CN103560207B - A kind of organic thin film solar cell and preparation method thereof - Google Patents
A kind of organic thin film solar cell and preparation method thereof Download PDFInfo
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- CN103560207B CN103560207B CN201310585152.8A CN201310585152A CN103560207B CN 103560207 B CN103560207 B CN 103560207B CN 201310585152 A CN201310585152 A CN 201310585152A CN 103560207 B CN103560207 B CN 103560207B
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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Abstract
The invention discloses a kind of organic thin film solar cell and preparation method thereof, its structure comprises substrate, transparent conductive anode ITO, anode buffer layer, photoactive layer, cathode buffer layer, metallic cathode.Be mixed with appropriate ultraviolet sensitivity glue in described photoactive layer, this ultraviolet sensitivity collagen material comprises following composition: unsaturated polyester resin or acrylic resin, Styrene and its derivatives, light trigger, sensitising agent and auxiliary agent.Invention increases the adhesive force between organic thin film solar cell anode buffer layer and photoactive layer, solve the interface mismatch problem between anode buffer layer and photoactive layer, add the stability of device simultaneously, improve its working life.
Description
Technical field
The invention belongs to organic polymer photovoltaic device or organic semiconductor thin-film area of solar cell, be specifically related to a kind of organic thin film solar cell and preparation method thereof.
Background technology
The problem such as energy scarcity and ecological deterioration has become the major issue that human survival and development faces.Because the mankind excessively develop limited non-renewable energy resources, make the mankind current relied on traditional energy such as coal, oil and natural gas etc. occur resource exhaustion, and consequent global energy fight is reached the decisive stage the stage day by day.As everyone knows, the kind of clean energy resource has wind energy, water energy, geothermal energy and solar energy etc., but former three is limited to region or development cost, and spread does not use at present.And solar energy occupies more than 99% of earth gross energy, and do not pollute, become one of new forms of energy of scientist's development and utilization.Although silicon single crystal solar cell photoelectric conversion efficiency is very high and technology is comparatively ripe, its processing technology is very complicated, and material requirements is harsh and not easily carry out large area flexible processing, and some material has toxicity preparation cost is remained high.Organic thin film solar cell is easy with its materials synthesis, raw material sources are extensive, manufacture craft is simple and with low cost, power consumption less, flexible device can be made and be easy to the advantages such as large-scale production, obtain great attention and the great interest of scientist.
Through development for many years, theoretical research and the performance optimization of organic thin film solar cell are day by day enriched, but for the research of its commercial applications, also compare shortcoming.In the face of environment complicated and changeable, the job stability of people to organic thin film solar cell proposes more requirement.Affect in the factor of organic thin film solar cell stability numerous, the mismatch problem of anode modification layer and photoactive layer, be a masty difficult problem always.The anode modification layer material PEDOT:PSS of usual employing is hydrophilic material, and the material of photoactive layer is hydrophobic material, obviously, therebetween exist in conjunction with unstable problem, thus can cause the interface of anode modification layer and photoactive layer under the effect of stress, produce the phenomenon departing from, peel off, the parameters such as the short circuit current of device, fill factor, curve factor are reduced, causes the fast decay of device performance.Therefore, solve the matching problem at interface between anode buffer layer and photoactive layer, have very important effect to the working life improving organic thin film solar cell.
Summary of the invention
The present invention is directed to above-mentioned weak point and provide a kind of organic thin film solar cell and preparation method thereof, object improves the adhesive force between organic thin film solar cell anode buffer layer and photoactive layer, solve the interface mismatch problem between anode buffer layer and photoactive layer, increase the stability of device simultaneously, improve the working life of device.
To achieve these goals, technical scheme of the present invention is: a kind of organic thin film solar cell, it is characterized in that, this solar battery structure is followed successively by from top to bottom: substrate, transparent conductive anode ITO, anode buffer layer, photoactive layer, cathode buffer layer, metallic cathode, be mixed with ultraviolet sensitivity glue in described photoactive layer, the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95-99.5%
Styrene and its derivatives 0.2-2%
Light trigger 0.1-2%
Sensitising agent and auxiliary agent 0.2-3%
Wherein light trigger is for comprising benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and sensitising agent comprises benzophenone, and auxiliary agent comprises plasticizer, thixotropic agent and filler.
Further, described acrylic resin comprises polyester-acrylate, epoxy-acrylate and polyethers-acrylate.
Further, described plasticizer comprises three vinyl butyl ether base phosphates, isopropyl titanate, tetrabutyl titanate, citrate, trimellitic acid (2-ethyl) own ester, decanedioic acid two (2-ethyl) own ester, Diethylene Glycol Dibenzoate, dipropylene glycol dibenzoate and chlorosulfonated polyethylene.
Further, the mass ratio that described ultraviolet sensitivity glue is shared in photoactive layer is 0.02-5%.
Further, described photoactive layer is mixed with by electron donor material PTB7 and electron acceptor material PCBM and forms, and described PTB7:PCBM mixed solution mass ratio is 1:20-5:1, and described solution concentration is 1-30mg/ml, and thickness is 40-250nm.
Further, described anode buffer layer material is poly-(3,4-sub-second dioxy thiophene): polystyrolsulfon acid (PEDOT:PSS) or molybdenum oxide (MoO
x) in one, thickness is 10-80nm.
Further, described cathode cushioning layer material is the one in TPBi, BCP, Bphen, LiF, and thickness is 1-10nm.
Further, described metallic cathode material is the one in Ag, Al, Cu, and thickness is 100-300nm.
Further, described substrate is rigid substrate or flexible substrate, described rigid substrate is glass or sapphire, described flexible substrate is metal forming, and flexible substrate also can be the thin polymer films such as polyethylene, PETG, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid.
A preparation method for organic thin film solar cell, comprises the following steps:
1. first the substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. anode buffer layer is prepared at transparent conductive anode ITO surface rotary coating, printing or spraying PEDOT:PSS solution, or at transparent conductive anode ITO surface rotary coating, printing or spraying MoO
xsolution prepares anode buffer layer, and formed film is carried out annealing in process;
3. the PTB7:PCBM solution being mixed with ultraviolet sensitivity glue in anode buffer layer surface rotary coating, printing or spraying prepares photoactive layer, and formed film is carried out annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95-99.5%
Styrene and its derivatives 0.2-2%
Light trigger 0.1-2%
Sensitising agent and auxiliary agent 0.2-3%
Wherein light trigger is for comprising benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and sensitising agent comprises benzophenone, and auxiliary agent comprises plasticizer, thixotropic agent and filler;
4. treatment with ultraviolet light is carried out to the photoactive layer that 3. step obtains;
5. cathode buffer layer is prepared in photoactive layer surface evaporation, rotary coating or spraying;
6. at cathode buffer layer surface evaporation metal negative electrode.
