CN102208550B - Substrate for flexible photoelectronic device and preparation method thereof - Google Patents
Substrate for flexible photoelectronic device and preparation method thereof Download PDFInfo
- Publication number
- CN102208550B CN102208550B CN 201110097184 CN201110097184A CN102208550B CN 102208550 B CN102208550 B CN 102208550B CN 201110097184 CN201110097184 CN 201110097184 CN 201110097184 A CN201110097184 A CN 201110097184A CN 102208550 B CN102208550 B CN 102208550B
- Authority
- CN
- China
- Prior art keywords
- ultraviolet light
- curing
- light polymerization
- carry out
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a substrate for a flexible photoelectronic device, comprising a flexible substrate and a conductive layer. The substrate for the flexible photoelectronic device is characterized in that the conductive layer is a graphene film while the flexible substrate is an adhesive needing to be doubly cured; 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 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.
The extensive use of organic material in opto-electronic device is that the effect of adding fuel to the flames has been played in the development of photoelectron technology.From 1987, the people such as Deng of Kodak high official position were after the sandwich structure organic electroluminescence device has been invented on the basis of summing up forefathers, and organic optoelectronic device enters the period of high speed development.The organic material fields such as photodetection, solar cell, display device that are widely used.By the application of organic material, the production cost decrease of opto-electronic device, performance has had large increase.
Organic optoelectronic device mostly is that preparation is at rigid substrates (on glass or silicon chip), although they have good device performance, anti-vibration at present, shock proof ability a little less than, weight is relatively heavier, and it is very not convenient to carry, and is very restricted in the application of some occasion.People begin to attempt to be deposited on organic optoelectronic device on the flexible base, board rather than on the rigid substrates.
With flexible base, board replace the benefit of rigid substrates be product lighter, be difficult for broken, institute takes up space little and be more convenient for carrying.But, although these advantages are arranged, replace rigid substrates also to have many restrictions with flexible base, board, the preparation of flexible device still has many underlying issues to need to solve.As owing to comparing with rigid substrate, the profile pattern of flexible substrate is far away from glass substrate, and to process equipment and the technology difficulty of wanting special larger and flexible substrate is carried out surface smoothing, improved the production cost of substrate; Thereby the electrode material of organic optoelectronic device is the very easily oxidized decline that causes device performance in oxygen containing environment; Adhesion is low between conventional electrode layer and the flexible substrate, is easy to peel off; The water of flexible base, board, oxygen permeability are much larger than rigid substrates, cause opto-electronic device to be subjected to the water effect of oxygen that sees through from substrate, reduced performance of devices, therefore whether can address these problems be flexible device whether can the crucial factor that is widely used.
Summary of the invention
Technical 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 poor problem of adhesion between conductive layer surface roughness large 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 base board for flexible optoelectronic part 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, 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, 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 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:
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:
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 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:
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:
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:
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, 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 or 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 and 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.
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, 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 or 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 copper foil or iron foil sheet or nickel foil sheet) of 1nm, dries up with drying nitrogen after cleaning;
2. adopt the method for chemical vapour deposition (CVD) to prepare graphene film at the rigid substrates of cleaning, its preparation condition comprises: the carbon source that adopts is one or more in methane, ethane, propane, butane, methyl alcohol, the ethanol, and the chemical vapor deposition growth environment of graphene film is: temperature is under 700 ℃～1000 ℃ the normal pressure or negative pressure;
3. spin coating or spraying need the adhesive layer of dual cure 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 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 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 to have intensity high for Graphene, make flexible base, board of the present invention by alternating bending after, the graphene conductive layer can fracture, the phenomenon that conductivity also can not occur descending; 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; Employing needs the adhesive layer of dual cure as flexible substrate, increases the adhesion between conductive layer and the flexible substrate.
Description of drawings
Fig. 1 is the structural representation of the base board for flexible optoelectronic part of embodiment of the invention 1-6;
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.
Need each composition of stick of dual cure glue 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;
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:
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:
The effect of light trigger is after it absorbs the ultraviolet light energy, produces free radical through decomposing, thus the unsaturated bond polymerization in the initiator system, and crosslinking curing becomes an integral body.Radical photoinitiator commonly used has cracking type and puies forward Hydrogen two large classes.
