CN102208558B - Substrate for flexible luminescent device and preparation method thereof - Google Patents
Substrate for flexible luminescent device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a substrate for a flexible luminescent device, comprising a flexible substrate and a conductive layer. The substrate for the flexible luminescent device is characterized in that the conductive layer is a graphene film while the flexible substrate is an adhesive needing to be doubly cured, wherein the adhesive needing to be doubly cured is doped with an organic luminescent material; and the adhesive needing to be doubly cured comprises an ultraviolet curing-heat curing system, an ultraviolet curing-microwave curing system, an ultraviolet curing-anaerobic curing system and an ultraviolet curing-electron beam curing system. According to the substrate, the problems of large roughness of the conductive layer and poor bonding force between the conductive layer and the flexible substrate are solved, the bonding force between the conductive layer and the flexible substrate is increased and the blocking capability of the substrate to water and oxygen is also improved.
Description
Technical field
The present invention relates to the organic optoelectronic technical field, be specifically related to a kind of flexible luminescent device substrate 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, photoelectron 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, 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 of opto-electronic device reduces significantly, and performance has had large increase.
Organic optoelectronic device mostly is that preparation is at rigid substrates (on glass or silicon chip), though they have good device performance, anti-vibration at present, shock proof ability a little less than, weight is heavier relatively, 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 compare with rigid substrate, the profile pattern of flexible substrate is far away from glass substrate, and to handle equipment and the technology difficulty of wanting special bigger and flexible substrate is carried out surface smoothing, improved substrate production cost; 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 influence of the water oxygen that sees through from substrate, reduced the performance of device, 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 flexible luminescent device substrate and preparation method thereof is provided, this substrate has solved the problem of adhesion difference between conductive layer surface roughness big and conductive layer and the flexible substrate, has improved adhesion between conductive layer and the flexible substrate and substrate to the obstructing capacity of water oxygen.
Technical problem proposed by the invention is to solve like this: a kind of flexible luminescent device substrate is provided, comprise flexible substrate and conductive layer, it is characterized in that, described conductive layer is graphene film, described flexible substrate is the adhesive that needs dual cure of doping luminous organic material, and the described adhesive of dual cure that needs comprises ultraviolet light polymerization-heat cured system, ultraviolet light polymerization-microwave curing system, ultraviolet light polymerization-anaerobic curing system and ultraviolet light polymerization-electronic beam curing system:
1. free radical type ultraviolet light polymerization-heat cured system, raw material comprises the component of following weight portion:
Solidification process is: carry out ultraviolet light polymerization earlier, then be heating and curing, carry out ultraviolet light polymerization again; Perhaps be heating and curing earlier, then carry out ultraviolet light polymerization, be heating and curing again;
2. free radical type ultraviolet light polymerization-microwave curing system, raw material comprises the component of following weight portion:
Solidification process is: carry out ultraviolet light polymerization earlier, then carry out microwave curing, carry out ultraviolet light polymerization again; Perhaps carry out microwave curing earlier, then carry out ultraviolet light polymerization, again heating or microwave curing;
3. free radical type ultraviolet light polymerization-anaerobic curing system, raw material comprises the component of following weight portion:
Solidification process is: at first carry out ultraviolet light polymerization, then be not subjected to illumination and be in adhesive segment under the anoxia condition carrying out the anaerobic curing reaction automatically, carry out ultraviolet light polymerization again;
4. free radical type ultraviolet light polymerization-electronic beam curing system, raw material comprises the component of following weight portion:
Solidification process is: at first carry out ultraviolet light polymerization, then carry out electronic beam curing under vacuum, carry out ultraviolet light polymerization again;
5. cation type ultraviolet photo-curing-heat cured system, raw material comprises the component of following weight portion:
Solidification process is: carry out ultraviolet light polymerization earlier, then be heating and curing, carry out ultraviolet light polymerization again; Perhaps be heating and curing earlier, then carry out ultraviolet light polymerization, be heating and curing again;
6. cation type ultraviolet photo-curing-microwave curing system, raw material comprises the component of following weight portion:
Solidification process is: carry out ultraviolet light polymerization earlier, then carry out microwave curing, carry out ultraviolet light polymerization again; Perhaps carry out microwave curing earlier, then carry out ultraviolet light polymerization, again heating or microwave curing;
7. cation type ultraviolet photo-curing-anaerobic curing system, raw material comprises the component of following weight portion:
Solidification process is: at first carry out ultraviolet light polymerization, then be not subjected to illumination and be in adhesive segment under the anoxia condition carrying out the anaerobic curing reaction automatically, carry out ultraviolet light polymerization again;
8. cation type ultraviolet photo-curing-electronic beam curing system, raw material comprises the component of following weight portion:
Solidification process is: at first carry out ultraviolet light polymerization, then carry out electronic beam curing under vacuum, carry out ultraviolet light polymerization again.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that the doping mass ratio of described luminous organic material is less than or equal to 40%.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that described luminous organic material comprises fluorescence luminous organic material, phosphorescence luminous organic material and their mixed system thereof.