CN102208556B - Flexible substrate used in luminescent device and preparation method thereof - Google Patents
Flexible substrate used in luminescent device and preparation method thereof Download PDFInfo
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- CN102208556B CN102208556B CN201110096413.0A CN201110096413A CN102208556B CN 102208556 B CN102208556 B CN 102208556B CN 201110096413 A CN201110096413 A CN 201110096413A CN 102208556 B CN102208556 B CN 102208556B
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Abstract
The invention discloses a flexible substrate used in a luminescent device. The substrate comprises a flexible substrate base and a conducting layer and is characterized in that the conducting layer is a graphite alkene film, the flexible substrate base is an adhesive which is doped with inorganic luminescent nanometer particles and needs a dual solidification, the adhesive needing the dual solidification comprises an ultraviolet light solidification - heat solidification system, an ultraviolet light solidification - microwave solidification system, an ultraviolet light solidification - anaerobic solidification system and an ultraviolet light solidification - electron beam solidification system. According to the substrate, the problems that the surface roughness of the conducting layer is too large and the bonding force between the conducting layer and the flexible substrate base is small are solved, the bonding force between the conducting layer and the flexible substrate base and the obstruction capability of the substrate against water and oxygen are improved.
Description
Technical field
The present invention relates to organic optoelectronic technical field, be specifically related to a kind of substrate used in luminescent device and preparation method thereof.
Background technology
Photoelectron technology is the very high industry of scientific and technological content developing 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.Meanwhile, opto-electronic information technology, in the extensive use of social life every field, has also been created growing great market.Developed country is all using optoelectronic information industry as one of field of giving priority to, and the competition of the field of opto-electronic information just launches at world wide.
The effect of adding fuel to the flames has been played in the development that the extensive use of organic material in opto-electronic device is photoelectron technology.From people such as 1987 Deng of Nian， Kodak high official positions, on summary forefathers' basis, invented after sandwich structure organic electroluminescence device, organic optoelectronic device enters the period of high speed development.The organic material fields such as photodetection, solar cell, display device that are widely used.By the application of organic material, the production cost of opto-electronic device significantly reduces, and performance has had large increase.
Organic optoelectronic device is mostly 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 in the application of some occasion, is very restricted.People start to attempt organic optoelectronic device is deposited on flexible base, board rather than on rigid substrates.
With flexible base, board, replacing the benefit of rigid substrates is that lighter, the difficult fragmentation of product, institute take up space little and be more convenient for carrying.But, although there are these advantages, with flexible base, board, replace rigid substrates also to have many restrictions, 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 also far away from glass substrate, and flexible substrate is carried out to surface smoothing, to process equipment and the technology difficulty of wanting special larger, 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; Between conventional electrode layer and flexible substrate, adhesion is low, 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 subject to the impact of the water oxygen that sees through from substrate, reduced the performance of device, therefore whether can address these problems by be flexible device whether can the crucial factor being widely used.
Summary of the invention
Problem to be solved by this invention is: how a kind of substrate used in luminescent device and preparation method thereof is provided, this substrate has solved the poor problem of adhesion between conductive layer surface poor flatness and conductive layer and flexible substrate, has improved conductivity and the obstructing capacity of substrate to water oxygen of conductive layer.
Technical problem proposed by the invention is to solve like this: a kind of substrate used in luminescent device is provided, comprise flexible substrate and conductive layer, it is characterized in that, described conductive layer is graphene film, described flexible substrate is the adhesive that needs dual cure of doping inorganic light-emitting nano particle, 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: first carry out ultraviolet light polymerization, be then heating and curing, then carry out ultraviolet light polymerization; Or be first heating and curing, then carry out ultraviolet light polymerization, then be heating and curing;
2. free radical type ultraviolet light polymerization-microwave curing system, raw material comprises the component of following weight portion:
Solidification process is: first carry out ultraviolet light polymerization, then carry out microwave curing, then carry out ultraviolet light polymerization; Or first carry out microwave curing, then carry out ultraviolet light polymerization, then 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: first carry out ultraviolet light polymerization, be not then subject to illumination and the adhesive segment under anoxia condition and can automatically carry out anaerobic curing reaction, then carry out ultraviolet light polymerization;
4. free radical type ultraviolet light polymerization-electronic beam curing system, raw material comprises the component of following weight portion:
Solidification process is: first carry out ultraviolet light polymerization, then under vacuum, carry out electronic beam curing, then carry out ultraviolet light polymerization;
5. cation type ultraviolet photo-curing-heat cured system, raw material comprises the component of following weight portion:
