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CN102299118A - Method for packaging photoelectronic device - Google Patents

Method for packaging photoelectronic device Download PDF

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Publication number
CN102299118A
CN102299118A CN2011101324767A CN201110132476A CN102299118A CN 102299118 A CN102299118 A CN 102299118A CN 2011101324767 A CN2011101324767 A CN 2011101324767A CN 201110132476 A CN201110132476 A CN 201110132476A CN 102299118 A CN102299118 A CN 102299118A
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opto
electronic device
agent
layer
ultraviolet
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于军胜
张磊
李金川
蒋亚东
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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Abstract

The invention discloses a method for packaging a photoelectronic device. The method is used for packaging a prepared device by a film packaging method, wherein the photoelectronic device is covered by a film packaging layer. The method is characterized in that the film packaging layer is formed by alternate overlap of inorganic film packaging material layers and ultraviolet sensitive material layers, wherein the ultraviolet sensitive material comprises the following components: a multi-sulfur alcohol-polyene system, mono-functional or multi-functional acrylic acid, a photo initiator, a photosensitizer and auxiliaries. The method has the following beneficial effects: the problem that the photoelectronic device is sensitive to water and oxygen is solved; the method is beneficial to improvement of the device performances and prolonging of the device life; and meanwhile, the process is simplified and the cost is lowered.

Description

A kind of method for packing of opto-electronic device
Technical field
The present invention relates to the photoelectron technology field, be specifically related to a kind of method for packing of opto-electronic device.
Background technology
Photoelectron technology is the very high industry of scientific and technological content that develops rapidly after microelectric technique.Along with the fast development of photoelectron technology, photoelectron products such as light-emitting diode, Organic Light Emitting Diode, solar cell, thin-film transistor are all full-fledged gradually, and they have improved people's life greatly.Simultaneously, opto-electronic information technology has also been created growing great market in the extensive use of social life every field, and the competition of the field of opto-electronic information just launches at world wide.
Present opto-electronic device, include organic electroluminescence devices, inorganic light-emitting diode, organic solar batteries, inorganic solar cell, OTFT, inorganic thin-film transistors, ultraviolet light detector, infrared detector etc., the particularly fast development of organic optoelectronic device, be fit to global social low-carbon environment-friendly, the tool development potentiality of green living and the opto-electronic device of application market, its part mostly are to adopt the organic material preparation on rigidity (as glass or silicon chip) or flexible base, board.Though they have good device performance and since device to external world environment have very strong sensitiveness, especially in organic optoelectronic device, the water in the atmospheric environment and oxygen etc. become branch's negative effect serious to material production.Can not make that device performance reduces gradually after thereby packaged device is placed in atmospheric environment, even lose performance fully.Oxygen makes organic material produce oxidation and can generate carbonyls, and this compound is serious quencher, and in addition, material is rotten will to form blackspot, and follows device performance to descend.The influence of steam is more apparent, and its main failure mode is the hydrolysis of conductive electrode to the organic layer compound, and stability is descended greatly.For this reason, degeneration and the inefficacy of device in the long-term work process is inhibited, steady operation reaches enough life-spans, must encapsulate device, and adopt which kind of encapsulating material and which kind of method for packing also just to become another break-through point of dealing with problems.
Summary of the invention
Technical problem to be solved by this invention is the method for packing how a kind of opto-electronic device is provided, this method for packing has solved the sensitive question of opto-electronic device to water and oxygen etc., can enhance device to the obstructing capacity of water and oxygen, the stability and the life-span of having improved device.
Technical problem proposed by the invention is to solve like this: the method for packing that a kind of opto-electronic device is provided, adopt film encapsulation method to encapsulate to opto-electronic device, thin-film encapsulation layer coats opto-electronic device, it is characterized in that, described thin-film encapsulation layer replaces overlapping the composition by inorganic thin film encapsulating material layer and ultraviolet sensitivity material layer with periodicity n, 1≤n≤20 wherein, described ultraviolet sensitivity material comprises the component of following mass percent:
Polythiol-polyenoid system 94～99.5%
Simple function group or polyfunctional group acrylic acid 0.2～1%
Light trigger 0.1～5%
Sensitising agent and auxiliary agent 0.2～4%
Wherein light trigger is an acetophenone derivative, and sensitising agent is thia anthraquinone or Michler's keton, and auxiliary agent comprises antistatic agent, fire retardant and coupling agent.
Method for packing according to opto-electronic device provided by the present invention is characterized in that, described polythiol-polyenoid system comprises the material of following structural formula:
Figure BSA00000501092200021
Method for packing according to opto-electronic device provided by the present invention, it is characterized in that, described coupling agent is 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, gamma-aminopropyl-triethoxy-silane, 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 or γ-sulfydryl propyl-triethoxysilicane.
Method for packing according to opto-electronic device provided by the present invention is characterized in that, described inorganic thin film encapsulating material is metal oxide or metal sulfide or metal nitride, and wherein, metal oxide comprises calcium oxide (CaO), tantalum pentoxide (Ta 2O 5), titanium dioxide (TiO 2), zirconium dioxide (ZrO 2), cupric oxide (CuO), zinc oxide (ZnO), alundum (Al (Al 2O 3), chrome green (Cr 2O 3), tin ash (SnO 2), nickel oxide (NiO), antimony pentoxide (Sb 2O 5), metal sulfide comprises titanium disulfide (TiS 2), iron sulfide (FeS), chromium hemitrisulfide (Cr 2S 3), copper sulfide (CuS), zinc sulphide (ZnS), stannic disulfide (SnS 2), nickel sulfide (NiS), cobalt sesquisulfide (Co 2S 3), antimonous sulfide (Sb 2S 3), vulcanized lead (PbS), three the sulfuration two lanthanum (La 2S 3), cerium sulphide (CeS), curing zirconium (ZrS 2), nitride comprises silicon nitride (Si 3N 4), aluminium nitride (AlN).
