CN102208570B - Substrate for flexible luminescent device and preparation method thereof - Google Patents
Substrate for flexible luminescent device and preparation method thereof Download PDFInfo
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- CN102208570B CN102208570B CN201110097100.7A CN201110097100A CN102208570B CN 102208570 B CN102208570 B CN 102208570B CN 201110097100 A CN201110097100 A CN 201110097100A CN 102208570 B CN102208570 B CN 102208570B
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Abstract
The invention discloses a substrate for a flexible luminescent device. The substrate comprises a flexible substrate and a conducting layer, wherein the flexible substrate and the conducting layer are formed by one of the following two ways: (1) the flexible substrate is an ultraviolet cured silicone adhesive; the conducting layer is a silver nanowire film; and the gap of the silver nanowire film is filled with inorganic luminescent nanoparticles; and (2) the flexible substrate is an inorganic luminescent nanoparticle doped ultraviolet cured silicone adhesive; the conducting layer is a silver nanowire film; and the gap of the silver nanowire film is filled with the inorganic luminescent nanoparticle doped ultraviolet cured silicone adhesive. The substrate has the beneficial effects of solving the problems of high roughness of the silver nanowire film and poor binding force between the silver nanowire film and the flexible substrate and improving the surface evenness of the silver nanowire film and the binding force between the silver nanowire film and the flexible substrate.
Description
Technical field
The present invention relates to organic optoelectronic technical field, be specifically related to a kind of substrate used in luminescent device and preparation method thereof.
Background technology
Photoelectron technology is the very high industry of scientific and technological content developing rapidly after microelectric technique.Along with the fast development of photoelectron technology, the O-E Products such as solar cell, optical image transducer, flat-panel screens, thin-film transistor are all full-fledged gradually, and they have improved people's life greatly.Meanwhile, opto-electronic information technology, in the extensive use of social life every field, has also been created growing great market.Developed country is all using optoelectronic information industry as one of field of giving priority to, and the competition of the field of opto-electronic information just launches at world wide.
Organic optoelectronic device is mostly that preparation is at rigid substrates (on glass or silicon chip), although they have good device performance, anti-vibration at present, shock proof ability a little less than, weight is relatively heavier, and it is very not convenient to carry, and in the application of some occasion, is very restricted.People start to attempt organic optoelectronic device is deposited on flexible base, board rather than on rigid substrates.
With flexible base, board, replacing the benefit of rigid substrates is that lighter, the difficult fragmentation of product, institute take up space little and be more convenient for carrying.But, although there are these advantages, with flexible base, board, replace rigid substrates also to have many restrictions, the preparation of flexible device still has many underlying issues to need to solve.For flexible substrate, because the profile pattern of flexible substrate is far away from rigid substrate, and flexible substrate is carried out to surface smoothing, to process equipment and the technology difficulty of wanting special larger, improved the production cost of substrate; The water of flexible substrate, oxygen permeability be much larger than rigid substrate, causes opto-electronic device to be subject to the impact of the water oxygen that sees through from substrate, reduced the performance of device.
For electrode layer, conventional electrode layer material In
2o
3: SnO
2(ITO) there is following shortcoming in the electrode as flexible base, board: the indium in (1) ITO has severe toxicity, harmful in preparation and application; (2) In in ITO
2o
3expensive, cost is higher; (3) ito thin film is vulnerable to the reduction of hydrogen plasma, and effect reduces, and this phenomenon also can occur under low temperature, low plasma density; (4) can there is because of the bending of flexible substrate the phenomenon that conductivity declines in the ito thin film in flexible substrate; (5) adopt thick ITO layer can reduce light transmittance, the light of 50-80% sponges at glass, ITO and organic layer, adopts thin ITO layer process difficulty larger.In recent years, because nano silver wire film has the electrode material that higher conductivity and visible light transmissivity have become potential replaced ITO, but nano silver wire film exists the poor shortcoming of adhesion between surface roughness large and nano silver wire film and flexible substrate, reduced the performance of the opto-electronic device based on nano silver wire membrane electrode.
Therefore,, if can solve above-mentioned these problems, will make opto-electronic device obtain applying more widely and development more fast.
Summary of the invention
Problem to be solved by this invention is: how a kind of substrate used in luminescent device and preparation method thereof is provided, this substrate has solved the poor problem of adhesion between nano silver wire Film roughness large and nano silver wire film and flexible substrate, has improved adhesion between the evenness of nano silver wire film surface and nano silver wire film and flexible substrate.
