CN102208565B - Substrate for flexible luminous device and preparation method thereof - Google Patents
Substrate for flexible luminous device and preparation method thereof Download PDFInfo
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- CN102208565B CN102208565B CN 201110096929 CN201110096929A CN102208565B CN 102208565 B CN102208565 B CN 102208565B CN 201110096929 CN201110096929 CN 201110096929 CN 201110096929 A CN201110096929 A CN 201110096929A CN 102208565 B CN102208565 B CN 102208565B
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Abstract
The invention discloses a substrate for a flexible luminous device. The substrate comprises a flexible substrate and a conductive layer. The substrate is characterized in that: the conductive layer is a graphene film, and the flexible substrate is inorganic luminous nano particle-doped ultraviolet cured organic silicon adhesive. Through the substrate, the problems of high surface roughness of the conductive layer and poor bonding force between the conductive layer and the flexible substrate are solved, and the bonding force between the conductive layer and the flexible substrate and the water and oxygen blocking capacity of the substrate are improved.
Description
Technical field
The present invention relates to the 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 that develops 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.Simultaneously, opto-electronic information technology has also been created growing great market in the extensive use of social life every field.Developed country all the optoelectronic information industry as one of field of giving priority to, the competition of the field of opto-electronic information just launches at world wide.
The extensive use of organic material in opto-electronic device is that the effect of adding fuel to the flames has been played in the development of photoelectron technology.From 1987, the people such as Deng of Kodak high official position were after the sandwich structure organic electroluminescence device has been invented on the basis of summing up forefathers, and organic optoelectronic device enters the period of high speed development.The organic material fields such as photodetection, solar cell, display device that are widely used.By the application of organic material, the production cost decrease of opto-electronic device, performance has had large increase.
Organic optoelectronic device mostly is 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 is very restricted in the application of some occasion.People begin to attempt to be deposited on organic optoelectronic device on the flexible base, board rather than on the rigid substrates.
With flexible base, board replace the benefit of rigid substrates be product lighter, be difficult for broken, institute takes up space little and be more convenient for carrying.But, although these advantages are arranged, replace rigid substrates also to have many restrictions with flexible base, board, the preparation of flexible device still has many underlying issues to need to solve.As owing to comparing with rigid substrate, the profile pattern of flexible substrate is far away from glass substrate, and to process equipment and the technology difficulty of wanting special larger and flexible substrate is carried out surface smoothing, improved the production cost of substrate; Thereby the electrode material of organic optoelectronic device is the very easily oxidized decline that causes device performance in oxygen containing environment; Adhesion is low between conventional electrode layer and the flexible substrate, is easy to peel off; The water of flexible base, board, oxygen permeability are much larger than rigid substrates, cause opto-electronic device to be subjected to the water effect of oxygen that sees through from substrate, reduced performance of devices, therefore whether can address these problems be flexible device whether can the crucial factor that is widely used.
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 conductive layer surface poor flatness and conductive layer and the flexible substrate, has improved the conductivity of conductive layer and substrate to the obstructing capacity of water oxygen.
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, described conductive layer is graphene film, described flexible substrate is the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, and 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, the doping mass ratio of described inorganic light-emitting nano particle is 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 as luminous host, with the light-emitting particles of rare earth lanthanide as activator and co-activator take sulfide, oxide, fluoride, phosphate, vanadate, niobates, aluminate, molybdate etc.
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, the good triaryl salt compounded of iodine of diaryl group iodized salt.
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 kind of preparation method of substrate used in luminescent device is characterized in that, may further comprise the steps:
1. the effects on surface roughness is cleaned less than the rigid substrates (such as copper foil or iron foil sheet or nickel foil sheet) of 1nm, dries up with drying nitrogen after cleaning;
2. adopt the method for chemical vapour deposition (CVD) to prepare graphene film at the rigid substrates of cleaning, its preparation condition comprises: the carbon source that adopts is one or more in methane, ethane, propane, butane, methyl alcohol, the ethanol, and the chemical vapor deposition growth environment of graphene film is: temperature is under 700 ℃～1000 ℃ the normal pressure or negative pressure;
3. the organic silicon adhesive of the ultraviolet light polymerization of spin coating or spraying doping inorganic light-emitting nano particle on graphene 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;
4. ultraviolet light polymerization being carried out on the rigid substrates surface processed 30 seconds;
5. the organic silicon adhesive layer of the doping inorganic light-emitting nano particle after graphene film and the curing is peeled off the rigid substrates surface, form the compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
Beneficial effect of the present invention: conductive layer of the present invention adopts graphene film, because the conductivity of Graphene has improved the conductivity of conductive layer in the flexible base, board considerably beyond general conductor; Because to have intensity high for Graphene, make flexible base, board of the present invention by alternating bending after, the graphene conductive layer can fracture, the phenomenon that conductivity also can not occur descending; There is the inorganic light-emitting nano particle in the substrate layer, makes substrate layer luminous under exciting light irradiation, not only strengthened the luminous intensity based on the luminescent device of this substrate, and simplified based on the structure of the luminescent device of this substrate and required material; Because graphene film has fine and close structure, make water oxygen be difficult to by, the organic silicon adhesive layer of the ultraviolet light polymerization after solidifying also has fine and close structure simultaneously, has improved the obstructing capacity of flexible base, board to water oxygen; Prepare the organic silicon adhesive layer of conductive layer and ultraviolet light polymerization at the little rigid substrates of roughness, form flexible base, board by the method for peeling off, improved the evenness of conductive layer surface; The organic silicon adhesive of the ultraviolet light polymerization in the flexible substrate of the present invention has high visible light transmissivity, caking ability and quick-setting characteristics, improved the visible light transmissivity of flexible base, board, increase the adhesion between conductive layer and the flexible substrate, reduced the preparation required time of flexible base, board.
