CN108822606B - Coating material - Google Patents

Abstract

The invention belongs to the field of coatings. The coating comprises conventional coating components and blue long-afterglow fluorescent powder, wherein the blue long-afterglow fluorescent powder is uniformly distributed in the conventional coating components, and the addition amount of the blue long-afterglow fluorescent powder is 1-30%; the chemical composition general formula of the blue long afterglow phosphor is Ca_{1‑x‑ y}AlO₂Cl:xEu²⁺,yRe³⁺Wherein Re is one or a combination of more of Tm, Gd and La, and the value ranges of x and y are respectively as follows: x is more than or equal to 0.01 and less than or equal to 0.1, and y is more than or equal to 0.01 and less than or equal to 0.1. The luminescent center of the fluorescent powder is Eu²⁺Ions, by introduction of Tm³⁺，Gd³⁺And La³⁺The long afterglow effect can be effectively enhanced by the rare earth impurity ions. The paint provided by the invention has high afterglow brightness and long afterglow time, and can be used in the fields of building materials, household appliances, image storage and the like.

Description

Coating material

The application is a divisional application, and the application date of the original application is as follows: 2017-11-02, original application number: 2017110616282,

the invention name of the original application: a blue long afterglow phosphor and a preparation method thereof.

Technical Field

The invention belongs to the field of coatings.

Background

The long afterglow material is a material capable of emitting fluorescent afterglow within a relatively long time (more than several seconds to ten hours) after an external excitation source (ultraviolet-visible light, X ray, β ray and the like) stops, the long afterglow phenomenon is found in Chinese paintings thousands of years ago, and scientific description of the long afterglow phenomenon can be traced back to 17 th century at the earliestAt present, the long afterglow SrAl material₂O₄: Eu²⁺In which Dy is co-doped³⁺The afterglow intensity can be greatly enhanced. Meanwhile, Takasaki and the like also find that Co codoping in ZnS: Cu can greatly improve the afterglow strength. Since then, the research of the long afterglow materials enters a new stage. At present, the long afterglow material is widely applied to passive night marks and various warning and tracing devices.

At present, the research on the long-afterglow luminescent materials mainly focuses on blue-green luminescent materials, and research systems mainly comprise sulfide, aluminate, silicate and the like. Early research on sulfide system found that rare earth ion Dy³⁺And Tm³⁺The activated sulfide may emit blue light. The long afterglow phosphor of aluminate matrix system emits mostly in blue-green light region, and the preferable blue long afterglow phosphor is CaAl₂O₄: Eu²⁺, Nd³⁺The peak wavelength of the emission spectrum is 446nm, and the afterglow time can reach 1000 min. In addition, the long afterglow luminescent materials using silicate as matrix are related to 2MO, MgO, 2SiO₂Eu, Dy (M is an alkaline earth metal element) is the most widely studied, and the light emission range can be from blue-violet light to yellow-green light by controlling the host composition and the concentration of the dopant ions. Wherein, the material with better performance of the long afterglow material emitting blue light is Sr₂MgSi₂O₇: Eu²⁺, Dy^{3 +}Its main emission peak is at 469nm, its afterglow time can be over 10 hr, and its luminous performance is superior to that of CaAl₂O₄: Eu²⁺, Nd^{3 +}And Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺Has good chemical stability and thermal stability, and the raw material of the high-purity silicon dioxide is cheap and easy to obtain, so the high-purity silicon dioxide is always valued by people.

Disclosure of Invention

In order to overcome a series of problems of weak luminous intensity, short afterglow time and the like of the blue long afterglow material in the prior art, the invention provides the blue long afterglow fluorescent powder and the preparation method thereof.

In order to solve the defects of the prior art, the technical scheme adopted by the invention is as follows:

the chemical composition general formula of the blue long afterglow phosphor powder is Ca_1-x-yAlO₂Cl:xEu²⁺,yRe³⁺Wherein Re is one or a combination of more of Tm, Gd and La, and the value ranges of x and y are respectively as follows: x is more than or equal to 0.01 and less than or equal to 0.1, and y is more than or equal to 0.01 and less than or equal to 0.1. Preferably, the luminescent center of the phosphor is Eu²⁺Ions, by introduction of rare earth ions Tm³⁺、Gd³⁺And La³⁺One or a combination of several of the above provides a trap energy level, and effectively enhances the long-afterglow luminescence effect.

A preparation method of blue long afterglow fluorescent powder is characterized by comprising the following steps:

(1) preparing materials: as high purity CaCO₃、CaCl2、Al₂O₃、Eu₂O₃、Tm₂O₃、Gd₂O₃And La₂O₃As a raw material, according to the chemical composition formula Ca_1-x-yAlO₂Cl:xEu²⁺,yRe³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials;

(2) mixing materials: putting the raw materials into an agate mortar for grinding and uniformly mixing, adding absolute ethyl alcohol serving as a grinding medium according to the total mass ratio of 1:1 during grinding, and grinding for 0.5-1 hour;

(3) drying: placing the obtained slurry-like mixture in a drying oven, keeping the temperature and drying for 4 hours at the temperature of 80 ℃, taking out a sample after drying is finished, and grinding and dispersing to obtain uniformly mixed raw materials;

(4) and (3) sintering: putting the uniformly mixed raw materials into a high-temperature tube furnace for presintering, wherein the sintering temperature is 1000-1300 ℃, the sintering time is 4-6 hours, the heating rate is 7.5 ℃/min, and the sintering atmosphere is 5% H₂/95%N₂After sintering, cooling the mixed gas to room temperature along with the furnace to obtain a sintered body;

(5) selecting powder: and (4) performing ball milling and crushing on the sintered body obtained in the step (4), and classifying the crushed powder according to the particle size by using an airflow classifier to obtain the blue long-afterglow fluorescent powder.

Compared with the prior art, the invention has the beneficial effects that:

(1) the invention provides a novel blue long afterglow phosphor, the matrix composition of which is CaAlO₂Cl, by rare earth ion Eu²⁺Blue light emission is obtained by doping, by introducing rare earth ions Tm³⁺、Gd³⁺And La³⁺One or a plurality of combinations of the above provide trap energy level, effectively enhance the afterglow brightness and time of the fluorescent powder;

(2) the blue long afterglow fluorescent powder provided by the invention has the advantages of good chemical stability, high afterglow brightness, long afterglow time and the like.

The invention also discloses a blue long afterglow luminescent element, which is a substrate made of the blue long afterglow phosphor.

The invention also discloses a blue long afterglow luminescent element, which comprises a substrate and a long afterglow luminescent film attached to the substrate, wherein the long afterglow luminescent film is the blue long afterglow luminescent powder or the blue long afterglow luminescent powder sheet.

The invention also discloses a blue long afterglow luminescent element which comprises a substrate and a long afterglow luminescent film attached to the substrate, wherein the long afterglow luminescent film is blue long afterglow luminescent powder or a blue long afterglow luminescent powder sheet.

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

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

The preparation method of the blue long afterglow luminescent element comprises the following steps: a suspension of blue long persistent phosphor powder particles as described above is coated on a substrate as described above.

Although the light-emitting element satisfying the requirements of the present invention can be prepared by preparing the suspension from the suspension solvent of the blue long-afterglow phosphor powder particles as described above and then coating the suspension on the substrate, when the suspension further contains a high molecular substance, the sensitivity and accuracy of the finally prepared light-emitting element can be further improved.