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that, in the described fluorescence luminous organic material, red dye is 3-(dicyano methylene)-5,5-dimethyl-1-(dimethyl amido-styrene) cyclic ethylene, 4-(methylene dicyanoethyl)-2-spy-butyl-6-(1,1,7,7-tetramethyl julolidine-4-yl-vinyl)-the 4H-pyrans, 4-(methylene dicyanoethyl)-2-spy-butyl-6-(1,1,7,7-tetramethyl julolidine-9-enyl)-the 4H-pyrans, 4-(methylene dicyanoethyl)-2-i-propyl group-6-(1,1,7,7-tetramethyl julolidine-9-enyl)-the 4H-pyrans, 4-(methylene dicyanoethyl)-2-methyl-6-(4-dimethylamino styryl)-4H-pyrans, one or more of 4-(dicyano methylene)-2-methyl-6-(p-dimethylamino-styryl)-4H-pyrans; The green glow dyestuff is oxine aluminium, two (2-methyl-oxine) (p-phenyl phenol) aluminium, quinacridone QA, N, N '-dimethyl-quinacridone, coumarin 6, one or more of cumarin C-545T; The blue light dyestuff be difluoro [the different methylene acetone-N-of 6-(2-(1H)-quinoline methyl-kN)-(the different methylene acetone of 6--2-quinoline methyl-kN1)] boron, 9,10-two-(2-naphthyl) anthracene ADN, N, and N '-two (naphthal-1-yl)-N, N '-two (phenyl)-benzidine, 4,4 '-two (2,2-diphenylethyllenes)-1,1 '-biphenyl, 2-(4-biphenyl)-5-(4-tertiary amine-butyl phenyl)-1,3, the 4-oxadiazoles, 3-(4-hexichol)-4-benzene-5-tert-butylbenzene-1,2, the 4-124 Triazole, 1,3-two [(4-tertiary amine-butyl phenyl)-1,3,4-diazo acid-5-yl] benzene, 2-spy-butyl-9, the 10-22 (anthracene of naphthyl-2-yl), 4,4 '-two (9-ethyls-3-carbazole vinyl)-1,1 '-biphenyl, 1, two [2-(the 3-N-ethane carbazole) vinyl] benzene of 4-, one or more of 1-4-two-[4-(N, N-two-benzene) amido] styryl-Ben ， perylenes, the gold-tinted dyestuff is 5,6,11,12-tetraphenyl aphthacene.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that, described phosphorescence luminous organic material comprises Ir, Pt, Os, Re metal complex series, red dye is three (1-benzisoquinoline) complex of iridium, two (1-benzisoquinoline) (acetylacetone,2,4-pentanedione) complex of iridium, two (2-benzene [b] thiophene-2-yl-pyridine) (acetylacetone,2,4-pentanedione) complex of iridium, two-hexichol [f, h] quinoxaline-N, C
2) (acetylacetone,2,4-pentanedione), two (2,4-hexichol quinoxaline-N, C
2') (acetylacetone,2,4-pentanedione) complex of iridium, two-(2-benzene quinoline-N, C
2') (acetylacetone,2,4-pentanedione) complex of iridium, 2,3,7,8,12,13,17,18-octaethyl-21H, one or more of 23H-porphyrin platinum complex; The green glow dyestuff is three (2-benzene pyridine) complex of iridium, two (1,2-hexichol-1H-benzene imidazoles) (acetylacetone,2,4-pentanedione) complex of iridium, two (2-benzene pyridine) (acetylacetone,2,4-pentanedione) complex of iridium, three [2-(p-tolyl) pyridine] complex of iridium, two [3,5-two (2-pyridine)-1,2, the 4-triazole] platinum complex, one or more of 3,5-two (2-pyridine) chlorotoluene platinum complex; The blue light dyestuff is two (3,5-two fluoro-2-(2-pyridine) benzene-(2-carboxyl pyridine)) complex of iridium, two (2,4-, two fluorobenzene pyridines) four (1-pyrazoles) boric acid complex of iridium, three ((3,5-two fluoro-4-cyanophenyls) complex of iridium pyridine), three (N-dibenzofurans-N '-methylimidazole) complex of iridium, two [3,5-two (2-pyridine)-1,2,4-triazole] one or more of platinum complex; The gold-tinted dyestuff is 2-(to the tert-butyl group-phenyl)-benzothiazole (acetylacetone,2,4-pentanedione) complex of iridium, two (2-[4-morpholinodithio) (acetylacetone,2,4-pentanedione) complex of iridium, it is two that (2-(9,9-diethyl-9H-fluorenes-2-yl)-1-benzene-1H-benzimidazole-N, C3) (acetylacetone,2,4-pentanedione) complex of iridium, one or more of two (2-methyl biphenyl formyl-[f, h] quinoxaline) (acetylacetone,2,4-pentanedione) complex of iridium.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that, described free radical thermal curing agents comprises: ethylenediamine, hexamethylene diamine, triethylene tetramine, the ethoxy diethylenetriamine, hydroxyl isopropyl diethylenetriamine, poly-ethanedioic acid adipamide, diformazan ammonia propylamine, 4-methyl-diaminopropane, dicyandiamide, two amido diphenyl sulfones, two amido diphenyl methanes, m-phenylene diamine (MPD), diethyl toluene diamine, N-(aminopropyl)-toluenediamine, dimethylethanolamine, dimethyl Bian amine, triethyl group benzyl ammonium chloride, benzyl-dimethylamine, the N-benzyl dimethylamine, 2,4,6,-three-(dimethylamino methyl)-phenol, the phenol formaldehyde (PF) hexamethylene diamine, N, the N-dimethyl benzylamine, the 2-ethyl imidazol(e), the 2-phenylimidazole, glyoxal ethyline, the 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 1-(2-amino-ethyl)-glyoxal ethyline, maleic anhydride, the diphenyl ether tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, the tetrabromo-benzene dicarboxylic acid anhydride, gather acetic anhydride in the ninth of the ten Heavenly Stems, sebacic dihydrazide, adipic dihydrazide, carbonic acid two hydrazides, oxalic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide, the amino polyacrylamide of N-, the decanedioic acid hydrazides, the M-phthalic acid hydrazides, to the Para Hydroxy Benzoic Acid hydrazides, azelaic acid two hydrazides, isophthalic dihydrazide, the ferrocene tetrafluoroborate, triallyl cyanurate, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, hexamethylene diisocyanate, the trimethyl hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, XDI, tetramethylxylylene diisocyanate, the methyl styrene isocyanates, the hexahydrotoluene vulcabond, triphenyl first-4,4 ', 4 '-triisocyanate, diaminodiphenyl-methane, the chlorophenyl of N--N-N-dimethyl urea, 3-phenyl-1, the 1-dimethyl urea, 3-rubigan-1, the 1-dimethyl urea, 4,4 '-the diamino-diphenyl bis-phenol, polyurethanes, Lauxite, epoxy-ethylenediamine carbamate, 2,4,6-three (dimethylamino methyl) phenol, 2, the 4-diaminotoluene, polyurethane, the methyl-etherified Lauxite, three (3-aminopropyl) amine, 2-amino-ethyl-two (3-aminopropyl) amine, 4,4 '-MDA, 4,4 '-the diamino-diphenyl bis-phenol, 4,4 '-diamino-diphenyl sulfone, three (3-aminopropyl) amine, melmac, the benzoguanamine resin, hexamethylol melamine resin, the hexamethoxymethyl melamine resin, urea-melamine resin, the polyester melamine, the TCCA ester, aminotriazine resins, urethane acrylate, the 4-aminopyridine resin, the amino mylar of N-β-aminoethyl, the α-An Jibiding resin, aminodiphenylether resin, the phosphoramidic acid resin, the hydroxyethylamino mylar; Described microwave curing adhesive and hot setting adhesive use same material or different materials; Described anaerobic curing adhesive comprises: methacrylate tetraethylene-glycol ester, methacrylate multicondensed ethylene glycol ester, the triethylene Glycol double methyl methacrylate, the methacrylate glycol ester, hydroxyethyl methacrylate or hydroxypropyl acrylate, the methoxylated polyethylene glycol methacrylate, the phthalic acid Triethylene Glycol, Jia Jibingxisuanβ-Qiang Yizhi, the triethylene Glycol double methyl methacrylate, methacrylate sulfo-diethylene glycol (DEG) ester, phthalic acid two (diethylene glycol (DEG) acrylate), the ethoxylation bisphenol a dimethacrylate, dimethacrylate bisphenol-A ethylene glycol fat, second diester methacrylate, the triethylene-glycol dimethylacrylate, the condensed ethandiol double methyl methacrylate, glycol methacrylate, one diethyl acetal double methyl methacrylate, the epoxy resin methacrylate, methacrylate diglycol ester; Described electronic beam curing adhesive comprises: triphenol methylmethane tetraglycidel ether epoxy resin, the bicyclopentadiene bisphenol-type epoxy resin, the bisphenol A-type vinyl ester resin, epoxy vinyl ester resin, Epocryl, maleimide resin, 4,4 '-diphenyl methane dimaleimide, bisphenol-A-diphenyl ether bismaleimides, bisphenol-A maleic acid vinylite, ethylene bromide base ester resin, the phenolic aldehyde epoxy vinyl ester resin, the methylolation bisphenol A type epoxy resin, the bisphenol-A acrylate, urethane acrylate, the bisphenol-A epoxy vinyl ester resin, bisphenol A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, the bisphenol-a epoxy acrylate resin, bisphenol A diglycidyl ether or bisphenol-A epoxy chloropropene acid esters resin.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that, described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether, acetophenone derivative and benzoin isopropyl ether, cation light initiator comprises aromatic sulfonium salts, salt compounded of iodine and luxuriant molysite class, sensitising agent comprises benzophenone, thia anthraquinone, Michler's keton, and auxiliary agent comprises plasticizer and coupling agent.