Description of drawings
Fig. 1 is the structural representation of the substrate used in luminescent device of embodiment of the invention 1-9;
Fig. 2 is the visible light transmissivity of the substrate in the embodiment of the invention 1.
Wherein, 1, flexible substrate, 2, conductive layer.
Embodiment
The invention will be further described below in conjunction with accompanying drawing and embodiment:
Technical scheme of the present invention provides 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.
It is graphene film that conductive layer 2 requires that good conductive capability, described conductive layer are arranged.
Each composition of organic silicon adhesive of invention medium ultraviolet photocuring is described as follows:
The excellent specific property of the ultraviolet photocureable materials such as the ultraviolet curing organic silicon adhesive is owing to not only having the premium properties of organosilyl heatproof, weather-proof, electrical insulation capability, low surface tension and low-surface-energy, and also having can 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 soft 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 there is dark reaction in this system, and the viscosity of system will increase gradually, and the hot strength of cured film descends.
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, can obtain desirable viscosity by adjusting prescription; But in Light Curing, often with volume contraction, produce shrinkage stress.Under many occasions, shrinking all is a unfavorable factor.Acrylate-basedization polysiloxane coated is on the base materials such as metal, glass, plastics the time, and contraction can cause coating adhesion to descend; When being coated on the flexible substrate (such as paper product, plastic film), contraction can cause the 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.
Cation photocuring when occuring in the epoxy radicals of epoxy radicals polysiloxanes, and the epoxy radicals with ring strain is opened, and forms tension-free ehter bond, and volume contraction is very little, even be zero, becomes the major product in the cation photocuring system.The epoxy compounds that contains unsaturated double-bond mainly is to contain vinyl or allylic epoxy compounds, such as allyl glycidyl ether, glycidyl acrylate, dicyclohexyl pentadiene and 4-vinyl epoxidized cyclohexene, what wherein the 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 hydrosilylation, obtain alicyclic epoxy radicals polysiloxanes.The epoxy radicals polysiloxanes can mix with Multiple components, and filler, pigment, crosslinking agent, catalyst, UV absorbers etc. can be applied in the epoxy radicals polysiloxanes system.Now, the application of epoxy radicals polysiloxanes UV curing system is more and more extensive, becomes the main product in the cation photocuring system.
The great advantage of styryl polysiloxanes UV curing system is inexpensive, wherein styryl is owing to having higher photopolymerization reaction activity, styryl can be incorporated into and carry out ultraviolet light polymerization in the silicon-oxygen backbone, its purpose mainly is 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, and is high, inflammable such as volatility, smell large, reaction speed waits more slowly, and curing performance is also not as other UV curing system.
The monomer of vinyl ether group polysiloxanes is the monomer that contains the HZC=CH-O-base.Because, 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 the 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 used in kind of the photocuring system, such as radically curing system, cationic curing system and mix curing system.The vinyl ethers prepolymer has that toxicity is low, smell is little, reactivity, and cured product has and shrinks the performances such as little, that 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 to use at home and abroad.
Light trigger: in the ultraviolet photo-curing cementing agent, often need to add Photoactive compounds, with the carrying out of initiation or accelerated reaction.Difference by its mechanism of action can be divided into light trigger and sensitising agent.Difference is that light trigger when the reaction beginning, absorbs the luminous energy of suitable wavelength and intensity, photophysical process occurs reach its a certain excitation state, if this excited energy then produces free radical polymerization greater than the needed energy of breaking bonds; And sensitiser absorption luminous energy is to its a certain excitation state, just with energy in molecule or intermolecular the transfer, produce free radical polymerization by another molecule that obtains energy.Compare with light trigger, sensitising agent itself does not consume or change structure, and it can be regarded as photochemically reactive catalyst.Its mechanism of action roughly has three kinds: the one, and the energy transfer mechanism, the 2nd, take hydrogen mechanism by force, the 3rd, the photosensitive mechanism that shifts 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 needs reasonable selection of different occasions.Such 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 when causing with benzophenone, only be 15s curing time, and simultaneously the light transmittance of solidfied material also can difference be larger owing to the wavelength difference, and this will be according to the actual conditions reasonable selection.
The effect of light trigger is after it absorbs the ultraviolet light energy, produces free radical through decomposing, thus the unsaturated bond polymerization in the initiator system, and crosslinking curing becomes an integral body.Radical photoinitiator commonly used has cracking and puies forward Hydrogen two large classes.
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 the unsaturated group polymerization.Benzoin ethers (styrax ethers) comprising: styrax (Benzoin), benzoin methyl ether, benzoin ethyl ether (Benzoin ethyl ether), benzoin isobutyl ether (Benzoin butyl ether), styrax lose (Benzoin oxime), benzoin isopropyl ether; Acylphosphine oxide comprises: 2; 4; 6 trimethylbenzene formyl diphenyl phosphine oxides (TPO) and (2; 4; 6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO phenyl bis (2; 4; 6-trimethyl benzoyl) phosphine oxide); two (2,4, the 6-trimethylbenzoyl) phosphine oxides (819) of phenyl; tetramethylpiperidone oxide (TMPO); triethyl phosphate (TEPO); they are more satisfactory light triggers; have very high light-initiated activity, the long wave near ultraviolet ray is had absorption, be applicable to the thicker situation of whitewash and film; and have good stability, can variable color or fade.
