CN107739610A - A kind of yellow longpersistent fluorescent material and preparation method thereof - Google Patents

A kind of yellow longpersistent fluorescent material and preparation method thereof Download PDF

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Publication number
CN107739610A
CN107739610A CN201711061603.2A CN201711061603A CN107739610A CN 107739610 A CN107739610 A CN 107739610A CN 201711061603 A CN201711061603 A CN 201711061603A CN 107739610 A CN107739610 A CN 107739610A
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acid
fluorescent material
ester
enumerate
yellow longpersistent
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CN107739610B (en
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杨道救
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Cixi Flying North Electronic Technology Co., Ltd.
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Hangzhou Qingqing Science And Technology Co Ltd
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Priority to CN201810767988.2A priority Critical patent/CN108531071A/en
Priority to CN201810767987.8A priority patent/CN108690606A/en
Priority to CN201810767986.3A priority patent/CN108841144A/en
Priority to CN201810767996.7A priority patent/CN108753278A/en
Priority to CN201711061603.2A priority patent/CN107739610B/en
Priority to CN201810767966.6A priority patent/CN108949164A/en
Publication of CN107739610A publication Critical patent/CN107739610A/en
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    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
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    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
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Abstract

The invention discloses a kind of yellow longpersistent fluorescent material and preparation method thereof, it is desirable to provide a kind of phosphor material powder with yellow longpersistent luminescent properties, belongs to long after glow luminous material technical field.The chemical composition formula of the fluorescent material is Sr5‑x‑ySiB2O10:xEu2+,yRe3+, wherein Re is Dy, the one or more combination in Gd and La, and x and y span are respectively：0.01≤x≤0.05,0.01≤y≤0.10.The centre of luminescence of the fluorescent material is Eu2+Ion, by introducing Dy3+, Gd3+And La3+It can effectively strengthen its long afterglow effect Deng rare earth impurities ion.Long lad phosphor provided by the invention has the characteristics that after-glow brightness is high, persistence is long, available for fields such as safety sign, urgent route sign, traffic sign and night displays.

Description

A kind of yellow longpersistent fluorescent material and preparation method thereof
Technical field
The invention belongs to phosphor technologies field, more particularly to a kind of yellow longpersistent fluorescent material and preparation method thereof.
Background technology
Long-persistence luminous is a kind of very important luminescence phenomenon, and it is even several to show as a few minutes after stopping illumination to sample In hour, sample remains in that a kind of luminous phenomenon, increasingly attracts people's attention.Originally, long-persistence luminous material Material is applied primarily to safety sign, urgent route sign, traffic sign and night display etc., and these subsequent materials are also used for Optical storage medium, radiation detection and structural damage sensor etc., at present again have increasing field such as Solar use and Vivo biodistribution imaging etc. can also solve relevant issues using long lad phosphor.The long-persistence luminous material of different substrates series The luminosity spectral characteristic of material is different, due to its glow color, luminous intensity, persistence it is different and with before different applications Scape, therefore respective advantage be present.
For human eye visually perceives the glow color of long after glow luminous material, mixing can be passed through in theory The three primary colors of different proportion obtain any color, but due to the limitation of some objective factors, and this method is in practice but It is difficult to fully achieve.So far, the three primary colors long after glow luminous material of commercialization is mainly SrAl2O4：Eu2+, Dy3+ （Green）、CaAl2O4：Eu2+, La3+（Blueness）And Y2O2S：Eu3+, Mg2+, Ti4+（It is red）, but the above two persistence is all Exceed 24 hours, and the yellow longpersistent luminescent material Y that the decay of afterglow time is most long2O2S：Eu3+, Mg2+, Ti4+Twilight sunset when Between only 5 to 10 hours, therefore be difficult be consistent the decay of afterglow process of three kinds of different colours long-afterglow materials, finally lead Cause the unstable of twilight sunset color.In addition, most of long after glow luminous material can not effectively be excited by identical excitation source, because This, it is desirable to obtain stable white or yellow longpersistent lights, research and development new type long-persistence luminescent material then must can not It is few.In document report in recent years, new type long-persistence luminescent material is still based on green and blue emitting material, and long wave is sent out The long after glow luminous material penetrated is less, only Sr3SiO5: Eu2+, Dy3+（570nm, 6h）, Y2O2S: Sm3+（606nm, 1.5h）, Sr3Al2O5Cl2: Eu2+, Tm3+（610nm, 4h）, Sr2Si5N8: Eu2+, Tm3+（612nm, 10min）, Sr2SnO4: Sm3+（624nm, 1h）And Y2O2S: Eu3+, Mg2+, Ti4+（627nm, 5h）Deng a few, and for yellow For long after glow luminous material, because the wave-length coverage of spectrum is narrower（560-590nm）, relevant report is less, therefore, is badly in need of out Send out some novel yellow long after glow luminous material.
The content of the invention
Yellow longpersistent luminescent material shortage in the prior art, in order to overcome above-mentioned yellow longpersistent in the prior art to light The problems such as luminous intensity of material is weaker, persistence is shorter, the invention provides a kind of novel yellow long lad phosphor and Its preparation method, the fluorescent material has the advantages that after-glow brightness is high, persistence is long, available for safety sign, urgent route mark The fields such as will, traffic sign and night display.
Because the species of long after glow luminous material is more, different materials has a different luminous mechanisms, and some materials Luminescence mechanism be also not clear at present, therefore, seek suitable matrix and active ions opening for new type long-persistence material Send out most important.Further, since the preparation method of long after glow luminous material is more, and has respective advantage and disadvantage, thus it is right The optimum organization of the preparation method of various long after glow luminous material will also be played to the popularization and application of long after glow luminous material and closed very much The effect of key.
To solve above-mentioned the deficiencies in the prior art, the technical solution adopted in the present invention is as follows：
1. a kind of yellow longpersistent fluorescent material, the chemical composition formula of the fluorescent material is Sr5-x-ySiB2O10: xEu2+,yRe3+, wherein Re is Dy, the one or more combination in Gd and La, and x and y span are respectively：0.01≤x≤0.05, 0.01≤y≤0.10.Preferably, the centre of luminescence of the fluorescent material is Eu2+Ion, by introducing rare earth ion Dy3+、Gd3+ And La3+In one or more combination provide trap level, effectively strengthen long afterglow effect.
A kind of preparation method of yellow longpersistent fluorescent material, it is characterised in that comprise the following steps：
（1）With the SrCO of high-purity3、SiO2、H3BO3、Eu2O3、Dy2O3、Gd2O3And La2O3As raw material, lead to according to chemical composition Formula Sr5-x-ySiB2O10: xEu2+, yRe3+The proportioning of middle each element, accurately weigh each raw material；
（2）Each raw material is put into agate mortar simultaneously, and is mixed uniformly by way of hand lapping, each sample Milling time is 20 ~ 30min；
（3）Above-mentioned well mixed raw material is put into corundum crucible, and is sintered in high temperature process furnances, sintering temperature is 1000 ~ 1400 DEG C, sintering time is 4 ~ 6 hours, and heating rate is 10 DEG C/min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mix Gas is closed, cools to room temperature after the completion of sintering with the furnace, obtains sintered body；
（4）By step（3）The sintered body of acquisition is ground crushing, produces the yellow longpersistent fluorescent material.
Compared with prior art, the beneficial effects of the invention are as follows：
（1）The invention provides a kind of novel yellow long lad phosphor, its matrix composition is Sr5SiB2O10, by rare earth from Sub- Eu2+Doping obtains yellow emission, further through introducing rare earth ion Dy3+、Gd3+And La3+In one or more combination provide Trap level, effectively enhance after-glow brightness and the time of the fluorescent material；
（2）Yellow longpersistent fluorescent material provided by the invention have chemical stability is good, after-glow brightness is high, persistence length etc. it is excellent Point.
The invention also discloses a kind of yellow longpersistent light-emitting component, using base made of above-mentioned yellow longpersistent fluorescent material Piece.
The invention also discloses a kind of yellow longpersistent light-emitting component, including substrate to send out with the long afterglow being attached in substrate Optical thin film, described long-persistence luminous film are thin for above-mentioned yellow longpersistent phosphor powder or yellow longpersistent fluorescent material Piece.
The invention also discloses a kind of yellow longpersistent light-emitting component, including substrate to send out with the long afterglow being attached in substrate Optical thin film, described long-persistence luminous film are yellow longpersistent phosphor powder or yellow longpersistent fluorescent material thin slice.
Preferably, the thickness of long-persistence luminous film is 1-10mm.
The substrate of the present invention, can be rigid basement, or flexible substrates.Preferably, the rigid basement can So that PDMS (polydimethylsiloxanes can be selected from selected from glass, silicon, steel, ceramics, cement, timber and stone, the flexible substrates Alkane) film, PET (polyethylene terephthalate) film, PS (polystyrene) film, PU (polyurethane) film, PI (polyimides) film With PVA (polyvinyl alcohol) film.