The content of the blue long-afterglow phosphor powder particles may also vary within a wide range, and preferably the content of the blue long-afterglow phosphor powder particles is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the suspension.

Preferably, the high molecular substance is selected from one or more of PVA, EVA (ethylene vinyl acetate), PDMS, PU, PMMA (polymethyl methacrylate), PAM (polyacrylamide), PVP (polyvinyl pyrrolidone), starch, cellulose, vegetable gum, animal gum, carboxymethyl starch, starch acetate, hydroxymethyl cellulose, and carboxymethyl cellulose.

According to the invention, the content of the polymer substance can also vary within wide limits, preferably from 1 to 10 parts by weight, preferably from 3 to 8 parts by weight, based on 100 parts by weight of the suspension.

According to the present invention, the solvent may be various solvents conventionally used in the art, and preferably selected from one or more of water, methanol, ethanol, acetone, ethylene glycol, isopropyl alcohol, diethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, kosmol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, diacetone alcohol, tridecanol, tetradecanol, dioctyl phthalate, ethyl acetate, butyl acetate, cyclohexanone, xylene, dicyclohexyl, cyclohexane, n-butanol, methyl ethyl ketone, dimethyl phthalate, and sorbitol.

According to the present invention, the method for coating the suspension of the blue long-afterglow phosphor powder particles on the surface of the substrate can be selected conventionally in the art, for example, a coating method such as spray coating, spin coating, etc. can be adopted, and a printing technology can also be adopted. The invention preferably prints the suspension of blue long-afterglow phosphor powder particles on the surface of the substrate by using a printing technology, so that the sensitivity and the accuracy of the prepared sensor are further improved. Wherein the printing technique may be selected from one of dispensing, ink jet printing, water transfer printing, screen printing, and roll-to-roll printing. When the suspension of the blue long-afterglow phosphor powder particles is printed on the surface of a substrate by using a printing technology, the suspension is preferably prepared into ink by blending and stirring or blending and ultrasonically dispersing the suspension.

The invention also discloses a blue long-afterglow luminescent element, which comprises a high polymer material and the blue long-afterglow phosphor powder, wherein the blue long-afterglow phosphor powder is uniformly distributed in the high polymer material, and the addition amount of the blue long-afterglow phosphor powder is 1-90%; preferably 10 to 80%. The polymeric material may be selected from PDMS (polydimethylsiloxane), PET (polyethylene terephthalate), PS (polystyrene), PU (polyurethane), PI (polyimide), and PVA (polyvinyl alcohol) films. In order to improve the processing performance, a coupling agent, a lubricant, a plasticizer and the like can be added into the film material.

The invention also discloses ink which comprises conventional ink components and the blue long-afterglow fluorescent powder, wherein the blue long-afterglow fluorescent powder is uniformly distributed in the conventional ink components, and the addition amount of the blue long-afterglow fluorescent powder is 1-30%; preferably 5 to 10%. The ink resin system may be polyamide, chlorinated polypropylene, polyurethane or acrylic. The ink may be either an oil-based ink or a water-based ink.

The invention also discloses a coating, which comprises conventional coating components and the blue long-afterglow fluorescent powder, wherein the blue long-afterglow fluorescent powder is uniformly distributed in the conventional coating components, and the addition amount of the blue long-afterglow fluorescent powder is 1-30%; preferably 5 to 10%. The coating resin system may be polyamide, chlorinated polypropylene, polyurethane or acrylic. The paint may be either an oil paint or a water paint.

The blue long afterglow phosphor is incorporated into the surface of an exterior material such as ordinary paper, synthetic paper, polymer materials such as epoxy resin, polyethylene terephthalate, polyester, polypropylene, and polyvinyl chloride, natural rubber or synthetic rubber, glass, ceramics, metal, wood, artificial fiber or natural fiber, concrete, or a combination thereof, or a processed product thereof, or the blue long afterglow phosphor is incorporated therein.

The blue long afterglow light emitting element of the present invention can be used as illumination and for safe display. For example, the following are: lighting devices such as a vibration lamp and a wind power lamp; emergency, abnormal notification, emergency equipment, hazard display, emergency light, emergency sign, sign for life saving tool, signboard, display device; safety fences, tension ropes hung around factory buildings, animal guard rails; a step tread, a handrail, and a destination line body provided in a state of being half-buried in a road or the like; health equipment, walking aids (walking sticks for walking aids, light-emitting notification antennas, etc.); earrings, necklaces, and other jewelry; a pole for supporting a flag, a road-cutting rod of a road-cutting machine for a railway or the like, an exterior or interior member of a bicycle, an automobile, an electric car, a ship, an airplane or the like, a fishing tool (e.g., a lure, a fishing rod, a fishing net, etc.; a luminescent fiber structure, a luminescent fishing tool, a fishing line, a fishing net, etc.), a float (e.g., a float, a buoy); position display of pets such as humans, dogs, cats, and livestock such as cattle, pigs, sheep, and chickens; fans (blades of wind power generation, fan fans, etc.), clothing (shoes, sportswear, artificial lighting cloth, artificial lighting filaments, artificial lighting fibers, etc.); packages (boxes, holders, devices, envelopes, cardboard, outer skin packages, external coatings), medical articles (breathing aids, devices for experimental research), robots (artificial luminous hair structures, artificial luminous skin, artificial luminous body), and the like. Examples of applications in which the blue long-afterglow phosphor is contained in a coating composition, an ink composition, an adhesive, and a surface coating agent include: post products such as pressure-bonded postcard sheets containing a blue long afterglow phosphor in an adhesive used in financial organizations, public organizations, credit card companies, distribution industries, and the like; furniture such as chairs and beds; building materials such as flooring, tiles, wall materials, prefabricated plate materials, paving materials, wood, steel, concrete, and the like; an automatic navigation system device mounted on a vehicle; an operation device for operating an audio device, an air conditioner, and the like; input devices such as home electric appliances, portable devices, and electronic computers; digital cameras, CCD cameras, film, photo, image storage means, and the like.

Since a new appearance can be created by emitting light from the blue long afterglow phosphor, the development of the phosphor into amusement goods such as toys and sports goods and living goods is also considered. Examples thereof include: dynamic toys, kites, carp-shaped banners and other wind banner, swings, fast scooters, hobbyhorses, arches and the like; a non-power type light emitting device (wind bell, etc.) that generates sound and light simultaneously by wind force. Luminescent balls (golf balls, baseball balls, table tennis balls, billiards balls, etc.), windmill with luminescent mechanism; a balloon; the sheet structure is paper, coiled flute, folded paper, paper balloon, folding fan, congratulation plate and picture book; sports goods (pole for pole jump, fencing, arrow and other long-sized objects); pressure sensitive sealing element for confirming golf club score, circuit tester for tennis court, dynamic decorative body, dynamic carving and dynamic memorial; a dynamic display device; a light-emitting decoration device; acoustic devices such as speakers, musical instruments (stringed instruments such as violins and guitars, percussion instruments such as xylophones and drums, wind instruments such as trumpets and flute, diaphragms such as glass), tuning forks, and the like; entertainment goods such as event goods; aquatic plants and containers such as ornamental tanks for aquariums; a light emitting watch, a light emitting sand timer or a sand timer type light emitting device; a light-emitting type simulated candle device; an artificial plant capable of emitting light; an artificial eye; cosmetic compositions containing an adhesive polymer, printed matter and securities which can be visually recognized as counterfeit, printing inks containing long afterglow luminescent particles, bills, checks, stocks, bonds, various securities, commodity tickets, book tickets, tickets for transportation organizations, tickets for toll facilities, admission tickets for projects, lottery tickets, winning tickets for public sports competitions, banknotes, identification cards, tickets, passes, and the like, passports, printed matter for writing organic cipher texts, sealing seals, and the like.