According to flexible luminescent device substrate provided by the present invention, it is characterized in that described plasticizer comprises: dioctyl phthalate, dibutyl phthalate, three vinyl butyl ether base phosphates, polyvinyl butyral resin, tributyl 2-acetylcitrate, repefral, diethyl phthalate, adipic acid two (butoxy ethyoxyl) ethyl ester, isopropyl titanate, tetrabutyl titanate, citrate, the own ester of trimellitic acid (2-ethyl), the own ester of phthalic acid two (2-ethyl), the own ester of decanedioic acid two (2-ethyl), the diglycol dibenzoate, phthalic anhydride, dipropylene glycol dibenzoate or chlorosulfonated polyethylene; Described coupling agent comprises the methyl ethylene dichlorosilane, methyl hydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-An Bingjisanjiayangjiguiwan, dimethyl silicone polymer, poly-hydrogen methylsiloxane, poly-methyl methoxy radical siloxane, γ-methacrylic acid third vinegar base trimethoxy silane, gamma-aminopropyl-triethoxy-silane, 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-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxy, third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ-Qiu Jibingjisanjiayangjiguiwan or γ-sulfydryl propyl-triethoxysilicane.
A kind of flexible luminescent device is characterized in that with the preparation method of substrate, may further comprise the steps:
1. the rigid substrates (as copper foil or iron foil sheet or nickel foil sheet) of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen;
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 adhesive layer that needs dual cure of spin coating or spraying doping luminous organic material on graphene film, described dual cure by two independently cure stage finish, one of them stage is to react by ultraviolet light polymerization, another stage is dark reaction, the described adhesive of dual cure that needs comprises ultraviolet light polymerization-heat cured system, ultraviolet light polymerization-microwave curing system, ultraviolet light polymerization-anaerobic curing system and ultraviolet light polymerization-electronic beam curing system, when using ultraviolet light polymerization-hot curing or ultraviolet light polymerization-microwave curing system, the order that adopts is to be heating and curing earlier or microwave curing, carry out ultraviolet light polymerization then, be heating and curing again or microwave curing; Perhaps carry out ultraviolet light polymerization earlier, be heating and curing then or microwave curing, carry out ultraviolet light polymerization again;
4. the adhesive layer that needs dual cure of the doping luminous organic material after graphene film and the curing is peeled off the rigid substrates surface, form the compliant conductive substrate;
5. 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 Graphene has advantages of high strength, make flexible base, board of the present invention by alternating bending after, the graphene conductive layer can not rupture, the phenomenon that conductivity also can not occur descending; There is luminous organic material 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 adhesive layer that needs dual cure after solidifying also has fine and close structure simultaneously, has improved the obstructing capacity of flexible base, board to water oxygen; At roughness little rigid substrates preparation conductive layer and the adhesive layer that needs dual cure, form flexible base, board by the method for peeling off, improved the evenness of conductive layer surface; The adhesive that needs dual cure 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 that the flexible luminescent device of embodiment of the invention 1-6 is used substrate;
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
Be further described below in conjunction with accompanying drawing and the present invention of embodiment:
Technical scheme of the present invention provides a kind of flexible luminescent device substrate, 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 favorable conductive ability, described conductive layer are arranged.
Need each composition of stick of dual cure glue to be described as follows among the present invention:
UV-curing technology is owing to adopted ultraviolet light as solidifying the energy, determined there is the limitation of self, mainly show: to using the base material shape certain restriction is arranged, low to band color system curing rate, deep layer and object shadow region are difficult to solidify, and solidify the back volume contraction and cause problems such as poor adhesive force and light trigger be residual more greatly.These deficiencies have influenced further developing and using of UV-curing technology, and solidify the range of application that volume contraction bigger shortcoming in back has also had a strong impact on ultraviolet photocureable material.Dual cure (dual-curing) technology is the combination of photocuring and other curing.
In the dual cure system, the crosslinked or polymerization reaction of system is to finish by two stages that independently have the differential responses principle, and one of them stage is by photocuring reaction, and another stage is undertaken by dark reaction.Wherein, photocuring can be the free radical ultraviolet light polymerization, also can be the cation ultraviolet light polymerization; Dark curing can be hot curing, electronic beam curing, anaerobic curing and microwave polymerization etc.So just can utilize photocuring to make the system fast shaping or reach surface drying, and utilize dark reaction to make dash area or bottom partly solidified fully.
The stage of photocuring and dark curing can be at free radical type and cationic ultra-violet curing adhesive, so have free radical type and cationic hot curing etc.
Be some typical system of lifting below, and some concrete operating parameters.
The free radical type ultraviolet curable agent comprises: polyester-acrylate, epoxy-acrylate, amino first
The cation type ultraviolet photo-curing agent comprises: epoxy resin or modified epoxy.
Plasticizer comprises dioctyl phthalate, dibutyl phthalate, three vinyl butyl ether base phosphates, polyvinyl butyral resin, tributyl 2-acetylcitrate, repefral, diethyl phthalate, adipic acid two (butoxy ethyoxyl) ethyl ester, isopropyl titanate, tetrabutyl titanate, citrate, the own ester of trimellitic acid (2-ethyl), the own ester of phthalic acid two (2-ethyl), the own ester of decanedioic acid two (2-ethyl), the diglycol dibenzoate, phthalic anhydride, dipropylene glycol dibenzoate and chlorosulfonated polyethylene; Described coupling agent comprises the methyl ethylene dichlorosilane, methyl hydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-An Bingjisanjiayangjiguiwan, dimethyl silicone polymer, poly-hydrogen methylsiloxane, poly-methyl methoxy radical siloxane, γ-methacrylic acid third vinegar base trimethoxy silane, gamma-aminopropyl-triethoxy-silane, 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-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxy, third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane.
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, N-vinyl pyrrolidone, 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, the propoxylation trihydroxy is through the methylpropane 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 UV curing technology, they reveal the big 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 big shortcoming of excitant, also should have higher activity and state of cure.As ethoxylation trihydroxy methyl propane triol triacrylate (TMP (EO) TMA), propoxylation trihydroxy methyl propane triol triacrylate (TMP (PO) TMA), propoxylation 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 the excitant of monomer simultaneously.