Above-mentioned yellow longpersistent light-emitting component preparation method, including：By yellow longpersistent phosphor as described above The suspension of last particle is coated in substrate as described above.
Although suspension will be prepared into yellow longpersistent phosphor powder particle suspension liquid solvent as described above, then Coated on can prepare the light-emitting component that meets application claims in the substrate, but when also containing high score in the suspension During sub- material, the sensitivity of final prepared light-emitting component and precision can be lifted further.
The content of the yellow longpersistent phosphor powder particle can also change in wider scope, preferable case Under, the suspension based on 100 parts by weight, the content of the yellow longpersistent phosphor powder particle is 0.5-10 weight Part, preferably 1-5 parts by weight.
Preferably, the polymer substance is selected from PVA, EVA (ethene-vinyl acetate copolymer), PDMS, PU, PMMA (gather Methyl methacrylate), PAM (polyacrylamide), PVP (polyvinylpyrrolidone), starch, cellulose, natural plant gum, animal One or more in glue, CMS, acetic starch, hydroxymethyl cellulose and carboxymethyl cellulose.
According to the present invention, the content of the polymer substance can also change in wider scope, under preferable case, base In the suspension of 100 parts by weight, the high molecular content is 1-10 parts by weight, preferably 3-8 parts by weight.
According to the present invention, the solvent can be various solvents commonly used in the art, be preferably selected from water, methanol, second Alcohol, acetone, ethylene glycol, isopropanol, diethylene glycol (DEG), ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether, ethylene glycol phenyl ether, second two Alcohol benzyl oxide, health alcohol, diethylene glycol methyl ether, diethylene glycol ether, butyl carbitol, triethylene glycol methyl ether, diacetone alcohol, tridecanol, 14 Alcohol, dioctyl phthalate, ethyl acetate, butyl acetate, cyclohexanone, dimethylbenzene, bicyclohexyl, hexamethylene, n-butanol, One or more in butanone, repefral and D-sorbite.
According to the present invention, by the suspension of the yellow longpersistent phosphor powder particle coated on the substrate surface Method can be the conventional selection in this area, it is for instance possible to use the painting method such as spraying, spin coating, can also use and print Technology.The suspension of yellow longpersistent phosphor powder particle is imprinted on the surface of substrate by present invention printing technique preferred herein On, so that the sensitivity for the sensor being prepared and precision are further lifted.Wherein, the printing technique can With one kind in dispensing, inkjet printing, water transfer, silk-screen printing and volume to volume printing.When use printing technique is by described in When the suspension of yellow longpersistent phosphor powder particle is printed on the surface of the substrate, the suspension is preferably prepared into ink Water, the preparation method of the ink is by the way that the suspension blending and stirring or blending ultrasonic disperse are obtained.
The invention also discloses a kind of yellow longpersistent light-emitting component, the yellow longpersistent light-emitting component includes macromolecule material Material and described yellow longpersistent phosphor powder, yellow longpersistent phosphor powder are evenly distributed in high polymer material, yellow The addition of color long lad phosphor powder is 1 ~ 90%；Preferably 10 ~ 80%.High polymer material can be selected from PDMS (poly- diformazans Radical siloxane), PET (polyethylene terephthalate), PS (polystyrene), PU (polyurethane), PI (polyimides) and PVA (polyvinyl alcohol) is thin.Appropriateness in order to improve the performance of processing, the thin-film material can also add coupling agent, lubricant, plasticising Agent etc..
The invention also discloses a kind of ink, the ink includes ink conventional ingredient and described yellow longpersistent fluorescent material Powder, yellow longpersistent phosphor powder are evenly distributed in ink conventional ingredient, the addition of yellow longpersistent phosphor powder Measure as 1 ~ 30%；Preferably 5 ~ 10%.Ink resin system can be polyamide, chlorination polypropylene, polyurethane or acrylic acid.Both may be used To be that oil-based ink can also be water-based ink.
The invention also discloses a kind of coating, the coating includes coating conventional ingredient and described yellow longpersistent fluorescent material Powder, yellow longpersistent phosphor powder are evenly distributed in coating conventional ingredient, the addition of yellow longpersistent phosphor powder Measure as 1 ~ 30%；Preferably 5 ~ 10%.Coating resin system can be polyamide, chlorination polypropylene, polyurethane or acrylic acid.Both may be used To be that oil paint can also be water paint.
In addition, it is formed at common paper, synthetic paper or epoxy resin, poly- second by the way that yellow longpersistent fluorescent material will be included The macromolecule such as alkene, polyethylene terephthalate, polyester, polypropylene, polyvinyl chloride raw material, natural rubber or synthesis rubber Glue, glass, ceramics, metal, wood, artificial fiber or natural fiber, concrete or combinations thereof and their fabricated product Deng exterior trim surface, or by internally containing yellow longpersistent fluorescent material.
Yellow longpersistent light-emitting component of the present invention can as illumination, for safety display utilization.For example,：Device Vibrate the ligthing paraphernalias such as lamp, wind power lamp；Promptly, abnormal notification, very apparatus, dangerous display, very lamp, non-conventional mark, rescue Mark, signboard, the display device of life instrument；Safety guard, nervous rope, the animal guard rail hung on around shop building； Use filament the pedal of ladder, handrail and the mesh that is set in the state of road etc. is partly embedded in；Health promoting appliance, walking are auxiliary Help utensil (walking auxiliary walking stick, luminous notification antenna etc.)；The jewellery such as earrings, necklace；Support cutting for pillar, the railway of flag etc. The exterior trim part or build-in components of road Ji Jie roads rod, bicycle, automobile, electric car, ship, aircraft etc., fishing tackle (simulation Bait, fishing rod, fishing net etc.；Photism fiber construct, photism fishing gear, fishing line, fishing net etc.), buoy (float, buoy)； The position display of the domestic animals such as the pets such as people, dog, cat, ox, pig, sheep, chicken etc.；Fan (blade of wind-power electricity generation, ventilating fan etc. etc.), Clothes (shoes, gym suit, manually light cloth, artificial luminous filament, artificial luminescent fibre etc.)；Pack (case, support, device, letter Envelope, ground paper, crust packaging, outside overlay film), medical products (breathing assistance utensil, experimental study equipment) robot it is (artificial luminous Hair structure body, artificial shiny skin, manually light body) etc..
As the utilization example containing yellow longpersistent fluorescent material in coating composition, ink composition, cement, surface dopant, It can enumerate：Contain in bonding agent used in financial institution, community organization, credit card company, circulation industry etc., stickup The mail pieces such as the crimping postcard sheet material of yellow longpersistent fluorescent material；The furniture such as chair, bed；Flooring material, ceramic tile, wall material The building materials such as material, prefabricated board material, paveio(u)r, timber steel concrete；It is equipped on the automated navigation system device of vehicle； For operating the operation device of audio devices and air-conditioning etc.；The input units such as family's electrical article, portable machine, electronic computer； Image storage means such as digital camera, CCD camera, film, photo, image etc..
New outward appearance can be produced by making yellow longpersistent light-emitting phosphor, therefore is also contemplated for toy, movable business Product etc. entertain the expansion of commodity, daily necessities.Such as it can enumerate：It is the wind long narrow flags such as dynamic toy, kite, carp shape flag, swing, fast Ski-running driving, carrousel, bow and arrow etc.；Pass through wind-force while the Powerless type light-emitting device (windbell etc.) of generation sound and light.Hair Photosphere (golf, the ball of baseball, table tennis ball, the ball etc. of billiard ball), the windmill of luminous mechanism；Balloon；Laminated structure thing For paper, batch flute, paper folding, paper balloon, folding fan, New Year card, paint this；(jumping pole, fencing, bow and arrow are isometric for sporting goods Size objects etc.)；It is the score confirmation pressure sensitive sealant part of golf club, tennis court line tester, dynamic ornamentation body, dynamic State engraving, dynamic souvenir；Dynamic Display device；Luminous decorative device；The PA-systems such as loudspeaker, musical instrument (violin, guitar Deng diaphragms such as the wind instruments such as the percussion instruments such as stringed musical instrument, xylophone, drum, trumpet, flute, glass), tuning fork etc.；Lipuid goods etc. are given pleasure to Happy commodity；The pasture and water with tank etc., container are viewed and admired in aquarium；Luminous wrist watch, luminous sand timer or sand timer type light Device；Light emitting-type simulates candle device；The artificial plant that can be lighted；Artificial eye；Cosmetics group containing tack polymer Compound, the printed article and marketable securities, the printer's ink containing long-persistence luminous particle, ticket that forgery can be distinguished under visual state According to, the admission of check, stock, bond, various security, exchange ticket, books certificate, the ticket of traffic organization, toll facility, project Middle lottery ticket of ballot certificate that certificate, lottery ticket, Public Physical Education are competed etc., bank note, identity card, ticket, the pass etc., passport, writing are organic The printed article of ciphertext book seals seal etc..