Solidification process is: first carry out ultraviolet light polymerization, be then heating and curing, then carry out ultraviolet light polymerization; Or be first heating and curing, then carry out ultraviolet light polymerization, then be heating and curing;
6. cation type ultraviolet photo-curing-microwave curing system, raw material comprises the component of following weight portion:
Solidification process is: first carry out ultraviolet light polymerization, then carry out microwave curing, then carry out ultraviolet light polymerization; Or first carry out microwave curing, then carry out ultraviolet light polymerization, then 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: first carry out ultraviolet light polymerization, be not then subject to illumination and the adhesive segment under anoxia condition and can automatically carry out anaerobic curing reaction, then carry out ultraviolet light polymerization;
8. cation type ultraviolet photo-curing-electronic beam curing system, raw material comprises the component of following weight portion:
Solidification process is: first carry out ultraviolet light polymerization, then under vacuum, carry out electronic beam curing, then carry out ultraviolet light polymerization.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described inorganic light-emitting nanoparticle size is 1～100nm, the doping mass ratio of described inorganic light-emitting nano particle is less than or equal to 40%.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described inorganic light-emitting nano particle is that to take sulfide, oxide, fluoride, phosphate, vanadate, niobates, aluminate, molybdate etc. be luminous host, usings the light-emitting particles of rare earth lanthanide as activator and co-activator.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described sulfide comprises zinc sulphide, lanthanum sulfide, calcium sulfide, cerium sulphide, praseodymium sulfide, neodymium sulfide, samaric sulfide and gadolinium sulfide; Described oxide comprises zinc oxide, yittrium oxide, titanium oxide, gadolinium oxide and luteium oxide; Described fluoride comprises yttrium fluoride, gadolinium fluoride, lanthanum fluoride and cerium fluoride; Described phosphate comprises lanthanum orthophosphate, Gadolinium monophosphate, strontium phosphate, yttrium phosphate and barium phosphate; Described vanadate comprises gadolinium vanadate, Yttrium Orthovanadate, vanadic acid lanthanum, cerium vanadate, vanadic acid calcium, lead vanadate and vanadic acid strontium; Described niobates comprises calcium niobate, niobic acid yttrium, niobic acid gadolinium and niobic acid lutetium; Described aluminate comprises yttrium aluminate, barium aluminate, aluminic acid gadolinium, calcium aluminate and strontium aluminate; Described molybdate comprises lanthanum molybdate, strontium molybdate and barium molybdate; Described rare earth lanthanide comprises europium, samarium, erbium, neodymium, terbium, dysprosium, samarium, cerium, ytterbium and praseodymium.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described free radical thermal curing agents comprises: ethylenediamine, hexamethylene diamine, triethylene tetramine, 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, N-benzyl dimethylamine, 2,4,6 ,-tri--(dimethylamino methyl)-phenol, phenol formaldehyde (PF) hexamethylene diamine, N, N-dimethyl benzylamine, 2-ethyl imidazol(e), 2-phenylimidazole, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 1-(2-amino-ethyl)-glyoxal ethyline, maleic anhydride, diphenyl ether tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, tetrabromo-benzene dicarboxylic acid anhydride, gather acetic anhydride in the ninth of the ten Heavenly Stems, sebacic dihydrazide, adipic dihydrazide, carbon acid dihydrazide, grass acid dihydrazide, succinic acid hydrazide ii, adipic dihydrazide, the amino polyacrylamide of N-, decanedioic acid hydrazides, M-phthalic acid hydrazides, to Para Hydroxy Benzoic Acid hydrazides, azelaic acid two hydrazides, isophthalic dihydrazide, ferrocene tetrafluoroborate, triallyl cyanurate, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, XDI, tetramethylxylylene diisocyanate, methyl styrene isocyanates, hexahydrotoluene vulcabond, triphenyl first-4,4 ', 4 '-triisocyanate, diaminodiphenyl-methane, N-is to chlorophenyl-N-N-dimethyl urea, 3-phenyl-1,1-dimethyl urea, 3-rubigan-1,1-dimethyl urea, 4,4 '-diamino-diphenyl bis-phenol, polyurethanes, Lauxite, epoxy-ethylenediamine carbamate, 2,4,6-tri-(dimethylamino methyl) phenol, 2,4-diaminotoluene, polyurethane, methyl-etherified Lauxite, three (3-aminopropyl) amine, 2-amino-ethyl-bis-(3-aminopropyl) amine, 4,4 '-MDA, 4,4 '-diamino-diphenyl bis-phenol, 4,4 '-diamino-diphenyl sulfone, three (3-aminopropyl) amine, melmac, benzoguanamine resin, hexamethylol melamine resin, hexamethoxymethyl melamine resin, urea-melamine resin, polyester melamine, TCCA ester, aminotriazine resins, urethane acrylate, 4-aminopyridine resin, N-β-aminoethyl Amino Polyester resin, α-aminopyridine resin, aminodiphenylether resin, phosphoramidic-resin, hydroxyethylamino mylar, described microwave curing adhesive and hot setting adhesive are used same material or different materials, described anaerobic curing adhesive comprises: methacrylate tetraethylene-glycol ester, methacrylate multicondensed ethylene glycol ester, triethylene Glycol double methyl methacrylate, ethyleneglycol dimethyacrylate, hydroxyethyl methacrylate or hydroxypropyl acrylate, methoxylated polyethylene glycol methacrylate, phthalic acid Triethylene Glycol, β-hydroxyethyl methacry-late, triethylene Glycol double methyl methacrylate, Dimethacryloylethylthioether, phthalic acid two (diethylene glycol (DEG) acrylate), ethoxylation bisphenol a dimethacrylate, dimethacrylate bisphenol-A ethylene glycol fat, second diester methacrylate, triethylene-glycol dimethylacrylate, triethlene glycol bismethylacrylate, glycol methacrylate, one diethyl acetal double methyl methacrylate, epoxy resin methacrylate, methacrylate diglycol ester, described electronic beam curing adhesive comprises: triphenol methylmethane tetraglycidel ether epoxy resin, bicyclopentadiene bisphenol-type epoxy resin, 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, methylolation bisphenol A type epoxy resin, bisphenol-A acrylate, urethane acrylate, bisphenol-A epoxide vinylester resin, bisphenol A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, bisphenol-a epoxy acrylate resin, bisphenol A diglycidyl ether or bisphenol-A epoxy chloropropene acid esters resin.