The long-afterglow phosphor-photocatalyst composite obtained by activating the photocatalyst attached to the surface of the blue long-afterglow phosphor by the light emission of the long-afterglow phosphor can be used for: antibacterial, bactericidal, treatment of non-human animals, decontamination of dirt from antibacterial articles such as handrails and grips of vehicles, and decontamination by flow energy of fluid on the inner wall surface of piping or the like located in a dark place. The long afterglow luminescent material can also promote crosslinking by activating a photocrosslinking agent in the polymer resin by luminescence.

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

The long-lasting phosphor of the present invention can also be formed by further adding another inorganic material or organic material to the resin composition of the present invention to form a composite material.

For example, when the resin is an epoxy resin, an acrylic resin, or the like, 1 to 200 parts by mass of the blue long-afterglow phosphor is blended with 100 parts by mass of the resin, and when the resin is a polyethylene resin, a soft vinyl chloride resin, or the like, 30 to 300 parts by mass of the blue long-afterglow phosphor is blended with 100 parts by mass of the resin. The compound can be used to prepare 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.

When a long-afterglow light-emitting body is formed from the resin composition, for example, when a sheet-like long-afterglow light-emitting body is obtained, for example, 50 to 200 parts by mass of the above-mentioned blue long-afterglow phosphor, 3 to 5 parts by mass of a calcium-zinc stabilizer, and 30 to 100 parts by mass of dioctyl phthalate as a plasticizer are blended with 100 parts by mass of a polyvinyl chloride resin, and kneaded at 150 to 200 ℃ by means of a two-roll mill, whereby a flexible sheet-like long-afterglow light-emitting body can be obtained.

When a long-afterglow light-emitting body in the form of a film is obtained, for example, a long-afterglow light-emitting body in the form of a film can be obtained by blending 20 to 50 parts by mass of the blue long-afterglow phosphor with 100 parts by mass of a polyethylene terephthalate resin, kneading the resulting mixture at 250 to 300 ℃ using a twin-screw extruder or an inflation machine, and molding the kneaded mixture.

When a long-afterglow luminescent material having another shape is obtained, for example, a long-afterglow luminescent material in the form of a band, a plate, a rod or a pellet can be obtained by blending 5 to 100 parts by mass of a blue long-afterglow phosphor with 100 parts by mass of a polypropylene resin, kneading the resulting mixture at 170 to 200 ℃ in a twin-screw extruder, and molding the kneaded mixture. The long-afterglow phosphor in a three-dimensional shape can be obtained by processing and molding the long-afterglow phosphor in a pellet form at 170 to 200 ℃ using an injection molding machine.

Examples of the thermoplastic resin include styrene polymers and copolymers such AS low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene and the like, polypropylene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, acrylonitrile-butadiene-styrene copolymer (ABS resin) and the like, polyamides such AS 6-nylon, 66-nylon, 12-nylon and the like, polyamideimide, polyimide, polyetherimide, acrylic resins such AS polyurethane, polymethyl methacrylate and the like, polyvinyl acetate, ethylene-vinyl acetate copolymers, polyvinylidene fluoride, fluorine resins such AS polytetrafluoroethylene and the like, fluorine resins such AS alkenyl aromatic resins, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyesters such AS polylactic acid and the like, polycarbonates such AS bisphenol A polycarbonate and the like, polyacetals, polyvinyl pentenes, polymethyl cellulose, polyvinyl alcohol, polyvinyl acetate, polyacrylic acid such AS polyacrylonitrile and the like, styrene-acrylonitrile copolymers (vinyl ester resins), polyphenylene ether (PPE), polyphenylene sulfide, polysulfone, polyether sulfone, copolymers of ethylene-propylene-1-ethylene-vinyl acetate copolymers, ethylene-propylene-ethylene-vinyl acetate copolymers (1-propylene-ethylene-vinyl acetate copolymers) and the like, copolymers of other acrylic monomers such AS ethylene-vinyl fluoride, polyphenylene ether-acrylonitrile copolymers, polyphenylene ether-acrylonitrile, polyphenylene ether-1-ethylene-propylene-vinyl acetate copolymers, polyphenylene ether-ethylene-1-propylene-ethylene-1-propylene copolymers, polyphenylene ether-propylene-ethylene-1-propylene copolymers and the like.

The thermoplastic resin may be used alone or in combination of 2 or more. When the thermoplastic resin is a copolymer, the thermoplastic resin may be a copolymer in any form such as a random copolymer or a block copolymer. Examples of the thermosetting resin include: phenol resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, epoxy resins, silicone resins, alkyd resins, polyimides, polyaminobismaleimides, casein resins, furan resins, polyurethane resins, and the like. Further, there may be mentioned: resins cured by ultraviolet rays or radiation rays.

Further, there may be mentioned: rubber-based materials such as natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene-diene rubber, butyl rubber, chloroprene rubber, acrylonitrile butadiene rubber, and silicone rubber.

In addition, a pigment, a dye, a lubricant, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a flame retardant, a bactericide, an antibacterial agent, a curing catalyst, a photopolymerization initiator, and the like may be mixed with the blue long afterglow phosphor of the present invention and molded into any shape such as a rod, a plate, a film, a fiber, a film, a needle, a sphere, a foil, a granule, a sand, a flake, a sheet, a liquid, a gel, a sol, a suspension, an aggregate, a capsule, and the like.

Examples of the pigment include inorganic pigments and organic pigments.

Examples of the inorganic pigment include: titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, carmine (red iron (III) oxide), cadmium red, ultramarine, chromium oxide green, cobalt green, ochre color, titanium black, synthetic iron black, carbon black, mica, alumina covered with titanium oxide, iron oxide, mica covered with titanium oxide, iron oxide, glass flake, holographic pigment, and the like. In addition, examples of the metal powder pigment include: aluminum powder, copper powder, stainless steel powder, metal colloid, transparent pearl mica having an interference action, colored mica, interference alumina, interference silica (interference glass), and the like.

Examples of the organic pigment include: azo pigments (monoazo yellow, condensed azo yellow, azomethine yellow, etc.), yellow pigments such as yellow iron oxide, titanium yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow, etc.; orange pigments such as permanent orange; red pigments such AS red iron oxide, naphthol AS-based azo reds, anthanthrone, anthraquinone reds, pyrene reddish brown, quinacridone reds, diketopyrrolopyrrole reds, permanent reds, and the like; violet pigments such as cobalt violet, quinacridone violet, and dioxazine violet; blue pigments such as cobalt blue, phthalocyanine-based pigments (such as phthalocyanine blue), and anthracene blue; green pigments such as phthalocyanine green, and organic dyes such as azo-based disperse dyes and anthraquinone-based disperse dyes.