Using along with the luminous of long lad phosphor, the photochemical catalyst for being attached to yellow longpersistent phosphor surface is set to live Obtained from change, long-lasting phosphor-photochemical catalyst complex can be used for：Antibacterial, sterilization, the treatment to non-human animal, car Handrail, the antibacterial articles such as handle dirt purification, utilize the fluid of the internal wall such as pipe arrangement positioned at dark place The purification of energy of flow.Long-lag phosphor activates the photocrosslinking agent in macromolecule resin, can also promoted by lighting Crosslinking.
By the way that with being mixed in resin, the yellow longpersistent fluorescent material of the present invention can be formed into the resin combination of the present invention Thing.
In addition, formed again by further adding other inorganic material or organic material in the resin combination of the present invention Condensation material, the long-lasting phosphor of the present invention can also be formed.
For example, in the case that resin is epoxy resin, acrylic resin etc., relative in the compounding of the mass parts of resin 100 1~200 part of yellow longpersistent fluorescent material is stated, in the case that resin is polyvinyl resin, flexible vinyl chloride resin etc., relative to tree The mass parts of fat 100 are compounded the above-mentioned mass parts of yellow longpersistent fluorescent material 30~300.Blend can be by using tapered mixing The mixers such as machine, V-Mixer, ribbon mixer, Henschel mixer, banbury mixers, triple-roller mill make resin Composition.
In addition, in the case of forming long-lasting phosphor by the resin combination, such as obtain the long-persistence luminous of sheet During body, such as relative to the parts by weight of Corvic 100, be compounded the above-mentioned mass parts of yellow longpersistent fluorescent material 50~200, Calcium-the mass parts of zinc system stabilizer 3~5, the mass parts of dioctyl phthalate 30~100 as plasticizer, are existed with two-roller mill It is kneaded at 150~200 DEG C, so as to obtain the long-lasting phosphor of the sheet with pliability.
When obtaining the long-lasting phosphor of film-form, such as relative to the mass of pet resin 100 Part, the above-mentioned mass parts of yellow longpersistent fluorescent material 20~50 are compounded, with double screw extruder, inflation processing machine at 250~300 DEG C Under be kneaded, be molded, so as to obtain the long-lasting phosphor of film-form.
When obtaining the long-lasting phosphor of other shapes, such as relative to the mass parts of acrylic resin 100, compounding yellow length The mass parts of persistence phosphor 5~100, it is kneaded, is molded at 170~200 DEG C with double screw extruder, so as to obtain Banding, tabular, bar-shaped, partical long-lasting phosphor.In addition, by using injection (mo(u)lding) machine at 170~200 DEG C to grain The long-lasting phosphor of material shape is processed shaping, can obtain the long-lasting phosphor of three-dimensional shape.
As above-mentioned resin or other organic materials, can enumerate：Resin as thermoplastic resin, thermosetting resin. As thermoplastic resin, such as can enumerate：Low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), linear, low density The polyethylene such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, acrylonitrile-butadiene- The polyamide such as the styrene polymers such as styrol copolymer (ABS resin) or copolymer, 6- nylon, 66- nylon, 12- nylon, gather The acrylic resins such as amide imide, polyimides, PEI, polyurethane, polymethyl methacrylate, poly- acetic acid second The fluororesin such as alkene ester, vinyl-vinyl acetate copolymer, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), alkenyl aroma hydroxy-aromatic resin, gather The polyester such as ethylene glycol terephthalate, polybutylene terephthalate (PBT), PEN, PLA, bisphenol-A Be the makrolon such as makrolon, polyacetals, polyphenylene sulfide, polymethylpentene, cellulose, polyvinyl alcohol, polyvinyl acetate, It is the polyacrylic acid such as polyacrylonitrile, SAN (AS resins), polyphenylene oxide (PPE), MODIFIED PP E, polyarylate, poly- Diphenyl sulfide, polysulfones, polyether sulfone, polyethers nitrile, polyether-ketone, polyketone, copolymer, ethene or the propylene of liquid crystal polymer ethene and propylene With copolymer, ethene and other olefinic insatiable hungers of other alpha-olefins (1- butylene, 1- amylenes, 1- hexenes, 4-methyl-1-pentene etc.) With the copolymer of monomer (vinyl acetate, acrylic acid, acrylate, methacrylic acid, methacrylate, vinyl alcohol etc.) Deng.
Thermoplastic resin can be used alone or in combination of two or more kinds.It should be noted that thermoplastic resin is copolymerization Can be the copolymer of any forms such as random copolymer, block copolymer during thing.As thermosetting resin, can enumerate：Phenol Urea formaldehyde, urea resin, melmac, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, Organic siliconresin, alkyd resin, polyimides, PABM, casein resin, furane resins, polyurethane resin Deng.It can additionally enumerate：Utilize ultraviolet, the resin of radiation curing.
And then it can enumerate：Natural rubber, polyisoprene rubber, butadiene-styrene rubber, polybutadiene rubber, ethene-the third The rubber-based materials such as alkene-diene rubber, butyl rubber, neoprene, acrylonitrile butadiene rubber, silicon rubber.
In addition, can be by pigment, dyestuff, lubricant, antioxidant, ultra-violet absorber, light stabilizer, antistatic Agent, fire retardant, bactericide, antiseptic, solidification catalyst, Photoepolymerizationinitiater initiater etc. and the yellow longpersistent fluorescent material of the present invention It is mixed together, is shaped to bar-shaped, tabular, film-form, threadiness, membranaceous, needle-like, spherical, foil-like, graininess, sand shape, scale The arbitrary shapes such as shape, sheet, liquid, gel, colloidal sol shape, suspension, aggregation, capsule-type.
As pigment, inorganic pigment, organic pigment can be enumerated.
As inorganic pigment, can enumerate：Titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, Kermes (red iron oxide (III)), cadmium red, ultramarine, dark blue, chrome oxide green, cobalt green, chocolate, titanium is black, synthesis is iron black, carbon black, Mica, the aluminum oxide covered by titanium oxide, iron oxide, mica, glass flake, the holographic pigment covered by titanium oxide, iron oxide Deng.In addition, as metallic powdery pigment, can enumerate：Aluminium powder, copper powders, powder of stainless steel, metallic colloid, conduct There are transparent emerylite, coloring mica, interference mica, interference aluminum oxide, the interference silica (interference glass) of interference effect Deng.
As organic pigment, can enumerate：Azo pigment (monoazo yellow, condensation azophosphine, azomethine Huang etc.), Huang Color iron oxide, titan yellow, pucherite, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent Huang etc. Yellow uitramarine；The orange pigments such as permanent orange；Red iron oxide, naphthols AS systems azophloxine, anthanthrone, anthraquinone is red, pyrene is reddish brown, quinoline The red pigments such as acridone is red, diketopyrrolopyrrolecocrystals are red, permanent red；The purple face such as cobalt violet, quinacridone violet, dioxazine violets Material；The blue pigments such as cobalt blue, phthualocyanine pigment (phthalocyanine blue etc.), anthracene indigo plant；The viridine greens such as phthalocyanine green, azo system disperse dyes, Organic dyestuff such as anthraquinone system disperse dyes etc..
As dyestuff, can enumerate：Azo dyes, anthraquinone dye, bipseudoindoxyl dye, sulfur dye, triphenhlmethane dye, Pyrazolone dye, Stilbene dyestuff, diphenylmethane dye, Xanthene dyes, alizarin dyes, acridine dye, quinoneimine dye (piperazine Dyestuff, oxazine dyes, thiazine dye), thiazole dye, first alkynes dyestuff, nitro dye and nitroso-dyes etc..
As antioxidant, can enumerate：Hindered phenol series compound, phosphite ester based compound, phosphinate system chemical combination Thing and thioether based compound etc..