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 with epoxy resin.Vinyl ether monomers has: 1,2,3-propanetriol-diglycidyl-ether (EPON-812), triethylene glycol divinyl ether (DVE-3), 1,4-butanediol 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, the vinyl n-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 epoxy compounds 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, methacrylic acid epoxy-ester, water-soluble itaconic acid epoxy ester resin:
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 the cracking type and puies forward Hydrogen two big 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 phenylbis (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 situation that whitewash and film are thicker; 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.Triplet state carbonyl free radical than more likely extracting hydrogen on the secondary carbon or on the methyl, is connected on hydrogen on the hetero-atoms such as oxygen or nitrogen than the easier extraction of the hydrogen on the carbon atom 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 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, 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.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; 37-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-benzoyl phenyl 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; mainly comprise: 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; amino ferrocene.
Ultraviolet light polymerization-heat cured system: the mechanical performance of cured product is significantly improved after the discovery heat treatment, and along with the increase of epoxy component, hybrid systems has good adhesion property at grounds such as metals, this is because epoxy compounds shrinks little cause when solidifying on the one hand, is owing to eliminated the internal stress that produces when radical photoinitiator solidifies during hot curing on the other hand.According to flexible luminescent device substrate provided by the present invention, it is characterized in that the thermal curing agents in the described hot curing mode comprises: epoxy resin, isocyanates, amino resins class and free radical thermal curing agents.
Epoxy resin comprises: aliphat amine, aromatic amine, dicyandiamide class, imidazoles, organic acid anhydride class, organic hydrazides class, lewis acid amine and microcapsules class.
The aliphat amine comprises: ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, the ethoxy diethylenetriamine, hydroxyl isopropyl diethylenetriamine, poly-ethanedioic acid adipamide, diethanol amine, tetramethylethylenediamine, the glycyrrhizic acid diamines, N-(2-ethoxy) ethylenediamine, two (4-amido phenoxy group)-phenyl phosphorous oxide, two (3-aminocarbonyl phenyl) phenyl phosphorous oxide, the tetrapropyleneglycol diamines, N-hydroxyethyl-ethylenediamine, methyl ring pentanediamine, polyetheramine, pnenolic aldehyde amine hardener (T-31), AEEA, IPD, the Meng alkane diamines, diformazan ammonia propylamine, two (4-amino-3-methylcyclohexyl) methane, 4-methyl-diaminopropane, amine epoxy curing agent modified (593), fat amine epoxy hardener (3380, TG-03, LX-502, D230), fatty amine modification addition product (HB-206, HB-205, HB-2512, HB-9305, HB-9409).
The dicyandiamide class comprises: dicyandiamide, 3, the cyanoguanidine derivative of 5 disubstituted benzenes amine modifications (HT 2833, HT 2844), dicyandiamide (MD 02, made by expoxy propane and dicyandiamide reaction), modification cyanoguanidine derivative (AEHD-610, AEHD-210) and the derivative that contains following molecular formula.
Aromatic amine comprises: two amido diphenyl sulfones (DDS), two amido diphenyl methanes (DDM), m-phenylene diamine (MPD) (m PDA), 8 naphthylenediamines, diethyl toluene diamine, o-phenylenediamine, p-phenylenediamine (PPD), pi-allyl fragrance diamines, N-(aminopropyl)-toluenediamine, IPD, dimethylethanolamine, dimethyl Bian amine, triethyl group benzyl ammonium chloride, benzyl-dimethylamine, the N-benzyl dimethylamine, 2,4,6,-three-(dimethylamino methyl)-phenol, the phenol formaldehyde (PF) hexamethylene diamine, N, N-dimethyl benzylamine (BDMA), the carboxyl phenyl succinimide of N-(p-CPMD).
Imidazoles comprises: the 1-methylimidazole, the 2-ethyl imidazol(e), the 2-phenylimidazole, glyoxal ethyline, 1-8-amino-ethyl-glyoxal ethyline (AMz), 2-undecyl imidazole adipic acid disalt, the 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole (2E4Mz), 1-(2-amino-ethyl)-glyoxal ethyline, 1-cyano group-2-ethyl-4-methylimidazole, 2-heptadecyl imidazoles, 2-ethyl-4-methylimidazole-carboxyl, 3-dihydroxymethyl substituted ramification of imidazole, the chloride of 1,3-diphenyl-glyoxal ethyline, 1-decyl-2-ethyl imidazol(e), modified imidazole (JH-0511, JH-0512, JH-0521).
The organic acid anhydride class comprises: epoxidized polybutadiene/acid anhydrides, maleic anhydride, 70# acid anhydrides (synthetic by butadiene and maleic anhydride), 647# acid anhydrides (synthetic by dicyclopentadiene and maleic anhydride), 308 tung oil acid anhydrides are (by tung oil-modified maleic anhydride, methyl inner methylidyne tetrahydric phthalic anhydride (MNA) is synthetic), pyromellitic acid anhydride (PMTA) (pyromellitic acid anhydride mixes with maleic anhydride), methyl hexahydrophthalic anhydride (MeHHPA), the diphenyl ether tetracarboxylic dianhydride, phthalic anhydride (PA), hexahydrophthalic anhydride (HHPA), tetrahydrochysene phthalate anhydride (THPA), methyl tetrahydrochysene phthalate anhydride, epoxidized polybutadiene/acid anhydrides, trimellitic anhydride (TMA), the tetrabromo-benzene dicarboxylic acid anhydride, poly-acetic anhydride in the ninth of the ten Heavenly Stems (PAPA).
Organic hydrazides class comprises: sebacic dihydrazide (SDH), adipic dihydrazide, carbonic acid two hydrazides, oxalic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide, the amino polyacrylamide of N-, N (CH
2CH
2CO-NHNH
2)
3, (H
2NHNCOCH
2CH
2)
2NCH
2CH
2N (CHCHCONHNH
2)
2, butanedioic acid hydrazides, decanedioic acid hydrazides, M-phthalic acid hydrazides, to Para Hydroxy Benzoic Acid hydrazides (POBH), azelaic acid two hydrazides, isophthalic dihydrazide.
The lewis acid amine is by BF
3, AlCl
3, ZnCl
2, PF
5Form complex compound and form Deng lewis acid and primary amine or secondary amine, comprising: cyclopentadienyl group isopropylbenzene iron hexafluorophosphate (Irgacure 261), boron trifluoride, ferrocene tetrafluoroborate.
The microcapsules class comprises: cellulose, gelatin, polyvinyl alcohol, polyester, polysulfones.
Isocyanates comprises: triallyl cyanurate, toluene di-isocyanate(TDI) (TDI), '-diphenylmethane diisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), hexamethylene diisocyanate (HDI), IPDI (IPDI), trimethyl hexamethylene diisocyanate (TMDI), dicyclohexyl methyl hydride diisocyanate (HMDI), XDI (XDI), tetramethylxylylene diisocyanate (TMXDI), methyl styrene isocyanates (TMI), hexahydrotoluene vulcabond (HTDI), acrylonitrile-butadiene rubber, Heptad isocyanate, triphenyl first-4,4 ', 4 '-triisocyanate, tri o cresyl thiophosphate (4-NCO phenyl ester), tetraisocyanate, Heptad isocyanate, biuret polyisocyanate, oxolane PPG-epoxy resin-isocyanates, trihydroxy PPOX polyalcohol-isocyanates.
