CN101916815A - Light-emitting diode and preparation method thereof - Google Patents
Light-emitting diode and preparation method thereof Download PDFInfo
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- CN101916815A CN101916815A CN 201010222583 CN201010222583A CN101916815A CN 101916815 A CN101916815 A CN 101916815A CN 201010222583 CN201010222583 CN 201010222583 CN 201010222583 A CN201010222583 A CN 201010222583A CN 101916815 A CN101916815 A CN 101916815A
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Abstract
The invention discloses a light-emitting diode (LED). The LED at least comprises a bracket, an LED chip and a light-emitting layer on the LED chip and is characterized in that: the light-emitting layer is a mixed system of one or more kinds of fluorescent powder which can emit various colors of light and an adhesive which needs to be cured by ultraviolet light; and the adhesive is the mixed system of a free radical type UV-curing adhesive and a cationic UV-curing adhesive. The light-emitting layer solves the problems of colloid coagulation and fluorescent powder precipitation in a fluorescent powder coating process, improves the uniformity of the fluorescent powder on the chip, increases the adhesive property of the light-emitting layer and the chip, and shortens the curing time of the light-emitting layer at the same time. The cationic UV-curing adhesive and the free radical type UV-curing adhesive are unified integrally, so as to fulfill the aim of utilizing fully light energy and fulfill the aim of mutual modification. The cured product of the cationic UV-curing adhesive and the free radical type UV-curing adhesive centralizes the respective advantages of epoxy resin and acrylic ester, and simultaneously overcomes certain defects and creates a new system.
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.
Along with the fast development of LED industry, the range of application of efficient LED correspondingly also proposes higher requirement to its performance day by day in progressively extension, comprises brightness, color developing, photochromic consistency etc.Improve and how to apply fluorescent material comprising of LED performance need primary study, gelling is consolidated and fluorescent material disperses problem inhomogeneous and the fluorescent material precipitation in colloid in order to solve in a glue process, the container of the used equipment of dot fluorescent powder, dress glue etc. all needs the temperature that keeps certain and constantly stirs, but these problems are not well solved.Therefore, how to solve in a glue process colloid solidification and fluorescent material and in colloid, disperse problem inhomogeneous and the fluorescent material precipitation, to improving the performance of LED, even increase the service life, have very important realistic meaning for the sustainable development that promotes whole industry.
Summary of the invention
Technical 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 colloid solidification and the fluorescent material easy problem that precipitates in colloid in the fluorescent material process of applying, improved the uniformity of plastic emitting in the some glue process, increased the consistency of luminescent layer in the light-emitting diode, increased the caking ability of luminescent layer and chip, reduced luminescent layer simultaneously and solidified the required time; This scheme is simple, effective, can reduce the production cost and the technology difficulty of device greatly, improves the yields of related device significantly.
Technical problem proposed by the invention is to solve like this: a kind of light-emitting diode is provided, at least comprise support, led chip and the luminescent layer on led chip, it is characterized in that, described luminescent layer material can be sent out the fluorescent material of shades of colour light for one or more and need the mixed system of the adhesive composition of ultraviolet light polymerization, described adhesive is the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 10: 1～1: 10 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 90～99.5%
Monomer 0.2～3%
Light trigger 0.1～3%
Sensitising agent and auxiliary agent 0.2～6%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 90～99.5%
Diluent 0.4～8%
Cation light initiator 0.1～3%
Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or acetophenone derivative; Sensitising agent comprises benzophenone, thia anthraquinone or Michler's keton, auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant or coupling agent, and described diluent comprises various active epoxy diluent resins or various cyclic ethers, cyclic lactone, the vinyl ether monomers diluent as light-cured resin; Described cation light initiator comprises diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts or triaryl selenium salt; Described base resin comprises unsaturated polyester resin, acrylic resin or polythiol-polyenoid system; Described monomer comprises styrene and derivative, simple function group or multi-functional acrylate; Described cationic monomer comprises various epoxy resin or modified epoxy or fluorine-containing and not fluorine-containing hybrid resin or aliphat and bis-phenol D-type blending epoxy.
According to light-emitting diode provided by the present invention, it is characterized in that described acrylic resin comprises polyester-acrylate, epoxy-acrylate, carbamate-acrylate and polyethers-acrylate.
According to light-emitting diode provided by the present invention, it is characterized in that described polythiol-polyenoid system comprises the material of following structural formula:
According to light-emitting diode provided by the present invention, it is characterized in that, described mixed system raw material comprises bisphenol A epoxide resin, sulphion hexafluorophosphate and sulphion hexafluoro antimonate, butyl glycidyl ether, long carbochain glycidol ether, carboxylic monomer, the polycaprolactone polyol of two senses and trifunctional.
According to light-emitting diode provided by the present invention, it is characterized in that, described mixed system raw material comprises the tetraethylene-glycol dimethylacrylate, 3, and 4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, Alpha-hydroxy cyclohexyl benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, the styrax dimethyl ether, the hexafluorophosphoric acid diphenyl iodnium.
According to light-emitting diode provided by the present invention, it is characterized in that described mixed system raw material comprises 2-ethylene glycol allyl ether, epoxy acrylic resin, xylyl salt compounded of iodine, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl propiophenone.
