyethanol ester and modified silicone, etc.

Examples of fatty acids include oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montanic acid, and the like. fatty acids with 6 to 40 carbon atoms. Examples of fatty acid metal salts include sodium laurate, potassium laurate, magnesium laurate, calcium laurate, zinc laurate, barium laurate, sodium stearate, potassium stearate, magnesium stearate, stearic acid Calcium Behenate, Zinc Stearate, Barium Stearate, Sodium Behenate, Potassium Behenate, Magnesium Behenate, Calcium Behenate, Zinc Behenate, Barium Behenate, Sodium Montanate, and Calcium Montanate Alkali (earth) metal salts of fatty acids with 6 to 40 carbon atoms.

Examples of oxo fatty acids include 1,2-oxostearic acid and the like.

Examples of the paraffin include those having 18 or more carbon atoms, such as liquid paraffin, natural paraffin, microcrystalline wax, and petrolatum.

Examples of low molecular weight polyolefins include polyolefins having a molecular weight of 5000 or less such as polyethylene wax, maleic acid-modified polyethylene wax, oxidized polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Specific examples of fatty amides include fatty amides having 6 or more carbon atoms, such as oleamide, erucamide, and behenamide.

Examples of alkylene bis fatty acid amides include: methylene bis stearamide, ethylene bis stearamide, and N,N-bis(2-hydroxyethyl) stearamide, etc., having 6 or more carbon atoms. Alkyl bis fatty acid amides.

Examples of the aliphatic ketone include aliphatic ketones having 6 or more carbon atoms, such as higher aliphatic ketones. As fatty acid partial saponification ester, montanic acid partial saponification ester etc. are mentioned.

Examples of fatty acid lower alcohol esters include stearate, oleate, linoleate, linolenate, adipate, behenate, arachidonic acid ester, montanate, and isohard Fatty acid esters, etc.

Examples of fatty acid polyol esters include: glycerin tristearate, glycerin distearate, glycerin monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate , pentaerythritol dimyristate, pentaerythritol monostearate, pentaerythritol adipate stearate and sorbitan monobehenate, etc.

Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters, polytrimethylene glycol fatty acid esters, and polypropylene glycol fatty acid esters.

Examples of modified silicones include polyether-modified silicones, higher fatty acid alkoxy-modified silicones, higher fatty acid-containing silicones, higher fatty acid ester-modified silicones, and methacrylic modified silicones. Silicon and fluorine modified silicone, etc.

Examples of catalysts for curing include: (tert-butyl peroxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, etc.), azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), etc. Organic Peroxide, Tin Octanoate, Dibutyltin Di(2-Ethylhexanoate), Dioctyltin Di(2-Ethylhexanoate), Dioctyltin Diacetate, Dibutyltin Dilaurate, Dioctyltin dilaurate, dibutyltin oxide, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc caprylate, zinc naphthenate, zinc fatty acid, cobalt naphthenate, Calcium octoate, copper naphthenate, lead 2-ethylhexanoate octoate and tetra-n-butyl titanate and other metals and organic and inorganic acid salts and other organic metal derivatives, hydrochloric acid, nitric acid, sulfuric acid and other inorganic acids, para Sulfonic acid compounds such as toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalene disulfonic acid, amine neutralization products of sulfonic acid compounds, organic amines such as triethylamine, phosphoric acid, Pyrophosphoric acid, phosphoric acid monoester or phosphoric acid diester, etc. As phosphoric acid monoester, monooctyl phosphate, monopropyl phosphate, monolauryl phosphate, etc. are mentioned, for example. Examples of phosphoric acid diesters include dioctyl phosphate, dipropyl phosphate, and dilauryl phosphate. Further, phosphoric acid compounds such as mono(2-(meth)acryloyloxyethyl) acid phosphate, diazabicycloundecene-based catalysts, Lewis acids, acid anhydrides, and the like can be mentioned.