Method for packing according to opto-electronic device provided by the present invention is characterized in that, specifically may further comprise the steps:
1. the rigid substrates (as glass or silicon chip) of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen;
2. take the mode of high vacuum vapor deposition or spin coating or self assembly or inkjet printing or silk screen printing on the rigid substrates of cleaning, to prepare opto-electronic device;
3. to prepared opto-electronic device, preparation inorganic encapsulated material thin-layer prepares the ultraviolet sensitivity material thin-layer more thereon earlier, and described ultraviolet sensitivity material thin-layer comprises the component of following mass percent:
Polythiol-polyenoid system 94～99.5%
Simple function group or polyfunctional group acrylic acid 0.2～1%
Light trigger 0.1～5%
Sensitising agent and auxiliary agent 0.2～4%
Wherein light trigger is an acetophenone derivative, and sensitising agent is thia anthraquinone or Michler's keton, and auxiliary agent comprises antistatic agent, fire retardant and coupling agent;
4. ultraviolet light polymerization being carried out on the rigid substrates surface handled 30 seconds;
5. to the device behind the ultraviolet light polymerization, 3. and operation 4. continue repeating step, repeat n time 1≤n≤20 continuously;
6. the life-span of device and other parameters after the test package.
Method for packing according to opto-electronic device provided by the present invention, it is characterized in that, the encapsulation foil of described inorganic encapsulated material and ultraviolet sensitivity material adopts vacuum evaporation, ion cluster bundle deposition, ion plating, dc sputtering deposition, the RF sputter coating, ion beam sputtering deposition, ion beam assisted depositing, plasma reinforced chemical vapour deposition, high density inductance coupling high formula plasma source chemical vapor deposition, the catalyst chemical vapour deposition (CVD), magnetron sputtering, inkjet printing, electroplate, spraying, spin coating, dip-coating, one or several modes in roller coat and the LB film and forming.
Method for packing according to opto-electronic device provided by the present invention, it is characterized in that, described opto-electronic device is between a kind of photoelectricity, electric between and can carry out the device of signal and power conversion between the electric light, comprise organic electroluminescent LED, inorganic light-emitting diode, organic solar batteries, inorganic solar cell, OTFT, inorganic thin-film transistors, photo-detector.
Beneficial effect of the present invention: in the encapsulating material of opto-electronic device, organic encapsulating material is comparatively rare, the invention provides a kind of routine, effective organic encapsulating material, because organic encapsulating material possesses good ultraviolet sensitivity characteristic, behind the preparation opto-electronic device, substrate is carried out suitable ultraviolet and handle.The organic ultraviolet sensitive material has good curing agent, stability, adhesion strength, light transmittance and high-purity, and the various preferred proportions and the technological parameter that provide among the present invention are provided, and can obtain more excellent device performance.Encapsulated layer of the present invention adopts inorganic encapsulated material thin-layer and described organic ultraviolet sensitive material film to replace overlapping composition, not only can reduce cost, and simplifies technology, importantly can improve device stability well, prolongs device lifetime.
Description of drawings
Fig. 1 is the opto-electronic device encapsulating structure schematic diagram among the embodiment 1～5 provided by the invention;
Fig. 2 is the opto-electronic device encapsulating structure schematic diagram among the embodiment 6～10 provided by the invention;
Fig. 3 is the opto-electronic device encapsulating structure schematic diagram among the embodiment 11～13 provided by the invention;
Fig. 4 is the opto-electronic device encapsulating structure schematic diagram among the embodiment 14～18 provided by the invention;
Fig. 5 is the opto-electronic device encapsulating structure schematic diagram among the embodiment 19 provided by the invention;
Fig. 6 is the opto-electronic device encapsulating structure schematic diagram among the embodiment 20 provided by the invention.
Wherein, the 1st, opto-electronic device, wherein, the 11st, substrate, the 12nd, anode layer, the 131st, hole transmission layer, the 132nd, electron donor layer, the 133rd, P type semiconductor, the 141st, electron transfer layer, the 142nd, electron acceptor layer, the 143rd, N type semiconductor, the 15th, metal electrode layer, the 16th, insulating barrier, the 17th, functional activation layer, the 2nd, encapsulated layer of the present invention, alternately overlap with certain periodicity n by 21 and 22, the 21st, inorganic thin film encapsulating material, the 22nd, ultraviolet sensitivity agent thin layer.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described:
Substrate 11 is the support of electrode and organic thin film layer among the present invention, it has the good light transmittance energy in the visible region, the ability that the infiltration of certain anti-steam and oxygen is arranged, profile pattern is preferably arranged, it can be glass or flexible substrate, and flexible substrate adopts a kind of material or the thin metal in polyesters, the poly-phthalimide compound.
The anode layer 12 of organic electroluminescence device is as the articulamentum of organic electroluminescence device forward voltage among the present invention, and it requires to have electric conductivity, visible transparent and higher work function preferably.Usually adopt the metal material (as gold, copper, silver, platinum etc.) of inorganic, metal oxide (as tin indium oxide ITO, zinc oxide ZnO etc.), organic conductive polymer (as PEDOT:PSS, PANI etc.) or high work function.
The cathode layer 15 of organic electroluminescence device is as the articulamentum of device negative voltage among the present invention, its requires to have electric conductivity and lower work function preferably, and negative electrode is generally the alloy of the lower metal of work functions such as low workfunction metal material lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold, silver; Perhaps the buffer insulation layer that one deck is very thin is (as LiF, MgF 2Deng) and metal or alloy noted earlier.
The inorganic thin film encapsulating material 21 of organic electroluminescence device is metal oxide or metal sulfide or metal nitride among the present invention, and wherein, metal oxide comprises calcium oxide (CaO), tantalum pentoxide (Ta 2O 5), titanium dioxide (TiO 2), zirconium dioxide (ZrO 2), cupric oxide (CuO), zinc oxide (ZnO), alundum (Al (Al 2O 3), chrome green (Cr 2O 3), tin ash (SnO2), nickel oxide (NiO), antimony pentoxide (Sb 2O 5), metal sulfide comprises titanium disulfide (TiS 2), iron sulfide (FeS), chromium hemitrisulfide (Cr 2S 3), copper sulfide (CuS), zinc sulphide (ZnS), stannic disulfide (SnS 2), nickel sulfide (NiS), cobalt sesquisulfide (Co 2S 3), antimonous sulfide (Sb 2S 3), vulcanized lead (PbS), three the sulfuration two lanthanum (La 2S 3), cerium sulphide (CeS), curing zirconium (ZrS 2), nitride comprises silicon nitride (Si 3N 4), aluminium nitride (AlN).