According to substrate used in luminescent device provided by the present invention, it is characterized in that, described light trigger comprises benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether, 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, Michler's keton, and auxiliary agent comprises plasticizer and coupling agent.
According to substrate used in luminescent device 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 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, aminopropyl silsesquioxane, γ-methacryloxypropyl trimethoxy silane, 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 preparation method for substrate used in luminescent device, is characterized in that, comprises the following steps:
1. the rigid substrates (as copper foil or iron foil sheet or nickel foil sheet) that effects on surface roughness is less than 1nm cleans, and after cleaning, with drying nitrogen, dries up;
2. adopt the method for chemical vapour deposition (CVD) to prepare graphene film on clean rigid substrates, its preparation condition comprises: the carbon source adopting is one or more in methane, ethane, propane, butane, methyl alcohol, ethanol, and the chemical vapor deposition growth environment of graphene film is: temperature is under the normal pressure or negative pressure of 700 ℃～1000 ℃;
3. the adhesive layer that needs dual cure of spin coating or spraying doping inorganic light-emitting nano particle on graphene film, described dual cure by two independently cure stage complete, 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 adopting is to be first heating and curing or microwave curing, then carry out ultraviolet light polymerization, be heating and curing again or microwave curing, or first carry out ultraviolet light polymerization, be then heating and curing or microwave curing, then carry out ultraviolet light polymerization,
4. the adhesive layer that needs dual cure of the doping inorganic light-emitting nano particle by graphene film and after solidifying is peeled off rigid substrates surface, forms 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 is considerably beyond general conductor, has improved the conductivity of conductive layer in flexible base, board; Due to Graphene, to have intensity high, and after making flexible base, board of the present invention by alternating bending, graphene conductive layer can not rupture, and conductivity also there will not be the phenomenon of decline; In substrate layer, there is inorganic light-emitting nano particle, make substrate layer luminous under exciting light irradiates, not only strengthened the luminous intensity of the luminescent device based on this substrate, and simplified the structure of the luminescent device based on this substrate and required material; Because graphene film has fine and close structure, make water oxygen be difficult to by, simultaneously the adhesive layer that needs dual cure after curing also has fine and close structure, has improved the obstructing capacity of flexible base, board to water oxygen; On the little rigid substrates of roughness, prepare conductive layer and the adhesive layer that needs dual cure, by the method for peeling off, form flexible base, board, improved the evenness of conductive layer surface; The adhesive that needs dual cure in flexible substrate of the present invention has high visible light transmissivity, caking ability and quick-setting feature, improved the visible light transmissivity of flexible base, board, increased the adhesion between conductive layer and flexible substrate, reduced and prepared the required time of flexible base, board.
Accompanying drawing explanation
Fig. 1 is the structural representation of the substrate used in luminescent device of embodiment of the present invention 1-6;
Fig. 2 is the visible light transmissivity of the substrate in the embodiment of the present invention 1.
Wherein, 1, flexible substrate, 2, conductive layer.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described:
Technical scheme of the present invention is to provide a kind of substrate used in luminescent device, and as shown in Figure 1, the structure of device comprises flexible substrate 1, conductive layer 2.
The support that in the present invention, flexible substrate 1 is conductive layer, it has good bending performance, the ability that has certain anti-steam and oxygen infiltration, there are good chemical stability and thermal stability, conductive layer 2 requires to have good conductive capability, flexible substrate 1 and conductive layer 2 consist of following two kinds of modes: 1. described flexible substrate is the adhesive that needs dual cure, and described conductive layer is graphene film, is filled with inorganic light-emitting nano particle in the space of described graphene film; 2. described flexible substrate is the adhesive that needs dual cure of doping inorganic light-emitting nano particle, described conductive layer is graphene film, the adhesive that needs dual cure that is filled with doping inorganic light-emitting nano particle in the space of described graphene 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.
