CN102208563B - Substrate for flexible luminescent device and preparation method thereof - Google Patents

Substrate for flexible luminescent device and preparation method thereof Download PDF

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CN102208563B
CN102208563B CN 201110096755 CN201110096755A CN102208563B CN 102208563 B CN102208563 B CN 102208563B CN 201110096755 CN201110096755 CN 201110096755 CN 201110096755 A CN201110096755 A CN 201110096755A CN 102208563 B CN102208563 B CN 102208563B
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cementing agent
ultraviolet photo
curing cementing
agent
curing
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CN102208563A (en
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于军胜
陈苏杰
王娜娜
蒋亚东
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University of Electronic Science and Technology of China
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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 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 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 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

A kind of substrate used in luminescent device and preparation method thereof
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.
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.For flexible substrate, because the profile pattern of flexible substrate is far away from rigid substrate, 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; The water of flexible substrate, oxygen permeability cause opto-electronic device to be subjected to the water effect of oxygen that sees through from substrate much larger than rigid substrate, have reduced performance of devices.
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 among (1) ITO has severe toxicity, and is harmful in preparation and application; (2) In among the 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) phenomenon that conductivity descends can appear because of the bending of flexible substrate in the ito thin film on 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 the nano silver wire film has the electrode material that higher conductivity and visible light transmissivity have become potential replaced ITO, but there is the poor shortcoming of adhesion between surface roughness large and nano silver wire film and the flexible substrate in the nano silver wire film, has reduced the performance based on the opto-electronic device of nano silver wire membrane electrode.
Therefore, if can solve above-mentioned these problems, will make opto-electronic device obtain using more widely and more fast development.
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 the flexible substrate, has improved adhesion between the evenness of nano silver wire film surface and nano silver wire film and the 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, described flexible substrate and conductive layer are made of a kind of in the following dual mode: 1. described flexible substrate is ultraviolet photo-curing cementing agent, described conductive layer is the nano silver wire film, is filled with the inorganic light-emitting nano particle in the space of described nano silver wire film; 2. described flexible substrate is the ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle, described conductive layer is the nano silver wire film, be filled with the ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle in the space of described nano silver wire film, described ultraviolet photo-curing cementing agent comprises free radical type ultraviolet photo-curing cementing agent, cation type ultraviolet photo-curing cementing agent and their mixed system.
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 the kind mode 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 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 mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 10: 1～1: 10 in the mixed system of described free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described free radical type ultra-violet curing adhesive comprises the component of following mass percent: 90～99.5% base resin, 0.2～3% monomer, 0.1～3% light trigger and 0.2～6% sensitising agent and auxiliary agent; Described cation type ultraviolet photo-curing cementing agent comprises the component of following mass percent: 90～99.5% cationic monomer, 0.4～8% diluent and 0.1～3% cation light initiator.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described base resin comprises unsaturated polyester resin, acrylic resin and polythiol-polyenoid system; Described monomer comprises Styrene and its derivatives, simple function group or polyfunctional group acrylic acid; Described light trigger comprises benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether, the pure and mild acetophenone derivative of benzoin isopropyl; Sensitising agent comprises benzophenone, thia anthraquinone and Michler's keton, and auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, crosslinking agent, fire retardant and coupling agent; Described cationic monomer comprises various epoxy resin or modified epoxy or fluorine-containing and not fluorine-containing hybrid resin or aliphat and bis-phenol D-type blending epoxy; Described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin and various ring ether, cyclic lactone, vinyl ether monomers; Described cation light initiator has iodine triaryl salt compounded of iodine, triaryl sulfonium salts and triaryl selenium salt.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described acrylic resin comprises polyester-acrylate, epoxy-acrylate, carbamate-acrylate and polyethers-acrylate.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described polythiol-polyenoid system comprises following four kinds of materials:
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 glass or silicon chip) of 1nm, dries up with drying nitrogen after cleaning;
2. take the mode of spin coating or spraying or self assembly or inkjet printing or silk screen printing at the substrate preparation nano silver wire film of cleaning;
3. the ultraviolet photo-curing cementing agent layer of spin coating or spraying doping inorganic light-emitting nano particle on the nano silver wire film, or first spin coating or drip and to be coated with or to spray the solution that contains the inorganic light-emitting nano particle, again spin coating or spraying ultraviolet photo-curing cementing agent layer, described ultraviolet photo-curing cementing agent comprises free radical type ultraviolet photo-curing cementing agent, cation type ultraviolet photo-curing cementing agent and their mixed system;
4. ultraviolet light polymerization being carried out on the rigid substrates surface processed 30 seconds;
5. the ultraviolet photo-curing cementing agent layer after nano silver wire film and the curing or the ultraviolet light polymerization jelly layer of doping inorganic light-emitting nano particle are 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: have the inorganic light-emitting nano particle in the conductive layer of the present invention, make conductive layer luminous under the 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 the nano silver wire that conductive layer adopts can improve the luminous intensity of inorganic light-emitting nano particle, further increased the luminous intensity based on the luminescent device of this substrate simultaneously; Conductive layer of the present invention prepares at the little rigid substrates of roughness, be filled with the ultraviolet photo-curing cementing agent of inorganic light-emitting nano particle or doping inorganic light-emitting nano particle in the conductive layer space, form the conductive layer of flexible base, board by the method for peeling off, improved the evenness of conductive layer surface; Ultraviolet photo-curing cementing agent 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 1-18;
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.