Technical problem proposed by the invention is to solve like this: a kind of substrate used in luminescent device is provided, comprise flexible substrate and conductive layer, it is characterized in that, a kind of in following two kinds of modes forms for described flexible substrate and conductive layer: the organic silicon adhesive that 1. described flexible substrate is ultraviolet light polymerization, described conductive layer is nano silver wire film, is filled with inorganic light-emitting nano particle in the space of described nano silver wire film; 2. described flexible substrate is the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, described conductive layer is nano silver wire film, the organic silicon adhesive that is filled with the ultraviolet light polymerization of doping inorganic light-emitting nano particle in the space of described nano silver wire film, the organic silicon adhesive raw material of described ultraviolet light polymerization comprises the component of following mass percent: the polysiloxanes of 92～99.5% light sensitivity, 0.1～5% light trigger and 0.4～6% diluent and auxiliary agent.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described inorganic light-emitting nanoparticle size is 1～100nm, 2. in kind mode the doping mass ratio of inorganic light-emitting nano particle be less than or equal to 40%.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described inorganic light-emitting nano particle is that to take sulfide, oxide, fluoride, phosphate, vanadate, niobates, aluminate, molybdate etc. be luminous host, usings the light-emitting particles of rare earth lanthanide as activator or co-activator.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described sulfide comprises zinc sulphide, lanthanum sulfide, calcium sulfide, cerium sulphide, praseodymium sulfide, neodymium sulfide, samaric sulfide and gadolinium sulfide; Described oxide comprises zinc oxide, yittrium oxide, titanium oxide, gadolinium oxide and luteium oxide; Described fluoride comprises yttrium fluoride, gadolinium fluoride, lanthanum fluoride and cerium fluoride; Described phosphate comprises lanthanum orthophosphate, Gadolinium monophosphate, strontium phosphate, yttrium phosphate and barium phosphate; Described vanadate comprises gadolinium vanadate, Yttrium Orthovanadate, vanadic acid lanthanum, cerium vanadate, vanadic acid calcium, lead vanadate and vanadic acid strontium; Described niobates comprises calcium niobate, niobic acid yttrium, niobic acid gadolinium and niobic acid lutetium; Described aluminate comprises yttrium aluminate, barium aluminate, aluminic acid gadolinium, calcium aluminate and strontium aluminate; Described molybdate comprises lanthanum molybdate, strontium molybdate and barium molybdate; Described rare earth lanthanide comprises europium, samarium, erbium, neodymium, terbium, dysprosium, samarium, cerium, ytterbium and praseodymium.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, the polysiloxanes of described light sensitivity comprises mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes, epoxy-functional polysiloxanes, styryl polysiloxanes and vinyl ether functional polysiloxanes.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described light trigger comprises benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, acetophenones, benzophenone and 2-hydroxy-2-methyl-1-phenylacetone, alkyl phenyl ketone, alpha-hydroxyalkyl benzophenone class, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt and triaryl salt compounded of iodine.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers, cyclic lactone and vinyl ether monomers; Described auxiliary agent comprises filler, stabilizer and crosslinking agent.
A preparation method for substrate used in luminescent device, is characterized in that, comprises the following steps:
1. the rigid substrates (as glass or silicon chip) that effects on surface roughness is less than 1nm cleans, and after cleaning, with drying nitrogen, dries up;
2. take the mode of spin coating or spraying or self assembly or inkjet printing or silk screen printing on clean substrate, to prepare nano silver wire film;
3. the organic silicon adhesive layer of the ultraviolet light polymerization of spin coating or spraying doping inorganic light-emitting nano particle on nano silver wire film, first spin coating or drip to be coated with or spraying containing the solution of inorganic light-emitting nano particle, spin coating or drip to be coated with or the organic silicon adhesive layer of spraying ultraviolet light polymerization again, the organic silicon adhesive raw material of described ultraviolet light polymerization comprises the component of following mass percent: the polysiloxanes of 92～99.5% light sensitivity, 0.1～5% light trigger and 0.4～6% diluent and auxiliary agent;
4. ultraviolet light polymerization being carried out in rigid substrates surface processes 30 seconds;
5. the organic silicon adhesive layer of the ultraviolet light polymerization of the organic silicon adhesive layer of the ultraviolet light polymerization by nano silver wire film and after solidifying or doping inorganic light-emitting nano particle is peeled off rigid substrates surface, forms compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
Beneficial effect of the present invention: have inorganic light-emitting nano particle in conductive layer of the present invention, make conductive layer luminous under exciting light irradiates, not only strengthened the luminous intensity of the luminescent device based on this substrate, and the structure of the luminescent device based on this substrate and required material have been simplified, the nano silver wire simultaneously adopting due to conductive layer can improve the luminous intensity of inorganic light-emitting nano particle, has further increased the luminous intensity of the luminescent device based on this substrate; Conductive layer of the present invention is prepared on the little rigid substrates of roughness, in conductive layer space, be filled with the organic silicon adhesive of the ultraviolet light polymerization of inorganic light-emitting nano particle or doping inorganic light-emitting nano particle, by the method for peeling off, form the conductive layer of flexible base, board, improved the evenness of conductive layer surface; The organic silicon adhesive of the ultraviolet light polymerization in flexible substrate of the present invention has high visible light transmissivity, caking ability and quick-setting feature, improved the visible light transmissivity of flexible base, board, increased the adhesion between conductive layer and flexible substrate, reduced and prepared the required time of flexible base, board.
Accompanying drawing explanation
Fig. 1 is the structural representation of the substrate used in luminescent device of embodiment of the present invention 1-9;
Fig. 2 is the visible light transmissivity of the substrate in the embodiment of the present invention 1.
Wherein, 1, flexible substrate, 2, conductive layer.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described:
Technical scheme of the present invention is to provide a kind of substrate used in luminescent device, and as shown in Figure 1, the structure of device comprises flexible substrate 1, conductive layer 2.
The support that in the present invention, flexible substrate 1 is conductive layer, it has good bending performance, the ability that has certain anti-steam and oxygen infiltration, there are good chemical stability and thermal stability, conductive layer 2 requires to have good conductive capability, flexible substrate 1 and conductive layer 2 consist of following two kinds of modes: the organic silicon adhesive that 1. described flexible substrate is ultraviolet light polymerization, and described conductive layer is nano silver wire film, is filled with inorganic light-emitting nano particle in the space of described nano silver wire film; 2. described flexible substrate is the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, described conductive layer is nano silver wire film, is filled with the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
Each composition of the organic silicon adhesive of medium ultraviolet photocuring of the present invention 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, the excellent specific property of the ultraviolet photocureable material such as also having can cold curing, solidification rate is fast, pollution-free.Its prepolymer mainly comprises: mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes, epoxy-functional polysiloxanes, styryl polysiloxanes and vinyl ether functional polysiloxanes.