In the present invention, need each composition of stick of dual cure glue to be described as follows:
UV-curing technology is owing to having adopted ultraviolet light as the curing energy, determined there is the limitation of self, be mainly manifested in: application base material shape is had to certain restriction, low to band color system curing rate, deep layer and object shadow region are difficult to solidify, and after solidifying, volume contraction causes more greatly poor adhesive force and the problem such as light trigger is residual.These deficiencies have affected further developing and applying 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 complete by two stages independently with differential responses principle, and one of them stage is by photocuring reaction, and another stage is undertaken by dark reaction.Wherein, photocuring can be free radical ultraviolet light polymerization, can be also 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 make system fast shaping or reach surface drying, and utilize dark reaction make dash area or bottom partly solidified completely.
The stage of photocuring and dark curing can be for free radical type and cationic ultra-violet curing adhesive, so there is free radical type and cationic hot curing etc.
Some typical system of lifting below, and some concrete operating parameters.
Free radical type ultraviolet curable agent comprises: the material of polyester-acrylate, epoxy-acrylate, carbamate-acrylate, polyethers-acrylate and following molecular structure;
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 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, aminopropyl silsesquioxane, γ-methacryloxypropyl trimethoxy silane, 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.
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.
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.
Difunctionality reactive diluent has: triethylene glycol diacrylate, tripropylene glycol diacrylate, glycol diacrylate, polyethylene glycol diacrylate alcohol ester, neopentylglycol diacrylate and propoxyl group neopentylglycol diacrylate, acrylate-functional monomer mainly contains 1,6-hexanediyl ester (HDDA), BDO diacrylate (BDDA), propylene glycol diacrylate (DPGDA), glycerol diacrylate (TPGDA), the trihydroxy methyl propane triacrylate (TMPTA) of trifunctional, pentaerythritol triacrylate (PETA), trihydroxy methyl propane triol triacrylate (TMPTMA), trimethylolpropane triacrylate, propoxylation trihydroxy is through 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, 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 is mainly in molecule, to introduce ethyoxyl or propoxyl group, has overcome the large shortcoming of excitant, also should have higher activity and state of cure.As ethoxylation trihydroxy methyl propane triol triacrylate (TMP (EO) TMA), propoxylation trihydroxy methyl propane triol triacrylate (TMP (PO) TMA), propoxylation glycerol triacrylate (G (PO) TA).Third generation acrylic monomers is mainly the acrylate that contains methoxyl group, preferably resolves the contradiction of high curing rate and shrinkage, low state of cure.This class material has 1,6-hexylene glycol methoxyl group mono acrylic ester (HDOMEMA), ethoxylation neopentyl glycol methoxyl group mono acrylic ester (TMP (PO) MEDA).In molecule, introduce after alkoxyl, can reduce the viscosity of monomer, reduce the excitant of monomer simultaneously.
The introducing of alkoxyl is also improved a lot to the compatibility of diluent monomer, and vinyltriethoxysilane (A15I), gamma-methyl allyl acyloxypropyl trimethoxysilane (A174) can be used as monomer.
Cruel in various active epoxy diluent resins and various cyclic ethers, 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), 1, 4-butanediol vinyl ethers (HBVE), cyclohexyl vinyl ether (CHVE), perfluoro methyl vinyl ether (PMVE), perfluor n-propyl vinyl ether, IVE, hydroxy butyl vinyl ether, vinyl ethyl ether, ethyl vinyl ether, 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:
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 to absorb after ultraviolet light energy at it, through decomposing, produces free radical, thus the unsaturated bond polymerization in initiator system, and crosslinking curing becomes an integral body.Conventional radical photoinitiator has cracking type and puies forward the large class of Hydrogen two.
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 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), phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide (819), tetramethylpiperidone oxide (TMPO), triethyl phosphate (TEPO), they are more satisfactory light triggers, there is very high light-initiated activity, long wave near ultraviolet ray is had to absorption, be applicable to the situation that whitewash and film are thicker, and there is good stability, can variable color or fade.
Carry Hydrogen initator: carry Hydrogen initator and mainly contain benzophenone and thioxanthones etc.Wherein thioxanthone photoinitiator at the maximum absorption wavelength in black light district at 380-420nm, and absorbability and hydrogen-taking capacity strong, there is higher efficiency of initiation.Carrying Hydrogen initator must have hydrogen donor as collaborative composition, otherwise efficiency of initiation is too low, so that can not be put to application.Triplet state carbonyl free radical is than more likely extracting hydrogen on secondary carbon or on methyl from the tertiary carbon of hydrogen donor molecule, and the hydrogen being connected on the hetero-atoms such as oxygen or nitrogen more easily extracts than the hydrogen on carbon atom.This class hydrogen donor has amine, hydramine (triethanolamine, methyl diethanolamine, triisopropanolamine etc.), mercaptan, N, N-diethyl-and to dimethylamino benzamide.