As hindered phenol series compound, can enumerate：Alpha-tocopherol, butylated hydroxytoluene, sinapinic alcohol, vitamin E, positive ten Eight alkyl-β-(4 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) propionic ester, the 2- tert-butyl groups -6- (3 '-tert-butyl group -5 '-methyl -2 ' - Hydroxybenzyl) -4- aminomethyl phenyls acrylate, 2,6- di-t-butyls -4- (N, N- dimethylaminomethyl) phenol, the uncles of 3,5- bis- Butyl -4- benzylphosphonic acids diethyl ester, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), 2,2 '-di-2-ethylhexylphosphine oxide (4- ethyl -6- tert-butyl phenols), 4,4 '-methylene-bis(2,6-di-t-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl -6- Cyclohexylphenol), 2,2 '-dimethylene-bis- (6- Alpha-Methyls-benzyl-paracresol) 2,2 '-ethidine-bis- (4,6- di-t-butyls Phenol), 2,2 '-butane-bis- (4- methyl-6-tert-butylphenols), 4,4 '-butane double (3 methy 6 tert butyl phenol), Double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic esters of triethylene glycol-N-, double [3- (the bis- tertiary fourths of 3,5- of 1,6-HD Base -4- hydroxy phenyls) propionic ester], double [the 2- tert-butyl group -4- methyl 6- (the 3- tert-butyl group -5- methyl -2- hydroxybenzyls) phenyl] it is right Double { 2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propiono the epoxide] -1,1- dimethyl second of phthalic acid ester, 3,9- Base } -2,4,8,10- four oxaspiro [5,5] hendecane, 4,4 '-thiobis (the 6- tert-butyl groups-metacresol), 4,4 '-thiobis (3- Methyl-6-tert-butylphenol), 2,2 '-thiobis (4- methyl-6-tert-butylphenols), double (3,5- di-t-butyl -4- hydroxyl benzyls Base) thioether, 4,4 '-two thio bis(2,6-di-butyl phenol)s, 4,4 '-three thio bis(2,6-di-butyl phenol)s, 2,2- Double (just pungent sulfenyl) -6- (the 4- hydroxyls of thiodiethylene pair-[3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], 2,4- Base -3 ', 5 '-di-tert-butyl amido) -1,3,5- triazines, N, N '-hexamethylene bis-(3,5- di-t-butyl -4- hydroxy groups Cinnamamide), N, N '-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionos] hydrazine, (2- methyl -4- the hydroxyls of 1,1,3- tri- Base -5- tert-butyl-phenyls) butane, 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, three (3,5- Di-tert-butyl-hydroxy phenyl) isocyanuric acid ester, three (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid esters, 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) isocyanuric acid ester, the [3- (3,5- di-t-butyl -4- hydroxy benzenes of 1,3,5- 32 Base) propiono epoxide] ethyl isocyanurate and four [methylene -3- (3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic esters] Methane etc..
As phosphite ester based compound, triphenyl phosphite, phosphorous acid three (nonyl phenyl) ester, phosphorous acid can be enumerated Three decyl esters, phosphorous acid trioctylphosphine ester, phosphorous acid three (octadecyl) ester, phosphorous acid didecyl list phenylester, phosphorous acid two are pungent Base mono-phemyol ester, phosphorous acid diisopropyl list phenylester, phosphorous acid monobutyl diphenyl, phosphorous acid list decyl diphenyl, Phosphorous acid list octyl diphenyl, phosphorous acid three (diethyl phenyl) ester, phosphorous acid three (diisopropyl phenyl) ester, phosphorous acid three (di-n-butyl phenyl) ester, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, phosphorous acid three (2,6- di-tert-butyl-phenyls) ester, two Stearyl pentaerythritol diphosphites, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, double (bis- tertiary fourths of 2,6- Base -4- aminomethyl phenyls) pentaerythritol diphosphites, double (2,6- di-t-butyl -4- ethylphenyls) pentaerythrite diphosphorous acids Ester, double { double (1- methyl isophthalic acids-phenylethyl) phenyl of 2,4- } pentaerythritol diphosphites, phenyl bisphenol-A pentaerythrite two are sub- Phosphate, double (nonyl phenyl) pentaerythritol diphosphites and dicyclohexyl pentaerythritol diphosphites etc..It is used as other Phosphite ester based compound, it can enumerate and be reacted with dihydric phenol class so as to the phosphite ester based compound with cyclic structure.
As phosphinate based compound, can enumerate：Four (2,4- di-tert-butyl-phenyls) -4,4 '-biphenylene two is sub- Phosphonate ester, four (2,4- di-tert-butyl-phenyls) -4,3 '-biphenylens, four (2,4- di-tert-butyl-phenyls) -3, 3 '-biphenylen, four (2,6- di-tert-butyl-phenyls) -4,4 '-biphenylens, four (2,6- bis- Tert-butyl-phenyl) -4,3 '-biphenylen, four (2,6- di-tert-butyl-phenyls) -3,3 '-biphenylenes, two sub- phosphine Acid esters, double (2,4- di-tert-butyl-phenyls) -4- phenyl-phenyls phosphinates, double (2,4- di-tert-butyl-phenyls) -3- phenyl-benzene Base phosphinate, double (2,6- di-n-butyls phenyl) -3- phenyl-phenyls phosphinates, double (2,6- di-tert-butyl-phenyls) -4- benzene Base-phenylphosphite ester and double (2,6- di-tert-butyl-phenyls) -3- phenyl-phenyl phosphinates etc..
As thioether based compound, can enumerate：Thiodipropionate dilauryl, thio-2 acid two (tridecyl) Ester, thio-2 acid myristyl ester, thio-2 acid distearyl base ester, (the 3- lauryl propane thioic acids of pentaerythrite-four Ester), pentaerythrite-four (3- laurylthiopropionates), pentaerythrite-four (3- octadecyls thiopropionate), season penta Tetrol four (3- myristyls thiopropionate) and pentaerythrite-four (3- stearyl-thios propionic ester) etc..
As the light stabilizer comprising ultra-violet absorber, can enumerate：Benzophenone based compound, enumerate BTA system chemical combination Thing, aromatic series benzoic ether based compound, oxanilide based compound, cyanoacrylate based compound and the amine system chemical combination that is obstructed Thing etc..
As benzophenone based compound, can enumerate：Benzophenone, 2,4 dihydroxyl benzophenone, 2,2 '-dihydroxy Benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, ESCALOL 567,2,2 '-dihydroxy -4,4 '-two Methoxy benzophenone, 2,2 '-dihydroxy -4,4 '-dimethoxy -5- sulfonyls benzophenone, 2- hydroxyl -4- octyloxy hexichol Ketone, 2- hydroxyl -4- dodecyloxy benzophenones, 2- hydroxyl -4- octyloxybenzophenones, 2- hydroxyl -4- methoxyl group -5- sulphurs Acyl group benzophenone, 5- chlorine-2-hydroxyls benzophenone, 2- hydroxyl -4- octyloxybenzophenones, 2- hydroxyl -4- methoxyl groups -2 ' - Carboxyl benzophenone and 2- hydroxyls -4- (2- hydroxy-3-methyls-acryloxy isopropoxy) benzophenone etc..
As BTA based compound, can enumerate：2- (5- methyl -2- hydroxy phenyls) BTA, 2- (3,5- bis- The tert-butyl group -2- hydroxy phenyls) BTA, 2- (tertiary pentyl -2- hydroxy phenyls of 3,5- bis-) BTA, 2- (3 ', 5 '-two uncles Butyl -4 '-methyl -2 '-hydroxy phenyl) BTA, 2- (tertiary pentyl -2- hydroxy phenyls of 3,5- bis-) -5- chlorobenzotriazoles, 2- (the 5- tert-butyl group -2- hydroxy phenyls) BTA, 2- [2 '-hydroxyl -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] benzo three Azoles, 2- [2 '-hydroxyl -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] -2H- BTAs and 2- (4 '-octyloxies -2 '-hydroxyl Phenyl) BTA etc..
As aromatic series benzoic ether based compound, can enumerate：Salicylic acid is to tert-butyl benzene base ester, salicylic acid to octyl group Salicylic acid alkyl phenyl esters such as phenylester etc..
As oxanilide based compound, can enumerate：2- ethyoxyls -2 '-ethyloxanilide, 2- ethyoxyls -5- The tert-butyl group -2 '-ethyloxanilide and 2- ethyoxyls -3 '-dodecyl butoxanilide etc..
As cyanoacrylate based compound, can enumerate：Ethyl -2- cyano group -3,3 '-diphenylacrylate ester, 2- Ethylhexyl-cyano group -3,3 '-diphenylacrylate ester etc..
