CN102064273A - Light-emitting diode (LED) and preparation method thereof - Google Patents
Light-emitting diode (LED) and preparation method thereof Download PDFInfo
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- CN102064273A CN102064273A CN2010105149071A CN201010514907A CN102064273A CN 102064273 A CN102064273 A CN 102064273A CN 2010105149071 A CN2010105149071 A CN 2010105149071A CN 201010514907 A CN201010514907 A CN 201010514907A CN 102064273 A CN102064273 A CN 102064273A
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Abstract
The invention discloses a light-emitting diode (LED). The LED comprises a base, an LED chip and a reflector cup which are arranged on the base, a focusing lens arranged on the LED chip and fluorescent powder containing transparent glass arranged on the reflector cup. The LED is characterized in that the focusing lens is made of silicone adhesives needing to be cured by ultraviolet. Because the ultraviolet cured adhesives have the advantages of quick curing, high light transmittance and high refractive index, the manufacturing efficiency of the focusing lens and the light extraction efficiency of the LED chip are improved, and the formed focusing lens can effectively converge the light emitted by the LED chip, thus improving the intensity of the light generated due to excitation on the fluorescent powder and improving the brightness and light-emitting efficiency of the LED.
Description
Technical field
The present invention relates to the opto-electronic device technical field, be specifically related to a kind of light-emitting diode and preparation method thereof.
Background technology
Light-emitting diode (Light-Emitting Diode, be called for short LED) is the luminescent device that sends ultraviolet, visible or infrared light when applying forward voltage at semiconductor p-n junction two ends, is the solid luminescence light source of a new generation.Because it has characteristics such as volume is little, the life-span is long, driving voltage is low, reaction speed is fast, shatter-proof, heat-resisting, since first light-emitting diode in 1964 comes out, people never stop the step of researching and developing, along with the exploitation of luminescent material and the improvement of semiconductor fabrication process, and structure, optical microcavity and the quantum well structure etc. of in the chip growth course, having introduced the distributed Bragg reflection, the light-emitting diodes tube efficiency that semiconductor lighting is used was being improved constantly in recent years.
In the LED use, the loss that the photon that radiation recombination produces produces when outwards launching mainly comprises three aspects: the absorption of chip internal structure defective and material; The reflection loss that photon causes owing to refringence at the outgoing interface; And owing to incidence angle is lost greater than the total reflection that the cirtical angle of total reflection causes.Therefore, a lot of light can't shine the outside from chip.Because having, the semi-conducting material part of light-emitting diode chip for backlight unit obviously surpasses 3 refractive index, and in the light-emitting diode of routine, usually has obviously lower refractive index with the medium of chip adjacency, the big index jump of bringing thus on the interface between the medium of light-emitting diode chip for backlight unit and adjacency causes a quite little limiting angle of total reflection, so the overwhelming majority of the electromagnetic radiation that produces in an active region of chip is all returned in the chip from this boundary reflection.By applying the higher relatively transparent dielectric layer of one deck refractive index at chip surface, owing to this dielectric layer is between chip and the air, thereby effectively reduced the loss of photon at the interface, improved and got optical efficiency.
Because led light source is a lambertian distribution, the outgoing beam angle of divergence is big, and light distribution is inhomogeneous, if light beam is not converged, is difficult to satisfy the required high brightness requirement of illumination.Therefore, the lambertian distribution light that chip is sent converges, and makes it to become Gauss light and distributes, and have the specific angle of divergence, can effectively increase the luminosity of LED device, improves the luminous efficiency of LED device.
Summary of the invention
Problem to be solved by this invention is: how a kind of light-emitting diode and preparation method thereof is provided, this scheme has solved photon in the light-emitting diode chip for backlight unit loss at the interface and the big problem of the outgoing beam angle of divergence of light-emitting diode chip for backlight unit, improved the light extraction efficiency of light-emitting diode chip for backlight unit, and the light beam that light-emitting diode chip for backlight unit is sent is converged, the fluorescent material light that produces that is stimulated is enhanced, and has improved the luminous efficiency of light-emitting diode.
Technical problem proposed by the invention is to solve like this: a kind of light-emitting diode is provided, comprise base, place light-emitting diode chip for backlight unit and reflector on the base, place the condenser lens on the light-emitting diode chip for backlight unit and place the clear glass that contains fluorescent material on the reflector, it is characterized in that, described condenser lens material is the organic silicon adhesive that needs ultraviolet light polymerization, and this adhesive raw materials is the component of following mass percent:
Photosensitive polysiloxane 92～99.5%
Light trigger 0.1～5%
Diluent and auxiliary agent 0.4～6%
Described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers, cyclic lactone or vinyl ether monomers, and auxiliary agent comprises filler, stabilizer or crosslinking agent; Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, acetophenones, benzophenone and 2-hydroxy-2-methyl-1-phenylacetone, alkyl phenyl ketone, alpha-hydroxyalkyl benzophenone class, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt or triaryl salt compounded of iodine.
According to light-emitting diode provided by the present invention, it is characterized in that described photosensitive polysiloxane comprises: mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes, epoxy-functional polysiloxanes, styryl polysiloxanes or vinyl ether functional polysiloxanes.
According to light-emitting diode provided by the present invention, it is characterized in that described light-emitting diode chip for backlight unit is the chip of blue light-emitting or ultraviolet light; Described fluorescent material is a kind of by blue light or ultraviolet excitation and luminous fluorescent material.
According to light-emitting diode provided by the present invention, it is characterized in that the described clear glass that contains fluorescent material is to mix in the fluorescent material or to be applied to glass surface outward.
A kind of preparation method of light-emitting diode is characterized in that, may further comprise the steps:
1. select the light-emitting diode chip for backlight unit with the fluorescent material coupling, the effective excitated fluorescent powder of the luminous energy that light-emitting diode chip for backlight unit is sent;
2. select suitable crystal-bonding adhesive that light-emitting diode chip for backlight unit is bonded on the base;
3. extraction electrode on light-emitting diode chip for backlight unit;
4. reflector is placed on the base;
5. spot printing needs the organic silicon adhesive of ultraviolet light polymerization on light-emitting diode chip for backlight unit, described adhesive forms the shape of convex under capillary effect, solidify to form condenser lens under the irradiation of ultraviolet light fast, described adhesive raw materials is the component of following mass percent:
Photosensitive polysiloxane 92～99.5%
Light trigger 0.1～5%
Diluent and auxiliary agent 0.4～6%
Described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers, cyclic lactone or vinyl ether monomers, and auxiliary agent comprises filler, stabilizer or crosslinking agent; Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, acetophenones, benzophenone and 2-hydroxy-2-methyl-1-phenylacetone, alkyl phenyl ketone, alpha-hydroxyalkyl benzophenone class, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt or triaryl salt compounded of iodine;
6. adopt the clear glass contain fluorescent material that the above-mentioned light-emitting diode for preparing is encapsulated, mix in the described fluorescent material or be applied to glass surface outward;
7. the every photoelectric properties and the parameter of test component.
The present invention proposes to adopt the adhesive that needs ultraviolet light polymerization to form the condenser lens that covers on the light-emitting diode chip for backlight unit for the first time.Owing to need the adhesive of ultraviolet light polymerization to have light transmittance height, advantage that refractive index is big, make light-emitting diode chip for backlight unit light extraction efficiency be improved, the condenser lens that employing needs the adhesive of ultraviolet light polymerization to form can effectively converge the emergent light of light-emitting diode chip for backlight unit, increased that fluorescent material is stimulated and the light intensity that produces; This condenser lens is to utilize the adhesive that needs ultraviolet light polymerization to form the shape of convex under capillary effect, under the irradiation of ultraviolet light, solidify to form fast, simultaneously owing to need the adhesive of ultraviolet light polymerization to have Heat stability is good, advantage that stress is little, make the condenser lens of preparation have very high consistency, this method is simply effective, is convenient to large-scale production.
Description of drawings
Fig. 1 is a light-emitting diode structure schematic diagram provided by the present invention;
Fig. 2 is the performance comparison figure of two kinds of light-emitting diodes, and wherein light-emitting diode A is the light-emitting diode in the comparative example 1, and light-emitting diode B is the light-emitting diode in the embodiment of the invention 1;
Wherein, 1, base, 2, light-emitting diode chip for backlight unit, 3 condenser lenses, 4, reflector, 5, contain the clear glass of fluorescent material.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and embodiment.