Carry the Hydrogen initator: carry the Hydrogen initator and mainly contain benzophenone and thioxanthones etc.Wherein at 380-420nm, and absorbability and hydrogen-taking capacity are strong, have higher efficiency of initiation at the maximum absorption wavelength in black light district for thioxanthone photoinitiator.Carrying the Hydrogen initator must have hydrogen donor as collaborative composition, otherwise efficiency of initiation is too low, so that can not be put to use.Than more likely extracting hydrogen on the secondary carbon or on the methyl, the hydrogen that is connected on the hetero-atoms such as oxygen or nitrogen more easily extracts than the hydrogen on the carbon atom triplet state carbonyl free radical from the tertiary carbon of hydrogen donor molecule.This class hydrogen donor has amine, hydramine (triethanolamine, methyl diethanolamine, triisopropanolamine etc.), mercaptan, N, the N-diethyl-and to the dimethylamino benzamide.
The benzophenone light initiation system, benzophenone need to be with alcohol, ether or amine and with just making vinyl monomer carry out photopolymerization.Mainly comprise: benzophenone, the thia anthraquinone, Michler's keton, dimethoxy benzene acetophenone (DMPA), alpha-hydroxy-2,2 dimethyl acetophenones (1173), Alpha-hydroxy cyclohexyl-phenyl ketone (184), α-amine alkyl phenones, 2-methyl isophthalic acid (4-first coloured glaze base phenyl)-2-morpholinyl acetone (MMMP), 2 ' 2-dibenzamidodiphenyl disulfide (DBMD), (4-dimethylamino phenyl)-(1-piperidyl)-ketone, isopropyl thioxanthone (ITX), (4-dimethylamino phenyl)-(4-morpholinyl)-ketone, 2-hydroxy-2-methyl-1-phenyl-1-phenyl-1-acetone, two phenoxy group benzophenone, hydroxy-2-methyl phenyl-propane-1-ketone.And mixed system, as eliminating oxygen in the glued membrane to the benzophenone of the inhibition of Raolical polymerizable and the initiator system that cooperates of uncle's ammonia; Michler's keton and benzophenone are used 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, and also have stability after epoxy resin cooperates, so be widely used in the cationic curing system.But their the most apneusis receipts wavelength does not absorb in the near ultraviolet band in the far-ultraviolet region, generally will add light sensitizer, as: radical initiator or light-sensitive coloring agent carry out sensitizing.
This type of initator comprises: xylyl iodine hexafluorophosphate (PI810); hydroxy phenyl salt compounded of iodine (HTIB); 4; the two detergent alkylate iodine hexafluoro antimonates of 4-; the xylyl salt compounded of iodine; diphenyl hexafluoroarsenate salt compounded of iodine; [4-(2-hydroxyl-3-butoxy-1-propoxyl group) phenyl] benzene iodo-hexafluoro antimonate; [4-(to the benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate; [4-(4-benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate; 4-(to the benzoyl thiophenyl) benzene] the phenyl-iodide hexafluorophosphate; 4; 4 '-dimethyl diphenyl salt compounded of iodine hexafluorophosphate (IHT-PI 820); 4; 4 '-the diacetylamino diphenyl iodine hexafluorophosphate; 3; 7 one dinitro dibenzo ring-type salt compounded of iodine and 3; 7 one dinitro dibenzo ring-type bromine salt; the tetrafluoro boric acid diaryl group iodized salt; 3; 3 '-the dinitro diphenyl salt compounded of iodine; 3; 3 '-dinitro diphenyl salt compounded of iodine and several 2; 2 '-two replace (iodine; bromine; chlorine)-5; 5 '-the dinitrophenyl salt compounded of iodine; iodate 2-[2-(3-indolizine) vinyl]-1-methylquinoline salt; iodate 4-(2-benzoxazole)-N-picoline salt; 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate; triaryl phosphine glyoxalidine salt; triaryl phosphine 1; 1 '-dinaphthalene glyoxalidine ring salt; 3; 7-dinitro dibenzo bromine five rings salt; p-methyl benzenesulfonic acid triphenyl sulfosalt; bromination triphenyl sulfosalt; (4-thiophenyl-phenyl) diphenyl sulphur hexafluorophosphate; 4-(thiophenyl) triphenyl sulphur hexafluorophosphate; 3; 3 '-dinitro diphenyl iodine hexafluorophosphate; 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate; the triphenyl sulfosalt; 4-chlorphenyl diphenyl sulphur hexafluorophosphate; 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate; 4-acetamido phenyl diphenyl sulphur hexafluorophosphate; 3-benzoylphenyl diphenyl sulphur hexafluorophosphate; triphenyl sulphur borofluoride; triphenyl sulphur hexafluorophosphate; triphenyl sulphur hexafluoro antimonate; 4-tolyl diphenyl sulphur hexafluorophosphate; the phosphorus hexafluoride triaryl sulfonium salts; the antimony hexafluoride triaryl sulfonium salts; [4-(to the benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate; 1-(4 '-bromo-2 '-luorobenzyl) pyridiniujm; [4-(to the benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate; 4-[4-(p-nitrophenyl formoxyl) thiophenyl] and benzene } the phenyl-iodide hexafluorophosphate; 4-[4-(to methyl benzoyl) thiophenyl] and benzene } the phenyl-iodide hexafluorophosphate; 4-[4-(to methyl benzoyl) phenoxy group] and benzene } the phenyl-iodide hexafluorophosphate; [4-(to the benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate; 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 that develops after two fragrant salt compounded of iodine and three aromatic sulfonium salts, luxuriant molysite ion at first forms the aromatic radical ligand under illumination, produce simultaneously the complex compound with the unsaturated iron of epoxy compounds molecule coordination, the lewis acidic characteristics of this complex compound tool are also followed the complex compound that forms with the coordination of three epoxy compounds molecules, but one of them epoxy compounds open loop forms cation, it can cause cationic ring-opening polymerization, forms polymer.At normal temperatures because the formation of ferrocene salt-epoxy radicals complex, epoxy compounds cationic species needs the time, therefore under the condition that needs to heat in the external world, to improve polymerization speed.
