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CN102208542B - A substrate for flexible optoelectronic devices and its preparation method - Google Patents

A substrate for flexible optoelectronic devices and its preparation method Download PDF

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Publication number
CN102208542B
CN102208542B CN 201110096775 CN201110096775A CN102208542B CN 102208542 B CN102208542 B CN 102208542B CN 201110096775 CN201110096775 CN 201110096775 CN 201110096775 A CN201110096775 A CN 201110096775A CN 102208542 B CN102208542 B CN 102208542B
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curing
resin
bisphenol
substrate
adhesive
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CN102208542A (en
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于军胜
于欣格
黄江
蒋亚东
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University of Electronic Science and Technology of China
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

本发明公开了一种柔性光电子器件用基板，包括柔性衬底和导电层，所述柔性衬底和导电层由以下两种方式中的一种构成：①所述柔性衬底为需要双重固化的胶粘剂，所述导电层为银纳米线薄膜，所述银纳米线薄膜的空隙中填充有石墨烯；②所述柔性衬底为掺杂石墨烯的需要双重固化的胶粘剂，所述导电层为银纳米线薄膜，所述银纳米线薄膜的空隙中填充有掺杂石墨烯的需要双重固化的胶粘剂，所述需要双重固化的胶粘剂包括紫外光固化-热固化体系、紫外光固化-微波固化体系、紫外光固化-厌氧固化体系和紫外光固化-电子束固化体系。

Figure 201110096775

The invention discloses a substrate for a flexible optoelectronic device, which includes a flexible substrate and a conductive layer, and the flexible substrate and the conductive layer are composed of one of the following two methods: ①The flexible substrate needs double curing Adhesive, the conductive layer is a silver nanowire film, and graphene is filled in the gaps of the silver nanowire film; ②The flexible substrate is an adhesive doped with graphene that needs double curing, and the conductive layer is silver The nanowire film, the interstices of the silver nanowire film are filled with graphene-doped adhesives that require dual curing, and the adhesives that require dual curing include UV curing-thermal curing systems, UV curing-microwave curing systems, UV curing-anaerobic curing system and UV curing-electron beam curing system.

Figure 201110096775

Description

A kind of base board for flexible optoelectronic part and preparation method thereof
Technical field
The present invention relates to the organic optoelectronic technical field, be specifically related to a kind of base board for flexible optoelectronic part 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 base board for flexible optoelectronic part and preparation method thereof is provided, this substrate has solved the nano silver wire Film roughness greatly and the poor problem of adhesion between nano silver wire film and the flexible substrate, improve the conductivity of nano silver wire film and the evenness on surface, increased adhesion between nano silver wire film and the flexible substrate.
Technical problem proposed by the invention is to solve like this: a kind of base board for flexible optoelectronic part 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 the adhesive that needs dual cure, described conductive layer is the nano silver wire film, is filled with Graphene in the space of described nano silver wire film; 2. described flexible substrate is the adhesive that needs dual cure of doped graphene, described conductive layer is the nano silver wire film, be filled with the adhesive that needs dual cure of doped graphene in the space of described nano silver wire film, 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:
Figure BSA00000475963800021
Solidification process is: carry out first ultraviolet light polymerization, then be heating and curing, carry out ultraviolet light polymerization again; Perhaps be heating and curing first, 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 first ultraviolet light polymerization, then carry out microwave curing, carry out ultraviolet light polymerization again; Perhaps carry out first microwave curing, 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:
Figure BSA00000475963800031
Solidification process is: at first carry out ultraviolet light polymerization, then be not subject to illumination and be in adhesive segment under the anoxia condition automatically carrying out the anaerobic curing reaction, 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:
Figure BSA00000475963800032
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:
Figure BSA00000475963800033
Solidification process is: carry out first ultraviolet light polymerization, then be heating and curing, carry out ultraviolet light polymerization again; Perhaps be heating and curing first, 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:
Figure BSA00000475963800034
Solidification process is: carry out first ultraviolet light polymerization, then carry out microwave curing, carry out ultraviolet light polymerization again; Perhaps carry out first microwave curing, 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:
Figure BSA00000475963800041
Solidification process is: at first carry out ultraviolet light polymerization, then be not subject to illumination and be in adhesive segment under the anoxia condition automatically carrying out the anaerobic curing reaction, 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:
Figure BSA00000475963800042
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 base board for flexible optoelectronic part provided by the present invention, it is characterized in that, be less than or equal to 40% at the doping mass ratio of 2. planting Graphene in the structure.