Each composition is described as follows among the present invention:
Polythiol-polyenoid system: specifically comprise following structural formula:
Figure BSA00000501092200051
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 (200) 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) and trifunctional three through methylpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), trihydroxy methyl propane triol triacrylate (TMPTMA), trimethylolpropane triacrylate, propoxylation three is through the methylpropane triacrylate, pentaerythrite three propylene alcohol esters and 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 UV curing technology, they reveal the big shortcoming of the excitant of skin.
Overcome the big shortcoming of excitant, also had higher activity and state of cure firmly.Second generation acrylic acid polyfunctional monomer mainly is to introduce ethyoxyl or propoxyl group in molecule, 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 advantage, 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:
Figure BSA00000501092200071
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:
Figure BSA00000501092200072
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 (CH2OCCH2CH2SH) system, use benzoin methyl ether, benzoin ethyl ether respectively, benzoin isopropyl ether causes, be respectively 18s, 20s and 25s curing time, and when causing with benzophenone, only be 15s curing time, and simultaneously the light transmittance of solidfied material also can difference be bigger owing to the wavelength difference, and this will rationally select for use according to actual conditions.
The effect of light trigger is after it absorbs the ultraviolet light energy, produces free radical through decomposing, thus the unsaturated bond polymerization in the initiator system, and crosslinking curing becomes an integral body.Radical photoinitiator commonly used has cracking and puies forward Hydrogen two big classes.
Crack type photoinitiator: crack type photoinitiator mainly contains benzoin ethers (styrax ethers), benzil ketals and acetophenone etc.Crack type photoinitiator is homolysis 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: this type of initator of aromatic sulfonium salts and salt compounded of iodine has excellent high-temperature stability, and also has 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, thus the solidification effect that obtains.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 (CH2OCCH2CH2SH) under the initiation of benzophenone, if the silicone couplet CH2=CHSi (OCH2CH2OCH3) 3 of adding 1%, behind ultraviolet light polymerization, place under the environment of 80～100% humidity, do not find after 1 year to change, and if do not add coupling agent, under the same terms, white erosion just takes place in the bonded part after 2 days, and 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) (F, OH) 2], magnesium silicon muscovite [K 2((Fe 2+ Mg) (Fe 3+ Al) 3(Si 7AlO 20) (OH) 4)], montmorillonite [Na x(H 2O) 4{ (Al 2-xMg 0.33) [Si 4O 10] (OH) 2], bentonite [Na x(H 2O) 4(Al 2-xMg 0.83) Si 4O 10) (OH) 2], kaolin, red mud (Al 1-xO x), calcium sulfate, acrylate high polymer, butyl polyacrylate, polyurethane.
Dispersant impels material particles to be dispersed in the medium, forms the reagent of stable suspension.Dispersant generally is divided into inorganic dispersant and organic dispersing agent two big classes.Inorganic dispersant commonly used has silicates (for example waterglass) and alkali metal phosphonates (Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium, Amino Trimethylene Phosphonic Acid potassium, HEDP sodium, the HEDP disodium, HEDP four sodium, HEDP potassium, ethylene diamine tetra methylene phosphonic acid five sodium, diethylene triamine pentamethylene phosphonic five sodium, diethylenetriamine pentamethylene phosphonic acids seven sodium, diethylene triamine pentamethylene phosphonic sodium, 2-phosphonic acids butane-1,2,4-tricarboxylic acids four sodium, hexamethylene diamine tetramethyl fork phosphonic acids sylvite, two 1,6 hexylidene triamine, five methylenephosphonic acid sodium, the trimerization Alendronate, calgon and sodium pyrophosphate etc.).Organic dispersing agent comprises triethyl group hexyl phosphonic acids; Amino Trimethylene Phosphonic Acid; HEDP (HEDP); ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS); ethylene diamine tetra methylene phosphonic acid (EDTMPA); diethylene triamine pentamethylene phosphonic (DTPMP); 2-phosphonic acids butane-1; 2; 4-tricarboxylic acids (PBTCA); PAPE (PAPE); 2-HPAA (HPAA); hexamethylene diamine tetramethyl fork phosphonic acids (HDTMPA); polyamino polyether base methylenephosphonic acid (PAPEMP); two 1,6 hexylidene triamine, five methylenephosphonic acids (BHMTPMPA); lauryl sodium sulfate; polyacrylic acid (PAA); Sodium Polyacrylate (PAAS); HPMA (HPMA); maleic acid-acrylic acid copolymer (MA-AA); acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer (AA/AMPS); acrylic acid-hydroxypropyl acrylate copolymer; acrylic acid-acrylate-phosphonic acids-sulfonate quadripolymer; acrylic acid-acrylate-sulfonate terpolymer; phosphono-carboxylic acids copolymer (POCA); polyacrylate; carboxylate-sulfonate-nonionic terpolymer; polyepoxy sodium succinate (PESA); poly (sodium aspartate) (PASP); the base amylalcohol; cellulose derivative; polyacrylamide; guar gum; fatty acid polyethylene glycol ester etc.
Antioxidant is the auxiliary agent of major function to suppress the fluoropolymer resin thermal oxidative degradation, belongs to the category of anti-oxidant reagent.Antioxidant is the topmost type of plastics stabilizing additive, and nearly all fluoropolymer resin all relates to the application of antioxidant.According to the mechanism of action, traditional antioxidant systems generally comprises primary antioxidant, auxiliary antioxidant and heavy metal ion passivator etc.Primary antioxidant is a major function to catch the polymer peroxy radical, and the title of " peroxy radical trapping agent " and " chain termination type antioxidant " is arranged again, relates to aromatic amine compounds and hindered phenol compound two big series of products.Aromatic amine antioxidant has: diphenylamines, p-phenylenediamine (PPD), N, N-pair-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propiono] hexamethylene diamine, dihydroquinoline; Hinered phenols antioxidant has: 2,5-ditert-butylhydro quinone, 2,6-di-tert-butyl-4-methy phenol, TBHQ, 2,5-ditert-butylhydro quinone (DBHQ), 2, three grades of butyl of 6--4-methylphenol, two (3, three grades of butyl of 5--4-hydroxy phenyl) thioether, four [β-(3, three grades of butyl of 5--4-hydroxy phenyl) propionic acid] pentaerythritol ester; Triphenyl phosphite (TPPi), phosphite ester three (2,4-di-tert-butyl phenyl) ester, pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) dimer and the trimerical compound, 3 of ester, many alkyl bisphenol-A phosphite ester, 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, β-(4-hydroxy phenyl-3, the 5-di-t-butyl) the positive octadecanol ester of propionic acid, 1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-hydroxy benzenes methyl) benzene.Auxiliary antioxidant has the effect of decomposing copolymer per-compound, also claims " peroxide decomposer " to comprise sulfo-dicarboxylic ester class and bi-ester of phosphite, and common and primary antioxidant is used.The two octadecyl esters (DSTP) of two 12 carbon alcohol esters, two ten four carbon alcohols esters, thio-2 acid, thio-2 acid dibasic acid esters, two octadecanol ester, the two lauryls of thio-2 acid, three monooctyl esters, three the last of the ten Heavenly stems ester, three (12 carbon alcohol) ester and three (16 carbon alcohol) ester, 3,6,9-trioxa decane-1,11-glycol-two-n-dodecane mercaptopropionic acid ester, triphenyl phosphate TPP, trisnonyl phenyl phosphite, phosphorous acid octyl group diphenyl.
