JP6137619B2 - Raw material composition for stress luminescent material, stress luminescent material, and application thereof - Google Patents

Description

The present invention relates to a raw material composition for stress luminescent materials, a stress luminescent material, and applications thereof (specifically, a stress luminescent coating composition, a resin composition, and a stress luminescent material using the stress luminescent material).

A light-emitting material that emits visible light near room temperature when a substance is given an external stimulus is known. In particular, a material that emits light in response to a mechanical stimulus of an externally applied force (compression, displacement, friction, impact, etc.) is called a stress luminescent material.

As stress-stimulated luminescent materials, stress-stimulated luminescent materials based on aluminate have been reported (for example, Patent Documents 1 and 2). However, in the conventional stress light emitting material, practical light emission luminance has not been obtained yet, and a stress light emitting material having higher light emission luminance has been demanded.

Japanese Patent No. 3511083 Japanese Patent No. 5007971

An object of the present invention is to provide a raw material composition for providing a stress-stimulated luminescent material that has excellent stress luminescent properties and has practically sufficient light emission luminance, and a stress-stimulated luminescent material obtained from the raw material composition.

The inventors have found that when the raw material composition contains a certain amount of Li, the light emission luminance of the stress-stimulated luminescent material is improved as compared with the case where Li is not contained.

That is, the first aspect of the present invention includes alumina and / or aluminum hydroxide,
A strontium compound,
A europium compound,
Containing 0.01 to 0.30 mol% of Li with respect to 100 mol% of the aluminum element,
The present invention relates to a raw material composition for a stress luminescent material for synthesizing a europium activated strontium aluminate-based stress luminescent material.

In a preferred embodiment, the composition further contains at least one element of rare earth elements other than europium as a coactivator.

The 2nd aspect of this invention is related with the stress luminescent material manufactured from the raw material composition for stress luminescent materials.

The third and fourth aspects of the present invention relate to a stress-luminescent coating composition and a resin composition containing the stress-luminescent material of the second aspect.

A fifth aspect of the present invention relates to a stress-stimulated luminescent material formed from the resin composition of the fourth aspect.

According to ordinary knowledge, a stress-stimulated luminescent material containing impurities is expected to have a reduced luminance, whereas according to the present invention, when a certain amount of Li is added to a stress-stimulated luminescent material composition, On the other hand, the light emission luminance of the stress-stimulated luminescent material obtained is improved. Thereby, the light emission luminance of the stress luminescent material can be increased.

The results of Examples and Comparative Examples shown in Table 1 are graphed. The relative stress luminescence intensity on the vertical axis represents a relative value (%) when the stress luminescence intensity when no additive element (alkali metal or alkaline earth metal) is contained (Comparative Example 1) is 100%. The relationship between the addition amount of Li and the stress luminescence intensity is graphed. The relative stress luminescence intensity on the vertical axis represents the relative value (%) when the stress luminescence intensity when Li is not contained (Comparative Example 1) is 100%. The horizontal axis represents the Li content (mol%) when the amount of aluminum element is 100 mol%.

<Definition>
Before describing the present invention, first, terms used in the present specification will be described. In the present specification and claims, drawings and abstracts (hereinafter referred to as “the present specification and the like”), “stress luminescent material” means an externally applied force (compression, displacement, friction, impact, etc.). It refers to the material itself that emits light under mechanical stimulation. A material obtained by molding the stress luminescent material alone or in combination with another material (for example, resin) is referred to as “stress luminescent material”.

In the specification of the present application, the “raw material composition for stress-stimulated luminescent material” refers to a mixture containing a component that is a raw material of the stress-stimulated luminescent material and itself does not have a stress-stimulated luminescence ability.

<Raw material composition for stress luminescent material>
First, the raw material composition for a stress-stimulated luminescent material which is the first embodiment of the present invention will be described. This composition is a composition containing alumina and / or aluminum hydroxide, a strontium compound, a europium compound, and a certain amount of Li.

The alumina (aluminum oxide) is not particularly limited, and any alumina such as α alumina, θ alumina, κ alumina, δ alumina, η alumina, χ alumina, γ alumina, and ρ alumina may be used.

The aluminum hydroxide is not particularly limited, and aluminum hydroxide having a crystalline phase such as gibbsite, bayerite, boehmite or the like is used.

Strontium aluminate serving as a base material for the stress-stimulated luminescent material is obtained by reacting the above-mentioned alumina or aluminum hydroxide with a strontium compound. Therefore, the raw material composition for a stress-stimulated luminescent material contains a strontium compound. Examples of the strontium compound include, but are not limited to, strontium carbonate, strontium oxide, strontium hydroxide, strontium halide (such as strontium chloride), strontium sulfate, strontium nitrate, and strontium hydrogen phosphate.

The raw material composition is a composition for synthesizing a europium activated strontium aluminate-based stress luminescent material. Therefore, the raw material composition contains a europium compound. Europium (Eu) acts as an activator. The europium compound is not particularly limited, and examples thereof include europium carbonate, europium oxide, europium chloride, europium sulfate, europium nitrate, and europium acetate.

The raw material composition for a stress-stimulated luminescent material contains a certain amount of Li element. Specifically, an amount of Li compound corresponding to the desired amount is added. There is no limitation in particular as Li compound used as the source of Li element. Examples include lithium halide (lithium chloride, lithium bromide, etc.), lithium carbonate, lithium acetate, lithium nitrate, lithium sulfate and the like.

The amount of Li (as an element) contained in the stress luminescent material composition is 0.01 to 0.30 mol%, preferably 0.01 to 0.25 mol% with respect to 100 mol% of the aluminum element. More preferably, it is 0.03-0.1 mol%. It has been considered that when an element such as alkali metal or alkaline earth metal is mixed in a stress-stimulated luminescent material, the physical properties are usually adversely affected. On the other hand, when the said raw material composition for stress luminescent materials contains Li element in the quantity of 0.01-0.30 mol% with respect to 100 mol% of aluminum elements, the said stress luminescent material of the stress luminescent material obtained. It has been found that an effect which cannot be predicted from conventional common knowledge that light emission characteristics, particularly light emission luminance, is improved as compared with a case where Li is not contained.

If the amount of Li (as an element) contained in the stress luminescent material composition is less than 0.01 mol% with respect to 100 mol% of the aluminum element, the emission intensity is not improved, and if it exceeds 0.30 mol%, the emission intensity is not improved. Will decline.