Examples of photopolymerization initiators include: hydroxybenzoyl compounds (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether etc.), benzoylformate compounds (methylbenzoylformate, etc.), thioxanthone compounds (isopropylthioxanthone, etc.), benzophenone compounds (benzophenone, etc.), phosphoric acid Ester compounds (1,3,5-trimethylbenzoyl diphenylphosphine oxide, etc.) and benzil dimethyl ketal, etc.

Furthermore, the long-lasting luminescent paint composition of the present invention can also be produced by blending the blue long-lasting phosphor of the present invention in a paint.

The long-lasting luminescent paint composition of the present invention can be used to coat the surface of other materials.

In addition, since the long-lasting luminous paint composition of the present invention containing the blue long-lasting phosphor of the present invention has high luminance, it can be painted with high visibility.

As the coating composition, a coating composition containing a film-forming resin can be used. The coating composition may also contain, if necessary: solvents, dispersants, fillers, thickeners, leveling agents, curing agents, crosslinking agents, pigments, defoamers, antioxidants, photostabilizers containing ultraviolet absorbers Additives for coatings such as additives, flame retardants, catalysts for curing, fungicides and antibacterial agents.

Various resins such as thermosetting resins, room temperature curable resins, ultraviolet curable resins, and radiation curable resins can be used as materials for the coating composition. Examples include: acrylic resins, alkyd resins, and polyurethane resins. , polyester resin, amino resin, etc., organic silicate, organic titanate, etc.

Examples of ink film forming materials include polyurethane resins, acrylic resins, polyamide resins, vinyl chloride-vinyl acetate resins, and chlorinated propylene resins.

Examples of solvents include: aliphatic hydrocarbons, aromatic hydrocarbons (C7-10, such as toluene, xylene, and ethylbenzene), esters or ether esters (C4-10, such as methoxybutyl acetate) , Ether (C4~10, such as tetrahydrofuran, monoethyl ether of EG, monobutyl ether of EG, monomethyl ether of PG and monoethyl ether of DEG), ketone (C3~10, such as methyl isobutyl ketone, di-n-butyl ketone), alcohol (C1-10, such as methanol, ethanol, n-propanol and isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol, 2-ethylhexyl alcohol) , amides (C3-6, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (C2-4, such as dimethylsulfoxide), and two or more of them Mixed solvents, water or the aforementioned mixed solvents, etc. As the dispersant, as long as it is a polymer dispersant, examples include formalin condensate of naphthalenesulfonate [alkali metal (Na and K, etc.) salt, ammonium salt, etc.], polystyrenesulfonate (same as above), polyacrylate (same as above), poly(2-4) carboxylic acid (maleic acid/glycerin/monoallyl ether copolymer, etc.) salt (same as above), carboxymethyl cellulose element (Mn2000～10000) and polyvinyl alcohol (Mn2000～100000), etc.

Examples of the low-molecular dispersant include the following.

(1) Polyoxyalkylene type

AO(C2~4) 1~30 mole addition of aliphatic alcohol (C4~30), [alkyl(C1~30)]phenol, aliphatic (C4~30) amine and aliphatic (C4~30) amide things.

As aliphatic alcohols, there are n-butanol, isobutanol, sec-butanol and tert-butanol, octanol, dodecanol, etc.; as (alkyl)phenols, there are phenol, methylphenol, nonylphenol, etc.; as As the aliphatic amine, there are laurylamine, methylstearylamine and the like; and as the aliphatic amide, there are stearamide and the like.

(2) Polyol type

Monoester compounds of C4-30 fatty acids (lauric acid, stearic acid, etc.) and polyhydric (2-6 or more) alcohols (such as GR, PE, sorbitol and sorbitan).

(3) Carboxylate type

Alkali metal (same as above) salt of C4-30 fatty acid (same as above).

(4) Sulfate type

C4-30 aliphatic alcohol (same as above) and AO (C2-4) 1-30 mole adduct of aliphatic alcohol alkali metal sulfate (same as above) salt, etc.