According to light-emitting diode provided by the present invention, it is characterized in that described led chip is the chip of blue light-emitting or ultraviolet light; Described fluorescent material is by a kind of blue light or ultraviolet excitation and luminous fluorescent material.
A kind of preparation method of light-emitting diode may further comprise the steps:
1. select the led chip with the fluorescent material coupling, the effective excitated fluorescent powder of the luminous energy that led chip is sent;
2. select suitable crystal-bonding adhesive that led chip is bonded on the support, when respectively there is an electrode above and below of led chip, require crystal-bonding adhesive to conduct electricity and can heat conduction; When two electrodes are arranged above the led chip, require crystal-bonding adhesive to insulate and can heat conduction;
3. extraction electrode on led chip;
4. on led chip, apply the luminescent layer material, described luminescent layer is fluorescent material and the mixed system that needs the adhesive of ultraviolet light polymerization, described adhesive is the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 10: 1～1: 10 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 90～99.5%
Monomer 0.2～3%
Light trigger 0.1～3%
Sensitising agent and auxiliary agent 0.2～6%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 90～99.5%
Diluent 0.4～8%
Cation light initiator 0.1～3%
Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and acetophenone derivative; Sensitising agent comprises benzophenone, thia anthraquinone and Michler's keton, auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant and coupling agent, and described diluent comprises various active epoxy diluent resins and various cyclic ethers, cyclic lactone, the vinyl ether monomers diluent as light-cured resin; Described cation light initiator has diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts, triaryl selenium salt;
5. the luminescent layer that 4. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
6. the above-mentioned light-emitting diode for preparing is encapsulated;
7. the every photoelectric properties and the parameter of test component.
Preparation method according to light-emitting diode provided by the present invention is characterized in that, step 4. in, the luminescent layer material mixing directly is prepared on the led chip after evenly, perhaps is prepared on the led chip through behind the organic solvent diluting; Described luminescent layer be coated with by dripping, one or several modes in the spin coating, dip-coating, coating, inkjet printing, roller coat, LB film form.
The mixed system that the adhesive that the present invention proposes to adopt one or more fluorescent material that can send out shades of colour light and need ultraviolet light polymerization is for the first time formed, by regulating the ratio of the adhesive component that wherein needs ultraviolet light polymerization, obtain the suitable colloid of viscosity, fluorescent material can evenly be disperseed in colloid, improved the plastic emitting uniformity, and solved the problem that fluorescent material precipitates in colloid, this has not only increased the consistency that applies fluorescent material in the some glue process, improved the consistency of the bright dipping of LED, because fluorescent material is uniformly dispersed, increased the luminous efficiency of LED simultaneously in colloid; Because the adhesive in the luminescent layer of the present invention is by ultraviolet light polymerization, solved the problem of colloid solidification in a glue process, thereby need be in a glue process equipment used to dot fluorescent powder, the container of dress glue etc. all needs the temperature that keeps certain and constantly stirs, reduced production cost, simultaneously, at the solidification process that applies after fluorescent material is finished, only need luminescent layer is carried out the UV-irradiation of short time, not only increased the caking ability of fluorescent material on chip, and, reduced the required time of solidification process owing to do not need long baking-curing; Cationic and free radical type ultra-violet curing adhesive are unified in one, both reached the purpose that makes full use of luminous energy, reached the purpose of mutual modification again, its cured product has been concentrated epoxy resin and acrylate advantage separately, simultaneously overcome some defective again, started a brand-new system.
Description of drawings
Fig. 1 is a light emitting diode construction schematic diagram provided by the present invention;
Fig. 2 is the structural representation of embodiment 1～4 provided by the present invention;
Fig. 3 is the structural representation of embodiment 5～10 provided by the present invention;
Fig. 4 is the luminescent properties comparison diagram of two kinds of LED, and wherein device A is LED in the embodiment of the invention 4, and device B is the LED that the adhesive of luminescent layer adopts conventional colloid.
Wherein, 1, support, 2, crystal-bonding adhesive, 3, led chip, 4, spun gold, 5, luminescent layer, 6, outer package glue.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Technical scheme of the present invention provides a kind of light-emitting diode, and as shown in Figure 2, the structure of device comprises support 1, crystal-bonding adhesive 2, and led chip 3, spun gold 4, luminescent layer 5, outer package glue 6, wherein led chip 3 is positioned at support 1 surface, and luminescent layer 5 is positioned at led chip 3 surfaces.
As shown in Figure 3, the structure of device comprises support 1, crystal-bonding adhesive 2, and led chip 3, spun gold 4, luminescent layer 5, outer package glue 6, wherein led chip 3 is positioned at support 1 surface, and luminescent layer 5 is positioned at led chip 3 surfaces.
Medium-height trestle 1 of the present invention is the support of light-emitting diode, and it requires to have good chemical stability and thermal stability, good electrical conductivity and thermal conductivity.
Crystal-bonding adhesive 2 is used for led chip 3 is bonded to support among the present invention, when respectively there is an electrode above and below of led chip, requires crystal-bonding adhesive to conduct electricity and can heat conduction; When two electrodes are arranged above the led chip, require crystal-bonding adhesive to insulate and can heat conduction.
Led chip 3 is as the excitated fluorescent powder luminous light source among 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.