Technical scheme of the present invention provides a kind of light-emitting diode, comprises base 1, places on the base 1 light-emitting diode chip for backlight unit 2 and reflector 4, places the condenser lens 3 on the light-emitting diode chip for backlight unit 2 and places the clear glass that contains fluorescent material 5 on the reflector 4.
Base 1 is the support of light-emitting diode in the light-emitting diode of the present invention, and it requires to have good thermal stability and chemical stability, good electrical conductivity and thermal conductivity.
Light-emitting diode chip for backlight unit 2 is as the excitated fluorescent powder luminous light source in the light-emitting diode of the present invention, and its requires to have preferably luminous power and emission wavelength and fluorescent material that good coupling is arranged, and adopts blue light or ultraviolet light chip usually.
Condenser lens 3 is to utilize the organic silicon adhesive that needs ultraviolet light polymerization in the light-emitting diode of the present invention, described adhesive forms the shape of convex under capillary effect, solidify to form condenser lens under the irradiation of ultraviolet light fast, described adhesive raw materials is the component of following mass percent:
Photosensitive polysiloxane 92～99.5%
Light trigger 0.1～5%
Diluent and auxiliary agent 0.4～6%
Described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers, cyclic lactone or vinyl ether monomers, and auxiliary agent comprises filler, stabilizer or crosslinking agent; Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, acetophenones, benzophenone and 2-hydroxy-2-methyl-1-phenylacetone, alkyl phenyl ketone, alpha-hydroxyalkyl benzophenone class, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt or triaryl salt compounded of iodine.
The clear glass 5 that contains fluorescent material in the light-emitting diode of the present invention is to mix in the fluorescent material or to be applied to glass surface outward.
Each composition of the organic silicon adhesive of medium ultraviolet photocuring of the present invention is described as follows:
The excellent specific property of ultraviolet photocureable materials such as the ultraviolet curing organic silicon adhesive is owing to not only have the premium properties of organosilyl heatproof, weather-proof, electrical insulation capability, low surface tension and low-surface-energy, and also having can cold curing, solidification rate is fast, pollution-free.Its prepolymer mainly comprises: mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes, epoxy-functional polysiloxanes, styryl polysiloxanes and vinyl ether functional polysiloxanes.
The early stage research of vinylated polysiloxanes ultraviolet light polymerization system is more.The speed of photoresponse of this system is fast, particularly under light trigger promotes, is not subjected to poly-interference of resistance of oxygen basically, can form soft and whippy cured film.Product can be applicable to fiber or other base material, comprises paper, metal, glass and polyethylene, polypropylene and polyester film etc.But there is dark reaction in this system, and the viscosity of system will increase gradually, and the hot strength of cured film descends.
Acrylate-basedization polysiloxanes ultraviolet light polymerization system is good to the adhesiveness of base material, the solidification rate height, and the chemistry of cured layer, physical stability are good, can obtain desirable viscosity by adjusting prescription; But in the photocuring process,, produce shrinkage stress often with volume contraction.Under many occasions, shrinking all is a unfavorable factor.Acrylate-basedization polysiloxane coated is on base materials such as metal, glass, plastics the time, and contraction can cause coating adhesion to descend; When being coated on the flexible substrate (as paper product, plastic film), contraction can cause the rolls wrinkle.But one flaw cannot mar the jade, acrylate-basedization polysiloxanes with its high reaction activity and cheaply advantage won market, become the focus of ultraviolet curing organic silicon prepolymer research field.
Cation photocuring when taking place in the epoxy radicals of epoxy radicals polysiloxanes, and the epoxy radicals with ring strain is opened, and forms tension-free ehter bond, and volume contraction is very little, even be zero, becomes the major product in the cation photocuring system.The epoxy compounds that contains unsaturated double-bond mainly is to contain vinyl or allylic epoxy compounds, as allyl glycidyl ether, glycidyl acrylate, dicyclohexyl pentadiene and 4-vinyl epoxidized cyclohexene, what wherein the photocuring activity was the highest is epoxidized cyclohexene.For example, the end si-h bond of 4-vinyl epoxidized cyclohexene and polysiloxanes is carried out hydrosilylation, obtain alicyclic epoxy radicals polysiloxanes.The epoxy radicals polysiloxanes can mix with multiple composition, and filler, pigment, crosslinking agent, catalyst, UV absorbers etc. can be applied in the epoxy radicals polysiloxanes system.Now, the application of epoxy radicals polysiloxanes ultraviolet light polymerization system more and more widely becomes the main product in the cation photocuring system.
The great advantage of styryl polysiloxanes ultraviolet light polymerization system is inexpensive, wherein styryl is owing to have higher photopolymerization reaction activity, styryl can be incorporated into and carry out ultraviolet light polymerization in the silicon-oxygen backbone, its purpose mainly is to improve the hardness of organosilicon material and the performance of other terms of mechanics.But the shortcoming that this system exists is also more, as the volatility height, inflammable, smell big, reaction speed waits more slowly, curing performance is also not as other ultraviolet light polymerization system.
The monomer of vinyl ether group polysiloxanes is the monomer that contains the HZC=CH-O-base.Because, the lone pair electrons of oxygen atom and two key generation conjugation, the cloud density of two keys is increased causing the C=C of vinyl ether group is the electron rich group, polymerization activity is higher than general vinyl monomer, under ultraviolet light irradiation, can carry out reactions such as radical polymerization, cationic charge transfer complex alternating copolymerization.Therefore, the uv curable oligomer of vinyl ethers can be used in kind of the photocuring system, as radically curing system, cationic curing system and mix curing system.The vinyl ethers prepolymer has that toxicity is low, smell is little, reactivity, and cured product has performances such as shrinking little, impact strength height, and its potential application is extensive.But, make vinyl ethers ultraviolet curing organic silicon material also not obtain widespread usage at home and abroad because the price of vinyl ethers monomer is higher.
Light trigger: in the ultraviolet photo-curing cementing agent, often need to add Photoactive compounds, with the carrying out of initiation or accelerated reaction.Difference by its mechanism of action can be divided into light trigger and sensitising agent.Difference is that light trigger when the reaction beginning, absorbs the luminous energy of suitable wavelength and intensity, photophysical process takes place reach its a certain excitation state, if this excited energy greater than the breaking bonds energy needed, then produces free radical polymerization; And sensitiser absorption luminous energy is to its a certain excitation state, just with energy in molecule or intermolecular the transfer, produce free radical polymerization by another molecule that obtains energy.Compare with light trigger, sensitising agent itself does not consume or changes structure, and it can be regarded as photochemically reactive catalyst.Its mechanism of action roughly has three kinds: the one, and the energy transfer mechanism, the 2nd, take hydrogen mechanism by force, the 3rd, through generating the photosensitive mechanism that electric charge shifts.The light trigger of having developed with practical value has styrax and derivative and acetophenone derivative, and sensitising agent has benzophenone, thia anthraquinone and Michler's keton.The stability of various initators, yellowing resistance, trigger rate have nothing in common with each other, and in different resin systems, efficiency of initiation is also different, should rationally select for use according to the needs of different occasions.As cyanacrylate and C (CH
2OCCH
2CH
2SH) system, use benzoin methyl ether, benzoin ethyl ether respectively, benzoin isopropyl ether causes, be respectively 18s, 20s and 25s curing time, and when causing with benzophenone, only be 15s curing time, and simultaneously the light transmittance of solidfied material also can difference be bigger owing to the wavelength difference, and this will rationally select for use according to actual conditions.
The effect of light trigger is after it absorbs the ultraviolet light energy, produces free radical through decomposing, thus the unsaturated bond polymerization in the initiator system, and crosslinking curing becomes an integral body.Radical photoinitiator commonly used has cracking and puies forward Hydrogen two big classes.