Flexible substrate 1 is the support of conductive layer among the present invention, it has preferably bending performance, the ability that the infiltration of certain anti-steam and oxygen is arranged, good chemical stability and thermal stability are arranged, conductive layer 2 requires to have good conductive capability, flexible substrate and conductive layer are made of following dual mode: 1. described flexible substrate is ultraviolet photo-curing cementing agent, and described conductive layer is the nano silver wire film, is filled with the inorganic light-emitting nano particle in the space of described nano silver wire film; 2. described flexible substrate is the ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle, described conductive layer is the nano silver wire film, be filled with the ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle in the space of described nano silver wire film, described ultraviolet photo-curing cementing agent comprises free radical type ultraviolet photo-curing cementing agent, cation type ultraviolet photo-curing cementing agent and their mixed system.
Each composition among the present invention in free radical type ultraviolet photo-curing cementing agent and the cation type ultraviolet photo-curing cementing agent is described as follows:
Base resin: comprise unsaturated polyester resin, acrylic resin and polythiol-polyenoid system.
Unsaturated polyester resin: unsaturated polyester (UP) is by the mixed linear polyesters that reacts and make under the effect of initator with fractional saturation binary acid (or acid anhydrides) and dihydroxylic alcohols of undersaturated binary acid (or acid anhydrides).In its molecular structure, there is undersaturated vinyl monomer to exist, if with active vinyl monomer and the undersaturated vinyl monomer copolymerization of this class, crosslinking curing and become three-dimensional-structure then.In general, the adhesive that is got by this resin since in the solidification process volume contraction larger, the internal stress of gluded joint is very large.Easily micro-crack occurs and cause splicing power to diminish in the inside of glue-line; Simultaneously, owing to containing ester bond in the macromolecular chain, meet acid, alkali easily is hydrolyzed, thereby resistance to medium and resistance to water are relatively poor, in how easily distortion under the wet environment of high temperature; In addition, its curing rate is slower, therefore, shows relatively poor combination property, therefore mostly use as non-structure glue.By reducing unsatisfied chemical bond content, adopt the low monomer of polymerization shrinkage, adding the means such as inorganic filler and thermal plastic high polymer, can improve its overall performance.
Acrylic resin: this resin system curing rate is fast, studies at present morely.
Polythiol-polyenoid system: specifically comprise following structural formula:
Figure BSA00000475936700051
Simple function group or polyfunctional group acrylic resin: this resin system curing rate is fast, studies at present morely.
Monomer (Styrene and its derivatives etc.) usually and resin be used in conjunction with, one side makes glue have the viscosity of constructability as diluent; Have again on the other hand reactivity, solidify the laggard resin network that enters, the final performance of solidfied material is had certain improvement.The monomer of early application is Styrene and its derivatives, and this class diluent crosslinking rate is slow, volatility is large and poisonous, poor heat resistance.Now, simple function group or polyfunctional group (methyl) acrylate of adopting more, such as methyl methacrylate, ethyl acrylate, acrylic acid propylene glycol ester, n-butyl acrylate etc., the relatively poor problem of adhesive ubiquity thermal endurance of these ester preparations, and also there is the large defective of volatility in the lower ester of some molecular weight.If introduce aromatic rings in the molecular structure, then can improve intensity and the resistance to water of glue, prolong the storage period of glue.Requirement to monomer mainly is: the respond of low viscosity, highly diluted effect and height, also to take into account simultaneously volatility, toxicity and peculiar smell little, and good etc. to the compatibility of resin.In order to regulate various performance parameters, often adopt mix monomer, mix monomer is as follows: free radical activity diluent and cation activity diluent.