Examples of the dye include: azo dyes, anthraquinone dyes, indigo dyes, sulfur dyes, triphenylmethane dyes, pyrazolone dyes, stilbene dyes, diphenylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, quinonimine dyes (oxazine dyes, thiazine dyes), thiazole dyes, alkyne dyes, nitro dyes, nitroso dyes, and the like.

Examples of the antioxidant include: hindered phenol compounds, phosphite compounds, phosphonite compounds, thioether compounds, and the like.

Examples of the hindered phenol-based compound include α -tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, N-octadecyl- β - (4 '-hydroxy-3', 5 '-di-tert-butylphenyl) 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, diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, 2 '-methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 4 '-methylenebis (2, 6-di-tert-butylphenol), 2' -methylenebis (4-methyl-6-cyclohexylphenol), 2 '-dimethylenebis (6- α -methyl-benzyl-p-cresol) 2, 2' -ethylylbis (4, 6-di-tert-butylphenol), 2 '-ethylylbis-bis (3, 5-di-tert-butylphenyl) propionate, 3' -butylthiodipropyl) isocyanurate, 3-butyltris (3, 5-tert-butylphenyl) isocyanurate, 3-butyltris (3, 5-butylthiodipropylphenylmethyl-butyl-6-octylpropionyl) bis (3, 5-tert-butyl-5-butyloxyphenyl) isocyanurate, 3-butyltris [ 4-5-butylbis (3-tert-butyl-5-butyl-methyl) phenol), tris (3-5-butyl-5-butyl-tert-5-octylphenol), tris (3-6-octylamino) benzene-6-butyl-6-tert-butyl-6-butyl-6-butyl-6-tert-butyl-6-tert-butyl-6-butyl) phenol), tris (3-butyl-6-butyl-6-tert-butyl-6-butyl) phenol), tris (3, 3-6-butyl-6-4-butyl-tert-butyl-6-butyl-methyl) phenol) benzene), tris (3-6-tert-butyl-6-tert-butyl-6-tert-butyl-4-methyl) phenol) benzene-butyl-6-4-butyl-6-butyl) phenol) benzene), tris (3, 3-butyl-4-butyl-4-butyl-4-6-4-butyl-4-butyl-4-5) benzene-4-butyl-4-butyl-5) benzene), tris (3-4-butyl-4-butyl-5) phenol), tris (3, 3-5) benzene-.

Examples of the phosphite-based compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecylmonophenyl phosphite, dioctylmonophenyl phosphite, diisopropyl monophenyl phosphite, monobutyldiphenyl phosphite, monodecyl diphenyl phosphite, monooctyldiphenyl phosphite, tris (diethylphenyl) phosphite, tris (diisopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2, 6-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, Bis (2, 6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2, 4-bis (1-methyl-1-phenylethyl) phenyl } pentaerythritol diphosphite, phenyl bisphenol a pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like. Examples of the phosphite ester compound include phosphite ester compounds having a cyclic structure obtained by reacting a diphenol with the phosphite ester compound.

Examples of the phosphonite-based compound include: tetrakis (2, 4-di-tert-butylphenyl) -4,4 '-biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -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 phosphonite, bis (2, 4-di-tert-butylphenyl) -3-phenyl phosphonite, bis (2, 4-di-tert-butylphenyl) -3, Bis (2, 6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2, 6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2, 6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite and the like.

Examples of the thioether-based compound include: dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), and the like. Examples of the light stabilizer containing an ultraviolet absorber include: benzophenone-based compounds, benzotriazole-based compounds, aromatic benzoate-based compounds, oxalanilide-based compounds, cyanoacrylate-based compounds, hindered amine-based compounds, and the like.

Examples of the benzophenone-based compound include: benzophenone, 2, 4-dihydroxybenzophenone, 2 ', 4,4 ' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone, 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, 2,4 ' -dihydroxybenzophenone, 2 ' -dihydroxy-4-octyloxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2 ' -hydroxy-4-methoxy-5-sulfonylbenzophenone, a, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-methoxy-2' -carboxybenzophenone, and 2-hydroxy-4- (2-hydroxy-3-methyl-acryloyloxy-isopropoxy) benzophenone, and the like.

Examples of the benzotriazole-based compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3, 5-di-tert-pentyl-2-hydroxyphenyl) benzotriazole, 2- (3 ', 5' -di-tert-butyl-4 '-methyl-2' -hydroxyphenyl) benzotriazole, 2- (3, 5-di-tert-pentyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2 '-hydroxy-3', 5 '-bis (α -dimethylbenzyl) phenyl ] benzotriazole, 2- [ 2' -hydroxy-3 ', 5' -bis (α -dimethylbenzyl) phenyl ] -2H-benzotriazole, and 2- (4 '-octyloxy-2' -hydroxyphenyl) benzotriazole.

Examples of the aromatic benzoate-based compound include: and alkylphenyl salicylates such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate.

Examples of the oxalanilide compound include: 2-ethoxy-2 ' -ethyloxanilide, 2-ethoxy-5-tert-butyl-2 ' -ethyloxanilide, 2-ethoxy-3 ' -dodecyloxanilide, and the like.

Examples of the cyanoacrylate-based compound include: ethyl-2-cyano-3, 3 '-diphenylacrylate, 2-ethylhexyl-cyano-3, 3' -diphenylacrylate, and the like.

Examples of the hindered amine-based compound include 4-acetoxy-2, 2,6, 6-tetramethylpiperidine, 4-stearoyloxy-2, 2,6, 6-tetramethylpiperidine, 4-acryloyloxy-2, 2,6, 6-tetramethylpiperidine, 4- (phenylacetyloxy) -2,2,6, 6-tetramethylpiperidine, 4-benzoyloxy-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-tetramethylpiperidine, 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, 2,2,6, 6-tetramethylpiperidine, 4- (tetramethylcarbamoyloxy) -2,6, 6-tetramethylpiperidine, 2, 6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,6, 6-tetramethylpiperidine, 2, 6-tetramethylpiperidine, 4- (3-tetramethylpiperidine, 6-bis (bis-tetramethyloxa-tetramethylpiperidine) malonate, 3-bis (bis-tetramethylpiperidine), bis (2, 6-tetramethylpiperidine), bis (bis-tetramethyloxa-tetramethylpropionyl) -2, 6-tetramethylpiperidine), bis (4-tetramethyloxa-tetramethylpiperidine), bis (4-tetramethylpiperidine), bis (2-tetramethylphenyl) -2, 6-tetramethylpiperidine), bis (4-tetramethylphenyl) -2, 6-tetramethylpiperidine), bis (4-tetramethylpiperidine), bis (3-tetramethylphenyl) -2, 6-bis (3-tetramethylpiperidine), bis (3-tetramethylphenyl) -2, 6-tetramethylpiperidine), bis (3-tetramethylphenyl) -2, 6-tetramethylphenyl) malonate, 6-tetramethylpiperidine), bis (3-bis (3-bis-tetramethylphenyl) -2, 6-tetramethyl.

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

Examples of the flame retardant include: bromine flame retardants, phosphorus flame retardants, chlorine flame retardants, triazine flame retardants, and salts of phosphoric acid and piperazine.