According to base board for flexible optoelectronic part 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, N-is to chlorophenyl-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, N-β-aminoethyl Amino Polyester resin, the α-aminopyridine resin, aminodiphenylether resin, phosphoramidic-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, ethyleneglycol dimethyacrylate, hydroxyethyl methacrylate or hydroxypropyl acrylate, the methoxylated polyethylene glycol methacrylate, the phthalic acid Triethylene Glycol, β-hydroxyethyl methacry-late, the triethylene Glycol double methyl methacrylate, Dimethacryloylethylthioether, 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, triethlene glycol bismethylacrylate, 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 Bismaleimide, bisphenol-A maleic acid vinylite, ethylene bromide base ester resin, phenol formaldehyde epoxy vinyl ester resin/, the methylolation bisphenol A type epoxy resin, the bisphenol-A acrylate, urethane acrylate, bisphenol-A epoxide vinylester resin, bisphenol A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, the bisphenol-a epoxy acrylate resin, bisphenol A diglycidyl ether and bisphenol-A epoxy chloropropene acid esters resin.
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that, described light trigger comprises benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether, acetophenone derivative or benzoin isopropyl ether, cation light initiator comprises aromatic sulfonium salts, salt compounded of iodine or luxuriant molysite class, sensitising agent comprises benzophenone, thia anthraquinone or Michler's keton, and auxiliary agent comprises plasticizer or coupling agent.
According to base board for flexible optoelectronic part 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, hexanedioic 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), Diethylene Glycol 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-aminopropyltrimethoxysilane, dimethyl silicone polymer, poly-hydrogen methylsiloxane, poly-methyl methoxy radical siloxane, γ-methacrylic acid the 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-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 and γ-sulfydryl propyl-triethoxysilicane.
A kind of preparation method of base board for flexible optoelectronic part 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 rigid substrates preparation nano silver wire film of cleaning;
3. on the nano silver wire film spin coating or the spraying doped graphene the adhesive layer that needs dual cure, or first spin coating or drip the solution be coated with or spray graphene-containing, spin coating or spraying need the adhesive layer of dual cure again, 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 first or microwave curing, then carry out ultraviolet light polymerization, be heating and curing again or microwave curing; Perhaps carry out first ultraviolet light polymerization, then be heating and curing or microwave curing, carry out again ultraviolet light polymerization;
4. the adhesive layer that needs dual cure after nano silver wire film and the curing or the adhesive layer that needs dual cure of doped graphene are 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 prepares at the little rigid substrates of roughness, be filled with the adhesive that needs dual cure of Graphene or doped graphene in the conductive layer space, with conductive layer from the rigid substrates sur-face peeling, form the conductive layer of flexible base, board, not only improve the evenness of conductive layer surface, and increased the conductivity of conductive layer; 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 of the base board for flexible optoelectronic part of embodiment of the invention 1-12;
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 base board for flexible optoelectronic part, 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 1 and conductive layer 2 are made of following dual mode: 1. described flexible substrate is the adhesive that needs dual cure, and described conductive layer is the nano silver wire film, is filled with Graphene in the space of described nano silver wire film; 2. described flexible substrate is the adhesive that needs dual cure of doped graphene, described conductive layer is the nano silver wire film, be filled with the adhesive that needs dual cure of doped graphene in the space of described nano silver wire film, 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.
Need each composition of adhesive of dual cure to be described as follows among the present invention:
UV-curing technology is owing to having adopted ultraviolet light as solidifying the energy, determined there is the limitation of self, be mainly manifested in: 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 volume contraction causes more greatly the problems such as poor adhesive force and light trigger be residual after solidifying.These deficiencies have affected further developing and using of UV-curing technology, and solidify the range of application that the rear larger shortcoming of volume contraction has also had a strong impact on ultraviolet photocureable material.Dual cure (dual-curing) technology is the combination of photocuring and other curing.
In dual UV curable paint, 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 Emulsifier-Free 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 for free radical type and cationic ultra-violet curing adhesive, so have free radical type and cationic hot curing etc.
The below is some typical system of lifting, and some concrete operating parameters.
