CN103579504B - 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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Abstract
The invention discloses a kind of organic thin film solar cell and preparation method thereof, the substrate that this solar battery structure sets gradually from bottom to up, transparent conductive anode ITO, anode buffer layer, photoactive layer, cathode buffer layer and metallic cathode, ultraviolet sensitivity glue is mixed with in described photoactive layer, the component of ultraviolet sensitivity glue and the mass ratio of each component are: the polysiloxanes 93.5 ~ 97% of light sensitivity, light trigger 1.5 ~ 5%, diluent and auxiliary agent 1.5 ~ 3%; Diluent comprises toluene, dimethylbenzene, reactive epoxies diluent, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent.The invention solves the problem of tack difference between organic thin film solar cell anode buffer layer and photoactive layer, add the interphase match between anode buffer layer and photoactive layer, improve energy conversion efficiency simultaneously, delay the rate of decay.
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
Along with the increase year by year of global energy requirements amount, energy problem becomes the matter of utmost importance that countries in the world economic development runs into.Solar energy is as a kind of green energy resource, inexhaustible, is one of new forms of energy of various countries scientist development and utilization.1954, the Bel research institute of the U.S. successfully developed silicon solar cell, has started the beginning of opto-electronic conversion research.Research afterwards about solar cell develops rapidly, and mainly concentrating on monocrystalline silicon is at first the inorganic solar cell of active material.The nineties in 20th century has developed again the devices such as GaAs, cadmium telluride and lamination GaInP/GaAs/Ge, and they are made up of monocrystalline, polycrystalline or noncrystal membrane.Because inorganic solar cell cost of material is high, the serious photoetch of complex manufacturing and narrow gap semiconductor makes solar power generation can not spread.Make solar power generation obtain large-scale application, just must reduce costs.
Organic semiconducting materials is the most cheap and has the solar cell material of development potentiality most, and its Heterosis is: on the one hand, and because organic material synthesis cost is low, function and structure is easy to adjustment, and pliability and film forming are all better; On the other hand, because the organic solar batteries course of processing is relatively simple, can low-temperature operation, element manufacturing cost also decreases.In addition, the potential advantages of organic solar batteries also comprise: can realize large area manufacture, can use flexible substrate, environmental friendliness, light portable etc., are expected to be applied in the systems such as wrist-watch, hand-held calculator, toy, flexible rollable system and power.Through the development of two more than ten years, the conversion efficiency of organic thin film solar cell has had larger progress, and theory have also been obtained perfect further, just progressively strides forward to mass market.
In addition to efficiency, the stability of organic thin film solar cell is also the emphasis that researchers pay close attention to.A desirable solar photovoltaic device needs to possess following speciality: under illumination, long-time retention is constant, insensitive to the repetitious change such as cold/hot, light/dark, dry/wet.But still there is many bottleneck problems at present, govern the commercialization of organic thin film solar cell.The interphase match of anode buffer layer and photoactive layer is one of them significant problem.What usually adopt due to anode buffer layer is this hydrophilic material of PEDOT:PSS, and photoactive layer normally hydrophobic material, this causes in the middle of device fabrication process, photoactive layer material is not easily opened at anode buffer layer surface spreading, make the final photoactive layer film morphology formed poor, and can interfacial separation be produced under the effect of interior external carbuncle, and then the efficiency of transmission of charge carrier is adversely affected, reduce the energy conversion efficiency of device.Therefore, solve the interphase match sex chromosome mosaicism of anode buffer layer and photoactive layer, huge impetus can be served to the commercialization process of organic thin film solar cell.
Summary of the invention
Problem to be solved by this invention how to provide a kind of organic thin film solar cell and preparation method thereof, object is the problem solving tack difference between organic thin film solar cell anode buffer layer and photoactive layer, increase the interphase match between anode buffer layer and photoactive layer, improve the energy conversion efficiency of device simultaneously, delay the rate of decay of device performance.
To achieve these goals, the technical solution used in the present invention is:
A kind of organic thin film solar cell, it is characterized in that, substrate (1), transparent conductive anode ITO(2 that this solar battery structure sets gradually from bottom to up), anode buffer layer (3), photoactive layer (4), cathode buffer layer (5) and metallic cathode (6), described photoactive layer is mixed with ultraviolet sensitivity glue in (4), and the component of described ultraviolet sensitivity glue and the mass ratio of each component are:
The polysiloxanes 93.5 ~ 97% of light sensitivity
Light trigger 1.5 ~ 5%
Diluent and auxiliary agent 1.5 ~ 3%;
Described diluent comprises toluene, dimethylbenzene, reactive epoxies diluent, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent.