Crack type photoinitiator: crack type photoinitiator mainly contains benzoin ethers (styrax ethers), benzil ketals and acetophenone etc.Crack type photoinitiator is chapped after absorbing ultraviolet light, produces two free radicals, and free radical causes the unsaturated group polymerization.Benzoin ethers (styrax ethers) comprising: styrax (Benzoin), benzoin methyl ether, benzoin ethyl ether (Benzoin ethyl ether), benzoin isobutyl ether (Benzoin butyl ether), styrax lose (Benzoin oxime), benzoin isopropyl ether; Acylphosphine oxide comprises: 2; 4; 6 trimethylbenzene formyl diphenyl phosphine oxides (TPO) and (2; 4; 6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO phenyl bis (2; 4; 6-trimethyl benzoyl) phosphine oxide); two (2,4, the 6-trimethylbenzoyl) phosphine oxides (819) of phenyl; tetramethylpiperidone oxide (TMPO); triethyl phosphate (TEPO); they are more satisfactory light triggers; have very high light-initiated activity, the long wave near ultraviolet ray is had absorption, be applicable to the situation that whitewash and film are thicker; and have good stability, can variable color or fade.
Carry the Hydrogen initator: carry the Hydrogen initator and mainly contain benzophenone and thioxanthones etc.Wherein at 380-420nm, and absorbability and hydrogen-taking capacity are strong, have higher efficiency of initiation at the maximum absorption wavelength in black light district for thioxanthone photoinitiator.Carrying the Hydrogen initator must have hydrogen donor as collaborative composition, otherwise efficiency of initiation is too low, so that can not be put to use.Triplet state carbonyl free radical than more likely extracting hydrogen on the secondary carbon or on the methyl, is connected on hydrogen on the hetero-atoms such as oxygen or nitrogen than the easier extraction of the hydrogen on the carbon atom from the tertiary carbon of hydrogen donor molecule.This class hydrogen donor has amine, hydramine (triethanolamine, methyl diethanolamine, triisopropanolamine etc.), mercaptan, N, the N-diethyl-and to the dimethylamino benzamide.
The benzophenone light initiation system, benzophenone need be with alcohol, ether or amine and with just making vinyl monomer carry out photopolymerization.Mainly comprise: benzophenone, the thia anthraquinone, Michler's keton, dimethoxy benzene acetophenone (DMPA), alpha-hydroxy-2,2 dimethyl acetophenones (1173), Alpha-hydroxy cyclohexyl-phenyl ketone (184), α-amine alkyl phenones, 2-methyl isophthalic acid (4-first coloured glaze base phenyl)-2-morpholinyl acetone (MMMP), 2 ' 2-dibenzamidodiphenyl disulfide (DBMD), (4-dimethylamino phenyl)-(1-piperidyl)-ketone, isopropyl thioxanthone (ITX), (4-dimethylamino phenyl)-(4-morpholinyl)-ketone, 2-hydroxy-2-methyl-1-phenyl-1-phenyl-1-acetone, two phenoxy group benzophenone, hydroxy-2-methyl phenyl-propane-1-ketone.And mixed system, as eliminating oxygen in the glued membrane to the benzophenone of the inhibition of Raolical polymerizable and the initiator system that cooperates of uncle's ammonia; Michler's keton and benzophenone are used, and can obtain more cheap and effectively initiator system.
Cationic photoinitiator: aromatic sulfonium salts and salt compounded of iodine class initator have excellent high-temperature stability, and also have stability after epoxy resin cooperates, so be widely used in the cationic curing system.But their the most apneusis receipts wavelength does not absorb in the near ultraviolet band in the far-ultraviolet region, generally will add light sensitizer, as: radical initiator or light-sensitive coloring agent carry out sensitizing.
This type of initator comprises: xylyl iodine hexafluorophosphate (P1810); hydroxy phenyl salt compounded of iodine (HTIB); 4; the two detergent alkylate iodine hexafluoro antimonates of 4-; the xylyl salt compounded of iodine; diphenyl hexafluoroarsenate salt compounded of iodine; [4-(2-hydroxyl-3-butoxy-1-propoxyl group) phenyl] benzene iodo-hexafluoro antimonate; [4-(to the benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate; [4-(4-benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate; 4-(to the benzoyl thiophenyl) benzene] the phenyl-iodide hexafluorophosphate; 4; 4 '-dimethyl diphenyl salt compounded of iodine hexafluorophosphate (IHT-PI 820); 4; 4 '-the diacetylamino diphenyl iodine hexafluorophosphate; 3; 7 one dinitro dibenzo ring-type salt compounded of iodine and 3; 7 one dinitro dibenzo ring-type bromine salt; the tetrafluoro boric acid diaryl group iodized salt; 3; 3 '-the dinitro diphenyl salt compounded of iodine; 3; 3 '-dinitro diphenyl salt compounded of iodine and several 2; 2 '-two replace (iodine; bromine; chlorine)-5; 5 '-the dinitrophenyl salt compounded of iodine; iodate 2-[2-(3-indolizine) vinyl]-1-methylquinoline salt; iodate 4-(2-benzoxazole)-N-picoline salt; 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate; triaryl phosphine glyoxalidine salt; triaryl phosphine 1; 1 '-dinaphthalene glyoxalidine ring salt; 3; 7-dinitro dibenzo bromine five rings salt; p-methyl benzenesulfonic acid triphenyl sulfosalt; bromination triphenyl sulfosalt; (4-thiophenyl-phenyl) diphenyl sulphur hexafluorophosphate; 4-(thiophenyl) triphenyl sulphur hexafluorophosphate; 3; 3 '-dinitro diphenyl iodine hexafluorophosphate; 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate; the triphenyl sulfosalt; 4-chlorphenyl diphenyl sulphur hexafluorophosphate; 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate; 4-acetamido phenyl diphenyl sulphur hexafluorophosphate; 3-benzoyl phenyl diphenyl sulphur hexafluorophosphate; triphenyl sulphur borofluoride; triphenyl sulphur hexafluorophosphate; triphenyl sulphur hexafluoro antimonate; 4-tolyl diphenyl sulphur hexafluorophosphate; the phosphorus hexafluoride triaryl sulfonium salts; the antimony hexafluoride triaryl sulfonium salts; [4-(to the benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate; 1-(4 '-bromo-2 '-luorobenzyl) pyridiniujm; [4-(to the benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate; 4-[4-(p-nitrophenyl formoxyl) thiophenyl] and benzene } the phenyl-iodide hexafluorophosphate; 4-[4-(to methyl benzoyl) thiophenyl] and benzene } the phenyl-iodide hexafluorophosphate; 4-[4-(to methyl benzoyl) phenoxy group] and benzene } the phenyl-iodide hexafluorophosphate; [4-(to the benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate; 4, the two detergent alkylate iodine hexafluoro antimonates of 4-.
Luxuriant molysite class: luxuriant molysite class light initiation system is a kind of new cation light initiator that develops after two fragrant salt compounded of iodine and three aromatic sulfonium salts, luxuriant molysite ion at first forms the aromatic radical ligand under illumination, produce complex compound simultaneously with the unsaturated iron of epoxy compounds molecule coordination, the lewis acidic characteristics of this complex compound tool are also followed the complex compound that forms with the coordination of three epoxy compounds molecules, but one of them epoxy compounds open loop forms cation, it can cause cationic ring-opening polymerization, forms polymer.At normal temperatures because the formation of ferrocene salt-epoxy radicals complex, epoxy compounds cationic species needs the time, so under the condition that needs to heat, to improve polymerization speed in the external world.