Amino resins comprises: diaminodiphenyl-methane (DDM), the chlorophenyl of N--N-N-dimethyl urea, 3-phenyl-1, the 1-dimethyl urea, 3-rubigan-1, the 1-dimethyl urea, 4,4 '-the diamino-diphenyl bis-phenol, polyurethanes, Lauxite, epoxy-ethylenediamine carbamate, N, N, N ', N '-four propargyl-4,4 '-diaminourea-diphenyl-methane (TPDDM), 2,4,6-three (dimethylamino methyl) phenol, 2, the 4-diaminotoluene, 4,6-three (dimethylamino methyl) phenol, polyurethane, the methyl-etherified Lauxite, three (3-aminopropyl) amine, 2-amino-ethyl-two (3-aminopropyl) amine, N, N, N ', N '-four (3-aminopropyl) ethylenediamine, 1-[two (3-aminopropyl) amino]-the 2-propyl alcohol; N-(2-amino-ethyl)-N-(3-aminopropyl) amine, the 1-[(2-amino-ethyl)-(3-aminopropyl) amino]-1-ethanol, the 1-[(2-amino-ethyl)-(3-aminopropyl) amino]-the 2-propyl alcohol, the 3-dimethylaminopropylamine, 4,4 '-MDA (DDM), 4,4 '-the diamino-diphenyl bis-phenol, 4,4 '-diamino-diphenyl sulfone (DDS), three (3-aminopropyl) amine, melmac, the benzoguanamine resin, hexamethylol melamine resin, the methyl-etherified melmac, methyl-etherified benzoguanamine resin, methyl-etherified urea melamine condensation copolymerization resin, hexamethoxymethyl melamine resin (TMMM), methyl alcohol modification trimethylol melamine, urea-melamine resin, the polyester melamine, 2-secondary butyl phenenyl-N-methylamino acid esters, the DCCA ester, the TCCA ester, aminotriazine resins, urethane acrylate, the 4-aminopyridine resin, the amino mylar of N-β-aminoethyl, the α-An Jibiding resin, aminodiphenylether resin, amino silicones, the phosphoramidic acid resin, the maleopimaric acid polyester amino resin, piperazine aminodithioformic acid type chelating resin, the hydroxyethylamino mylar.
The free radical thermal curing agents comprises: cumyl peroxide, the acrylic acid epoxy monoesters, benzoic acid uncle fourth fat, urethane acrylate, polyurethane diol, the polyester triol, two (hexafluorophosphoric acid esters), polymethyl methacrylate (PMMA), cinnamic acrylic ester, polybutadiene type crylic acid hydroxy ester, the polyester urethane acrylate, the acrylic acid epoxy monoesters, butadiene-methyl methacrylate-benzene diene copolymers, butadiene-methyl methacrylate, ethylene-acrylate, polyacrylate, chlorination polypropylene-acrylate, polymethyl methacrylate, polyethyl methacrylate, cyanoacrylate, 2-acrylic acid-1, the 2-propylene glycol monoester, methyl methacrylate, EMA, butyl methacrylate, hydroxyethyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, EHMA, methacrylic acid 2 methylamino ethyl esters, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid 2 hydroxy propyl esters, hydroxy-ethyl acrylate, Isooctyl acrylate monomer, vinylacetate-butyl acrylate, polymethyl methacrylate.
Ultraviolet light polymerization-microwave curing system: the microwave curing agent in the microwave curing mode is identical with thermal curing agents in the hot curing mode.Its technical characterstic is to use the mode of microwave curing that thermal curing agents is solidified.Microwave is because of " in the molecule " even mode of heating of uniqueness, make that resin solidification is even, speed is fast, be easy to control, save the energy, equipment investment is few, microwave replaces hot curing more and more to come into one's own in the research aspect thermosetting resin and the composite material solidification thereof in recent years.
Ultraviolet light polymerization-anaerobic curing system: the anaerobic curing agent in the anaerobic curing system comprises: methacrylate tetraethylene-glycol ester, methacrylate multicondensed ethylene glycol ester is (as the happy Thailand 290 of the U.S. and the happy Thailand of mixing with fumaric acid bisphenol-A unsaturated polyester (UP) 271, the happy Qin 277 etc.), the triethylene Glycol double methyl methacrylate, the methacrylate glycol ester, hydroxyethyl methacrylate or hydroxypropyl acrylate are (as homemade anchor 302, the triple bond 1030 of Japan), the bisphenol-A epoxy ester is (as homemade Y-150, GY-340 etc. are the mixtures of epoxy-ester and multicondensed ethylene glycol ester), the product of hydroxyethyl methacrylate alkyl phenol and polyalcohol is (as happy safe 372 of the U.S., homemade GY-168, anchor 352 and BN-601), polyurethane, the different hydrogen acid ether (hydrogen acid ester) of polyurethane, hydroxy propyl methacrylate, hydroxy propyl methacrylate-polyethers, hydroxy polybutadiene type polyurethane, polyurethane-acrylate, hydroxypropyl acrylate (HPA), glycol methacrylate, cumyl hydroperoxide, acrylic acid o-cresol formaldehyde epoxy-ester, the methoxylated polyethylene glycol methacrylate, the phthalic acid Triethylene Glycol, Jia Jibingxisuanβ-Qiang Yizhi, trimethylol-propane trimethacrylate, the triethylene Glycol double methyl methacrylate, the multicondensed ethylene glycol double methyl methacrylate, methacrylate sulfo-diethylene glycol (DEG) ester, phthalic acid two (diethylene glycol (DEG) acrylate), the ethoxylation bisphenol a dimethacrylate, dimethacrylate bisphenol-A ethylene glycol fat, second diester methacrylate, the condensed ethandiol double methyl methacrylate, glycol methacrylate, one diethyl acetal double methyl methacrylate, phthalic anhydride diglycol ethylene double methyl methacrylate, epoxy resin (methyl) acrylate, methacrylate diglycol ester, double methyl methacrylate triethylene glycol ester, propenoic methyl carbamate, the a-Methyl 2-cyanoacrylate, the a-cyanacrylate, glycidyl methacrylate, polyethylene glycol dimethacrylate, the triethylene glycol dimethylacrylate, methacrylic acid bicyclic pentadiene one oxygen monoethyl ester, the methyl-prop dimethylaminoethyl acrylate.