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, 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 can eliminate oxygen in glued membrane to the benzophenone of the inhibition of Raolical polymerizable the initiator system that coordinates with tertiary 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, also have stability with epoxy resin after coordinating, so be widely used in cationic curing system.This type of initator comprises: xylyl iodine hexafluorophosphate (PI810), hydroxy phenyl salt compounded of iodine (HTIB), the two detergent alkylate iodine hexafluoro antimonates of 4,4-, xylyl salt compounded of iodine, diphenyl hexafluoroarsenate salt compounded of iodine, [4-(2-hydroxyl-3-butoxy-1-propoxyl group) phenyl] iodo-hexafluoro antimonate of benzene, [4-(to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, [4-(4-benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate, 4-(to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, 4,4 '-dimethyl diphenyl salt compounded of iodine hexafluorophosphate (IHT-PI 820), 4,4 '-diacetylamino diphenyl iodine hexafluorophosphate, 37-dinitro dibenzo ring-type salt compounded of iodine and 3,7 one dinitro dibenzo ring-type bromine salt, tetrafluoro boric acid diaryl group iodized salt, 3,3 '-dinitro diphenyl salt compounded of iodine, 3,3 '-dinitro diphenyl salt compounded of iodine and several 2,2 '-bis-replaces (iodine, bromine, chlorine)-5,5 '-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, 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, phosphorus hexafluoride triaryl sulfonium salts, antimony hexafluoride triaryl sulfonium salts, [4-(to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, 1-(4 '-bromo-2 '-luorobenzyl) pyridiniujm, [4-(to benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate, 4-[4-(p-nitrophenyl formoxyl) thiophenyl] and benzene } phenyl-iodide hexafluorophosphate, 4-[4-(to methyl benzoyl) thiophenyl] and benzene } phenyl-iodide hexafluorophosphate, 4-[4-(to methyl benzoyl) phenoxy group] and benzene } phenyl-iodide hexafluorophosphate, [4-(to 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 developing after two fragrant salt compounded of iodine and three aromatic sulfonium salts, mainly comprises: cyclopentadienyl group-iron-benzene salt, cyclopentadienyl group-iron-toluene salt, cyclopentadienyl group-iron-paraxylene salt, cyclopentadienyl group-iron-naphthalene salts, cyclopentadienyl group-iron-biphenyl salt, cyclopentadienyl group-iron-2,4-dimethyl acetophenone salt, acetyl group-cyclopentadienyl group-iron-paraxylene salt, cyclopentadienyl group-iron-methyl phenyl ethers anisole salt, cyclopentadienyl group-iron-diphenyl ether salt, cyclopentadienyl group-iron-2,4-diethoxybenzene salt, 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-Isosorbide-5-Nitrae-diethoxybenzene salt, cyclopentadienyl group-iron-chlorobenzene salt, cyclopentadienyl group-iron-(Isosorbide-5-Nitrae-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 '-bis-(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 '-dibenzoyl ferrocene, (3-carboxyl propionyl group) ferrocene, 1,1 '-dibromo ferrocene, Aminoferrocene.
Ultraviolet light polymerization-heat cured system: after discovery heat treatment, the mechanical performance of cured product is significantly improved, and along with the increase of epoxy component, hybrid systems has good adhesion property on the grounds such as metal, this is to shrink little cause while solidifying due to epoxy compounds on the one hand, is the internal stress producing while having eliminated radical UV curing during due to hot curing on the other hand.According to substrate used in luminescent device provided by the present invention, it is characterized in that, the thermal curing agents in 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.
Aliphat amine comprises: ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, ethoxy diethylenetriamine, hydroxyl isopropyl diethylenetriamine, poly-ethanedioic acid adipamide, diethanol amine, tetramethylethylenediamine, glycyrrhizic acid diamines, N-(2-ethoxy) ethylenediamine, two (4-amido phenoxy group)-phenyl phosphorous oxide, two (3-aminocarbonyl phenyl) phenyl phosphorous oxide, 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).
Dicyandiamide class comprises: dicyandiamide, 3, the cyanoguanidine derivative of 5 disubstituted benzenes amine modifications (HT 2833, HT 2844), dicyandiamide (MD 02, reacted and makes with dicyandiamide by expoxy propane), 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, N-benzyl dimethylamine, 2, 4, 6,-tri--(dimethylamino methyl)-phenol, phenol formaldehyde (PF) hexamethylene diamine, N, N-dimethyl benzylamine (BDMA), N-is to carboxyl phenyl succinimide (p-CPMD).