Further, the polysiloxanes of described light sensitivity is one or more in mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes or vinyl ether functional's polysiloxanes.
Further, described light trigger is one or more in styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt or triaryl salt compounded of iodine.
Further, the mass ratio that described ultraviolet sensitivity glue is shared in photoactive layer is 0.05 ~ 6.5%.
Further, described photoactive layer is mixed with by electron donor material P3HT and electron acceptor material ICBA and forms, and described P3HT:ICBA 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): polystyrene-based benzene sulfonic 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 the one in rigid substrate and flexible substrate, and described rigid substrate comprises glass and sapphire, and described flexible substrate comprises metal forming and thin polymer film.
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, dry process;
2. at transparent conductive anode ITO surface rotary coating, printing or spraying anode buffer layer, and formed film is carried out annealing in process;
3. be mixed with the photoactive layer of ultraviolet sensitivity glue in anode buffer layer surface rotary coating, printing or spraying, and formed film is carried out annealing in process, the component of described ultraviolet sensitivity glue and the mass ratio of each component are:
The polysiloxanes 93.5 ~ 97% of light sensitivity
Light trigger 1.5 ~ 5%
Diluent and auxiliary agent 1.5 ~ 3%,
Diluent comprises toluene, dimethylbenzene, reactive epoxies diluent, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent;
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, the present invention has following beneficial effect: (1) adds the photoactive layer of ultraviolet sensitivity glue by treatment with ultraviolet light, improves the tack of anode buffer layer and photoactive layer; (2) photoactive layer after treatment with ultraviolet light, its degree of crystallinity is higher, and carrier mobility increases, and improves energy conversion efficiency; (3) photoactive layer after treatment with ultraviolet light, crosslinked this layer that make of ultraviolet sensitivity glue forms finer and close structure, effectively intercepts water oxygen and enters photoactive layer, improve performance and the stability of device; (4) adding of appropriate ultraviolet sensitivity glue, the absorption of photoactive layer is not affected.
Accompanying drawing explanation
Fig. 1 is organic thin film solar cell structural representation provided by the present invention;
Fig. 2 does not adopt ultraviolet sensitivity glue and embodiment of the present invention 1(to have employed ultraviolet sensitivity glue) the current density voltage curve of organic thin film solar cell;
Mark in figure: 1, substrate, 2, transparent conductive anode ITO, 3, anode buffer layer, 4, photoactive layer, 5, cathode buffer layer, 6, metallic cathode.
Embodiment
The invention will be further described below in conjunction with the accompanying drawings and the specific embodiments, and described embodiment is only the present invention's part embodiment, is not whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments used obtained under creative work prerequisite, belongs to protection scope of the present invention.
Composition graphs 1, organic thin film solar cell of the present invention, comprise the substrate 1, transparent conductive anode ITO2, anode buffer layer 3, photoactive layer 4, cathode buffer layer 5 and the metallic cathode 6 that set gradually from bottom to up, be mixed with ultraviolet sensitivity glue in described photoactive layer, the component of described ultraviolet sensitivity glue and the mass ratio of each component are:
The polysiloxanes 93.5 ~ 97% of light sensitivity
Light trigger 1.5 ~ 5%
Diluent and auxiliary agent 1.5 ~ 3%,
Described diluent comprises toluene, dimethylbenzene, reactive epoxies diluent, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent.
Further, the polysiloxanes of light sensitivity is one or more in mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes or vinyl ether functional's polysiloxanes.
Further, light trigger is one or more in styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt or triaryl salt compounded of iodine.
Further, photoactive layer is mixed with by electron donor material P3HT and electron acceptor material ICBA and forms, and described P3HT:ICBA mixed solution mass ratio is 1:20 ~ 5:1, and described solution concentration is 1 ~ 30mg/ml, and thickness is 40 ~ 250nm.
Further, anode buffer layer material is poly-(3,4-sub-second dioxy thiophene): polystyrene-based benzene sulfonic acid (PEDOT:PSS) or molybdenum oxide (MoO
x) in one, thickness is 10 ~ 80nm.
Further, cathode cushioning layer material is the one in TPBi, BCP, Bphen, LiF, and thickness is 1-10nm.