The composition of the present invention may further contain a coactivator. Although it does not specifically limit as a co-activator, The compound or ion of rare earth elements other than the above-mentioned europium is mentioned. Examples of rare earth elements other than Eu include one or more selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and the like. These elements are mentioned. These are preferable because substitution by elements having different ionic radii and valences results in the formation of lattice defects, and the crystal structure is more easily distorted. Among these, Nd, Dy, and Ho are particularly preferable from the viewpoint of obtaining high light emission luminance when used as a coactivator.

In addition, examples of rare earth element compounds added to the composition include carbonates, oxides, chlorides, sulfates, nitrates, and acetates of the above elements.

You may add the dispersing agent for improving the dispersibility of particle | grains to the said composition further. Although it does not specifically limit as an example of a dispersing agent, An anionic surfactant and a nonionic surfactant are used. Examples of anionic surfactants include ammonium polycarboxylate, sodium polycarboxylate, sodium hexametaphosphate, and the like. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene. Examples include mono fatty acid esters and polyoxyethylene sorbitan mono fatty acid esters. These may be used alone or in combination of two or more.

In addition, a flux component not containing Li may be added to the composition in order to increase the crystallinity of the particles. The flux component is not particularly limited, but calcium fluoride, magnesium fluoride, aluminum fluoride, ammonium fluoride, sodium chloride, potassium chloride, lithium chloride, ammonium bromide, ammonium iodide, potassium iodide, hydroxide Examples of the compound include sodium, potassium hydroxide, ammonium sulfate, sodium sulfate, potassium sulfate, sodium nitrate, ammonium nitrate, boric acid, and sodium borate. These may be used alone or in combination of two or more.

The raw material composition of the present invention can be obtained by mixing these components. The mixing means is not particularly limited, and known mixing means can be used. In particular, in order to perform mixing efficiently, wet mixing is preferably performed in the presence of a dispersion medium (for example, water) in a reaction vessel equipped with a pulverizing medium stirring type pulverizer. Here, the pulverization medium stirring type pulverizer refers to the pulverization medium that is put into the pulverization container and stirred together with the object to be pulverized by rotating and rotating (rotating or revolving) the pulverization container. This is a pulverizer that performs pulverization with direct stirring. An example of the pulverization medium stirring type pulverizer is not particularly limited, but is preferably any one selected from the group consisting of a planetary mill, a bead mill, and a vibration mill. Among these, a planetary mill with rotation and revolution is particularly preferable. After the wet mixing, the raw material composition of the present invention can be produced by removing the dispersion medium and drying.

Furthermore, a stress luminescent material can be manufactured by baking the raw material composition for stress luminescent materials. This stress-stimulated luminescent material also constitutes one embodiment of the present invention. The production conditions of the stress-stimulated luminescent material are not particularly limited, and can be performed according to a general firing method. Although not particularly limited, for example, the obtained stress luminescent material composition is baked by firing (for example, 1000 ° C. or higher, in a reducing atmosphere) and, if necessary, pulverized and sized, etc. Can be manufactured.

The stress-stimulated luminescent material of the present invention is physically and chemically stable under various environments, and the lattice defect or the carrier of the lattice defect and the luminescent center is excited by being deformed by applying a mechanical external force. When it returns to the base, it emits light. The stress-stimulated luminescent material obtained by molding the stress-stimulated luminescent material of the present invention can be applied under various environments, for example, in air, in vacuum, in a reducing or oxidizing atmosphere, of course, Light is emitted by mechanical external force even in various solution environments such as water, inorganic solution, and organic solution. Therefore, it is effective for stress detection under various environments.

A method for utilizing such a stress-stimulated luminescent material is not particularly limited, but the following may be considered.

A light emitting layer containing a stress light emitting material is made of ordinary paper, synthetic paper, or a polymer material such as epoxy resin, polyethylene, polyethylene terephthalate, polyester, polypropylene, polyvinyl chloride, natural rubber or synthetic rubber, glass, ceramics, metal, By forming it on the exterior surface of wood, artificial fiber or natural fiber, concrete, or a combination thereof, and their processed products, or by containing a stress luminescent material inside, anomalies can be detected or shock waves can be detected. It is possible to diagnose deterioration of various structures and members by applying (stress-strain detection, stress distribution measurement). For example, large buildings such as buildings, viaducts, bridges, roads, railway rails, columns, towers, pipelines and tunnels, flooring, tiles, wall materials, block materials, paving materials, building materials such as wood, steel, concrete, Power transmission members such as gears and cams, exterior parts or built-in parts (engine parts, tires, belts, etc.) used for bicycles, automobiles, trains, ships, airplanes, bearing parts, bearing cages, and light These are fastening parts such as bearings with sensors, screws, bolts, nuts and washers. As its application, it is expected to detect leakage of a storage battery, a valve seat, a water pipe, a sprinkler head, a non-aqueous electrolyte secondary battery into which an electrolyte or polymer electrolyte is injected. Further, the stress distribution in the adhesive layer of the adhesive containing the stress luminescent material can be visualized, and the crack of the adhesive can be grasped.

Stress light emitting materials using light emitting elements include pressure sensitive devices, touch pads, touch sensors, photodiodes or phototransistors, piezoelectric actuators or electrostatic actuators, light emitting polymer actuators, liquid volume detection devices, impact force detection devices, Can be used for electronic devices and devices such as optical waveguides, optical waveguide devices, mechanical optical devices, detection devices, information processing devices, switches, operation buttons, input devices, key input devices, non-contact control of devices and systems, Enables automated process, remote operation. For example, height measuring device for connecting terminals of semiconductor parts, measuring device for cavitation generation amount, measuring device for sound pressure intensity distribution, sound pressure intensity distribution and energy density distribution measuring device by ultrasonic for medical examination, living bone or simulation Measuring device for distribution of stress / strain acting on members such as implants attached to bone, transmission cable, transmission device and laser processing device, device for detecting twisting amount of steering shaft, radiation imaging device for specifying position of imaging part , Parallelism check device for flow velocity detector mold press machine, solid-state imaging device that can generate and generate stress corresponding to thermal energy of infrared light, friction force, shear force, impact force, pressure, etc. A light emitting head that converts mechanical external force into an optical signal and transmits it, a remote switch system that remotely operates the mechanical device using the light emitting head, In addition, a detection system that detects the couple using the light emitting head, a detachable body that is detachably mounted on the main body of various electrical, electronic, and mechanical devices, for example, an ink cartridge of an ink jet printer or a mounting state of a paper tray In addition, a detection device for a removable body that can detect an unmounted state, and a removable body; an imprint device that can inspect ultraviolet curable resin remaining on an uneven portion in a short time, an operation device that does not require wiring, in vivo or dark And a small and wireless light source (stress luminescent particles) that can be introduced at a place, an inspection apparatus including the light source, an inspection method, a stress history recording system, and the like. It can also be used for measuring the sealing properties of gaskets and packings, measuring the contact surface shape and distribution of contact pressure of tires, measuring dental occlusal force, measuring devices for contact parts of tires, and measuring the amount of cavitation.