This type of salt comprises: cyclopentadienyl group-iron-benzene salt; cyclopentadienyl group-iron-toluene salt; cyclopentadienyl group-iron-paraxylene salt; cyclopentadienyl group-iron-naphthalene salts; cyclopentadienyl group-iron-biphenyl salt; cyclopentadienyl group-iron-2; 4-dimethyl acetophenone salt; acetyl group-cyclopentadienyl group-iron-paraxylene salt; cyclopentadienyl group-iron-methyl phenyl ethers anisole salt; cyclopentadienyl group-iron-diphenyl ether salt; cyclopentadienyl group-iron-2; 4-diethoxybenzene salt; the ferrocene tetrafluoroborate; the luxuriant iron tetrafluoroborate of toluene; cyclopentadienyl group-iron-methyl phenyl ethers anisole salt; cyclopentadienyl group-iron-diphenyl ether salt; cyclopentadienyl group-iron-1; 4-diethoxybenzene salt; cyclopentadienyl group-iron-chlorobenzene salt; cyclopentadienyl group-iron-(1; the 4-diethoxybenzene) hexafluorophosphate; cyclopentadienyl group-iron-diphenyl ether hexafluorophosphate; 1; 10-phenanthrolene ferrous perchlorate salt; 1; 10-phenanthrolene ferrous sulfate cyclopentadienyl group-iron-methyl phenyl ethers anisole salt; cyclopentadienyl group-iron-diphenyl ether salt; [1; 1 '-two (diphenylphosphine) ferrocene] Nickel Chloride; vinyl ferrocene; N; N '-di-ferrocene methylene butanediamine quaternary ammonium salt; ferrocene formamide; ferrocene acyl propionic acid; ferrocenyl methyl ketone; ethyl dicyclopentadienyl iron; Butyrylferrocene; butyl ferrocene; N; N-dimethyl-amine methyl ferrocene; 1; 1 '-the dibenzoyl ferrocene; (3-carboxyl propionyl group) ferrocene; 1,1 '-the dibromo ferrocene; Aminoferrocene.
The light trigger of macromolecule loading: in the photocuring system, light trigger often is not to exhaust fully 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 with the light trigger producing high-molecular.The relatively low molecular initator of the initator of producing high-molecular has following advantage: A, energy transfer and intermolecular reaction become and be more prone in polymer chain, make the high-molecular optical initator have higher activity.B, by with nonactive group copolymerization, regulates and the distance of design photosensitive group, or change the distance of optical active group and main chain, thereby acquisition has different photoactive initators.C, can introduce different optical active groups 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, since most of photolysis debris still be connected on the 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 the 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 the tetraacrylate.
The compatibility of various light triggers also is a research direction in recent years, re-uses through behind the compatibility, both can reduce cost, can enlarge again the zone of absorbing wavelength, improves the absorption of ultraviolet radiation energy, thereby obtains good solidification effect.The compatibility of light trigger both can be between the same type, as be both free radical type, for example the new Irgacure-1700 that releases of Ciba be exactly by 25% (2,4,6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO) and 75% alpha-hydroxy-2,2 dimethyl acetophenones (1173) 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, such as light trigger compatibility free radical type and cationic, for example, triaryl thiaxanthene salt and benzophenone are cooperated, the curing rate of epoxy compounds is 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 the 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 the ultraviolet photo-curing cementing agent, such as plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent etc.Although their shared components in adhesive are few, sometimes processing characteristics or the adhesive property of glue produced vital effect.Such 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, behind ultraviolet light polymerization, place under the environment of 80～100% humidity, find to change after 1 year, and if do not add coupling agent, under the same terms, just white erosion occurs in the bonded part after 2 days, glue-line strips down fully after the week.
Plasticizer comprises: diisooctyl azelate (DIOZ), dioctyl azelate (DOZ), phthalic acid two is ester (DHP), separate two dioctyl phthalates (DOS), hexanedioic acid dioctyl ester (DOA), diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), dibutyl phthalate (DBP), dipropyl phthalate (DAP), three vinyl butyl ether base phosphates, polyvinyl butyral resin, tributyl 2-acetylcitrate, repefral (DMP), diethyl phthalate (DEP), hexanedioic acid two (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), 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 (PROCESS OIL637), soybean oil, naphthenic processing oil (310), W150 softening oil (petroleum hydrocarbon, hydrogenation artificial oil), zirconium aluminium is coupling agent, WB215 (aliphatic acid 18%; Fatty acid ester 52%; Calcium carbonate 20%).