(5) Sulfonate type

[Alkyl(C1-30)]phenol (same as above) sulfonic acid alkali metal (same as above) salt.

(6) Phosphate type

C4-30 aliphatic alcohol (same as above) and aliphatic alcohol AO (C2-4) 1-30 mole adduct monophosphate or diphosphate salt [alkali metal (same as above) salt, Quaternary ammonium salts, etc.].

(7) Primary to tertiary amine salt type

C4-30 aliphatic amines [primary amines (laurylamine, etc.), secondary amines (dibutylamine, etc.) and tertiary amines (dimethylstearylamine, etc.)] hydrochloride, triethanolamine and C4-30 Inorganic acid (hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, etc.) salts of monoesters of fatty acids (the same as above).

(8) Quaternary ammonium salt type

Inorganic acid (same as above) salts of C4-30 quaternary ammonium (butyltrimethylammonium, diethyllaurylmethylammonium, dimethyldistearylammonium, etc.), etc.

Examples of the inorganic dispersant include alkali metal (same as above) salts of polyphosphoric acid, phosphoric acid-based dispersants (phosphoric acid, monoalkyl phosphate, dialkyl phosphate, etc.), and the like.

Examples of fillers include oxide-based inorganic substances represented by silica, alumina, zirconia, and mica, fine powders of non-oxide-based inorganic substances such as silicon carbide and silicon nitride, or acrylic resins, Organic compounds such as fluororesins. In addition, metal powders such as aluminum, zinc, and copper may be added depending on the application. Furthermore, specific examples of fillers include sols such as silica sol, zirconia sol, alumina sol, and titania sol; silica-based materials such as silica sand, quartz, homogeneous quartz salt, and diatomaceous earth; Synthetic amorphous silica; kaolinite, mica, talc, wollastonite, asbestos, calcium silicate, aluminum silicate and other silicates; glass powder, glass balls, hollow glass balls, glass flakes, bubble glass balls, etc. Glass body; boron nitride, boron carbide, aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, titanium nitride, titanium carbide and other non-oxide inorganic substances; calcium carbonate; zinc oxide, aluminum oxide, Metal oxides such as magnesium oxide, titanium oxide, and beryllium oxide; inorganic substances such as barium sulfate, molybdenum disulfide, tungsten disulfide, and carbon fluoride; metal powders such as aluminum, bronze, lead, stainless steel, and zinc; and carbon black, coke, Graphite, pyrolytic carbon, carbon bodies such as hollow carbon spheres, etc.

Examples of thickeners include montmorillonite-based clay minerals, bentonite containing these minerals, inorganic filler-based thickeners such as colloidal alumina, methylcellulose, carboxymethylcellulose, and hexylmethylcellulose. Cellulose-based thickeners such as cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose, polyurethane resin-based thickeners, polyethylene-based thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinyl benzyl ether copolymers , polyether dialkyl ester, polyether dialkyl ether, polyether epoxy modified polyether resin thickener, urethane modified polyether and other associative thickener, polyether Special polymer non-ionic thickeners such as polyol-based polyurethane resins, non-ionic surfactant-based thickeners, protein-based thickeners such as casein, sodium caseinate, and ammonium caseinate, and algae Acrylic thickeners such as sodium bicarbonate, etc.

As leveling agent, can enumerate: PEG type nonionic surfactant (nonylphenol EO1～40 mole adduct, stearic acid EO1～40 mole adduct, etc.), polyol type nonionic surfactant ( Sorbitan monopalmitate, sorbitan stearate monoester, sorbitan stearate triester, etc.), fluorine-containing surfactants (perfluoroalkyl EO1-50 mole adducts, perfluoroalkyl Fluoroalkyl carboxylates, perfluoroalkyl betaines, etc.), and modified silicone oils [polyether-modified silicone oils, (meth)acrylate-modified silicone oils, etc.], etc.