Compared with prior art, beneficial effect of the present invention is: (1) adds the photoactive layer of ultraviolet sensitivity glue by treatment with ultraviolet light, can strengthen the tack between anode buffer layer and photoactive layer significantly; (2) photoactive layer being mixed with appropriate ultraviolet sensitivity glue after treatment with ultraviolet light, forms finer and close structure by crosslinked this layer that make between unsaturated bond, effectively intercepts water oxygen and enter photoactive layer, increase performance and the stability of organic thin film solar cell.
Accompanying drawing explanation
Fig. 1 is organic thin film solar cell structural representation provided by the present invention, is followed successively by from top to bottom: substrate (1), transparent conductive anode ITO(2), anode buffer layer (3), photoactive layer (4), cathode buffer layer (5), metallic cathode (6);
Fig. 2 is the life characteristic of the organic thin film solar cell do not adopted in ultraviolet sensitivity glue and embodiment 4.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described:
Technical scheme of the present invention how to provide a kind of organic thin film solar cell and preparation method thereof, and as shown in Figure 1, device architecture is followed successively by from top to bottom: substrate 1, transparent conductive anode ITO2, anode buffer layer 3, photoactive layer 4, cathode buffer layer 5, metallic cathode 6.
In organic thin film solar cell in the present invention, substrate 1 is the support of electrode and organic thin film layer, it has good light transmission in visible region, there is the ability of certain anti-steam and oxygen infiltration, there is good profile pattern, it can be rigid substrate or flexible substrate, rigid substrate can be the one in glass or sapphire, and flexible substrate can be the thin polymer film such as metal forming or polyethylene, PETG, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid; Anode buffer layer 2 is poly-(3,4-sub-second dioxy thiophene): polystyrolsulfon acid (PEDOT:PSS) or molybdenum oxide (MoO
x) in one, thickness is 10-80nm; Photoactive layer is mixed with by electron donor material PTB7 and electron acceptor material PCBM and forms, and described PTB7:PCBM mixed solution mass ratio is 1:20-5:1, and described solution concentration is 1-30mg/ml, and thickness is 40-250nm; Be mixed with ultraviolet sensitivity glue in photoactive layer, the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95-99.5%
Styrene and its derivatives 0.2-2%
Light trigger 0.1-2%
Sensitising agent and auxiliary agent 0.2-3%
Wherein light trigger is for comprising benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and sensitising agent comprises benzophenone, and auxiliary agent comprises plasticizer, thixotropic agent and filler; The mass ratio of described ultraviolet sensitivity glue shared by photoactive layer is 0.02-5%; Described acrylic resin comprises polyester-acrylate, epoxy-acrylate and polyethers-acrylate; Described plasticizer comprises three vinyl butyl ether base phosphates, isopropyl titanate, tetrabutyl titanate, citrate, trimellitic acid (2-ethyl) own ester, decanedioic acid two (2-ethyl) own ester, Diethylene Glycol Dibenzoate, dipropylene glycol dibenzoate and chlorosulfonated polyethylene; Described cathode cushioning layer material is TPBi, BCP, Bphen or LiF, and described thickness of thin layer is 1-10nm; Described metallic cathode material is Ag, Al or Cu, and thickness is 100-300nm.During measurement, sunlight is incident from substrate surface, and electrode anode and cathode is connected with test circuit anode and cathode, the voltage-current curve of test component.
In the present invention, each composition is described as follows:
Unsaturated polyester resin: unsaturated polyester (UP) to react under the effect of initator the linear polyesters made with fractional saturation binary acid (or acid anhydrides) and dihydroxylic alcohols by undersaturated binary acid (or acid anhydrides) is mixed.In its molecular structure, there is undersaturated vinyl monomer to exist, if with active vinyl monomer and this kind of undersaturated vinyl monomer copolymerization, then crosslinking curing and become three-dimensional-structure.In general, the adhesive obtained by this resin-made due to volume contraction in solidification process comparatively large, the internal stress of gluded joint is very large.Easily there is micro-crack in the inside of glue-line and cause splicing power to diminish; Meanwhile, due in macromolecular chain containing ester bond, meet acid, alkali be easily hydrolyzed, thus resistance to medium and resistance to water poor, be easily out of shape under the environment of high temperature and humidity; In addition, its curing rate is comparatively slow, therefore, shows poor combination property, therefore mostly uses as non-structural glue.By reducing unsatisfied chemical bond content, adopting the low monomer of polymerization shrinkage, adding the means such as inorganic filler and thermal plastic high polymer, its overall performance can be improved.
Acrylic resin: this resin system curing rate is fast, studies more at present.
Monomer (Styrene and its derivatives etc.) usually and resin complex use, one side, as diluent, makes glue have the viscosity of constructability; Again there is reactivity on the other hand, enter resin web network after solidification, to the final performance of solidfied material, there is certain improvement.The monomer of early application is Styrene and its derivatives, and this kind of diluent crosslinking rate is slow, volatility is large and poisonous, poor heat resistance.Now, many employings simple function group or polyfunctional group (methyl) acrylate, as methyl methacrylate, ethyl acrylate, acrylic acid propylene glycol ester, n-butyl acrylate etc., the poor problem of adhesive ubiquity thermal endurance of these esters preparation, and also there is the large defect of volatility in the lower ester of some molecular weight.If introduce aromatic rings in molecular structure, then can improve intensity and the resistance to water of glue, extend the storage period of glue.To the requirement of monomer mainly: the respond of low viscosity, highly diluted effect and height, also to take into account volatility, toxicity and peculiar smell little simultaneously, good etc. to the compatibility of resin.In order to regulate various performance parameter, often adopt mix monomer, mix monomer is as follows: free radical activity diluent and cation activity diluent.
Free radical activity diluent is divided into exploitation first generation polyfunctional acrylate monomer comparatively early, the second generation polyfunctional acrylate monomer of recent development and more excellent third generation acrylic monomers.
Monofunctional reactive diluent has: styrene, NVP, Isooctyl acrylate monomer, hydroxy-ethyl acrylate and isobornyl acrylate, methacrylate phosphate and isobornyl methacrylate, and latter two is the good toughness reinforcing monomer of plasticising.