Application as a tactile sensor element is also possible. For example, a human cooperative robot, a prosthetic hand, a prosthetic finger, a prosthetic limb, a palpation device for diagnosis, and a hardness / softness tester of various industries are included. In addition, by measuring the luminescence energy generated by the action with radiation, it can be expected to measure the radiation exposure dose and the exposure intensity distribution.

In addition to the above-described measuring device, it can be used as a display for illumination or safety. For example, lighting fixtures such as device vibration lamps and wind lamps; emergency, abnormality notification, emergency equipment, danger indications, emergency lights, emergency signs, life-saving equipment signs, signs, display devices; safety fences, around factory buildings Tension ropes, animal repellent fences; streaks for joints that are semi-embedded in stairs steps, handrails, passages, etc .; health equipment, walking aids (walking aids, light emitting notification antennas, etc.); earrings, necklaces, etc. Accessories; flag support pillars, railroad barrier breakers, bicycles, cars, trains, ships, airplanes and other exterior parts or built-in parts, fishing gear (pseudo baits, fishing rods, fish nets, etc.), light emission Fiber structure, luminescent fishing gear, fishing line and fishing net, buoy; float, buoy; human, dog, cat and other pets, cattle, pigs, sheep, chickens and other livestock, etc .; fans (wind power generation, fans, etc.) ), Clothing ( , Sportswear, artificial luminescent fabric, artificial luminescent yarn, artificial luminescent fiber, etc.); packaging (boxes, holders, vessels, envelopes, cartons, overwrapping, external coatings, etc.), medical products (breathing aids, test and research equipment) ) Robots (artificial luminescent hair structure, artificial luminescent skin, artificial luminescent body) and the like.

Examples of utilization of paint compositions, ink compositions, bonding agents, and surface coatings containing stress-stimulated illuminants include those used in financial institutions, public institutions, credit card companies, distribution industries, etc. Postage sheets such as pressure-bonded postcard sheets containing stress luminescent materials in adhesives; furniture such as chairs and beds; flooring materials, tiles, wall materials, block materials, paving materials, building materials such as wood, steel, and concrete. Car navigation devices mounted on vehicles; operation devices for operating audio devices and air conditioners; input devices for home appliances, portable devices, electronic computers, etc .; digital cameras, CCD cameras, films, photographs, videos, etc. Examples include storage means.

Since it is possible to generate a new design by emitting light, it is also possible to develop it into amusement products such as toys and event goods and household goods. For example, dynamic toys, streamers such as kites and carp streamers, swings, roller coasters, rotating horses, bows and arrows, etc .; non-powered light emitting devices (wind chimes, etc.) that simultaneously generate sound and light by wind power; luminous balls (golf balls, baseballs) Ball, table tennis ball, billiard ball, etc.), windmill with light emission mechanism; balloon; sheet-like structure is paper, winding whistle, origami, paper balloon, harsen, greeting card, picture book; Rods, fencing, bows and arrows, etc.); pressure-sensitive seals for hitting golf clubs, tennis court line tapes, dynamic decorations, dynamic sculptures, dynamic monuments; dynamic display devices; Equipment; Acoustic equipment such as speakers, musical instruments (stringed instruments such as violins and guitars, percussion instruments such as xylophone and drums, wind instruments such as trumpet and flute, bee Diaphragms such as B), tuning forks, etc .; amusement products such as event goods; aquariums, aquarium ornamental aquariums, containers; luminous watches, luminous hourglass or hourglass type luminous devices; luminous type pseudo candle devices; Artificial eye; cosmetic composition containing adhesive polymer, printed matter and securities that can be forged and discerned visually, printing ink containing stress luminescent particles, bills, checks, stock certificates, corporate bonds, various securities, products Tickets, book tickets, transportation tickets, entrance tickets for paid facilities and events, lottery tickets, winning tickets for public competition ballots, banknotes, identification cards, tickets, pass tickets, passports, confidential documents, etc. Printed materials, seals and the like.

Stress-stimulated phosphor-photocatalyst complex, which activates the photocatalyst attached to the surface using light emission due to stress, is antibacterial, antibacterial, treatment for non-human animals, vehicle suspension, handle, etc. It can be used for purification of dirt on articles and purification by flow energy of fluid on internal wall surfaces such as pipes in a dark place. It is possible that the photocrosslinking agent in the polymer resin is activated by the light emission of the stress-stimulated luminescent substance and promotes crosslinking.

The stress-stimulated luminescent material of the present invention may be combined with other inorganic materials or organic materials to form a composite material. For example, the resin composition may be formed by mixing or embedding the stress-stimulated luminescent material of the present invention in an organic material such as resin or plastic at an arbitrary ratio. The amount of the stress-stimulated luminescent material in the resin composition can be appropriately selected according to the desired application and the characteristics of the resin used. For example, in the case of an epoxy resin or an acrylic resin, 1 to 200 parts by mass of the stress-stimulated luminescent material with respect to 100 parts by mass of the resin. 30-300 parts by mass of the material is blended. A resin composition can be prepared by using a blender such as a conical blender, a V blender, a ribbon blender, a Henschel mixer, a Banbury mixer, or a three roll roll.

Moreover, a stress light-emitting body can be formed from the resin composition. When obtaining a sheet-like stress luminescent material, for example, 50 to 200 parts by mass of the stress-stimulated luminescent material with respect to 100 parts by mass of the polyvinyl chloride resin, 3 to 5 parts by mass of a calcium-zinc stabilizer, and dioctyl as a plasticizer. A flexible sheet-like stress-stimulated luminescent material can be obtained by blending 30 to 100 parts by mass of phthalate and kneading at 150 to 200 ° C. with two rolls.

When obtaining a film-like stress luminescent material, for example, 20 to 50 parts by mass of the stress luminescent material is blended with 100 parts by mass of polyethylene terephthalate resin, and kneaded at 250 to 300 ° C. with a biaxial extruder or inflation machine. -A film-like stress luminescent material can be obtained by molding.

When obtaining stress luminescent materials of other shapes, for example, by blending 5 to 100 parts by mass of the stress luminescent material with respect to 100 parts by mass of the polypropylene resin, kneading and molding at 170 to 200 ° C. with a biaxial extruder. A cord-like, plate-like, rod-like, or pellet-like stress luminescent material can be obtained. Moreover, a three-dimensional stress light-emitting body can be obtained by processing and molding the pellet-shaped stress light-emitting body at 170 to 200 ° C. using an injection molding machine.