As the amine compound that is obstructed, can enumerate：4- acetoxyl group -2,2,6,6- tetramethyl piperidines, 4- stearoyl ketos Base -2,2,6,6- tetramethyl piperidines, 4- acryloxy -2,2,6,6- tetramethyl piperidines, 4- (phenylacetyl epoxide) -2,2,6, 6- tetramethyl piperidines, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, 4- methoxyl group -2,2,6,6- tetramethyl piperidines, 4- ten Eight alkyl oxy -2,2,6,6- tetramethyl piperidines, 4- cyclohexyl epoxide -2,2,6,6- tetramethyl piperidines, 4- benzyls epoxide -2,2, 6,6- tetramethyl piperidines, 4- phenoxy group -2,2,6,6- tetramethyl piperidines, 4- (ethylcarbamoyl epoxide) -2,2,6,6- tetramethyls Phenylpiperidines, 4- (cyclohexyl carboxyamide epoxide) -2,2,6,6- tetramethyl piperidines, 4- (phenylcarbamoyl epoxide) -2,2,6, 6- tetramethyl piperidines, double (2,2,6,6- tetramethyl -4- piperidyls) carbonic esters, double (2,2,6,6- tetramethyl -4- piperidyls) grass Acid esters, double (2,2,6,6- tetramethyl -4- piperidyls) malonates, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, Double (2,2,6,6- tetramethyl -4- piperidyls) adipate esters, double (2,2,6,6- tetramethyl -4- piperidyls) terephthalates, 1,2- double (2,2,6,6- tetramethyl -4- piperidyls epoxide)-ethane, α, α '-bis- (2,2,6,6- tetramethyl -4- piperidyl oxygen Base)-paraxylene, double (2,2,6,6- tetramethyl -4- piperidyls)-toluylene -2,4- diurethanes, it is double (2,2, 6,6- tetramethyl -4- piperidyls)-hexa-methylene -1,6- diurethanes, three (2,2,6,6- tetramethyl -4- piperidyls) - Benzene -1,3,5- tricarboxylic esters, three (2,2,6,6- tetramethyl -4- piperidyls)-benzene -1,3,4- tricarboxylic esters, 1,2- { 3- (3,5- Di-tert-butyl-hydroxy phenyl) propiono epoxide } -2,2,6,6- tetramethyl piperidines and 1,2,3,4- BTCAs and 1, 2,2,6,6- pentamethyl -4- hydroxy piperidines and β, β, β ', the β '-tetramethyl -3,9- [oxaspiros (5,5) of 2,4,8,10- tetra- 11 Alkane] dimethanol condensation product etc..
As antistatic additive, can enumerate：The toner bodies such as carbon black, graphite, tin antimony composite oxides, antimony indium tin are answered Close the metal oxygens such as oxide, indium tin composite oxides, the electric conductivity indium oxide for being doped with Sn, F, Cl etc., tin oxide, zinc oxide Inorganic system's antistatic additive such as the various metallic particles such as compound, copper, nickel, silver, gold, aluminium (powder) or metallic fiber and (β-bay Acid amides propiono) quaternary ammonium salt system, sulfonate based compound, the alkyl phosphate such as trimethyl ammonium sulfate, neopelex Antistatic additive of the organic systems such as based compound etc..
As fire retardant, can enumerate：Bromide fire retardant, phosphorus flame retardant, chlorine-based flame retardant, triazine flame retardant, with And other inorganic flame retardants such as salt of phosphoric acid and piperazine etc..
As bromide fire retardant, can enumerate：Brominated Polystyrene, brominated polyacrylate, brominated polyphenylether, bromination are double Phenol A types epoxy resin, brominated bisphenol a type epoxy resin molecule chain end glycidyl part or all by envelope The modifier at end, the polycarbonate oligomer of Material synthesis, the phthalimide chemical combination of bromination two are used as using brominated bisphenol A The compounds such as the brominated diphenyl base alkane such as thing, bromination Biphenyl Ether and 1,2- bis- (penta-bromophenyl) ethane.Wherein it is possible to enumerate：Poly- three The brominated Polystyrenes such as bromstyrol, poly- (dibromobenzene aether), decabrominated dipheny base ether, double (tribromophenoxy) ethane, 1,2- bis- (five Bromophenyl) ethane, ethene-bis--(tetrabromo phthalimide), tetrabromobisphenol A, brominated polycarbonate oligomer, poly- tribromo The brominated Polystyrenes such as styrene, 1,2- bis- (penta-bromophenyl) ethane etc..
As phosphorus flame retardant, can enumerate：Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate (2- second Base hexyl) ester, tributoxyethyl phosphate, triphenyl phosphate, lindol, tricresyl phosphate (xylyl) ester, phosphoric acid Three (isopropyl phenyl) esters, tricresyl phosphate (phenyl) ester, tricresyl phosphate naphthyl ester, tricresyl phosphate base diphenyl, phosphoric acid diformazan Phenyl diphenyl, diphenyl phosphate (2- ethylhexyls) ester, di(2-ethylhexyl)phosphate (isopropyl phenyl) phenylester, mono phosphoric acid ester isodecyl Ester, 2- acryloyl-oxyethyls phosphate ester acid, 2- methacryloxyethyls phosphate ester acid, diphenyl -2- acryloyls Epoxide ethyl phosphonic acid ester, diphenyl -2- methacryloxyethyls phosphate, melamine phosphate, two (melamines) Phosphate, melamine pyrophosphoric ester, triphenylphosphine oxide, trimethylphenyl phosphine oxide, methanephosphonic acid diphenyl ester, phenyl-phosphonic acid two The phosphates such as ethyl ester, resorcinol Polyphenyl phosphate, 1,3- phenylenes double (2,6- dimethylphenylphosphates), resorcinols Poly- (two -2,6- xylyls) phosphate, polymer with bis phenol A tolyl phosphate, bisphenol-A Polyphenyl phosphate, the poly- (2,6- bis- of quinhydrones Tolyl) condensed phosphoric acid esters such as the aromatic condensation phosphate such as phosphate and their condensation product etc..
As chlorine-based flame retardant, can enumerate：The cyclodecane of pentachloro- five, hexachloro-benzene, toluene pentachloride, tetrachlorobisphenol A and polychlorostyrene Styrene etc..
As triazine flame retardant, can enumerate：Melamine, methyl guanamines, benzoguanamine, acryloyl guanamines, 2,4- diaminos Base -6- nonyl -1,3,5- triazines, 2,4- diaminourea -6- hydroxyl -1,3,5- triazines, 2- amino -4,6- dihydroxy -1,3,5- three Piperazine, 2,4- diaminourea -6- methoxyl group -1,3,5- triazines, 2,4- diaminourea -6- ethyoxyl -1,3,5- triazines, 2,4- diaminourea - 6- propoxyl group -1,3,5- triazines, 2,4- diaminourea -6- isopropoxy -1,3,5- triazines, 2,4- diaminourea -6- sulfydryls -1,3,5- Triazine and 2- amino -4,6- dimercapto -1,3,5- triazines etc..
As phosphoric acid and the salt of piperazine, can enumerate：Orthophosphoric acid piperazine, piperazine pyrophosphate and polyphosphoric acid piperazine etc..
As inorganic flame retardant, can enumerate：The antimonials such as antimony trioxide, Antimony pentachloride, Firebrake ZB, Boratex, Aluminium hydroxide, magnesium hydroxide and red phosphorus etc..
As bactericide, can enumerate：The copper fungicides such as copper 8-hydroxyquinolinate, zineb (Zineb), maneb (Maneb) etc. have The organochlorine such as machine thiophanate fungicide, captan, Bravo system bactericide, thiophanate-methyl, benomyl, carbendazim, thiabendazole etc. The acyls such as the dicarboximide system such as benzimidazole system bactericide, iprodione, vinclozolin, procymidone bactericide, furametpyr The morpholine system bactericide such as the phenylpyrrole such as amine system bactericide, fludioxonil system bactericide, dimethomorph, Fluoxastrobin, kresoxim-methyl, The anilino-pyrimidine system bactericide such as the methoxy acrylate such as ORIBRIGHT system bactericide, mepanipyrim, cyprodinil, pyrimethanil, The soil fungicides such as the ergosterol biosynthesis inhibitors such as triazolone, fluorine bacterium azoles, trichloronitromethane, PCNB and fluorine pyridine Amine, o-phenyl phenol (OPP), diphenyl, chlorodiphenyl base, cresols, 1,2- double (acetyl bromide epoxide) ethane, cinnamic acid, acetic acid benzene The bromo- 3- itrile groups propionyl of ester, allyl isothiocyanate, Alpha-Methyl acetophenone, thymol, full-chloro-cyclopentadiene, bromoacetic acid, 2,2- bis- Amine, ethyl chloroacetate, butyl chloroacetate, methyl chloroacetate, 5- chloro-2-methyl isothiazoline -3- ketone, glutaraldehyde and Hinokitiol Deng.
As antiseptic, can enumerate：Make silver, zinc, one kind of copper or antibiotic property Metal Supported of more than two kinds in inorganization Inorganic system's powder obtained from compound.As load, can enumerate：Zeolite, apatite, basic zirconium phosphate, titanium oxide, silica Gel, aluminum sulfate hydroxide, calcium phosphate, calcium silicates etc..It can in addition contain enumerate：With phosphate, boric acid system, silicic acid system Be respectively glass one kind or two or more glass as glass forming constituents in containing silver, zinc, copper one kind or two or more Antibiotic property metal obtained from antibacterial glass powder.
