CN103594628B - 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 PDF

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Publication number
CN103594628B
CN103594628B CN201310589687.2A CN201310589687A CN103594628B CN 103594628 B CN103594628 B CN 103594628B CN 201310589687 A CN201310589687 A CN 201310589687A CN 103594628 B CN103594628 B CN 103594628B
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ultraviolet sensitivity
sensitivity glue
buffer layer
glue
photoactive layer
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CN103594628A (en
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于军胜
王煦
李�杰
王瀚雨
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
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  • Adhesives Or Adhesive Processes (AREA)
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Abstract

The invention discloses a kind of organic thin film solar cell and preparation method thereof, this solar battery structure is followed successively by substrate, transparent conductive anode ITO, anode buffer layer, photoactive layer, cathode buffer layer and metallic cathode from top to bottom, and in described photoactive layer, being mixed with mass ratio is the ultraviolet sensitivity glue of 0.03-6%; Described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue. The invention solves the poor problem of tack between the anode buffer layer of organic thin film solar cell and photoactive layer, increase the interphase match between anode buffer layer and photoactive layer, improved the high-low temperature resistant characteristic of device simultaneously, particularly heat-resisting ability, has improved the working life of device.

Description

A kind of organic thin film solar cell and preparation method thereof
Technical field
The invention belongs to organic polymer photovoltaic device or organic semiconductor thin-film area of solar cell, concreteRelate 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. PeopleClass is the limited non-renewable energy resources of exploitation excessively, make current the relied on traditional energy of the mankind as coal, oil andThere is resource exhaustion in natural gases etc., and consequent global energy fight is reached the decisive stage the stage day by day. ManyInstitute is known, and the kind of clean energy resource has wind energy, water energy, geothermal energy and solar energy etc., but former three is limited to groundTerritory or development cost, spread does not use at present. And solar energy occupy earth gross energy 99% withUpper, and do not pollute, one of new forms of energy of scientist's development and utilization become. Although silicon single crystal solar-electricityPond energy conversion efficiency is very high and technology is comparatively ripe, but its processing technology is very complicated, material requirements harshnessAnd be difficult for carrying out large area flexible processing, and some material has toxicity and makes preparation cost high. OrganicThin-film solar cells is synthetic easily with its material, raw material sources are extensive, manufacture craft is simple and with low cost,Consume energy less, can make flexible device and be easy to the advantages such as large-scale production, obtained scientist's great attentionAnd great interest.
By development in recent years, the energy conversion efficiency of organic thin film solar cell has had carrying of advancing by leaps and boundsHeight, constantly approaches 15% practical level. But the service life of organic thin film solar cell is on the low side,It is the bottleneck that hinders its marketing development always. Due to the complexity of real environment for use, organic thin film solar devicePart need to have good high-low temperature resistant characteristic and water-fast oxygen characteristic, the even bending for flexible device, curvedFolding characteristic. The interface mismatch of anode buffer layer and photoactive layer is one of poor numerous reasons of device stability.Because the PEDOT:PSS anode buffer layer conventionally adopting is hydrophilic, and normally hydrophobicity of photoactive layer, cause anode buffer layer and photoactive layer adhesion poor, be heated or catch a cold when interfacial stress is changedThe phenomenon that very easily departs from, peels off, decays rapidly device performance. How solving anode buffer layer and light livesProperty bed boundary adhesion problem, to increase organic thin film solar cell job stability, improve deviceLife-span plays a very important role.
Summary of the invention
Problem to be solved by this invention is how a kind of organic thin film solar cell and preparation method thereof is provided,Object is to solve the poor problem of tack between the anode buffer layer of organic thin film solar cell and photoactive layer,Increase the interphase match between anode buffer layer and photoactive layer, improve organic thin film solar cell simultaneouslyHigh-low temperature resistant characteristic, particularly heat-resisting ability, the working life of raising organic thin film solar cell.
To achieve these goals, the technical solution used in the present invention is:
A kind of organic thin film solar cell, is characterized in that, this solar battery structure is followed successively by from top to bottomSubstrate, transparent conductive anode ITO, anode buffer layer, photoactive layer, cathode buffer layer and metallic cathode, instituteState and in photoactive layer, be mixed with the ultraviolet sensitivity glue that mass ratio is 0.03-6%; Described ultraviolet sensitivity glue is free radicalThe mixed system of type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue.
Further, described free radical type ultraviolet sensitivity collagen material comprises base resin, the 0.2-1% of 97-99.5%Monomer, the light trigger of 0.1-1% and the sensitising agent of 0.2-2% and auxiliary agent; Described cationic ultravioletResponsive collagen material comprises cationic monomer, the diluent of 0.4-2% and the cation of 0.1-2% of 97-99.5%Light trigger.
Further, described base resin comprises unsaturated polyester resin, acrylic resin and polythiol-manyAlkene system; Described monomer comprises Styrene and its derivatives, simple function group or multi-functional acrylate; DescribedLight trigger comprises benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and acetylBenzene derivative; Sensitising agent comprises benzophenone, thia anthraquinone and Michler's keton; Auxiliary agent comprise plasticizer, thixotropic agent,Filler, antistatic agent, fire retardant and coupling agent; Described cationic monomer comprises epoxy resin or modified epoxyResin or fluorine-containing and not fluorine-containing hybrid resin or aliphatic and bis-phenol D-type blending epoxy; DescribedDiluent comprises that active epoxy diluent resin and cyclic ethers, cyclic lactone, vinyl ether monomers set as photocuringThe diluent of fat; Described cation light initiator has diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulphurSalt, triaryl selenium salt.
Further, described acrylic resin comprises polyester-acrylate, epoxy-acrylate, amino firstAcid esters-acrylate and polyethers-acrylate.
Further, the material that described polythiol-polyenoid system is following structural:
Further, described mixed system raw material comprises epoxy resin E-51, diaryl group iodized salt and diisopropylBase thiazolone.
Further, described mixed system raw material comprises bisphenol A epoxide resin, sulphion hexafluorophosphate andSulphion hexafluoro antimonate, butyl glycidyl ether, long carbochain glycidol ether, carboxylic monomer, two sensesPolycaprolactone polyol with trifunctional.
Further, described mixed system raw material comprises tetraethylene-glycol dimethylacrylate, 3,4-ringOxygen cyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, Alpha-hydroxy cyclohexyl benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, dimethoxybenzoin, hexafluorophosphoric acid diphenyl iodnium.
Further, described mixed system raw material comprises 2-ethylene glycol allyl ether, epoxy acrylic resin,Xylyl salt compounded of iodine, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl propiophenone.
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 after cleaning;
2. at transparent conductive anode ITO surface rotary coating, printing or spraying anode buffer layer, and by formFilm carry out annealing in process;
3. be mixed with in anode buffer layer surface rotary coating, printing or spraying the ultraviolet that mass ratio is 0.03-6%The photoactive layer of responsive glue, and formed film is carried out to annealing in process, described ultraviolet sensitivity glue is free radicalThe mixed system of type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light;
5. at photoactive layer surface evaporation, rotary coating or sprayed cathode cushion;
6. at cathode buffer layer surface evaporation metal negative electrode.
Compared with prior art, beneficial effect of the present invention is: (1) adds ultraviolet through treatment with ultraviolet lightThe photoactive layer of responsive glue, part unsaturated bond is crosslinked at anode buffer layer and photoactive layer interface, has increasedAdhesive force between this is two-layer, makes this interface more stable in high and low temperature environment, thereby improves the resistance to height of deviceLow temperature ability; (2) photoactive layer that is mixed with appropriate ultraviolet sensitivity glue after treatment with ultraviolet light, unsaturated bondBetween the crosslinked photoactive layer that makes finer and close, intercepted the impact of water oxygen on photoelectric conversion process, improve organicThe air stability of thin-film solar cells; (3) adding of appropriate ultraviolet sensitivity glue, can be to photolytic activityThe absorption of layer exerts an influence.
Brief description of the drawings
Fig. 1 is organic thin film solar cell structural representation provided by the present invention;
Fig. 2 does not adopt the organic thin film solar cell of ultraviolet sensitivity glue and embodiment of the present invention 1(to adopt purpleOuter responsive glue) the organic thin film solar cell normalization efficiency of working at varying environment temperature become with temperatureChange curve map;
Mark in figure: 1, substrate, 2, transparent conductive anode ITO, 3, anode buffer layer, 4, photoactive layer,5, cathode buffer layer, 6, metallic cathode.