This type of salt comprises: cyclopentadienyl group-iron-benzene salt; cyclopentadienyl group-iron-toluene salt; cyclopentadienyl group-iron-paraxylene salt; cyclopentadienyl group-iron-naphthalene salts; cyclopentadienyl group-iron-biphenyl salt; cyclopentadienyl group-iron-2; 4-dimethyl acetophenone salt; acetyl group-cyclopentadienyl group-iron-paraxylene salt; cyclopentadienyl group-iron-methyl phenyl ethers anisole salt; cyclopentadienyl group-iron-diphenyl ether salt; cyclopentadienyl group-iron-2; 4-diethoxybenzene salt; the ferrocene tetrafluoroborate; the luxuriant iron tetrafluoroborate of toluene; cyclopentadienyl group-iron-methyl phenyl ethers anisole salt; cyclopentadienyl group-iron-diphenyl ether salt; cyclopentadienyl group-iron-1; 4-diethoxybenzene salt; cyclopentadienyl group-iron-chlorobenzene salt; cyclopentadienyl group-iron-(1; the 4-diethoxybenzene) hexafluorophosphate; cyclopentadienyl group-iron-diphenyl ether hexafluorophosphate; 1; 10-phenanthrolene ferrous perchlorate salt; 1; 10-phenanthrolene ferrous sulfate cyclopentadienyl group-iron-methyl phenyl ethers anisole salt; cyclopentadienyl group-iron-diphenyl ether salt; [1; 1 '-two (diphenylphosphine) ferrocene] Nickel Chloride; vinyl ferrocene; N; N '-di-ferrocene methylene butanediamine quaternary ammonium salt; ferrocene formamide; ferrocene acyl propionic acid; ferrocenyl methyl ketone; ethyl dicyclopentadienyl iron; Butyrylferrocene; butyl ferrocene; N; N-dimethyl-amine methyl ferrocene; 1; 1 '-the dibenzoyl ferrocene; (3-carboxyl propionyl group) ferrocene; 1,1 '-the dibromo ferrocene; amino ferrocene.
The light trigger of macromolecule loading: in the photocuring system, light trigger often is not to exhaust fully in the photocuring process, and the part of photodissociation can not moved to coating surface, makes coating yellowing and aging, influences the quality of product; On the other hand, some initators and system are incompatible or compatibility is bad, and its application is restricted.For addressing these problems, people are with the light trigger producing high-molecular.The low molecular relatively initator of the initator of producing high-molecular has following advantage: A, energy transfer and intermolecular reaction become and be more prone in polymer chain, make the high-molecular optical initator have higher activity.B, by with nonactive group copolymerization, regulates and the distance of design photosensitive group, or change the distance of optical active group and main chain, thereby acquisition has different photoactive initators.C, can introduce different optical active groups, utilize their cooperative effect to improve light sensitive effect at same macromolecular chain.The producing high-molecular of D, initator has limited the migration of initator, prevents coating flavescence and aging.E, since most of photolysis debris still be connected on the macromolecule matrix, therefore, can reduce the smell and the toxicity of system.
The producing high-molecular of initator can directly be connected in initator on the chain of macromolecule or oligomer, as thioxanthone or acidic group phosphine oxide etc. are introduced on the macromolecular chain; Also can in initator, introduce the functional group that polymerization can take place, make it in the photocuring process, realize producing high-molecular, as benzophenone structural is introduced in the tetraacrylate.
The compatibility of various light triggers also is a research direction in recent years, re-uses through behind the compatibility, both can reduce cost, and can enlarge the zone of absorbing wavelength again, improves the absorption of ultraviolet radiation energy, thereby obtains good solidification effect.The compatibility of light trigger both can be between the same type, as be both free radical type, for example the new Irgacure-1700 that releases of Ciba be exactly by 25% (2,4,6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO) and 75% alpha-hydroxy-2,2 dimethyl acetophenones (1173) are formed, and Irgacure-1800 is made up of 25% BAPO and 75% Alpha-hydroxy cyclohexyl-phenyl ketone (184) etc.; Also can form,, for example, triaryl thiaxanthene salt and benzophenone be cooperated, the curing rate of epoxy compounds is improved as light trigger compatibility free radical type and cationic by dissimilar initators.
Reactive diluent is mainly used in the viscosity of regulation system, also can influence solidification rate and material property, comprises toluene, dimethylbenzene, n-hexane, active epoxy diluent resin, cyclic ethers, cyclic lactone and vinyl ether monomers.
Catalyst can be selected two (2 ethyl hexanoic acid) dibutyl tin, dibutyltin diacetate or dibutyl tin laurate etc. for use.Wherein the dibutyltin diacetate catalytic activity is big, and curing rate is fast.Dibutyl tin laurate active less, curing rate is slow.
Auxiliary agent: in general,, also need to add various auxiliary agents in the ultraviolet photo-curing cementing agent, as plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent etc. for adapting to the bonding requirement of varying environment.Though their shared components in adhesive are few, processing characteristics or the adhesive property to glue produces crucial effects sometimes.As cyanacrylate and C (CH
2OCCH
2CH
2SH) under the initiation of benzophenone, if the silicone couplet CH of adding 1%
2=CHSi (OCH
2CH
2OCH
3)
3, behind ultraviolet light polymerization, place under the environment of 80～100% humidity, find after 1 year to change, and if do not add coupling agent, under the same terms, white erosion just to take place in the bonded part after 2 days, glue-line strips down fully after the week.
Plasticizer comprises: diisooctyl azelate (DIOZ), dioctyl azelate (DOZ), DHP (DHP), separate two dioctyl phthalates (DOS), dioctyl adipate (DOA), diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), dibutyl phthalate (DBP), dipropyl phthalate (DAP), three vinyl butyl ether base phosphates, polyvinyl butyral resin, tributyl 2-acetylcitrate, repefral (DMP), diethyl phthalate (DEP), adipic acid two (butoxy ethyoxyl) ethyl ester, isopropyl titanate, tetrabutyl titanate, triethyl citrate, tributyl citrate, tributyl 2-acetylcitrate, tri trimellitate (2-ethyl) own ester (TOTM), the own ester of phthalic acid two (2-ethyl), decanedioic acid two (2-ethyl) own ester (DOS), diglycol dibenzoate (DEDB), phthalic anhydride, dipropylene glycol dibenzoate, separate diacid dibenzyl ester (DBS), BS (BS), chlorosulfonated polyethylene (toughening elastic body), triphenyl phosphate (TPP), tricresyl phosphate (dimethylbenzene) ester (TXP), polytrimethylene adipate (PPA), epoxidized soybean oil (ESO), octyl epoxy stearate (OES2), chlorinated paraffin-42 (CP-42), chlorinated paraffin wax-48 (CP-48), chlorinated paraffin-52 (CP-52), distearyl acid diethylene glycol (DEG) (DEDR), tricresyl phosphate benzene methyl (TCP), diphenyl octyl phosphate (DPO), poly-adipic acid butylidene ester (PBA), butyl epoxy stearate (BES), askarel (CDP), dimethylbenzene methylal resin (plasticizer FH), pumice wax pattern base oil (PROCESS OIL637), soybean oil, naphthenic processing oil (310), W150 softening oil (petroleum hydrocarbon, hydrogenation artificial oil), zirconium aluminium is coupling agent, WB215 (aliphatic acid 18%; Fatty acid ester 52%; Calcium carbonate 20%).
Coupling agent is the material that a class has the both sexes structure, and a part of group in their molecules can react with the chemical group on inorganic matter surface, forms strong chemical bonding; Another part group then has close organic character, can twine with reactive organic molecule or physics, thus the material strong bonded that two kinds of character are varied in size.The coupling agent of present industrial use is divided into silanes, acyl esters of gallic acid, zirconium class and Organic Chromium complex compound four big classes by chemical constitution.Wherein using more in adhesive is silanes, as the methyl ethylene dichlorosilane, methyl hydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-An Bingjisanjiayangjiguiwan, dimethyl silicone polymer, poly-hydrogen methylsiloxane, poly-methyl methoxy radical siloxane, γ-methacrylic acid third vinegar base trimethoxy silane (KH-570), gamma-aminopropyl-triethoxy-silane (KH-550), γ-glycidol ether propyl trimethoxy silicane, the aminopropyl silsesquioxane, γ-methacryloxypropyl trimethoxy silane, the chain alkyl trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-chloropropyl triethoxysilane, two-(the silica-based propyl group of γ-triethoxy), anilinomethyl triethoxysilane, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane.
Levelling agent is the flow leveling that is used for improving resin, prevent the generation of coating disadvantages such as shrinkage cavity and pinprick, make smooth coating, and can improve glossiness, comprise mixed solvent, organosilicon, polyacrylate, acetate butyrate fiber, nitrocellulose and polyvinyl butyral resin.Wherein silicone based, comprise diphenyl polysiloxanes, methyl phenyl silicone, organic group modified polyorganosiloxane, polyethers organosilicon.