Base resin 90～99.5%
Monomer 0.2～3%
Light trigger 0.1～3%
Sensitising agent and auxiliary agent 0.2～6%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 90～99.5%
Diluent 0.4～8%
Cation light initiator 0.1～3%
The present invention China and foreign countries packaging plastic 6 is used for packaging LED chips 3 and luminescent layer 5, and it has the ability of excellent waterproof vapour and oxygen infiltration, and good chemical stability and thermal stability are arranged, and adopts the epoxy resin of hot curing usually.
Each composition of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is described as follows among the present invention:
Base resin: comprise unsaturated polyester resin, acrylic resin and polythiol-polyenoid system.
Unsaturated polyester resin: unsaturated polyester (UP) is to mix the linear polyesters that reacts and make with fractional saturation binary acid (or acid anhydrides) and dihydroxylic alcohols by undersaturated binary acid (or acid anhydrides) under action of evocating.In its molecular structure, there is undersaturated vinyl monomer to exist, if with active vinyl monomer and the undersaturated vinyl monomer copolymerization of this class, crosslinking curing and become three-dimensional-structure then.In general, the adhesive that makes by this resin since in the solidification process volume contraction bigger, the internal stress of gluded joint is very big.Micro-crack occurs easily and cause splicing power to diminish in the inside of glue-line; Simultaneously,, meet acid, the easy hydrolysis of alkali, thereby resistance to medium and resistance to water are relatively poor, easy deformation under the how wet environment of high temperature owing to contain ester bond in the macromolecular chain; In addition, its curing rate is slower, therefore, shows relatively poor combination property, so mostly use as non-structure glue.By reducing unsatisfied chemical bond content, adopt the low monomer of polymerization shrinkage, adding means such as inorganic filler and thermal plastic high polymer, can improve its overall performance.
Acrylic resin: this resin system curing rate is fast, studies morely at present.
Polythiol-polyenoid system: specifically comprise following structural formula:
Simple function group or polyfunctional group acrylic resin: this resin system curing rate is fast, studies morely at present.
Monomer (styrene and derivative thereof etc.) usually and resin be used, one side is as diluent, the viscosity that glue is had be convenient to construct; Have reactivity on the other hand again, solidify the laggard resin network of going into, the final performance of solidfied material is had certain improvement.The early stage monomer that uses is styrene and derivative thereof, and this class diluent crosslinking rate is slow, volatility is big and poisonous, poor heat resistance.Now, simple function group or polyfunctional group (methyl) acrylate of adopting more, as methyl methacrylate, ethyl acrylate, acrylic acid propylene glycol ester, n-butyl acrylate etc., the relatively poor problem of adhesive ubiquity thermal endurance of these ester preparations, and also there is the big defective of volatility in the lower ester of some molecular weight.If introduce aromatic rings in the molecular structure, then can improve the intensity and the resistance to water of glue, prolong the storage period of glue.Requirement to monomer mainly is: the respond of low viscosity, highly diluted effect and height, it is little also will to take into account volatility, toxicity and peculiar smell simultaneously, good etc. to the compatibility of resin.In order to regulate various performance parameters, often adopt mix monomer, mix monomer is as follows: free radical activity diluent and cation activity diluent.
The free radical activity diluent is divided into exploitation first generation acrylic acid polyfunctional monomer, the second generation acrylic acid polyfunctional monomer of recent development and more excellent third generation acrylic monomers early.
The simple function reactive diluent has: styrene, N-vinyl pyrrolidone, Isooctyl acrylate monomer, hydroxy-ethyl acrylate and isobornyl acrylate, methacrylate phosphate and isobornyl methacrylate, latter two is the good toughness reinforcing monomer of plasticising.
The difunctionality reactive diluent has: triethylene glycol diacrylate, tripropylene glycol diacrylate, glycol diacrylate, polyethylene glycol diacrylate alcohol ester, neopentylglycol diacrylate and propoxyl group neopentylglycol diacrylate, the acrylate-functional monomer mainly contains 1,6-hexanediyl ester (HDDA), 1,4-butanediol diacrylate (BDDA), propylene glycol diacrylate (DPGDA), glycerol diacrylate (TPGDA), the trihydroxy methyl propane triacrylate (TMPTA) of trifunctional, pentaerythritol triacrylate (PETA), trihydroxy methyl propane triol triacrylate (TMPTMA), trimethylolpropane triacrylate, propoxylation trihydroxy methyl propane triacrylate, pentaerythrite three propylene alcohol esters, pentaerythritol propoxylate propylene alcohol ester, N, N-dihydroxy ethyl-3 amido methyl propionate, triethylene glycolbismethyl-acrylate, long-chain fat hydrocarbon glycidol ether acrylic acid, the resorcinol bisglycidyl ether, double pentaerythritol C5 methacrylate, tri (propylene glycol) diacrylate, phthalic acid diethanol diacrylate (PDDA).They have replaced active little first generation acrylic acid monofunctional monomer.But along with the develop rapidly of ultra-violet curing technology, they reveal the big shortcoming of the excitant of skin.