Imidazoles comprises: 1-methylimidazole, 2-ethyl imidazol(e), 2-phenylimidazole, glyoxal ethyline, 1-8-amino-ethyl-glyoxal ethyline (AMz), 2-undecyl imidazole adipic acid disalt, 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, 1, the chloride of 3-diphenyl-glyoxal ethyline, 1-decyl-2-ethyl imidazol(e), modified imidazole (JH-0511, JH-0512, JH-0521).
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), 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), 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, carbon acid dihydrazide, careless acid dihydrazide, 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.
Lewis acid amine is by BF
3, AlCl
3, ZnCl
2, PF
5deng lewis acid and primary amine or secondary amine, form complex compound and form, comprising: cyclopentadienyl group isopropylbenzene iron hexafluorophosphate (Irgacure 261), boron trifluoride, ferrocene tetrafluoroborate.
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, 1-dimethyl urea, 3-rubigan-1, 1-dimethyl urea, 4, 4 '-diamino-diphenyl bis-phenol, polyurethanes, Lauxite, epoxy-ethylenediamine carbamate, N, N, N ', N '-tetra-propargyl-4, 4 '-diaminourea-diphenyl-methane (TPDDM), 2, 4, 6-tri-(dimethylamino methyl) phenol, 2, 4-diaminotoluene, 4, 6-tri-(dimethylamino methyl) phenol, polyurethane, methyl-etherified Lauxite, three (3-aminopropyl) amine, 2-amino-ethyl-bis-(3-aminopropyl) amine, N, N, N ', N '-tetra-(3-aminopropyl) ethylenediamine, 1-[bis-(3-aminopropyl) amino]-2-propyl alcohol, N-(2-amino-ethyl)-N-(3-aminopropyl) amine, 1-[(2-amino-ethyl)-(3-aminopropyl) amino]-1-ethanol, 1-[(2-amino-ethyl)-(3-aminopropyl) amino]-2-propyl alcohol, 3-dimethylaminopropylamine, 4,4 '-MDA (DDM), 4,4 '-diamino-diphenyl bis-phenol, 4,4 '-diamino-diphenyl sulfone (DDS), three (3-aminopropyl) amine, melmac, benzoguanamine resin, hexamethylol melamine resin, 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, polyester melamine, 2-secondary butyl phenenyl-N-methylamino acid esters, DCCA ester, TCCA ester, aminotriazine resins, urethane acrylate, 4-aminopyridine resin, N-β-aminoethyl Amino Polyester resin, α-aminopyridine resin, aminodiphenylether resin, amino silicones, phosphoramidic-resin, maleopimaric acid polyester amino resin, piperazine aminodithioformic acid type chelating resin, hydroxyethylamino mylar.
Free radical thermal curing agents comprises: cumyl peroxide, acrylic acid epoxy monoesters, the tertiary fourth fat of benzoic acid, urethane acrylate, polyurethane diol, polyester triol, two (hexafluorophosphoric acid esters), polymethyl methacrylate (PMMA), cinnamic acrylic ester, polybutadiene type crylic acid hydroxy ester, polyester urethane acrylate, 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 microwave curing mode is identical with the thermal curing agents in 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 molecule " homogeneous heating mode of uniqueness, make that resin solidification is even, speed is fast, be easy to control, save the energy, equipment investment is few, microwave replaces hot curing more and more to come into one's own in the research aspect thermosetting resin and composite material solidification thereof in recent years.
Ultraviolet light polymerization-anaerobic curing system: the anaerobic curing agent in anaerobic curing system comprises: methacrylate tetraethylene-glycol ester, methacrylate multicondensed ethylene glycol ester is (as the happy Thailand 271 of finding pleasure in Thailand 290 and mixing with fumaric acid bisphenol-A unsaturated polyester (UP) of the U.S., happy safe 277 etc.), triethylene Glycol double methyl methacrylate, ethyleneglycol dimethyacrylate, hydroxyethyl methacrylate or hydroxypropyl acrylate are (as domestic anchor 302, the triple bond 1030 of Japan), bisphenol-A epoxy ester is (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 (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, methoxylated polyethylene glycol methacrylate, phthalic acid Triethylene Glycol, β-hydroxyethyl methacry-late, trimethylol-propane trimethacrylate, triethylene Glycol double methyl methacrylate, multicondensed ethylene glycol double methyl methacrylate, Dimethacryloylethylthioether, phthalic acid two (diethylene glycol (DEG) acrylate), 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, a-Methyl 2-cyanoacrylate, a-cyanacrylate, glycidyl methacrylate, polyethylene glycol dimethacrylate, TEGDMA, methacrylic acid dicyclopentadiene-oxygen-ethyl ester, methyl-prop dimethylaminoethyl acrylate.
Ultraviolet light polymerization-electronic beam curing system: the electronic beam curing agent in electronic beam curing mode comprises: triphenol methylmethane tetraglycidel ether epoxy resin, 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, 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, methylolation bisphenol-type epoxy resin, bisphenol-A acrylate, urethane acrylate, bisphenol-A epoxide vinylester resin, bisphenol A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, bisphenol-a epoxy acrylate resin, bisphenol A diglycidyl ether, bisphenol-A epoxy chloropropene acid esters resin.