Difunctional reactive diluents has: triethylene glycol diacrylate, tripropylene glycol diacrylate, glycol diacrylate, polyethylene glycol (200) diacrylate alcohol ester, neopentylglycol diacrylate and propoxyl group neopentylglycol diacrylate, acrylate functional monomers mainly contains 1,6-hexanediyl ester (HDDA), BDO diacrylate (BDDA), propylene glycol diacrylate (DPGDA), glycerol diacrylate (TPGDA) and trifunctional three through propane tri (TMPTA), pentaerythritol triacrylate (PETA), trihydroxy methyl propane triol triacrylate (TMPTMA), trimethylolpropane triacrylate, propoxylation three is through propane tri, pentaerythrite three propylene alcohol ester 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, resorcinol bisglycidyl ether, double pentaerythritol C5 methacrylate, tri (propylene glycol) diacrylate.They instead of active little first generation acrylic acid monofunctional monomer.But along with the develop rapidly of UV curing technology, their shortcomings large to the excitant of skin reveal.
Overcome the shortcoming that excitant is large, also should have higher activity and state of cure.Second generation polyfunctional acrylate monomer mainly introduces ethyoxyl or propoxyl group in the molecule, as ethoxylation trihydroxy methyl propane triol triacrylate (TMP (EO) TMA), propoxylation trihydroxy methyl propane triol triacrylate (TMP (PO) TMA), propoxylated glycerine triacrylate (G (PO) TA).Third generation acrylic monomers is mainly the acrylate containing methoxyl group, preferably resolves the contradiction of high curing rate and shrinkage, low state of cure.This kind of 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 molecule, the viscosity of monomer can be reduced, reduce the excitant of monomer simultaneously.
The compatibility of introducing to diluent monomer of alkoxyl also improves a lot, and vinyltriethoxysilane (A15I), gamma-methyl allyl acyloxypropyl trimethoxysilane (A174) can be used as monomer.
Cruel in various reactive epoxies diluent and various cyclic ethers, ring, vinyl ether monomers etc. can as the diluent of cation photocuring resin.Wherein vinyl ethers compound and oligomer curing rate fast, modest viscosity, tasteless, nontoxic advantage, can with epoxy resin with the use of.Vinyl ether monomers has: 1, 2, 3-propanetriol-diglycidyl-ether (EPON-812), triethyleneglycol divinylether (DVE-3), 1, 4-butanediol vinyl ethers (HBVE), cyclohexyl vinyl ether (CHVE), perfluoro methyl vinyl ether (PMVE), perfluoropropylvinylether, IVE, hydroxy butyl vinyl ether, vinyl ethyl ether, ethyl vinyl ether, ethyl vinyl ether propylene, ethylene glycol monoallyl ether, hydroxy butyl vinyl ether, butyl vinyl ether, chlorotrifluoroethylene (CTFE), triethylene glycol divinyl ether, methoxy ethylene, vinyl butyl ether, dodecyl vinyl (DDVE), cyclohexyl vinyl ether, tribenzyl-benzene phenol polyethenoxy base ether, tetrafluoroethylene-perfluoro propyl vinyl ether, tetrafluoroethylene-perfluoro propyl vinyl ether, tert-Butyl vinyl ether:
Epoxy compounds monomer has: 3,4-expoxycyclohexyl formic acid-3', 4'-expoxycyclohexyl methyl esters (ERL-4221), bisphenol A type epoxy resin (EP), epoxy acrylate, epoxy vinyl ester, acrylic acid epoxy ester, epoxymethacrylate, water-soluble itaconic acid epoxy ester resin:
Light trigger: in ultraviolet photo-curing cementing agent, often needs to add Photoactive compounds, to cause or the carrying out of accelerated reaction.Light trigger and sensitising agent can be divided into by the difference of its mechanism of action.Difference is that light trigger is when reacting beginning, absorbs the luminous energy of suitable wavelength and intensity, photophysical process occurs and reaches its a certain excitation state, if this excited energy is greater than the energy required for breaking bonds, then produce free radical polymerization; And after sensitiser absorption luminous energy to its a certain excitation state, just by energy in molecule or intermolecularly to shift, produce free radical polymerization by another molecule obtaining energy.Compared with light trigger, sensitising agent itself does not consume or change structure, and it can be regarded as photochemically reactive catalyst.Its mechanism of action roughly has three kinds: one to be energy transfer mechanism, and two is take hydrogen mechanism by force, and three is the photosensitive mechanism through generating Charger transfer.The light trigger with practical value developed has benzoin and its derivatives and acetophenone derivative, and sensitising agent has benzophenone, thia anthraquinone and Michler's keton.The stability of various initator, yellowing resistance, trigger rate are different, and in different resin systems, efficiency of initiation is also different, should need reasonable selection according to different occasion.As cyanacrylate and C (CH
2oCCH
2cH
2sH) system, use benzoin methyl ether, benzoin ethyl ether respectively, benzoin isopropyl ether causes, curing time is respectively 18s, 20s and 25s, and when causing with benzophenone, curing time is only 15s, and simultaneously the light transmittance of solidfied material also can difference be comparatively large because wavelength is different, and this will according to actual conditions reasonable selection.
The effect of light trigger is after it absorbs UV energy, produces free radical through decomposing, thus the unsaturated bond polymerization in initiator system, crosslinking curing becomes an entirety.Conventional radical photoinitiator has cracking and puies forward the large class of Hydrogen two.
Crack type photoinitiator: crack type photoinitiator mainly contains benzoin ethers (styrax ethers), benzil ketals and acetophenone etc.Crack type photoinitiator is homolysis after absorption ultraviolet light, produces two free radicals, and free radical causes unsaturated group polymerization.Benzoin ethers (styrax ethers) comprising: styrax (Benzoin), benzoin methyl ether, benzoin ethyl ether (Benzoinethylether), benzoin isobutyl ether (Benzoinbutylether), styrax lose (Benzoinoxime), benzoin isopropyl ether, acylphosphine oxide comprises: 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide (TPO) and (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide (BAPOphenylbis (2, 4, 6-trimethylbenzoyl) phosphineoxide), phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide (819), tetramethylpiperidone oxide (TMPO), triethyl phosphate (TEPO), they are more satisfactory light triggers, there is very high space charge force, absorption is had to long wave near ultraviolet ray, be applicable to whitewash and the thicker situation of film, and there is good stability, can not variable color or fade.
Carry Hydrogen initator: carry Hydrogen initator and mainly contain benzophenone and thioxanthones etc.Wherein thioxanthone photoinitiator is at the maximum absorption wavelength in black light district at 380-420nm, and absorbability and hydrogen-taking capacity are strong, have higher efficiency of initiation.Carry Hydrogen initator and must have hydrogen donor as collaborative composition, otherwise efficiency of initiation is too low, so that application can not be put to.Triplet state carbonyl free radical more likely extracts hydrogen than on secondary carbon or on methyl from the tertiary carbon of hydrogen donor molecule, and the hydrogen be connected on the hetero-atom such as oxygen or nitrogen more easily extracts than the hydrogen on carbon atom.This kind of hydrogen donor has amine, hydramine (triethanolamine, methyl diethanolamine, triisopropanolamine etc.), mercaptan, N, N-diethyl-and to dimethylamino benzamide.