Detailed description of the invention
The invention will be further described below in conjunction with the accompanying drawings and the specific embodiments, and described embodiment onlyBeing only the present invention's part embodiment, is not whole embodiment. Based on the embodiment in the present invention, abilityThe those of ordinary skill in territory, not making other embodiment used that obtain under creative work prerequisite, all belongs toIn protection scope of the present invention.
In conjunction with Fig. 1, organic thin film solar cell provided by the invention, comprises the lining setting gradually from bottom to upThe end 1, transparent conductive anode ITO2, anode buffer layer 3, photoactive layer 4, cathode buffer layer 5 and metal the moonThe utmost point 6, in photoactive layer 4, being mixed with mass ratio is the ultraviolet sensitivity glue of 0.03-6%; Described ultraviolet sensitivity glue is certainlyBy the mixed system of fundamental mode ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue.
Substrate 1 is the support of electrode and organic thin film layer, and it has good light transmission in visible region,The ability that has certain anti-steam and oxygen infiltration, has good profile pattern. Substrate 1 can be rigidity liningThe end or flexible substrate; Rigid substrate can be glass or sapphire, and flexible substrate can be metal forming or polymerFilm, thin polymer film can be polyethylene, PETG, polymethyl methacrylate,Merlon, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin or polyacrylic acid film.
Anode buffer layer 3 is poly-(the sub-second dioxy thiophene of 3,4-) and mixture (this of polystyrene-based benzene sulfonic acidThe technical staff in field is referred to as PEDOT:PSS) or molybdenum oxide (MoOx); The thickness of anode buffer layerFor 10-80nm.
Cathode buffer layer 5 materials are the one in TPBi, BCP, Bphen, LiF, the thickness of anode buffer layerFor 1-10nm.
Metallic cathode 6 materials are the one in Ag, Al, Cu, and the thickness of metallic cathode layer is 100-300nm.
Photoactive layer 4 be mixed with by electron donor material (PCDTBT) and electron acceptor material (PCBM) andBecome, 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.
Free radical type ultraviolet sensitivity collagen material comprises base resin, the monomer of 0.2-1%, the 0.1-1% of 97-99.5%Light trigger and sensitising agent and the auxiliary agent of 0.2-2%; Cationic ultraviolet sensitivity collagen material comprisesThe cation light initiator of the cationic monomer of 97-99.5%, the diluent of 0.4-2% and 0.1-2%.
Base resin comprises unsaturated polyester resin, acrylic resin and polythiol-polyenoid system; Described listBody comprises Styrene and its derivatives, simple function group or multi-functional acrylate.
Unsaturated polyester resin: unsaturated polyester (UP) is mixed with fractional saturation by undersaturated binary acid (or acid anhydrides)The linear polyesters that binary acid (or acid anhydrides) and dihydroxylic alcohols react and make under the effect of initator. At its moleculeIn structure, there is undersaturated vinyl monomer to exist, if by active vinyl monomer and the undersaturated second of this classAlkenyl monomer copolymerization, crosslinking curing and become three-dimensional-structure. What in general, obtained by this resin is gluingAgent is because volume contraction in solidification process is larger, and the internal stress of gluded joint is very large. Inside at glue-line easily goes outShow micro-crack and cause splicing power to diminish; Meanwhile, owing to containing ester bond in macromolecular chain, meet acid, the easy water of alkaliSeparate, thus resistance to medium and resistance to water poor, under the environment of high temperature and humidity easily distortion; In addition, it solidifiesSpeed is slower, therefore, shows poor combination property, therefore mostly use as non-structure glue. By reducingUnsatisfied chemical bond content, adopt the low monomer of polymerization shrinkage, add inorganic filler and thermal plastic high polymer etc.Means, can improve its overall performance.
Acrylic resin: this resin system curing rate is fast. Acrylic resin comprise polyester-acrylate,Epoxy-acrylate, carbamate-acrylate and polyethers-acrylate.
The material that polythiol-polyenoid system is following structural:
Monomer conventionally and resin cooperationUse, on the one hand as diluent, make glue there is the viscosity of constructability; There is again on the other hand reactivity,Solidify laggard enter resin network, the final performance of solidfied material is had to certain improvement. Monomer is styrene, benzeneThe combination of one or more in ethene derivatives, simple function group acrylate or multi-functional acrylate; SingleFunctional group or multi-functional acrylate be for example: methyl methacrylate, ethyl acrylate, acrylic acid propane diolsEster, n-butyl acrylate etc.
To the requirement of monomer mainly: the respond of low viscosity, highly diluted effect and height, also to hold concurrently simultaneouslyTurn round and look at volatility, toxicity and peculiar smell little, good etc. to the compatibility of resin.
As the preferred mode of one, in order to regulate various performance parameters, adopt mix monomer, mix monomer asUnder: free radical activity diluent and cation activity diluent.
Free radical activity diluent comprises first generation acrylic acid polyfunctional monomer, second generation acrylic acid polyfunctional monomerMore excellent third generation acrylic monomers.
Simple function reactive diluent has: styrene, NVP, Isooctyl acrylate monomer, acrylic acidHydroxyl ethyl ester and isobornyl acrylate, methacrylate phosphate and isobornyl methacrylate.
Difunctionality reactive diluent has: triethylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycolDiacrylate, polyethylene glycol diacrylate alcohol ester, neopentylglycol diacrylate and propoxyl group neopentyl glycol twoAcrylate, acrylate-functional monomer has: 1,6-hexanediyl ester (HDDA), Isosorbide-5-Nitrae-DingOmega-diol diacrylate (BDDA), propylene glycol diacrylate (DPGDA), glycerine diacrylateThe trihydroxy methyl propane triacrylate (TMPTA) of ester (TPGDA), trifunctional, pentaerythriteTriacrylate (PETA), trihydroxy methyl propane triol triacrylate (TMPTMA), three hydroxyl firstBase propane triacrylate, propoxylation trihydroxy methyl propane triacrylate, pentaerythrite three propylene alcohol esters,Pentaerythritol propoxylate propylene alcohol ester, N, N-dihydroxy ethyl-3 amido methyl propionate, triethylene-glycol pairMethacrylate, double pentaerythritol C5 methacrylate, tri (propylene glycol) diacrylate, phthalic acidDiethanol diacrylate (PDDA). They have replaced active little first generation acrylic acid monofunctional monomer.
Second generation acrylic acid polyfunctional monomer is mainly in molecule, to introduce ethyoxyl or propoxyl group, has excitantLittle, also there is higher activity and state of cure. As ethoxylation trihydroxy methyl propane triol triacrylate(TMP (EO) TMA), propoxylation trihydroxy methyl propane triol triacrylate (TMP (PO) TMA),Propoxylation glycerine triacrylate (G (PO) TA).
Third generation acrylic monomers is mainly the acrylate that contains methoxyl group, preferably resolves high curing rateContradiction with shrinkage factor, low state of cure. This class material has 1,6-hexylene glycol methoxyl group mono acrylic ester(HDOMEMA), ethoxylation neopentyl glycol methoxyl group mono acrylic ester (TMP (PO) MEDA).In molecule, introduce after alkoxyl, can reduce the viscosity of monomer, reduce the excitant of monomer simultaneously.
The introducing of alkoxyl is also improved a lot to the compatibility of diluent monomer, VTES(A15I), gamma-methyl allyl acyloxypropyl trimethoxysilane (A174) can be used as monomer.