Coupling agent is the material that a class has the both sexes structure, and a part of group in their molecules can react with the chemical group on inorganic matter surface, forms strong chemical bonding; Another part group then has close organic character, can twine with reactive organic molecule or physics, thus the material strong bonded that two kinds of character are varied in size.The coupling agent of present industrial use is divided into silanes, acyl esters of gallic acid, zirconium class and Organic Chromium complex compound four large classes by chemical constitution.Wherein using more in adhesive is silanes, such as the 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, the aminopropyl silsesquioxane, γ-methacryloxypropyl trimethoxy silane, the chain alkyl trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-chloropropyl triethoxysilane, two-(the silica-based propyl group of γ-triethoxy), anilinomethyl triethoxysilane, N-β (aminoethyl)-γ-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 the flow leveling that improves 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 to prevent from and eliminate coating producing bubble in manufacturing and use procedure, prevents that coating from producing the disadvantages such as pinprick.Phosphate, fatty acid ester and organosilicon etc. can be made defoamer.Tributyl phosphate is specifically arranged, dibutylphosphoric acid ester, phosphate foam inhibitor (AD-14L), froth breaking king (FAG470), defoamer (FAG470), defoamer (BYK-141), defoamer (BYK 037), three (butoxyethyl group) phosphate, triethyl phosphate, the Tributyl phosphate ester, triethyl phosphate, tricresyl phosphate chloro isopropyl ester, three butoxy ethyl ester of phosphoric acid, the mixture of polyoxyethylene polyoxypropylene and glycol or three alcohol ethers (light yellow to the water white transparency thick liquid), dimethyl silicone polymer, glycerine polyethenoxy ether (GP330), laureth, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, 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 to reduce polymerization occurs when depositing, and improves the storage stability of resin.Polymerization inhibitor commonly used generally is divided into molecule-type polymerization inhibitor and stabilized free fundamental mode polymerization inhibitor, the former mainly contains: hydroquinones, 1,4-benzoquinone, phenothiazine, the beta-phenyl naphthylamines, p-tert-butyl catechol, methylene blue, three (N-nitroso-N-Phenylhydroxylamine) aluminium salt, stannous chloride, 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-, 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), hydroquinones, allyl acetate, MEHQ (MEHQ), the NO free radical piperidine alcohols, phosphorous acid (2,2,6, the 6-tetramethyl piperidine nitrogen oxygen free radical) mixed ester, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen radical (TMHPHA), 8% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt: 92% 2-phenolic group ethoxy propylene acid esters, 4% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt, 96% ethyoxyl list oil triacrylate, MEHQ hydroquinone monomethyl ether, the polymerization inhibitor mantoquita, adjacent methyl hydroquinone, 2,6-di-t-butyl cresols, the dimethyl hydroquinones, p-tert-butyl catechol (TBC), catechol, p methoxy phenol, 2.6-BHT, 2.5-di-tert-butyl hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, 1.4-naphthoquinones, phenthazine, TBHQ (TBHQ), o-sec-butyl-4,6 dinitrophenol (DNBP), ethylene glycol ether, the benzene sulfonamide amine acid salt, 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, the 5-ditert-butylhydro quinone, adjacent methyl is to benzene two adjacent methyl 1,4-benzoquinone, 3-tertiary butyl-4-hydroxyanisol (BHA), 2,6-dinitro-p-cresol (DNPC), polyvinyl acetal, the NO free radical piperidine alcohols, 4,6-dinitro o sec-butyl phenol, DMSS (DMSS), propilolic alcohol.
Thixotropic agent adds in the resin, can make resin adhesive liquid that higher denseness is arranged when static, becomes 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).Then with cellulose derivatives such as hydroxyethylcelluloses, polyvinyl alcohol, polyacrylic acid, poly(ethylene oxide), polymethylacrylic acid, Lauxite, melamine resin, resol, phenolic resins water-soluble resin are thickener in water-based system.
The effect of filler is the Partial Replacement binding agent, reduces the consumption of binding agent, to reach the effect of filling, reinforcement, anti-attrition and reduction cost.Filler requires particle carefully to spare, and can be scattered in equably in the slurries, and is good to binding agent and other component associativities.The consumption of filler should be suitable, otherwise also can affect the serous coat quality.Comprise inorganic mineral bentonite acrylonitrile-butadiene rubber (NBR), potassium aluminosilicate sodium (nepheline), calcium carbonate, moisture Petimin [Mg
3[Si
4O
10] (OH)
2], wollastonite (CaSiO
3), muscovite [KAl
2(AlSi
3O
10) (OH)
2)], phlogopite [KMg
3(AlSi
3O
10) (F, OH)
2], magnesium silicon muscovite [K
2((Fe
2+ Mg) (Fe
3+ Al)
3(Si
7AlO
20) (OH)
4)], montmorillonite [Na
x(H
2O)
4{ (Al
2-xMg
0.33) [Si
4O
10] (OH)
2], bentonite [Na
x(H
2O)
4(Al
2-xMg
0.83) (Si
4O
10) (OH)
2], kaolin, red mud (Al
1-xO
x), calcium sulfate, acrylate high polymer, butyl polyacrylate, polyurethane.