Ultraviolet light polymerization-electronic beam curing system: the electronic beam curing agent in the electronic beam curing mode comprises: triphenol methylmethane tetraglycidel ether epoxy resin, the bicyclopentadiene bisphenol-type epoxy resin, bisphenol A-type vinyl ester resin (V-411), epoxy vinyl ester resin (V-901), Epocryl (BRT2000), maleimide resin, 4,4 '-diphenyl methane dimaleimide, bisphenol-A-diphenyl ether bismaleimides, bisphenol-A maleic acid vinylite, vinyl ester resin, ethylene bromide base ester resin, fumaric acid mixed ethylene base ester resin, acrylic acid mixed ethylene base ester resin, carbamate mixed ethylene base ester resin, the rubber mix vinyl ester resin, the phenolic aldehyde epoxy vinyl ester resin, the hybrid epoxidized acrylate of isocyanates, toluene di-isocyanate(TDI) mixing acrylic acid-hydroxyl ethyl ester, the methylolation bisphenol-type epoxy resin, the bisphenol-A acrylate, urethane acrylate, the bisphenol-A epoxy vinyl ester resin, bisphenol-A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, the bisphenol-a epoxy acrylate resin, bisphenol A diglycidyl ether, bisphenol-A epoxy chloropropene acid esters resin.
Below be specific embodiments of the invention:
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping luminous organic material, and the doping mass ratio of described luminous organic material is 2%, and conductive layer 2 adopts graphene films.
The preparation method is as follows:
1. the copper foil of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen;
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 propane 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. at the adhesive that needs dual cure of graphene film spraying doping luminous organic material, the doping mass ratio of described luminous organic material is 2%, and adhesive raw materials comprises following component:
4. ultraviolet light polymerization being carried out on the copper foil surface handled 30 seconds;
5. hot curing is carried out on the copper foil surface and handled, temperature is 110 ℃;
6. reuse UV-irradiation copper foil surface, carry out photocuring;
7. the adhesive layer of the dual cure after graphene film and the curing is peeled off the copper foil surface, form the compliant conductive substrate;
8. 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 adhesive that needs dual cure of doping luminous organic material, and the doping mass ratio of described luminous organic material is 10%, and conductive layer 2 adopts graphene films, and described adhesive raw materials comprises following component:
The preparation method is similar to embodiment 1.
Embodiment 3
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping luminous organic material, and the doping mass ratio of described luminous organic material is 15%, and conductive layer 2 adopts graphene films, and described adhesive raw materials comprises following component:
The preparation method is similar to embodiment 1.
Embodiment 4
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping luminous organic material, and the doping mass ratio of described luminous organic material is 25%, and conductive layer 2 adopts graphene films, and described adhesive raw materials comprises following component:
The preparation method is similar to embodiment 1.
Embodiment 5
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping luminous organic material, and the doping mass ratio of described luminous organic material is 30%, and conductive layer 2 adopts graphene films, and described adhesive raw materials comprises following component:
The preparation method is similar to embodiment 1.
Embodiment 6
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping luminous organic material, and the doping mass ratio of described luminous organic material is 40%, and conductive layer 2 adopts graphene films, and described adhesive raw materials comprises following component:
The preparation method is similar to embodiment 1.
Claims (9)
1. flexible luminescent device substrate, comprise flexible substrate and conductive layer, it is characterized in that, described conductive layer is graphene film, described flexible substrate is the adhesive that needs dual cure of doping luminous organic material, and the described adhesive of dual cure that needs comprises ultraviolet light polymerization-heat cured system, ultraviolet light polymerization-microwave curing system, ultraviolet light polymerization-anaerobic curing system or ultraviolet light polymerization-electronic beam curing system:
1. free radical type ultraviolet light polymerization heat cured system, raw material comprises the component of following weight portion:
30～40 parts of unsaturated polyester resin or acrylic resin or polythiol-polyenoid
45 parts of epoxy resin or isocyanates or amino resins class or free radical thermal curing agents
0.2～3 part in styrene and derivative thereof or simple function group or polyfunctional group acrylic acid
0.1～3 part of light trigger
0.2～6 part of sensitising agent and auxiliary agent
Solidification process is: carry out ultraviolet light polymerization earlier, then be heating and curing, carry out ultraviolet light polymerization again; Perhaps be heating and curing earlier, then carry out ultraviolet light polymerization, be heating and curing again;
2. free radical type ultraviolet light polymerization microwave curing system, raw material comprises the component of following weight portion:
30～40 parts of unsaturated polyester resin or acrylic resin or polythiol-polyenoid
35～45 parts of epoxy resin or isocyanates or amino resins class or free radical thermal curing agents
0.2～3 part in styrene and derivative thereof or simple function group or polyfunctional group acrylic acid
0.1～3 part of light trigger
0.2～6 part of sensitising agent and auxiliary agent
Solidification process is: carry out ultraviolet light polymerization earlier, then carry out microwave curing, carry out ultraviolet light polymerization again; Perhaps carry out microwave curing earlier, then carry out ultraviolet light polymerization, again heating or microwave curing;
3. free radical type ultraviolet light polymerization-anaerobic curing system, raw material comprises the component of following weight portion:
55～65 parts of unsaturated polyester resin or acrylic resin or polythiol-polyenoid
20～30 parts of many acetals of methacrylate ester or many acetals of bisphenol-A epoxy esters
0.2～3 part in styrene and derivative thereof or simple function group or polyfunctional group acrylic acid
0.1～3 part of light trigger
0.2～6 part of sensitising agent and auxiliary agent
Solidification process is: at first carry out ultraviolet light polymerization, then be not subjected to illumination and be in adhesive segment under the anoxia condition carrying out the anaerobic curing reaction automatically, carry out ultraviolet light polymerization again;
4. free radical type ultraviolet light polymerization electronic beam curing system, raw material comprises the component of following weight portion:
35～40 parts of unsaturated polyester resin or acrylic resin or polythiol-polyenoid
50～55 parts of bisphenol A-type vinyl vinegar resins
O.2～3 part styrene and derivative thereof or simple function group or polyfunctional group acrylic acid
0.1～3 part of light trigger
0.2～6 part of sensitising agent and auxiliary agent
Solidification process is: at first carry out ultraviolet light polymerization, then carry out electronic beam curing under vacuum, carry out ultraviolet light polymerization again;
5. cation type ultraviolet photo-curing heat cured system, raw material comprises the component of following weight portion:
35～45 parts of epoxy resin or modified epoxies
40～45 parts of epoxy resin or isocyanates or amino resins class or free radical thermal curing agents
0.4～9 part of diluent
0.1～3 part of cation light initiator
0.2～3 part of sensitising agent and auxiliary agent
Solidification process is: carry out ultraviolet light polymerization earlier, then be heating and curing, carry out ultraviolet light polymerization again; Perhaps be heating and curing earlier, then carry out ultraviolet light polymerization, be heating and curing again;
6. cation type ultraviolet photo-curing-microwave curing system, raw material comprises the component of following weight portion:
35～45 parts of epoxy resin or modified epoxies
40～45 parts of epoxy resin or isocyanates or amino resins class or free radical thermal curing agents
0.4～9 part of diluent
0.1～3 part of cation light initiator
0.2～3 part of sensitising agent and auxiliary agent
Solidification process is: carry out ultraviolet light polymerization earlier, then carry out microwave curing, carry out ultraviolet light polymerization again; Perhaps carry out microwave curing earlier, then carry out ultraviolet light polymerization, again heating or microwave curing;
7. cation type ultraviolet photo-curing anaerobic curing system, raw material comprises the component of following weight portion:
60～65 parts of epoxy resin or modified epoxies
25～30 parts of many acetals of methacrylate ester or many acetals of bisphenol-A epoxy esters
0.4～9 part of diluent
0.1～3 part of cation light initiator
0.2～3 part of sensitising agent and auxiliary agent
Solidification process is: at first carry out ultraviolet light polymerization, then be not subjected to illumination and be in adhesive segment under the anoxia condition carrying out the anaerobic curing reaction automatically, carry out ultraviolet light polymerization again;
3. cation type ultraviolet photo-curing electronic beam curing system, raw material comprises the component of following weight portion:
30～35 parts of epoxy resin or modified epoxies
50～55 parts of bisphenol A-type vinyl ester resins
0.4～6 part of diluent
0.1～3 part of cation light initiator
0.2～3 part of sensitising agent and auxiliary agent
Solidification process is: at first carry out ultraviolet light polymerization, then carry out electronic beam curing under vacuum, carry out ultraviolet light polymerization again.