Cruel in various active epoxy diluent resins and various cyclic ethers, ring, vinyl ether monomers etc. can be served asCation activity diluent. Wherein fast, the modest viscosity of vinyl ethers compound and oligomer curing rate, nothingTaste, nontoxic, can be used in conjunction with epoxy resin. Vinyl ether monomers has: triethylene glycol divinyl ether(DVE-3), BDO vinyl ethers (HBVE), cyclohexyl vinyl ether (CHVE), completeMethyl fluoride vinyl ethers (PMVE), perfluor n-propyl vinyl ether, IVE, hydroxyl butyl secondAlkene ether, vinyl ethyl ether, ethyl vinyl ether, ethyl vinyl ether propylene, ethylene glycol monoallyl ether,Hydroxy butyl vinyl ether, butyl vinyl ether, CTFE (CTFE), triethylene glycol divinyl ether,Methoxy ethylene, vinyl butyl ether, dodecyl vinyl (DDVE), cyclohexyl vinyl ether,Tribenzyl-benzene phenol polyethenoxy base ether, tetrafluoroethene-perfluoro propyl vinyl ether, tetrafluoroethene-perfluoro propyl secondAlkene ether, tert-Butyl vinyl ether:
Epoxide monomer has: 3,4-epoxy radicals hexahydrobenzoid acid-3 ', 4 '-epoxy radicals cyclohexyl methyl esters(ERL-4221), bisphenol A type epoxy resin (EP), epoxy acrylate, epoxy vinyl ester, thirdOlefin(e) acid epoxy-ester, epoxymethacrylate, water-soluble itaconic acid epoxy ester resin:
Light trigger: in ultraviolet photo-curing cementing agent, often need to add Photoactive compounds, to cause or to addThe carrying out of speed reaction. Can be divided into light trigger and sensitising agent by the difference of its mechanism of action. Difference is that light drawsSend out agent in the time that reaction starts, absorb the luminous energy of suitable wavelength and intensity, photophysical process occurs and reach it and a certainly swashSend out state, if this excited energy is greater than the needed energy of breaking bonds, produce free radical polymerization; And lightQuick dose absorbs luminous energy to its a certain excitation state, just by energy in molecule or intermolecular transfer, by obtainingAnother molecule that obtains energy produces free radical polymerization. Compared with light trigger, itself does not disappear sensitising agentConsumption or change structure, it can be regarded as photochemically reactive catalyst. Its mechanism of action roughly has three kinds:The one, energy transfer mechanism, the 2nd, take hydrogen mechanism by force, the 3rd, the photosensitive mechanism shifting through generating electric charge. DevelopThe light trigger with practical value has benzoin and its derivatives and acetophenone derivative, and sensitising agent has hexichol firstKetone, thia anthraquinone and Michler's keton. The stability of various initators, yellowing resistance, trigger rate are different,In different resin systems, efficiency of initiation is also different, should be according to the reasonable selection that needs of different occasions. AsCyanacrylate and C (CH2OCCH2CH2SH) system, uses respectively benzoin methyl ether, styraxEther, benzoin isopropyl ether causes, and is respectively 18s, 20s and 25s hardening time, and uses benzophenoneWhen initiation, be only 15s hardening time, and simultaneously the light transmittance of solidfied material also can due to wavelength difference, difference be larger,This will be according to actual conditions reasonable selection.
The effect of light trigger is to absorb after ultraviolet light energy at it, produces free radical through decomposing, thus primosomeUnsaturated bond polymerization in system, crosslinking curing becomes an entirety. Conventional radical photoinitiator has cracking typeWith put forward the large class of Hydrogen two.
Crack type photoinitiator: crack type photoinitiator mainly contains benzoin ethers (styrax ethers), benzene is evenAcyl ketal and acetophenone etc. Crack type photoinitiator is chapped after absorption ultraviolet light, produces two free radicals, fromCause unsaturated group polymerization by base. Benzoin ethers (styrax ethers) comprising: styrax (Benzoin),Benzoin methyl ether, benzoin ethyl ether (Benzoinethylether), benzoin isobutyl ether (Benzoinbutylether),Styrax loses (Benzoinoxime), benzoin isopropyl ether; Acylphosphine oxide comprises: 2,4,6 front threesBase benzoyl diphenyl phosphine oxide (TPO) and (2,4,6-trimethylbenzene formyl) phenyl phosphine oxide [BAPOphenylBis(2,4,6-trimethylbenzoyl) phosphineoxide], two (2,4, the 6-trimethylbenzene first of phenylAcyl group) phosphine oxide (819), tetramethylpiperidone oxide (TMPO), triethyl phosphate (TEPO),They are more satisfactory light triggers, have very high light-initiated activity, and long wave near ultraviolet ray is had to absorption,Be applicable to the situation that whitewash and film are thicker, and there is good stability, can variable color or fade.
Carry Hydrogen initator: carry Hydrogen initator and mainly contain benzophenone and thioxanthones etc. Wherein thiaAnthrone photoinitiator at the maximum absorption wavelength in black light district at 380-420nm, and absorbability and taking by forceHydrogen Energy power is strong, has higher efficiency of initiation. Carrying Hydrogen initator must have hydrogen donor as collaborative composition,Otherwise efficiency of initiation is too low, so that can not be put to application. Triplet state carbonyl free radical is from three of hydrogen donor moleculeOn level carbon, than more likely extracting hydrogen on secondary carbon or on methyl, be connected on hydrogen on the hetero atom such as oxygen or nitrogen more former than carbonHydrogen on son more easily extracts. This class hydrogen donor has amine, hydramine (triethanolamine, methyl diethanolamine, three isopropylsHydramine etc.), mercaptan, N, N-diethyl-to dimethylamino benzamide.
Benzophenone light initiation system, benzophenone need to gather with alcohol, ether or amine and with just making vinyl monomer carry out lightClose. Mainly comprise: benzophenone, thia anthraquinone, Michler's keton, dimethoxy benzene acetophenone (DMPA),Alpha-hydroxy-2,2 dimethyl acetophenones (1173), Alpha-hydroxy cyclohexyl-phenyl ketone (184), α-amine alkylBenzophenone, 2-methyl isophthalic acid (4-first coloured glaze base phenyl)-2-morpholinyl acetone (MMMP), 2 ' 2-dibenzoyl ammoniaBase Diphenyl disulfide compound (DBMD), (4-dimethylamino phenyl)-(1-piperidyl)-ketone, isopropylBase 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 mixtureSystem, as eliminated the benzophenone of inhibition and the joining of tertiary ammonia to Raolical polymerizable of oxygen in glued membraneClose initiator system; Michler's keton and benzophenone are used in conjunction with, and can obtain more cheap and effectively initator bodySystem.
Cationic photoinitiator: aromatic sulfonium salts and salt compounded of iodine class initator have excellent high-temperature stability,After coordinating with epoxy resin, also there is stability, so be widely used in cationic curing system. But theyThe longest absorbing wavelength, in far-ultraviolet region, does not absorb near ultraviolet band, generally will add light sensitizer, as: fromCarry out sensitizing by base initator or light-sensitive coloring agent.
This type of initator comprises: xylyl iodine hexafluorophosphate (PI810), hydroxy phenyl salt compounded of iodine (HTIB),The two detergent alkylate iodine hexafluoro antimonates of 4,4-, xylyl salt compounded of iodine, diphenyl hexafluoroarsenate salt compounded of iodine,[4-(2-hydroxyl-3-butoxy-1-propoxyl group) phenyl] iodo-hexafluoro antimonate of benzene, [4-(is to BenzoylbenzeneSulfenyl) benzene] phenyl-iodide hexafluorophosphate, [4-(4-benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphoric acidSalt, 4-(are to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, 4,4 '-dimethyl diphenyl iodineHexafluorophosphate salt (IHT-PI820), 4,4 ' diacetylamino diphenyl iodine hexafluorophosphate, 3,7 one twoNitro dibenzo ring-type salt compounded of iodine and 3,7 one dinitro dibenzo ring-type bromine salt, tetrafluoro boric acid diaryl iodineSalt, 3,3 '-dinitro diphenyl salt compounded of iodine, 3,3 '-dinitro diphenyl salt compounded of iodine and several 2,2 '-bis-is gotFor (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 sulphurHexafluorophosphate, triaryl phosphine glyoxalidine salt, triaryl phosphine 1,1 '-dinaphthalene glyoxalidine ring salt, 3,7-dinitro dibenzo bromine five rings salt, p-methyl benzenesulfonic acid triphenyl sulfosalt, bromination triphenyl sulfosalt, (4-Thiophenyl-phenyl) diphenyl sulphur hexafluorophosphate, 4-(thiophenyl) triphenyl sulphur hexafluorophosphate, 3,3 '-dinitro diphenyl iodine hexafluorophosphate, 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate, triphenyl sulphurSalt, 4-chlorphenyl diphenyl sulphur hexafluorophosphate, 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate, 4-acetamideBase phenyl diphenyl sulphur hexafluorophosphate, 3-benzoylphenyl diphenyl sulphur hexafluorophosphate, triphenyl sulphur fluorineBorate, triphenyl sulphur hexafluorophosphate, triphenyl sulphur hexafluoro antimonate, 4-tolyl diphenyl sulphur hexafluoro phosphorusHydrochlorate, phosphorus hexafluoride triaryl sulfonium salts, antimony hexafluoride triaryl sulfonium salts, [4-(is to Benzoylbenzene sulphurBase) benzene] phenyl-iodide hexafluorophosphate, 1-(4 '-bromo-2 '-luorobenzyl) pyridiniujm, [4-(is to benzoylThiophenyl) benzene] phenyl-iodide hexafluorophosphate, 4-[4-(p-nitrophenyl formoxyl) and thiophenyl] benzene } phenyl-iodideHexafluorophosphate, { 4-[4-(is to methyl benzoyl) thiophenyl] benzene } phenyl-iodide hexafluorophosphate, { 4-[4-(to methyl benzoyl) phenoxy group] benzene } phenyl-iodide hexafluorophosphate, [4-(is to benzoyl phenoxy group)Benzene] phenyl-iodide hexafluorophosphate, 4, the two detergent alkylate iodine hexafluoro antimonates of 4-.