Benzophenone light initiation system, benzophenone needs with alcohol, ether or amine also with vinyl monomer just can be made to carry out photopolymerization.Mainly comprise: benzophenone, thia anthraquinone, Michler's keton, dimethoxy benezene phenyl ketone (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-morpholinopropanone (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 the oxygen in glued membrane can be eliminated initiator system is coordinated to the benzophenone of the inhibition of Raolical polymerizable and tertiary ammonia; Michler's keton and benzophenone with the use of, more cheap and effectively initiator system can be obtained.
Cationic photoinitiator: aromatic sulfonium salts and this type of initator of salt compounded of iodine have excellent high-temperature stability, also have stability, so be widely used in Cationic curing systems with epoxy resin after coordinating.But their the longest absorbing wavelength does not absorb near ultraviolet band in 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), the two detergent alkylate iodine hexafluoro antimonate of 4,4-, xylyl salt compounded of iodine, diphenyl hexafluoroarsenate salt compounded of iodine, [4-(2-hydroxyl-3-butoxy-1-propoxyl group) phenyl] the iodo-hexafluoro antimonate of benzene, [4-(is to benzoylphenylsulfanyl) benzene] phenyl-iodide hexafluorophosphate, [4-(4-benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate, 4-(is to benzoylphenylsulfanyl) benzene] phenyl-iodide hexafluorophosphate, 4,4'-dimethyl diphenyl salt compounded of iodine hexafluorophosphate (IHT-PI820), 4,4'-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, tetrafluoro boric acid diaryl group iodized salt, 3,3'-dinitro diphenyl salt compounded of iodine, 3,3'-dinitro diphenyl salt compounded of iodine and several 2,2'-bis-replaces (iodine, bromine, chlorine)-5,5'-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-Phenylsulfanyl-phenyl) diphenyl sulphur hexafluorophosphate, 4-(thiophenyl) triphenyl sulphur hexafluorophosphate, 3,3'-dinitro diphenyl iodine hexafluorophosphate, 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate, triphenyl sulfosalt, 4-chlorphenyl diphenyl sulphur hexafluorophosphate, 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate, 4-acetamidophenyl diphenyl sulphur hexafluorophosphate, 3-benzoylphenyl diphenyl sulphur hexafluorophosphate, triphenyl sulphur borofluoride, triphenyl sulphur hexafluorophosphate, triphenyl sulphur hexafluoro antimonate, 4-tolyl diphenyl sulphur hexafluorophosphate, phosphorus hexafluoride triaryl sulfonium salts, antimony hexafluoride triaryl sulfonium salts, [4-(is to benzoylphenylsulfanyl) benzene] phenyl-iodide hexafluorophosphate, the bromo-2'-luorobenzyl of 1-(4'-) pyridiniujm, [4-(is to benzoylphenylsulfanyl) benzene] phenyl-iodide hexafluorophosphate, 4-[4-(p-nitrophenyl formoxyl) thiophenyl] benzene } phenyl-iodide hexafluorophosphate, 4-[4-(is to methyl benzoyl) thiophenyl] benzene } phenyl-iodide hexafluorophosphate, 4-[4-(is to methyl benzoyl) phenoxy group] benzene } phenyl-iodide hexafluorophosphate, [4-(is to benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate, the two detergent alkylate iodine hexafluoro antimonate of 4,4-.
Luxuriant molysite class: luxuriant molysite class light initiation system is the new cation light initiator of one developed after two aromatic iodonium salt and three aromatic sulfonium salts, first luxuriant molysite ion forms aromatic radical ligand under light illumination, produce the complex compound with the unsaturated iron of an epoxy compounds molecular complexes simultaneously, the lewis acidic feature of this complex compound tool also then forms the complex compound with three epoxy compounds molecular complexes, one of them epoxy compounds open loop can form 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, therefore under the condition that need heat in the external world, to improve polymerization speed.
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, 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-Isosorbide-5-Nitrae-diethoxybenzene salt, cyclopentadienyl group-iron-chlorobenzene salt, cyclopentadienyl group-iron-(Isosorbide-5-Nitrae-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, [two (diphenylphosphine) ferrocene of 1,1'-] 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'-dibenzoyl ferrocene, (3-carboxyl propionyl group) ferrocene, 1,1'-dibromof errocene, Aminoferrocene.
The light trigger of macromolecule loading: in photocuring system, light trigger is not often exhaust completely in Light Curing, and the part of non-photodissociation can move to coating surface, makes coating yellowing and aging, affects the quality of product; On the other hand, some initators and system is incompatible or compatibility is bad, make it apply and are restricted.For addressing these problems, people are by light trigger producing high-molecular.The initator tool of the initator low relative molecular of producing high-molecular has the following advantages: A, in polymer chain, energy transfer and intermolecular reaction become and be more prone to, and make Polymeric photoinitiators have higher activity.B, by with nonactive group copolymerization, regulates and design the distance of photosensitive group, or changing the distance of optical active group and main chain, thus acquisition has different photoactive initator.C, different optical active groups can be introduced at same macromolecular chain, utilize their cooperative effect to improve light sensitive effect.The producing high-molecular of D, initator, limits the migration of initator, prevent coating turn yellow and aging.E, because most of photolysis debris is still connected on macromolecule matrix, therefore, smell and the toxicity of system can be reduced.
Initator can directly be connected on the chain of macromolecule or oligomer by the producing high-molecular of initator, as introduced on macromolecular chain by thioxanthone or acidic group phosphine oxide etc.; Also can introduce the functional group that can occur to be polymerized in initator, make it in Light Curing, realize producing high-molecular, as introduced in tetraacrylate by benzophenone structural.
The compatibility of various light trigger is also a research direction in recent years, re-uses, both can reduce costs, can expand again the region of absorbing wavelength after compatibility, improves the absorption of ultraviolet radiation energy, thus the solidification effect obtained.The compatibility of light trigger both can be between same type, as being both free radical type, the Irgacure-1700 that such as Ciba newly releases is exactly by 25% (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (BAPO) and 75% alpha-hydroxy-2,2 dimethyl acetophenones (1173) form, and Irgacure-1800 is made up of the Alpha-hydroxy cyclohexyl-phenyl ketone (184) of the BAPO of 25% and 75%; Also can be made up of dissimilar initator, as free radical type with cationic light trigger compatibility, such as, triaryl thiaxanthene salt and benzophenone are coordinated, the curing rate of epoxy compounds can be made to be improved.