Crack type photoinitiator: crack type photoinitiator mainly contains benzoin ethers (styrax ethers), benzil ketals and acetophenone etc.Crack type photoinitiator is chapped after absorbing ultraviolet light, produces two free radicals, and free radical causes the unsaturated group polymerization.Benzoin ethers (styrax ethers) comprising: styrax (Benzoin), benzoin methyl ether, benzoin ethyl ether (Benzoin ethyl ether), benzoin isobutyl ether (Benzoin butyl ether), styrax lose (Benzoin oxime), benzoin isopropyl ether; Acylphosphine oxide comprises: 2; 4; 6 trimethylbenzene formyl diphenyl phosphine oxides (TPO) and (2; 4; 6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO phenyl bis (2; 4; 6-trimethyl benzoyl) phosphine oxide); two (2,4, the 6-trimethylbenzoyl) phosphine oxides (819) of phenyl; tetramethylpiperidone oxide (TMPO); triethyl phosphate (TEPO); they are more satisfactory light triggers; have very high light-initiated activity, the long wave near ultraviolet ray is had absorption, be applicable to the thicker situation of whitewash and film; and have good stability, can variable color or fade.
Carry the Hydrogen initator: carry the Hydrogen initator and mainly contain benzophenone and thioxanthones etc.Wherein at 380-420nm, and absorbability and hydrogen-taking capacity are strong, have higher efficiency of initiation at the maximum absorption wavelength in black light district for thioxanthone photoinitiator.Carrying the Hydrogen initator must have hydrogen donor as collaborative composition, otherwise efficiency of initiation is too low, so that can not be put to use.Than more likely extracting hydrogen on the secondary carbon or on the methyl, the hydrogen that is connected on the hetero-atoms such as oxygen or nitrogen more easily extracts than the hydrogen on the carbon atom triplet state carbonyl free radical from the tertiary carbon of hydrogen donor molecule.This class hydrogen donor has amine, hydramine (triethanolamine, methyl diethanolamine, triisopropanolamine etc.), mercaptan, N, the N-diethyl-and to the dimethylamino benzamide.
The benzophenone light initiation system, benzophenone need to be with alcohol, ether or amine and with just making vinyl monomer carry out photopolymerization.Mainly comprise: benzophenone, the thia anthraquinone, Michler's keton, dimethoxy benzene acetophenone (DMPA), alpha-hydroxy-2,2 dimethyl acetophenones (1173), Alpha-hydroxy cyclohexyl-phenyl ketone (184), α-amine alkyl phenones, 2-methyl isophthalic acid (4-first coloured glaze base phenyl)-2-morpholinyl acetone (MMMP), 2,2 '-dibenzamidodiphenyl disulfide (DBMD), (4-dimethylamino phenyl)-(1-piperidyl)-ketone, isopropyl thioxanthone (ITX), (4-dimethylamino phenyl)-(4-morpholinyl)-ketone, 2-hydroxy-2-methyl-1-phenyl-1-phenyl-1-acetone, two phenoxy group benzophenone, hydroxy-2-methyl phenyl-propane-1-ketone.And mixed system, as eliminating oxygen in the glued membrane to the benzophenone of the inhibition of Raolical polymerizable and the initiator system that cooperates of uncle's ammonia; Michler's keton and benzophenone are used in conjunction with, and can obtain more cheap and effectively initiator system.
Cationic photoinitiator: aromatic sulfonium salts and salt compounded of iodine class initator have excellent high-temperature stability, and also have stability after epoxy resin cooperates, so be widely used in the cationic curing system.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.
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.
Below be specific embodiments of the invention:
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure, and conductive layer 2 adopts graphene films.
The preparation method is as follows:
1. the effects on surface roughness is cleaned less than the copper foil of 1nm, dries up with drying nitrogen after cleaning;
2. adopt the method for chemical vapour deposition (CVD) to prepare graphene film at the rigid substrates of cleaning; Its preparation condition comprises: the carbon source that adopts 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. need the adhesive of dual cure in the graphene film spraying, described adhesive raw materials comprises following component:
4. ultraviolet light polymerization being carried out on the copper foil surface processed 30 seconds;
5. hot curing is carried out on the copper foil surface and processed, 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, 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, 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, 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, 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, and conductive layer 2 adopts graphene films, and described adhesive raw materials comprises following component:
The preparation method is similar to embodiment 1.
Claims (5)
1. base board for flexible optoelectronic part, comprise flexible substrate and conductive layer, it is characterized in that, described conductive layer is Graphene, described flexible substrate is the adhesive that needs dual cure, 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, 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:
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:
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:
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 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:
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:
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:
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. base board for flexible optoelectronic part 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, 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 or bisphenol-A epoxy chloropropene acid esters resin.
3. base board for flexible optoelectronic part according to claim 1, it is characterized in that, described light trigger comprises benzoin and its derivatives benzoin methyl ether, 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.
4. base board for flexible optoelectronic part according to claim 3, 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), 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 or γ-sulfydryl propyl-triethoxysilicane.