Luxuriant molysite class: luxuriant molysite class light initiation system develops after two fragrant salt compounded of iodine and three aromatic sulfonium saltsA kind of new cation light initiator, under illumination, first luxuriant molysite ion forms aromatic radical ligand, produces simultaneouslyWith the complex compound of the unsaturated iron of epoxide molecule coordination, the lewis acidic feature of this complex compound tool alsoThen the complex compound of formation and the coordination of three epoxide molecules, one of them epoxide can form in open loopCation, it can cause cationic ring-opening polymerization, forms polymer. At normal temperatures due to ferrocene salt-The formation of epoxy radicals complex, epoxide cationic species needs the time, therefore need be at the bar of external world's heatingUnder part, 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, ringPentadienyl-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-phenanthroleneFerrous perchlorate's salt, 1,10-phenanthrolene ferrous sulfate cyclopentadienyl group-iron-methyl phenyl ethers anisole salt, cyclopentadieneBase-iron-diphenyl ether salt, [1,1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride, vinyl ferrocene, N, N '-Di-ferrocene methylene butanediamine quaternary ammonium salt, ferrocene formamide, ferrocene acyl propionic acid, ferrocenyl methyl ketone,Ethyl dicyclopentadienyl iron, Butyrylferrocene, butyl ferrocene, N, N-dimethyl-amine methyl ferrocene, 1,1 '-bis-Benzoyl ferrocene, (3-carboxyl propionyl group) ferrocene, 1,1 '-dibromo ferrocene, Aminoferrocene.
The light trigger of macromolecule loading: in photocuring system, light trigger is not often in Light CuringExhaust completely, the part of photodissociation can not move to coating surface, makes coating yellowing and aging, affects the matter of productAmount; On the other hand, some initators and system are incompatible or compatibility is bad, and its application is restricted. ForAddress these problems, people are by light trigger producing high-molecular. The relatively low molecular initiation of the initator of producing high-molecularAgent tool has the following advantages: A, in polymer chain, energy transfer and intermolecular reaction become and be more prone to, and make heightMolecule light trigger has higher activity. B, by with nonactive group copolymerization, regulate and design photosensitive baseThe distance of group, or the distance of change optical active group and main chain, have different photoactive initators thereby obtain.C, can introduce different optical active groups at same macromolecular chain, utilize their cooperative effect to improve lightQuick effect. The producing high-molecular of D, initator, has limited the migration of initator, prevents coating flavescence and aging.E, because most of photolysis debris are still connected on macromolecule matrix, therefore, can reduce smell and the poison of systemProperty.
The producing high-molecular of initator can directly be connected in initator on the chain of macromolecule or oligomer, as by thiaAnthrone or acidic group phosphine oxide etc. are introduced on macromolecular chain; Also can in initator, introduce the official that polymerization can occurCan roll into a ball, make it in Light Curing, realize producing high-molecular, as benzophenone structural is introduced in tetraacrylate.
The compatibility of various light triggers is also a research direction in recent years, after compatibility, re-uses, and both canTo reduce costs, can expand again the region of absorbing wavelength, improve the absorption of ultraviolet radiation energy, thereby obtainSolidification effect that must be good. The compatibility of light trigger can be both between same type, as was both free radical type,The new Irgacure-1700 releasing of for example Ciba is exactly by (2,4,6-trimethylbenzene formyl) phenyl phosphine oxide of 25%(BAPO) and 75% alpha-hydroxy-2,2 dimethyl acetophenones (1173) composition, Irgacure-1800Be exactly to be formed etc. by 25% BAPO and 75% Alpha-hydroxy cyclohexyl-phenyl ketone (184); Also can beFormed by dissimilar initator, as light trigger compatibility free radical type and cationic, for example, willTriaryl thiaxanthene salt and benzophenone coordinate, and can make the curing rate of epoxide be improved.
Auxiliary agent: in general, for adapting to the bonding requirement of varying environment, also need in ultraviolet photo-curing cementing agentAdd various auxiliary agents, as plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent etc. ItAlthough in adhesive shared component few, the processing characteristics to glue or adhesive property produce to closing sometimesImportant effect. As cyanacrylate and C (CH2OCCH2CH2SH) in the initiation of benzophenoneUnder, if add the silicone couplet CH of l%2=CHSi(OCH2CH2OCH3)3, after ultraviolet light polymerization, be placed inUnder the environment of 80-100% humidity, after 1 year do not find change, and if do not add coupling agent, under the same terms, 2Just there is white erosion in bonded part in the future, and after one week, glue-line strips down completely.
Plasticizer comprises: diisooctyl azelate (DIOZ), dioctyl azelate (DOZ), adjacent benzene twoFormic acid two ester (DHP), separate two dioctyl phthalates (DOS), hexanedioic acid dioctyl ester (DOA), adjacent benzeneDioctyl phthalate diisobutyl ester (DIBP), dioctyl phthalate (DOP), dibutyl phthalate (DBP),Dipropyl phthalate (DAP), three vinyl butyl ether base phosphates, polyvinyl butyral resin, acetyl lemonLemon acid tributyl, repefral (DMP), diethyl phthalate (DEP), hexanedioic acidTwo (butoxy ethyoxyl) ethyl ester, isopropyl titanate, tetrabutyl titanate, triethyl citrate, citric acid threeButyl ester, tributyl 2-acetylcitrate, tri trimellitate (2-ethyl) own ester (TOTM), phthalic acidTwo (2-ethyl) own ester, decanedioic acid two (2-ethyl) own ester (DOS), diglycol dibenzoic acidEster (DEDB), phthalic anhydride, dipropylene glycol dibenzoate, separate diacid dibenzyl ester (DBS),BS (BS), chlorosulfonated polyethylene (toughening elastic body), triphenyl phosphate (TPP), phosphorusAcid three (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 is coupling agent, WB215(aliphatic acid 18%; Fatty acid ester 52%; Calcium carbonate20%）。
Coupling agent is the material that a class has both sexes structure, a part of group in their molecules can with inorganic matter tableThe chemical group reaction of face, forms strong chemical bonding; Another part group has close organic character,Can be wound around with reactive organic molecule or physics, thus the material strong bonded that two kinds of character are varied in size.The coupling agent of current industrial use is divided into silanes, acyl esters of gallic acid, zirconium class and Organic Chromium complexing by chemical constitutionThe large class of thing four. Wherein in adhesive, applying more is silanes, as methyl ethylene dichlorosilane, methylHydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-aminopropylTrimethoxy silane, dimethyl silicone polymer, poly-hydrogen methylsiloxane, poly-methyl methoxy radical siloxane, γ-Methacrylic acid the third vinegar base trimethoxy silane (KH-570), gamma-aminopropyl-triethoxy-silane (KH-550),γ-glycidol ether propyl trimethoxy silicane, aminopropyl silsesquioxane, γ-methacryloxypropylTrimethoxy silane, chain alkyl trimethoxy silane, VTES, vinyl trimethoxySilane, γ-chloropropyl triethoxysilane, two-(the silica-based propyl group of γ-triethoxy), anilinomethyl three ethoxiesBase silane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylTriethoxysilane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxyThe third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ-sulfydryl propyl groupTrimethoxy silane, γ-sulfydryl propyl-triethoxysilicane.