Defoamer is to be used for preventing and to eliminate coating producing bubble in manufacturing and use, prevents that coating from producing disadvantages such as pinprick.Phosphate, fatty acid ester and organosilicon etc. can be made defoamer.Tributyl phosphate is specifically arranged, dibutylphosphoric acid ester, phosphate foam inhibitor (AD-14L), froth breaking king (FAG470), defoamer (FAG470), defoamer (BYK-141), defoamer (BYK 037), three (butoxyethyl group) phosphate, triethyl phosphate, the Tributyl phosphate ester, triethyl phosphate, tricresyl phosphate chloro isopropyl ester, three butoxy ethyl ester of phosphoric acid, the mixture of polyoxyethylene polyoxypropylene and glycol or three alcohol ethers (light yellow) to the water white transparency thick liquid, dimethyl silicone polymer, glycerine polyethenoxy ether (GP330), laureth, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polyoxypropylene glycerin ether and polyoxypropylene, polyethers, cithrol, metallic soap of stearic acid, polyureas, the fatty acid ester compounded thing of higher alcohols; Silicone defoaming agent has organic silicon modified by polyether oxygen alkane, organopolysiloxane mixture, silicone emulsion.
Polymerization inhibitor is to be used for reducing polymerization takes place when depositing, and improves the storage stability of resin.Polymerization inhibitor commonly used generally is divided into molecule-type polymerization inhibitor and stabilized free fundamental mode polymerization inhibitor, the former mainly contains: hydroquinones, 1,4-benzoquinone, phenothiazine, the beta-phenyl naphthylamines, p-tert-butyl catechol, methylene blue, three (N-nitroso-N-Phenylhydroxylamine) aluminium salt, stannous chloride, inorganic matters such as ferric trichloride and Sulfur etc. also can be made polymerization inhibitor stabilized free fundamental mode polymerization inhibitor and mainly contain 1, the bitter hydrazine (DPPH) of 1-diphenyl-2-, 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), hydroquinones, allyl acetate, MEHQ (MEHQ), NO free radical piperidines alcohol, phosphorous acid (2,2,6, the 6-tetramethyl piperidine nitrogen oxygen free radical) mixed ester, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen radical (TMHPHA), 8% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt: 92% 2-phenolic group ethoxy propylene acid esters, 4% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt, 96% ethyoxyl list oil triacrylate, MEHQ hydroquinone monomethyl ether, the polymerization inhibitor mantoquita, adjacent methyl hydroquinone, 2,6-di-t-butyl cresols, the dimethyl hydroquinones, p-tert-butyl catechol (TBC), catechol, p methoxy phenol, 2.6-BHT, 2.5-di-tert-butyl hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, 1.4-naphthoquinones, phenthazine, TBHQ (TBHQ), o-sec-butyl-4,6 dinitrophenol (DNBP), ethylene glycol ether, the benzene sulfonamide amine acid salt, right-t-butyl catechol, methyl methacrylate (MMA), 2,4,6-trinitrophenol (TNP), 2,4-dimethyl-6-tert-butyl phenol (TBX), N, N-diethyl hydroxylamine (DEHA), to t-butyl catechol, 2, the 5-ditert-butylhydro quinone, adjacent methyl is to benzene two adjacent methyl 1,4-benzoquinone, 3-tertiary butyl-4-hydroxyanisol (BHA), 2,6-dinitro-p-cresol (DNPC), polyvinyl acetal, NO free radical piperidines alcohol, 4,6-dinitro o sec-butyl phenol, DMSS (DMSS), propilolic alcohol.
Thixotropic agent adds in the resin, can make resin adhesive liquid that higher denseness is arranged when static, becomes the material of low denseness fluid under external force again.Organobentonite acrylonitrile-butadiene rubber (NBR), montmorillonite (Na
x(H
2O)
4{ (Al
2-xMg
0.33) [Si
4O
10] (OH)
2), bentonite [(Na
x(H
2O)
4(Al
2-xMg
0.83) Si
4O
10) (OH)
2], diatomite (unbodied SiO
2Form, and contain small amount of Fe
2O
3, CaO, MgO, Al
2O
3And organic impurities), asbestos, wollastonite (CaSiO
3), muscovite (KAl
2(AlSi
3O
10) (OH)
2), phlogopite (KMg
3(AlSi
3O
10) (FOH)
2), magnesium silicon muscovite [K
2((Fe
2+ Mg) (Fe
3+ Al)
3(Si
7AlO
20) (OH)
4)], montmorillonite [Na
x(H
2O)
4{ (Al
2-xMg
0.33) [Si
4O
10] (OH)
2], bentonite [Na
x(H
2O)
4(Al
2-xMg
0.83) (Si
4O
10) (OH)
2], rilanit special, fumed silica, metallic soap (lead stearate, barium, cadmium, calcium, zinc, magnesium, aluminium, rare earth).Then with cellulose derivatives such as hydroxyethylcelluloses, polyvinyl alcohol, polyacrylic acid, poly(ethylene oxide), polymethylacrylic acid, Lauxite, melamine resin, resol, phenolic resins water-soluble resin are thickener in water-based system.
The effect of filler is that part replaces binding agent, reduces the consumption of binding agent, with the effect that reaches filling, reinforcement, anti-attrition and reduce cost.Filler requires particle carefully to spare, and can be scattered in equably in the slurries, and is good to binding agent and other component associativities.The consumption of filler should be suitable, otherwise also can influence the serous coat quality.Comprise inorganic mineral bentonite acrylonitrile-butadiene rubber (NBR), potassium aluminosilicate sodium (nepheline), calcium carbonate, moisture Petimin [Mg
3[Si
4O
10] (OH)
2], wollastonite (CaSiO
3), muscovite [KAl
2(AlSi
3O
10) (OH)
2)], phlogopite [KMg
3(AlSi
3O
10) (F, OH)
2], magnesium silicon muscovite [K
2((Fe
2+ Mg) (Fe
3+ Al)
3(Si
7AlO
20) (OH)
4)], montmorillonite [Na
x(H
2O)
4{ (Al
2-xMg
0.33) [Si
4O
10] (OH)
2], bentonite [Na
x(H
2O)
4(Al
2-xMg
0.83) (Si
4O
10) (OH)
2], kaolin, red mud (Al
1-xO
x), calcium sulfate, acrylate high polymer, butyl polyacrylate, polyurethane.
Dispersant impels material particles to be dispersed in the medium, forms the reagent of stable suspension.Dispersant generally is divided into inorganic dispersant and organic dispersing agent two big classes.Inorganic dispersant commonly used has silicates (for example waterglass) and alkali metal phosphonates (Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium, Amino Trimethylene Phosphonic Acid potassium, HEDP sodium, the HEDP disodium, HEDP four sodium, HEDP potassium, ethylene diamine tetra methylene phosphonic acid five sodium, diethylene triamine pentamethylene phosphonic five sodium, diethylenetriamine pentamethylene phosphonic acids seven sodium, diethylene triamine pentamethylene phosphonic sodium, 2-phosphonic acids butane-1,2,4-tricarboxylic acids four sodium, hexamethylene diamine tetramethyl fork phosphonic acids sylvite, two 1,6 hexylidene triamine, five methylenephosphonic acid sodium, the trimerization Alendronate, calgon and sodium pyrophosphate etc.).Organic dispersing agent comprises triethyl group hexyl phosphonic acids; Amino Trimethylene Phosphonic Acid; HEDP (HEDP); ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS); ethylene diamine tetra methylene phosphonic acid (EDTMPA); diethylene triamine pentamethylene phosphonic (DTPMP); 2-phosphonic acids butane-1; 2; 4-tricarboxylic acids (PBTCA); PAPE (PAPE); 2-HPAA (HPAA); hexamethylene diamine tetramethyl fork phosphonic acids (HDTMPA); polyamino polyether base methylenephosphonic acid (PAPEMP); two 1,6 hexylidene triamine, five methylenephosphonic acids (BHMTPMPA); lauryl sodium sulfate; polyacrylic acid (PAA); Sodium Polyacrylate (PAAS); HPMA (HPMA); maleic acid-acrylic acid copolymer (MA-AA); acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer (AA/AMPS); acrylic acid-hydroxypropyl acrylate copolymer; acrylic acid-acrylate-phosphonic acids-sulfonate quadripolymer; acrylic acid-acrylate-sulfonate terpolymer; phosphono-carboxylic acids copolymer (POCA); polyacrylate; carboxylate-sulfonate-nonionic terpolymer; polyepoxy sodium succinate (PESA); poly (sodium aspartate) (PASP); the base amylalcohol; cellulose derivative; polyacrylamide; guar gum; fatty acid polyethylene glycol ester etc.