Dispersant impels material particles to be dispersed in the medium, forms the reagent of stable suspension.Dispersant generally is divided into inorganic dispersant and organic dispersing agent two large classes.Inorganic dispersant commonly used has silicates (for example waterglass) and alkali metal phosphonates (Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium, Amino Trimethylene Phosphonic Acid potassium, HEDP sodium, the HEDP disodium, HEDP four sodium, HEDP potassium, ethylene diamine tetra methylene phosphonic acid five sodium, diethylene triamine pentamethylene phosphonic five sodium, diethylenetriamine pentamethylene phosphonic acids seven sodium, diethylene triamine pentamethylene phosphonic sodium, 2-phosphonic acids butane-1,2,4-tricarboxylic acids four sodium, hexamethylene diamine tetramethyl fork phosphonic acids sylvite, two 1,6 hexylidene triamine, five methylenephosphonic acid sodium, the trimerization Alendronate, calgon and sodium pyrophosphate etc.).Organic dispersing agent comprises triethyl group hexyl phosphonic acids; Amino Trimethylene Phosphonic Acid; HEDP (HEDP); ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS); ethylene diamine tetra methylene phosphonic acid (EDTMPA); diethylene triamine pentamethylene phosphonic (DTPMP); 2-phosphonic acids butane-1; 2; 4-tricarboxylic acids (PBTCA); PAPE (PAPE); 2-HPAA (HPAA); hexamethylene diamine tetramethyl fork phosphonic acids (HDTMPA); polyamino polyether base methylenephosphonic acid (PAPEMP); two 1,6 hexylidene triamine, five methylenephosphonic acids (BHMTPMPA); lauryl sodium sulfate; polyacrylic acid (PAA); Sodium Polyacrylate (PAAS); HPMA (HPMA); maleic acid-acrylic acid copolymer (MA-AA); acrylic acid-2-acrylamide-2-methyl propane sulfonic 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); the base amylalcohol; cellulose derivative; polyacrylamide; guar gum; fatty acid polyethylene glycol ester etc.
Antioxidant belongs to the category of anti-oxidant reagent to suppress the fluoropolymer resin thermal oxidative degradation as the auxiliary agent of major function.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 has again the title of " peroxy radical capturing agent " and " chain termination type antioxidant " to catch the polymer peroxy radical as major function, relates to aromatic amine compounds and hindered phenol compound two large series of products.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, three grades of butyl of 6--4-methylphenol, two (3, three grades of butyl of 5--4-hydroxy phenyl) thioether, four [β-(three grades of butyl of 3,5--4-hydroxy phenyl) propionic acid] pentaerythritol ester; Triphenyl phosphite (TPPi), phosphite ester three (2,4-di-tert-butyl phenyl) ester, pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) dimer and the trimerical compound, 3 of ester, many alkyl bisphenol-A phosphite ester, 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, β-(4-hydroxy phenyl-3, the 5-di-t-butyl) the positive octadecanol ester of propionic acid, 1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-hydroxy benzenes methyl) benzene.Auxiliary antioxidant has the effect of decomposing copolymer per-compound, also claims " peroxide decomposer " to comprise sulfo-dicarboxylic ester class and bi-ester of phosphite, and common and primary antioxidant is used 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-two-n-dodecane mercaptopropionic acid ester, triphenyl phosphate TPP, trisnonyl phenyl phosphite, phosphorous acid octyl group diphenyl.
Heavy metal ion passivator is commonly called as " copper resistant agent ", can the complexing transition metal ions, prevent the oxidative degradation of its catalytic polymerization resin, typical structure such as hydrazide kind compound etc.Recent years, along with going deep into of polymer antioxygen theoretical research, certain variation has also occured 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 the polymer alkyl diradical, is equivalent to set up one in traditional antioxidant system the defence line.This type of stabilizing additive mainly comprises 2-ethyl benzofuran ketone, 2-methyl benzofuranone, Dihydrobenzofuranes ketone, benzofuranone, dibenzopyrone, 3-aryl-benzofuran-2-ones, 3-aryl benzofuranone, 2-aryl Dihydrobenzofuranes ketone, 2-aryl benzofuranone, 5-cyano group-1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 5-replaces 1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 2,3-dihydroxy-2,2-dimethyl-7-benzofuran phenol, 3-(2-acyloxyethoxyphenyl) benzofuran-2-ones, isobenzofuranone, 5-[(imidazo [4,5-b] pyridin-3-yl) methyl] benzofuranone, 1,2,3,4-tetrahydrochysene-benzofuranone, 2,3-dihydro-2-methyl-2-alkyl and furanone, 4-ethyoxyl bisphenol-A-diacrylate, (2-10)-ethoxyquin bisphenol-A-dimethylacrylate, 2-[1-(2-hydroxyl-3,5-two tertiary amyl phenyl)-and ethyl]-4,6-two tertiary amyl phenyl acrylate, bisphenol-A-glycerol double methyl methacrylate, bisphenol-A-dimethylacrylate, 4-ethyoxyl bisphenol-A-dimethylacrylate, N, the N-dibenzyl hydroxylamine, N-ethyl-N-aminoethyle alcohol, N, the N-diethyl hydroxylamine, IPD acrylamide HAS, isopropylhydroxyla, hydroxylamine hydrochloride, the chlorination hydroxylammonium, hydrogen chlorine azanol, N-methyl-azanol, acetohydroxamic acid, the N-hydroxyl acetamide.