When a mechanical external force is applied to the stress light emitter, light is emitted by mechanical deformation. Such a resin composition and a stress-stimulated luminescent material also constitute one embodiment of the present invention.

Examples of the organic material include resins such as thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, acrylonitrile-butadiene-styrene. Styrene polymers or copolymers such as copolymers (ABS resins), polyamide resins such as 6-nylon, 66-nylon, 12-nylon, polyamideimide, polyimide, polyetherimide, polyurethane, polymethyl methacrylate, and other acrylic resins , Fluorinated resins such as polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinylidene fluoride, polytetrafluoroethylene, alkenyl aromatic resins, polyethylene terephthalate, polybutylene terephthalate, poly Polyethylene such as tylene naphthalate, polyester such as polylactic acid, polycarbonate such as bisphenol A polycarbonate, polyacetal, polyphenylene sulfide, polymethylpentene, cellulose, polyvinyl alcohol, polyvinyl acetal, polyacrylonitrile, and styrene-acrylonitrile copolymer ( AS resin), polyphenylene ether (PPE), modified PPE, polyarylate, polyphenylene sulfide, polysulfone, polyethersulfone, polyethernitrile, polyetherketone, polyketone, liquid crystal polymer copolymer of ethylene and propylene, ethylene or propylene And other α-olefins (butene-1, pentene-1, hexene-1, 4-methylpentene-1, etc.), ethylene and Examples thereof include copolymers with other ethylenically unsaturated monomers (vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, vinyl alcohol, etc.).

A thermoplastic resin is used individually or in combination of 2 or more types. When the thermoplastic resin is a copolymer, it may be a copolymer of any form such as a random copolymer or a block copolymer.

Thermosetting resins include phenolic resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicon resin, alkyd resin, polyimide, polyaminobismaleimide, casein resin, furan resin, urethane resin, etc. Can be mentioned. In addition, resins that can be cured by ultraviolet rays or radiation can also be used.

Further, 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 can be used.

Other than this, pigments, dyes, lubricants, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, flame retardants, bactericides, antibacterial agents, curing catalysts, photopolymerization initiators, etc. Mixed with materials, rod, plate, film, fiber, membrane, needle, sphere, foil, particle, sand, scale, sheet, liquid, gel, sol, suspension , Aggregates, capsules, etc.

Examples of the pigment include inorganic pigments and organic pigments. Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, Amber, titanium black, synthetic iron black, carbon black, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, glass flake, hologram pigment and the like. In addition, examples of the metal powder pigment include aluminum powder, copper powder, stainless steel powder, metal colloid, and transparent pearl mica, colored mica, interference mica, interference alumina, interference silica (interference glass) and the like having interference action.

Organic pigments include azo pigments (monoazo yellow, condensed azo yellow, azomethine yellow, etc.), yellow iron oxide, titanium yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow Yellow pigments such as permanent orange; red pigments such as red iron oxide, naphthol AS azo red, ansanthrone, anthraquinonyl red, perylene maroon, quinacridone red, diketopyrrolopyrrole red, permanent red, etc .; cobalt violet Purple pigments such as quinacridone violet and dioxazine violet; blue pigments such as cobalt blue, phthalocyanine pigments (phthalocyanine blue, etc.) and selenium blue; phthalocyanine Can be mentioned green pigments such emissions, azo disperse dyes, organic dyes such as anthraquinone disperse dyes.

As dyes, azo dyes, anthraquinone dyes, indigoid dyes, sulfur dyes, triphenylmethane dyes, pyrazolone dyes, stilbene dyes, diphenylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, quinoneimine dyes (azine dyes, oxazine dyes, thiazine dyes) ), Thiazole dyes, methine dyes, nitro dyes, and nitroso dyes.

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

Examples of hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyr 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, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (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-butylphenol), 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-t rt-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′-di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (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-hydroxyhydrocinnamide), N, N '-Bis [3- (3,5-di-tert-butyl-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- Droxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethyl) Benzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ′, 5 '-Di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like.

Phosphite compounds include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl mono Phenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) ) Phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentae Thritol 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, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite. Other phosphite compounds include those that react with dihydric phenols and have a cyclic structure.

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphospho Knight, 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- -Tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples include -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like.

As thioether compounds, dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), pentaerythritol- Tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), and pentaerythritol-tetrakis (3-stearylthiopropionate) Nate) and the like.

Examples of the light stabilizer including the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, and the like.

Examples of the benzophenone 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-sulfobenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy -2 - carboxy benzophenone, and 2-hydroxy-4- (2-hydroxy-3-methyl - acryloxy-isopropoxyphenyl) benzophenone.

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

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

Examples of the oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, and 2-ethoxy-3 ′. -Dodecyl oxalic acid bisanilide and the like.

Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3'-diphenyl acrylate, 2-ethylhexyl-cyano-3,3'-diphenyl acrylate, and the like.

Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -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- (ethylcarba Yloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethylpi-4-peridyl) adipate, bis (2,2,6,6-tetramethylpi-4-peridyl) terephthalate, 1,2-bis (2,2,6,6-tetramethylpi-4-peridylo) Cis) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) -Tolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl -4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 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 Between 6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol Examples include condensates.

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

Examples of the flame retardant include a brominated flame retardant, a phosphorus flame retardant, a chlorine flame retardant, a triazine flame retardant, a salt of phosphoric acid and piperazine, and an inorganic flame retardant.

Brominated flame retardants include some or all of the glycidyl groups at the molecular chain ends of brominated polystyrene, brominated polyacrylates, brominated polyphenylene ethers, brominated bisphenol A type epoxy resins, and brominated bisphenol A type epoxy resins. Stopped modified products, polycarbonate oligomers synthesized from brominated bisphenol A, brominated diphthalimide compounds, brominated biphenyl ethers, and compounds such as brominated diphenylalkanes such as 1,2-di (pentabromophenyl) ethane Can be mentioned. Among these, brominated polystyrene such as polytribromostyrene, poly (dibromophenylene oxide), decabromodiphenyl ether, bis (tribromophenoxy) ethane, 1,2-di (pentabromophenyl) ethane, ethylene-bis- (tetra Bromophthalimide), tetrabromobisphenol A, brominated polycarbonate oligomer, brominated polystyrene such as polytribromostyrene, 1,2-di (pentabromophenyl) ethane, and the like.