The early stage research of vinylated polysiloxanes UV curing system is more.The speed of photoresponse of this system is fast, particularly, under light trigger promotes, not disturbed 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-basedization polysiloxanes UV curing system is good to the adhesiveness of base material, and solidification rate is high, and the chemistry of cured layer, physical stability are good, by adjustment, are filled a prescription and can be obtained desirable viscosity; But often with volume contraction, produce shrinkage stress in Light Curing.Under many occasions, shrinking is all a unfavorable factor.Acrylate-basedization polysiloxane coated is on the base materials such as metal, glass, plastics time, and contraction can cause coating adhesion to decline; While being coated on flexible substrate (as paper product, plastic film), contraction can cause rolls wrinkle.But one flaw cannot mar the jade, acrylate-basedization polysiloxanes with its high reaction activity and cheaply advantage won market, become the focus of study of UV-curable silicone prepolymers research field.
In the epoxy radicals of epoxy radicals polysiloxanes when there is cation photocuring, 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 is mainly containing vinyl or allylic epoxy compounds, as allyl glycidyl ether, glycidyl acrylate, dicyclohexyl pentadiene and 4-vinyl epoxidized cyclohexene, what wherein photocuring activity was the highest is epoxidized cyclohexene.For example, the end si-h bond of 4-vinyl epoxidized cyclohexene and polysiloxanes is carried out to hydrosilylation, obtain alicyclic epoxy radicals polysiloxanes.Epoxy radicals polysiloxanes can mix with Multiple components, and filler, pigment, crosslinking agent, catalyst, UV absorbers etc. can be applied in epoxy radicals polysiloxanes system.Now, the application of epoxy radicals polysiloxanes UV curing system is more and more extensive, becomes the main product in cation photocuring system.
The great advantage of styryl 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 is mainly to improve 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 etc., curing performance is also not as other UV curing system.
The monomer of vinyl ether group polysiloxanes is the monomer that contains HZC=CH-O-base.Due to, the lone pair electrons of oxygen atom and two key generation conjugation, the cloud density of two keys is increased causing the C=C of vinyl ether group is electron rich group, polymerization activity is higher than general vinyl monomer, under ultraviolet light irradiation, can carry out the reactions such as radical polymerization, cationic charge transfer complex alternating copolymerization.Therefore, the uv curable oligomer of vinyl ethers can be applied in kind of photocuring system, as radically curing system, cationic curing system 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, make vinyl ethers ultraviolet curing organic silicon material also not obtain generally application at home and abroad.
Light trigger: in ultraviolet photo-curing cementing agent, often need to add Photoactive compounds, to cause or the carrying out of accelerated reaction.By the difference of its mechanism of action, can be divided into light trigger and sensitising agent.Difference is that light trigger, when reaction starts, absorbs the luminous energy of suitable wavelength and intensity, photophysical process occurs and reach its a certain excitation state, if this excited energy is greater than the needed energy of breaking bonds, produces free radical polymerization; And sensitiser absorption luminous energy is to its a certain excitation state, just by energy in molecule or intermolecular transfer, by another molecule that obtains energy, produce free radical polymerization.Compare 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: the one, and energy transfer mechanism, the 2nd, take hydrogen mechanism by force, the 3rd, the photosensitive mechanism shifting through generating electric charge.The light trigger with practical value of having developed has benzoin and its derivatives and acetophenone derivative, and sensitising agent has benzophenone, thia anthraquinone and Michler's keton.The stability of various initators, yellowing resistance, trigger rate are different, and in different resin systems, efficiency of initiation is also different, should be according to the reasonable selection that needs of different occasions.As cyanacrylate and C (CH
2oCCH
2cH
2sH) system, use respectively benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether causes, be respectively 18s, 20s and 25s curing time, and while causing with benzophenone, be only 15s curing time, and simultaneously the light transmittance of solidfied material also can due to wavelength difference, difference be larger, and this will be according to actual conditions reasonable selection.
The effect of light trigger is to absorb after ultraviolet light energy at it, through decomposing, produces free radical, thus the unsaturated bond polymerization in initiator system, and crosslinking curing becomes an integral body.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 absorbing 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 (Benzoin ethyl ether), benzoin isobutyl ether (Benzoin butyl ether), styrax lose (Benzoin oxime), benzoin isopropyl ether, acylphosphine oxide comprises: 2, 4, 6 trimethylbenzene formyl diphenyl phosphine oxides (TPO) and (2, 4, 6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO phenylbis (2, 4, 6-trimethyl benzoyl) phosphine oxide), 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 light-initiated activity, 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 thioxanthone photoinitiator at the maximum absorption wavelength in black light district at 380-420nm, and absorbability and hydrogen-taking capacity strong, there is 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 than more likely extracting hydrogen on secondary carbon or on methyl from the tertiary carbon of hydrogen donor molecule, and the hydrogen being connected on the hetero-atoms such as oxygen or nitrogen more easily extracts than the hydrogen on carbon atom.This class hydrogen donor has amine, hydramine (triethanolamine, methyl diethanolamine, triisopropanolamine etc.), mercaptan, N, N-diethyl-and to dimethylamino benzamide.