Second generation acrylic acid polyfunctional monomer mainly is to introduce ethyoxyl or propoxyl group in molecule, has overcome the big shortcoming of excitant, also should have higher activity and state of cure.As ethoxylation trihydroxy methyl propane triol triacrylate [TMP (EO) TMA], propoxylation trihydroxy methyl propane triol triacrylate [TMP (PO) TMA], propoxylation glycerol triacrylate [G (PO) TA].Third generation acrylic monomers is mainly the acrylate that contains methoxyl group, preferably resolves the contradiction of high curing rate and shrinkage, low state of cure.This class material has 1,6-hexylene glycol methoxyl group mono acrylic ester (HDOMEMA), ethoxylation neopentyl glycol methoxyl group mono acrylic ester [TMP (PO) MEDA].After introducing alkoxyl in the molecule, can reduce the viscosity of monomer, reduce the excitant of monomer simultaneously.
The introducing of alkoxyl is also improved a lot to the compatibility of diluent monomer, and vinyltriethoxysilane (A15I), gamma-methyl allyl acyloxypropyl trimethoxysilane (A174) can be used as monomer.
Cruel in various active epoxy diluent resins and various cyclic ethers, the ring, vinyl ether monomers etc. can be as the diluent of cation photocuring resin.Therein ethylene pyridyl ethers compound and oligomer curing rate are fast, modest viscosity, tasteless, nontoxic, can be used with epoxy resin.Vinyl ether monomers has: 1,2,3-propanetriol-diglycidyl-ether (EPON-812), triethylene glycol divinyl ether (DVE-3), 1,4-butanediol vinyl ethers (HBVE), cyclohexyl vinyl ether (CHVE), perfluoro methyl vinyl ether (PMVE), the perfluor n-propyl vinyl ether, IVE, hydroxy butyl vinyl ether, vinyl ethyl ether, ethyl vinyl ether, the ethyl vinyl ether propylene, ethylene glycol monoallyl ether, hydroxy butyl vinyl ether, butyl vinyl ether, chlorotrifluoroethylene (CTFE), triethylene glycol divinyl ether, methoxy ethylene, the vinyl n-butyl ether, dodecyl vinyl (DDVE), cyclohexyl vinyl ether, tribenzyl-benzene phenol polyethenoxy base ether, tetrafluoroethene-perfluoro propyl vinyl ether, tetrafluoroethene-perfluoro propyl vinyl ether, tert-Butyl vinyl ether:
The epoxy compounds monomer has: 3,4-epoxy radicals hexahydrobenzoid acid-3 ', 4 '-epoxy radicals cyclohexyl methyl esters (ERL-4221), bisphenol A type epoxy resin (EP), epoxy acrylate, epoxy vinyl ester, acrylic acid epoxy ester, methacrylic acid epoxy-ester, water-soluble itaconic acid epoxy ester resin:
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 the cracking type 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 (PI810); 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.
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.
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 one di-t-butyl cresols, phenothiazine, anthraquinone etc.
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) (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], 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) (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], 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, fat
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.
Cationic photocuring system mainly utilizes the photodissociation under ultraviolet irradiation of aromatic series diazol, aromatic series salt compounded of iodine, aromatic series sulfonium salt to produce Bronsted acid, and Bronsted acid trigger monomer again carries out cationic polymerization.Compare with the radically curing system, it has, and cure shrinkage is little, the inhibition that is not subjected to various oxygen and if there is not nucleophilic impurity to exist, in case cause polymerization advantage such as will continue for a long time.But the Bronsted acid that light trigger discharges when rayed can produce corrosiveness to glued matrix.In theory, all monomers that can carry out cationic polymerization may be used to cationic curing, and still, at present the most frequently used is various epoxy resin or modified epoxy.Various active epoxy diluent resins and various cyclic ethers, cyclic lactone, vinyl ether monomers etc. can be as the diluents of light-cured resin, and cation light initiator has diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts, triaryl selenium salt etc.At present, more and more round the research of this system, for example there is report to utilize fluorine-containing and not fluorine-containing hybrid resin to cause at above-mentioned cationic initiator, made the adjustable accurate adhesive of low-shrinkage and refractive index; In disc making, the adhesive that the epoxy resin that utilizes cation to cause makes is that 96h does not have erosion to be taken place under 95% the experiment condition at 85 ℃, relative humidity; When the assembling of hollow devices, the aliphat and the bis-phenol D-type blending epoxy that utilize sulfonium salt to cause can make low linear expansion coefficient and have the adhesive of good moisture resistance.
2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide (TPO); the luxuriant molysite of virtue, organic aluminium compound/silane systems, dialkyl benzene acid methyl sulphur father-in-law salt; the reaction of the cation photocuring of triaryl sulphur hexafluorophosphate cation light initiator-tung oil-modified novolac epoxy resin (TMPE) and E-44 epoxy resin compound system. studied of the influence of various conditions by the mensuration of gel fraction to laser curing velocity, and coating structure before and after this reaction system photocuring reaction that utilized infrared spectrum analysis.The result shows that the kind of light trigger and concentration can change laser curing velocity effectively, and the initiating activity of Omnicat 550 is better than Omnicat 432 and proportional with its concentration; The punishment of photoactivate such as anthracene, BPO has certain sensibilization to system, and the phenthazine effect is not obvious; Different types of epoxy and vinyl ethers reactive diluent have considerable influence to laser curing velocity; Increase laser curing velocity increase along with epoxide group concentration in the resin proportioning; This diagram of system reveals " solidify the back " phenomenon.