Regarding the curing agent, examples of polyol-based curing agents include: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, diphenyl Methyl methane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate, lysine diisocyanate, nurate body of polyisocyanate compound, Buret body, adducts of polyisocyanate compounds and polyols such as ethylene glycol, propylene glycol, and trimethylolpropane, monomers such as blocked polyisocyanate curing agents, or mixtures of two or more of them, and polyol additions thereof Isocyanates that can be cured at room temperature, such as products, their copolymers, block polymers, etc. Examples of the curing agent for epoxy resins include acid anhydrides, phenol resins, polyamide resins, amine adducts, urea resins, melamine resins, and isocyanates.

Examples of the crosslinking agent include melamine resins, urea resins, polyisocyanate compounds, blocked polyisocyanate compounds, epoxy compounds or resins, carboxyl group-containing compounds or resins, acid anhydrides, alkoxysilyl group-containing compounds or resins, and Hexamethoxymethylated melamine, N,N,N',N'-tetrahydroxymethylsuccinamide, tetramethoxymethylated urea, 2,4,6-tetrahydroxymethylated phenol, etc. base, and compounds such as methoxymethyl, or ethoxymethyl.

As pigments, in addition to the aforementioned pigments, vanadium compounds such as vanadium pentoxide, calcium vanadate, magnesium vanadate, and ammonium metavanadate; Magnesium dihydrogen, magnesium phosphate calcium eutectoid, magnesium phosphate cobalt eutectoid, magnesium phosphate nickel eutectoid, magnesium phosphite, magnesium phosphite calcium eutectoid, aluminum dihydrogen tripolyphosphate, three poly Magnesium phosphate, magnesium oxide-treated products of aluminum dihydrogen tripolyphosphate, magnesium oxide-treated products of zinc dihydrogen tripolyphosphate, and magnesium oxide-treated products of metal phosphate salts, and phosphoric acid such as silica-modified magnesium phosphate Phosphate-based antirust pigments such as silica-modified magnesium compounds; zinc-containing antirust pigments such as zinc phosphate, zinc-free antirust pigments such as magnesium-treated aluminum dihydrogen tripolyphosphate, and calcium-treated calcium phosphate; containing orthosilicon Calcium silicate such as calcium silicate or calcium metasilicate composite calcium silicate; metal ion-exchanged silica such as calcium ion-exchanged silica, magnesium ion-exchanged silica; rust paint etc.

Examples of antifoaming agents include silicone-based antifoaming agents such as silicone oil, dimethyl polysiloxane, organo-modified polysiloxane, and fluorine-modified polysiloxane, mineral oil-based antifoaming agents, Non-silicon and polymer-based antifoaming agents, antifoaming agents containing at least one selected from organically modified fluorine compounds and polyoxyalkylene compounds, and antifoaming agents containing aliphatic alcohols with 18 or more carbon atoms Wait.

Examples of antioxidants, light stabilizers including ultraviolet absorbers, flame retardants, catalysts for curing, bactericides, antibacterial agents, and the like include the aforementioned substances.

Description of drawings

Fig. 1 provides the excitation and emission spectrum of embodiment 1～3 sample for the present invention;

Fig. 2 provides the afterglow spectrogram of embodiment 1～3 sample for the present invention;

Fig. 3 provides the afterglow spectrogram of embodiment 4～6 sample for the present invention.

Detailed ways

The present invention will be described in further detail below in conjunction with accompanying drawings 1-3 and specific embodiments.

Example 1

A blue long afterglow phosphor, the chemical composition is Ca _0.96 AlO ₂ Cl: 0.02Eu ²⁺ , 0.02Tm ³⁺ .