DER383
DER383-TBBA
Below specific embodiments of the invention:
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping inorganic light-emitting nano particle, described inorganic light-emitting nano particle is of a size of 1nm, and the doping mass ratio of described inorganic light-emitting nano particle is 5%, and conductive layer 2 adopts graphene film.
Preparation method is as follows:
1. the copper foil that effects on surface roughness is less than 1nm cleans, and after cleaning, with drying nitrogen, dries up;
2. adopt the method for chemical vapour deposition (CVD) to prepare graphene film on clean copper foil; 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 the normal pressure or negative pressure of 700 ℃～1000 ℃;
3. on graphene film, spray the adhesive that needs dual cure of doping inorganic light-emitting nano particle, the doping mass ratio of described inorganic light-emitting nano particle is 5%, and adhesive raw materials comprises following component:
4. ultraviolet light polymerization being carried out in copper foil surface processes 30 seconds;
5. hot curing processing is carried out in copper foil surface, temperature is 110 ℃;
6. reuse UV-irradiation copper foil surface, carry out photocuring;
7. the adhesive layer of the dual cure by graphene film and after solidifying is peeled off copper foil surface, forms compliant conductive substrate;
8. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping inorganic light-emitting nano particle, described inorganic light-emitting nano particle is of a size of 15nm, the doping mass ratio of described inorganic light-emitting nano particle is 10%, conductive layer 2 adopts graphene film, and described adhesive raw materials comprises following component:
Preparation method is similar to embodiment 1.
Embodiment 3
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping inorganic light-emitting nano particle, the doping mass ratio of described inorganic light-emitting nano particle is 20%, and conductive layer 2 adopts graphene film, and described adhesive raw materials comprises following component:
Preparation method is similar to embodiment 1.
Embodiment 4
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping inorganic light-emitting nano particle, described inorganic light-emitting nano particle is of a size of 35nm, the doping mass ratio of described inorganic light-emitting nano particle is 25%, conductive layer 2 adopts graphene film, and described adhesive raw materials comprises following component:
Preparation method is similar to embodiment 1.
Embodiment 5
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping inorganic light-emitting nano particle, described inorganic light-emitting nano particle is of a size of 50nm, the doping mass ratio of described inorganic light-emitting nano particle is 30%, conductive layer 2 adopts graphene film, and described adhesive raw materials comprises following component:
Preparation method is similar to embodiment 1.
Embodiment 6
Board structure as shown in Figure 1, flexible substrate 1 adopts the adhesive that needs dual cure of doping inorganic light-emitting nano particle, described inorganic light-emitting nano particle is of a size of 100nm, the doping mass ratio of described inorganic light-emitting nano particle is 40%, conductive layer 2 adopts graphene film, and described adhesive raw materials comprises following
Component:
Preparation method is similar to embodiment 1.
Claims (8)
1. a substrate used in luminescent device, comprise flexible substrate and conductive layer, it is characterized in that, described conductive layer is graphene film, described flexible substrate is the adhesive that needs dual cure of doping inorganic light-emitting nano particle, 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: first carry out ultraviolet light polymerization, be then heating and curing, then carry out ultraviolet light polymerization; Or be first heating and curing, then carry out ultraviolet light polymerization, then be heating and curing;
2. free radical type ultraviolet light polymerization-microwave curing system, raw material comprises the component of following weight portion:
Solidification process is: first carry out ultraviolet light polymerization, then carry out microwave curing, then carry out ultraviolet light polymerization; Or first carry out microwave curing, then carry out ultraviolet light polymerization, then 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: first carry out ultraviolet light polymerization, be not then subject to illumination and the adhesive segment under anoxia condition and can automatically carry out anaerobic curing reaction, then carry out ultraviolet light polymerization;
4. free radical type ultraviolet light polymerization-electronic beam curing system, raw material comprises the component of following weight portion:
Solidification process is: first carry out ultraviolet light polymerization, then under vacuum, carry out electronic beam curing, then carry out ultraviolet light polymerization;
5. cation type ultraviolet photo-curing-heat cured system, raw material comprises the component of following weight portion:
Solidification process is: first carry out ultraviolet light polymerization, be then heating and curing, then carry out ultraviolet light polymerization; Or be first heating and curing, then carry out ultraviolet light polymerization, then be heating and curing;
6. cation type ultraviolet photo-curing-microwave curing system, raw material comprises the component of following weight portion:
Solidification process is: first carry out ultraviolet light polymerization, then carry out microwave curing, then carry out ultraviolet light polymerization; Or first carry out microwave curing, then carry out ultraviolet light polymerization, then 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: first carry out ultraviolet light polymerization, be not then subject to illumination and the adhesive segment under anoxia condition and can automatically carry out anaerobic curing reaction, then carry out ultraviolet light polymerization;
8. cation type ultraviolet photo-curing-electronic beam curing system, raw material comprises the component of following weight portion:
Solidification process is: first carry out ultraviolet light polymerization, then under vacuum, carry out electronic beam curing, then carry out ultraviolet light polymerization.