Further, metallic cathode material is the one in Ag, Al, Cu, and thickness is 100 ~ 300nm.
Further, substrate is the one in rigid substrate and flexible substrate, and described rigid substrate comprises glass and sapphire, and described flexible substrate comprises metal forming and thin polymer film.
Substrate 1 is the support of electrode and organic thin film layer, and it has good light transmission in visible region, has the ability of certain anti-steam and oxygen infiltration, has good profile pattern.Substrate 1 can be rigid substrate or flexible substrate; Rigid substrate can be glass or sapphire, flexible substrate can be metal forming or thin polymer film, and thin polymer film can be polyethylene, PETG, polymethyl methacrylate, Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic film.
Anode buffer layer 3 is mixture (those skilled in the art is referred to as PEDOT:PSS) or the molybdenum oxide (MoO of poly-(3,4-sub-second dioxy thiophene) and polystyrene-based benzene sulfonic acid
x); The thickness of anode buffer layer is 10 ~ 80nm.
Cathode buffer layer 5 material is the one in TPBi, BCP, Bphen, LiF, and the thickness of anode buffer layer is 1 ~ 10nm.
Metallic cathode 6 material is the one in Ag, Al, Cu, and the thickness of metal cathode layer is 100 ~ 300nm.
Photoactive layer 4 is mixed with by electron donor material PCDTBT and electron acceptor material PCBM and forms, and PCDTBT:PCBM mixed solution mass ratio is 1:20 ~ 5:1, and solution concentration is 1 ~ 30mg/ml; The thickness of photoactive layer is 40 ~ 250nm; Be mixed with ultraviolet sensitivity glue in photoactive layer 4, the mass ratio of ultraviolet sensitivity glue shared by photoactive layer is 0.05 ~ 6.5%.
In the present invention, each composition is described as follows: ultraviolet curing organic silicon adhesive is owing to not only having the premium properties of organosilyl heatproof, weather-proof, electrical insulation capability, low surface tension and low-surface-energy, and also having can the excellent specific property of the ultraviolet photocureable material such as cold curing, solidification rate be fast, pollution-free.Its prepolymer mainly comprises: mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes and vinyl ether functional's polysiloxanes.
Vinyl functionalized polysiloxane UV curing system is studied more in early days.The speed of photoresponse of this system is fast, particularly under light trigger promotes, does not substantially disturb by the inhibition of oxygen, can form softness and whippy cured film.Product can be applicable to fiber or other base material, comprises paper, metal, glass and polyethylene, polypropylene and polyester film etc.But this system exists dark reaction, the viscosity of system will increase gradually, and the hot strength of cured film declines.
Acrylate functional polysiloxanes UV curing system is good to the adhesiveness of base material, and solidification rate is high, and chemistry, the physical stability of cured layer are good, can obtain desirable viscosity by adjustment formula; But normal with volume contraction in Light Curing, produce shrinkage stress.In many situations, shrinking is all a unfavorable factor.When acrylate functional polysiloxane coated is on the base materials such as metal, glass, plastics, contraction can cause coating adhesion to decline; When being coated on flexible substrate (as paper product, plastic film), contraction can cause rolls to be wrinkled.But one flaw cannot mar the jade, acrylate functional polysiloxanes has won market with the advantage of its high reaction activity and low cost, becomes the focus of study of UV-curable silicone prepolymers research field.
When there is cation photocuring in the epoxy radicals of epoxy radicals polysiloxanes, the epoxy radicals with ring strain is opened, and forms tension-free ehter bond, and volume contraction is very little, is even zero, becomes the major product in cation photocuring system.Epoxy compounds containing unsaturated double-bond mainly contains vinyl or allylic epoxy compounds, as allyl glycidyl ether, glycidyl acrylate, dicyclohexyl pentadiene and 4-vinyl epoxy cyclohexene, what wherein photocuring activity was the highest is epoxidized cyclohexene.Such as, the end si-h bond of 4-vinyl epoxy cyclohexene and polysiloxanes is carried out hydrosilylation, obtain alicyclic epoxy polysiloxanes.Epoxy polysiloxanes can mix with Multiple components, and filler, pigment, crosslinking agent, catalyst, UV absorbers etc. can be applied in epoxy polymeric siloxane systems.Now, the application of epoxy polysiloxanes UV curing system is more and more extensive, becomes the main product in cation photocuring system.