Using high-purity CaCO ₃ , CaCl2, Al ₂ O ₃ , Eu ₂ O ₃ and Tm ₂ O ₃ as raw materials, according to the chemical composition Ca _0.96 AlO ₂ Cl: 0.02Eu ²⁺ , 0.02Tm ³⁺ in the ratio of each element , and accurately weigh each raw material; put the above-mentioned raw materials into an agate mortar and grind and mix them evenly, add absolute ethanol as the grinding medium according to the total mass ratio of 1:1 during grinding, and the grinding time is 0.5 hour; the slurry obtained above The mixture was placed in an oven, and was heat-preserved and dried at 80°C for 4 hours. After drying, the samples were taken out and ground and dispersed to obtain uniformly mixed raw materials; the uniformly mixed raw materials were put into a high-temperature tube furnace for pre-sintering. The sintering temperature is 1300°C, the sintering time is 4 hours, the heating rate is 7.5°C/min, and the sintering atmosphere is a hydrogen-nitrogen mixture of 5%H ₂ /95%N ₂ . After the sintering is completed, it is cooled to room temperature with the furnace to obtain a sintered body Perform ball milling on the obtained sintered body, and use an airflow classifier to classify the pulverized powder according to the particle size, so as to obtain the blue long-lasting phosphor.

Example 2

A blue long afterglow phosphor, the chemical composition is Ca _0.98 AlO ₂ Cl: 0.01Eu ²⁺ , 0.01Gd ³⁺ .

Using high-purity CaCO ₃ , CaCl2, Al ₂ O ₃ , Eu ₂ O ₃ and Gd ₂ O ₃ as raw materials, according to the chemical composition Ca _0.98 AlO ₂ Cl: 0.01Eu ²⁺ , 0.01Gd ³⁺ in the ratio of each element , and accurately weigh each raw material; put the above-mentioned raw materials into an agate mortar and grind and mix them evenly, add absolute ethanol as the grinding medium according to the total mass ratio of 1:1 during grinding, and the grinding time is 0.5 hour; the slurry obtained above The mixture was placed in an oven, and was heat-preserved and dried at 80°C for 4 hours. After drying, the samples were taken out and ground and dispersed to obtain uniformly mixed raw materials; the uniformly mixed raw materials were put into a high-temperature tube furnace for pre-sintering. The sintering temperature is 1300°C, the sintering time is 5 hours, the heating rate is 7.5°C/min, and the sintering atmosphere is a hydrogen-nitrogen mixture of 5%H ₂ /95%N ₂ . After the sintering is completed, it is cooled to room temperature with the furnace to obtain a sintered body Perform ball milling on the obtained sintered body, and use an airflow classifier to classify the pulverized powder according to the particle size, so as to obtain the blue long-lasting phosphor.

Example 3

A blue long-lasting phosphor, the chemical composition is Ca _0.94 AlO ₂ Cl: 0.04Eu ²⁺ , 0.02La ³⁺ .

Using high-purity CaCO ₃ , CaCl2, Al ₂ O ₃ , Eu ₂ O ₃ and La ₂ O ₃ as raw materials, according to the chemical composition Ca _0.94 AlO ₂ Cl: 0.04Eu ²⁺ , 0.02La ³⁺ in the ratio of each element , accurately weigh each raw material; put the above-mentioned raw materials into an agate mortar and grind and mix evenly, add absolute ethanol as the grinding medium according to the total mass ratio of 1:1 during grinding, and the grinding time is 1 hour; the slurry obtained above The mixture was placed in an oven, and was heat-preserved and dried at 80°C for 4 hours. After drying, the samples were taken out and ground and dispersed to obtain uniformly mixed raw materials; the uniformly mixed raw materials were put into a high-temperature tube furnace for pre-sintering. The sintering temperature is 1100°C, the sintering time is 6 hours, the heating rate is 7.5°C/min, and the sintering atmosphere is a hydrogen-nitrogen mixture of 5%H ₂ /95%N ₂ . After the sintering is completed, it is cooled to room temperature with the furnace to obtain a sintered body Perform ball milling on the obtained sintered body, and use an airflow classifier to classify the pulverized powder according to the particle size, so as to obtain the blue long-lasting phosphor.