Examples of the bromine-based flame retardant include: brominated polystyrene, brominated polyacrylate, brominated polyphenylene oxide, brominated bisphenol a epoxy resin, a modified product in which a part or all of glycidyl groups at molecular chain terminals of brominated bisphenol a epoxy resin are capped, a polycarbonate oligomer synthesized from brominated bisphenol a as a raw material, a brominated diphenylene compound such as brominated bis-phthalimide compound, brominated diphenyl ether, and 1, 2-bis (pentabromophenyl) ethane, and the like. Among them, there are: brominated polystyrene such as polytribromostyrene, poly (dibromophenylene ether), decabromodiphenyl ether, bis (tribromophenoxy) ethane, 1, 2-bis (pentabromophenyl) ethane, ethylene-bis- (tetrabromophthalimide), tetrabromobisphenol A, brominated polycarbonate oligomer, brominated polystyrene such as polytribromostyrene, and 1, 2-bis (pentabromophenyl) ethane.

Examples of the phosphorus-based flame retardant include: trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, tri (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, tolyldiphenyl phosphate, ditolyl 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, melamine phosphate, di (melamine) phosphate, melamine pyrophosphate, methyl ethyl phosphate, methyl propyl phosphate, And condensed phosphates such as triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate and the like, resorcinol polyphenyl phosphate, 1, 3-phenylene bis (2, 6-dimethylphenyl phosphate), resorcinol poly (di-2, 6-xylyl) phosphate, bisphenol a polytoluene phosphate, bisphenol a polyphenyl phosphate, hydroquinone poly (2, 6-xylyl) phosphate, and aromatic condensed phosphates such as condensates thereof.

Examples of the chlorine-based flame retardant include: pentachloropentadecane, hexachlorobenzene, pentachlorotoluene, tetrachlorobisphenol A, polychlorostyrene, and the like. Examples of triazine flame retardants include: melamine, methylguanamine, benzoguanamine, acrylylylylguanamine, 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-methoxy-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.

Examples of the salt of phosphoric acid and piperazine include: piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate, and the like.

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 bactericide include copper bactericides such as oxine-copper, organosulfur bactericides such as Zineb (Zineb) and Maneb (Maneb), organochlorine bactericides such as captan and chlorothalonil, thiophanate-methyl, bennett, carbendazim and benzimidazole-based bactericides such as thiabendazole, dicarboximide bactericides such as iprodione, vinclozolin and procymidone, amide bactericides such as furametpyr, phenylpyrrole bactericides such as fludioxonil, morpholine bactericides such as dimethomorph, strobilurin-based bactericides such as oribrit, fenamidone, cyprodinil and pyrimethanil, anilinopyrimidine-based bactericides such as triazolone and fluconazole biosynthesis inhibitors, nitrotrichloromethane, PCNB, soil bactericides such as fluazinam, Orthophenylphenol (OPP), diphenyl, chlorodiphenyl, cresol, 1, 2-bis (bromoacetoxy) ethane, cinnamic aldehyde, phenyl acetate, allyl acetate, α, methyl ethyl methyl-propionate, 2-bromoxyacetate, 2-ethyl-bromoxyacetate, bromoxymethyl-5-ethyl acetate, bromoxymethyl-ethyl acetate, and the like.

Examples of the antibacterial agent include: an inorganic powder obtained by supporting an inorganic compound with one or more than 2 antibacterial metals of silver, zinc and copper. Examples of the carrier include: zeolites, apatites, zirconium phosphates, titanium oxides, silica gels, aluminum sulfate hydroxides, calcium phosphates, calcium silicates, and the like. Further, there can be mentioned: an antibacterial glass powder obtained by adding one or more than 2 antibacterial metals of silver, zinc and copper to glass which is composed of one or more than 2 kinds of phosphoric, boric and silicic acid glasses.

Examples of the lubricant include: fatty acids, fatty acid metal salts, oxofatty acids, paraffins, low molecular weight polyolefins, fatty amides, alkylenebis fatty amides, fatty ketones, partially saponified esters of fatty acids, fatty acid lower alcohol esters, fatty acid polyol esters, fatty acid polyethylene esters, modified silicones, and the like.

Examples of the fatty acid include: and fatty acids having 6 to 40 carbon atoms such as oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montanic acid, and mixtures thereof. Examples of the fatty acid metal salt include: alkali (earth) metal salts of fatty acids having 6 to 40 carbon atoms such as sodium laurate, potassium laurate, magnesium laurate, calcium laurate, zinc laurate, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, sodium behenate, potassium behenate, magnesium behenate, calcium behenate, zinc behenate, barium behenate, sodium montanate, and calcium montanate.

Examples of the oxofatty acid include: 1, 2-oxostearic acid, and the like.

Examples of the paraffin wax include: liquid paraffin, natural paraffin, microcrystalline wax and vaseline with carbon number of more than 18.

Examples of the low-molecular-weight polyolefin include: polyolefin 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 the fatty amide include: fatty amides having 6 or more carbon atoms such as oleamide, erucamide, and behenamide.

Examples of the alkylene bis-fatty amide include: alkylene bis fatty amides having 6 or more carbon atoms such as methylene bis stearamide, ethylene bis stearamide and N, N-bis (2-hydroxyethyl) stearamide.

Examples of the aliphatic ketone include: aliphatic ketones having 6 or more carbon atoms such as higher aliphatic ketones. Examples of the partially saponified fatty acid ester include: partially saponified montanic acid ester, and the like.

Examples of the fatty acid lower alcohol ester include: stearate, oleate, linoleate, linolenate, adipate, behenate, arachidonate, montanate, isostearate and the like.

As the fatty acid polyol ester, there may be mentioned: glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol monostearate, pentaerythritol adipate stearate, sorbitan monobehenate, and the like.

Examples of the fatty acid polyglycol ester include: polyethylene glycol fatty acid esters, polytrimethylene glycol fatty acid esters, polypropylene glycol fatty acid esters, and the like.

Examples of the modified silicone include: polyether-modified silicone, higher fatty acid alkoxy-modified silicone, silicone containing higher fatty acid, higher fatty acid ester-modified silicone, methacrylic acid-modified silicone, fluorine-modified silicone, and the like.

Examples of the curing catalyst include: organic peroxides such as t-butyl peroxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, tin octylate, dibutyltin bis (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, dioctyltin oxide, dibutyltin fatty acid salts, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, zinc fatty acid salts, cobalt naphthenate, calcium octylate, copper naphthenate, lead 2-ethylhexanoate, lead octylate, and tetra-n-butyltitanate, and organic metal derivatives such as salts of metals with organic and inorganic acids, such as hydrochloric acid, nitric acid, sulfuric acid, and other inorganic acids, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and other acids, and salts of organic and inorganic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and other salts, Sulfonic acid compounds such as dinonylnaphthalene disulfonic acid, amine-neutralized products of sulfonic acid compounds, organic amines such as triethylamine, phosphoric acid, pyrophosphoric acid, phosphoric monoesters or phosphoric diesters, and the like. Examples of the phosphoric monoester include: mono octyl phosphate, mono propyl phosphate, mono lauryl phosphate, and the like. Examples of the phosphoric acid diester include: dioctyl phosphate, dipropyl phosphate, dilauryl phosphate, and the like. Further, there may be mentioned: phosphoric acid compounds such as mono (2- (meth) acryloyloxyethyl) acid phosphate, diazabicycloundecene-based catalysts, lewis acids, acid anhydrides, and the like.