Heavy metal ion passivator is commonly called as " copper resistant agent ", can the complexing transition metal ions, prevent the oxidative degradation of its catalytic polymerization resin, typical structure such as hydrazide kind compound etc.Recent years, along with going deep into of polymer antioxygen theoretical research, certain variation has also taken place in the classification of antioxidant, and the most outstanding feature is a notion of having introduced " carbon radicals trapping agent ".This radical scavenger is different from traditional primary antioxidant, and they can catch the polymer alkyl diradical, is equivalent to set up one in traditional antioxidant system the defence line.This type of stabilizing additive mainly comprises 2-ethyl benzofuran ketone, 2-methyl benzofuranone, Dihydrobenzofuranes ketone, benzofuranone, dibenzopyrone, 3-aryl-benzofuran-2-ones, 3-aryl benzofuranone, 2-aryl Dihydrobenzofuranes ketone, 2-aryl benzofuranone, 5-cyano group-1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 5-replaces 1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 2,3-dihydroxy-2,2-dimethyl-7-benzofuran phenol, 3-(2-acyloxyethoxyphenyl) benzofuran-2-ones, isobenzofuranone, 5-[(imidazo [4,5-b] pyridin-3-yl) methyl] benzofuranone, 1,2,3,4-tetrahydrochysene-benzofuranone, 2,3-dihydro-2-methyl-2-alkyl and furanone, 4-ethyoxyl bisphenol-A-diacrylate, (2-10)-ethoxyquin bisphenol-A-dimethylacrylate, 2-[1-(2-hydroxyl-3,5-two tertiary amyl phenyl)-and ethyl]-4,6-two tertiary amyl phenyl acrylate, bisphenol-A-glycerol double methyl methacrylate, bisphenol-A-dimethylacrylate, 4-ethyoxyl bisphenol-A-dimethylacrylate, N, the N-dibenzyl hydroxylamine, N-ethyl-N-aminoethyle alcohol, N, the N-diethyl hydroxylamine, IPD acrylamide HAS, isopropylhydroxyla, hydroxylamine hydrochloride, the chlorination hydroxylammonium, hydrogen chlorine azanol, N-methyl-azanol, acetohydroxamic acid, the N-hydroxyl acetamide.
Modifier is intended to improve plasticizing capacity, improves the modified additive of resin melt viscoelasticity and promotion resin melt-flow, and this analog assistant is based on acrylic acid esters co-polymer (ACR).
Anti-impact modifier improves the auxiliary agent of rigid polymer goods shock resistance.Mainly comprise haloflex (CPE), acrylate copolymer (ACR), methacrylate-diene-ethylene copolymer (MBS), ethene-thiazolinyl acetate copolymer (EVA) and acrylonitrile-diene-ethylene copolymer (ABS) etc.The ethylene propylene diene rubber (EPDM) that uses in polypropylene toughness-increasing modified also belongs to rubber toughened scope.
The function of antistatic agent is to reduce the sheet resistance of polymer product, eliminates the electrostatic hazard that accumulation of static electricity may cause, and mainly is included as cationic surfactant and anion surfactant.Cationic surfactant has: the alkyl phosphate diethanolamine salt, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, stearmide, stearoyl dimethyl-penten ammonium chloride, N, two (2-ethoxy)-N-(3 '-dodecyloxy-2 '-hydroxypropyl) the first ammonium Methylsulfate salt of N-, trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, N, N-cetyl ethyl morpholine ethyl-sulfate salt, (dodecanamide propyl trimethyl ammonium) Methylsulfate salt dibrominated N, N-two (octadecyl dimethyl)-3-oxa--1,5-penta 2 ammoniums, styrene polymer type quaternary ammonium salt, the palmitate quaternary ammonium salt, the alkylphenol-polyethenoxy based quaternary ammonium salt, dialkyl quaternary ammonium salt, the polyacrylamide quaternary ammonium salt, octadecyl dimethyl ethoxy quaternary ammonium nitrate, ammonium polystyrene sulphonate salt, propyl-dimethyl-beta-hydroxyethyl nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, 2,2 '-nitrilo-di-methylcarbinol and the poly-(oxygen-1 of α-three decyls-ω-hydroxyl, 2-second two bases) polymer of phosphate, the polyethylene glycol tridecyl ether phosphate, diethanolamine salt, the oleic acid diethanolamine salt, triethanol amine oleate, ethoxylated amine, N, N-dihydroxy ethyl octadecylamine, N, the N-dihydroxyethyl p-toluidine, the alkylphenol-polyethenoxy based quaternary ammonium salt, ethoxyl quaternary ammonium salt, the fluorine-containing quaternary ammonium salt of oxa-; Anion surfactant has: fatty alcohol ether phosphate, phenolic ether phosphate (TXP-4), phenolic ether phosphate (TXP-10), different tridecanol phosphate, Tryfac 5573 (MA24P), fatty alcohol ether phosphate potassium (MOA-3PK), phenolic ether phosphate kalium salt (NP-4PK), phenolic ether phosphate kalium salt (NP-10PK), different tridecanol ether phosphate sylvite, Tryfac 5573 sylvite (MA24PK), fatty alcohol phosphate sylvite, ALS; Non-ionic surface active agent: the condensation product of alkylamine and oxirane, alkanolamide, AEO, aliphatic acid polyethenoxy ether, two (beta-hydroxyethyl) coco amine, two (beta-hydroxyethyl) stearylamine, two (beta-hydroxyethyl) beef tallow amine, HMPA, perfluoroalkyl ethanol APEO.