The great advantage of styrenyl polysiloxanes UV curing system is inexpensive, wherein styryl is active owing to having higher photopolymerization reaction, styryl can be incorporated in silicon-oxygen backbone and carry out ultraviolet light polymerization, its object mainly improves the hardness of organosilicon material and the performance of other terms of mechanics.But the shortcoming that this system exists is also more, as high in volatility, inflammable, smell large, reaction speed is slower, curing performance is also not as other UV curing system.
The monomer of vinyl ether group polysiloxanes is the monomer containing HZC=CH-O-base.Due to, the lone pair electrons of oxygen atom and double bond generation conjugation, the cloud density of double bond is increased causes the C=C of vinyl ether group to be electron rich group, polymerization activity is higher than general vinyl monomer, under ultraviolet light irradiation, the reaction such as radical polymerization, cationic charge transfer complex alternating copolymerization can be carried out.Therefore, the uv curable oligomer of vinyl ethers can be applied in kind of photocuring system, as radically curing system, Cationic curing systems and mix curing system.Vinyl ethers prepolymer has that toxicity is low, smell is little, reactivity, and cured product has and shrinks the performances such as little, impact strength is high, and its potential application is extensive.But because the price of vinyl ethers monomer is higher, vinyl ethers ultraviolet curing organic silicon material is not at home and abroad also obtained and generally applies.
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 chapped 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 oxides (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 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 salt compounded of iodine class initator 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, 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.
Reactive diluent, is mainly used in the viscosity of regulation system, also can affect solidification rate and material property, comprises toluene, dimethylbenzene, n-hexane, reactive epoxies diluent, cyclic ethers and vinyl ether monomers.
Catalyst can select two (2 ethyl hexanoic acid) dibutyl tin, dibutyltin diacetate or dibutyl tin laurate etc.Wherein dibutyltin diacetate catalytic activity is large, and curing rate is fast.The activity of dibutyl tin laurate is less, and curing rate is slow.
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), phthalic acid two is ester (DHP), separate adipate (DOS), hexanedioic acid dioctyl ester (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), hexanedioic acid two (Butoxyethoxy) ethyl ester, isopropyl titanate, tetrabutyl titanate, triethyl citrate, tributyl citrate, tributyl 2-acetylcitrate, tri trimellitate (2-ethyl) own ester (TOTM), phthalic acid two (2-ethyl) own ester, decanedioic acid two (2-ethyl) own ester (DOS), Diethylene Glycol 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), 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, prevent the generation of the defects of coatings such as shrinkage cavity and pinprick, make smooth coating, and can glossiness be improved, comprise mixed solvent, organosilicon, polyacrylate, acetate butyrate fiber, nitrocellulose and polyvinyl butyral resin.Wherein silicone based, comprise diphenylpolysiloxane, methyl phenyl silicone, Organo-modified polysiloxanes, polyether silicones.
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, 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, 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) (FOH)
2), magnesium silicon muscovite [K
2((Fe
2+ Mg) (Fe
3+ Al)
3(Si
7alO
20) (OH)
4)], montmorillonite [Na
x(H
2o)
4{ (Al
2-xmg
0.33) [Si
4o
10] (OH)
2], bentonite [Na
x(H
2o)
4(Al
2-xmg
0.83) (Si
4o
10) (OH)
2], rilanit special, fumed silica, metallic soap (lead stearate, barium, cadmium, calcium, zinc, magnesium, aluminium, rare earth).Then with cellulose derivatives such as hydroxyethylcelluloses 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.
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-di-t-butyl cresols, phenothiazine, anthraquinone, tertiary amine etc.
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 P3HT:ICBA(1:20,40nm) 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 P3HT:ICBA 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 component:
The polysiloxanes 93.5% of light sensitivity
Light trigger 5%
Diluent 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 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 P3HT:ICBA(5:1,250nm) 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 P3HT:ICBA 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 component:
The polysiloxanes 94% of light sensitivity
Light trigger 3%
Diluent 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.
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 P3HT:ICBA(1:1,200nm) in be mixed with ultraviolet sensitivity glue, the mass ratio shared in photoactive layer of described ultraviolet sensitivity glue is 0.3%.
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 P3HT:ICBA 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 component:
The polysiloxanes 95% of light sensitivity
Light trigger 3.5%
Diluent 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 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 P3HT:ICBA(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 P3HT:ICBA 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 component:
The polysiloxanes 95.5% of light sensitivity
Light trigger 1.5%
Diluent 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.