Auxiliary agent: in general, for adapting to the bonding requirement of varying environment, also needs in ultraviolet photo-curing cementing agent to add various auxiliary agent, as plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent etc.Although their components shared in adhesive are few, sometimes vital effect is produced to the processing characteristics of glue or adhesive property.As cyanacrylate and C (CH
2oCCH
2cH
2sH) under the initiation of benzophenone, if add the silicone couplet CH of l%
2=CHSi (OCH
2cH
2oCH
3)
3, after ultraviolet light polymerization, under being placed in the environment of 80-100% humidity, after 1 year, do not find change, and if do not add coupling agent, under the same terms, after 2 days just there is white erosion in bonded part, one week afterwards glue-line strip down completely.
Plasticizer comprises: diisooctyl azelate (DIOZ), dioctyl azelate (DOZ), separate adipate (DOS), hexanedioic acid dioctyl ester (DOA), three vinyl butyl ether base phosphates, hexanedioic acid two (Butoxyethoxy) ethyl ester, isopropyl titanate, tetrabutyl titanate, triethyl citrate, tributyl citrate, tri trimellitate (2-ethyl) own ester (TOTM), decanedioic acid two (2-ethyl) own ester (DOS), Diethylene Glycol Dibenzoate (DEDB), dipropylene glycol dibenzoate, separate diacid dibenzyl ester (DBS), BS (BS), chlorosulfonated polyethylene (toughening elastic body), triphenyl phosphate (TPP), tricresyl phosphate (dimethylbenzene) ester (TXP), poly-hexanedioic acid propylidene ester (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-hexanedioic acid butylidene ester (PBA), butyl epoxy stearate (BES), askarel (CDP), dimethylbenzene methylal resin (plasticizer FH), pumice wax pattern base oil (PROCESSOIL637), soybean oil, naphthenic processing oil (310), W150 softening oil (petroleum hydrocarbon, hydrogenation artificial oil), zirconium aluminium system coupling agent, WB215(aliphatic acid 18%, fatty acid ester 52%, calcium carbonate 20%).
Coupling agent is the material that a class has both sexes structure, and a part of group in their molecules can react with the chemical group of mineral surfaces, forms strong chemical bonding; Another part group then has close organic character, can with reactive organic molecule or physical entanglement, thus the material strong bonded that two kinds of character vary in size.The coupling agent of current industrial use is divided into the large class of silanes, acyl esters of gallic acid, zirconium class and organochromium complexes four by chemical constitution.Wherein applying more in adhesive is silanes, as methylvinyldichlorosilane, methyl hydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-aminopropyltrimethoxysilane, 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, aminopropyl silsesquioxane, γ-methacryloxypropyl trimethoxy silane, 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-aminopropyltrimethoxysilane, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ mercaptopropyitrimethoxy silane, γ-Mercaptopropyltriethoxysilane.
Levelling agent is used to the flow leveling improving resin, prevents the generation of the defects of coatings such as shrinkage cavity and pinprick, makes smooth coating, and can improve glossiness, comprises mixed solvent, organosilicon, polyacrylate, acetate butyrate fiber and nitrocellulose.Wherein silicone based, comprise diphenylpolysiloxane, methyl phenyl silicone, Organo-modified polysiloxanes, polyether silicones.
Stabilizer is used to be polymerized when minimizing is deposited, and improves the storage stability of resin.Conventional stabilizer has hydroquinones, p methoxy phenol, 1,4-benzoquinone, 2,6 one di-t-butyl cresols, phenothiazine, anthraquinone etc.
Defoamer is used to prevent and eliminate coating and produces bubble in manufacture and use procedure, prevents coating from producing the disadvantages such as pinprick.Phosphate, fatty acid ester and organosilicon etc. can make defoamer.Specifically there is tributyl phosphate, dibutylphosphoric acid ester, phosphate foam inhibitor (AD-14L), froth breaking king (FAG470), defoamer (FAG470), defoamer (BYK-141), defoamer (BYK037), three (butoxyethyl group) phosphate, triethyl phosphate, Tributyl phosphate ester, triethyl phosphate, tricresyl phosphate chloro isopropyl ester, three butoxy ethyl ester of phosphoric acid, the mixture (light yellow to water white transparency thick liquid) of polyoxyethylene polyoxypropylene and glycol or three alcohol ethers, dimethyl silicone polymer, glycerine polyethenoxy ether (GP330), laureth, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether 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 used to be polymerized when minimizing is deposited, and improves the storage stability of resin.Conventional polymerization inhibitor is generally divided into molecule-type polymerization inhibitor and stabilized free fundamental mode polymerization inhibitor, and the former mainly contains: hydroquinones, 1,4-benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-tert-butyl catechol, methylene blue, three (N-nitroso-N-Phenylhydroxylamine) aluminium salt, stannous chloride, inorganic matter and the Sulfurs etc. such as ferric trichloride also can be made polymerization inhibitor stabilized free fundamental mode polymerization inhibitor and mainly contain the bitter hydrazine (DPPH) of 1,1-diphenyl-2-, TEMPO (TMP), hydroquinones, allyl acetate, MEHQ (MEHQ), NO free radical piperidine alcohols, phosphorous acid (TEMPO) mixed ester, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen radical (TMHPHA), 8% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt: the 2-phenolic group ethoxy acrylate of 92%, 4% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt, 96% ethyoxyl list oil triacrylate, MEHQ hydroquinone monomethyl ether, polymerization inhibitor mantoquita, adjacent methyl hydroquinone, 2,6-di-t-butyl cresols, dimethyl hydroquinones, p-tert-butyl catechol (TBC), catechol, p methoxy phenol, BHT, 2,5-di-tert-butyl hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, 1,4-naphthoquinone, phenthazine, TBHQ (TBHQ), o-sec-butyl-4,6 dinitrophenol (DNBP), ethylene glycol ether, alkylbenzenesulfonate amine salt, p-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, 2,5-ditert-butylhydro quinone, adjacent methyl is to the adjacent methyl-p-benzoquinone of benzene two, 3-tertiary butyl-4-hydroxyanisol (BHA), 2,6-dinitro-p-cresol (DNPC), polyvinyl acetal, NO free radical piperidine alcohols, 4,6-dinitro o sec-butyl phenol, DMSS (DMSS), propilolic alcohol.
Thixotropic agent adds in resin, can make resin adhesive liquid when static, have higher denseness, becomes again the material of low denseness fluid under external force.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
2composition, and containing a 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 in water-based system, polyvinyl alcohol, polyacrylic acid, poly(ethylene oxide), polymethylacrylic acid, Lauxite, melamine resin, resol, phenolic resins water-soluble resin are thickener.