Figure BSA00000501092200161
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.
Below be specific embodiments of the invention:
Embodiment 1
As shown in Figure 1,1 is organic electroluminescence device, and anode layer 12 is ITO, hole transmission layer 131 is NPB, be N, and N '-two (naphthal-1-yl)-N, N '-two (phenyl)-benzidine, electron transfer layer 141 is TPBi, promptly 1,3,5-(three N-phenyl-2-benzimidazolyl-2 radicals) benzene 41, negative electrode 15 is the Mg:Ag alloy, and inorganic thin film encapsulating material layer 21 is Al 2O 3, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 94%, 1% simple function group or polyfunctional group acrylic acid, 1% light trigger and 4% sensitising agent and auxiliary agent, and periodicity n is 8, and device architecture is:
Glass substrate/ITO/NPB (50nm)/TPBi (30nm)/Mg:Ag (200nm)/[Al 2O 3(200nm)/ultraviolet sensitivity material 22 (100nm)] 8
The preparation method is as follows:
1. utilize washing agent, acetone soln, ethanolic solution and deionized water ultrasonic cleaning substrate and dry up with nitrogen;
2. clean substrate is reached the high vacuum evaporation chamber, the pressure that keeps organic chamber and wire chamber respectively is 3.0 * 10 -4Pa and 3.0 * 10 -3Below the Pa, utilize the high vacuum vapor deposition method to prepare each organic function layer and cathodic metal layer;
3. to the above-mentioned not organic electroluminescence device of encapsulation, utilize plasma enhanced chemical meteorology deposition (hereinafter to be referred as PECVD) method to prepare inorganic thin film encapsulating material Al 2O 3, the thickness of deposition is 200nm;
4. device is reached in the cavity with ultraviolet sensitivity material, and spraying ultraviolet sensitivity material, the thickness of spraying is 100nm;
5. device being carried out ultraviolet light polymerization handled 30 seconds;
6. repeat above-mentioned steps 3.～5., the manufacturing cycle number is the inorganic thin film encapsulating material of (n-1) and the thin layer that the ultraviolet sensitivity material is alternately formed again;
The life-span of test component and parameters thereof.
Table 1 is that encapsulated layer replaces overlapping periodicity n and is respectively 0,3,8,12 and the performance comparison of 18 o'clock device lifetime among the embodiment 1.
Table 1
Figure BSA00000501092200181
Embodiment 2
As shown in Figure 1, device architecture is similar to embodiment 1.Wherein, inorganic thin film encapsulating material layer 21 is Al 2O 3, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 99.5%, 0.2% simple function group or polyfunctional group acrylic acid, 0.1% light trigger and 0.2% sensitising agent and auxiliary agent, and periodicity n is 2, and device architecture is:
Glass substrate/ITO/NPB (50nm)/TPBi (30nm)/Mg:Ag (200nm)/[Al 2O 3(200nm)/ultraviolet sensitivity material 22 (100nm)] 2
The preparation method is similar to embodiment 1.
Embodiment 3
As shown in Figure 1, device architecture is similar to embodiment 1.Wherein, inorganic thin film encapsulating material layer 21 is Al 2O 3, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 93%, 1% simple function group or polyfunctional group acrylic acid, 5% light trigger and 1% sensitising agent and auxiliary agent, and periodicity n is 1, and device architecture is:
Glass substrate/ITO/NPB (50nm)/TPBi (30nm)/Mg:Ag (200nm)/[Al 2O 3(200nm)/ultraviolet sensitivity material 22 (100nm)] 1
The preparation method is similar to embodiment 1.
Embodiment 4
As shown in Figure 1, the 1st, organic electroluminescence device, hole transmission layer 131 is NPB, and electron transfer layer 141 is TPBi, and negative electrode 15 is the Mg:Ag alloy, and inorganic thin film encapsulating material layer 21 is Si 3N 4, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 96%, 1% simple function group or polyfunctional group acrylic acid, 2% light trigger and 1% sensitising agent and auxiliary agent, and periodicity n is 20, and device architecture is:
Glass substrate/ITO/NPB (50nm)/TPBi (30nm)/Mg:Ag (200nm)/[Si 3N 4(100nm)/ultraviolet sensitivity material 22 (80nm)] 20
The preparation method is similar to embodiment 1.
Embodiment 5
As shown in Figure 1, the 1st, organic electroluminescence device, hole transmission layer 131 is NPB, and electron transfer layer 141 is TPBi, and negative electrode 15 is the Mg:Ag alloy, and inorganic thin film encapsulating material layer 21 is SiO 2, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 97%, 1.5% simple function group or polyfunctional group acrylic acid, 1% light trigger and 0.5% sensitising agent and auxiliary agent, and periodicity n is 8, and device architecture is:
Glass substrate/ITO/NPB (50nm)/TPBi (30nm)/Mg:Ag (200nm)/[SiO 2(100nm)/ultraviolet sensitivity material 22 (80nm)] 8
The preparation method is similar to embodiment 1.
Embodiment 6
As shown in Figure 2,1 is the organic solar batteries device, and anode layer 12 is ITO, and electron donor 132 is CuPc (CuPc), and electron acceptor 142 is fullerene (C 60), negative electrode 15 is Ag, inorganic thin film encapsulating material layer 21 is Al 2O 3, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 98%, 1% simple function group or polyfunctional group acrylic acid, 0.5% light trigger and 0.5% sensitising agent and auxiliary agent, and periodicity n is 2, and device architecture is:
Glass substrate/ITO/CuPc (20nm)/C60 (40nm)/Ag (150nm)/[Al 2O 3(1000nm)/ultraviolet sensitivity material 22 (800nm)] 2
The preparation method is similar to embodiment 1.
Embodiment 7
As shown in Figure 2,1 is the organic solar batteries device, and electron donor 132 is CuPc, and electron acceptor 142 is C60, and negative electrode 15 is Ag, and inorganic thin film encapsulating material layer 21 is Si 3N 4, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 99%, 0.5% simple function group or polyfunctional group acrylic acid, 0.3% light trigger and 0.2% sensitising agent and auxiliary agent, and periodicity n is 12, and device architecture is:
Glass substrate/ITO/CuPc (20nm)/C60 (40nm)/Ag (150nm)/[Si 3N 4(500nm)/ultraviolet sensitivity material 22 (500nm)] 12
The preparation method is similar to embodiment 1.