The free radical activity diluent is divided into exploitation first generation acrylic acid polyfunctional monomer, the second generation acrylic acid polyfunctional monomer of recent development and more excellent third generation acrylic monomers early.
The simple function reactive diluent has: styrene, NVP, Isooctyl acrylate monomer, hydroxy-ethyl acrylate and isobornyl acrylate, methacrylate phosphate and isobornyl methacrylate, latter two is the good toughness reinforcing monomer of plasticising.
The difunctionality reactive diluent has: triethylene glycol diacrylate, tripropylene glycol diacrylate, glycol diacrylate, polyethylene glycol diacrylate alcohol ester, neopentylglycol diacrylate and propoxyl group neopentylglycol diacrylate, the acrylate-functional monomer mainly contains 1,6-hexanediyl ester (HDDA), 1,4-butanediol diacrylate (BDDA), propylene glycol diacrylate (DPGDA), glycerol diacrylate (TPGDA), the trihydroxy methyl propane triacrylate (TMPTA) of trifunctional, pentaerythritol triacrylate (PETA), trihydroxy methyl propane triol triacrylate (TMPTMA), trimethylolpropane triacrylate, propoxylation trihydroxy methyl propane triacrylate, pentaerythrite three propylene alcohol esters, pentaerythritol propoxylate propylene alcohol ester, N, N-dihydroxy ethyl-3 amido methyl propionate, triethylene glycolbismethyl-acrylate, long-chain fat hydrocarbon glycidol ether acrylic acid, the resorcinol bisglycidyl ether, double pentaerythritol C5 methacrylate, tri (propylene glycol) diacrylate, phthalic acid diethanol diacrylate (PDDA).They have replaced active little first generation acrylic acid monofunctional monomer.But along with the develop rapidly of ultra-violet curing technology, they reveal the large shortcoming of the excitant of skin.
Second generation acrylic acid polyfunctional monomer mainly is to introduce ethyoxyl or propoxyl group in molecule, has overcome the large shortcoming of excitant, also should have higher activity and state of cure.Such as ethoxylation trihydroxy methyl propane triol triacrylate [TMP (EO) TMA], propoxylation trihydroxy methyl propane triol triacrylate [TMP (PO) TMA], propoxylation glycerol triacrylate [G (PO) TA].Third generation acrylic monomers is mainly the acrylate that contains methoxyl group, preferably resolves the contradiction of high curing rate and shrinkage, low state of cure.This class material has 1,6-hexylene glycol methoxyl group mono acrylic ester (HDOMEMA), ethoxylation neopentyl glycol methoxyl group mono acrylic ester [TMP (PO) MEDA].After introducing alkoxyl in the molecule, can reduce the viscosity of monomer, reduce simultaneously the excitant of monomer.
The introducing of alkoxyl is also improved a lot to the compatibility of diluent monomer, and vinyltriethoxysilane (A15I), gamma-methyl allyl acyloxypropyl trimethoxysilane (A174) can be used as monomer.