Phosphorus flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, Tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acetate Acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, di melamine phosphate, melamine pyrophosphate, triphenyl phosphine oxide, tricresyl phosphine oxide, methanephosphonate diphenyl, phenylphosphonic acid diethyl and phosphoric acid esters. Resorcinol polyphenyl phosphate, 1,3-phenylene bis (2,6-dimethylphenyl phosphate), resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, bisphenol A polyphenyl phosphate, hydroquinone poly ( 2,6-xylyl) phosphate and condensed phosphates such as aromatic condensed phosphates such as condensates thereof.

Examples of the chlorine-based flame retardant include pentachloropentacyclodecane, hexachlorobenzene, pentachlorotoluene, tetrachlorobisphenol A, polychlorostyrene, and the like.

As triazine flame retardants, melamine, acetoguanamine, benzoguanamine, acrylic guanamine, 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, 2-amino-4,6-dimercapto-1,3,5-triazine and the like can be mentioned.

Examples of the salt 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, and red phosphorus.

As fungicides, copper fungicides such as oxine copper, organic sulfur fungicides such as dineb and mannebu, organochlorine fungicides such as captan and chlorothalonil, benzimidazole fungicides such as thiophanate methyl, benomyl, carbendazole and thiabendazole, Dicarboximide fungicides such as iprodione, vinclozolin and procimidone, acid amide fungicides such as flametopil, phenylpyrrole fungicides such as fludioxonil, morpholine fungicides such as dimethomorph, azoxystrobin, cresoxime methyl, and olibrite Such as methoxyacrylate fungicides such as mepanipyrim, cyprodinil, pyrimethanil and the like, ergosterol biosynthesis inhibitors such as triazimephone and triflumizole, chlorpicrin, PCNB, etc. Fungicide, other fluazinam, o-phenylphenol (OPP), diphenyl, chlorodiphenyl, cresol, 1,2-bis (bromoacetoxy) ethane, cinnamic aldehyde, phenyl acetate, allyl isothiocyanate, α-methylacetophenone, thymol Perchlorocyclopentadiene, bromoacetic acid, 2,2-dibromo-3-nitrilepropionamide, ethyl chloroacetate, butyl chloroacetate, methyl chloroacetate, 5-chloro-2-methylisothiazolin-3-one, glutaraldehyde, and And hinokitiol.

Examples of the antibacterial agent include inorganic powders in which one or more antibacterial metals of silver, zinc, and copper are supported on an inorganic compound. Examples of the support include zeolite, apatite, zirconium phosphate, titanium oxide, silica gel, aluminum sulfate hydroxide, calcium phosphate, and calcium silicate. In addition, an antibacterial glass containing one or two or more kinds of antibacterial metals such as silver, zinc, and copper in a glass containing one or more kinds of phosphoric acid, boric acid and silicic acid glasses. A powder is also mentioned.

Lubricants include fatty acids, fatty acid metal salts, oxy fatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partial saponified esters, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acid poly Examples include glycol esters and modified silicones.

Examples of the fatty acid include 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. Can be mentioned. Fatty acid metal salts include sodium laurate, potassium laurate, magnesium laurate, calcium laurate, zinc laurate, barium laurate, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate Alkali (earth) metals of fatty acids having 6 to 40 carbon atoms such as sodium behenate, potassium behenate, magnesium behenate, calcium behenate, zinc behenate, barium behenate, sodium montanate, and calcium montanate Salt.

Examples of the oxy fatty acid include 1,2-oxysteric acid.

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

Examples of the low molecular weight polyolefin include those having a molecular weight of 5000 or less, such as polyethylene wax, maleic acid-modified polyethylene wax, oxidation type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Specific examples of the fatty acid amide include those having 6 or more carbon atoms such as oleic acid amide, erucic acid amide, and behenic acid amide.

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

Examples of the aliphatic ketone include those having 6 or more carbon atoms such as higher aliphatic ketones.

Examples of the fatty acid partial saponified ester include a montanic acid partial saponified ester.

Examples of fatty acid lower alcohol esters include stearic acid esters, oleic acid esters, linoleic acid esters, linolenic acid esters, adipic acid esters, behenic acid esters, arachidonic acid esters, montanic acid esters, and isostearic acid esters.

Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol Examples include tall monostearate, pentaerythritol adipate stearate, and sorbitan monobehenate.

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 the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.

Curing catalysts include organic peroxides such as (t-butylperoxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, etc.) and azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), tin octylate , Dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, dioctyltin oxide, dibutyltin fatty acid salt , Metals such as lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zinc, cobalt naphthenate, calcium octylate, copper naphthenate, lead 2-ethylhexanoate lead octylate and tetra n-butyl titanate And organic and nothing Organic acid derivatives such as salts with acids, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid and other sulfonic acid compounds, sulfonic acid compounds Examples include neutralized amines, organic amines such as triethylamine, phosphoric acid, pyrophosphoric acid, and phosphoric acid mono- or diesters. Examples of the phosphoric acid monoester include monooctyl phosphate, monopropyl phosphate, and monolauryl phosphate. Examples of the phosphoric acid diester include dioctyl phosphate, dipropyl phosphate, and dilauryl phosphate. Furthermore, phosphoric acid compounds such as mono (2- (meth) acryloyloxyethyl) acid phosphate, diazabicycloundecene-based catalysts, Lewis acids, acid anhydrides, and the like can be given.

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 (such as isopropylthioxanthone), benzophenone compounds (such as benzophenone), phosphate ester compounds (such as 1,3,5-trimethylbenzoyldiphenylphosphine oxide), and benzyldimethyl ketal.

Furthermore, it can also be set as a stress luminescent coating composition by mix | blending a stress luminescent material with a coating material. This stress-luminescent coating composition also constitutes one aspect of the present invention. The stress-luminescent coating composition can be applied to the surface of another material. When a mechanical external force is applied to the material to which the light-emitting material is applied, the light-emitting material layer on the material surface emits light by deformation. Moreover, since the coating composition containing the luminescent material of the present invention has high emission luminance, it can be applied with high visibility.

As the coating composition, a coating composition containing a film-forming resin is used. The coating composition of the present invention comprises a light containing a solvent, a dispersant, a filler, a thickener, a leveling agent, a curing agent, a crosslinking agent, a pigment, an antifoaming agent, an antioxidant, and an ultraviolet absorber as necessary. It may contain paint additives such as stabilizers, flame retardants, curing catalysts, bactericides, and antibacterial agents.

Various materials such as thermosetting resins, room temperature curable resins, ultraviolet curable resins, and radiation curable resins can be used as materials used in the coating composition, such as acrylic resins, alkyd resins, urethane resins, and polyester resins. Amino resins, organosilicates, organotitanates, and the like. Examples of the ink film forming material include urethane resin, acrylic resin, polyamide resin, vinyl chloride-vinyl acetate resin, and chlorinated propylene resin.