The free radical type ultraviolet curable agent comprises: the material of polyester-acrylate, epoxy-acrylate, carbamate-acrylate, polyethers-acrylate and following molecular structure;
Figure BSA00000475963800081
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), Diethylene Glycol 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-aminopropyltrimethoxysilane, dimethyl silicone polymer, poly-hydrogen methylsiloxane, poly-methyl methoxy radical siloxane, γ-methacrylic acid the 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-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.
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, 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 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:
Figure BSA00000475963800101
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, epoxymethacrylate, water-soluble itaconic acid epoxy ester resin:
Figure BSA00000475963800102
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 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 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.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-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; 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; Aminoferrocene.
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 because the internal stress that produces when having eliminated radical UV curing during hot curing on the other hand.According to base board for flexible optoelectronic part 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), fatty amines 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.
Figure BSA00000475963800131
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), N-is to carboxyl phenyl succinimide (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, MNA (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 polyoxypropylene polyol-isocyanates.
Amino resins comprises: diaminodiphenyl-methane (DDM), N-is to chlorophenyl-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, N-β-aminoethyl Amino Polyester resin, the α-aminopyridine resin, aminodiphenylether resin, amino silicones, phosphoramidic-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-1,2-PD monoesters, 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 " homogeneous heating mode of uniqueness, so that resin solidification is even, speed 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 (such as the happy Thailand 290 of the U.S. and the happy Thailand 271 of mixing with fumaric acid bisphenol-A unsaturated polyester (UP), happy safe 277 etc.), the triethylene Glycol double methyl methacrylate, ethyleneglycol dimethyacrylate, hydroxyethyl methacrylate or hydroxypropyl acrylate are (such as domestic anchor 302, the triple bond 1030 of Japan), the bisphenol-A epoxy ester is (such as domestic 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 (such as happy safe 372 of the U.S., domestic 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, β-hydroxyethyl methacry-late, trimethylol-propane trimethacrylate, the triethylene Glycol double methyl methacrylate, the multicondensed ethylene glycol double methyl methacrylate, Dimethacryloylethylthioether, phthalic acid two (diethylene glycol (DEG) acrylate), the ethoxylation bisphenol a dimethacrylate, dimethacrylate bisphenol-A ethylene glycol fat, second diester methacrylate, triethlene glycol bismethylacrylate, 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, TEGDMA, methacrylic acid dicyclopentadiene-oxygen-ethyl 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 Bismaleimide, 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, phenol formaldehyde 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, bisphenol-A epoxide vinylester 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.
Figure BSA00000475963800161
Below be specific embodiments of the invention:
Embodiment 1
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure, and conductive layer 2 adopts the nano silver wire films, fills Graphene in the space of described nano silver wire film.
The preparation method is as follows:
1. the effects on surface roughness is cleaned less than the glass 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 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 70 nanometers;
3. drip the solution that is coated with graphene-containing at the nano silver wire film, glass substrate was placed 30 minutes in 80 ℃ environment, remove solvent remaining in the nano silver wire film, need the adhesive of dual cure in the nano silver wire thin film coatings again, described adhesive raw materials comprises following component:
4. glass baseplate surface being carried out ultraviolet light polymerization processed 30 seconds;
5. glass baseplate surface is carried out hot curing and process, temperature is 110 ℃;
6. reuse the UV-irradiation glass baseplate surface, carry out photocuring;
7. the adhesive layer of the dual cure after nano silver wire film and the curing is peeled off glass baseplate surface, form the compliant conductive substrate;
8. 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 adhesive that needs dual cure, and conductive layer 2 adopts the nano silver wire films, fills Graphene in the space of described nano silver wire film, 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, and conductive layer 2 adopts the nano silver wire films, fills Graphene in the space of described nano silver wire film, 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, and conductive layer 2 adopts the nano silver wire films, fills Graphene in the space of described nano silver wire film, and described adhesive raw materials comprises following component:
Figure BSA00000475963800182
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, and conductive layer 2 adopts the nano silver wire films, fills Graphene in the space of described nano silver wire film, 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, and conductive layer 2 adopts the nano silver wire films, fills Graphene in the space of described nano silver wire film, and described adhesive raw materials comprises following component:
Figure BSA00000475963800191
The preparation method is similar to embodiment 1.
Embodiment 7
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doped graphene, the doping mass ratio of described Graphene is 5%, conductive layer 2 adopts the nano silver wire film, fill the adhesive that needs dual cure of doped graphene in the space of described nano silver wire film, described adhesive raw materials comprises following component:
Figure BSA00000475963800192
The preparation method is similar to embodiment 1.