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 P3HT:ICBA(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 P3HT:ICBA 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 component:
The polysiloxanes 96% of light sensitivity
Light trigger 2.5%
Diluent 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 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 P3HT:ICBA(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 P3HT:ICBA 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 component:
The polysiloxanes 96.5% of light sensitivity
Light trigger 1.5%
Diluent and auxiliary agent 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) for flexible PETG (PET) substrate, anode buffer layer (3) be PEDOT:PSS(20nm), cathode buffer layer (5) is TPBi(8nm), metallic cathode (6) is Ag(150nm).Photoactive layer (4) is P3HT:ICBA(1:1,200nm) in be mixed with ultraviolet sensitivity glue, the mass ratio shared in photoactive layer of described ultraviolet sensitivity glue is 6.5%.
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 P3HT:ICBA 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 component:
The polysiloxanes 97% of light sensitivity
Light trigger 1.5%
Diluent 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.
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, substrate (1), transparent conductive anode ITO(2 that this solar battery structure sets gradually from bottom to up), anode buffer layer (3), photoactive layer (4), cathode buffer layer (5) and metallic cathode (6), described photoactive layer is mixed with ultraviolet sensitivity glue in (4), and the component of described ultraviolet sensitivity glue and the mass ratio of each component are:
The polysiloxanes 93.5 ~ 97% of light sensitivity
Light trigger 1.5 ~ 5%
Diluent and auxiliary agent 1.5 ~ 3%;
Described diluent comprises toluene, dimethylbenzene, reactive epoxies diluent, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent.
2. organic thin film solar cell according to claim 1, is characterized in that, the polysiloxanes of described light sensitivity is one or more in mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes or vinyl ether functional's polysiloxanes.
3. organic thin film solar cell according to claim 1, it is characterized in that, described light trigger is one or more in styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt or triaryl salt compounded of iodine.
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 0.05 ~ 6.5%.
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 P3HT and electron acceptor material ICBA and forms, described P3HT:ICBA 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): the one in polystyrene-based benzene sulfonic acid or molybdenum oxide, 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, is characterized in that, described substrate is the one in rigid substrate and flexible substrate, and described rigid substrate comprises glass and sapphire, and described flexible substrate comprises metal forming and thin polymer film.
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, dry process;
2. at transparent conductive anode ITO surface rotary coating, printing or spraying anode buffer layer, and formed film is carried out annealing in process;
3. be mixed with the photoactive layer of ultraviolet sensitivity glue in anode buffer layer surface rotary coating, printing or spraying, and formed film is carried out annealing in process, the component of described ultraviolet sensitivity glue and the mass ratio of each component are:
The polysiloxanes 93.5 ~ 97% of light sensitivity
Light trigger 1.5 ~ 5%
Diluent and auxiliary agent 1.5 ~ 3%,
Diluent comprises toluene, dimethylbenzene, reactive epoxies diluent, cyclic ethers and vinyl ether monomers, and auxiliary agent comprises filler, stabilizer and crosslinking agent;
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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| CN106867318A (en) * | 2017-04-24 | 2017-06-20 | 于军胜 | A kind of high-adhesion alcohol radical nano silver wire conductive ink containing ultraviolet sensitivity glue |
| CN108574045B (en) * | 2018-05-07 | 2021-10-26 | 太原理工大学 | Organic photovoltaic cell with high photoelectric conversion efficiency |
| CN112239195B (en) * | 2020-10-16 | 2024-07-19 | 南开大学 | Preparation method of artificial electric projection device based on nano oxide film/electrolyte vertical structure |
| CN114843007B (en) * | 2021-02-02 | 2023-05-16 | 湖南文理学院 | Method for preparing poly (3, 4-dioxyethylene thiophene) nano pattern by micelle etching |
| CN113571649B (en) * | 2021-07-05 | 2023-11-17 | 南开大学 | Preparation method of ATMP-K doped tin oxide electron transport layer and application of ATMP-K doped tin oxide electron transport layer in perovskite solar cell |
| CN116247116B (en) * | 2023-03-09 | 2023-09-05 | 南开大学 | 2-amino-5-bromobenzamide material passivated inorganic perovskite-based solar cell and preparation method thereof |
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| CN202025807U (en) * | 2011-03-31 | 2011-11-02 | 厦门惟华光能有限公司 | Organic solar cell structure |
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