As lubricant, can enumerate：Aliphatic acid, fatty acid metal salts, oxo aliphatic acid, paraffin, low molecule amount it is poly- Alkene, fatty acid amide, alkylenebisfatty acid amides, aliphatic ketone, fatty acid part saponification ester, aliphatic acid low-carbon-ester, fat Acid polyol ester, fatty acid polyglycol ethanol ester and modified organic silicon etc..
As aliphatic acid, can enumerate：Oleic acid, stearic acid, laurate, hydroxy stearic acid, behenic acids, arachidonic acid, The aliphatic acid of the carbon numbers 6~40 such as linoleic acid, leukotrienes, ricinoleic acid, palmitic acid, montanic acid and their mixture.As fat Fat acid metal salt, it can enumerate：It is sodium laurate, potassium laurate, Magnesium dilaurate, calcium laurate, zinc laurate, barium laurate, hard Resin acid sodium, potassium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, behenic acid sodium, behenic acid potassium, behenic acids Alkali (soil) gold of the aliphatic acid of carbon number 6~40 such as magnesium, behenic acid calcium, behenic acid zinc, behenic acids barium, montanic acid sodium and montanic acid calcium Belong to salt.
As oxo aliphatic acid, can enumerate：1,2- stearoxylic acids etc..
As paraffin, can enumerate：The paraffin of the carbon numbers such as atoleine, natural paraffin wax, microwax and vaseline more than 18.
As the polyolefin of low molecule amount, can enumerate：Tissuemat E, maleic acid modified Tissuemat E, the poly- second of oxidized form The polyolefin of alkene wax, haloflex wax and polypropylene wax equimolecular quantity below 5000., specifically can be with as fatty acid amide Enumerate：The fatty acid amide of the carbon numbers more than 6 such as oleamide, erucic amide, Shan Yu acid amides.
As alkylenebisfatty acid amides, can enumerate：Methylene bis stearamide, ethylenebisstearamide and N, N- The alkylenebisfatty acid amides of the carbon numbers more than 6 such as double (2- hydroxyethyls) stearmides.
As aliphatic ketone, can enumerate：The aliphatic ketone of the carbon numbers such as higher aliphatic ketone more than 6.As fatty acid moieties Divide saponification ester, can enumerate：Partly-hydrolysed ester of montanic acid etc..
As aliphatic acid low-carbon-ester, can enumerate：Stearate, oleate, linoleate, linolenate, adipic acid Ester, behenic acids ester, arachidonate, montanate and isostearate etc..
As polyol esters of fatty acids, can enumerate：Glycerine tristearate, glycerine distearate, glycerine Monostearate, pentaerythritol tetrastearate, pentaerythrite tristearate, the myristinate of pentaerythrite two, Ji Wusi Alcohol monostearate, pentaerythritol adipate stearate and anhydrous sorbitol Dan behenic acid esters etc..
As fatty acid polyglycol ethanol ester, can enumerate：Cithrol, polytrimethylene diol fatty acid ester and Polypropylene glycol fatty acid esters etc..
As modified organic silicon, can enumerate：The alkoxy-modified organosilicon of organic silicon modified by polyether, higher fatty acids, contain Organosilicon, high-grade aliphatic ester modified organic silicon, methacrylic modified organic silicon and the fluorine richness for having higher fatty acids have Machine silicon etc..
As solidification catalyst, can enumerate：(peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidating first and second Ketone etc.) and organic peroxide, octyl group acid tin, the dibutyl such as azo-compound (azodiisobutyronitrile and AMBN etc.) Tin two (2 ethyl hexanoic acid ester), dioctyl tin two (2 ethyl hexanoic acid ester), dioctyl tin diacetate esters, dibutyltindilaurylmercaptide cinnamic acid Ester, dioctyl tin dilaurate, Dibutyltin oxide, dioctyl tin oxide, dibutyl tin soap, 2 ethyl hexanoic acid Lead, zinc octoate, zinc naphthenate, fatty acid zinc class, cobalt naphthenate, calcium octoate, copper naphthenate, 2 ethyl hexanoic acid lead lead octoate and four The inorganic acids such as Organometallic derivatives, hydrochloric acid, nitric acid, the sulfuric acid such as the metals such as n-butyl titanate and organic and inorganic acid salt, The sulfoacid compounds such as p-methyl benzenesulfonic acid, DBSA, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, sulfoacid compound Amine corrective, organic amine, phosphoric acid, the pyrophosphoric acid such as triethylamine etc., phosphate monoester or di-phosphate ester etc..As phosphate monoester, Such as it can enumerate：Mono-octyl phosphate, mono phosphoric acid ester propyl ester and mono phosphoric acid ester lauryl etc..As di-phosphate ester, such as can enumerate： Dioctylphosphoric acid ester, phosphoric acid dipropyl and didodecyl phosphate etc..And then it can enumerate：Single (2- (methyl) acryloxy second Base) phosphate cpd, diazabicyclo endecatylene series catalysts, lewis acid and the acid anhydrides such as phosphate ester acid etc..
As Photoepolymerizationinitiater initiater, can enumerate：(2-hydroxybenzoyl) compound (2- hydroxy-2-methyl -1- phenyl-propanes - 1- ketone, 1- hydroxycyclohexylphenylketones, benzoin alkylether etc.), benzoyl formic acid ester compounds (methylbenzoyl formate Deng), thioxanthone compounds (isopropyl thioxanthone etc.), benzophenone cpd (benzophenone etc.), phosphate compound (1,3, 5- trimethylbenzoyl diphenyl phosphine oxides etc.) and benzil dimethyl ketal etc..
And then coating is mixed in so as to which the length of the present invention can also be made by the way that the yellow longpersistent fluorescent material of the present invention is matched somebody with somebody Afterglow coating composition.
The long-persistence luminous property coating composition of the present invention can be coated with the surface of other materials.
In addition, the hair of the long-persistence luminous property coating composition of the invention of the yellow longpersistent fluorescent material containing the present invention Brightness is high, therefore can carry out visual high application.
As coating composition, the coating composition containing overlay film formative resin can be used.In coating composition, root It can also contain according to needs：Solvent, dispersant, filler, thickener, levelling agent, curing agent, crosslinking agent, pigment, defoamer, The coating such as antioxidant, the light stabilizer comprising ultra-violet absorber, fire retardant, solidification catalyst, bactericide and antiseptic Use additive.
As the material used in coating composition, thermosetting resin, normal temperature cure resin, ultraviolet can also be used The various resins such as curable resin, radiation curing resin, such as can enumerate：Acrylic resin, alkyd resin, poly- ammonia Ester resin, polyester resin, amino resins etc., organosilicon acid esters, organic titanate etc..
As black film formation material, can enumerate：Polyurethane resin, acrylic resin, polyamide, vinyl chloride- Vinyl acetate resin and propylene dichloride resin etc..
As solvent, can enumerate：Aliphatic hydrocarbon, aromatic hydrocarbon (C7~10, such as toluene, dimethylbenzene and ethyl Benzene), ester or ether-ether (C4~10, such as methoxybutyl acetic acid esters), ether (C4~10, such as tetrahydrofuran, EG single ethyl Ether, EG single-butyl ether, PG monomethyl ether and DEG single ethylether), (C3~10, such as methyl iso-butyl ketone (MIBK), two are just for ketone Butyl ketone), alcohol (C1~10, such as methanol, ethanol, normal propyl alcohol and isopropanol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, 2- ethylhexyl alcohols), acid amides (C3~6, such as dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE), sulfoxide (C2~4, such as dimethyl sulfoxide (DMSO)) and their mixed solvent of more than two kinds, water or foregoing mixed solvent.
As dispersant, as long as being macromolecule dispersing agent, can enumerate：Naphthalene sulfonate [alkali metal (Na and K etc.) salt, ammonium Salt etc.] formaline condensates, poly styrene sulfonate (same as described above), polyacrylate (same as described above), poly- (2 ~4) carboxylic acid (maleic acid/glycerine/monoallyl ether copolymer etc.) salt (same as described above), carboxymethyl cellulose (Mn2000~ And polyvinyl alcohol (Mn2000~100000) etc. 10000).
As low molecule dispersant, following substances can be enumerated.
(1) poly (oxyalkylene) fundamental mode
Aliphatic alcohol (C4~30), [alkyl (C1~30)] phenol, aliphatic (C4~30) amine and aliphatic (C4~30) acid amides 1~30 mole of addition product of AO (C2~4).
As aliphatic alcohol, there are n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, octanol, dodecanol etc.；As (alkane Base) phenol, there are phenol, methylphenol and nonyl phenol etc.；As aliphatic amine, there are lauryl amine and methyl stearic amine etc.； With as aliphatic amide, there is stearmide etc..