Antioxidant is the auxiliary agent of major function to suppress the fluoropolymer resin thermal oxidative degradation, belongs to the category of anti-oxidant reagent.Antioxidant is the topmost type of plastics stabilizing additive, and nearly all fluoropolymer resin all relates to the application of antioxidant.According to the mechanism of action, traditional antioxidant systems generally comprises primary antioxidant, auxiliary antioxidant and heavy metal ion passivator etc.Primary antioxidant is a major function to catch the polymer peroxy radical, and the title of " peroxy radical trapping agent " and " chain termination type antioxidant " is arranged again, relates to aromatic amine compounds and hindered phenol compound two big series of products.Aromatic amine antioxidant has: diphenylamines, p-phenylenediamine (PPD), N, N-pair-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propiono] hexamethylene diamine, dihydroquinoline; Hinered phenols antioxidant has: 2,5-ditert-butylhydro quinone, 2,6-di-tert-butyl-4-methy phenol, TBHQ, 2,5-ditert-butylhydro quinone (DBHQ), 2, three grades of butyl of 6--4-methylphenol, two (3, three grades of butyl of 5--4-hydroxy phenyl) thioether, four [β-(3, three grades of butyl of 5--4-hydroxy phenyl) propionic acid] pentaerythritol ester; Triphenyl phosphite (TPPi), phosphite ester three (2,4-di-tert-butyl phenyl) ester, pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) dimer and the trimerical compound, 3 of ester, many alkyl bisphenol-A phosphite ester, 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, β-(4-hydroxy phenyl-3, the 5-di-t-butyl) the positive octadecanol ester of propionic acid, 1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-hydroxy benzenes methyl) benzene.Auxiliary antioxidant has the effect of decomposing copolymer per-compound, also claims " peroxide decomposer " to comprise sulfo-dicarboxylic ester class and bi-ester of phosphite, and common and primary antioxidant is used.The two octadecyl esters (DSTP) of two 12 carbon alcohol esters, two ten four carbon alcohols esters, thio-2 acid, thio-2 acid dibasic acid esters, two octadecanol ester, the two lauryls of thio-2 acid, three monooctyl esters, three the last of the ten Heavenly stems ester, three (12 carbon alcohol) ester and three (16 carbon alcohol) ester, 3,6,9-trioxa decane-1,11-glycol-two-n-dodecane mercaptopropionic acid ester, triphenyl phosphate TPP, trisnonyl phenyl phosphite, phosphorous acid octyl group diphenyl.
Heavy metal ion passivator is commonly called as " copper resistant agent ", can the complexing transition metal ions, prevent the oxidative degradation of its catalytic polymerization resin, typical structure such as hydrazide kind compound etc.Recent years, along with going deep into of polymer antioxygen theoretical research, certain variation has also taken place in the classification of antioxidant, and the most outstanding feature is a notion of having introduced " carbon radicals trapping agent ".This radical scavenger is different from traditional primary antioxidant, and they can catch the polymer alkyl diradical, is equivalent to set up one in traditional antioxidant system the defence line.This type of stabilizing additive mainly comprises 2-ethyl benzofuran ketone, 2-methyl benzofuranone, Dihydrobenzofuranes ketone, benzofuranone, dibenzopyrone, 3-aryl-benzofuran-2-ones, 3-aryl benzofuranone, 2-aryl Dihydrobenzofuranes ketone, 2-aryl benzofuranone, 5-cyano group-1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 5-replaces 1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 2,3-dihydroxy-2,2-dimethyl-7-benzofuran phenol, 3-(2-acyloxyethoxyphenyl) benzofuran-2-ones, isobenzofuranone, 5-[(imidazo [4,5-b] pyridin-3-yl) methyl] benzofuranone, 1,2,3,4-tetrahydrochysene-benzofuranone, 2,3-dihydro-2-methyl-2-alkyl and furanone, 4-ethyoxyl bisphenol-A-diacrylate, (2-10)-ethoxyquin bisphenol-A-dimethylacrylate, 2-[1-(2-hydroxyl-3,5-two tertiary amyl phenyl)-and ethyl]-4,6-two tertiary amyl phenyl acrylate, bisphenol-A-glycerol double methyl methacrylate, bisphenol-A-dimethylacrylate, 4-ethyoxyl bisphenol-A-dimethylacrylate, N, the N-dibenzyl hydroxylamine, N-ethyl-N-aminoethyle alcohol, N, the N-diethyl hydroxylamine, IPD acrylamide HAS, isopropylhydroxyla, hydroxylamine hydrochloride, the chlorination hydroxylammonium, hydrogen chlorine azanol, N-methyl-azanol, acetohydroxamic acid, the N-hydroxyl acetamide.
Modifier is intended to improve plasticizing capacity, improves the modified additive of resin melt viscoelasticity and promotion resin melt-flow, and this analog assistant is based on acrylic acid esters co-polymer (ACR).
Anti-impact modifier improves the auxiliary agent of rigid polymer goods shock resistance.Mainly comprise haloflex (CPE), acrylate copolymer (ACR), methacrylate-diene-ethylene copolymer (MBS), ethene-thiazolinyl acetate copolymer (EVA) and acrylonitrile-diene-ethylene copolymer (ABS) etc.The ethylene propylene diene rubber (EPDM) that uses in polypropylene toughness-increasing modified also belongs to rubber toughened scope.
The function of antistatic agent is to reduce the sheet resistance of polymer product, eliminates the electrostatic hazard that accumulation of static electricity may cause, and mainly is included as cationic surfactant and anion surfactant.Cationic surfactant has: the alkyl phosphate diethanolamine salt, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, stearmide, stearoyl dimethyl-penten ammonium chloride, N, two (2-ethoxy)-N-(3 '-dodecyloxy-2 '-hydroxypropyl) the first ammonium Methylsulfate salt of N-, trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, N, N-cetyl ethyl morpholine ethyl-sulfate salt, (dodecanamide propyl trimethyl ammonium) Methylsulfate salt dibrominated N, N-two (octadecyl dimethyl)-3-oxa--1,5-penta 2 ammoniums, styrene polymer type quaternary ammonium salt, the palmitate quaternary ammonium salt, the alkylphenol-polyethenoxy based quaternary ammonium salt, dialkyl quaternary ammonium salt, the polyacrylamide quaternary ammonium salt, octadecyl dimethyl ethoxy quaternary ammonium nitrate, ammonium polystyrene sulphonate salt, propyl-dimethyl-beta-hydroxyethyl nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, 2,2 '-nitrilo-di-methylcarbinol and the poly-(oxygen-1 of α-three decyls-ω-hydroxyl, 2-second two bases) polymer of phosphate, the polyethylene glycol tridecyl ether phosphate, diethanolamine salt, the oleic acid diethanolamine salt, triethanol amine oleate, ethoxylated amine, N, N-dihydroxy ethyl octadecylamine, N, the N-dihydroxyethyl p-toluidine, the alkylphenol-polyethenoxy based quaternary ammonium salt, ethoxyl quaternary ammonium salt, the fluorine-containing quaternary ammonium salt of oxa-; Anion surfactant has: fatty alcohol ether phosphate, phenolic ether phosphate (TXP-4), phenolic ether phosphate (TXP-10), different tridecanol phosphate, Tryfac 5573 (MA24P), fatty alcohol ether phosphate potassium (MOA-3PK), phenolic ether phosphate kalium salt (NP-4PK), phenolic ether phosphate kalium salt (NP-10PK), different tridecanol ether phosphate sylvite, Tryfac 5573 sylvite (MA24PK), fatty alcohol phosphate sylvite, ALS; Non-ionic surface active agent: the condensation product of alkylamine and oxirane, alkanolamide, AEO, aliphatic acid polyethenoxy ether, two (beta-hydroxyethyl) coco amine, two (beta-hydroxyethyl) stearylamine, two (beta-hydroxyethyl) beef tallow amine, HMPA, perfluoroalkyl ethanol APEO.