Because light-initiated IONENE G cording has light-initiated not ideal enough, defectives such as curing rate is slow, cost height, limited it in industrial popularization, someone is unified in one with the cationic polymerization of epoxy resin and the radical polymerization of acrylate, both reached the purpose that makes full use of luminous energy, reached the purpose of mutual modification again, its cured product has been concentrated epoxy resin and acrylate advantage separately, has overcome some defective again simultaneously, has started a brand-new system.Make light trigger with benzhydryl iodine hexafluorophosphate (DPI.PF6), cause bisphenol A epoxide resin E
51Made low viscosity, curing time weak point, bonding layer shear strength height, the good adhesive of water-fast boiling property with the hybrid resin of acrylic ester prepolymer AE, the advantage of epoxy resin and acrylate is all shown up.Below enumerated the composition of several mixed systems:
1, epoxy resin E-51 (bisphenol-A (2, and the epoxychloropropane linear polymer that polycondensation is synthesized in alkaline medium two (4-hydroxy phenyl) propane of 2-)), (51 represent the representative fraction 50% of epoxy), diaryl group iodized salt (CD-1012), the cationic photopolymerization initiator system that sensitising agent diisopropyl thiazolone (ITX) is formed.
2, bisphenol A epoxide resin (epoxy resin 128), cationic initiator sulphion hexafluorophosphate (6992) and sulphion hexafluoro antimonate (6976) are sulfosalt, reactive diluent butyl glycidyl ether (669), long carbochain glycidol ether (114), carboxylic monomer (0200), the polycaprolactone polyol of two senses and trifunctional (0301).
3, one methacrylate/glycidyl methacrylate copolymer is grafted on the polyurethane, in amine and after make self-emulsifying type acrylic resin grafted polyurethane, strengthened the compatibility of polyurethane and acrylic resin, improved the cost performance of resin.
4, tetraethylene-glycol dimethylacrylate, tetraethylene-glycol dimethylacrylate are respectively with 3,4-epoxycyclohexyl methyl-3 ', 4 '-the epoxycyclohexane carboxylate mixing, light trigger is an Alpha-hydroxy cyclohexyl benzophenone (Irgacure184), 2,2-dimethoxy-2-phenyl acetophenone (Irgacure 651), styrax dimethyl ether, hexafluorophosphoric acid diphenyl iodnium.
5,2-ethylene glycol allyl ether and epoxy acrylic resin (CG602) mixture, cationic photoinitiator xylyl salt compounded of iodine or radical photoinitiator 2,2-dimethoxy-2-phenyl acetophenone (Irgacure651) or 2-hydroxy-2-methyl propiophenone (Darocur 1173).
6,4-epoxycyclohexyl formic acid-3,4-epoxycyclohexyl methyl ester (CY179), caprolactone trihydroxy alcohol, triaryl sulfonium salts, benzophenone and acrylate monomer.
7, vinyl ethers compound have that curing rate is fast, viscosity is low, be not afraid of oxygen inhibition, tasteless, nontoxic advantage.The photocuring system of forming with acrylic ester oligomer, triethylene Glycol divinyl ether, xylyl salt compounded of iodine, Alpha-hydroxy cyclohexyl benzophenone (Irgacure184) that mixes has that curing rate is fast, solvent resistance good, need not " solidify the back " and to characteristics such as polyester base material adhesive force are good.
Below be specific embodiments of the invention:
Device architecture as shown in Figure 2, led chip 3 adopts blue-light LED chips, and luminescent layer 5 adopts fluorescent material that is subjected to blue-light excited generation gold-tinted and the mixed system that needs the adhesive of ultraviolet light polymerization, and support 1 adopts the copper stent of electroplate.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive that blue-light LED chip is bonded on the support;
2. extraction electrode on led chip;
3. on led chip, spray the luminescent layer material, described luminescent layer is gold-tinted fluorescent material and the mixed system that needs the adhesive of ultraviolet light polymerization, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 10: 1 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 90%
Sensitising agent and auxiliary agent 5%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 90%
Diluent 8%
Cation light initiator 2%
4. the luminescent layer that 3. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
5. the above-mentioned light-emitting diode for preparing is encapsulated;
6. the every photoelectric properties and the parameter of test component.
Device architecture as shown in Figure 2, led chip 3 adopts blue-light LED chips, and luminescent layer 5 adopts fluorescent material that is subjected to blue-light excited generation green glow and the mixed system that needs the adhesive of ultraviolet light polymerization, and support 1 adopts the copper stent of electroplate.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive that blue-light LED chip is bonded on the support;
2. extraction electrode on led chip;
3. spin coating luminescent layer material on led chip, before the spin coating luminescent layer material was stirred 20 hours with the adhesive raw materials that ethanol carries out dilution in 1: 10, rotating speed is 3000 revolutions per seconds during spin coating, duration one minute, described luminescent layer is green light fluorescent powder and the mixed system that needs the adhesive of ultraviolet light polymerization, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 7: 1 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 92%
Sensitising agent and auxiliary agent 3%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 94%
Diluent 4%
Cation light initiator 2%
4. the luminescent layer that 3. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
5. the above-mentioned light-emitting diode for preparing is encapsulated;
6. the every photoelectric properties and the parameter of test component.