Solvents include aliphatic hydrocarbons, aromatic hydrocarbons (C7-10, such as toluene, xylene and ethylbenzene), esters or ether esters (C4-10, such as methoxybutyl acetate), ethers (C4-10, such as , Tetrahydrofuran, EG monoethyl ether, EG monobutyl ether, PG monomethyl ether and DEG monoethyl ether), ketones (C3-10, eg methyl isobutyl ketone, di-n-butyl ketone), alcohols (C1-10) E.g. methanol, ethanol, n- and i-propanol, n-, i-, sec- and t-butanol, 2-ethylhexyl alcohol), amides (C3-6, e.g. dimethylformamide, dimethylacetamide, N-methylpyrrole) Emissions, etc.), sulfoxides (C2-4, such as dimethyl sulfoxide), and mixed and the solvent of two or more of these, and mixed solvents of water and aforementioned

As the dispersant, if it is a polymer dispersant, a formalin condensate of naphthalene sulfonate [alkali metal (Na and K) salt, ammonium salt, etc.], polystyrene sulfonate (same as above), polyacrylic acid Salt (same as above), poly (2-4) carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer etc.) salt (same as above), carboxymethylcellulose (Mn2,000-10,000) and polyvinyl alcohol (Mn 2,000 to 100,000).

The following are mentioned as a low molecular weight dispersing agent.
(1) AO (C2-4) of polyoxyalkylene type aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic (C4-30) amine and aliphatic (C4-30) amide 1-30 mol adduct fatty alcohols include n-, i-, sec- and t-butanol, octanol, dodecanol and the like; (alkyl) phenols include phenol, methylphenol and nonylphenol; aliphatic amines , Laurylamine, methylstearylamine, etc .; and aliphatic amides such as stearamide, etc. (2) polyhydric alcohol type C4-30 fatty acids (lauric acid, stearic acid, etc.) and polyvalent (2-6 or more) ) Monoesters of alcohols (eg GR, PE, sorbitol and sorbitan) Compound (3) Carboxylate type C4-30 fatty acid (same as above) alkali metal (same as above) salt (4) Sulfate ester type C4-30 aliphatic alcohol (same as above) and aliphatic alcohol AO (C2-4) 1-30 mol adduct sulfate metal alkali metal (same as above), etc. (5) Sulfonate type [alkyl (C1-30)] Phenol (same as above) alkali sulfonate Metal (same as above) salt (6) Phosphoric ester type C4-30 aliphatic alcohol (same as above) and AO (C2-4) 1-30 mol adduct of mono- or diphosphate of aliphatic alcohol Salt [alkali metal (same as above) salt, quaternary ammonium salt, etc.]
(7) Primary to tertiary amine salt type C4-30 aliphatic amine [primary (laurylamine etc.), secondary (dibutylamine etc.) and tertiary amine (dimethylstearylamine etc.) hydrochloride, triethanolamine And inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) of monoesters of C4-30 fatty acids (same as above) (8) Quaternary ammonium salt type C4-30 quaternary ammonium (butyltrimethylammonium, diethyl) Inorganic acid (same as above) salts of laurylmethylammonium, dimethyldistearylammonium and the like.

Examples of inorganic dispersants include alkali metal (same as above) salts of polyphosphoric acid and phosphoric acid dispersants (such as phosphoric acid, monoalkyl phosphoric acid ester, and dialkyl phosphoric acid ester).

Examples of the filler include silica, alumina, zirconia, mica and other oxide inorganic substances, fine powders of non-oxide inorganic substances such as silicon carbide and silicon nitride, and organic compounds such as acrylic resins and fluororesins. Depending on the application, metal powders such as aluminum, zinc and copper can be added. 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, novaculite, and diatomaceous earth; synthetic amorphous silica; kaolinite, mica, talc, wo Silicates such as lastnite, asbestos, calcium silicate, aluminum silicate; glass bodies such as glass powder, glass sphere, hollow glass sphere, glass flake, foam glass sphere; boron nitride, boron carbide, aluminum nitride, aluminum carbide Non-oxide inorganic materials such as silicon nitride, silicon carbide, titanium boride, titanium nitride, titanium carbide; calcium carbonate; metal oxides such as zinc oxide, alumina, magnesia, titanium oxide, beryllium oxide; barium sulfate, disulfide Molybdenum, tungsten disulfide, carbon fluoride and other inorganic materials; aluminum , Bronze, lead, stainless steel, metal powder such as zinc; and carbon black, coke, graphite, pyrolytic carbon, carbon and the like of the hollow carbon spheres, and the like.

Thickeners include montmorillonite clay minerals, bentonites containing these minerals, inorganic filler thickeners such as colloidal alumina, and cellulose thickeners such as methylcellulose, carboxymethylcellulose, hexylmethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose. Agent, urethane resin thickener, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl benzyl ether copolymer and other polyvinyl thickeners, polyether dialkyl ester, polyether dialkyl ether, polyether epoxy modified products, etc. Thickeners, associative thickener thickeners such as urethane-modified polyethers, special polymer nonionic thickeners such as polyether polyol urethane resins, nonionic surfactants, etc. Mosquito Inn, casein sodium, protein thickeners such as ammonium caseinate, and sodium alginate and acrylic acid-based thickener, and the like.

Leveling agents include PEG type nonionic surfactants (nonylphenol EO 1 to 40 mol adduct, stearic acid EO 1 to 40 mol adduct, etc.), polyhydric alcohol type nonionic surfactants (sorbitan palmitic acid monoester, sorbitan stearic acid) Monoesters, sorbitan stearic acid triesters, etc.), fluorine-containing surfactants (perfluoroalkyl EO 1-50 mol adducts, perfluoroalkyl carboxylates, perfluoroalkyl betaines, etc.), and modified silicone oils [polyether-modified silicones] Oil, (meth) acrylate-modified silicone oil, etc.].

As the curing agent for polyols, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, hydrogenated trihydride. Diisocyanate, lysine diisocyanate, polyisocyanate compound nurate, burette, adduct of polyisocyanate compound with polyols such as ethylene glycol, propylene glycol, trimethylolpropane, blocked polyisocyanate curing agent, etc. Mixtures of more than one species, these polyol adducts, their copolymers and block weights Like body such include isocyanates which can cure at room temperature. Examples of the curing agent for epoxy resins include acid anhydrides, phenol resins, polyamide resins, amine adducts, urea resins, melamine resins, and isocyanates.