Cruel in various active epoxy diluent resins and various cyclic ethers, the ring, vinyl ether monomers etc. can be as the diluent of cation photocuring resin.Therein ethylene pyridyl ethers compound and oligomer curing rate are fast, modest viscosity, tasteless, nontoxic, can be used in conjunction with epoxy resin.Vinyl ether monomers has: 1,2,3-propanetriol-diglycidyl-ether (EPON-812), triethylene glycol divinyl ether (DVE-3), BDO vinyl ethers (HBVE), cyclohexyl vinyl ether (CHVE), perfluoro methyl vinyl ether (PMVE), the perfluor n-propyl vinyl ether, IVE, hydroxy butyl vinyl ether, vinyl ethyl ether, ethyl vinyl ether, the ethyl vinyl ether propylene, ethylene glycol monoallyl ether, hydroxy butyl vinyl ether, butyl vinyl ether, chlorotrifluoroethylene (CTFE), triethylene glycol divinyl ether, methoxy ethylene, vinyl butyl ether, dodecyl vinyl (DDVE), cyclohexyl vinyl ether, tribenzyl-benzene phenol polyethenoxy base ether, tetrafluoroethene-perfluoro propyl vinyl ether, tetrafluoroethene-perfluoro propyl vinyl ether, tert-Butyl vinyl ether:
The oxygen compound monomer has: 3,4-epoxy radicals hexahydrobenzoid acid-3 ', 4 '-epoxy radicals cyclohexyl methyl esters (ERL-4221), bisphenol A type epoxy resin (EP), epoxy acrylate, epoxy vinyl ester, acrylic acid epoxy ester, epoxymethacrylate, water-soluble itaconic acid epoxy ester resin:
Figure BSA00000475936700072
Figure BSA00000475936700081
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 type 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 acetamido 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-two-methyl-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.
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), 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 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.
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 one di-t-butyl cresols, phenothiazine, anthraquinone etc.
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) (F, OH) 2), magnesium silicon muscovite [K 2((Fe 2+ Mg) (Fe 3+ Al) 3(Si 7AlO 20) (OH) 4)], montmorillonite [Na x(H 2O) 4{ (Al 2-xMg 0.33) [Si 4O 10] (OH) 2)], bentonite [Na x(H 2O) 4(Al 2-xMg 0.83) (Si 4O 10) (OH) 2], rilanit special, fumed silica, metallic soap (lead stearate, barium, cadmium, calcium, zinc, magnesium, aluminium, rare earth).Then with cellulose derivatives such as hydroxyethylcelluloses, 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) (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], 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.
Figure BSA00000475936700171
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.
Cationic photocuring system mainly utilizes the photodissociation under the ultraviolet ray irradiation of aromatic series diazol, aromatic series salt compounded of iodine, aromatic series sulfonium salt to produce Bronsted acid, and Bronsted acid again trigger monomer carries out cationic polymerization.Compare with the radically curing system, if it have cure shrinkage little, be not subjected to the inhibition of various oxygen and do not have nucleophilic impurity to exist, in case cause the polymerization advantage such as will continue for a long time.But the Bronsted acid that light trigger discharges when irradiation can produce corrosiveness to cementing matrix.In theory, all monomers that can carry out cationic polymerization may be used to cationic curing, and still, at present the most frequently used is various epoxy resin or modified epoxy.Various active epoxy diluent resins and various cyclic ethers, cyclic lactone, vinyl ether monomers etc. can be as the diluents of light-cured resin, and cation light initiator has diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts, triaryl selenium salt etc.At present, more and more round the research of this system, for example there is report to utilize fluorine-containing and not fluorine-containing hybrid resin to cause at above-mentioned cationic initiator, made the adjustable accurate adhesive of low-shrinkage and refractive index; In disc making, the adhesive that the epoxy resin that utilizes cation to cause makes is that the non-corrosive phenomenon of 96h occurs under 95% the experiment condition at 85 ℃, relative humidity; When the assembling of hollow devices, the aliphat and the bis-phenol D-type blending epoxy that utilize sulfonium salt to cause can make low linear expansion coefficient and have the adhesive of good moisture resistance.
2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide (TPO); the luxuriant molysite of virtue, organic aluminium compound/silane systems, dialkyl benzene acid methyl sulfosalt; the reaction of the cation photocuring of triaryl sulphur hexafluorophosphate cation light initiator-tung oil-modified novolac epoxy resin (TMPE) and E-44 epoxy resin compound system. studied various conditions to the impact of laser curing velocity by the mensuration of gel fraction, and coating structure before and after this reaction system photocuring reaction that utilized infrared spectrum analysis.The result shows, the kind of light trigger and concentration can change laser curing velocity effectively, and the initiating activity of Omnicat 550 is better than Omnicat 432 and proportional with its concentration; The punishment of the photoactivate such as anthracene, BPO has certain sensibilization to system, and the phenthazine effect is not obvious; Different types of epoxy and vinyl ethers reactive diluent have considerable influence to laser curing velocity; Increase laser curing velocity increase along with epoxide group concentration in the resin proportioning; This diagram of system reveals " rear curing " phenomenon.