The effect of filler is that part replaces binding agent, reduces the consumption of binding agent, with the effect reaching filling, reinforcement, anti-attrition and reduce costs.Filler require particle thin and even, can be scattered in slurries equably, to binding agent and other component associativities good.The consumption of filler should be suitable, otherwise also can affect 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 polymers, butyl polyacrylate, polyurethane.
Dispersant impels material particles to be dispersed in medium, forms the reagent of stable suspension.Dispersant is generally divided into inorganic dispersant and the large class of organic dispersing agent two.Conventional inorganic dispersant has silicates (such as waterglass) and alkali metal phosphonates (Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium, Amino Trimethylene Phosphonic Acid potassium, HEDP sodium, HEDP disodium, HEDP four sodium, HEDP potassium, ethylene diamine tetra methylene phosphonic acid five sodium, diethylene triamine pentamethylene phosphonic five sodium, diethylenetriamine penta seven sodium, diethylene triamine pentamethylene phosphonic sodium, 2-phosphonobutane-1, 2, 4-tricarboxylic acids four sodium, hexapotassium sylvite, two 1, 6 hexamethylene triamine five methylenephosphonic acid sodium, 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-phosphonobutane-1,2,4-tricarboxylic acids (PBTCA), PAPE (PAPE), 2-HPAA (HPAA), hexapotassium (HDTMPA), polyamino polyether base methylenephosphonic acid (PAPEMP), two 1,6 hexamethylene 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 copolymer (AA/AMPS), acrylic acid-acrylic acid hydroxypropyl acrylate copolymer, acrylic acid-acrylic ester-phosphonic acids-sulfonate quadripolymer, acrylic acid-acrylic ester-sulfonate terpolymer, copolymer of phosphono carboxylic acid (POCA), polyacrylate, carboxylate-sulfonate-nonionic terpolymer, polyepoxy sodium succinate (PESA), poly (sodium aspartate) (PASP), base amylalcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester etc.
Antioxidant, with the auxiliary agent suppressing fluoropolymer resin thermal oxidative degradation to be major function, 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, to catch polymer peroxy radical for major function, has again the title of " peroxy radical capturing agent " and " chain termination type antioxidant ", relates to aromatic amine compounds and the large series of products of hindered phenol compound two.Aromatic amine antioxidant has: diphenylamines, p-phenylenediamine (PPD), N, N-be two-and [3-(3,5-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), 2,6-tri-grades of butyl-4-methylphenols, two (3,5-tri-grades of butyl-4-hydroxy phenyls) thioether, four [β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) 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) ester, the dimer of many alkyl bisphenol A phosphite ester and trimerical compound, 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, 1,3,5-trimethyl-2,4,6-tri-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene.Auxiliary antioxidant has the effect of decomposing copolymer per-compound, also claims " peroxide decomposer ", comprises sulfo-dicarboxylic ester class and bi-ester of phosphite, usually and primary antioxidant with the use of.The two lauryl of the two octadecyl ester (DSTP) of two Lauryl Alcohol ester, two ten four carbon alcohols esters, thio-2 acid, thio-2 acid dibasic acid esters, two octadecanol ester, thio-2 acid, three monooctyl esters, three the last of the ten Heavenly stems ester, three (Lauryl Alcohol) esters and three (16 carbon alcohol) ester, 3,6,9-trioxa decane-1,11-glycol-bis--n-dodecane mercaptopropionic acid ester, triphenyl phosphate TPP, trisnonyl phenyl phosphite, phosphorous acid octyl diphenyl.
Heavy metal ion passivator, is commonly called as " copper resistant agent ", can complexed transition metal ion, and prevent the oxidative degradation of its catalytic polymerization resin, typical structure is as hydrazide kind compound etc.Recent years, along with going deep into of polymer antioxygen theoretical research, the classification of antioxidant also there occurs certain change, and the most outstanding feature is the introduction of the concept of " carbon free radical trapers ".This radical scavenger is different from traditional primary antioxidant, and they can catch polymer alkyl diradical, is equivalent to set up one defence line in traditional antioxidant system.This type of stabilizing additive mainly comprises 2-ethyl benzofuran ketone, 2-methyl benzofuran ketone, Dihydrobenzofuranes ketone, benzofuranone, dibenzopyrone, 3-aryl-benzofuran-2-ones, 3-arylben-zofuranone, 2-aryl Dihydrobenzofuranes ketone, 2-arylben-zofuranone, 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 furanone, 4-ethoxylated bisphenol-A-diacrylate, (2-10)-ethoxylated bisphenol-A-dimethylacrylate, 2-[1-(2-hydroxyl-3,5-bis-tertiary amyl phenyl)-ethyl]-4,6-bis-tertiary amyl phenyl acrylates, bisphenol-A-glycerol double methyl methacrylate, bisphenol-A-dimethylacrylate, 4-ethoxylated bisphenol-A-dimethylacrylate, N, N-dibenzyl hydroxylamine, N-ethyl-N-hvdroxv ethamine, N, N-diethyl hydroxylamine, IPD acrylamide HAS, isopropylhydroxyla, hydroxylamine hydrochloride, hydroxylammonium chloride, hydrogen chlorine azanol, N-methyl-hydroxylamine, acetohydroxamic acid, N-hydroxyl acetamide.
Modifier is intended to improve plasticizing capacity, improves resin melt viscoelasticity and promotes the modified additive that resin melting flows, and this analog assistant is based on acrylic acid esters co-polymer (ACR).
Anti-impact modifier improves the auxiliary agent of hard polymer article 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) of polypropylene toughness-increasing modified middle use also belongs to rubber toughened scope.
The function of antistatic agent is the sheet resistance reducing polymer product, eliminates the electrostatic hazard that accumulation of static electricity may cause, mainly comprises for cationic surfactant and anion surfactant.Cationic surfactant has: alkyl phosphate diethanolamine salt, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, stearmide, stearoyl dimethyl-penten ammonium chloride, two (2-ethoxy)-the N-(3 '-dodecyloxy-2 of N, N-'-hydroxypropyl) first ammonium Methylsulfate salt, trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, N, N-cetyl ethyl morpholine ethyl-sulfate salt, (dodecanamide propyl trimethyl ammonium) Methylsulfate salt dibrominated N, N-bis-(octadecyldimethyl)-3-oxa--1,5-penta 2 ammonium, styrene polymer type quaternary ammonium salt, palmitate quaternary ammonium salt, alkylphenol-polyethenoxy based quaternary ammonium salt, dialkyl quaternary ammonium salt, polyacrylamide quaternary ammonium salt, octadecyldimethyl ethoxy quaternary ammonium nitrate, ammonium polystyrene sulphonate salt, propyl-dimethyl-beta-hydroxyethyl nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, the polymer of 2,2'-nitrilo-di-methylcarbinol and poly-(oxygen-1, the 2-second two base) phosphate of α-three decyl-ω-hydroxyl, polyethylene glycol tridecyl ether phosphate, diethanolamine salt, oleic acid diethanolamine salt, triethanol amine oleate, ethoxylated amine, N, N-dihydroxy ethyl octadecylamine, N, N-dihydroxyethyl p-toluidine, 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 tridecyl alcohol phosphate ester, 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.