Embodiment 8
As shown in Figure 2, device architecture is similar to embodiment 6.Wherein, inorganic thin film encapsulating material layer 21 is Si 3N 4, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 95%, 1.5% simple function group or polyfunctional group acrylic acid, 2% light trigger and 1.5% sensitising agent and auxiliary agent, and periodicity n is 16, and device architecture is:
Glass substrate/ITO/CuPc (20nm)/C60 (35nm)/Ag (150nm)/[Si 3N 4(1000nm)/ultraviolet sensitivity material 22 (800nm)] 16
The preparation method is similar to embodiment 1.
Embodiment 9
As shown in Figure 2,1 is the organic solar batteries device, and inorganic thin film encapsulating material layer 21 is SiO 2, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 95%, 0.8% simple function group or polyfunctional group acrylic acid, 4% light trigger and 0.2% sensitising agent and auxiliary agent, and periodicity n is 12, and device architecture is:
Glass substrate/ITO/CuPc (20nm)/C60 (40nm)/Ag (150nm)/[SiO 2(500nm)/ultraviolet sensitivity material 22 (500nm)] 12
The preparation method is similar to embodiment 1.
Embodiment 10
As shown in Figure 2, device architecture is similar to embodiment 9.Wherein, inorganic thin film encapsulating material layer 21 is SiO 2, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 97%, 1.2% simple function group or polyfunctional group acrylic acid, 0.3% light trigger and 1.5% sensitising agent and auxiliary agent, and periodicity n is 9, and device architecture is:
Glass substrate/ITO/CuPc (30nm)/C60 (40nm)/Ag (150nm)/[SiO 2(500nm)/ultraviolet sensitivity material 22 (500nm)] 9
The preparation method is similar to embodiment 1.
Embodiment 11
As shown in Figure 3,1 is the polysilicon solar cell device, and 11 is glass substrate, and anode layer 12 is Ag, and P type semiconductor 133 is with the silicon doping boron element, and N type semiconductor 143 is with the silicon doping arsenic element, and metal electrode 15 is Ag, and inorganic thin film encapsulating material layer 21 is Al 2O 3, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 95%, 1% simple function group or polyfunctional group acrylic acid, 3% light trigger and 1% sensitising agent and auxiliary agent, and periodicity n is 12, and device architecture is:
Glass substrate/ITO/Si:P (80nm)/Si:As/Ag (200nm)/[Al 2O 3(300nm)/ultraviolet sensitivity material 22 (500nm)] 12
The preparation method is as follows:
1. clean the glass substrate that is coated with ITO respectively with acetone, deionized water and alcohol successively, and dry up with nitrogen;
2. adopt plasma reinforced chemical vapour deposition system (hereinafter to be referred as PEVCD) preparation P type and N type amorphous silicon, the glass that is coated with silicon thin film is continued heating 3 hours down at 600 ℃, amorphous silicon then is converted into polysilicon, subsequently 900 ℃ high-temperature quick thermal annealing 2 minutes;
3. on above-mentioned silicon chip, adopt high vacuum vapor deposition method evaporation metal Ag, thickness is 200nm;
4. to the polysilicon solar cell of above-mentioned preparation, utilize the PECVD method to prepare inorganic thin film encapsulating material Al 2O 3, the thickness of deposition is 300nm;
5. device is reached in the cavity with ultraviolet sensitivity material, and spraying ultraviolet sensitivity material, the thickness of spraying is 500nm;
6. device being carried out ultraviolet light polymerization handled 30 seconds;
7. repeat above-mentioned steps 4.～6., the manufacturing cycle number is the inorganic thin film encapsulating material of (n-1) and the thin layer that the ultraviolet sensitivity material is alternately formed again;
8. the life-span of test component and parameters thereof.
Embodiment 12
As shown in Figure 3,1 is the polysilicon solar cell device, and device architecture is similar to Example 11, and inorganic thin film encapsulating material layer 21 is Si 3N 4, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 98%, 0.4% simple function group or polyfunctional group acrylic acid, 0.8% light trigger and 0.8% sensitising agent and auxiliary agent, and periodicity n is 15, and device architecture is:
Glass substrate/ITO/Si:P (80nm)/Si:As/Ag (100nm)/[Si 3N 4(300nm)/ultraviolet sensitivity material 22 (500nm)] 15
The preparation method is similar to embodiment 11.
Embodiment 13
As shown in Figure 3,1 is the polysilicon solar cell device, and device architecture is similar to Example 11, and inorganic thin film encapsulating material layer 21 is SiO 2, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 99%, 0.3% simple function group or polyfunctional group acrylic acid, 0.4% light trigger and 0.3% sensitising agent and auxiliary agent, and periodicity n is 16, and device architecture is:
Glass substrate/ITO/Si:P (80nm)/Si:As/Ag (100nm)/[SiO 2(300nm)/ultraviolet sensitivity material 22 (500nm)] 16
The preparation method is similar to embodiment 11.
Embodiment 14
As shown in Figure 4,1 is the film transistor device based on ZnO, and substrate 11 is Si, and insulating barrier 16 is SiO 2, functional activation layer 17 is ZnO, and metal electrode 15 is Au, and inorganic thin film encapsulating material layer 21 is Al 2O 3, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 97%, 0.4% simple function group or polyfunctional group acrylic acid, 2.2% light trigger and 0.4% sensitising agent and auxiliary agent, and periodicity n is 12, and device architecture is:
Si substrate/SiO 2(200nm)/ZnO (80nm)/Au (100nm)/[SiO 2(300nm)/ultraviolet sensitivity material 22 (500nm)] 12
The preparation method is as follows:
1. utilize monocrystalline silicon Si as backing material, and silicon chip is polished and clean;
2. on clean silicon chip, by the high temperature oxidation process layer insulating SiO that grows 2, that continues carries out thermal annealing, and temperature is 600 ℃, and the time is 10 hours, and thickness is 200nm;
3. utilize the magnetically controlled sputter method growing ZnO thin-film, the vacuum degree of magnetron sputtering growth room is 3.0 * 10 -4Pa, the purity of used ZnO ceramic target is 99.99%, Ar and O 2Flow-rate ratio be 3: 1, sputtering pressure is 0.7Pa, sputtering power is a room temperature for the 100W growth temperature, the thickness of deposition is 80nm, recently substrate is reached the preparation that wire chamber carries out metal electrode;
4. to the above-mentioned not organic electroluminescence device of encapsulation, utilize plasma enhanced chemical meteorology deposition (hereinafter to be referred as PECVD) method to prepare inorganic thin film encapsulating material Al 2O 3, the thickness of deposition is 300nm;
5. device is reached in the cavity with ultraviolet sensitivity material, and spraying ultraviolet sensitivity material, the thickness of spraying is 500nm;
6. device being carried out ultraviolet light polymerization handled 30 seconds;
7. repeat above-mentioned steps 4.～6., the manufacturing cycle number is the inorganic thin film encapsulating material of (n-1) and the thin layer that the ultraviolet sensitivity material is alternately formed again;
8. the life-span of test component and parameters thereof.