Light-initiated not ideal enough, curing rate is slow because light-initiated IONENE G cording has, the high in cost of production defective, limited it in industrial popularization, someone is unified in one with the cationic polymerization of epoxy resin and the radical polymerization of acrylate, both reached the purpose that takes full advantage of luminous energy, reached again the purpose of mutual modification, its cured product has been concentrated epoxy resin and acrylate advantage separately, has overcome again some defective simultaneously, has started a brand-new system.With benzhydryl iodine hexafluorophosphate (DPI.PF 6) make light trigger, cause bisphenol A epoxide resin E 51Made with the hybrid resin of acrylic ester prepolymer AE that low viscosity, curing time are short, the good adhesive of high, water-fast the boiling property of bonding layer shear strength, the advantage of epoxy resin and acrylate is all shown up.Below enumerated the composition of several mixed systems:
1, epoxy resin E-51 (bisphenol-A (2, and the epoxychloropropane linear polymer that polycondensation is synthesized in alkaline medium two (4-hydroxy phenyl) propane of 2-)), (51 represent the representative fraction 50% of epoxy), diaryl group iodized salt (CD-1012), the cationic photopolymerization initiator system that sensitising agent diisopropyl thiazolone (ITX) forms.
2, bisphenol A epoxide resin (epoxy resin 128), cationic initiator sulphion hexafluorophosphate (6992) and sulphion hexafluoro antimonate (6976) are sulfosalt, reactive diluent butyl glycidyl ether (669), long carbochain glycidol ether (114), carboxylic monomer (0200), the polycaprolactone polyol of two senses and trifunctional (0301).
3, one methacrylate/glycidyl methacrylate copolymer is grafted on the polyurethane, in amine and after make self-emulsifying type acrylic resin grafted polyurethane, strengthened the compatibility of polyurethane and acrylic resin, improved the cost performance of resin.
4, tetraethylene-glycol dimethylacrylate, tetraethylene-glycol dimethylacrylate are respectively with 3,4-epoxycyclohexyl methyl-3 ', 4 '-the epoxycyclohexane carboxylate mixing, light trigger is Alpha-hydroxy cyclohexyl benzophenone (Irgacure 184), 2,2-dimethoxy-2-phenyl acetophenone (Irgacure 651), dimethoxybenzoin, hexafluorophosphoric acid diphenyl iodnium.
5,2-ethylene glycol allyl ether and epoxy acrylic resin (CG602) mixture, cationic photoinitiator xylyl salt compounded of iodine or radical photoinitiator 2,2-dimethoxy-2-phenyl acetophenone (Irgacure651) or 2-hydroxy-2-methyl propiophenone (Darocur 1173).
6,4-epoxycyclohexyl formic acid-3,4-epoxycyclohexyl methyl ester (CY179), caprolactone trihydroxy alcohol, triaryl sulfonium salts, benzophenone and acrylate monomer.
7, vinyl ethers compound have advantages of that curing rate is fast, viscosity is low, be not afraid of oxygen inhibition, tasteless, nontoxic.The hybrid UV curable paint that forms with acrylic ester oligomer, triethylene Glycol divinyl ether, xylyl salt compounded of iodine, Alpha-hydroxy cyclohexyl benzophenone (Irgacure 184) has that curing rate is fast, solvent resistance good, need not " rear curing " and to characteristics such as polyester base material adhesive force are good.
Below be specific embodiments of the invention:
Embodiment 1
Board structure as shown in Figure 1, flexible substrate 1 adopts the free radical type ultraviolet photo-curing cementing agent, described free radical type ultraviolet photo-curing cementing agent comprises 94% base resin, 1% monomer, 1% light trigger and 4% sensitising agent and auxiliary agent, conductive layer 2 adopts the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 10nm.