Modifier is intended to improve plasticizing capacity, improves the resin melt viscoelasticity and promotes the modified additive that resin melting flows, and this analog assistant is 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 mainly is included as cationic surfactant and anion surfactant.Cationic surfactant has: the alkyl phosphate diethanolamine salt, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, stearmide, stearoyl dimethyl-penten ammonium chloride, N, two (2-ethoxy)-N-(3 '-dodecyloxy-2 '-hydroxypropyl) the first ammonium Methylsulfate salt of N-, trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, N, N-cetyl ethyl morpholine ethyl-sulfate salt, (dodecanamide propyl trimethyl ammonium) Methylsulfate salt dibrominated N, N-two (octadecyl dimethyl)-3-oxa--1,5-penta 2 ammoniums, styrene polymer type quaternary ammonium salt, the palmitate quaternary ammonium salt, the alkylphenol-polyethenoxy based quaternary ammonium salt, dialkyl quaternary ammonium salt, the polyacrylamide quaternary ammonium salt, octadecyl dimethyl ethoxy quaternary ammonium nitrate, ammonium polystyrene sulphonate salt, propyl-dimethyl-beta-hydroxyethyl nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, 2,2 '-nitrilo-di-methylcarbinol and the poly-(oxygen-1 of α-three decyls-ω-hydroxyl, 2-second two bases) polymer of phosphate, the polyethylene glycol tridecyl ether phosphate, diethanolamine salt, the oleic acid diethanolamine salt, triethanol amine oleate, ethoxylated amine, N, N-dihydroxy ethyl octadecylamine, N, the N-dihydroxyethyl p-toluidine, the alkylphenol-polyethenoxy based quaternary ammonium salt, ethoxyl quaternary ammonium salt, the fluorine-containing quaternary ammonium salt of oxa-; Anion surfactant has: the 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.
The negative and positive amphoteric surfactant comprises: dodecyl-dimethyl quaternary ammonium second inner salt, dodecyl dimethyl quaternary ammonium second inner salt, alkyl dihydroxy ethyl ammonium second inner salt, the N-alkylaminoacid salts, epoxy tripolymer acid inner salt, carboxybetaine, tridecyl dimethyl (2-sulfurous acid) ethyl ammonium second inner salt, N-dodecyl alanine, the 3-chloro propyl amine hydrochloric acid salt, N-tertbutyloxycarbonyl-D-3-(2-naphthyl)-alanine, N-tert-butoxycarbonyl-D-2-naphthylalanine, tertbutyloxycarbonyl-D-2-naphthylalanine, tertbutyloxycarbonyl-D-3-(2-naphthyl)-alanine, N-tertbutyloxycarbonyl-L-2-trifluoromethyl-phenylalanine, glyphosate isopropyl amine salt.
Polymer Antistatic Agent comprises: poly(ethylene oxide) (PEO), the 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), the amphipathic copolymer that methacrylic acid stearyl (SMA)+polyethylene glycol methacrylate-styrene polymer (PEGMA) forms.
Inorganic combustion inhibitor comprises antimonous oxide, zinc molybdate, zinc oxide, iron oxide, tin oxide, aluminium hydroxide, magnesium hydroxide, antimony oxide, Firebrake ZB and red phosphorus in the fire retardant; Organic fire-retardant comprises deca-BDE, three (2, the 3-dibromopropyl) phosphate, HBCD, poly-2, the 6-dibromobenzene aether, chlorinated paraffin wax, polyphosphate, red phosphorus, two (tetrabromo phthalimide) ethane, the Dowspray 9 homopolymers, melamine, cyanurate, the isodecyl diphenyl phosphoester, ethylhexyl diphenyl phosphate, tricresyl phosphate 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 and insensitive, but have mould sensitivity owing to its goods work in-process has added the material that plasticizer, lubricant, fatty acid soaps class etc. can grow der Pilz.Plastics are a lot of with the chemical substance that mould inhibitor comprises, and more common kind comprises organo-metallic compound (such as organic mercury, organotin, organic copper, organo-arsenic etc.), organic compounds containing nitrogen, organic compounds containing sulfur, organic halogen compound and phenol derivatives etc.Comprising phenol, pentachlorophenol, phenyl mercury oleate, copper 8-quinolinolate, chlorination three second or tributyl tin, copper sulphate, mercury chloride, sodium fluoride.
Sensitizer is to the dimethylamino benzamide; Aminopropyl silsesquioxane and Versamid mass ratio are 3: 1 in the promoter.
Stabilizer is to reduce polymerization occurs when depositing, and improves the storage stability of resin.Stabilizer commonly used has hydroquinones, p methoxy phenol, 1,4-benzoquinone, 2,6-di-t-butyl cresols, phenothiazine, anthraquinone, tertiary amine etc.
Below be specific embodiments of the invention:
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 nano particle is of a size of 10nm, the doping mass ratio of described inorganic light-emitting nano particle is 5%, the organic silicon adhesive of ultraviolet light polymerization comprises polysiloxanes, 2% light trigger and 3% diluent and the auxiliary agent of 95% light sensitivity, and conductive layer 2 adopts graphene films.
The preparation method is as follows:
1. the effects on surface roughness is cleaned less than the nickel foil sheet of 1nm, dries up with drying nitrogen after cleaning;
2. adopt the method for chemical vapour deposition (CVD) to prepare graphene film at the copper foil of cleaning; Its preparation condition comprises: the carbon source that adopts ethane to be, and the chemical vapor deposition growth environment of graphene film is: temperature is under 700 ℃～1000 ℃ the normal pressure or negative pressure;
3. spray the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle at graphene film, the doping mass ratio of described inorganic light-emitting nano particle is 5%, and the organic silicon adhesive of ultraviolet light polymerization comprises polysiloxanes, 2% light trigger and 3% diluent and the auxiliary agent of 95% light sensitivity;
4. ultraviolet light polymerization being carried out on nickel foil sheet surface processed 30 seconds;
5. with graphene film and the organic silicon adhesive layer of the ultraviolet light polymerization of the doping inorganic light-emitting nano particle after solidifying peel off nickel foil sheet surface, form the compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
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 nano particle is of a size of 20nm, the doping mass ratio of described inorganic light-emitting nano particle is 10%, the organic silicon adhesive of ultraviolet light polymerization comprises polysiloxanes, 5% light trigger and 3% diluent and the auxiliary agent of 92% light sensitivity, and conductive layer 2 adopts graphene films.