Examples of the photopolymerization initiator include: hydroxybenzoyl compounds (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether, etc.), benzoyl formate compounds (methyl benzoyl formate, etc.), thioxanthone compounds (isopropyl thioxanthone, etc.), benzophenone compounds (benzophenone, etc.), phosphate ester compounds (1,3, 5-trimethylbenzoyldiphenylphosphine oxide, etc.), benzil dimethyl ketal, and the like.

Further, the long-afterglow luminescent coating composition of the present invention can be produced by blending the blue long-afterglow phosphor of the present invention into a coating material.

The long afterglow luminescent coating composition of the present invention can be used for coating the surface of other materials.

Further, the long-afterglow luminescent coating composition of the present invention containing the blue long-afterglow phosphor of the present invention has high luminescent brightness, and thus can be coated with high visibility.

As the coating composition, a coating composition containing a film-forming resin can be used. The coating composition may contain, as necessary: a solvent, a dispersant, a filler, a thickener, a leveling agent, a curing agent, a crosslinking agent, a pigment, an antifoaming agent, an antioxidant, a light stabilizer including an ultraviolet absorber, a flame retardant, a curing catalyst, a bactericide, an antibacterial agent, and other additives for coating materials.

As the material used in the coating composition, various resins such as a thermosetting resin, a room temperature curable resin, an ultraviolet curable resin, and a radiation curable resin can be used, and examples thereof include: acrylic resins, alkyd resins, polyurethane resins, polyester resins, amino resins and the like, organosilicates, organotitanates and the like.

Examples of the ink film forming material include: polyurethane resins, acrylic resins, polyamide resins, vinyl chloride-vinyl acetate resins, chlorinated acrylic resins, and the like.

Examples of the solvent include: aliphatic hydrocarbons, aromatic hydrocarbons (C7-10, such as toluene, xylene, and ethylbenzene), esters or ether esters (C4-10, such as methoxybutylacetate), ethers (C4-10, such as tetrahydrofuran, monoethyl ether of EG, monobutyl ether of EG, monomethyl ether of PG, and monoethyl ether of DEG), ketones (C3-10, such as methyl isobutyl ketone, di-N-butyl ketone), alcohols (C1-10, such as methanol, ethanol, N-propanol, and isopropanol, N-butanol, isobutanol, sec-butanol, and tert-butanol, and 2-ethylhexyl alcohol), amides (C3-6, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone), sulfoxides (C2-4, such as dimethyl sulfoxide), and mixed solvents of 2 or more thereof, water, or the mixed solvents thereof. The dispersant may be a polymer dispersant, and examples thereof include: formalin condensates of naphthalenesulfonates [ alkali metal (Na, K, etc.) salts, ammonium salts, etc. ], polystyrene sulfonates (the same as those described above), polyacrylates (the same as those described above), salts of poly (2-4) carboxylic acids (maleic acid/glycerin/monoallyl ether copolymers, etc.) (the same as those described above), carboxymethylcellulose (Mn 2000-10000), polyvinyl alcohol (Mn 2000-100000), and the like.

Examples of the low-molecular-weight dispersant include the following.

(1) Polyoxyalkylene type

1 to 30 mol adduct of aliphatic alcohol (C4 to 30), alkyl (C1 to 30) phenol, aliphatic (C4 to 30) amine and aliphatic (C4 to 30) amide AO (C2 to 4).

As the aliphatic alcohol, there are n-butanol, isobutanol, sec-butanol, tert-butanol, octanol, dodecanol, etc.; as the (alkyl) phenol, there are phenol, methylphenol, nonylphenol and the like; as the aliphatic amine, lauryl amine, methyl stearyl amine, and the like; and as the aliphatic amide, stearamide and the like are mentioned.

(2) Polyhydric alcohol type

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

(3) Carboxylate salt form

An alkali metal salt (same as above) of a fatty acid (same as above) having C4-30.

(4) Sulfuric acid ester type

And alkali metal sulfates (same as above) of 1 to 30 mol adducts of aliphatic alcohols (same as above) and aliphatic alcohols AO (C2 to 4) of C4 to 30.

(5) Sulfonate type

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

(6) Phosphoric ester type

Salts of monophosphoric acid esters or diphosphoric acid esters of 1 to 30 mol adducts of aliphatic alcohols (same as described above) having 4 to 30 mol adducts with AO (C2 to 4) of aliphatic alcohols [ alkali metal salts (same as described above), quaternary ammonium salts, etc. ].

(7) Primary to tertiary amine salt forms

Salts of aliphatic amines [ primary amines (e.g., laurylamine), secondary amines (e.g., dibutylamine), and tertiary amines (e.g., dimethylstearylamine) ] hydrochloride of C4 to 30 and inorganic acids (e.g., hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid) of monoesters of triethanolamine and fatty acids (the same as described above) of C4 to 30.

(8) Quaternary ammonium salt type

And inorganic acid (same as above) salts of C4-30 quaternary ammonium (such as butyltrimethylammonium, diethyllaurylmethylammonium, and dimethyldistearylammonium).

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

Examples of the filler include: fine powders of inorganic oxides such as silica, alumina, zirconia and mica, fine powders of inorganic non-oxides such as silicon carbide and silicon nitride, and organic compounds such as acrylic resins and fluororesins. Further, metal powder such as aluminum, zinc, and copper may be added according to the application. Further, specific examples of the filler include: sols such as silica sol, zirconia sol, alumina sol, and titania sol; silica-based materials such as silica sand, quartz, dense quartz salt, diatomaceous earth, and the like; synthesizing amorphous silicon dioxide; silicates such as kaolinite, mica, talc, wollastonite, asbestos, calcium silicate, and aluminum silicate; glass bodies such as glass powder, glass spheres, hollow glass spheres, glass flakes, foam glass spheres and the like; non-oxide inorganic substances such as boron nitride, boron carbide, aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, titanium nitride, and titanium carbide; calcium carbonate; metal oxides such as zinc oxide, aluminum oxide, magnesium oxide, titanium oxide, and beryllium oxide: inorganic substances such as barium sulfate, molybdenum disulfide, tungsten disulfide, carbon fluoride and the like; metal powders of aluminum, bronze, lead, stainless steel, zinc, etc.; and carbon bodies such as carbon black, coke, graphite, pyrolytic carbon, hollow carbon spheres, and the like.

Examples of the thickener include: montmorillonite clay mineral, bentonite containing these minerals, inorganic filler thickeners such as colloidal alumina, cellulose thickeners such as methylcellulose, carboxymethylcellulose, hexylmethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose, polyethylene thickeners such as polyurethane resin thickeners, polyvinyl alcohol, polyvinylpyrrolidone and polyvinyl benzyl ether copolymers, polyether resin thickeners such as polyether dialkyl esters, polyether dialkyl ethers and polyether epoxy modified products, associative thickeners such as urethane modified polyethers, special polymer nonionic thickeners such as polyether polyol polyurethane resin, surfactant thickeners such as nonionic surfactants, protein thickeners such as casein, sodium caseinate and ammonium caseinate, and acrylic thickeners such as sodium alginate.

Examples of the leveling agent include: PEG-type nonionic surfactants (nonylphenol EO 1-40 mol adduct, stearic acid EO 1-40 mol adduct, etc.), polyol-type nonionic surfactants (sorbitan palmitate monoester, sorbitan stearate triester, etc.), fluorine-containing surfactants (perfluoroalkyl EO 1-50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), and modified silicone oils [ polyether-modified silicone oil, (meth) acrylate-modified silicone oil, etc. ].