5. the preparation method of a 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 of 1nm, dries up with drying nitrogen after cleaning;
2. adopt the method for chemical vapour deposition (CVD) to prepare graphene film at the rigid substrates of cleaning; Its preparation condition comprises: the carbon source that adopts is one or more in methane, ethane, propane, butane, methyl alcohol, the ethanol, and the chemical vapor deposition growth environment of graphene film is: temperature is under 700 ℃～1000 ℃ the normal pressure or negative pressure;
3. spin coating or spraying need the adhesive layer of dual cure on graphene layer, 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 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 graphene layer 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110097184 CN102208550B (en) | 2011-04-18 | 2011-04-18 | Substrate for flexible photoelectronic device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110097184 CN102208550B (en) | 2011-04-18 | 2011-04-18 | Substrate for flexible photoelectronic device and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102208550A CN102208550A (en) | 2011-10-05 |
| CN102208550B true CN102208550B (en) | 2013-01-02 |
Family
ID=44697281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110097184 Expired - Fee Related CN102208550B (en) | 2011-04-18 | 2011-04-18 | Substrate for flexible photoelectronic device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102208550B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019165585A1 (en) * | 2018-02-28 | 2019-09-06 | 邱永兴 | Waterproof adhesive for bonding base layer of photovoltaic panel |
| CN112079978B (en) * | 2020-08-31 | 2022-08-23 | 江苏东材新材料有限责任公司 | DCPD-bisphenol type benzoxazine resin and copper-clad plate composition and preparation method thereof |
| CN117820599B (en) * | 2024-03-04 | 2024-05-07 | 江苏一特新材料有限责任公司 | Preparation method of ultraviolet light curing softening and cracking preventing agent, positive electrode slurry and preparation method thereof, and preparation method of positive electrode plate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101465409A (en) * | 2008-12-31 | 2009-06-24 | 电子科技大学 | Substrate for flexible organic optoelectronic device and preparation method thereof |
| CN101976608A (en) * | 2010-09-27 | 2011-02-16 | 彩虹集团公司 | Method for preparing counter electrode of dye-sensitized solar cell |
-
2011
- 2011-04-18 CN CN 201110097184 patent/CN102208550B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101465409A (en) * | 2008-12-31 | 2009-06-24 | 电子科技大学 | Substrate for flexible organic optoelectronic device and preparation method thereof |
| CN101976608A (en) * | 2010-09-27 | 2011-02-16 | 彩虹集团公司 | Method for preparing counter electrode of dye-sensitized solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102208550A (en) | 2011-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101465409B (en) | Substrate for flexible organic optoelectronic device and preparation method thereof | |
| CN101930990B (en) | Active driving organic electroluminescent device and preparation method thereof | |
| CN102208542B (en) | Substrate for flexible photoelectronic device and preparation method thereof | |
| CN102208538B (en) | Substrate for flexible photoelectronic device and preparation method thereof | |
| CN102208558B (en) | Substrate for flexible luminescent device and preparation method thereof | |
| CN102208554B (en) | Substrate for flexible luminous device and preparation method thereof | |
| CN101916816A (en) | Light-emitting diode and preparation method thereof | |
| CN101465408B (en) | Substrate for flexible organic optoelectronic device and preparation method thereof | |
| CN101425560B (en) | Substrate for flexible organic optoelectric device and preparation thereof | |
| CN104766932A (en) | Biodegradable substrate for flexible optoelectronic device and method for manufacturing same | |
| CN102208556B (en) | Flexible substrate used in luminescent device and preparation method thereof | |
| CN102208571A (en) | Substrate for flexible luminescent device and preparation method thereof | |
| CN102208550B (en) | Substrate for flexible photoelectronic device and preparation method thereof | |
| CN115260226B (en) | Compound for packaging film and ultraviolet light curing ink based on compound | |
| CN102559134A (en) | Tung oil based material for solar battery packaging and packaging method and application thereof | |
| CN102208548B (en) | Flexible optoelectronic device substrate and preparation method thereof | |
| CN102208559B (en) | Substrate for flexible luminescent device and preparation method thereof | |
| CN102208540B (en) | Substrate for flexible photoelectronic device and preparation method thereof | |
| CN102208560A (en) | Substrate for flexible luminescent device and preparation method thereof | |
| CN102270749A (en) | Base plate used for flexible light-emitting device and preparation method thereof | |
| CN104953034B (en) | Degradable base board for flexible optoelectronic part and preparation method thereof | |
| CN103579502B (en) | A kind of organic field effect tube and preparation method thereof | |
| CN102208541A (en) | Flexible substrate used in opto electronic device and preparation method thereof | |
| CN101875715B (en) | Epoxy modified polyurethane, UV-curing coat and preparation method thereof | |
| CN102208537B (en) | Substrate for flexible photoelectronic device and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130102 Termination date: 20150418 |
|
| EXPY | Termination of patent right or utility model |