Embodiment 15
As shown in Figure 4,1 is the thin-film transistor based on ZnO, and device architecture is similar to embodiment 14, and inorganic thin film encapsulating material layer 21 is Al 2O 3, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 96%, 1% simple function group or polyfunctional group acrylic acid, 2% light trigger and 1% sensitising agent and auxiliary agent, and periodicity n is 18, and device architecture is:
Si substrate/SiO 2(200nm)/ZnO (80nm)/Au (100nm)/[SiO 2(200nm)/ultraviolet sensitivity material 22 (400nm)] 18
The preparation method is similar to embodiment 14.
Embodiment 16
As shown in Figure 4,1 is the thin-film transistor based on ZnO, and device architecture is similar to embodiment 14, and inorganic thin film encapsulating material layer 21 is Si 3N 4, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 95%, 1% simple function group or polyfunctional group acrylic acid, 2% light-initiated material and 2% sensitising agent and auxiliary agent, and periodicity n is 10, and device architecture is:
Si substrate/SiO 2(200nm)/ZnO (80nm)/Au (100nm)/[Si 3N 4(200nm)/ultraviolet sensitivity material 22 (500nm)] 10
The preparation method is similar to embodiment 14.
Embodiment 17
As shown in Figure 4,1 is the thin-film transistor based on ZnO, and device architecture is similar to embodiment 14, and inorganic thin film encapsulating material layer 21 is SiO 2, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 95%, 0.5% simple function group or polyfunctional group acrylic acid, 2.5% light trigger and 2% sensitising agent and auxiliary agent, and periodicity n is 12, and device architecture is:
Si substrate/SiO 2(200nm)/ZnO (80nm)/Au (100nm)/[SiO 2(200nm)/ultraviolet sensitivity material 22 (500nm)] 12
The preparation method is similar to embodiment 14.
Embodiment 18
As shown in Figure 4,1 is the OTFT device, and grid 12 is ITO, and insulating barrier 16 is polymethyl methacrylate (being called for short PMMA), and functional activation layer 17 is pentacene (being Pentacene), and metal electrode 15 is Au, and inorganic thin film encapsulating material layer 21 is Al 2O 3, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 95%, 0.5% simple function group or polyfunctional group acrylic acid, 2.5% light trigger and 2% sensitising agent and auxiliary agent, and periodicity n is 12, and device architecture is:
ITO/PMMA (200nm)/Pentacene (80nm)/Au (100nm)/[Al 2O 3(300nm)/ultraviolet sensitivity material 22 (500nm)] 12
The preparation method is as follows:
1. utilize washing agent, acetone, deionized water and absolute ethyl alcohol ultrasonic cleaning ITO substrate and dry up respectively with nitrogen;
2. with chloroform as solvent, configuration PMMA solution also is spin-coated on it on ITO substrate, that continues carries out thermal annealing, temperature is 600 ℃, the time is 10 hours, the thickness of PMMA is 200nm;
3. above-mentioned substrate is reached the high vacuum evaporation chamber, the pressure that keeps organic chamber and wire chamber respectively is 3.0 * 10 -4Pa and 3.0 * 10 -3Below the Pa, evaporation pentacene functional layer and metal A u electrode layer successively;
4. to the device of above-mentioned preparation, utilize plasma enhanced chemical meteorology deposition (hereinafter to be referred as PECVD) method to prepare inorganic thin film encapsulating material Al 2O 3, the thickness of deposition is 300nm;
5. device is reached in the cavity with ultraviolet sensitivity material, and spraying ultraviolet sensitivity material, the thickness of spraying is 500nm;
6. device being carried out ultraviolet light polymerization handled 30 seconds;
7. repeat above-mentioned steps 4.～6., the manufacturing cycle number is the inorganic thin film encapsulating material of (n-1) and the thin layer that the ultraviolet sensitivity material is alternately formed again;
8. the life-span of test component and parameters thereof.
Embodiment 19
As shown in Figure 5,1 is the inorganic light-emitting diode based on the Si substrate, the 133rd, and P-GaN, the 143rd, N-GaN, negative electrode 15 is the Au electrode, inorganic thin film encapsulating material layer 21 is Al 2O 3, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 95%, 0.5% simple function group or polyfunctional group acrylic acid, 2.5% light trigger and 2% sensitising agent and auxiliary agent, and periodicity n is 8, and device architecture is:
Au (100nm)/N-GaN (1000nm)/P-GaN (200nm)/Au (200nm)/[Al 2O 3(200nm)/ultraviolet sensitivity material 22 (100nm)] 8
The preparation method is as follows:
1. utilize the immersion of NaOH solution, acetone soln and deionized water ultrasonic cleaning Si substrate and dry up with nitrogen;
2. utilize metal-organic chemical vapor deposition equipment (hereinafter to be referred as MOCVD) method to prepare the GaN material, adopt the method for high vacuum vapor deposition to prepare metal electrode at last;
3. to the device of above-mentioned preparation, utilize plasma enhanced chemical meteorology deposition (hereinafter to be referred as PECVD) method to prepare inorganic thin film encapsulating material Al 2O 3, the thickness of deposition is 200nm;
4. device is reached in the cavity with ultraviolet sensitivity material, and spraying ultraviolet sensitivity material, the thickness of spraying is 100nm;
5. device being carried out ultraviolet light polymerization handled 30 seconds;
6. repeat above-mentioned steps 3.～5., the manufacturing cycle number is the inorganic thin film encapsulating material of (n-1) and the thin layer that the ultraviolet sensitivity material is alternately formed again;
7. the life-span of test component and parameters thereof.