As a crosslinking agent, in addition to melamine resin, urea resin, polyisocyanate compound, block polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride, alkoxysilane group-containing compound or resin, Hexamethoxymethylated melamine, N, N, N ′, N′-tetrahydroxymethyl succinamide, tetramethoxymethylated urea, 2,4,6-tetrahydroxymethylated phenol and other hydroxymethyl groups, and methoxymethyl groups Or a compound having an ethoxymethyl group or the like.

In addition to the pigments mentioned above, vanadium compounds such as vanadium pentoxide, calcium vanadate, magnesium vanadate and ammonium metavanadate; magnesium phosphate, magnesium phosphate / ammonium eutectoid, magnesium monohydrogen phosphate, phosphoric acid Magnesium dihydrogen, magnesium phosphate / calcium eutectoid, magnesium phosphate / cobalt eutectoid, magnesium phosphate / nickel eutectoid, magnesium phosphite, magnesium phosphite / calcium eutectoid, dihydrogen tripolyphosphate Treated with magnesium-containing compounds of metal phosphates such as aluminum, magnesium tripolyphosphate, magnesium dipolyphosphate treated with magnesium oxide, zinc trihydrogenphosphate treated with magnesium oxide, silica Phosphate-based antirust pigments such as silica-modified compounds of magnesium phosphate such as basic magnesium phosphate; antirust pigments containing zinc components such as zinc phosphate, magnesium-treated tripolyaluminum dihydrogen phosphate, calcium-treated calcium phosphate Zinc-free rust preventive pigments such as calcium silicates such as composite calcium silicates containing calcium orthosilicate or calcium metasilicate components; metal ion exchange silicas such as calcium ion exchange silica and magnesium ion exchange silica; and hexavalent chromium and lead Examples include rust preventive pigments and the like.

Examples of antifoaming agents include silicone-based antifoaming agents such as silicone oil, dimethylpolysiloxane, organically modified polysiloxane, and fluorine-modified polysiloxane, mineral oil-based antifoaming agents, non-silicone / polymer-based antifoaming agents, and organically modified fluorine. Examples thereof include an antifoaming agent comprising at least one selected from a compound and a polyoxyalkylene compound, and an antifoaming agent comprising an aliphatic alcohol having 18 or more carbon atoms.

The above-mentioned thing is mentioned about antioxidant, the light stabilizer containing a ultraviolet absorber, a flame retardant, a curing catalyst, a disinfectant, an antibacterial agent, etc.

In order to illustrate the present invention in detail, the following examples are given. However, the present invention is not limited to these examples.

(Example 1) (Stress luminescent material using 0.05 mol% of lithium with respect to 100 mol% of aluminum element in the raw material composition)
Strontium carbonate (SW-K, Sakai Chemical Industry Co., Ltd., 23.48 g), Lithium carbonate (Wako Pure Chemical Industries, Reagent, 0.0061 g), Europium oxide (Shin-Etsu Chemical Co., Ltd., 0.16 g) , Holmium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., 0.07 g), aluminum oxide (manufactured by Iwatani Chemical Industry Co., Ltd., activated alumina (mixture of θ alumina and η alumina), RG-40, 18.04 g), Charged into water (90 mL). Thereafter, a 3 mm diameter alumina ball (manufactured by Nikkato Co., Ltd., SSA-999W, 190 g) was used as a grinding medium, and a slurry was obtained by dispersing, grinding and mixing using a planetary ball mill. The resulting slurry was evaporated to dryness at 130 ° C. The obtained solid was crushed with a mortar to obtain a powdery composition. Next, 20 g of the composition was filled in an alumina crucible, heated to 1200 ° C. at 200 ° C./hour in a reducing atmosphere (2% hydrogen-containing nitrogen), held for 4 hours, and then at room temperature at 200 ° C./hour. The temperature was lowered. The fired product thus obtained was pulverized and sized in an alcohol solvent using a planetary ball mill, filtered and dried to obtain the desired stress luminescent material as a powder.

(Example 2) (Stress luminescent material using 0.25 mol% of lithium with respect to 100 mol% of aluminum element in the raw material composition)
Strontium carbonate (SW-K, Sakai Chemical Industry Co., Ltd., 23.41 g), lithium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., reagent, 0.03 g), europium oxide (Shin-Etsu Chemical Co., Ltd., 0.16 g) , Holmium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., 0.07 g), aluminum oxide (manufactured by Iwatani Chemical Industry Co., Ltd., activated alumina (mixture of θ alumina and η alumina), RG-40, 18.07 g) The stress-stimulated luminescent material was obtained as a powder by synthesizing in the same manner as in Example 1 except that the weighed values of the components were changed.

(Comparative Example 1) (Stress light emitter not using lithium)
As raw materials, strontium carbonate (SW-K, Sakai Chemical Industry Co., Ltd., 23.50 g), europium oxide (Shin-Etsu Chemical Co., Ltd., 0.16 g), holmium oxide (Shin-Etsu Chemical Co., Ltd., 0.07 g) , Synthesized in the same manner as in Example 1 except that aluminum oxide (produced by Iwatani Chemical Industry Co., Ltd., activated alumina (a mixture of θ alumina and η alumina), RG-40, 18.03 g) was used. Was obtained as a powder.

(Comparative Example 2) (Stress light emitter using 0.5 mol% of lithium with respect to 100 mol% of aluminum element in the raw material composition)
Strontium carbonate (SW-K, Sakai Chemical Industry Co., Ltd., 23.33 g), Lithium carbonate (Wako Pure Chemical Industries, Reagent, 0.06 g), Europium oxide (Shin-Etsu Chemical Co., Ltd., 0.16 g) Holmium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., 0.07 g), aluminum oxide (manufactured by Iwatani Chemical Industry Co., Ltd., activated alumina (mixture of θ alumina and η alumina), RG-40, 18.11 g) The stress-stimulated luminescent material was obtained as a powder by synthesizing in the same manner as in Example 1 except that the weighed values of the components were changed.

(Comparative Example 3) (Stress luminescent material using 1.5 mol% of lithium with respect to 100 mol% of aluminum element in the raw material composition)
Strontium carbonate (SW-K manufactured by Sakai Chemical Industry Co., Ltd., 23.00 g), lithium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., reagent, 0.18 g), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., 0.16 g) , Holmium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., 0.07 g), aluminum oxide (manufactured by Iwatani Chemical Industry Co., Ltd., activated alumina (mixture of θ alumina and η alumina), RG-40, 18.25 g) The stress-stimulated luminescent material was obtained as a powder by synthesizing in the same manner as in Example 1 except that the weighed values of the components were changed.