Benzophenone light initiation system, benzophenone need to be with alcohol, ether or amine and with just making vinyl monomer carry out photopolymerization.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 alkyl phenones, 2-methyl isophthalic acid (4-first coloured glaze base phenyl)-2-morpholinyl acetone (MMMP), 2 ' 2-dibenzamidodiphenyl disulfide (DBMD), (4-dimethylamino phenyl)-(1-piperidyl)-ketone, isopropyl thioxanthone (ITX), (4-dimethylamino phenyl)-(4-morpholinyl)-ketone, 2-hydroxy-2-methyl-1-phenyl-1-phenyl-1-acetone, two phenoxy group benzophenone, hydroxy-2-methyl phenyl-propane-1-ketone.And mixed system, as can eliminate oxygen in glued membrane to the benzophenone of the inhibition of Raolical polymerizable the initiator system that coordinates with tertiary ammonia; Michler's keton and benzophenone are used in conjunction with, and can obtain more cheap and effectively initiator system.
Cationic photoinitiator: aromatic sulfonium salts and salt compounded of iodine class initator have excellent high-temperature stability, also have stability with epoxy resin after coordinating, so be widely used in cationic curing system.But their the longest absorbing wavelength does not absorb in ， near ultraviolet band, 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 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-(to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, [4-(4-benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate, 4-(to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, 4,4 '-dimethyl diphenyl salt compounded of iodine hexafluorophosphate (IHT-PI 820), 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-thiophenyl-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-acetamido phenyl 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-(to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, 1-(4 '-bromo-2 '-luorobenzyl) pyridiniujm, [4-(to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, 4-[4-(p-nitrophenyl formoxyl) thiophenyl] and benzene } phenyl-iodide hexafluorophosphate, 4-[4-(to methyl benzoyl) thiophenyl] and benzene } phenyl-iodide hexafluorophosphate, 4-[4-(to methyl benzoyl) phenoxy group] and benzene } phenyl-iodide hexafluorophosphate, [4-(to benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate, the two detergent alkylate iodine hexafluoro antimonates of 4,4-.
Luxuriant molysite class: luxuriant molysite class light initiation system is a kind of new cation light initiator developing after two fragrant salt compounded of iodine and three aromatic sulfonium salts, under illumination, first luxuriant molysite ion forms aromatic radical ligand, produce the complex compound with the unsaturated iron of epoxy compounds molecule coordination simultaneously, the complex compound of the lewis acidic feature of this complex compound tool then formation and the coordination of three epoxy compounds molecules, one of them epoxy compounds can open loop form cation, it can cause cationic ring-opening polymerization, forms polymer.Formation due to ferrocene salt-epoxy radicals complex, epoxy compounds cationic species at normal temperatures needs the time, therefore need be under the condition of external world's heating, to improve polymerization speed.
This type of salt comprises: cyclopentadienyl group-iron-benzene salt, cyclopentadienyl group-iron-toluene salt, cyclopentadienyl group-iron-paraxylene salt, cyclopentadienyl group-iron-naphthalene salts, cyclopentadienyl group-iron-biphenyl salt, cyclopentadienyl group-iron-2,4-dimethyl acetophenone salt, acetyl group-cyclopentadienyl group-iron-paraxylene salt, cyclopentadienyl group-iron-methyl phenyl ethers anisole salt, cyclopentadienyl group-iron-diphenyl ether salt, cyclopentadienyl group-iron-2,4-diethoxybenzene salt, ferrocene tetrafluoroborate, the luxuriant iron tetrafluoroborate of toluene, cyclopentadienyl group-iron-methyl phenyl ethers anisole salt, cyclopentadienyl group-iron-diphenyl ether salt, cyclopentadienyl group-iron-Isosorbide-5-Nitrae-diethoxybenzene salt, cyclopentadienyl group-iron-chlorobenzene salt, cyclopentadienyl group-iron-(Isosorbide-5-Nitrae-diethoxybenzene) hexafluorophosphate, cyclopentadienyl group-iron-diphenyl ether hexafluorophosphate, 1,10-phenanthrolene ferrous perchlorate salt, 1,10-phenanthrolene ferrous sulfate cyclopentadienyl group-iron-methyl phenyl ethers anisole salt, cyclopentadienyl group-iron-diphenyl ether salt, [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 '-dibenzoyl 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 to exhaust completely in Light Curing, and the part of photodissociation can not move to coating surface, makes coating yellowing and aging, affects the quality of product; On the other hand, some initators and system are incompatible or compatibility is bad, and its application is restricted.For addressing these problems, people are by light trigger producing high-molecular.The relatively low molecular initator tool of the initator 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 high-molecular optical initator have higher activity.B, by with nonactive group copolymerization, regulates and design the distance of photosensitive group, or change the distance of optical active group and main chain, thereby acquisition has different photoactive initators.C, can introduce different optical active groups at same macromolecular chain, utilize their cooperative effect to improve light sensitive 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 toxicity of system.
The producing high-molecular of initator can directly be connected in initator on the chain of macromolecule or oligomer, as thioxanthone or acidic group phosphine oxide etc. are introduced on macromolecular chain; Also can in initator, introduce the functional group that polymerization can occur, 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 can reduce costs, and can expand again the region of absorbing wavelength, improves the absorption of ultraviolet radiation energy, thus the solidification effect having obtained.The compatibility of light trigger can be both between same type, as be both free radical type, for example the new Irgacure-1700 releasing of Ciba be exactly by 25% (2,4,6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO) and 75% alpha-hydroxy-2,2 dimethyl acetophenones (1173) form, and Irgacure-1800 is comprised of 25% BAPO and 75% Alpha-hydroxy cyclohexyl-phenyl ketone (184) etc.; Also can be formed by dissimilar initator, as light trigger compatibility free radical type and cationic, for example, triaryl thiaxanthene salt and benzophenone are coordinated, can make the curing rate of epoxy compounds 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, active epoxy diluent resin, cyclic ethers, cyclic lactone and vinyl ether monomers.