Embodiment 20
As shown in Figure 6,1 is photo-detector, and inorganic thin film encapsulating material layer 21 is Al 2O 3, ultraviolet sensitivity material 22 comprises polythiol-polyenoid system of 95%, 0.5% simple function group or polyfunctional group acrylic acid, 2.5% light trigger and 2% sensitising agent and auxiliary agent, and periodicity n is 8, and device architecture is:
Photo-detector 1/[Al 2O 3(200nm)/ultraviolet sensitivity material 22 (100nm)] 8
The preparation method is as follows:
1. utilize washing agent, acetone, deionized water and ethanol that substrate is carried out ultrasonic cleaning, dry up with nitrogen then;
2. on clean substrate, prepare the photo-detector original paper;
3. to the device of above-mentioned preparation, utilize plasma enhanced chemical meteorology deposition (hereinafter to be referred as PECVD) method to prepare inorganic thin film encapsulating material Al 2O 3, the thickness of deposition is 200nm;
4. device is reached in the cavity with ultraviolet sensitivity material, and spraying ultraviolet sensitivity material, the thickness of spraying is 100nm;
5. device being carried out ultraviolet light polymerization handled 30 seconds;
6. repeat above-mentioned steps 3.～5., the manufacturing cycle number is the inorganic thin film encapsulating material of (n-1) and the thin layer that the ultraviolet sensitivity material is alternately formed again;
7. the life-span of test component and parameters thereof.

Claims (7)

1. the method for packing of an opto-electronic device, adopt film encapsulation method to encapsulate to opto-electronic device, thin-film encapsulation layer coats opto-electronic device, it is characterized in that, described thin-film encapsulation layer replaces overlapping the composition by inorganic thin film encapsulating material layer and ultraviolet sensitivity material layer with periodicity n, 1≤n≤20 wherein, described ultraviolet sensitivity material comprises the component of following mass percent:
Polythiol-polyenoid system 94～99.5%
Simple function group or polyfunctional group acrylic acid 0.2～1%
Light trigger 0.1～5%
Sensitising agent and auxiliary agent 0.2～4%
Wherein light trigger is an acetophenone derivative, and sensitising agent is thia anthraquinone or Michler's keton, and auxiliary agent comprises antistatic agent, fire retardant and coupling agent.
2. the method for packing of opto-electronic device according to claim 1 is characterized in that, described polythiol-polyenoid system comprises the material of following structural formula:
Figure FSA00000501092100011
3. the method for packing of opto-electronic device according to claim 1, it is characterized in that, described coupling agent is 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, gamma-aminopropyl-triethoxy-silane, 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 or γ-sulfydryl propyl-triethoxysilicane.
4. the method for packing of opto-electronic device according to claim 1, it is characterized in that, described inorganic thin film encapsulating material is metal oxide or metal sulfide or metal nitride, metal oxide comprises calcium oxide, tantalum pentoxide, titanium dioxide, zirconium dioxide, cupric oxide, zinc oxide, alundum (Al, chrome green, tin ash, nickel oxide, antimony pentoxide, metal sulfide comprises titanium disulfide, iron sulfide, chromium hemitrisulfide, copper sulfide, zinc sulphide, stannic disulfide, nickel sulfide, cobalt sesquisulfide, antimonous sulfide, vulcanized lead, three sulfurations, two lanthanums, cerium sulphide, the curing zirconium, nitride comprises silicon nitride, aluminium nitride.
5. the method for packing of opto-electronic device according to claim 1 is characterized in that, specifically may further comprise the steps:
1. the rigid substrates of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen;
2. take the mode of high vacuum vapor deposition or spin coating or self assembly or inkjet printing or silk screen printing on the rigid substrates of cleaning, to prepare opto-electronic device;
3. to prepared opto-electronic device, preparation inorganic encapsulated material thin-layer prepares the ultraviolet sensitivity material thin-layer more thereon earlier, and described ultraviolet sensitivity material thin-layer comprises the component of following mass percent:
Polythiol-polyenoid system 94～99.5%
Simple function group or polyfunctional group acrylic acid 0.2～1%
Light trigger 0.1～5%
Sensitising agent and auxiliary agent 0.2～4%
Wherein light trigger is an acetophenone derivative, and sensitising agent is thia anthraquinone or Michler's keton, and auxiliary agent comprises antistatic agent, fire retardant and coupling agent;
4. ultraviolet light polymerization being carried out on the rigid substrates surface handled 30 seconds;
5. to the device behind the ultraviolet light polymerization, 3. and operation 4. continue repeating step, repeat n time 1≤n≤20 continuously;
6. the life-span of device and other parameters after the test package.
6. the method for packing of opto-electronic device according to claim 5, it is characterized in that, the encapsulation foil of described inorganic encapsulated material and ultraviolet sensitivity material adopts vacuum evaporation, ion cluster bundle deposition, ion plating, dc sputtering deposition, the RF sputter coating, ion beam sputtering deposition, ion beam assisted depositing, plasma reinforced chemical vapour deposition, high density inductance coupling high formula plasma source chemical vapor deposition, the catalyst chemical vapour deposition (CVD), magnetron sputtering, inkjet printing, electroplate, spraying, spin coating, dip-coating, one or several modes in roller coat and the LB film and forming.
7. according to the method for packing of the arbitrary described opto-electronic device of claim 1～6, it is characterized in that, described opto-electronic device is between a kind of photoelectricity, electric between and can carry out the device of signal and power conversion between the electric light, comprise organic electroluminescent LED, inorganic light-emitting diode, organic solar batteries, inorganic solar cell, OTFT, inorganic thin-film transistors, photo-detector.
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CN114156363B (en) * 2021-09-28 2024-04-30 福州大学 Antimony sulfide phototransistor and preparation method thereof
CN116875819A (en) * 2023-09-06 2023-10-13 江西赣锡工贸有限公司 Efficient tin extraction process based on tin-containing alkali liquor
CN116875819B (en) * 2023-09-06 2023-11-17 江西赣锡工贸有限公司 Efficient tin extraction process based on tin-containing alkali liquor

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Application publication date: 20111228