Embodiment 8
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doped graphene, the doping mass ratio of described Graphene is 10%, conductive layer 2 adopts the nano silver wire film, fill the adhesive that needs dual cure of doped graphene in the space of described nano silver wire film, described adhesive raw materials comprises following component:
Figure BSA00000475963800193
The preparation method is similar to embodiment 1.
Embodiment 9
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doped graphene, the doping mass ratio of described Graphene is 15%, conductive layer 2 adopts the nano silver wire film, fill the adhesive that needs dual cure of doped graphene in the space of described nano silver wire film, described adhesive raw materials comprises following component:
Figure BSA00000475963800201
The preparation method is similar to embodiment 1.
Embodiment 10
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doped graphene, the doping mass ratio of described Graphene is 20%, conductive layer 2 adopts the nano silver wire film, fill the adhesive that needs dual cure of doped graphene in the space of described nano silver wire film, described adhesive raw materials comprises following component:
Figure BSA00000475963800202
The preparation method is similar to embodiment 1.
Embodiment 11
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doped graphene, the doping mass ratio of described Graphene is 30%, conductive layer 2 adopts the nano silver wire film, fill the adhesive that needs dual cure of doped graphene in the space of described nano silver wire film, described adhesive raw materials comprises following component:
Figure BSA00000475963800203
The preparation method is similar to embodiment 1.
Embodiment 12
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doped graphene, the doping mass ratio of described Graphene is 40%, conductive layer 2 adopts the nano silver wire film, fill the adhesive that needs dual cure of doped graphene in the space of described nano silver wire film, described adhesive raw materials comprises following component:
Figure BSA00000475963800211

Claims (6)

1.一种柔性光电子器件用基板，包括柔性衬底和导电层，其特征在于，所述柔性衬底和导电层由以下两种结构中的一种构成：①所述柔性衬底为需要双重固化的胶粘剂，所述导电层为银纳米线薄膜，所述银纳米线薄膜的空隙中填充有石墨烯；②所述柔性衬底为掺杂石墨烯的需要双重固化的胶粘剂，所述导电层为银纳米线薄膜，所述银纳米线薄膜的空隙中填充有掺杂石墨烯的需要双重固化的胶粘剂，所述需要双重固化的胶粘剂包括紫外光固化-热固化体系、紫外光固化-微波固化体系、紫外光固化-厌氧固化体系或紫外光固化-电子束固化体系：1. A substrate for a flexible optoelectronic device, comprising a flexible substrate and a conductive layer, characterized in that the flexible substrate and the conductive layer are composed of one of the following two structures: 1. the flexible substrate requires double Cured adhesive, the conductive layer is a silver nanowire film, and graphene is filled in the gaps of the silver nanowire film; ②The flexible substrate is an adhesive doped with graphene that needs double curing, and the conductive layer It is a silver nanowire film, the gap of the silver nanowire film is filled with a graphene-doped adhesive that requires dual curing, and the adhesive that requires dual curing includes UV curing-thermal curing system, UV curing-microwave curing system, UV curing-anaerobic curing system or UV curing-electron beam curing system: ①自由基型紫外光固化-热固化体系，原料包括以下重量份的组份：① Radical UV curing-thermal curing system, the raw materials include the following components by weight:
Figure FSB00000878235400011
Figure FSB00000878235400011
 固化过程为：先进行紫外光固化，接着进行加热固化，再进行紫外光固化；或者先进行加热固化，接着进行紫外光固化，再加热固化；The curing process is: UV curing first, then heating and curing, and then UV curing; or heating and curing first, then UV curing, and then heating and curing; ②自由基型紫外光固化-微波固化体系，原料包括以下重量份的组份：② Radical UV curing-microwave curing system, the raw materials include the following components by weight:
Figure FSB00000878235400012
Figure FSB00000878235400012
 固化过程为：先进行紫外光固化，接着进行微波固化，再进行紫外光固化；或者先进行微波固化，接着进行紫外光固化，再加热或微波固化；The curing process is: UV curing first, then microwave curing, and then UV curing; or microwave curing first, then UV curing, and then heating or microwave curing; ③自由基型紫外光固化-厌氧固化体系，原料包括以下重量份的组份：③ Radical UV curing-anaerobic curing system, the raw materials include the following components by weight:
Figure FSB00000878235400013
Figure FSB00000878235400013
 固化过程是：首先进行紫外光固化，接着未受到光照且处于缺氧条件下的胶粘剂部分会自动进行厌氧固化反应，再进行紫外光固化；The curing process is: firstly carry out ultraviolet light curing, then the adhesive part which is not exposed to light and under anoxic conditions will automatically undergo anaerobic curing reaction, and then carry out ultraviolet light curing; ④自由基型紫外光固化-电子束固化体系，原料包括以下重量份的组份：④ Radical UV curing-electron beam curing system, the raw materials include the following components by weight:
Figure FSB00000878235400021
Figure FSB00000878235400021
 固化过程是：首先进行紫外光固化，接着在真空下进行电子束固化，再进行紫外光固化；The curing process is: first UV curing, then electron beam curing under vacuum, and then UV curing; 2.根据权利要求1所述的柔性光电子器件用基板，其特征在于，在第②种结构中所述石墨烯的掺杂质量比小于或等于40％。2. The substrate for flexible optoelectronic devices according to claim 1, characterized in that, in the second structure, the doping mass ratio of graphene is less than or equal to 40%. 3.根据权利要求1所述的柔性光电子器件用基板，其特征在于，所述自由基热固化剂包括：乙二胺、己二胺、三乙烯四胺、羟乙基二乙烯三胺、羟异丙基二乙烯三胺、聚乙二酸己二酰胺、二甲氨丙胺、四甲基丙二胺、双氰胺、二胺基二苯基砜、二胺基二苯基甲烷、间苯二胺、二乙基甲苯二胺、N-(氨丙基)-甲苯二胺、二甲基乙醇胺、二甲基卞胺、三乙基苄基氯化胺、苄基-二甲胺、N-苄基二甲胺、2，4，6，-三-(二甲胺基甲基)-苯酚、苯酚甲醛己二胺、N，N-二甲基苄胺、2-乙基咪唑、2-苯基咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、1-(2-氨基乙基)-2-甲基咪唑、顺丁烯二酸酐、二苯醚四酸二酐、邻苯二甲酸酐、偏苯三甲酸酐、四溴苯二甲酸酐、聚壬乙酸酐、癸二酸二酰肼、己二酰肼、碳酸二酰肼、草酸二酰肼、丁二酸二酰肼、己二酸二酰肼、N-氨基聚丙烯酰胺、癸二酸酰肼、间苯二甲酸酰肼、对羟基安息香酸酰肼、壬二酸二酰肼、间苯二甲酸二酰肼、二茂铁四氟硼酸盐、三聚氰酸三烯丙酯、甲苯二异氰酸酯、二苯甲烷二异氰酸酯、己二异氰酸酯、三甲基己二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、甲基苯乙烯异氰酸酯、六氢甲苯二异氰酸酯、三苯基甲-4，4′，4′-三异氰酸酯、二氨基二苯基甲烷、N-对氯代苯基-N-N-二甲基脲、3-苯基-1，1-二甲基脲、3-对氯苯基-1，1-二甲基脲、4，4′-二氨基二苯基双酚、聚氨基甲酸酯、脲醛树脂、环氧-乙二胺氨基甲酸酯、2，4，6-三(二甲氨基甲基)苯酚、2，4-二氨基甲苯、聚氨基甲酸脂、甲醚化脲醛树脂、三(3-氨基丙基)胺、2-氨基乙基-二(3-氨基丙基)胺、4，4′-二氨基二苯甲烷、4，4′-二氨基二苯基双酚、4，4′-二氨基二苯砜、三(3-氨基丙基)胺、三聚氰胺树脂、苯代三聚氰胺树脂、六羟甲基三聚氰胺树脂、六甲氧甲基三聚氰胺树脂、脲-三聚氰胺甲醛树脂、聚酯三聚氰胺、三氯异氰脲酸酯、氨基三嗪树脂、氨基甲酸酯丙烯酸酯、4-氨基吡啶树脂、N-β-氨乙基氨基聚酯树脂、α-氨基吡啶树脂、氨基二苯醚树脂、氨基磷酸树脂、羟乙氨基聚酯树脂；所述微波固化胶粘剂与热固化胶粘剂使用相同材料或者不同材料；所述厌氧固化胶粘剂包括：双甲基丙烯酸三缩四乙二醇酯、双甲基丙烯酸多缩乙二醇酯、三缩乙二醇双甲基丙烯酸酯、双甲基丙烯酸乙二醇酯、甲基丙烯酸羟乙酯或羟丙酯、甲氧基化聚乙二醇甲基丙烯酸酯、邻苯二甲酸二缩三乙二醇酯、甲基丙烯酸β-羟乙酯、三缩乙二醇双甲基丙烯酸酯、双甲基丙烯酸硫代二甘醇酯、邻苯二甲酸双(二甘醇丙烯酸酯)、乙氧基化双酚A二甲基丙烯酸酯、二甲基丙烯酸双酚A乙二醇脂、乙二酯甲基丙烯酸酯、二缩三乙二醇二甲基丙烯酸酯、缩乙二醇双甲基丙烯酸酯、乙二醇双甲基丙烯酸酯、一缩二乙醇双甲基丙烯酸酯、环氧树脂甲基丙烯酸酯、双甲基丙烯酸一缩二乙二醇酯；所述电子束固化胶粘剂包括：三酚基甲烷缩水甘油醚环氧树脂、二环戊二烯双酚型环氧树脂、双酚A型乙烯基酯树脂、环氧乙烯基酯树脂、环氧丙烯酸酯树脂、马来酰亚胺树脂、4，4’-二苯甲烷双马来酰亚胺、双酚A-二苯醚双马来酰亚胺、双酚A顺丁烯二酸乙烯基树脂、溴化乙烯基酯树脂、酚醛环氧乙烯基酯树脂、羟甲基化双酚A型环氧树脂、双酚A丙烯酸酯、聚氨酯丙烯酸酯、双酚A环氧乙烯基酯树脂、双酚A苯并噁嗪-环氧树脂、双酚芴环氧树脂、双酚A型环氧丙烯酸酯树脂、双酚A二缩水甘油醚或双酚A环氧氯丙烯酸酯树脂。