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, N-alkylaminoacid salts, epoxy tripolymer acid inner salt, carboxybetaine, tridecyl dimethyl (2-sulfurous acid) ethyl ammonium second inner salt, N-dodecyl alanine, 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.
Polymer Antistatic Agent comprises: the amphipathic copolymer that poly(ethylene oxide) (PEO), polyether ester acid imide, polyethylene glycol methacrylic acid copolymer body, 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), octadecyl methacrylate (SMA)+polyethylene glycol methacrylate-styrene polymer (PEGMA) forms.
In fire retardant, 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, organic fire-retardant comprises deca-BDE, three (2, 3-dibromopropyl) phosphate, HBCD, poly-2, 6-dibromobenzene aether, chlorinated paraffin wax, polyphosphate, red phosphorus, two (tetrabromo phthalimide) ethane, Dowspray 9 homopolymers, melamine, cyanurate, isodecyl diphenyl phosphate, ethylhexyl diphenyl phosphate, tricresyl phosphate isopropyl phenyl ester, two (2 chloroethyl) vinylphosphonate, ethylene two [three (2 cyanoethyl) bromination microcosmic salt], N, two (2 ethoxy) the AminomethylphosphoniAcid Acid diethylester of N, polyphenylene phosphonic acids diphenyl sulphone (DPS) ester, polyazodiphenylene phenyiphosphonate, polyphenylene phosphonic acids bisphenol-A ester.
Mould inhibitor, also known as microbial inhibitor, is the growth of microorganism such as a class mould fungus inhibition, prevents the stabilizing additive that fluoropolymer resin is degraded by microbial attack.Most polymeric material is insensitive to mould, but due to its goods work in-process with the addition of plasticizer, lubricant, fatty acid soaps class etc. can mould growth class material and there is mould sensitivity.The chemical substance that plastics mould inhibitor comprises is a lot, 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 dimethylamino benzamide; In promoter, aminopropyl silsesquioxane and Versamid mass ratio are 3:1.
Below specific embodiments of the invention:
Embodiment 1
As shown in Figure 1, substrate (1) is glass, and anode buffer layer (3) is PEDOT:PSS(10nm), cathode buffer layer (5) is TPBi(10nm), metallic cathode (6) is Ag(100nm).Photoactive layer (4) is PTB7:PCBM(1:20,40nm) in be mixed with ultraviolet sensitivity glue, the mass ratio shared in photoactive layer of described ultraviolet sensitivity glue is 0.02%.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution formed film is carried out annealing in process;
3. the PTB7:PCBM solution being mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer prepares photoactive layer, and formed film is carried out annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95%
Styrene and its derivatives 2%
Light trigger 2%
Sensitising agent and auxiliary agent 1%;
4. the photoactive layer 3. obtained step carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
Embodiment 2
As shown in Figure 1, substrate 1 is glass, and anode buffer layer 3 is PEDOT:PSS(40nm), cathode buffer layer 5 is TPBi(1nm), metallic cathode 6 is Ag(300nm).Photoactive layer 4 is PTB7:PCBM(5:1,250nm) in be mixed with ultraviolet sensitivity glue, the mass ratio shared in photoactive layer of described ultraviolet sensitivity glue is 0.05%.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution formed film is carried out annealing in process;
3. the PTB7:PCBM solution being mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer prepares photoactive layer, and formed film is carried out annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 96%
Styrene and its derivatives 2%
Light trigger 0.5%
Sensitising agent and auxiliary agent 1.5%;
4. the photoactive layer 3. obtained step carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
Embodiment 3
As shown in Figure 1, substrate 1 is glass, and anode buffer layer 3 is PEDOT:PSS(80nm), cathode buffer layer 5 is TPBi(8nm), metallic cathode 6 is Ag(150nm).Photoactive layer 4 is PTB7:PCBM(1:1,200nm) in be mixed with ultraviolet sensitivity glue, the mass ratio shared in photoactive layer of described ultraviolet sensitivity glue is 0.1%.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution formed film is carried out annealing in process;
3. the PTB7:PCBM solution being mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer prepares photoactive layer, and formed film is carried out annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 97%
Styrene and its derivatives 1%
Light trigger 1%
Sensitising agent and auxiliary agent 1%;
4. the photoactive layer 3. obtained step carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
Embodiment 4
As shown in Figure 1, substrate 1 is glass, and anode buffer layer 3 is PEDOT:PSS(20nm), cathode buffer layer 5 is TPBi(8nm), metallic cathode 6 is Ag(150nm).Photoactive layer 4 is PTB7:PCBM(1:1,200nm) in be mixed with ultraviolet sensitivity glue, the mass ratio shared in photoactive layer of described ultraviolet sensitivity glue is 0.5%.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution formed film is carried out annealing in process;
3. the PTB7:PCBM solution being mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer prepares photoactive layer, and formed film is carried out annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 98%
Styrene and its derivatives 0.2%
Light trigger 0.5%
Sensitising agent and auxiliary agent 1.3%;
4. the photoactive layer 3. obtained step carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
Embodiment 5
As shown in Figure 1, substrate 1 is glass, and anode buffer layer 3 is PEDOT:PSS(20nm), cathode buffer layer 5 is TPBi(8nm), metallic cathode 6 is Ag(150nm).Photoactive layer 4 is PTB7:PCBM(1:1,200nm) in be mixed with ultraviolet sensitivity glue, the mass ratio shared in photoactive layer of described ultraviolet sensitivity glue is 1%.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution formed film is carried out annealing in process;
3. the PTB7:PCBM solution being mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer prepares photoactive layer, and formed film is carried out annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 99%
Styrene and its derivatives 0.3%
Light trigger 0.1%
Sensitising agent and auxiliary agent 0.6%;
4. the photoactive layer 3. obtained step carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
Embodiment 6
As shown in Figure 1, substrate 1 is glass, and anode buffer layer 3 is PEDOT:PSS(20nm), cathode buffer layer 5 is TPBi(8nm), metallic cathode 6 is Ag(150nm).Photoactive layer 4 is PTB7:PCBM(1:1,200nm) in be mixed with ultraviolet sensitivity glue, the mass ratio shared in photoactive layer of described ultraviolet sensitivity glue is 3%.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution formed film is carried out annealing in process;
3. the PTB7:PCBM solution being mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer prepares photoactive layer, and formed film is carried out annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 99.5%
Styrene and its derivatives 0.2%
Light trigger 0.1%
Sensitising agent and auxiliary agent 0.2%;
4. the photoactive layer 3. obtained step carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
Embodiment 7
As shown in Figure 1, substrate 1 is flexible PETG (PET) substrate, and anode buffer layer 3 is PEDOT:PSS(20nm), cathode buffer layer 5 is TPBi(8nm), metallic cathode 6 is Ag(150nm).Photoactive layer 4 is PTB7:PCBM(1:1,200nm) in be mixed with ultraviolet sensitivity glue, the mass ratio shared in photoactive layer of described ultraviolet sensitivity glue is 5%.