Levelling agent is the flow leveling for improving resin, prevents the generation of the defects of coatings such as shrinkage cavity and pinprick, makesSmooth coating, and can improve glossiness, comprise mixed solvent, organosilicon, polyacrylate, acetate butyrateFiber, nitrocellulose and polyvinyl butyral resin. Wherein silicone based, comprise diphenyl polysiloxanes, firstBase phenyl polysiloxane, organic group modified polyorganosiloxane, polyethers organosilicon.
Stabilizing agent is, for reducing while depositing, polymerization occurs, and improves the storage stability of resin. Conventional stabilizing agentThere are hydroquinones, p methoxy phenol, 1,4-benzoquinone, 2,6 one di-t-butyl cresols, phenothiazine, anthraquinone etc.
Defoamer is for preventing and eliminate coating to produce bubble in manufacture and use procedure, preventing that coating from producingThe disadvantages such as pinprick. Phosphate, fatty acid ester and organosilicon etc. can be made defoamer. Specifically have 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 phosphineAcid esters, 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, poly-Dimethyl siloxane, glycerine polyethenoxy ether (GP330), laureth, polyoxyethylene polyoxypropylene seasonPenta tetrol ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxypropylene, polyethers, poly-second twoAlcohol fatty acid ester, metallic soap of stearic acid, polyureas, the fatty acid ester compounded thing of higher alcohols; Silicone defoaming agent has poly-Ether modified organic silicon oxygen alkane, organopolysiloxane mixture, silicone emulsion.
Polymerization inhibitor is, for reducing while depositing, polymerization occurs, and improves the storage stability of resin. Conventional polymerization inhibitorGenerally be divided into molecule-type polymerization inhibitor and stabilized free fundamental mode polymerization inhibitor, the former mainly contains: hydroquinones, 1,4-benzoquinone,Phenothiazine, beta-phenyl naphthylamines, p-tert-butyl catechol, methylene blue, three (N-nitroso-N-phenyl hydroxylAmine) inorganic matter and the Sulfur etc. such as aluminium salt, stannous chloride, ferric trichloride also can make polymerization inhibitor stabilized free fundamental modePolymerization inhibitor mainly contains 1,1-diphenyl-2-bitter hydrazine (DPPH), TEMPO(TMP), hydroquinones, allyl acetate, MEHQ (MEHQ), NO free radical piperidinesAlcohol, 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: 92% 2-phenolic group secondOxygen base acrylate, 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 are to benzeneDiphenol, p-tert-butyl catechol (TBC), catechol, p methoxy phenol, 2.6-di-t-butyl pairCresols, 2.5-di-tert-butyl hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, 1.4-naphthoquinones, phenthazine, the tert-butyl groupHydroquinones (TBHQ), o-sec-butyl-4,6 dinitrophenol (DNBP), ethylene glycol ether, alkaneBase benzene sulfonic acid amine salt, p-t-butyl catechol, methyl methacrylate (MMA), 2,4,6-trinitro-Phenol (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 are to the adjacent methyl 1,4-benzoquinone of benzene two, 3-spyButyl-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, under external force againBecome the material of low denseness fluid. Organobentonite acrylonitrile-butadiene rubber (NBR), montmorillonite（Nax(H2O)4{(Al2-xMg0.33)[Si4O10](OH)2), bentonite [(Nax(H2O)4(Al2-xMg0.83)Si4O10)(OH)2], diatomite (unbodied SiO2Composition, and contain a small amount of Fe2O3、CaO、MgO、Al2O3And organic impurities), asbestos, wollastonite (CaSiO3), muscovite (KAl2(AlSi3O10)(OH)2), Jin YunFemale (KMg3(AlSi3O10)(F,OH)2), magnesium silicon muscovite [K2((Fe2+Mg)(Fe3+Al)3(Si7AlO20)(OH)4)]、Montmorillonite [Nax(H2O)4{(Al2-xMg0.33)[Si4O10](OH)2], bentonite[Nax(H2O)4(Al2-xMg0.83)(Si4O10)(OH)2], rilanit special, fumed silica, metallic soap be (hardResin acid lead, barium, cadmium, calcium, zinc, magnesium, aluminium, rare earth). In water-based system with hydroxyethylcellulose etc.Cellulose derivative, polyvinyl alcohol, polyacrylic acid, PEO, 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 reach filling, reinforcement,Anti-attrition and the effect reducing costs. Filler requires particle thin and even, can be scattered in equably in slurries, to stickyKnot agent and other component associativities are good. The consumption of filler should be suitable, otherwise also can affect serous coat quality. BagDraw together inorganic mineral bentonite acrylonitrile-butadiene rubber (NBR), potassium aluminosilicate sodium (nepheline), calcium carbonate, moisture siliconAcid magnesium [Mg3[Si4O10](OH)2], wollastonite (CaSiO3), muscovite [KAl2(AlSi3O10）(OH)2]、Phlogopite [KMg3(AlSi3O10)(FOH)2], magnesium silicon muscovite [K2((Fe2+Mg)(Fe3+Al)3(Si7AlO20)(OH)4)], montmorillonite [Nax(H2O)4{(Al2-xMg0.33)[Si4O10](OH)2], bentonite[Nax(H2O)4(Al2-xMg0.83)(Si4O10)(OH)2], kaolin, red mud (Al1-xOx), calcium sulfate, propyleneAcid esters high polymer, butyl polyacrylate, polyurethane.
Dispersant impels material particles to be dispersed in medium, forms the reagent of stable suspension. Dispersant oneAs be divided into inorganic dispersant and the large class of organic dispersing agent two. Conventional inorganic dispersant has silicates (for example waterGlass) and alkali metal phosphonates (ATMP four sodium, ATMP five sodium, amino threeMethylenephosphonic 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, diethylAlkene triamine pentamethylene phosphonic acids seven sodium, diethylene triamine pentamethylene phosphonic sodium, 2-phosphonic acids butane-1,2,4-tricarboxylic acidsFour sodium, hexamethylene diamine four methylenephosphonic acid sylvite, two 1,6 hexylidene triamine five methylenephosphonic acid sodium, trimerization Alendronate,Calgon and sodium pyrophosphate etc.). Organic dispersing agent comprise triethyl group hexyl phosphonic acids, ATMP,HEDP (HEDP), ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS), ethylenediamine tetraacetic methenePhosphonic acids (EDTMPA), diethylene triamine pentamethylene phosphonic (DTPMP), 2-phosphonic acids butane-1,2,4-tricarboxylicAcid (PBTCA), PAPE (PAPE), 2-HPAA (HPAA), oneself twoAmine four methylenephosphonic acids (HDTMPA), polyamino polyether base methylenephosphonic acid (PAPEMP), two 1,6 sub-oneselfBase triamine five methylenephosphonic acids (BHMTPMPA), lauryl sodium sulfate, polyacrylic acid (PAA), poly-PAA (PAAS), HPMA (HPMA), maleic acid-acrylic acid copolymer (MA-AA),Acrylic acid-2-acrylamide-2-methyl propane sulfonic copolymer (AA/AMPS), acrylic acid-hydroxypropyl acrylateCopolymer, acrylic acid-acrylate-phosphonic acids-sulfonate quadripolymer, acrylic acid-acrylate-sulfonate threeMembered copolymer, copolymer of phosphono carboxylic acid (POCA), polyacrylate, carboxylate-sulfonate-nonionicTerpolymer, polyepoxy sodium succinate (PESA), poly (sodium aspartate) (PASP), base amylalcohol, fibreTie up plain derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester etc.