3. The substrate for flexible optoelectronic devices according to claim 1, wherein the free radical thermal curing agent comprises: ethylenediamine, hexamethylenediamine, triethylenetetramine, hydroxyethyldiethylenetriamine, hydroxyl Isopropyldiethylenetriamine, polyoxalate adipamide, dimethylaminopropylamine, tetramethylpropylenediamine, dicyandiamide, diaminodiphenylsulfone, diaminodiphenylmethane, m-phenyl Diamine, diethyltoluenediamine, N-(aminopropyl)-toluenediamine, dimethylethanolamine, dimethylbenylamine, triethylbenzylamine chloride, benzyl-dimethylamine, N -Benzyldimethylamine, 2,4,6,-tri-(dimethylaminomethyl)-phenol, phenol formaldehyde hexamethylenediamine, N,N-dimethylbenzylamine, 2-ethylimidazole, 2 -Phenylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-aminoethyl)-2-methylimidazole, maleic anhydride, Diphenyl ether tetra-acid dianhydride, phthalic anhydride, trimellitic anhydride, tetrabromophthalic anhydride, polynonacetic anhydride, sebacic acid dihydrazide, adipic dihydrazide, carbonate dihydrazide, oxalic acid dihydrazide Hydrazide, succinic acid dihydrazide, adipic acid dihydrazide, N-aminopolyacrylamide, sebacic acid hydrazide, isophthalic acid hydrazide, p-hydroxybenzoic acid hydrazide, azelaic acid dihydrazide , isophthalic acid dihydrazide, ferrocene tetrafluoroborate, triallyl cyanurate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, bicyclic Hexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, methyl styrene isocyanate, hexahydrotoluene diisocyanate, triphenylmethane-4,4',4'-tri Isocyanate, diaminodiphenylmethane, N-p-chlorophenyl-N-N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-p-chlorophenyl-1,1-di Methylurea, 4,4'-diaminodiphenylbisphenol, polyurethane, urea-formaldehyde resin, epoxy-ethylenediamine carbamate, 2,4,6-tris(dimethylaminomethyl ) phenol, 2,4-diaminotoluene, polyurethane, methyl etherified urea-formaldehyde resin, tris(3-aminopropyl)amine, 2-aminoethyl-bis(3-aminopropyl)amine, 4, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylbisphenol, 4,4'-diaminodiphenylsulfone, tris(3-aminopropyl)amine, melamine resin, benzomelamine resin , Hexamethylolmelamine Resin, Hexamethoxymethylmelamine Resin, Urea-Melamine Formaldehyde Resin, Polyester Melamine, Trichloroisocyanurate, Aminotriazine Resin, Urethane Acrylate, 4-Aminopyridine Resin , N-β-aminoethylaminopolyester resin, α-aminopyridine resin, aminodiphenylether resin, aminophosphoric acid resin, hydroxyethylaminopolyester resin; the microwave curing adhesive and thermal curing adhesive use the same material or different Material; the anaerobic curing adhesive includes: triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate Alcohol Esters, Hydroxyethyl or Propyl