Catalyst can be selected 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 need to add various auxiliary agents in ultraviolet photo-curing cementing agent, as plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent etc.Although their shared components in adhesive are few, sometimes the processing characteristics of glue or adhesive property produced to vital effect.As cyanacrylate and C (CH
2oCCH
2cH
2sH) under the initiation of benzophenone, if add 1% silicone couplet CH
2=CHSi (OCH
2cH
2oCH
3)
3, after ultraviolet light polymerization, be placed under the environment of 80～100% humidity, after 1 year, find not change, and if do not add coupling agent, under the same terms, just after 2 days there is white erosion in bonded part, one week afterwards glue-line strip down completely.
Plasticizer comprises: diisooctyl azelate (DIOZ), dioctyl azelate (DOZ), DHP (DHP), separate two dioctyl phthalates (DOS), dioctyl adipate (DOA), diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), dibutyl phthalate (DBP), dipropyl phthalate (DAP), three vinyl butyl ether base phosphates, polyvinyl butyral resin, tributyl 2-acetylcitrate, repefral (DMP), diethyl phthalate (DEP), adipic acid two (butoxy ethyoxyl) ethyl ester, isopropyl titanate, tetrabutyl titanate, triethyl citrate, tributyl citrate, tributyl 2-acetylcitrate, tri trimellitate (2-ethyl) own ester (TOTM), the own ester of phthalic acid two (2-ethyl), decanedioic acid two (2-ethyl) own ester (DOS), 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), polytrimethylene adipate (PPA), epoxidized soybean oil (ESO), octyl epoxy stearate (OES2), chlorinated paraffin-42 (CP-42), chlorinated paraffin wax-48 (CP-48), chlorinated paraffin-52 (CP-52), distearyl acid diethylene glycol (DEG) (DEDR), tricresyl phosphate benzene methyl (TCP), diphenyl octyl phosphate (DPO), poly-adipic acid butylidene ester (PBA), butyl epoxy stearate (BES), askarel (CDP), dimethylbenzene methylal resin (plasticizer FH), pumice wax pattern base oil (PROCESS OIL637), soybean oil, naphthenic processing oil (310), W150 softening oil (petroleum hydrocarbon, hydrogenation artificial oil), zirconium aluminium is coupling agent, WB215 (aliphatic acid 18%, fatty acid ester 52%, calcium carbonate 20%).
Coupling agent is the material that a class has both sexes structure, and a part of group in their molecules can react with the chemical group on inorganic matter surface, forms strong chemical bonding; Another part group 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 the large class of Organic Chromium complex compound four by chemical constitution.Wherein in adhesive, applying more is silanes, as methyl ethylene dichlorosilane, methyl hydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-aminopropyltrimethoxysilane, 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-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-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ mercaptopropyitrimethoxy silane, γ-sulfydryl propyl-triethoxysilicane.
Levelling agent is for improving the flow leveling of resin, prevent the generation of the defects of coatings such as shrinkage cavity and pinprick, make smooth coating, and can improve glossiness, comprise mixed solvent, organosilicon, polyacrylate, acetate butyrate fiber, nitrocellulose and polyvinyl butyral resin.Wherein silicone based, comprise diphenyl polysiloxanes, methyl phenyl silicone, organic group modified polyorganosiloxane, polyethers organosilicon.
Defoamer is for preventing and eliminate coating to produce bubble in manufacture and use procedure, preventing that coating from producing the disadvantages such as pinprick.Phosphate, fatty acid ester and organosilicon etc. can be made defoamer.Specifically there is tributyl phosphate, dibutylphosphoric acid ester, phosphate foam inhibitor (AD-14L), froth breaking king (FAG470), defoamer (FAG470), defoamer (BYK-141), defoamer (BYK 037), three (butoxyethyl group) phosphate, triethyl phosphate, Tributyl phosphate ester, triethyl phosphate, tricresyl phosphate chloro isopropyl ester, three butoxy ethyl ester of phosphoric acid, the mixture of polyoxyethylene polyoxypropylene and glycol or three alcohol ethers (light yellow to water white transparency thick liquid), 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, for reducing while depositing, polymerization occurs, 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, the inorganic matters such as ferric trichloride and Sulfur etc. also can be made polymerization inhibitor stabilized free fundamental mode polymerization inhibitor and mainly contain 1, the bitter hydrazine (DPPH) of 1-diphenyl-2-, 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: 92% 2-phenolic group ethoxy propylene acid esters, 4% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt, 96% ethyoxyl list oil triacrylate, MEHQ hydroquinone monomethyl ether, 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, benzene sulfonamide amine acid 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 1,4-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 under external force the material of low denseness fluid.Organobentonite acrylonitrile-butadiene rubber (NBR), montmorillonite (Na
x(H
2o)
4{ (Al
2-xmg
0.33) [Si
4o
10] (OH)
2), bentonite [(Na
x(H
2o)
4(Al
2-xmg
0.83) Si
4o
10) (OH)
2], diatomite (unbodied SiO
2form, and contain 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).In water-based system, with cellulose derivatives such as hydroxyethylcelluloses, polyvinyl alcohol, polyacrylic acid, poly(ethylene oxide), polymethylacrylic acid, Lauxite, melamine resin, resol, phenolic resins water-soluble resin are thickener.