Preparation method is as follows:
1. first the PET substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution formed film is carried out annealing in process;
3. the PTB7:PCBM solution being mixed with ultraviolet sensitivity glue at the surperficial rotary coating of anode buffer layer prepares photoactive layer, and formed film is carried out annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95%
Styrene and its derivatives 1%
Light trigger 1%
Sensitising agent and auxiliary agent 3%;
4. the photoactive layer 3. obtained step carries out treatment with ultraviolet light 30 seconds;
5. at photoactive layer surface evaporation cathode buffer layer TPBi;
6. at cathode buffer layer surface evaporation metal negative electrode Ag.
Table 1 is for adopting PET as the Performance comparision of the organic thin film solar cell of substrate, and a kind of is the device adding ultraviolet sensitivity glue in photoactive layer, and a kind of is the device not adding ultraviolet sensitivity glue.Wherein, bending radius is 10mm, and direction is for being bent outwardly.
Claims (10)
1. an organic thin film solar cell, it is characterized in that, this solar battery structure is followed successively by from top to bottom: substrate, transparent conductive anode ITO, anode buffer layer, photoactive layer, cathode buffer layer, metallic cathode, is mixed with ultraviolet sensitivity glue in described photoactive layer, the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95-99.5%
Styrene and its derivatives 0.2-2%
Light trigger 0.1-2%
Sensitising agent and auxiliary agent 0.2-3%
Wherein light trigger is for comprising benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and sensitising agent comprises benzophenone, and auxiliary agent comprises plasticizer, thixotropic agent and filler.
2. organic thin film solar cell according to claim 1, is characterized in that, described acrylic resin comprises polyester-acrylate, epoxy-acrylate and polyethers-acrylate.
3. organic thin film solar cell according to claim 1, it is characterized in that, described plasticizer comprises three vinyl butyl ether base phosphates, isopropyl titanate, tetrabutyl titanate, citrate, trimellitic acid (2-ethyl) own ester, decanedioic acid two (2-ethyl) own ester, Diethylene Glycol Dibenzoate, dipropylene glycol dibenzoate and chlorosulfonated polyethylene.
4. organic thin film solar cell according to claim 1, is characterized in that, the mass ratio of described ultraviolet sensitivity glue shared by photoactive layer is 0.02-5%.
5. organic thin film solar cell according to claim 1, it is characterized in that, described photoactive layer is mixed with by electron donor material PTB7 and electron acceptor material PCBM and forms, described PTB7:PCBM mixed solution mass ratio is 1:20-5:1, described solution concentration is 1-30mg/ml, and thickness is 40-250nm.
6. organic thin film solar cell according to claim 1, is characterized in that, described anode buffer layer material is poly-(3,4-sub-second dioxy thiophene): polystyrolsulfon acid (PEDOT:PSS) or molybdenum oxide (MoO
x) in one, thickness is 10-80nm.
7. organic thin film solar cell according to claim 1, is characterized in that, described cathode cushioning layer material is the one in TPBi, BCP, Bphen, LiF, and thickness is 1-10nm.
8. organic thin film solar cell according to claim 1, is characterized in that, described metallic cathode material is the one in Ag, Al, Cu, and thickness is 100-300nm.
9. organic thin film solar cell according to claim 1, it is characterized in that, described substrate is rigid substrate or flexible substrate, described rigid substrate is glass or sapphire, described flexible substrate is metal forming, and flexible substrate also can be polyethylene, PETG, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid.
10. a preparation method for organic thin film solar cell, is characterized in that, comprises the following steps:
1. first the substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, dry after cleaning;
2. anode buffer layer is prepared at transparent conductive anode ITO surface rotary coating, printing or spraying PEDOT:PSS solution, or at transparent conductive anode ITO surface rotary coating, printing or spraying MoO
xsolution prepares anode buffer layer, and formed film is carried out annealing in process;
3. the PTB7:PCBM solution being mixed with ultraviolet sensitivity glue in anode buffer layer surface rotary coating, printing or spraying prepares photoactive layer, and formed film is carried out annealing in process, and the raw material of described ultraviolet sensitivity glue comprises following composition:
Unsaturated polyester resin or acrylic resin 95-99.5%
Styrene and its derivatives 0.2-2%
Light trigger 0.1-2%
Sensitising agent and auxiliary agent 0.2-3%
Wherein light trigger is for comprising benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, and sensitising agent comprises benzophenone, and auxiliary agent comprises plasticizer, thixotropic agent and filler;
4. treatment with ultraviolet light is carried out to the photoactive layer that 3. step obtains;
5. cathode buffer layer is prepared in photoactive layer surface evaporation, rotary coating or spraying;
6. at cathode buffer layer surface evaporation metal negative electrode.
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| CN105440230B (en) * | 2016-01-06 | 2017-10-13 | 青岛大学 | A kind of organic RE solid micella and preparation method thereof and the method for improving solar cell photoelectric transformation efficiency |
| CN108530977B (en) * | 2017-03-06 | 2021-02-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Organic photoactive layer composite ink, organic solar cell and preparation method thereof |
| CN109410738A (en) * | 2017-08-16 | 2019-03-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of thermo-responsive label, preparation method and application method |
| CN107833970B (en) * | 2017-10-19 | 2020-04-28 | 华中科技大学鄂州工业技术研究院 | Surface modification method of perovskite film |
| CN110676391A (en) * | 2019-09-27 | 2020-01-10 | 苏州威格尔纳米科技有限公司 | Packaging method of perovskite thin film battery pack |
| CN112687807B (en) * | 2020-12-28 | 2022-08-02 | 河北工业大学 | 2D/3D hybrid perovskite solar cell prepared based on two-step method |
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