Device architecture as shown in Figure 2, led chip 3 adopts blue-light LED chips, and luminescent layer 5 adopts fluorescent material that is subjected to blue-light excited generation ruddiness and the mixed system that needs the adhesive of ultraviolet light polymerization, and support 1 adopts the copper stent of electroplate.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive that blue-light LED chip is bonded on the support;
2. extraction electrode on led chip;
3. on led chip, drip and be coated with the luminescent layer material, described luminescent layer is red light fluorescent powder and the mixed system that needs the adhesive of ultraviolet light polymerization, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 5: 1 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 90%
Sensitising agent and auxiliary agent 6%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 91%
Diluent 6%
Cation light initiator 3%
4. the luminescent layer that 3. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
5. the above-mentioned light-emitting diode for preparing is encapsulated;
6. the every photoelectric properties and the parameter of test component.
Device architecture as shown in Figure 2, led chip 3 adopts blue-light LED chips, and luminescent layer 5 adopts fluorescent material that is subjected to blue-light excited generation ruddiness and green glow and the mixed system that needs the adhesive of ultraviolet light polymerization, and support 1 adopts the copper stent of electroplate.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive that blue-light LED chip is bonded on the support;
2. extraction electrode on led chip;
3. on led chip, drip and be coated with the luminescent layer material, described luminescent layer is ruddiness and green light fluorescent powder and the mixed system that needs the adhesive of ultraviolet light polymerization, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 3: 1 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 99.5%
Monomer 0.2%
Light trigger 0.1%
Sensitising agent and auxiliary agent 0.2%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 90%
Diluent 8%
Cation light initiator 2%
4. the luminescent layer that 3. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
5. the above-mentioned light-emitting diode for preparing is encapsulated;
6. the every photoelectric properties and the parameter of test component.
Table 1 is the various performance parameters that the adhesive of luminescent layer adopts the light-emitting diode of the light-emitting diode of conventional colloid and embodiment 4.
| The adhesive of luminescent layer adopts the light-emitting diode of conventional colloid | The light-emitting diode of the embodiment of the |
|
| The highest luminosity (cd/m 2) | 22530 | 31370 |
| Color rendering index | 90 | 95 |
| Chromaticity coordinates | (0.313，0.324) | (0.332，0.326) |
| Life-span (hour) | ～30000 | ～35600 |
| Colour temperature (k) | 7163 | 7538 |
Device architecture as shown in Figure 3, led chip 3 adopts the ultraviolet leds chips, and luminescent layer 5 adopts the mixed system that is subjected to ultraviolet excitation to produce the fluorescent material of blue light and needs the adhesive of ultraviolet light polymerization, and support 1 adopts the copper stent of electroplate.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive the ultraviolet leds chip adhesive on support;
2. extraction electrode on led chip;
3. dip-coating luminescent layer material on led chip, described luminescent layer is blue light fluorescent powder and the mixed system that needs the adhesive of ultraviolet light polymerization, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 2: 1 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 90%
Sensitising agent and auxiliary agent 5%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 99.5%
Diluent 0.4%
Cation light initiator 0.1%
4. the luminescent layer that 3. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
5. the above-mentioned light-emitting diode for preparing is encapsulated;
6. the every photoelectric properties and the parameter of test component.
Device architecture as shown in Figure 3, led chip 3 adopts the ultraviolet leds chips, and luminescent layer 5 adopts the mixed system that is subjected to ultraviolet excitation to produce the fluorescent material of green glow and needs the adhesive of ultraviolet light polymerization, and support 1 adopts the copper stent of electroplate.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive the ultraviolet leds chip adhesive on support;
2. extraction electrode on led chip;
3. on led chip, form luminescent layer by LB film mode, described luminescent layer is green light fluorescent powder and the mixed system that needs the adhesive of ultraviolet light polymerization, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 1: 1 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 99.5%
Monomer 0.2%
Light trigger 0.1%
Sensitising agent and auxiliary agent 0.2%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 99.5%
Diluent 0.4%
Cation light initiator 0.1%
4. the luminescent layer that 3. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
5. the above-mentioned light-emitting diode for preparing is encapsulated;
6. the every photoelectric properties and the parameter of test component.
Embodiment 7
Device architecture as shown in Figure 3, led chip 3 adopts the ultraviolet leds chips, and luminescent layer 5 adopts the mixed system that is subjected to ultraviolet excitation to produce the fluorescent material of gold-tinted and needs the adhesive of ultraviolet light polymerization, and support 1 adopts the copper stent of electroplate.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive the ultraviolet leds chip adhesive on support;
2. extraction electrode on led chip;
3. spin coating luminescent layer material on led chip, to stir 20 hours with the adhesive raw materials that ethanol carries out diluting at 1: 10 before the spin coating, rotating speed is 2000 revolutions per seconds during spin coating, duration one minute, described luminescent layer is gold-tinted fluorescent material and the mixed system that needs the adhesive of ultraviolet light polymerization, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 1: 3 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 93%
Sensitising agent and auxiliary agent 3%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 95%
Diluent 3%
Cation light initiator 2%
4. the luminescent layer that 3. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
5. the above-mentioned light-emitting diode for preparing is encapsulated;
6. the every photoelectric properties and the parameter of test component.