The effect of filler is that part replaces binding agent, reduces the consumption of binding agent, with the effect that reaches filling, reinforcement, anti-attrition and reduce costs.Filler requires particle thin and even, can be scattered in equably in slurries, good to binding agent and other component associativities.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 high polymer, 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 (for example waterglass) and alkali metal phosphonates (Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium, Amino Trimethylene Phosphonic Acid potassium, HEDP sodium, HEDP disodium, HEDP four sodium, HEDP potassium, ethylene diamine tetra methylene phosphonic acid five sodium, diethylene triamine pentamethylene phosphonic five sodium, diethylenetriamine pentamethylene phosphonic acids seven sodium, diethylene triamine pentamethylene phosphonic sodium, 2-phosphonic acids butane-1, 2, 4-tricarboxylic acids four sodium, hexamethylene diamine four methylenephosphonic acid sylvite, two 1, 6 hexylidene 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-phosphonic acids butane-1,2,4-tricarboxylic acids (PBTCA), PAPE (PAPE), 2-HPAA (HPAA), hexamethylene diamine four methylenephosphonic acids (HDTMPA), polyamino polyether base methylenephosphonic acid (PAPEMP), two 1,6 hexylidene triamine five methylenephosphonic acids (BHMTPMPA), lauryl sodium sulfate, polyacrylic acid (PAA), Sodium Polyacrylate (PAAS), HPMA (HPMA), maleic acid-acrylic acid copolymer (MA-AA), acrylic acid-2-acrylamide-2-methyl propane sulfonic copolymer (AA/AMPS), acrylic acid-hydroxypropyl acrylate copolymer, acrylic acid-acrylate-phosphonic acids-sulfonate quadripolymer, acrylic acid-acrylate-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 be take and suppressed the auxiliary agent that fluoropolymer resin thermal oxidative degradation is 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 be take and caught polymer peroxy radical as 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-pair-[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, tri-grades of butyl-4-methylphenols of 6-, two (3, tri-grades of butyl-4-hydroxy phenyls of 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-tert-butyl phenyl) dimer and the trimerical compound, 3 of ester, many alkyl bisphenol-A phosphite ester, 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, tricresyl phosphite (2,4-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 methyl) benzene.Auxiliary antioxidant has the effect of decomposing copolymer per-compound, also claims " peroxide decomposer " to comprise sulfo-dicarboxylic ester class and bi-ester of phosphite, and common and primary antioxidant is used in conjunction with.The two octadecyl esters (DSTP) of two Lauryl Alcohol esters, two ten four carbon alcohols esters, thio-2 acid, thio-2 acid dibasic acid esters, two octadecanol ester, the two lauryls of thio-2 acid, three monooctyl esters, three the last of the ten Heavenly stems ester, three (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 group diphenyl.
Heavy metal ion passivator, is commonly called as " copper resistant agent ", can complexing transition metal ions, prevent the oxidative degradation of its catalytic polymerization resin, and typical structure is as hydrazide kind compound etc.Recent years, along with going deep into of polymer antioxygen theoretical research, also there is certain variation in the classification of antioxidant, and the most outstanding feature is the concept of having introduced " carbon radicals capturing agent ".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 benzofuranone, Dihydrobenzofuranes ketone, benzofuranone, dibenzopyrone, 3-aryl-benzofuran-2-ones, 3-aryl benzofuranone, 2-aryl Dihydrobenzofuranes ketone, 2-aryl benzofuranone, 5-cyano group-1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 5-replaces 1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 2,3-dihydroxy-2,2-dimethyl-7-benzofuran phenol, 3-(2-acyloxyethoxyphenyl) benzofuran-2-ones, isobenzofuranone, 5-[(imidazo [4,5-b] pyridin-3-yl) methyl] benzofuranone, 1,2,3,4-tetrahydrochysene-benzofuranone, 2,3-dihydro-2-methyl-2-alkyl furanone, 4-ethyoxyl bisphenol-A-diacrylate, (2-10)-ethoxyquin bisphenol-A-dimethylacrylate, 2-[1-(2-hydroxyl-3,5-bis-tertiary amyl phenyl)-ethyl]-4,6-bis-tertiary amyl phenyl acrylate, bisphenol-A-glycerol double methyl methacrylate, bisphenol-A-dimethylacrylate, 4-ethyoxyl bisphenol-A-dimethylacrylate, N, N-dibenzyl hydroxylamine, N-ethyl-N-aminoethyle alcohol, N, N-diethyl hydroxylamine, 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 promote the mobile modified additive of resin melting, and this analog assistant be take 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.The ethylene propylene diene rubber of polypropylene toughness-increasing modified middle use (EPDM) also belongs to rubber toughened scope.
The function of antistatic agent is to reduce the sheet resistance of polymer product, eliminates the electrostatic hazard that accumulation of static electricity may cause, and is mainly included as 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, N, two (2-ethoxy)-N-(3 '-dodecyloxy-2 '-hydroxypropyl) the first ammonium Methylsulfate salt of N-, trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, N, N-cetyl ethyl morpholine ethyl-sulfate salt, (dodecanamide propyl trimethyl ammonium) Methylsulfate salt dibrominated N, N-bis-(octadecyl dimethyl)-3-oxa--1,5-penta 2 ammoniums, styrene polymer type quaternary ammonium salt, palmitate quaternary ammonium salt, alkylphenol-polyethenoxy based quaternary ammonium 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) trimethyl ammonium Methylsulfate salt, the polymer of poly-(oxygen-1, the 2-second two bases) phosphate of 2,2 '-nitrilo-di-methylcarbinol and α-tri-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 tridecanol phosphate, Tryfac 5573 (MA24P), fatty alcohol ether phosphate potassium (MOA-3PK), phenolic ether phosphate kalium salt (NP-4PK), phenolic ether phosphate kalium salt (NP-10PK), different tridecanol ether phosphate sylvite, Tryfac 5573 sylvite (MA24PK), fatty alcohol phosphate sylvite, ALS, non-ionic surface active agent: the condensation product of alkylamine and oxirane, alkanolamide, AEO, aliphatic acid polyethenoxy ether, two (beta-hydroxyethyl) coco amine, two (beta-hydroxyethyl) stearylamine, two (beta-hydroxyethyl) beef tallow amine, HMPA, perfluoroalkyl ethanol APEO.