(Comparative example 4) (Stress light-emitting body using 0.25 mol% of sodium with respect to 100 mol% of aluminum element in the raw material composition)
As raw materials, strontium carbonate (SW-K, Sakai Chemical Industry Co., Ltd., 23.41 g), sodium carbonate (Wako Pure Chemical Industries, reagent, 0.04 g), europium oxide (Shin-Etsu Chemical Co., Ltd., 0 .16 g), holmium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., 0.07 g), aluminum oxide (manufactured by Iwatani Chemical Industry Co., Ltd., activated alumina (mixture of θ alumina and η alumina), RG-40, 18.04 g). The stress luminescent material was obtained as a powder by synthesizing in the same manner as in Example 1 except that it was used.

(Comparative Example 5) (Stress luminescent material using 0.25 mol% of potassium with respect to 100 mol% of aluminum element in the raw material composition)
As raw materials, strontium carbonate (SW-K, Sakai Chemical Industry Co., Ltd., 23.40 g), potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., reagent, 0.04 g), europium oxide (Shin-Etsu Chemical Co., Ltd., 0 .16 g), holmium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., 0.07 g), aluminum oxide (manufactured by Iwatani Chemical Industry Co., Ltd., activated alumina (mixture of θ alumina and η alumina), RG-40, 18.05 g). The stress luminescent material was obtained as a powder by synthesizing in the same manner as in Example 1 except that it was used.

(Comparative Example 6) (Stress luminescent material using 0.25 mol% magnesium with respect to 100 mol% aluminum element in the raw material composition)
As raw materials, strontium carbonate (SW-K, Sakai Chemical Industry Co., Ltd., 23.40 g), basic magnesium carbonate (GP-30N, Kamishima Chemical Industry Co., Ltd., 0.08 g), europium oxide (Shin-Etsu Chemical Co., Ltd.) 0.16 g), holmium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., 0.07 g), aluminum oxide (manufactured by Iwatani Chemical Industry Co., Ltd., activated alumina (mixture of θ alumina and η alumina), RG-40, 18.06 g ) Was used in the same manner as in Example 1 to obtain a stress-stimulated luminescent material as a powder.

(Comparative Example 7) (Stress luminescent material using 0.25 mol% of calcium with respect to 100 mol% of aluminum element in the raw material composition)
As raw materials, strontium carbonate (SW-K, Sakai Chemical Industry Co., Ltd., 23.40 g), calcium carbonate (CWS-20, Sakai Chemical Industry Co., Ltd., 0.09 g), europium oxide (Shin-Etsu Chemical Co., Ltd., 0 .16 g), holmium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., 0.07 g), aluminum oxide (manufactured by Iwatani Chemical Industry Co., Ltd., activated alumina (mixture of θ alumina and η alumina), RG-40, 18.05 g) Thus, except that the weighing value of each component was changed, synthesis was performed in the same manner as in Example 1 to obtain a stress luminescent material as powder.

Evaluation of the stress luminescence ability of the obtained powder was performed by the following method. In order to prepare circular pellets, powder and epoxy resin were added to a transparent plastic cell in a mass ratio of 1: 1, mixed by hand, and cured at 40 ° C. The round pellets that were cured were subjected to a load of 1000 N using a desktop precision universal testing machine (Shimadzu Corp., AGS-X), and light emission at that time was detected by a photomultiplier tube module (manufactured by Hamamatsu Photonics, H7827-011). did. The results are shown in Table 1. The relative intensity (unit:%) is shown when the stress luminescence intensity in the case where no additive element is contained (Comparative Example 1) is 100%.

As can be seen from Table 1, in the case of containing alkali metals (Na, K) other than Li (Comparative Examples 4 and 5) and in the case of containing alkaline earth metals (Mg, Ca) (Comparative Examples 6 and 7), The stress-stimulated luminescence intensity of the stress-stimulated luminescent material was reduced compared to the case where they were not included (Comparative Example 1). Thus, the reduction in the light emission characteristics of the stress light emitting material due to the mixing of impurities is an expected result in consideration of the knowledge so far. On the other hand, the stress-stimulated luminescent material having Li as an additive element showed a high stress luminescence intensity as compared with the case of containing other alkali metal elements. Based on the knowledge of the prior art, alkali metal elements have normally been discussed in parallel with no particular distinction. However, in the europium-activated strontium aluminate stress-stimulated luminescent material as shown above, when Na or K is included, In contrast to the fact that the emission characteristics were significantly reduced, the stress emission intensity was increased when Li, which is the same alkali metal, was included. Thus, it was shown that the stress-stimulated luminescent material of the present invention exhibits a synergistic effect by combining Eu as an activator with Li as an additive element.

Table 2 shows the amounts of Li added, in which Examples 1 and 2 and Comparative Examples 1 to 3 are arranged in the order of the amount of Li added. A graph of this is shown in FIG.

As can be seen from Table 2 and FIG. 2, when a small amount of Li was added, the relative stress luminescence intensity exceeded 100%. However, when the addition was further continued, the stress luminescence intensity gradually decreased and became lower than when Li was not added. As described above, it has been clarified that the light emission intensity of the stress-stimulated luminescent material is increased by adding Li in a specific range.

Claims (6)

A raw material composition for a stress luminescent material for synthesizing a europium-activated strontium aluminate-based stress luminescent material,
The stress-stimulated luminescent material is a fired product of the raw material composition,
The raw material composition is
Alumina and / or aluminum hydroxide;
A strontium compound,
A europium compound,
Containing 0.01 to 0.30 mol% of Li with respect to 100 mol% of the aluminum element ,
The alumina is at least one selected from the group consisting of α alumina, θ alumina, κ alumina, δ alumina, η alumina, χ alumina, γ alumina, and ρ alumina.
The strontium compound is at least one selected from the group consisting of strontium carbonate, strontium oxide, strontium hydroxide, strontium halide, strontium sulfate, strontium nitrate, and strontium hydrogen phosphate,
The europium compound is at least one selected from the group consisting of europium carbonate, europium oxide, europium chloride, europium sulfate, europium nitrate and europium acetate,
The Li is contained as at least one Li compound selected from the group consisting of lithium halide, lithium carbonate, lithium acetate, lithium nitrate, and lithium sulfate . The raw material composition for a stress-stimulated luminescent material according to claim 1, further comprising at least one element among rare earth elements other than europium as a coactivator. A stress-stimulated luminescent material , which is a fired product of the raw material composition for a stress-stimulated luminescent material according to claim 1. A stress-luminescent coating composition containing the stress-luminescent material according to claim 3. A resin composition containing the stress-stimulated luminescent material according to claim 3. A stress-stimulated luminescent material formed from the resin composition of claim 5.

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