(2) polyol type
The aliphatic acid (laurate, stearic acid etc.) of C4~30 and polynary (2~6 or its more than) alcohol (such as GR, PE, D-sorbite And anhydrous sorbitol) monoester compound.
(3) carboxylic acid type
Alkali metal (same as described above) salt of the aliphatic acid (same as described above) of C4~30.
(4) sulfuric acid ester type
The sulfuric ester of the aliphatic alcohol (same as described above) of C4~30 and AO (C2~4) 1~30 mole of addition product of aliphatic alcohol Alkali metal (same as described above) salt etc..
(5) sulfonate type
Sulfonate alkali metal (same as described above) salt of [alkyl (C1~30)] phenol (same as described above).
(6) phosphate type
The monophosphate of the aliphatic alcohol (same as described above) of C4~30 and AO (C2~4) 1~30 mole of addition product of aliphatic alcohol The salt of ester or bisphosphate [alkali metal (same as described above) salt, quaternary ammonium salt etc.].
(7) primary~tertiary amine salt form
Aliphatic amine [primary amine (lauryl amine etc.), secondary amine (dibutylamine etc.) and the tertiary amine (dimethylstearamine of C4~30 Deng)] inorganic acid (hydrochloric acid, sulfuric acid, the nitric acid of the monoesters of hydrochloride, triethanolamine and the aliphatic acid of C4~30 (same as described above) With phosphoric acid etc.) salt.
(8) quaternary
The inorganic acid of the quaternary ammonium (butyl trimethyl ammonium, diethyl lauryl methyl ammonium, dimethyl distearyl ammonium etc.) of C4~30 (same as described above) salt etc..
As inorganic dispersant, can enumerate：Alkali metal (same as described above) salt and phosphate dispersant (phosphorus of polyphosphoric acid Acid, monoalkyl phosphoric acid esters and dialkyl phosphate etc.) etc..
As filler, can enumerate：It is inorganic as the oxide system of representative using silica, aluminum oxide, zirconium oxide, mica The organic compounds such as the micro mist or acrylic resin, fluororesin of the non-oxidized substance based inorganic material such as thing, carborundum, silicon nitride.Separately Outside, the metal dusts such as aluminium, zinc, copper can also be added according to purposes.And then as the concrete example of filler, it can enumerate：Dioxy SiClx colloidal sol, zirconia sol, alumina sol, TiO 2 sol isosol；Silica sand, quartz, close quartzy salt, diatomite Etc. silica-based material；Synthesize amorphous silica；Kaolinite, mica, talcum, wollastonite, asbestos, calcium silicates, silicic acid The silicate such as aluminium；The vitreums such as glass powder, glass marble, hollow glass ball, glass flake, bulb glass ball；Boron nitride, carbonization The non-oxidized substance based inorganic material such as boron, aluminium nitride, aluminium carbide, silicon nitride, carborundum, titanium boride, titanium nitride, titanium carbide；Calcium carbonate； The metal oxides such as zinc oxide, aluminum oxide, magnesia, titanium oxide, beryllium oxide：Barium sulfate, molybdenum disulfide, tungsten disulfide, fluorination The inorganic matters such as carbon；The metal dusts such as aluminium, bronze, lead, stainless steel, zinc；With carbon black, coke, graphite, thermally decomposed carbon, hollow carbon balls Deng carbon body etc..
As thickener, can enumerate：Montmorillonite system clay mineral, the bentonite comprising these mineral, colloidal oxidation The inorganic filler such as aluminium system thickener, methylcellulose, carboxymethyl cellulose, hexyl methyl cellulose, hydroxyethyl cellulose, hydroxyl The cellulose-based thickeners such as propyl cellulose, polyurethane resin system thickener, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene The polyethers trees such as the polyethylene-based thickener such as benzyl ether copolymer, polyethers dialkyl ester, polyethers dialkyl ether, the epoxide modified thing of polyethers The association thickeners such as fat system thickener, urethane-modified polyethers system, polyurethane resin system of PPG system etc. are special The eggs such as the surfactant system such as macromolecule nonionic thickener, nonionic system thickener, casein, casein acid sodium, casein acid ammonium Acrylic thickeners such as white matter system thickener and mosanom etc..
As levelling agent, can enumerate：PEG types nonionic surfactant (nonyl phenol EO1~40 mole addition product, Stearic acid EO1~40 mole addition product etc.), polyol-based non-ionic surfactant (anhydrous sorbitol palm acid monoester, dehydration Sorbierite stearate monoesters, the ester of anhydrous sorbitol stearic acid three etc.), fluorine-containing surfactant (perfluoroalkyl EO1~50 mole plus Into thing, perfluoroalkyl carboxylate, perfluoroalkyl betain etc.) and modified silicon oil [polyether modified silicon oil, (methyl) acrylate Modified silicon oil etc.] etc..
For curing agent, as the curing agent of polyalcohols, can enumerate：Hexamethylene diisocyanate, trimethyl six Methylene diisocyanate, IPDI, hydrogenated diphenyl methane diisocyanate, the isocyanide of diphenyl methane two Acid esters, xylylene diisocyanate, hydrogenation xylylene diisocyanate, toluylene diisocya-nate, hydrogenation first generation Phenylene vulcabond, lysine diisocyanate, the nurate bodies of polyisocyanate compound, buret bodies, polyisocyanic acid The addition body of polyalcohol as ester compounds and ethylene glycol, propane diols, trimethylolpropane, by blocked polyisocyanic acid The monomers such as ester curing agent or mixture of more than two kinds, their polyalcohol addition product, their copolymer, block polymer etc. The isocyanates that can solidify at normal temperatures like that.As the curing agent of epoxy resin, can enumerate：Acid anhydrides, phenolic aldehyde tree Fat, polyamide, amine additives, urea resin, melmac and isocyanates etc..
As crosslinking agent, can enumerate：The more isocyanides of melmac, urea resin, polyisocyanate compound, block Ester compound, epoxide or resin, carboxylated compound or resin, acid anhydrides, based compound containing alkoxy silane or tree Fat and hexamethoxy methylated melamine, N, N, N ', N '-tetrakis hydroxymethyl phosphonium succinamide, tetramethoxymethylization urine Element, 2,4,6- tetrakis hydroxymethyl phosphonium phenol etc. have the compound of hydroxymethyl and methoxy or ethoxyl methyl etc..
As pigment, in addition to aforesaid pigments, can also enumerate：Vanadium pentoxide, calcium vanadate, vanadic acid magnesium and ammonium metavanadate Deng vfanadium compound；Magnesium phosphate, ammonium magnesium phosphate eutectoid thing, the hydrogen magnesium of phosphoric acid one, magnesium dihydrogen phosphate, magnesium phosphate calcium eutectoid thing, phosphorus Sour magnesium cobalt eutectoid thing, magnesium phosphate nickel eutectoid thing, phosphorous acid magnesium, phosphorous acid magnesium calcium eutectoid thing, three polyphosphoric acid aluminum dihydrogens, three The phosphate metals such as polyphosphoric acid magnesium, the magnesia processed material of three polyphosphoric acid aluminum dihydrogens, the magnesia processed material of three polyphosphoric acid dihydro zinc The silica modified chemical combination of magnesium phosphate as the processed material of the magnesium-containing compound of salt and then silica modified magnesium phosphate etc. The phosphate-based rust resisting pigment such as thing；The rust resisting pigment containing zinc composition such as trbasic zinc phosphate, magnesium handle three polyphosphoric acid aluminum dihydrogens, Calcium treatment Calcium phosphate etc. is without zinc rust resisting pigment；The calcium silicates such as the composite calcium silicate comprising calcium orthosilicate composition or calcium metasilicate composition；Calcium from Son exchanges silica, magnesium ion exchanges the metal ion exchanged silica such as silica；With preventing comprising Cr VI, lead etc. Become rusty pigment etc..
As defoamer, such as can enumerate：Silicone oil, dimethyl polysiloxane, organic modified polyorganosiloxane, fluorine richness gather The silicon-type such as siloxanes defoamer, mineral oil system defoamer, non-organic silicon polymer system defoamer, comprising changing selected from organic At least one kind of defoamer in property fluorine compounds and poly (oxyalkylene) based compound and the aliphatic alcohol for including carbon number more than 18 Defoamer etc..
Light stabilizer, fire retardant, solidification catalyst, bactericide for antioxidant, comprising ultra-violet absorber and Antiseptic etc., aforementioned substances can be enumerated.
Brief description of the drawings
Fig. 1 provides the excitation and emission spectra of the sample of embodiment 1 ~ 3 for the present invention；
Fig. 2 provides the after-glow light spectrogram of the sample of embodiment 1 ~ 3 for the present invention；
Fig. 3 provides the after-glow light spectrogram of the sample of embodiment 4 ~ 6 for the present invention.