Examples of the curing agent include polyol-based curing agents: isocyanates curable at ordinary temperature, such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate, lysine diisocyanate, nurate products of polyisocyanate compounds, buret products, adducts of polyisocyanate compounds with a polyol such as ethylene glycol, propylene glycol or trimethylolpropane, blocked polyisocyanate curing agents, or other monomers or mixtures of 2 or more types thereof, polyol adducts thereof, copolymers thereof, and block polymers thereof. Examples of the curing agent for epoxy resins include: acid anhydrides, phenol resins, polyamide resins, amine adducts, urea resins, melamine resins, isocyanates, and the like.

Examples of the crosslinking agent include: melamine resin, urea resin, polyisocyanate compound, blocked polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride, alkoxysilyl group-containing compound or resin, and a compound having a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group or the like, such as hexamethoxymethylated melamine, N' -tetrahydroxymethylsuccinamide, tetramethoxymethylated urea, 2,4, 6-tetrahydroxymethylated phenol.

Examples of the pigment include, in addition to the above pigments: vanadium compounds such as vanadium pentoxide, calcium vanadate, magnesium vanadate, and ammonium metavanadate; phosphate-based anticorrosive pigments such as magnesium phosphate, magnesium ammonium phosphate eutectoid, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium calcium phosphate eutectoid, magnesium cobalt phosphate eutectoid, magnesium nickel phosphate eutectoid, magnesium phosphite, magnesium calcium phosphite eutectoid, aluminum dihydrogen tripolyphosphate, magnesium oxide-treated products of aluminum dihydrogen tripolyphosphate, magnesium oxide-treated products of zinc dihydrogen tripolyphosphate, and magnesium phosphate-containing compounds such as magnesium phosphate-modified compounds of magnesium phosphate such as silica-modified magnesium phosphate; zinc-free rust preventive pigments such as zinc phosphate-containing rust preventive pigments, magnesium-treated aluminum dihydrogen tripolyphosphate, and calcium-treated calcium phosphate; calcium silicate such as calcium silicate complex containing calcium metasilicate component or calcium metasilicate component; metal ion-exchanged silica such as calcium ion-exchanged silica and magnesium ion-exchanged silica; and rust preventive pigments containing hexavalent chromium, lead, and the like.

Examples of the defoaming agent include: silicone defoaming agents such as silicone oil, dimethylpolysiloxane, organomodified polysiloxane, and fluorine-modified polysiloxane, mineral oil defoaming agents, non-silicone/polymer defoaming agents, defoaming agents containing at least 1 selected from the group consisting of organically modified fluorine compounds and polyoxyalkylene compounds, and defoaming agents containing aliphatic alcohols having 18 or more carbon atoms.

The antioxidant, light stabilizer including ultraviolet absorber, flame retardant, curing catalyst, bactericide, antibacterial agent and the like can be exemplified by those mentioned above.

Drawings

FIG. 1 is an excitation and emission spectrum of a sample according to examples 1-3 of the present invention;

FIG. 2 is an afterglow spectrum of samples of examples 1 to 3 according to the present invention;

FIG. 3 is an afterglow spectrum of samples of examples 4 to 6 according to the present invention.

Detailed Description

The invention will be described in further detail below with reference to the accompanying figures 1-3 and specific examples.

Example 1

A blue long-afterglow fluorescent powder contains Ca as chemical component_0.96AlO₂Cl: 0.02Eu²⁺, 0.02Tm³⁺。

As high purity CaCO₃、CaCl2、Al₂O₃、Eu₂O₃And Tm₂O₃As a raw material, Ca in accordance with the chemical composition_0.96AlO₂Cl: 0.02Eu²⁺, 0.02Tm³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; putting the raw materials into an agate mortar for grinding and mixing uniformly, adding absolute ethyl alcohol as a grinding medium according to the total mass ratio of 1:1 during grinding, wherein the grinding time is 0.5 hour; placing the obtained slurry-like mixture in a drying oven, keeping the temperature and drying for 4 hours at the temperature of 80 ℃, taking out a sample after drying is finished, and grinding and dispersing to obtain uniformly mixed raw materials; putting the uniformly mixed raw materials into a high-temperature tube furnace for presintering, wherein the sintering temperature is 1300 ℃, the sintering time is 4 hours, the heating rate is 7.5 ℃/min, and the sintering atmosphere is 5% H₂/95%N₂After sintering, cooling the mixed gas to room temperature along with the furnace to obtain a sintered body; and ball-milling and crushing the obtained sintered body, and classifying the crushed powder by using an airflow classifier according to the particle size to obtain the blue long-afterglow fluorescent powder.

Example 2

A blue long-afterglow fluorescent powder contains Ca as chemical component_0.98AlO₂Cl: 0.01Eu²⁺, 0.01Gd³⁺。

As high purity CaCO₃、CaCl2、Al₂O₃、Eu₂O₃And Gd₂O₃As a raw material, Ca in accordance with the chemical composition_0.98AlO₂Cl: 0.01Eu²⁺, 0.01Gd³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; putting the raw materials into an agate mortar for grindingGrinding and mixing uniformly, adding absolute ethyl alcohol as a grinding medium according to the total mass ratio of 1:1 during grinding, wherein the grinding time is 0.5 hour; placing the obtained slurry-like mixture in a drying oven, keeping the temperature and drying for 4 hours at the temperature of 80 ℃, taking out a sample after drying is finished, and grinding and dispersing to obtain uniformly mixed raw materials; putting the uniformly mixed raw materials into a high-temperature tube furnace for presintering, wherein the sintering temperature is 1300 ℃, the sintering time is 5 hours, the heating rate is 7.5 ℃/min, and the sintering atmosphere is 5% H₂/95%N₂After sintering, cooling the mixed gas to room temperature along with the furnace to obtain a sintered body; and ball-milling and crushing the obtained sintered body, and classifying the crushed powder by using an airflow classifier according to the particle size to obtain the blue long-afterglow fluorescent powder.

Example 3

A blue long-afterglow fluorescent powder contains Ca as chemical component_0.94AlO₂Cl: 0.04Eu²⁺, 0.02La³⁺。

As high purity CaCO₃、CaCl2、Al₂O₃、Eu₂O₃And La₂O₃As a raw material, Ca in accordance with the chemical composition_0.94AlO₂Cl: 0.04Eu²⁺, 0.02La³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; putting the raw materials into an agate mortar for grinding and uniformly mixing, adding absolute ethyl alcohol as a grinding medium according to the total mass ratio of 1:1 during grinding, and grinding for 1 hour; placing the obtained slurry-like mixture in a drying oven, keeping the temperature and drying for 4 hours at the temperature of 80 ℃, taking out a sample after drying is finished, and grinding and dispersing to obtain uniformly mixed raw materials; putting the uniformly mixed raw materials into a high-temperature tube furnace for presintering, wherein the sintering temperature is 1100 ℃, the sintering time is 6 hours, the heating rate is 7.5 ℃/min, and the sintering atmosphere is 5% H₂/95%N₂After sintering, cooling the mixed gas to room temperature along with the furnace to obtain a sintered body; and ball-milling and crushing the obtained sintered body, and classifying the crushed powder by using an airflow classifier according to the particle size to obtain the blue long-afterglow fluorescent powder.