Example 4

A blue long-lasting phosphor, the chemical composition is Ca _0.84 AlO ₂ Cl: 0.08Eu ²⁺ , 0.04Tm ³⁺ , 0.04Gd ³⁺ .

Using high-purity CaCO ₃ , CaCl2, Al ₂ O ₃ , Eu ₂ O ₃ , Tm ₂ O ₃ and Gd ₂ O ₃ as raw materials, according to the chemical composition Ca _0.84 AlO ₂ Cl: 0.08Eu ²⁺ , 0.04Tm ³⁺ , The ratio of each element in 0.04Gd ³⁺ , accurately weigh each raw material; put the above raw materials into an agate mortar and grind and mix evenly, add absolute ethanol as the grinding medium according to the total mass ratio of 1:1 during grinding, and the grinding time is 1 hour; put the slurry mixture obtained above in an oven, heat-preserve and dry at 80°C for 4 hours, take out the sample after drying, grind and disperse to obtain a uniformly mixed raw material; put the uniformly mixed raw material Put it into a high-temperature tube furnace for pre-sintering, the sintering temperature is 1100°C, the sintering time is 5 hours, the heating rate is 7.5°C/min, the sintering atmosphere is a hydrogen-nitrogen mixture of 5% _H2 /95% _N2 , and the sintering is completed Then cool down to room temperature with the furnace to obtain a sintered body; ball mill the obtained sintered body, and classify the pulverized powder according to the particle size with an airflow classifier to obtain the blue long-lasting phosphor.

Example 5

A blue long afterglow phosphor, the chemical composition is Ca _0.88 AlO ₂ Cl: 0.06Eu ²⁺ , 0.03Gd ³⁺ , 0.03La ³⁺ .

Using high-purity CaCO ₃ , CaCl2, Al ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ and La ₂ O ₃ as raw materials, according to the chemical composition Ca _0.88 AlO ₂ Cl: 0.06Eu ²⁺ , 0.03Gd ³⁺ , The ratio of each element in 0.03La3 ⁺ , accurately weigh each raw material; put the above-mentioned raw materials into an agate mortar and grind and mix evenly, add absolute ethanol as the grinding medium according to the total mass ratio of 1:1 during grinding, and the grinding time is 0.5 hours; put the slurry mixture obtained above in an oven, heat-preserve and dry at 80°C for 4 hours, take out the sample after drying, and grind and disperse to obtain uniformly mixed raw materials; put the uniformly mixed raw materials Put it into a high-temperature tube furnace for pre-sintering, the sintering temperature is 1200°C, the sintering time is 5 hours, the heating rate is 7.5°C/min, and the sintering atmosphere is a hydrogen-nitrogen mixture of 5% _H2 /95% _N2 , and the sintering is completed. Then cool down to room temperature with the furnace to obtain a sintered body; ball mill the obtained sintered body, and classify the pulverized powder according to the particle size with an airflow classifier to obtain the blue long-lasting phosphor.

Example 6

A blue long afterglow phosphor, the chemical composition is Ca _0.8 AlO ₂ Cl: 0.1Eu ²⁺ , 0.04Tm ³⁺ , 0.04Gd ³⁺ ,0.02La ³⁺ .

Using high-purity CaCO ₃ , CaCl2, Al ₂ O ₃ , Eu ₂ O ₃ , Tm ₂ O ₃ , Gd ₂ O ₃ and La ₂ O ₃ as raw materials, according to the chemical composition Ca _0.8 AlO ₂ Cl: 0.1Eu ²⁺ , 0.04Tm ³⁺ , 0.04Gd ³⁺ , 0.02La ³⁺ in the ratio of each element, accurately weigh each raw material; put the above raw materials into an agate mortar and mix them evenly, and add them according to the total mass ratio of 1:1 when grinding Anhydrous ethanol was used as the grinding medium, and the grinding time was 1 hour; the slurry mixture obtained above was placed in an oven, and dried at 80°C for 4 hours. After drying, the sample was taken out and ground and dispersed to obtain a uniform mixture. Raw materials: put the uniformly mixed raw materials into a high-temperature tube furnace for pre-sintering, the sintering temperature is 1200°C, the sintering time is 4 hours, the heating rate is 7.5°C/min, and the sintering atmosphere is 5%H ₂ /95% _N2 mixed gas of hydrogen and nitrogen, after the sintering is completed, cool down to room temperature with the furnace to obtain a sintered body; ball mill the obtained sintered body, and use an airflow classifier to classify the pulverized powder according to the particle size, that is, The blue long afterglow phosphor.