2. flexible luminescent device substrate according to claim 1 is characterized in that, the doping mass ratio of described luminous organic material is less than or equal to 40%.
3. flexible luminescent device substrate according to claim 1 is characterized in that, described luminous organic material comprises fluorescence luminous organic material, phosphorescence luminous organic material or their mixed system.
4. flexible luminescent device substrate according to claim 3, it is characterized in that, in the described fluorescence luminous organic material, red dye is 3-(dicyano methylene)-5,5-dimethyl-1-(dimethyl amido-styrene) cyclic ethylene, 4-(methylene dicyanoethyl)-2-spy-butyl-6-(1,1,7,7-tetramethyl julolidine-4-yl-vinyl)-the 4H-pyrans, 4-(methylene dicyanoethyl)-2-spy-butyl-6-(1,1,7,7-tetramethyl julolidine-9-enyl)-the 4H-pyrans, 4-(methylene dicyanoethyl)-2-i-propyl group-6-(1,1,7,7-tetramethyl julolidine-9-enyl)-the 4H-pyrans, 4-(methylene dicyanoethyl)-2-methyl-6-(4-dimethylamino styryl)-4H-pyrans, one or more of 4-(dicyano methylene)-2-methyl-6-(p-dimethylamino-styryl)-4H-pyrans; The green glow dyestuff is oxine aluminium, two (2-methyl-oxine) (p-phenyl phenol) aluminium, quinacridone QA, N, N '-dimethyl-quinacridone, coumarin 6, one or more of cumarin C-545T; The blue light dyestuff be difluoro [the different methylene acetone-N-of 6-(2-(1H)-quinoline methyl-kN)-(the different methylene acetone of 6--2-quinoline methyl-kN1)] boron, 9,10-two-(2-naphthyl) anthracene ADN, N, and N '-two (naphthal-1-yl)-N, N '-two (phenyl)-benzidine, 4,4 '-two (2,2-styryls)-1,1 '-biphenyl, 2-(4-biphenyl)-5-(4-tertiary amine-butyl phenyl)-1,3, the 4-oxadiazoles, 3-(4-hexichol)-4-benzene-5-tert-butylbenzene-1,2, the 4-124 Triazole, 1,3-two [(4-tertiary amine-butyl phenyl)-1,3,4-diazo acid-5-yl] benzene, 2-spy-butyl-9, the 10-22 (anthracene of naphthyl-2-yl), 4,4 '-two (9-ethyls-3-carbazole vinyl)-1,1 '-biphenyl, 1, two [2-(the 3-N-ethane carbazole) vinyl] benzene of 4-, one or more of 1-4-two-[4-(N, N-two-benzene) amido] styryl-Ben ， perylenes, the gold-tinted dyestuff is 5,6,11,12-tetraphenyl aphthacene.
5. flexible luminescent device substrate according to claim 3, it is characterized in that, described phosphorescence luminous organic material comprises Ir, Pt, Os, Re metal complex series, wherein, red dye is three (1-benzisoquinoline) complex of iridium, two (1-benzisoquinoline) (acetylacetone,2,4-pentanedione) complex of iridium, two (2-benzene [b] thiophene-2-yl-pyridine) (acetylacetone,2,4-pentanedione) complex of iridium, two-hexichol [f, h] quinoxaline-N, C
2) (acetylacetone,2,4-pentanedione), two (2,4-hexichol quinoxaline-N, C
2') (acetylacetone,2,4-pentanedione) complex of iridium, two-(2-benzene quinoline-N, C
2') (acetylacetone,2,4-pentanedione) complex of iridium, 2,3,7,8,12,13,17,18-octaethyl-21H, one or more of 23H-porphyrin platinum complex; The green glow dyestuff is three (2-benzene pyridine) complex of iridium, two (1,2-hexichol-1H-benzene imidazoles) (acetylacetone,2,4-pentanedione) complex of iridium, two (2-benzene pyridine) (acetylacetone,2,4-pentanedione) complex of iridium, three [2-(p-tolyl) pyridine] complex of iridium, two [3,5-two (2-pyridine)-1,2, the 4-triazole] platinum complex, one or more of 3,5-two (2-pyridine) chlorotoluene platinum complex; The blue light dyestuff is two (3,5-two fluoro-2-(2-pyridine) benzene-(2-carboxyl pyridine)) complex of iridium, two (2,4-, two fluorobenzene pyridines) four (1-pyrazoles) boric acid complex of iridium, three ((3,5-two fluoro-4-cyanophenyls) complex of iridium pyridine), three (N-dibenzofurans-N '-methylimidazole) complex of iridium, two [3,5-two (2-pyridine)-1,2,4-triazole] one or more of platinum complex; The gold-tinted dyestuff is 2-(to the tert-butyl group-phenyl)-benzothiazole (acetylacetone,2,4-pentanedione) complex of iridium, two (2-[4-morpholinodithio) (acetylacetone,2,4-pentanedione) complex of iridium, it is two that (2-(9,9-diethyl-9H-fluorenes-2-yl)-1-benzene-1H-benzimidazole-N, C3) (acetylacetone,2,4-pentanedione) complex of iridium, one or more of two (2-methyl biphenyl formyl-[f, h] quinoxaline) (acetylacetone,2,4-pentanedione) complex of iridium.