Example 4

A blue long-afterglow fluorescent powder contains Ca as chemical component_0.84AlO₂Cl: 0.08Eu²⁺, 0.04Tm³⁺, 0.04Gd^{3 +}。

As high purity CaCO₃、CaCl2、Al₂O₃、Eu₂O₃、Tm₂O₃And Gd₂O₃As a raw material, Ca in accordance with the chemical composition_0.84AlO₂Cl: 0.08Eu²⁺, 0.04Tm³⁺, 0.04Gd³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; putting the raw materials into an agate mortar for grinding and uniformly mixing, adding absolute ethyl alcohol as a grinding medium according to the total mass ratio of 1:1 during grinding, and grinding for 1 hour; placing the obtained slurry-like mixture in a drying oven, keeping the temperature and drying for 4 hours at the temperature of 80 ℃, taking out a sample after drying is finished, and grinding and dispersing to obtain uniformly mixed raw materials; putting the uniformly mixed raw materials into a high-temperature tube furnace for presintering, wherein the sintering temperature is 1100 ℃, the sintering time is 5 hours, the heating rate is 7.5 ℃/min, and the sintering atmosphere is 5% H₂/95%N₂After sintering, cooling the mixed gas to room temperature along with the furnace to obtain a sintered body; and ball-milling and crushing the obtained sintered body, and classifying the crushed powder by using an airflow classifier according to the particle size to obtain the blue long-afterglow fluorescent powder.

Example 5

A blue long-afterglow fluorescent powder contains Ca as chemical component_0.88AlO₂Cl: 0.06Eu²⁺, 0.03Gd³⁺, 0.03La^{3 +}。

As high purity CaCO₃、CaCl2、Al₂O₃、Eu₂O₃、Gd₂O₃And La₂O₃As a raw material, Ca in accordance with the chemical composition_0.88AlO₂Cl: 0.06Eu²⁺, 0.03Gd³⁺, 0.03La³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; putting the raw materials into an agate mortar for grinding and mixing uniformly, and adding absolute ethyl alcohol according to the total mass ratio of 1:1 during grindingGrinding medium, grinding time is 0.5 hour; placing the obtained slurry-like mixture in a drying oven, keeping the temperature and drying for 4 hours at the temperature of 80 ℃, taking out a sample after drying is finished, and grinding and dispersing to obtain uniformly mixed raw materials; putting the uniformly mixed raw materials into a high-temperature tube furnace for presintering, wherein the sintering temperature is 1200 ℃, the sintering time is 5 hours, the heating rate is 7.5 ℃/min, and the sintering atmosphere is 5% H₂/95%N₂After sintering, cooling the mixed gas to room temperature along with the furnace to obtain a sintered body; and ball-milling and crushing the obtained sintered body, and classifying the crushed powder by using an airflow classifier according to the particle size to obtain the blue long-afterglow fluorescent powder.

Example 6

A blue long-afterglow fluorescent powder contains Ca as chemical component_0.8AlO₂Cl: 0.1Eu²⁺, 0.04Tm³⁺, 0.04Gd³⁺,0.02La³⁺。

As high purity CaCO₃、CaCl2、Al₂O₃、Eu₂O₃、Tm₂O₃、Gd₂O₃And La₂O₃As a raw material, Ca in accordance with the chemical composition_0.8AlO₂Cl: 0.1Eu²⁺, 0.04Tm³⁺, 0.04Gd³⁺, 0.02La³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; putting the raw materials into an agate mortar for grinding and uniformly mixing, adding absolute ethyl alcohol as a grinding medium according to the total mass ratio of 1:1 during grinding, and grinding for 1 hour; placing the obtained slurry-like mixture in a drying oven, keeping the temperature and drying for 4 hours at the temperature of 80 ℃, taking out a sample after drying is finished, and grinding and dispersing to obtain uniformly mixed raw materials; putting the uniformly mixed raw materials into a high-temperature tube furnace for presintering, wherein the sintering temperature is 1200 ℃, the sintering time is 4 hours, the heating rate is 7.5 ℃/min, and the sintering atmosphere is 5% H₂/95%N₂After sintering, cooling the mixed gas to room temperature along with the furnace to obtain a sintered body; ball-milling and crushing the obtained sintered body, and classifying the crushed powder according to the particle size by using an airflow classifier to obtain the blueColor long afterglow fluorescent powder.

FIG. 1 shows excitation and emission spectra of samples according to examples 1 to 3 of the present invention, wherein the left curve is excitation spectrum, the monitoring wavelength is 448nm, the right curve is emission spectrum, the excitation wavelength is 275nm, and it can be seen from the graph that the effective excitation wavelength range of the sample is near ultraviolet (200-350 nm) region, the peak wavelength of the emission spectrum is in the 448nm blue region, and the luminescence center is divalent Eu²⁺Ions; FIGS. 2 and 3 are the afterglow spectrograms of examples 1 to 3 and examples 4 to 6, respectively, and it can be seen from these charts that Eu, the activated ion²⁺And impurity level ion Tm³⁺、Gd³⁺And La³⁺The doping concentration of the rare earth ions has important influence on the initial fluorescence intensity, the afterglow intensity and the afterglow time of a sample by introducing the rare earth ions Tm³⁺、Gd³⁺And La³⁺One or a combination of several of the above-mentioned materials can provide trap energy level, can effectively raise afterglow brightness and prolong afterglow time.

Starting from 90 s of the 20 th century, with Eu²⁺The luminescent mechanism of long-afterglow luminescent materials represented by activated alkaline earth aluminates has been a hot point of research. At present, the long afterglow luminescence mechanism is not completely understood, but at least the following consensus is obtained: (1) eu-doped²⁺Is a luminescent center; (2) various defects in the crystal have important influence on luminescence and afterglow; (3) co-doped with trivalent rare earth ion RE³⁺The addition of (b) produces more defect levels; (4) electrons and holes generated during excitation are respectively captured by the electron trap and the hole trap; (5) thermally perturbing electrons or holes trapped in the sunken well to release them at an appropriate rate; (6) the recombination of electrons and holes results in light emission. In the actual development process, because the variety of the long-lasting phosphor materials is large, different materials have different luminescence mechanisms, and the luminescence mechanism of some materials is not clear at present, the search for a proper matrix and an activated ion is crucial to the development of a novel long-lasting phosphor material. In addition, because the preparation methods of the long-afterglow luminescent materials are more and have respective advantages and disadvantages, the optimal combination of the preparation methods of various long-afterglow luminescent materials also can be used for the long afterglow luminescent materialsThe popularization and the application of the afterglow luminescent material play a very important role.

Claims (3)

1. The coating is characterized by comprising conventional coating components and blue long-afterglow fluorescent powder, wherein the blue long-afterglow fluorescent powder is uniformly distributed in the conventional coating components, and the addition amount of the blue long-afterglow fluorescent powder is 1-30%; the chemical composition general formula of the blue long afterglow phosphor is Ca_1-x-yAlO₂Cl:xEu²⁺,yRe³⁺Wherein Re is one or a combination of more of Tm, Gd and La, and the value ranges of x and y are respectively as follows: x is more than or equal to 0.01 and less than or equal to 0.1, and y is more than or equal to 0.01 and less than or equal to 0.1.

2. The paint as claimed in claim 1, wherein the amount of the blue long-afterglow phosphor powder added is 5-10%.

3. A paint as claimed in claim 1, which is oil-based or water-based.

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