Embodiment
1-3 and specific embodiment are described in further detail to the present invention below in conjunction with the accompanying drawings.
Embodiment 1
A kind of yellow longpersistent fluorescent material, chemical composition Sr4.94SiB2O10: 0.04Eu2+, 0.02Dy3+, with high-purity SrCO3、SiO2、H3BO3、Eu2O3And Dy2O3As raw material, according to chemical composition formula Sr4.94SiB2O10: 0.04Eu2+, 0.02Dy3+The proportioning of middle each element, accurately weigh each raw material；Each raw material is put into agate mortar simultaneously, and by grinding by hand The mode of mill is mixed uniformly, and the milling time of each sample is 20min；Above-mentioned well mixed raw material is put into corundum earthenware Crucible, and being sintered in high temperature process furnances, sintering temperature are 1200 DEG C, and sintering time is 4 hours, heating rate is 10 DEG C/ Min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixed gas, cool to room temperature after the completion of sintering with the furnace, obtain sintered body；It will obtain The sintered body obtained is ground crushing, produces the yellow longpersistent fluorescent material.
Embodiment 2
A kind of yellow longpersistent fluorescent material, chemical composition Sr4.96SiB2O10: 0.02Eu2+, 0.02Gd3+, with high-purity SrCO3、SiO2、H3BO3、Eu2O3And Gd2O3As raw material, according to chemical composition formula Sr4.96SiB2O10: 0.02Eu2+, 0.02Gd3+The proportioning of middle each element, accurately weigh each raw material；Each raw material is put into agate mortar simultaneously, and by grinding by hand The mode of mill is mixed uniformly, and the milling time of each sample is 30min；Above-mentioned well mixed raw material is put into corundum earthenware Crucible, and being sintered in high temperature process furnances, sintering temperature are 1400 DEG C, and sintering time is 6 hours, heating rate is 10 DEG C/ Min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixed gas, cool to room temperature after the completion of sintering with the furnace, obtain sintered body；It will obtain The sintered body obtained is ground crushing, produces the yellow longpersistent fluorescent material.
Embodiment 3
A kind of yellow longpersistent fluorescent material, chemical composition Sr4.98SiB2O10: 0.01Eu2+, 0.01La3+, with high-purity SrCO3、SiO2、H3BO3、Eu2O3And La2O3As raw material, according to chemical composition formula Sr4.98SiB2O10: 0.01Eu2+, 0.01La3+The proportioning of middle each element, accurately weigh each raw material；Each raw material is put into agate mortar simultaneously, and by grinding by hand The mode of mill is mixed uniformly, and the milling time of each sample is 25min；Above-mentioned well mixed raw material is put into corundum earthenware Crucible, and being sintered in high temperature process furnances, sintering temperature are 1000 DEG C, and sintering time is 5 hours, heating rate is 10 DEG C/ Min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixed gas, cool to room temperature after the completion of sintering with the furnace, obtain sintered body；It will obtain The sintered body obtained is ground crushing, produces the yellow longpersistent fluorescent material.
Embodiment 4
A kind of yellow longpersistent fluorescent material, chemical composition Sr4.92SiB2O10: 0.04Eu2+, 0.02Dy3+, 0.02Gd3+, with The SrCO of high-purity3、SiO2、H3BO3、Eu2O3、Dy2O3And Gd2O3As raw material, according to chemical composition formula Sr4.92SiB2O10: 0.04Eu2+, 0.02Dy3+, 0.02Gd3+The proportioning of middle each element, accurately weigh each raw material；Each raw material is put into agate simultaneously In mortar, and it is mixed uniformly by way of hand lapping, the milling time of each sample is 20min；By above-mentioned mixing Uniform raw material is put into corundum crucible, and is sintered in high temperature process furnances, and sintering temperature is 1200 DEG C, sintering time 6 Hour, heating rate is 10 DEG C/min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixed gas, cool to the furnace after the completion of sintering Room temperature, obtain sintered body；The sintered body of acquisition is ground crushing, produces the yellow longpersistent fluorescent material.
Embodiment 5
A kind of yellow longpersistent fluorescent material, chemical composition Sr4.96SiB2O10: 0.02Eu2+, 0.01Gd3+, 0.01La3+, with The SrCO of high-purity3、SiO2、H3BO3、Eu2O3、Gd2O3And La2O3As raw material, according to chemical composition formula Sr4.96SiB2O10: 0.02Eu2+, 0.01Gd3+, 0.01La3+The proportioning of middle each element, accurately weigh each raw material；Each raw material is put into agate simultaneously In mortar, and it is mixed uniformly by way of hand lapping, the milling time of each sample is 25min；By above-mentioned mixing Uniform raw material is put into corundum crucible, and is sintered in high temperature process furnances, and sintering temperature is 1300 DEG C, sintering time 4 Hour, heating rate is 10 DEG C/min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixed gas, cool to the furnace after the completion of sintering Room temperature, obtain sintered body；The sintered body of acquisition is ground crushing, produces the yellow longpersistent fluorescent material.
Embodiment 6
A kind of yellow longpersistent fluorescent material, chemical composition Sr4.85SiB2O10: 0.05Eu2+, 0.04Dy3+, 0.04Gd3+, 0.02La3+, with the SrCO of high-purity3、SiO2、H3BO3、Eu2O3、Dy2O3、Gd2O3And La2O3As raw material, according to chemical composition Formula Sr4.85SiB2O10: 0.05Eu2+, 0.04Dy3+, 0.04Gd3+, 0.02La3+The proportioning of middle each element, accurately weigh each Raw material；Each raw material is put into agate mortar simultaneously, and is mixed uniformly by way of hand lapping, each sample is ground Consume time as 30min；Above-mentioned well mixed raw material is put into corundum crucible, and is sintered in high temperature process furnances, is sintered Temperature is 1400 DEG C, and sintering time is 5 hours, and heating rate is 10 DEG C/min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mixing Gas, cool to room temperature after the completion of sintering with the furnace, obtain sintered body；The sintered body of acquisition is ground crushing, produces the Huang Color long lad phosphor.
Fig. 1 provides the excitation and emission spectra of the sample of embodiment 1 ~ 3 for the present invention, and left-most curve is excitation spectrum in figure, Monitoring wavelength is 565nm, and the right curve is emission spectrum in figure, excitation wavelength 420nm, it can be seen that the sample The wave-length coverage that can be effectively excited is black light to green glow（300~500nm）, the peak wavelength of emission spectrum is located at 565nm Yellow region, the centre of luminescence is divalence Eu2+Ion；Fig. 2 and Fig. 3 is respectively the twilight sunset spectrum of embodiment 1 ~ 3 and embodiment 4 ~ 6 Figure, it can be seen that active ions Eu2+With impurity energy level ion Dy3+、Gd3+And La3+Doping concentration to sample just Beginning fluorescence intensity and afterglow intensity and persistence by material impact, by introducing rare earth ion Dy3+、Gd3+And La3+In One or more combination provides trap level, can effectively strengthen after-glow brightness, extend persistence, wherein initial fluorescent intensity X=0.02 is more preferably selected as, it is Gd to contribute larger impurity energy level ion to raising afterglow intensity and time3+Ion.

Claims (2)

1. a kind of yellow longpersistent fluorescent material, it is characterised in that the chemical composition formula of the fluorescent material is Sr5-x-ySiB2O10:xEu2+, yRe3+, wherein Re is Dy, the one or more combination in Gd and La, and x and y span are respectively：0.01≤x ≤ 0.05,0.01≤y≤0.10.
2. a kind of preparation method of yellow longpersistent fluorescent material, it is characterised in that comprise the following steps：
（1）With the SrCO of high-purity3、SiO2、H3BO3、Eu2O3、Dy2O3、Gd2O3And La2O3As raw material, lead to according to chemical composition Formula Sr5-x-ySiB2O10: xEu2+, yRe3+The proportioning of middle each element, accurately weigh each raw material；
（2）Each raw material is put into agate mortar simultaneously, and is mixed uniformly by way of hand lapping, each sample Milling time is 20 ~ 30min；
（3）Above-mentioned well mixed raw material is put into corundum crucible, and is sintered in high temperature process furnances, sintering temperature is 1000 ~ 1400 DEG C, sintering time is 4 ~ 6 hours, and heating rate is 10 DEG C/min, sintering atmosphere 5%H2/95%N2Hydrogen nitrogen mix Gas is closed, cools to room temperature after the completion of sintering with the furnace, obtains sintered body；
（4）By step（3）The sintered body of acquisition is ground crushing, produces the yellow longpersistent fluorescent material.
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