6. flexible luminescent device substrate according to claim 1, it is characterized in that, described free radical thermal curing agents comprises: ethylenediamine, hexamethylene diamine, triethylene tetramine, the ethoxy diethylenetriamine, hydroxyl isopropyl diethylenetriamine, poly-ethanedioic acid adipamide, diformazan ammonia propylamine, 4-methyl-diaminopropane, dicyandiamide, two amido diphenyl sulfones, two amido diphenyl methanes, m-phenylene diamine (MPD), diethyl toluene diamine, N-(aminopropyl)-toluenediamine, dimethylethanolamine, dimethyl Bian amine, triethyl group benzyl ammonium chloride, benzyl-dimethylamine, the N-benzyl dimethylamine, 2,4,6,-three-(dimethylamino methyl)-phenol, the phenol formaldehyde (PF) hexamethylene diamine, N, the N-dimethyl benzylamine, the 2-ethyl imidazol(e), the 2-phenylimidazole, glyoxal ethyline, the 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 1-(2-amino-ethyl)-glyoxal ethyline, maleic anhydride, the diphenyl ether tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, the tetrabromo-benzene dicarboxylic acid anhydride, gather acetic anhydride in the ninth of the ten Heavenly Stems, sebacic dihydrazide, adipic dihydrazide, carbonic acid two hydrazides, oxalic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide, the amino polyacrylamide of N-, the decanedioic acid hydrazides, the M-phthalic acid hydrazides, to the Para Hydroxy Benzoic Acid hydrazides, azelaic acid two hydrazides, isophthalic dihydrazide, the ferrocene tetrafluoroborate, triallyl cyanurate, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, hexamethylene diisocyanate, the trimethyl hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, XDI, tetramethylxylylene diisocyanate, the methyl styrene isocyanates, the hexahydrotoluene vulcabond, triphenyl first-4,4 ', 4 '-triisocyanate, diaminodiphenyl-methane, the chlorophenyl of N--N-N-dimethyl urea, 3-phenyl-1, the 1-dimethyl urea, 3-rubigan-1, the 1-dimethyl urea, 4,4 '-the diamino-diphenyl bis-phenol, polyurethanes, Lauxite, epoxy-ethylenediamine carbamate, 2,4,6-three (dimethylamino methyl) phenol, 2, the 4-diaminotoluene, polyurethane, the methyl-etherified Lauxite, three (3-aminopropyl) amine, 2-amino-ethyl-two (3-aminopropyl) amine, 4,4 '-MDA, 4,4 '-the diamino-diphenyl bis-phenol, 4,4 '-diamino-diphenyl sulfone, three (3-aminopropyl) amine, melmac, the benzoguanamine resin, hexamethylol melamine resin, the hexamethoxymethyl melamine resin, urea-melamine resin, the polyester melamine, the TCCA ester, aminotriazine resins, urethane acrylate, the 4-aminopyridine resin, the amino mylar of N-β-aminoethyl, the α-An Jibiding resin, aminodiphenylether resin, the phosphoramidic acid resin, the hydroxyethylamino mylar; Described microwave curing adhesive and hot setting adhesive use same material or different materials; Described anaerobic curing adhesive comprises: methacrylate tetraethylene-glycol ester, methacrylate multicondensed ethylene glycol ester, the triethylene Glycol double methyl methacrylate, the methacrylate glycol ester, hydroxyethyl methacrylate or hydroxypropyl acrylate, the methoxylated polyethylene glycol methacrylate, the phthalic acid Triethylene Glycol, Jia Jibingxisuanβ-Qiang Yizhi, the triethylene Glycol double methyl methacrylate, methacrylate sulfo-diethylene glycol (DEG) ester, phthalic acid two (diethylene glycol (DEG) acrylate), the ethoxylation bisphenol a dimethacrylate, dimethacrylate bisphenol-A ethylene glycol fat, second diester methacrylate, the triethylene-glycol dimethylacrylate, the condensed ethandiol double methyl methacrylate, glycol methacrylate, one diethyl acetal double methyl methacrylate, the epoxy resin methacrylate, methacrylate diglycol ester; Described electronic beam curing adhesive comprises: triphenol methylmethane tetraglycidel ether epoxy resin, the bicyclopentadiene bisphenol-type epoxy resin, the bisphenol A-type vinyl ester resin, epoxy vinyl ester resin, Epocryl, maleimide resin, 4,4 '-diphenyl methane dimaleimide, bisphenol-A-diphenyl ether bismaleimides, bisphenol-A maleic acid vinylite, ethylene bromide base ester resin, the phenolic aldehyde epoxy vinyl ester resin, the methylolation bisphenol A type epoxy resin, the bisphenol-A acrylate, urethane acrylate, the bisphenol-A epoxy vinyl ester resin, bisphenol A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, the bisphenol-a epoxy acrylate resin, bisphenol A diglycidyl ether or bisphenol-A epoxy chloropropene acid esters resin.
7. flexible luminescent device substrate according to claim 1, it is characterized in that, described light trigger comprises styrax and derivative benzoin methyl ether thereof, benzoin ethyl ether, acetophenone derivative, benzoin isopropyl ether, cation light initiator comprises aromatic sulfonium salts, salt compounded of iodine or luxuriant molysite class, sensitising agent comprises benzophenone, thia anthraquinone, Michler's keton, and auxiliary agent comprises plasticizer and coupling agent.
8. flexible luminescent device substrate according to claim 7, it is characterized in that described plasticizer comprises: dioctyl phthalate, dibutyl phthalate, three vinyl butyl ether base phosphates, polyvinyl butyral resin, tributyl 2-acetylcitrate, repefral, diethyl phthalate, adipic acid two (butoxy ethyoxyl) ethyl ester, isopropyl titanate, tetrabutyl titanate, citrate, the own ester of trimellitic acid (2-ethyl), the own ester of phthalic acid two (2-ethyl), the own ester of decanedioic acid two (2-ethyl), the diglycol dibenzoate, phthalic anhydride, dipropylene glycol dibenzoate and chlorosulfonated polyethylene; Described coupling agent comprises the methyl ethylene dichlorosilane, methyl hydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-An Bingjisanjiayangjiguiwan, dimethyl silicone polymer, poly-hydrogen methylsiloxane, poly-methyl methoxy radical siloxane, γ-methacrylic acid third vinegar base trimethoxy silane, gamma-aminopropyl-triethoxy-silane, 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-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxy, third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ-Qiu Jibingjisanjiayangjiguiwan or γ-sulfydryl propyl-triethoxysilicane.
9. the preparation method of a flexible luminescent device usefulness substrate is characterized in that, may further comprise the steps:
1. the rigid substrates of surface roughness less than 1nm cleaned, clean the back and dry up with drying nitrogen; Described rigid substrates is copper foil or iron foil sheet or nickel foil sheet;
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 adhesive layer that needs dual cure of spin coating or spraying doping luminous organic material on the graphene layer film, described dual cure by two independently cure stage finish, one of them stage is to react by ultraviolet light polymerization, another stage is dark reaction, the described adhesive of dual cure that needs comprises ultraviolet light polymerization-heat cured system, ultraviolet light polymerization-microwave curing system, ultraviolet light polymerization-anaerobic curing system or ultraviolet light polymerization-electronic beam curing system, when using ultraviolet light polymerization-hot curing or ultraviolet light polymerization-microwave curing system, the order that adopts is to be heating and curing earlier or microwave curing, carry out ultraviolet light polymerization then, be heating and curing again or microwave curing; Perhaps carry out ultraviolet light polymerization earlier, be heating and curing then or microwave curing, carry out ultraviolet light polymerization again;
4. the adhesive layer that needs dual cure of the doping luminous organic material after graphene film and the curing is peeled off the rigid substrates surface, form the compliant conductive substrate;
5. test transmitance, the conductivity of compliant conductive substrate, the parameters of surface topography.
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