Fig. 1 provides the excitation and emission spectrum of embodiment 1～3 sample for the present invention, and the left curve in the figure is the excitation spectrum, and the monitoring wavelength is 448nm, and the right curve in the figure is the emission spectrum, and the excitation wavelength is 275nm, as can be seen from the figure , the sample can be effectively excited in the near-ultraviolet (200~350nm) region, the peak wavelength of the emission spectrum is in the blue region of 448nm, and the luminescent center is divalent Eu ²⁺ ions; Figure 2 and Figure 3 are the implementation The afterglow spectrograms of Examples 1-3 and Examples 4-6, as can be seen from the figure, the doping concentration of the activated ion Eu ²⁺ and the impurity level ions Tm ³⁺ , Gd ³⁺ and La ³⁺ has a great influence on the concentration of the sample. The initial fluorescence intensity, afterglow intensity and afterglow time are all greatly affected. By introducing one or more combinations of rare earth ions Tm ³⁺ , Gd ³⁺ and La ³⁺ to provide trap energy levels, the afterglow brightness can be effectively enhanced and the afterglow can be prolonged. time.

Since the 1990s, the luminescent mechanism of long-lasting luminescent materials represented by Eu ²⁺ -activated alkaline earth aluminates has been a research hotspot. Although the long-lasting luminescent mechanism is not fully understood, at least the following have been obtained: Consensus: (1) Doped Eu ²⁺ is the luminescent center; (2) Various defects in the crystal have an important impact on luminescence and afterglow; (3) The addition of co-doped trivalent rare earth ions RE ³⁺ produces More defect energy levels; (4) electrons and holes generated during excitation are captured by electron traps and hole traps respectively; (5) electrons or holes captured by traps are released at a suitable speed under thermal disturbance; (6) The recombination of electrons and holes leads to light emission. In the actual development process, due to the variety of long-lasting light-emitting materials, different materials have different light-emitting mechanisms, and the light-emitting mechanism of some materials is not yet clear. Therefore, it is necessary to seek suitable The matrix and active ions are crucial for the development of new long-lasting materials. In addition, since there are many preparation methods of long-lasting luminescent materials, and each has its own advantages and disadvantages, the optimal combination of preparation methods for various long-lasting luminescent materials will also play a key role in the popularization and application of long-lasting luminescent materials. .

Claims (4)

1. A kind of coating, it is characterized in that, this coating comprises coating conventional composition and blue long afterglow phosphor powder, blue long afterglow phosphor powder is evenly distributed in coating conventional composition, the add-on of blue long afterglow phosphor powder 1~30%; the chemical composition general formula of the blue long afterglow phosphor is Ca _1-xy AlO ₂ Cl: x Eu ²⁺ , y Re ³⁺ , wherein Re is one of Tm, Gd and La Or several combinations, the value ranges of x and y are: 0.01≤x≤0.1, 0.01≤y≤0.1. 2. A kind of coating according to claim 1, is characterized in that, the add-on of blue long-lasting phosphor powder is 5～10%. 3. A kind of coating according to claim 1, is characterized in that, coating resin system can be polyamide, chlorinated polypropylene, polyurethane or acrylic acid. 4. A kind of coating according to claim 1, is characterized in that, coating is oily coating also can be water-based coating.