Antioxidant to be to suppress the fluoropolymer resin thermal oxidative degradation auxiliary agent as major function, belongs to anti-oxidant reagentCategory. Antioxidant is the topmost type of plastics stabilizing additive, and nearly all fluoropolymer resin all relates toThe application of antioxidant. According to the mechanism of action, traditional antioxidant systems generally comprises primary antioxidant, auxiliary antioxygenAgent and heavy metal ion passivator etc. Primary antioxidant, to catch polymer peroxy radical as major function, has againThe title of " peroxy radical capturing agent " and " chain termination type antioxidant ", relates to aromatic amine compounds and hindered phenolThe large series of products of compounds two. Aromatic amine antioxidant has: diphenylamines, p-phenylenediamine (PPD), N, N-pair-[3-(3,5-Di-tert-butyl-hydroxy phenyl) propiono] hexamethylene diamine, EEDQ; Hinered phenols antioxidant has: 2,5-, bis-spiesButylhydroquinone, 2,6-di-tert-butyl-4-methy phenol, TBHQ, 2,5-di-tert-butyl is to benzeneDiphenol (DBHQ), 2, tri-grades of butyl-4-methylphenols of 6-, two (tri-grades of butyl-4-hydroxy phenyls of 3,5-)Thioether, four [β-(tri-grades of butyl-4-hydroxy phenyls of 3,5-) propionic acid] pentaerythritol ester; Triphenyl phosphite (TPPi),Phosphite ester three (2,4-di-tert-butyl phenyl) ester, pentaerythritol bis-phosphite two (2,4-di-t-butylbenzeneBase) dimer and the trimerical compound, 3 of ester, many alkyl bisphenol-A phosphite ester, 5-di-t-butyl-4-Hydroxybenzyl 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-hydroxy benzenes firstBase) benzene. Auxiliary antioxidant has the effect of decomposing copolymer per-compound, also claims " peroxide decomposer ",Comprise sulfo-dicarboxylic ester class and bi-ester of phosphite, common and primary antioxidant is used in conjunction with. Two Lauryl AlcoholsEster, two ten four carbon alcohols esters, the two octadecyl esters (DSTP) of thio-2 acid, thio-2 acid dibasic acid esters, two 18The two lauryls of carbon alcohol ester, thio-2 acid, three monooctyl esters, three the last of the ten Heavenly stems ester, three (Lauryl Alcohol) esters and three (16Carbon 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 group diphenyl.
Heavy metal ion passivator, is commonly called as " copper resistant agent ", can complexing transition metal ions, prevent its catalysisThe oxidative degradation of fluoropolymer resin, typical structure is as hydrazide kind compound etc. Recent years, along with poly-Going deep into of compound antioxygen theoretical research, also there is certain variation in the classification of antioxidant, and the most outstanding feature isIntroduce the concept of " carbon radicals capturing agent ". It is anti-that this radical scavenger is different from traditional masterOxygen agent, they can catch polymer alkyl diradical, are equivalent to set up in traditional antioxidant system anti-togetherLine. This type of stabilizing additive mainly comprises 2-ethyl benzofuran ketone, 2-methyl benzofuranone, dihydrobenzoFuranone, benzofuranone, dibenzopyrone, 3-aryl-benzofuran-2-ones, 3-aryl benzofuranKetone, 2-aryl Dihydrobenzofuranes ketone, 2-aryl benzofuranone, 5-cyano group-1-(4-fluorophenyl)-1,3-dihydro is differentBenzofuranone, 5-replace 1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 2,3-dihydroxy-2,2-bis-Methyl-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-ethyoxyl bisphenol-A-diacrylate, (2-10)-ethoxyquinBisphenol-A-dimethylacrylate, 2-[1-(2-hydroxyl-3,5-bis-tertiary amyl phenyl)-ethyl]-4,6-bis-tertiary amylsPhenyl acrylate, bisphenol-A-glycerine double methyl methacrylate, bisphenol-A-dimethylacrylate, 4-secondOxygen base bisphenol-A-dimethylacrylate, N, N-dibenzyl hydroxylamine, N-ethyl-N-aminoethyle alcohol, N, N-diethylBase azanol, IPD acrylamide HAS, isopropylhydroxyla, hydroxylamine hydrochloride, chlorination hydroxylammonium,Hydrogen chlorine azanol, N-methyl-azanol, acetohydroxamic acid, N-hydroxyl acetamide.
Modifier is intended to improve plasticizing capacity, improves resin melt viscoelasticity and promotes what resin melting flowedModified additive, this analog assistant is taking acrylic acid esters co-polymer (ACR) as main.
Anti-impact modifier improves the auxiliary agent of rigid polymer goods shock resistance. Mainly comprise haloflex(CPE), acrylate copolymer (ACR), methacrylate-diene-ethylene copolymer (MBS),Ethene-thiazolinyl acetate copolymer (EVA) and acrylonitrile-diene-ethylene copolymer (ABS) etc. PolypropyleneThe ethylene propylene diene rubber (EPDM) using in toughening modifying also belongs to rubber toughened scope.
The function of antistatic additive is to reduce the sheet resistance of polymer product, and elimination accumulation of static electricity may causeElectrostatic hazard, is mainly included as cationic surfactant and anion surfactant. Cation surface activatingAgent has: alkyl phosphate diethanolamine salt, stearyl dimethyl benzyl ammonium chloride, the chlorination of stearoyl trimethylAmmonium, stearmide, stearoyl dimethyl-penten ammonium chloride, N, two (2-ethoxy)-N-(3 '-12 of N-Alkoxyl-2 '-hydroxypropyl) first ammonium Methylsulfate salt, trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, tristearinAmido propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, N, N-cetyl ethyl morpholine ethyl-sulfate salt,(dodecanamide propyl trimethyl ammonium) Methylsulfate salt dibrominated N, N-bis-(octadecyl dimethyl)-3-oxygenAssorted-1,5-penta 2 ammoniums, styrene polymer type quaternary ammonium salt, palmitate quaternary ammonium salt, alkylphenol-polyethenoxy base seasonAmmonium salt, dialkyl quaternary ammonium salt, polyacrylamide quaternary ammonium salt, octadecyl dimethyl ethoxy quaternary ammonium nitrate,Ammonium polystyrene sulphonate salt, propyl-dimethyl-beta-hydroxyethyl nitrate, (3-dodecanamide propyl) trimethylAmmonium Methylsulfate salt, 2,2 '-nitrilo-di-methylcarbinol and α-tri-decyl-ω-hydroxyl gather (oxygen-1,2-second two bases) phosphoric acidThe polymer of ester, polyethylene glycol tridecyl ether phosphate, diethanolamine salt, oleic acid diethanolamine salt, oleic acidTriethanolamine salt, 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 tridecanol phosphorusAcid esters, Tryfac 5573 (MA24P), fatty alcohol ether phosphate potassium (MOA-3PK), phenolic ether phosphoric acidEster sylvite (NP-4PK), phenolic ether phosphate kalium salt (NP-10PK), different tridecanol ether phosphate sylvite,Tryfac 5573 sylvite (MA24PK), fatty alcohol phosphate sylvite, ALS; Nonionic tableSurface-active agent: the condensation product of alkylamine and oxirane, alkanolamide, AEO, aliphatic acidAPEO, two (beta-hydroxyethyl) coco amine, two (beta-hydroxyethyl) stearylamine, two (beta-hydroxyethyls)Beef tallow amine, HMPA, perfluoroalkyl ethanol APEO.
Negative and positive amphoteric surfactant comprises: dodecyl-dimethyl quaternary ammonium second inner salt, dodecyl diformazanBase 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: PEO (PEO), polyether ester acid imide, polyethylene second twoAlcohol methacrylic acid EVA, polyether ester amides (PEEA), polyether ester acetamide (PEAI), polyoxygenatedEthene, epoxy propane copolymer (PEO-ECH), polyethylene glycol methacrylate-styrene polymer (PEGMA), firstBase acrylic acid (MAA), methacrylic acid stearyl (SMA)+polyethylene glycol methacrylate-styrene polymer(PEGMA) the amphipathic copolymer of composition.
In fire retardant inorganic combustion inhibitor comprise antimony 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, polyphosphoric acidEster, red phosphorus, two (tetrabromo phthalimide) ethane, Dowspray 9 homopolymers, melamine, threeCyanuric acid salt, isodecyl diphenyl phosphoester, ethylhexyl diphenyl phosphate, tricresyl phosphate isopropyl phenyl ester, two(2 chloroethyl) vinylphosphonate, ethylene two [three (2 cyanoethyl) bromination microcosmic salt], N, two (2 hydroxyls of NEthyl) AminomethylphosphoniAcid Acid diethylester, polyphenylene phosphonic acids diphenyl sulphone (DPS) ester, polyazodiphenylene phenyiphosphonate, polyphenylBase phosphonic acids bisphenol-A ester.