The preparation method is as follows:
1. the effects on surface roughness is cleaned less than the silicon substrate of 1nm, dries up with drying nitrogen after cleaning;
2. nano silver wire is dispersed in the solvent, takes the spin coating mode at the silicon substrate preparation nano silver wire film of cleaning, rotating speed is 4000 revolutions per seconds during spin coating, duration 60 seconds, and thickness is about 80 nanometers;
3. the solution that contains the inorganic light-emitting nano particle in the spraying of nano silver wire film, silicon substrate was placed 30 minutes in 80 ℃ environment, remove solvent remaining in the nano silver wire film, again at nano silver wire film spraying free radical type ultraviolet photo-curing cementing agent, described free radical type ultraviolet photo-curing cementing agent comprises 94% base resin, 1% monomer, 1% light trigger and 4% sensitising agent and auxiliary agent;
4. ultraviolet light polymerization being carried out on the silicon substrate surface processed 30 seconds;
5. the free radical type ultraviolet photo-curing cementing agent layer after nano silver wire film and the curing is peeled off the silicon substrate surface, form the 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 free radical type ultraviolet photo-curing cementing agent, described free radical type ultraviolet photo-curing cementing agent comprises 99.5% base resin, 0.2% monomer, 0.2% light trigger and 0.1% sensitising agent and auxiliary agent, conductive layer 2 adopts the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 20nm.
The preparation method is similar to embodiment 1.
Embodiment 3
Board structure as shown in Figure 1, flexible substrate 1 adopts the free radical type ultraviolet photo-curing cementing agent, described free radical type ultraviolet photo-curing cementing agent comprises 91% base resin, 1% monomer, 2% light trigger and 6% sensitising agent and auxiliary agent, conductive layer 2 adopts the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 30nm.
The preparation method is similar to embodiment 1.
Embodiment 4
Board structure as shown in Figure 1, flexible substrate 1 adopts cation type ultraviolet photo-curing cementing agent, described cation type ultraviolet photo-curing cementing agent comprises 99% cationic monomer, 0.5% diluent and 0.5% cation light initiator, conductive layer 2 adopts the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 5nm.
The preparation method is similar to embodiment 1.
Embodiment 5
Board structure as shown in Figure 1, flexible substrate 1 adopts cation type ultraviolet photo-curing cementing agent, described cation type ultraviolet photo-curing cementing agent comprises 90% cationic monomer, 7% diluent and 3% cation light initiator, conductive layer 2 nano silver wire films, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 1nm.
The preparation method is similar to embodiment 1.
Embodiment 6
Board structure as shown in Figure 1, flexible substrate 1 adopts cation type ultraviolet photo-curing cementing agent, described cation type ultraviolet photo-curing cementing agent comprises 91% cationic monomer, 6% diluent and 3% cation light initiator, conductive layer 2 adopts the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 25nm.
The preparation method is similar to embodiment 1.
Embodiment 7
Board structure as shown in Figure 1, flexible substrate 1 adopts the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 10: 1 in the described mixed system, described free radical type ultraviolet photo-curing cementing agent comprises 91% base resin, 3% monomer, 2% light trigger and 4% sensitising agent and auxiliary agent, described cation type ultraviolet photo-curing cementing agent comprises 97% cationic monomer, 2% diluent and 1% cation light initiator, conductive layer 2 adopts the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 35nm.
The preparation method is similar to embodiment 1.
Embodiment 8
Board structure as shown in Figure 1, flexible substrate 1 adopts the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 5: 1 in the described mixed system, described free radical type ultraviolet photo-curing cementing agent comprises 95% base resin, 2% monomer, 2% light trigger and 1% sensitising agent and auxiliary agent, described cation type ultraviolet photo-curing cementing agent comprises 96% cationic monomer, 2% diluent and 2% cation light initiator, conductive layer 2 adopts the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 40nm.
The preparation method is similar to embodiment 1.
Embodiment 9
Board structure as shown in Figure 1, flexible substrate 1 adopts the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 2: 1 in the described mixed system, described free radical type ultraviolet photo-curing cementing agent comprises 97% base resin, 2% monomer, 0.3% light trigger and 0.7% sensitising agent and auxiliary agent, described cation type ultraviolet photo-curing cementing agent comprises 97% cationic monomer, 2% diluent and 1% cation light initiator, conductive layer 2 adopts the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 45nm.
The preparation method is similar to embodiment 1.
Embodiment 10
Board structure as shown in Figure 1, flexible substrate 1 adopts the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 1: 2 in the described mixed system, described free radical type ultraviolet photo-curing cementing agent comprises 96% base resin, 2% monomer, 1% light trigger and 1% sensitising agent and auxiliary agent, described cation type ultraviolet photo-curing cementing agent comprises 98% cationic monomer, 1.4% diluent and 0.6% cation light initiator, conductive layer 2 adopts the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 50nm.