The negative and positive amphoteric surfactant comprises: dodecyl-dimethyl quaternary ammonium second inner salt, dodecyl dimethyl quaternary ammonium second inner salt, alkyl dihydroxy ethyl ammonium second inner salt, the N-alkylaminoacid salts, epoxy tripolymer acid inner salt, carboxybetaine, tridecyl dimethyl (2-sulfurous acid) ethyl ammonium second inner salt, N-dodecyl alanine, the 3-chloro propyl amine hydrochloric acid salt, N-tertbutyloxycarbonyl-D-3-(2-naphthyl)-alanine, N-tert-butoxycarbonyl-D-2-naphthylalanine, tertbutyloxycarbonyl-D-2-naphthylalanine, tertbutyloxycarbonyl-D-3-(2-naphthyl)-alanine, N-tertbutyloxycarbonyl-L-2-trifluoromethyl-phenylalanine, glyphosate isopropyl amine salt.
The polymer electrolyte antistatic agent comprises: the amphipathic copolymer that poly(ethylene oxide) (PEO), polyether ester acid imide, polyethylene glycol methacrylic acid copolymer, polyether ester amides (PEEA), polyether ester acetamide (PEAI), polyethylene glycol oxide, epoxy propane copolymer (PEO-ECH), polyethylene glycol methacrylate-styrene polymer (PEGMA), methacrylic acid (MAA), methacrylic acid stearyl (SMA)+polyethylene glycol methacrylate-styrene polymer (PEGMA) are formed.
Inorganic combustion inhibitor comprises antimonous oxide, zinc molybdate, zinc oxide, iron oxide, tin oxide, aluminium hydroxide, magnesium hydroxide, antimony oxide, Firebrake ZB and red phosphorus in the fire retardant; Organic fire-retardant comprises deca-BDE, three (2, the 3-dibromopropyl) phosphate, HBCD, poly-2, the 6-dibromobenzene aether, chlorinated paraffin wax, polyphosphate, red phosphorus, two (tetrabromo phthalimide) ethane, the Dowspray 9 homopolymers, melamine, cyanurate, the isodecyl diphenyl phosphoester, ethylhexyl diphenyl phosphate, tricresyl phosphate isopropylbenzene ester, two (2 chloroethyl) vinylphosphonate, ethylene two [three (2 cyanoethyl) bromination microcosmic salt], N, two (2 ethoxy) the aminomethyl diethyl phosphonates of N, polyphenylene phosphonic acids diphenyl sulphone (DPS) ester, polyphenylene phosphonic acids hexichol azo ester, polyphenylene phosphonic acids bisphenol-A ester.
Mould inhibitor claims microbial inhibitor again, is growth of microorganism such as a class mould fungus inhibition, prevents the stabilizing additive that fluoropolymer resin is degraded by microbial attack.Most polymeric materials are to mould and insensitive, but have mould sensitivity owing to its goods work in-process has added the material that plasticizer, lubricant, fatty acid soaps class etc. can grow der Pilz.Plastics are a lot of with the chemical substance that mould inhibitor comprised, and more common kind comprises organo-metallic compound (as organic mercury, organotin, organic copper, organo-arsenic etc.), organic compounds containing nitrogen, organic compounds containing sulfur, organic halogen compound and phenol derivatives etc.Comprising phenol, pentachlorophenol, phenyl mercury oleate, copper 8-quinolinolate, chlorination three second or tributyl tin, copper sulphate, mercury chloride, sodium fluoride.
Sensitizer is to the dimethylamino benzamide; Aminopropyl silsesquioxane and Versamid mass ratio are 3: 1 in the promoter.
Stabilizer is to be used for reducing polymerization takes place when depositing, and improves the storage stability of resin.Stabilizer commonly used has hydroquinones, p methoxy phenol, 1,4-benzoquinone, 2,6-di-t-butyl cresols, phenothiazine, anthraquinone, tertiary amine etc.
Below be specific embodiments of the invention:
Embodiment 1
Light emitting diode construction as shown in Figure 1, light-emitting diode chip for backlight unit 2 adopts blue chip, and condenser lens 3 adopts the adhesive that needs ultraviolet light polymerization to form.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive that blue LED chip is bonded on the base;
2. extraction electrode on light-emitting diode chip for backlight unit;
3. reflector is placed on the base;
4. regulate the hydrophobic nature on light-emitting diode chip for backlight unit surface, spot printing needs the organic silicon adhesive that needs ultraviolet light polymerization of ultraviolet light polymerization on light-emitting diode chip for backlight unit then, described adhesive forms the shape of convex under capillary effect, form condenser lens after ultraviolet light polymerization is handled 30 seconds, described adhesive raw materials is the component of following mass percent:
Polysiloxanes 94%
Light trigger 5%
Diluent and auxiliary agent 1%
5. adopt the clear glass contain gold-tinted fluorescent material that the above-mentioned light-emitting diode for preparing is encapsulated, mix in the described gold-tinted fluorescent material or be applied to glass surface outward;
6. the every photoelectric properties and the parameter of test component.
Comparative example 1
Adopting silica gel is the condenser lens of light-emitting diode, in addition, similarly carries out with enforcement 1.
Table 1 is the various performance parameters of the light-emitting diode in embodiment 1 and the comparative example 1.
| Light-emitting diode among the embodiment 1 | Light-emitting diode in the comparative example 1 | |
| Life-span (h) | ～41306 | ～37258 |
| Colour temperature (k) | 7107 | 6634 |
| Color rendering index | 96 | 93 |
| Chromaticity coordinates (X, Y) | (0.332，0.328) | (0.325，0.324) |
Light emitting diode construction as shown in Figure 1, light-emitting diode chip for backlight unit 2 adopts blue chip, and condenser lens 3 adopts the adhesive that needs ultraviolet light polymerization to form.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive that blue LED chip is bonded on the base;
2. extraction electrode on light-emitting diode chip for backlight unit;
3. reflector is placed on the base;
4. spot printing needs the organic silicon adhesive of ultraviolet light polymerization on light-emitting diode chip for backlight unit, described adhesive forms the shape of convex under capillary effect, form condenser lens after ultraviolet light polymerization is handled 30 seconds, described adhesive raw materials is the component of following mass percent:
Polysiloxanes 92%
5. diluent and auxiliary agent 4%
6. adopt the clear glass contain red light fluorescent powder that the above-mentioned light-emitting diode for preparing is encapsulated, mix in the described red light fluorescent powder or be applied to glass surface outward;
7. the every photoelectric properties and the parameter of test component.
Embodiment 3
Light emitting diode construction as shown in Figure 1, light-emitting diode chip for backlight unit 2 adopts blue chip, and condenser lens 3 adopts the adhesive that needs ultraviolet light polymerization to form.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive that blue LED chip is bonded on the base;
2. extraction electrode on light-emitting diode chip for backlight unit;
3. reflector is placed on the base;
4. regulate the hydrophobic nature on light-emitting diode chip for backlight unit surface, spot printing needs the organic silicon adhesive of ultraviolet light polymerization on light-emitting diode chip for backlight unit then, described adhesive forms the shape of convex under capillary effect, form condenser lens after ultraviolet light polymerization is handled 30 seconds, described adhesive raw materials is the component of following mass percent:
Polysiloxanes 93%
Light trigger 1%
5. diluent and auxiliary agent 6%
6. adopt the clear glass contain green light fluorescent powder that the above-mentioned light-emitting diode for preparing is encapsulated, mix in the described green light fluorescent powder or be applied to glass surface outward;
7. the every photoelectric properties and the parameter of test component.
Light emitting diode construction as shown in Figure 1, light-emitting diode chip for backlight unit 2 adopts blue chip, and condenser lens 3 adopts the adhesive that needs ultraviolet light polymerization to form.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive that blue LED chip is bonded on the base;
2. extraction electrode on light-emitting diode chip for backlight unit;
3. reflector is placed on the base;
4. spot printing need need the organic silicon adhesive of ultraviolet light polymerization on light-emitting diode chip for backlight unit, described adhesive forms the shape of convex under capillary effect, form condenser lens after ultraviolet light polymerization is handled 30 seconds, described adhesive raw materials is the component of following mass percent:
Polysiloxanes 99.5%
Light trigger 0.1%
Diluent and auxiliary agent 0.4%
5. adopt the clear glass contain green glow and red light fluorescent powder that the above-mentioned light-emitting diode for preparing is encapsulated, mix in described green glow and the red light fluorescent powder or be applied to glass surface outward;
6. the every photoelectric properties and the parameter of test component.