The 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 the ultraviolet light polymerization of doping inorganic light-emitting nano particle, described inorganic light-emitting nano particle is of a size of 30nm, the doping mass ratio of described inorganic light-emitting nano particle is 15%, the organic silicon adhesive of ultraviolet light polymerization comprises polysiloxanes, 2% light trigger and 6% diluent and the auxiliary agent of 92% light sensitivity, and conductive layer 2 adopts graphene films.
The 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 nano particle is of a size of 40nm, the doping mass ratio of described inorganic light-emitting nano particle is 20%, the organic silicon adhesive of ultraviolet light polymerization comprises polysiloxanes, 0.1% light trigger and 0.4% diluent and the auxiliary agent of 99.5% light sensitivity, and conductive layer 2 adopts graphene films.
The 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 nano particle is of a size of 1nm, the doping mass ratio of described inorganic light-emitting nano particle is 25%, the organic silicon adhesive of ultraviolet light polymerization comprises polysiloxanes, 2% light trigger and 4% diluent and the auxiliary agent of 94% light sensitivity, and conductive layer 2 adopts graphene films.
The 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 nano particle is of a size of 50nm, the doping mass ratio of described inorganic light-emitting nano particle is 30%, the organic silicon adhesive of ultraviolet light polymerization comprises polysiloxanes, 1% light trigger and 3% diluent and the auxiliary agent of 96% light sensitivity, and conductive layer 2 adopts graphene films.
The 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 nano particle is of a size of 60nm, the doping mass ratio of described inorganic light-emitting nano particle is 35%, the organic silicon adhesive of ultraviolet light polymerization comprises polysiloxanes, 2% light trigger and 1% diluent and the auxiliary agent of 97% light sensitivity, and conductive layer 2 adopts graphene films.
The 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 nano particle is of a size of 100nm, the doping mass ratio of described inorganic light-emitting nano particle is 40%, the organic silicon adhesive of ultraviolet light polymerization comprises polysiloxanes, 1.6% light trigger and 0.4% diluent and the auxiliary agent of 98% light sensitivity, and conductive layer 2 adopts graphene films.
The 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 nano particle is of a size of 80nm, the doping mass ratio of described inorganic light-emitting nano particle is 35%, the organic silicon adhesive of ultraviolet light polymerization comprises polysiloxanes, 0.4% light trigger and 0.6% diluent and the auxiliary agent of 99% light sensitivity, and conductive layer 2 adopts graphene films.The preparation method is similar to embodiment 1.
Claims (8)
1. substrate used in luminescent device, comprise flexible substrate and conductive layer, it is characterized in that, described conductive layer is graphene film, described flexible substrate is the organic silicon adhesive of the ultraviolet light polymerization of doping inorganic light-emitting nano particle, and 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. flexible illuminating substrate according to claim 1 is characterized in that, described inorganic light-emitting nanoparticle size is 1～100nm, and the doping mass ratio of described inorganic light-emitting nano particle is less than or equal to 40%.
3. substrate used in luminescent device according to claim 1, it is characterized in that, described phosphor is take sulfide, oxide, fluoride, phosphate, vanadate, niobates, aluminate or molybdate as luminous host, with the light-emitting particles of rare earth lanthanide as activator or 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 and praseodymium.
5. flexible illuminating substrate according to claim 1, it is characterized in that, the polysiloxanes of described light sensitivity comprises mercaptan alkene functional polysiloxanes, acroleic acid esterification polysiloxanes, epoxy-functional polysiloxanes, styryl polysiloxanes and 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 and benzoin isopropyl ether, acetophenones, benzophenone and 2 hydroxyls, 2 methyl, 1 phenylacetone, alkyl phenyl ketone, α 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. the preparation method of a substrate used in luminescent device is characterized in that, may further comprise the steps:
1. the effects on surface roughness is cleaned less than the rigid substrates of 1nm, dries up with drying nitrogen after cleaning;
2. adopt the method for chemical vapour deposition (CVD) to prepare graphene film at the rigid substrates of cleaning, its preparation condition comprises: the carbon source that adopts is one or more in methane, ethane, propane, butane, methyl alcohol, the ethanol, and the chemical vapor deposition growth environment of graphene film is: temperature is under 700 ℃～1000 ℃ the normal pressure or negative pressure;
3. the organic silicon adhesive of the ultraviolet light polymerization of spin coating or spraying doping inorganic light-emitting nano particle on graphene 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;
4. ultraviolet light polymerization being carried out on the rigid substrates surface processed 30 seconds;
5. the organic silicon adhesive layer of the doping inorganic light-emitting nano particle after graphene film and the curing is peeled off the rigid substrates surface, form the compliant conductive substrate;
6. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
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| CN102593372A (en) * | 2012-03-21 | 2012-07-18 | 吉林大学 | Flexible top-emitting organic electroluminescent device having ultra-smooth anode |
| CN104505148B (en) * | 2014-11-13 | 2017-09-29 | 中国科学院重庆绿色智能技术研究院 | A kind of preparation method of the three-dimensional coplanar shape graphene film of flexible base |
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| CN101901640A (en) * | 2010-06-21 | 2010-12-01 | 南京邮电大学 | Method for preparing flexible and transparent conductive graphene membrane |
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