The preparation method is similar to embodiment 1.
Embodiment 11
Board structure as shown in Figure 1, flexible substrate 1 adopts the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 1: 5 in the described mixed system, described free radical type ultraviolet photo-curing cementing agent comprises 94% base resin, 2% monomer, 2% light trigger and 2% sensitising agent and auxiliary agent, described cation type ultraviolet photo-curing cementing agent comprises 92% cationic monomer, 5% diluent and 3% cation light initiator, lead conductive layer 2 and adopt the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 25nm.
The preparation method is similar to embodiment 1.
Embodiment 12
Board structure as shown in Figure 1, flexible substrate 1 adopts the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 1: 10 in the described mixed system, described free radical type ultraviolet photo-curing cementing agent comprises 92% base resin, 3% monomer, 3% light trigger and 2% sensitising agent and auxiliary agent, described cation type ultraviolet photo-curing cementing agent comprises 92% cationic monomer, 6% diluent and 2% cation light initiator, lead conductive layer 2 and adopt the nano silver wire film, fill the inorganic light-emitting nano particle in the space of described nano silver wire film, described inorganic light-emitting nanoparticle size is 20nm.
The preparation method is similar to embodiment 1.
Embodiment 13
Board structure as shown in Figure 1, flexible substrate 1 adopts the free radical type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 40nm, the doping mass ratio of described inorganic light-emitting nano particle is 5%, described free radical type ultraviolet photo-curing cementing agent comprises 93% base resin, 3% monomer, 3% light trigger and 1% sensitising agent and auxiliary agent, conductive layer 2 adopts the nano silver wire film, fills the free radical type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
The preparation method is similar to embodiment 1.
Embodiment 14
Board structure as shown in Figure 1, flexible substrate 1 adopts the free radical type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 30nm, the doping mass ratio of described inorganic light-emitting nano particle is 10%, described free radical type ultraviolet photo-curing cementing agent comprises 95% base resin, 2% monomer, 2% light trigger and 1% sensitising agent and auxiliary agent, conductive layer 2 adopts the nano silver wire film, fills the free radical type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
The preparation method is similar to embodiment 1.
Embodiment 15
Board structure as shown in Figure 1, flexible substrate 1 adopts the cation type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 20nm, the doping mass ratio of described inorganic light-emitting nano particle is 15%, described cation type ultraviolet photo-curing cementing agent comprises 99.5% cationic monomer, 0.4% diluent and 0.1% cation light initiator, conductive layer 2 adopts the nano silver wire film, fills the cation type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
The preparation method is similar to embodiment 1.
Embodiment 16
Board structure as shown in Figure 1, flexible substrate 1 adopts the cation type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle, described inorganic light-emitting nanoparticle size is 30nm, the doping mass ratio of described inorganic light-emitting nano particle is 20%, described cation type ultraviolet photo-curing cementing agent comprises 95% cationic monomer, 2% diluent and 3% cation light initiator, conductive layer 2 adopts the nano silver wire film, fills the cation type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle in the space of described nano silver wire film.
The preparation method is similar to embodiment 1.
Embodiment 17
Board structure as shown in Figure 1, flexible substrate 1 adopts the free radical type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle and the mixed system of cation type ultraviolet photo-curing cementing agent, described inorganic light-emitting nanoparticle size is 70nm, the doping mass ratio of described inorganic light-emitting nano particle is 30%, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 2: 1 in the described mixed system, described free radical type ultraviolet photo-curing cementing agent comprises 97% base resin, 2% monomer, 0.3% light trigger and 0.7% sensitising agent and auxiliary agent, described cation type ultraviolet photo-curing cementing agent comprises 98% cationic monomer, 1% diluent and 1% cation light initiator, conductive layer 2 adopts the nano silver wire film, fills the free radical type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle and the mixed system of cation type ultraviolet photo-curing cementing agent in the space of described nano silver wire film.
The preparation method is similar to embodiment 1.