Methacrylate, Methoxylated Polyethylene glycol methacrylate, triethylene glycol phthalate, β-hydroxyethyl methacrylate, triethylene glycol dimethacrylate, thiodiethylene glycol dimethacrylate ester, bis(diethylene glycol acrylate), ethoxylated bisphenol A dimethacrylate, bisphenol A glycol dimethacrylate, ethylene glycol methacrylate, bisphenol Triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, epoxy methacrylate, dimethyl Diethylene glycol acrylate; the electron beam curing adhesive includes: triphenolyl methane glycidyl ether epoxy resin, dicyclopentadiene bisphenol epoxy resin, bisphenol A vinyl ester resin, cyclo Oxyethylene ester resin, epoxy acrylate resin, maleimide resin, 4,4'-diphenylmethane bismaleimide, bisphenol A-diphenyl ether bismaleimide, bisphenol A maleic acid vinyl resin, brominated vinyl ester resin, novolac epoxy vinyl ester resin, methylolated bisphenol A type epoxy resin, bisphenol A acrylate, polyurethane acrylate, bisphenol A Epoxy vinyl ester resin, bisphenol A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, bisphenol A type epoxy acrylate resin, bisphenol A diglycidyl ether or bisphenol A epoxy chloride Acrylic resin. 4.根据权利要求1或3所述的柔性光电子器件用基板，其特征在于，所述光引发剂包括安息香及其衍生物安息香甲醚、安息香乙醚、乙酰苯衍生物或安息香异丙醚，阳离子光引发剂包括芳香硫鎓盐、碘鎓盐或或铁盐类，光敏剂包括二苯甲酮、硫杂蒽醌或米蚩酮，助剂包括增塑剂或偶联剂。4. The substrate for flexible optoelectronic devices according to claim 1 or 3, wherein the photoinitiator comprises benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether, acetophenone derivatives or benzoin isopropyl ether, cation The photoinitiator includes aromatic sulfonium salt, iodonium salt or iron salt, the photosensitizer includes benzophenone, thiaxanthraquinone or Michler's ketone, and the auxiliary agent includes plasticizer or coupling agent. 5.根据权利要求4所述的柔性光电子器件用基板，其特征在于所述增塑剂包括：邻苯二甲酸二辛酯、邻苯二甲酸二丁酯、三丁氧基乙烯基磷酸酯、聚乙烯醇缩丁醛、乙酰柠檬酸三丁酯、邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、己二酸二(丁氧基乙氧基)乙酯、钛酸异丙酯、钛酸正丁酯、柠檬酸酯、偏苯三酸(2-乙基)己酯、邻苯二甲酸二(2-乙基)己酯、癸二酸二(2-乙基)己酯、一缩二乙二醇二苯甲酸酯、邻苯二甲酸酐、二丙二醇二苯甲酸酯和氯磺化聚乙烯；所述偶联剂包括甲基乙烯基二氯硅烷、甲基氢二氯硅烷、二甲基二氯硅烷、二甲基一氯硅烷、乙烯基三氯硅烷、γ-氨丙基三甲氧基硅烷、聚二甲基硅氧烷、聚氢甲基硅氧烷、聚甲基甲氧基硅氧烷、γ-甲基丙烯酸丙醋基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚丙基三甲氧基硅烷、氨丙基倍半硅氧烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、长链烷基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、γ-氯丙基三乙氧基硅烷、双-(γ-三乙氧基硅基丙基)、苯胺甲基三乙氧基硅烷、N-β(氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷、N-β(氨乙基)-γ-氨丙基甲基二甲氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲基硅烷、γ-巯基丙基三甲氧基硅烷或γ-巯基丙基三乙氧基硅烷。5. The substrate for flexible optoelectronic devices according to claim 4, wherein the plasticizer comprises: dioctyl phthalate, dibutyl phthalate, tributoxy vinyl phosphate, Polyvinyl butyral, Acetyl tributyl citrate, Dimethyl phthalate, Diethyl phthalate, Bis(butoxyethoxy)ethyl adipate, Isopropyl titanate , n-butyl titanate, citrate, (2-ethyl)hexyl trimellitate, bis(2-ethyl)hexyl phthalate, bis(2-ethyl)hexyl sebacate , diethylene glycol dibenzoate, phthalic anhydride, dipropylene glycol dibenzoate and chlorosulfonated polyethylene; the coupling agent includes methyl vinyl dichlorosilane, methyl hydrogen