Embodiment 8
Device architecture as shown in Figure 3, led chip 3 adopts the ultraviolet leds chips, and luminescent layer 5 adopts the mixed system that is subjected to ultraviolet excitation to produce the fluorescent material of ruddiness and needs the adhesive of ultraviolet light polymerization, and support 1 adopts the copper stent of electroplate.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive the ultraviolet leds chip adhesive on support;
2. extraction electrode on led chip;
3. spin coating luminescent layer material on led chip, to stir 20 hours with the adhesive raw materials that ethanol carries out diluting at 1: 10 before the spin coating, rotating speed is 2000 revolutions per seconds during spin coating, duration one minute, described luminescent layer is red light fluorescent powder and the mixed system that needs the adhesive of ultraviolet light polymerization, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 1: 5 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 96%
Sensitising agent and auxiliary agent 1%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 98%
Diluent 1.2%
Cation light initiator 0.8%
4. the luminescent layer that 3. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
5. the above-mentioned light-emitting diode for preparing is encapsulated;
6. the every photoelectric properties and the parameter of test component.
Embodiment 9
Device architecture as shown in Figure 3, led chip 3 adopts the ultraviolet leds chips, and luminescent layer 5 adopts the mixed system that is subjected to ultraviolet excitation to produce the fluorescent material of blue light and gold-tinted and needs the adhesive of ultraviolet light polymerization, and support 1 adopts the copper stent of electroplate.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive the ultraviolet leds chip adhesive on support;
2. extraction electrode on led chip;
3. spin coating luminescent layer material on led chip, to stir 20 hours with the adhesive raw materials that ethanol carries out diluting at 1: 10 before the spin coating, rotating speed is 2000 revolutions per seconds during spin coating, duration one minute, described luminescent layer is blue light and gold-tinted fluorescent material and the mixed system that needs the adhesive of ultraviolet light polymerization, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 1: 7 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 97%
Monomer 0.7%
Light trigger 1.2%
Sensitising agent and auxiliary agent 1.1%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 96%
Diluent 2%
Cation light initiator 2%
4. the luminescent layer that 3. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
5. the above-mentioned light-emitting diode for preparing is encapsulated;
6. the every photoelectric properties and the parameter of test component.
Embodiment 10
Device architecture as shown in Figure 3, led chip 3 adopts the ultraviolet leds chips, and luminescent layer 5 adopts the mixed system that is subjected to ultraviolet excitation to produce the fluorescent material of blue light, green glow and ruddiness and needs the adhesive of ultraviolet light polymerization, and support 1 adopts the copper stent of electroplate.
The preparation method is as follows:
1. select suitable crystal-bonding adhesive the ultraviolet leds chip adhesive on support;
2. extraction electrode on led chip;
3. spin coating luminescent layer material on led chip, to stir 20 hours with the adhesive raw materials that ethanol carries out diluting at 1: 10 before the spin coating, rotating speed is 2000 revolutions per seconds during spin coating, duration one minute, described luminescent layer is blue light, green glow and red light fluorescent powder and the mixed system that needs the adhesive of ultraviolet light polymerization, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 1: 10 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 93%
Sensitising agent and auxiliary agent 1%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 95%
Diluent 2%
Cation light initiator 3%
4. the luminescent layer that 3. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
5. the above-mentioned light-emitting diode for preparing is encapsulated;
6. the every photoelectric properties and the parameter of test component.
Claims (9)
1. light-emitting diode, at least comprise support, led chip and the luminescent layer on led chip, it is characterized in that, described luminescent layer material can be sent out the fluorescent material of shades of colour light for one or more and need the mixed system of the adhesive composition of ultraviolet light polymerization, described adhesive is the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 10: 1～1: 10 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 90～99.5%
Monomer 0.2～3%
Light trigger 0.1～3%
Sensitising agent and auxiliary agent 0.2～6%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 90～99.5%
Diluent 0.4～8%
Cation light initiator 0.1～3%
Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or acetophenone derivative; Sensitising agent comprises benzophenone, thia anthraquinone or Michler's keton, auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant or coupling agent, and described diluent comprises various active epoxy diluent resins or various cyclic ethers, cyclic lactone, the vinyl ether monomers diluent as light-cured resin; Described cation light initiator comprises diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts or triaryl selenium salt; Described base resin comprises unsaturated polyester resin, acrylic resin or polythiol-polyenoid system; Described monomer comprises styrene and derivative, simple function group or multi-functional acrylate; Described cationic monomer comprises various epoxy resin or modified epoxy or fluorine-containing and not fluorine-containing hybrid resin or aliphat and bis-phenol D-type blending epoxy.
2. light-emitting diode according to claim 1 is characterized in that described acrylic resin comprises polyester-acrylate, epoxy-acrylate, carbamate-acrylate and polyethers-acrylate.
3. light-emitting diode according to claim 1 is characterized in that, described polythiol-polyenoid system comprises the material of following structural formula:
4. light-emitting diode according to claim 1, it is characterized in that, described mixed system raw material comprises bisphenol A epoxide resin, sulphion hexafluorophosphate and sulphion hexafluoro antimonate, butyl glycidyl ether, long carbochain glycidol ether, carboxylic monomer, the polycaprolactone polyol of two senses and trifunctional.
5. light-emitting diode according to claim 1, it is characterized in that, described mixed system raw material comprises the tetraethylene-glycol dimethylacrylate, 3, and 4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, Alpha-hydroxy cyclohexyl benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, the styrax dimethyl ether, the hexafluorophosphoric acid diphenyl iodnium.