Embodiment 18
Board structure as shown in Figure 1, flexible substrate 1 adopts the free radical type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle and the mixed system of cation type ultraviolet photo-curing cementing agent, described inorganic light-emitting nanoparticle size is 100nm, the doping mass ratio of described inorganic light-emitting nano particle is 40%, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 1: 2 in the described mixed system, described free radical type ultraviolet photo-curing cementing agent comprises 96% base resin, 2% monomer, 1% light trigger and 1% sensitising agent and auxiliary agent, described cation type ultraviolet photo-curing cementing agent comprises 99% cationic monomer, 0.4% diluent and 0.6% cation light initiator, conductive layer 2 adopts the nano silver wire film, fills the free radical type ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle and the mixed system of cation type ultraviolet photo-curing cementing agent in the space of described nano silver wire film.
The preparation method is similar to embodiment 1.

Claims (10)

1. substrate used in luminescent device, comprise flexible substrate and conductive layer, it is characterized in that, described flexible substrate and conductive layer are made of a kind of in the following dual mode: 1. described flexible substrate is ultraviolet photo-curing cementing agent, described conductive layer is the nano silver wire film, is filled with the inorganic light-emitting nano particle in the space of described nano silver wire film; 2. described flexible substrate is the ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle, described conductive layer is the nano silver wire film, be filled with the ultraviolet photo-curing cementing agent of doping inorganic light-emitting nano particle in the space of described nano silver wire film, ultraviolet photo-curing cementing agent described in the above-mentioned dual mode comprises free radical type ultraviolet photo-curing cementing agent or cation type ultraviolet photo-curing cementing agent or their mixed system.
2. substrate used in luminescent device 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 the 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 take sulfide, oxide, fluoride, phosphate, vanadate, niobates, aluminate or molybdate as luminous host, with 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 and praseodymium.
5. substrate used in luminescent device according to claim 1, it is characterized in that, the mass ratio of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent is 10: 1～1: 10 in the mixed system of described free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent.
6. substrate used in luminescent device according to claim 1 or 5, it is characterized in that, described free radical type ultra-violet curing adhesive comprises the component of following mass percent: 90～99.5% base resin, 0.2～3% monomer, 0.1～3% light trigger and 0.2～6% sensitising agent and auxiliary agent; Described cation type ultraviolet photo-curing cementing agent comprises the component of following mass percent: 90～99.5% cationic monomer, 0.4～8% diluent and 0.1～3% cation light initiator.
7. substrate used in luminescent device according to claim 6 is characterized in that, base resin comprises unsaturated polyester resin, acrylic resin and polythiol polyenoid system; Described monomer comprises Styrene and its derivatives, simple function group or polyfunctional group acrylic acid; Described light trigger comprises benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl propyl alcohol or acetophenone derivative; Sensitising agent comprises benzophenone, thia anthraquinone or Michler's keton, and auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, crosslinking agent, fire retardant or coupling agent; Described cationic monomer comprises various epoxy resin or modified epoxy or fluorine-containing and not fluorine-containing hybrid resin or aliphat and bis-phenol D type blending epoxy; Described diluent comprises toluene, dimethylbenzene, active epoxy diluent resin and various ring ether, cyclic lactone, vinyl ether monomers; Described cation light initiator has iodine triaryl salt compounded of iodine, triaryl sulfonium salts or triaryl selenium salt.
8. substrate used in luminescent device according to claim 7 is characterized in that, described acrylic resin comprises polyester acrylate, epoxy acrylate, urethane acrylate and polyether acrylate.
9. substrate used in luminescent device according to claim 7 is characterized in that, described polythiol polyenoid system comprises following four kinds of materials:
Figure FSB00000953202400031
10. 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. take the mode of spin coating or spraying or self assembly or inkjet printing or silk screen printing at the substrate preparation nano silver wire film of cleaning;
3. the ultraviolet photo-curing cementing agent layer of spin coating or spraying doping inorganic light-emitting nano particle on the nano silver wire film, or first spin coating or drip and to be coated with or to spray the solution that contains the inorganic light-emitting nano particle, again spin coating or spraying ultraviolet photo-curing cementing agent layer, described ultraviolet photo-curing cementing agent comprises free radical type ultraviolet photo-curing cementing agent, cation type ultraviolet photo-curing cementing agent and their mixed system;
4. ultraviolet light polymerization being carried out on the rigid substrates surface processed 30 seconds;
5. the ultraviolet photo-curing cementing agent layer after nano silver wire film and the curing or the ultraviolet light polymerization jelly layer of doping inorganic light-emitting nano particle are 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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