Dichlorosilane, dimethyldichlorosilane, dimethylmonochlorosilane, vinyltrichlorosilane, γ-aminopropyltrimethoxysilane, polydimethylsiloxane, polyhydrogenmethylsiloxane, Polymethylmethoxysiloxane, γ-propyltrimethoxysilane methacrylate, γ-aminopropyltriethoxysilane, γ-glycidyl ether propyltrimethoxysilane, aminopropyl times Semisiloxane, γ-methacryloxypropyltrimethoxysilane, long-chain alkyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-chloropropyltrimethoxysilane Ethoxysilane, bis-(γ-triethoxysilylpropyl), anilinomethyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(2,3-epoxy Propoxy)propyltrimethoxysilane, γ-(methacryloxy)propyltrimethylsilane, γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane. 6.一种柔性光电子器件用基板的制备方法，其特征在于，包括以下步骤：6. A method for preparing a substrate for a flexible optoelectronic device, comprising the following steps: ①对表面粗糙度小于1nm的刚性基板进行清洗，清洗后用干燥氮气吹干；① Clean the rigid substrate with surface roughness less than 1nm, and dry it with dry nitrogen after cleaning; ②采取旋涂或喷涂或自组装或喷墨打印或丝网印刷的方式在洁净的基板上制备银纳米线薄膜；② Preparation of silver nanowire film on a clean substrate by spin coating or spray coating or self-assembly or inkjet printing or screen printing; ③在银纳米线薄膜上旋涂或喷涂掺杂石墨烯的需要双重固化的胶粘剂层，或先旋涂或滴涂或喷涂含石墨烯的溶液，再旋涂或喷涂需要双重固化的胶粘剂层，所述双重固化是通过两个独立的固化阶段完成的，其中一个阶段是通过紫外光固化反应，另一个阶段是暗反应，所述需要双重固化的胶粘剂包括紫外光固化-热固化体系、紫外光固化-微波固化体系、紫外光固化-厌氧固化体系和紫外光固化-电子束固化体系，当使用紫外光固化-热固化或者紫外光固化-微波固化体系时，采用的顺序是先进行加热固化或者微波固化，然后进行紫外光固化，再进行加热固化或者微波固化；或者先进行紫外光固化，然后进行加热固化或者微波固化，再进行紫外光固化；③ Spin-coat or spray-coat the double-cured adhesive layer doped with graphene on the silver nanowire film, or first spin-coat or drop-coat or spray-coat a graphene-containing solution, and then spin-coat or spray-coat the double-cured adhesive layer, The dual curing is accomplished through two independent curing stages, one of which is through a UV curing reaction, and the other stage is a dark reaction, and the adhesives that require dual curing include UV curing-thermal curing systems, UV curing Curing-microwave curing system, UV curing-anaerobic curing system and UV curing-electron beam curing system, when using UV curing-thermal curing or UV curing-microwave curing system, the order used is to heat and cure first Or microwave curing, then UV curing, then heat curing or microwave curing; or UV curing first, then heat curing or microwave curing, and then UV curing; ④将银纳米线薄膜和固化后的需要双重固化的胶粘剂层或掺杂石墨烯的需要双重固化的胶粘剂剥离刚性基板表面，形成柔性导电基板；；④Peel the silver nanowire film and the cured adhesive layer that needs double curing or the adhesive doped with graphene that needs double curing to peel off the surface of the rigid substrate to form a flexible conductive substrate; ⑤将银纳米线薄膜和固化后的紫外光固化胶粘剂层或掺杂石墨烯的紫外光固化胶剂层剥离刚性基板表面，形成柔性导电基板；⑤Peel the silver nanowire film and the cured UV-curable adhesive layer or graphene-doped UV-curable adhesive layer off the surface of the rigid substrate to form a flexible conductive substrate; ⑥测试柔性导电基板的透过率、电导率和表面形貌的各项参数。⑥ Test the parameters of the transmittance, conductivity and surface morphology of the flexible conductive substrate.
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