Mould inhibitor claims again microbial inhibitor, is the growth of microorganism such as a class mould fungus inhibition, prevents fluoropolymer resinThe stabilizing additive of being degraded by microbial attack. Most polymeric materials are also insensitive to mould, but byAdd in its goods work in-process the material that plasticizer, lubricant, fatty acid soaps class etc. can be grown der PilzAnd there is mould sensitivity. The chemical substance that plastics comprise with mould inhibitor is a lot, and more common kind comprisesOrgano-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, oilAcid phenyl mercury, copper 8-quinolinolate, chlorination three second or tributyl tin, copper sulphate, mercury chloride, sodium fluoride.
Sensitizer is to dimethylamino benzamide; Aminopropyl silsesquioxane and Versamid in promoterMass ratio is 3:1.
Cationic photocuring system mainly utilizes aromatic series diazol, aromatic series salt compounded of iodine, aromatic series sulfonium salt to existUltraviolet ray is irradiated lower photodissociation and is produced Bronsted acid, and Bronsted acid again trigger monomer carries out cationic polymerization. Solid with free radicalChange system is compared, if it have cure shrinkage little, be not subject to the inhibition of various oxygen and there is no nucleophilic impurityExist, once cause the polymerization advantage such as will continue for a long time. But light trigger is released in the time of irradiationThe Bronsted acid of emitting, can produce corrosiveness to cementing matrix. In theory, all lists that can carry out cationic polymerizationBody may be used to cationic curing, and still, at present the most frequently used is various epoxy resin or modified epoxy.Various active epoxy diluent resins and various cyclic ethers, cyclic lactone, vinyl ether monomers etc. can be served as lightThe diluent of cured resin, cation light initiator has diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulphurSalt, triaryl selenium salt etc. At present, more and more round the research of this system, for example there is report profitCause at above-mentioned cationic initiator with fluorine-containing and not fluorine-containing hybrid resin, made low-shrinkage and refractionThe accurate adhesive that rate is adjustable; In disc making, the adhesive that the epoxy resin that utilizes cation to cause makesUnder the experiment condition that is 95% at 85 DEG C, relative humidity, the non-corrosive phenomenon of 96h occurs; In hollow devicesWhen assembling, the aliphatic and the bis-phenol D-type blending epoxy that utilize sulfonium salt to cause, can make low linear expansionCoefficient and there is the adhesive of good moisture resistance.
TMDPO (TPO), fragrant luxuriant molysite, organic aluminium compound/siliconAlkane system, dialkyl benzene acid methyl sulphur father-in-law salt, triaryl sulphur hexafluorophosphate cation light initiator-tung oilThe cation photocuring reaction of Modified phenolic epoxy resin (TMPE) and E-44 epoxy resin compound system. logicalCross the mensuration of gel fraction and studied the impact of various conditions on laser curing velocity, and utilized infrared spectrum analysis shouldCoating structure before and after reaction system photocuring reaction. Result shows, the kind of light trigger and concentration can be effectiveGround changes laser curing velocity, and the initiating activity of Omnicat550 is better than Omnicat432 and becomes ratio with its concentrationExample; The punishment of the photoactivate such as anthracene, BPO has certain sensibilization to system, and phenthazine effect is not obvious; NoCongener epoxy and vinyl ethers reactive diluent have considerable influence to laser curing velocity; Along with resin proportioningThe increase laser curing velocity of middle epoxide group concentration increases; This diagram of system reveals " solidifying afterwards " phenomenon.
Due to light-initiated IONENE G cording have light-initiated not ideal enough, curing rate is slow, high in cost of production is scarceFall into, limited it in industrial popularization, have people by the freedom of the cationic polymerization of epoxy resin and acrylateBase polymerization is unified in one, has both reached the object that makes full use of luminous energy, has reached again the object of mutual modification,Its cured product has been concentrated epoxy resin and acrylate advantage separately, has overcome again some defect simultaneously, opensCreate a brand-new system. With benzhydryl iodine hexafluorophosphate (DPI.PF6) make light trigger, drawSend out bisphenol A epoxide resin E51With the hybrid resin of acrylic ester prepolymer AE made low viscosity, solidify timeBetween short, the good adhesive of high, water-fast the boiling property of bonding layer shear strength, make the excellent of epoxy resin and acrylateGesture all shows up. Below enumerate the composition of several mixed systems:
1, epoxy resin E-51(bisphenol-A (2,2-two (4-hydroxy phenyl) propane)) and epoxychloropropane existThe synthetic linear polymer of polycondensation in alkaline medium, (51 represent the representative fraction 50% of epoxy), diarylSalt compounded of iodine (CD-1012), the cationic photopolymerization initiator system of sensitising agent diisopropyl thiazolone (ITX) composition.
2, bisphenol A epoxide resin (epoxy resin 128), cationic initiator sulphion hexafluorophosphate(6992) and sulphion hexafluoro antimonate (6976) be sulfosalt, reactive diluent butyl glycidyl ether(669), long carbochain glycidol ether (114), carboxylic monomer (0200), two senses and trifunctional poly-Caprolactone polyol (0301).
3, one methacrylate/glycidyl methacrylate copolymer is grafted on polyurethane, through amineAfter neutralization, make self-emulsifying type acrylic resin grafted polyurethane, strengthened the compatible of polyurethane and acrylic resinProperty, has improved the cost performance of resin.
4, tetraethylene-glycol dimethylacrylate, tetraethylene-glycol dimethylacrylate respectively with 3,4-Epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate is mixed, and light trigger is Alpha-hydroxy cyclohexyl benzophenone(Irgacure184), 2,2-dimethoxy-2-phenyl acetophenone (Irgacure651), dimethoxybenzoin,Hexafluorophosphoric acid diphenyl iodnium.
5,2-ethylene glycol allyl ether and epoxy acrylic resin (CG602) mixture, cationic light drawsSend out agent xylyl salt compounded of iodine or radical photoinitiator 2,2-dimethoxy-2-phenyl acetophenone (Irgacure651) or 2-hydroxy-2-methyl propiophenone (Darocur1173).
6,4-epoxycyclohexyl formic acid-3,4-epoxycyclohexyl methyl ester (CY179), caprolactone trihydroxylic alcohol,Triaryl sulfonium salts, benzophenone and acrylate monomer.
7, vinyl ethers compound have that curing rate is fast, viscosity is low, be not afraid of oxygen inhibition, tasteless, nothingThe advantage of poison. With acrylic ester oligomer, triethylene Glycol divinyl ether, xylyl salt compounded of iodine, α-The hybrid UV curable paint of hydroxy-cyclohexyl benzophenone (Irgacure184) composition has fast, the resistance to solvent of curing ratePerformance is good, without " solidifying afterwards " and to features such as polyester base material adhesive force are good.