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, polyether ester amides (PEEA), polyether ester acetamide (PEAI), polyethylene glycol oxide, epoxy propane copolymer (PEO-ECH), polyethylene glycol methacrylate-styrene polymer (PEGMA), methacrylic acid (MAA), methacrylic acid stearyl (SMA)+polyethylene glycol methacrylate-styrene polymer (PEGMA) form.
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 phosphoester, 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 diethylesters of N, polyphenylene phosphonic acids diphenyl sulphone (DPS) ester, polyazodiphenylene phenyiphosphonate, polyphenylene phosphonic acids bisphenol-A ester.
Mould inhibitor claims again 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 materials are to mould insensitive, but have mould sensitivity because its goods work in-process has added the material that plasticizer, lubricant, fatty acid soaps class etc. can grow der Pilz.The chemical substance that plastics comprise with mould inhibitor 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, for reducing while depositing, polymerization occurs, 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
Board structure as shown in Figure 1, flexible substrate 1 adopts the organic silicon adhesive of ultraviolet light polymerization, the organic silicon adhesive of described ultraviolet light polymerization comprises polysiloxanes, 2% light trigger and 3% diluent and the auxiliary agent of 95% light sensitivity, conductive layer 2 adopts nano silver wire film, in the space of described nano silver wire film, fill inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 10nm.
Preparation method is as follows:
1. the silicon substrate that effects on surface roughness is less than 1nm cleans, and after cleaning, with drying nitrogen, dries up;
2. nano silver wire is dispersed in solvent, takes spin coating mode on clean silicon substrate, to prepare nano silver wire film, during spin coating, rotating speed is 4000 revolutions per seconds, duration 60 seconds, and thickness is about 80 nanometers;
3. on nano silver wire film, spray the solution containing inorganic light-emitting nano particle, silicon substrate is placed 30 minutes in the environment of 80 ℃, remove solvent remaining in nano silver wire film, on nano silver wire film, spray the organic silicon adhesive of ultraviolet light polymerization, the organic silicon adhesive of described ultraviolet light polymerization comprises polysiloxanes, 2% light trigger and 3% diluent and the auxiliary agent of 95% light sensitivity again;
4. ultraviolet light polymerization being carried out in silicon substrate surface processes 30 seconds;
5. the organic silicon adhesive layer of the ultraviolet light polymerization by nano silver wire film and after solidifying is peeled off silicon substrate surface, forms compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
Embodiment 2
Board structure as shown in Figure 1, flexible substrate 1 adopts the organic silicon adhesive of ultraviolet light polymerization, the organic silicon adhesive of described ultraviolet light polymerization comprises polysiloxanes, 5% light trigger and 3% diluent and the auxiliary agent of 92% light sensitivity, conductive layer 2 adopts nano silver wire film, in the space of described nano silver wire film, fill inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 20nm.
Preparation method is similar to embodiment 1.
Embodiment 3
Board structure as shown in Figure 1, flexible substrate 1 adopts the organic silicon adhesive of ultraviolet light polymerization, the organic silicon adhesive of described ultraviolet light polymerization comprises polysiloxanes, 2% light trigger and 6% diluent and the auxiliary agent of 92% light sensitivity, conductive layer 2 adopts nano silver wire film, in the space of described nano silver wire film, fill inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 30nm.
Preparation method is similar to embodiment 1.
Embodiment 4
Board structure as shown in Figure 1, flexible substrate 1 adopts the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 1nm, the doping mass ratio of described inorganic light-emitting nano particle is 5%, the organic silicon adhesive of described ultraviolet light polymerization comprises polysiloxanes, 0.1% light trigger and 0.4% diluent and the auxiliary agent of 99.5% light sensitivity, conductive layer 2 adopts nano silver wire film, fills the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
Preparation method is similar to embodiment 1.
Embodiment 5
Board structure as shown in Figure 1, flexible substrate 1 adopts the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 25nm, the doping mass ratio of described inorganic light-emitting nano particle is 10%, the organic silicon adhesive of described ultraviolet light polymerization comprises polysiloxanes, 2% light trigger and 4% diluent and the auxiliary agent of 94% light sensitivity, conductive layer 2 adopts nano silver wire film, fills the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
Preparation method is similar to embodiment 1.
Embodiment 6
Board structure as shown in Figure 1, flexible substrate 1 adopts the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 35nm, the doping mass ratio of described inorganic light-emitting nano particle is 15%, the organic silicon adhesive of described ultraviolet light polymerization comprises polysiloxanes, 1% light trigger and 3% diluent and the auxiliary agent of 96% light sensitivity, conductive layer 2 adopts nano silver wire film, fills the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
Preparation method is similar to embodiment 1.
Embodiment 7
Board structure as shown in Figure 1, flexible substrate 1 adopts the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 15nm, the doping mass ratio of described inorganic light-emitting nano particle is 20%, the organic silicon adhesive of described ultraviolet light polymerization comprises polysiloxanes, 2% light trigger and 1% diluent and the auxiliary agent of 97% light sensitivity, conductive layer 2 adopts nano silver wire film, fills the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
Preparation method is similar to embodiment 1.
Embodiment 8
Board structure as shown in Figure 1, flexible substrate 1 adopts the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 70nm, the doping mass ratio of described inorganic light-emitting nano particle is 30%, the organic silicon adhesive of described ultraviolet light polymerization comprises polysiloxanes, 1.6% light trigger and 0.4% diluent and the auxiliary agent of 98% light sensitivity, conductive layer 2 adopts nano silver wire film, fills the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
Preparation method is similar to embodiment 1.