Embodiment 5
Light emitting diode construction as shown in Figure 1, light-emitting diode chip for backlight unit 2 adopts the ultraviolet light chip, and condenser lens 3 adopts the adhesive that needs ultraviolet light polymerization to form.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive the ultraviolet light-emitting diodes chip adhesive on base;
2. extraction electrode on light-emitting diode chip for backlight unit;
3. reflector is placed on the base;
4. regulate the hydrophobic nature on light-emitting diode chip for backlight unit surface, spot printing needs the organic silicon adhesive of ultraviolet light polymerization on light-emitting diode chip for backlight unit then, described adhesive forms the shape of convex under capillary effect, form condenser lens after ultraviolet light polymerization is handled 30 seconds, described adhesive raw materials is the component of following mass percent:
Polysiloxanes 94%
Light trigger 3%
Diluent and auxiliary agent 3%
5. adopt the clear glass contain blue light fluorescent powder that the above-mentioned light-emitting diode for preparing is encapsulated, mix in the described blue light fluorescent powder or be applied to glass surface outward;
6. the every photoelectric properties and the parameter of test component.
Light emitting diode construction as shown in Figure 1, light-emitting diode chip for backlight unit 2 adopts the ultraviolet light chip, and condenser lens 3 adopts the adhesive that needs ultraviolet light polymerization to form.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive the ultraviolet light-emitting diodes chip adhesive on base;
2. extraction electrode on light-emitting diode chip for backlight unit;
3. reflector is placed on the base;
4. spot printing needs the organic silicon adhesive of ultraviolet light polymerization on light-emitting diode chip for backlight unit, described adhesive forms the shape of convex under capillary effect, form condenser lens after ultraviolet light polymerization is handled 30 seconds, described adhesive raw materials is the component of following mass percent:
Polysiloxanes 95%
Diluent and auxiliary agent 3%
5. adopt the clear glass contain red light fluorescent powder that the above-mentioned light-emitting diode for preparing is encapsulated, mix in the described red light fluorescent powder or be applied to glass surface outward;
6. the every photoelectric properties and the parameter of test component.
Embodiment 7
Light emitting diode construction as shown in Figure 1, light-emitting diode chip for backlight unit 2 adopts the ultraviolet light chip, and condenser lens 3 adopts the adhesive that needs ultraviolet light polymerization to form.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive the ultraviolet light-emitting diodes chip adhesive on base;
2. extraction electrode on light-emitting diode chip for backlight unit;
3. reflector is placed on the base;
4. regulate the hydrophobic nature on light-emitting diode chip for backlight unit surface, spot printing needs the organic silicon adhesive of ultraviolet light polymerization on light-emitting diode chip for backlight unit then, described adhesive forms the shape of convex under capillary effect, form condenser lens after ultraviolet light polymerization is handled 30 seconds, described adhesive raw materials is the component of following mass percent:
Polysiloxanes 96%
Diluent and auxiliary agent 2%
5. adopt the clear glass contain green light fluorescent powder that the above-mentioned light-emitting diode for preparing is encapsulated, mix in the described green light fluorescent powder or be applied to glass surface outward;
6. the every photoelectric properties and the parameter of test component.
Light emitting diode construction as shown in Figure 1, light-emitting diode chip for backlight unit 2 adopts the ultraviolet light chip, and condenser lens 3 adopts the adhesive that needs ultraviolet light polymerization to form.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive the ultraviolet light-emitting diodes chip adhesive on base;
2. extraction electrode on light-emitting diode chip for backlight unit;
3. reflector is placed on the base;
4. spot printing needs the organic silicon adhesive of ultraviolet light polymerization on light-emitting diode chip for backlight unit, described adhesive forms the shape of convex under capillary effect, form condenser lens after ultraviolet light polymerization is handled 30 seconds, described adhesive raw materials is the component of following mass percent:
Polysiloxanes 97%
Light trigger 1.5%
Diluent and auxiliary agent 1.5%
5. adopt the clear glass contain gold-tinted fluorescent material that the above-mentioned light-emitting diode for preparing is encapsulated, mix in the described gold-tinted fluorescent material or be applied to glass surface outward;
6. the every photoelectric properties and the parameter of test component.
Claims (5)
1. light-emitting diode, comprise base, place light-emitting diode chip for backlight unit and reflector on the base, place the condenser lens on the light-emitting diode chip for backlight unit and place the clear glass that contains fluorescent material on the reflector, it is characterized in that, described condenser lens material is the organic silicon adhesive that needs ultraviolet light polymerization, and this adhesive raw materials is the component of following mass percent:
Photosensitive polysiloxane 92～99.5%
Light trigger 0.1～5%
Diluent and auxiliary agent 0.4～6%
Described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers, cyclic lactone or vinyl ether monomers, and auxiliary agent comprises filler, stabilizer or crosslinking agent; Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, acetophenones, benzophenone and 2-hydroxy-2-methyl-1-phenylacetone, alkyl phenyl ketone, alpha-hydroxyalkyl benzophenone class, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt or triaryl salt compounded of iodine.
2. light-emitting diode according to claim 1, it is characterized in that described photosensitive polysiloxane comprises: mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes, epoxy-functional polysiloxanes, styryl polysiloxanes or vinyl ether functional polysiloxanes.
3. light-emitting diode according to claim 1 is characterized in that, described light-emitting diode chip for backlight unit is the chip of blue light-emitting or ultraviolet light; Described fluorescent material is a kind of by blue light or ultraviolet excitation and luminous fluorescent material.
4. light-emitting diode according to claim 1 is characterized in that, the described clear glass that contains fluorescent material is to mix in the fluorescent material or to be applied to glass surface outward.
5. the preparation method of a light-emitting diode is characterized in that, may further comprise the steps:
1. select the light-emitting diode chip for backlight unit with the fluorescent material coupling, the effective excitated fluorescent powder of the luminous energy that light-emitting diode chip for backlight unit is sent;
2. select suitable crystal-bonding adhesive that light-emitting diode chip for backlight unit is bonded on the base;
3. extraction electrode on light-emitting diode chip for backlight unit;
4. reflector is placed on the base;
5. spot printing needs the organic silicon adhesive of ultraviolet light polymerization on light-emitting diode chip for backlight unit, described adhesive forms the shape of convex under capillary effect, solidify to form condenser lens under the irradiation of ultraviolet light fast, described adhesive raw materials is the component of following mass percent:
Photosensitive polysiloxane 92～99.5%
Light trigger 0.1～5%
Diluent and auxiliary agent 0.4～6%
Described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers, cyclic lactone or vinyl ether monomers, and auxiliary agent comprises filler, stabilizer or crosslinking agent; Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, acetophenones, benzophenone and 2-hydroxy-2-methyl-1-phenylacetone, alkyl phenyl ketone, alpha-hydroxyalkyl benzophenone class, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt or triaryl salt compounded of iodine;
6. adopt the clear glass contain fluorescent material that the above-mentioned light-emitting diode for preparing is encapsulated, mix in the described fluorescent material or be applied to glass surface outward;
7. the every photoelectric properties and the parameter of test component.
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| CN2010105149071A CN102064273A (en) | 2010-10-21 | 2010-10-21 | Light-emitting diode (LED) and preparation method thereof |
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| CN104231945A (en) * | 2014-09-12 | 2014-12-24 | 东莞市新懿电子材料技术有限公司 | Liquid-state optical cement |
| CN105937717A (en) * | 2015-03-06 | 2016-09-14 | 欧司朗股份有限公司 | Method used for manufacturing lighting module and lighting module |
| CN109082252A (en) * | 2015-12-17 | 2018-12-25 | 福建利豪电子科技股份有限公司 | A kind of high-peeling strength paper-based copper-coated board copper foil glue |
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| CN109082252A (en) * | 2015-12-17 | 2018-12-25 | 福建利豪电子科技股份有限公司 | A kind of high-peeling strength paper-based copper-coated board copper foil glue |
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Application publication date: 20110518 |