6. light-emitting diode according to claim 1 is characterized in that, described mixed system raw material comprises 2-ethylene glycol allyl ether, epoxy acrylic resin, xylyl salt compounded of iodine, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl propiophenone.
7. light-emitting diode according to claim 1 is characterized in that, described led chip is the chip of blue light-emitting or ultraviolet light; Described fluorescent material is by a kind of blue light or ultraviolet excitation and luminous fluorescent material.
8. the preparation method of a light-emitting diode may further comprise the steps:
1. select the led chip with the fluorescent material coupling, the effective excitated fluorescent powder of the luminous energy that led chip is sent;
2. select suitable crystal-bonding adhesive that led chip is bonded on the support, when respectively there is an electrode above and below of led chip, require crystal-bonding adhesive to conduct electricity and can heat conduction; When two electrodes are arranged above the led chip, require crystal-bonding adhesive to insulate and can heat conduction;
3. extraction electrode on led chip;
4. on led chip, apply the luminescent layer material, described luminescent layer is fluorescent material and the mixed system that needs the adhesive of ultraviolet light polymerization, described adhesive is the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 10: 1～1: 10 in the mixed system of described adhesive, and described free radical type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Base resin 90～99.5%
Monomer 0.2～3%
Light trigger 0.1～3%
Sensitising agent and auxiliary agent 0.2～6%
Described cation type ultraviolet photo-curing cementing agent raw material comprises the component of following mass percent:
Cationic monomer 90～99.5%
Diluent 0.4～8%
Cation light initiator 0.1～3%
Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and acetophenone derivative; Sensitising agent comprises benzophenone, thia anthraquinone and Michler's keton, auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant and coupling agent, and described diluent comprises various active epoxy diluent resins and various cyclic ethers, cyclic lactone, the vinyl ether monomers diluent as light-cured resin; Described cation light initiator has diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts, triaryl selenium salt;
5. the luminescent layer that 4. step is obtained carries out ultraviolet light polymerization processing 30 seconds;
6. the above-mentioned light-emitting diode for preparing is encapsulated;
7. the every photoelectric properties and the parameter of test component.
9. the preparation method of light-emitting diode according to claim 8 is characterized in that, step 4. in, the luminescent layer material mixing directly is prepared on the led chip after evenly, perhaps is prepared on the led chip through behind the organic solvent diluting; Described luminescent layer be coated with by dripping, one or several modes in the spin coating, dip-coating, coating, inkjet printing, roller coat, LB film form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102208566A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate used in luminescent device and preparation method thereof |
| CN102208557A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate for flexible luminescent device and preparation method thereof |
| CN102208559A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate for flexible luminescent device and preparation method thereof |
| CN102208568A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate used by flexible light-emitting device and preparation method thereof |
| CN103247744A (en) * | 2012-02-09 | 2013-08-14 | 威士玻尔光电(苏州)有限公司 | Remote fluorescent powder and preparation method thereof |
| CN103647003A (en) * | 2013-05-21 | 2014-03-19 | 长兴化学工业股份有限公司 | Photochromic conversion film and method for producing same |
| CN105870307A (en) * | 2016-04-30 | 2016-08-17 | 浙江单色电子科技有限公司 | Low-light-decay ultraviolet LED and manufacturing method thereof |
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| CN101465408A (en) * | 2008-12-31 | 2009-06-24 | 电子科技大学 | Substrate for flexible organic optoelectronic device and preparation method thereof |
| CN101694857A (en) * | 2009-10-16 | 2010-04-14 | 中外合资江苏稳润光电有限公司 | Manufacture method of low-attenuation white light LED |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102208566A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate used in luminescent device and preparation method thereof |
| CN102208557A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate for flexible luminescent device and preparation method thereof |
| CN102208559A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate for flexible luminescent device and preparation method thereof |
| CN102208568A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate used by flexible light-emitting device and preparation method thereof |
| CN102208559B (en) * | 2011-04-18 | 2013-03-27 | 电子科技大学 | Substrate for flexible luminescent device and preparation method thereof |
| CN102208557B (en) * | 2011-04-18 | 2013-03-27 | 电子科技大学 | Substrate for flexible luminescent device and preparation method thereof |
| CN102208568B (en) * | 2011-04-18 | 2013-03-27 | 电子科技大学 | Substrate used by flexible light-emitting device and preparation method thereof |
| CN103247744A (en) * | 2012-02-09 | 2013-08-14 | 威士玻尔光电(苏州)有限公司 | Remote fluorescent powder and preparation method thereof |
| CN103647003A (en) * | 2013-05-21 | 2014-03-19 | 长兴化学工业股份有限公司 | Photochromic conversion film and method for producing same |
| CN103647003B (en) * | 2013-05-21 | 2016-09-07 | 长兴材料工业股份有限公司 | Photochromic conversion film and method for producing same |
| CN105870307A (en) * | 2016-04-30 | 2016-08-17 | 浙江单色电子科技有限公司 | Low-light-decay ultraviolet LED and manufacturing method thereof |
| CN113980208A (en) * | 2021-10-20 | 2022-01-28 | 电子科技大学 | Multi-arm block type polycaprolactone color-changing polymer, light-operated color-changing sponge and preparation method thereof |
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