Embodiment 9
Board structure as shown in Figure 1, flexible substrate 1 adopts the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 100nm, the doping mass ratio of described inorganic light-emitting nano particle is 40%, the organic silicon adhesive of described ultraviolet light polymerization comprises polysiloxanes, 0.4% light trigger and 0.6% diluent and the auxiliary agent of 99% light sensitivity, conductive layer 2 adopts nano silver wire film, fills the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
Preparation method is similar to embodiment 1.
Claims (8)
1. a base board for flexible optoelectronic part, comprise flexible substrate and conductive layer, it is characterized in that, a kind of in following two kinds of modes forms for described flexible substrate and conductive layer: the organic silicon adhesive that 1. described flexible substrate is ultraviolet light polymerization, described conductive layer is nano silver wire film, in the space of described nano silver wire film, be filled with inorganic light-emitting nano particle, the organic silicon adhesive raw material of described ultraviolet light polymerization comprises the component of following mass percent: the polysiloxanes of 92～99.5% light sensitivity, 0.1～5% light trigger and 0.4～6% diluent and auxiliary agent, 2. described flexible substrate is the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, described conductive layer is nano silver wire film, the organic silicon adhesive that is filled with the ultraviolet light polymerization of doping inorganic light-emitting nano particle in the space of described nano silver wire film, the organic silicon adhesive raw material of described ultraviolet light polymerization comprises the component of following mass percent: the polysiloxanes of 92～99.5% light sensitivity, 0.1～5% light trigger and 0.4～6% diluent and auxiliary agent.
2. base board for flexible optoelectronic part according to claim 1, is characterized in that, described inorganic light-emitting nanoparticle size is 1～100nm, 2. the doping mass ratio of inorganic light-emitting nano particle described in kind mode be less than or equal to 40%.
3. substrate used in luminescent device according to claim 1, it is characterized in that, described inorganic light-emitting nano particle is to take sulfide, oxide, fluoride, phosphate, vanadate, niobates, aluminate or molybdate as luminous host, usings the light-emitting particles of rare earth lanthanide as activator and co-activator.
4. substrate used in luminescent device according to claim 3, is characterized in that, described sulfide comprises zinc sulphide, lanthanum sulfide, calcium sulfide, cerium sulphide, praseodymium sulfide, neodymium sulfide, samaric sulfide and gadolinium sulfide; Described oxide comprises zinc oxide, yittrium oxide, titanium oxide, gadolinium oxide and luteium oxide; Described fluoride comprises yttrium fluoride, gadolinium fluoride, lanthanum fluoride and cerium fluoride; Described phosphate comprises lanthanum orthophosphate, Gadolinium monophosphate, strontium phosphate, yttrium phosphate and barium phosphate; Described vanadate comprises gadolinium vanadate, Yttrium Orthovanadate, vanadic acid lanthanum, cerium vanadate, vanadic acid calcium, lead vanadate and vanadic acid strontium; Described niobates comprises calcium niobate, niobic acid yttrium, niobic acid gadolinium and niobic acid lutetium; Described aluminate comprises yttrium aluminate, barium aluminate, aluminic acid gadolinium, calcium aluminate and strontium aluminate; Described molybdate comprises lanthanum molybdate, strontium molybdate and barium molybdate; Described rare earth lanthanide comprises europium, samarium, erbium, neodymium, terbium, dysprosium, samarium, cerium, ytterbium or praseodymium.
5. substrate used in luminescent device according to claim 1, it is characterized in that, the polysiloxanes of described light sensitivity comprises mercaptan-alkene hydrocarbon functional polysiloxanes, acroleic acid esterification polysiloxanes, epoxy-functional polysiloxanes, styryl polysiloxanes or vinyl ether functional polysiloxanes.
6. substrate used in luminescent device according to claim 1, it is characterized in that, described light trigger comprises benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenones, benzophenone, 2-hydroxy-2-methyl-1-phenylacetone, alkyl phenyl ketone, alpha-hydroxyalkyl benzophenone class, acetophenone derivative, diphenyl iodnium, diaryl group iodized salt or triaryl salt compounded of iodine.
7. substrate used in luminescent device according to claim 1, is characterized in that, described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin, cyclic ethers, cyclic lactone or vinyl ether monomers; Described auxiliary agent comprises filler, stabilizer or crosslinking agent.
8. a preparation method for substrate used in luminescent device, is characterized in that, comprises the following steps:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and after cleaning, with drying nitrogen, dries up;
2. take the mode of spin coating or spraying or self assembly or inkjet printing or silk screen printing on clean substrate, to prepare nano silver wire film;
3. the organic silicon adhesive layer of the ultraviolet light polymerization of spin coating or spraying doping inorganic light-emitting nano particle on nano silver wire film, first spin coating or drip to be coated with or spraying containing the solution of inorganic light-emitting nano particle, spin coating or drip to be coated with or the organic silicon adhesive layer of spraying ultraviolet light polymerization again, the organic silicon adhesive raw material of described ultraviolet light polymerization comprises the component of following mass percent: the polysiloxanes of 92～99.5% light sensitivity, 0.1～5% light trigger and 0.4～6% diluent and auxiliary agent;
4. ultraviolet light polymerization being carried out in rigid substrates surface processes 30 seconds;
5. the organic silicon adhesive layer of the ultraviolet light polymerization of the organic silicon adhesive layer of the ultraviolet light polymerization by nano silver wire film and after solidifying or doping inorganic light-emitting nano particle is peeled off rigid substrates surface, forms compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
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