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), the moonUtmost point cushion 5 is TPBi(10nm), metallic cathode 6 is Ag(100nm). Photoactive layer 4 is PCDTBT:PCBM(1:20,40nm) in be mixed with ultraviolet sensitivity glue, ultraviolet sensitivity glue shared matter in photoactive layerAmount is than being 0.03%, and ultraviolet sensitivity glue is the mixing of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glueSystem.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, after cleaningDry;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and by formed filmCarry out annealing in process;
3. be mixed with the PCDTBT:PCBM solution system of ultraviolet sensitivity glue at anode buffer layer surface rotary coatingStandby photoactive layer, and formed film is carried out to annealing in process, described ultraviolet sensitivity glue is free radical type ultravioletThe mixed system of responsive glue and cationic ultraviolet sensitivity glue, the raw material of described free radical type ultraviolet sensitivity glue comprisesFollowing composition: 97% base resin, 1% monomer, 1% light trigger and 1% sensitising agent and helpAgent; Described cationic ultraviolet sensitivity collagen material comprises 97% cationic monomer, 2% diluent and 1%Cation light initiator;
4. the photoactive layer 3. step being obtained 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), the moonUtmost point cushion 5 is TPBi(1nm), metallic cathode 6 is Ag(300nm). Photoactive layer 4 is PCDTBT:PCBM(5:1,250nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue is shared in photoactive layerMass ratio be 0.05%, ultraviolet sensitivity glue is free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glueMixed system.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, after cleaningDry;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and by formed filmCarry out annealing in process;
3. be mixed with the PCDTBT:PCBM solution system of ultraviolet sensitivity glue at anode buffer layer surface rotary coatingStandby photoactive layer, and formed film is carried out to annealing in process, described ultraviolet sensitivity glue is free radical type ultravioletThe mixed system of responsive glue and cationic ultraviolet sensitivity glue, the raw material of described free radical type ultraviolet sensitivity glue comprisesFollowing composition: 97.5% base resin, 0.2% monomer, 0.3% light trigger and 2% sensitising agentAnd auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprise 97.5% cationic monomer, 0.5% rareRelease the cation light initiator of agent and 2%;
4. the photoactive layer 3. step being obtained 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), the moonUtmost point cushion 5 is TPBi(8nm), metallic cathode 6 is Ag(150nm). Photoactive layer 4 is PCDTBT:PCBM(1:1,200nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue is shared in photoactive layerMass ratio be 0.1%, ultraviolet sensitivity glue is free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glueMixed system.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, after cleaningDry;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and by formed filmCarry out annealing in process;
3. be mixed with the PCDTBT:PCBM solution system of ultraviolet sensitivity glue at anode buffer layer surface rotary coatingStandby photoactive layer, and formed film is carried out to annealing in process, described ultraviolet sensitivity glue is free radical type ultravioletThe mixed system of responsive glue and cationic ultraviolet sensitivity glue, the raw material of described free radical type ultraviolet sensitivity glue comprisesFollowing composition: 98% base resin, 0.9% monomer, 0.1% light trigger and 1% sensitising agent withAnd auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprises 98% cationic monomer, 1.5% diluentWith 0.5% cation light initiator;
4. the photoactive layer 3. step being obtained 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), the moonUtmost point cushion 5 is TPBi(8nm), metallic cathode 6 is Ag(150nm). Photoactive layer 4 is PCDTBT:PCBM(1:1,200nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue is shared in photoactive layerMass ratio be 0.5%, ultraviolet sensitivity glue is free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glueMixed system.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, after cleaningDry;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and by formed filmCarry out annealing in process;
3. be mixed with the PCDTBT:PCBM solution system of ultraviolet sensitivity glue at anode buffer layer surface rotary coatingStandby photoactive layer, and formed film is carried out to annealing in process, described ultraviolet sensitivity glue is free radical type ultravioletThe mixed system of responsive glue and cationic ultraviolet sensitivity glue, the raw material of described free radical type ultraviolet sensitivity glue comprisesFollowing composition: 98.5% base resin, 0.2% monomer, 0.4% light trigger and 0.9% sensitising agentAnd auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprises 98.5% cationic monomer, 1% dilutionAgent and 0.5% cation light initiator;
4. the photoactive layer 3. step being obtained 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), the moonUtmost point cushion (5) is TPBi(8nm), metallic cathode 6 is Ag(150nm). Photoactive layer 4 isPCDTBT:PCBM(1:1,200nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue light liveIn property layer, shared mass ratio is 1%, and ultraviolet sensitivity glue is free radical type ultraviolet sensitivity glue and cationic ultravioletThe mixed system of responsive glue.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, after cleaningDry;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and by formed filmCarry out annealing in process;
3. be mixed with the PCDTBT:PCBM solution system of ultraviolet sensitivity glue at anode buffer layer surface rotary coatingStandby photoactive layer, and formed film is carried out to annealing in process, described ultraviolet sensitivity glue is free radical type ultravioletThe mixed system of responsive glue and cationic ultraviolet sensitivity glue, the raw material of described free radical type ultraviolet sensitivity glue comprisesFollowing composition: 99% base resin, 0.5% monomer, 0.2% light trigger and 0.3% sensitising agentAnd auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprises 99% cationic monomer, 0.5% dilutionAgent and 0.5% cation light initiator;
4. the photoactive layer 3. step being obtained 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), the moonUtmost point cushion 5 is TPBi(8nm), metallic cathode 6 is Ag(150nm). Photoactive layer 4 is PCDTBT:PCBM(1:1,200nm) in be mixed with ultraviolet sensitivity glue, described ultraviolet sensitivity glue is shared in photoactive layerMass ratio be 3%, ultraviolet sensitivity glue is the mixed of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glueFit system.
Preparation method is as follows:
1. first the glass substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, after cleaningDry;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and by formed filmCarry out annealing in process;
3. be mixed with the PCDTBT:PCBM solution system of ultraviolet sensitivity glue at anode buffer layer surface rotary coatingStandby photoactive layer, and formed film is carried out to annealing in process, described ultraviolet sensitivity glue is free radical type ultravioletThe mixed system of responsive glue and cationic ultraviolet sensitivity glue, the raw material of described free radical type ultraviolet sensitivity glue comprisesFollowing composition: 99.5% base resin, 0.2% monomer, 0.1% light trigger and 0.2% photosensitiveAgent and auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprises 99.5% cationic monomer, 0.4%Diluent and 0.1% cation light initiator;
4. the photoactive layer 3. step being obtained 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, anode bufferLayer 3 is PEDOT:PSS(20nm), cathode buffer layer 5 is TPBi(8nm), metallic cathode 6For Ag(150nm). Photoactive layer 4 is PCDTBT:PCBM(1:1,200nm) in be mixed with purpleOuter responsive glue, described ultraviolet sensitivity glue shared mass ratio in photoactive layer is 6%, ultraviolet sensitivity glue is certainlyBy the mixed system of fundamental mode ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue.
Preparation method is as follows:
1. first the PET substrate of previously prepared good transparent conductive anode ITO is cleaned thoroughly, after cleaningDry;
2. at transparent conductive anode ITO surface rotary coating PEDOT:PSS solution and by formed filmCarry out annealing in process;
3. be mixed with the PCDTBT:PCBM solution system of ultraviolet sensitivity glue at anode buffer layer surface rotary coatingStandby photoactive layer, and formed film is carried out to annealing in process, described ultraviolet sensitivity glue is free radical type ultravioletThe mixed system of responsive glue and cationic ultraviolet sensitivity glue, the raw material of described free radical type ultraviolet sensitivity glue comprisesFollowing composition: 97% base resin, 1% monomer, 1% light trigger and 1% sensitising agent and helpAgent; Described cationic ultraviolet sensitivity collagen material comprises 97% cationic monomer, 2% diluent and 1%Cation light initiator;
4. the photoactive layer 3. step being obtained 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 Ratio of the organic thin film solar cell of substrate, and one is at lightIn active layer, add the organic thin film solar cell of ultraviolet sensitivity glue, a kind of is not add having of ultraviolet sensitivity glueMachine thin-film solar cells. Wherein, bending radius is 10mm, and direction is outwardly-bent.
Table 1

Claims (3)

1. an organic thin film solar cell, it is characterized in that, this solar battery structure is followed successively by substrate (1), transparent conductive anode ITO(2 from top to bottom), anode buffer layer (3), photoactive layer (4), cathode buffer layer (5) and metallic cathode (6), in described photoactive layer (4), being mixed with mass ratio is the ultraviolet sensitivity glue of 0.03-6%; Described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue.
2. organic thin film solar cell according to claim 1, is characterized in that, described mixed system raw material comprises epoxy resin E-51, diaryl group iodized salt and diisopropyl thiazolone.
3. 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 after cleaning;
2. at transparent conductive anode ITO surface rotary coating, printing or spraying anode buffer layer, and formed film is carried out to annealing in process;
3. be mixed with in anode buffer layer surface rotary coating, printing or spraying the photoactive layer that mass ratio is the ultraviolet sensitivity glue of 0.03-6%, and formed film is carried out to annealing in process, described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue;
4. the photoactive layer 3. step being obtained carries out treatment with ultraviolet light;
5. at photoactive layer surface evaporation, rotary coating or sprayed cathode cushion;
6. at cathode buffer layer surface evaporation metal negative electrode.
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