2. substrate used in luminescent device according to claim 1, is characterized in that, described inorganic light-emitting nanoparticle size is 1～100nm, and the doping mass ratio of described inorganic light-emitting nano particle is less than or equal to 40%.
3. substrate used in luminescent device according to claim 1, it is characterized in that, described inorganic light-emitting nano particle is to take sulfide, oxide, fluoride, phosphate, vanadate, niobates, aluminate or molybdate as luminous host, usings the light-emitting particles of rare earth lanthanide as activator and co-activator.
4. substrate used in luminescent device according to claim 3, is characterized in that, described sulfide comprises zinc sulphide, lanthanum sulfide, calcium sulfide, cerium sulphide, praseodymium sulfide, neodymium sulfide, samaric sulfide or gadolinium sulfide; Described oxide comprises zinc oxide, yittrium oxide, titanium oxide, gadolinium oxide or luteium oxide; Described fluoride comprises yttrium fluoride, gadolinium fluoride, lanthanum fluoride or cerium fluoride; Described phosphate comprises lanthanum orthophosphate, Gadolinium monophosphate, strontium phosphate, yttrium phosphate or barium phosphate; Described vanadate comprises gadolinium vanadate, Yttrium Orthovanadate, vanadic acid lanthanum, cerium vanadate, vanadic acid calcium, lead vanadate or vanadic acid strontium; Described niobates comprises calcium niobate, niobic acid yttrium, niobic acid gadolinium or niobic acid lutetium; Described aluminate comprises yttrium aluminate, barium aluminate, aluminic acid gadolinium, calcium aluminate or strontium aluminate; Described molybdate comprises lanthanum molybdate, strontium molybdate or barium molybdate; Described rare earth lanthanide comprises europium, samarium, erbium, neodymium, terbium, dysprosium, samarium, cerium, ytterbium or praseodymium.
5. substrate used in luminescent device according to claim 1, is characterized in that, described free radical thermal curing agents comprises: ethylenediamine, hexamethylene diamine, triethylene tetramine, 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, N-benzyl dimethylamine, 2,4,6 ,-tri--(dimethylamino methyl)-phenol, phenol formaldehyde (PF) hexamethylene diamine, N, N-dimethyl benzylamine, 2-ethyl imidazol(e), 2-phenylimidazole, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 1-(2-amino-ethyl)-glyoxal ethyline, maleic anhydride, diphenyl ether tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, tetrabromo-benzene dicarboxylic acid anhydride, gather acetic anhydride in the ninth of the ten Heavenly Stems, sebacic dihydrazide, adipic dihydrazide, carbon acid dihydrazide, grass acid dihydrazide, succinic acid hydrazide ii, adipic dihydrazide, the amino polyacrylamide of N-, decanedioic acid hydrazides, M-phthalic acid hydrazides, to Para Hydroxy Benzoic Acid hydrazides, azelaic acid two hydrazides, isophthalic dihydrazide, ferrocene tetrafluoroborate, triallyl cyanurate, first is lifted vulcabond, '-diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, XDI, tetramethylxylylene diisocyanate, methyl styrene isocyanates, hexahydrotoluene vulcabond, triphenyl first-4,4 ', 4 '-triisocyanate, diaminodiphenyl-methane, N-is to chlorophenyl-N-N-dimethyl urea, 3-phenyl-1,1-dimethyl urea, 3-rubigan-1,1-dimethyl urea, 4,4 '-diamino-diphenyl bis-phenol, polyurethanes, Lauxite, epoxy-ethyl-bis-amine carbamate, 2,4,6-tri-(dimethylamino methyl) phenol, 2,4-diaminotoluene, polyurethane, methyl-etherified Lauxite, three (3-aminopropyl) amine, 2-amino-ethyl-bis-(3-aminopropyl) amine, 4,4 '-MDA, 4,4 '-diamino-diphenyl bis-phenol, 4,4 '-diamino-diphenyl sulfone, three (3-aminopropyl) amine, melmac, benzoguanamine resin, hexamethylol melamine resin, hexamethoxymethyl melamine resin, urea-melamine resin, polyester melamine, TCCA ester, aminotriazine resins, urethane acrylate, 4-aminopyridine resin, N-β-aminoethyl Amino Polyester resin, α-aminopyridine resin, aminodiphenylether resin, phosphoramidic-resin, hydroxyethylamino mylar, described microwave curing adhesive and hot setting adhesive are used same material or different materials, described anaerobic curing adhesive comprises: methacrylate tetraethylene-glycol ester, methacrylate multicondensed ethylene glycol ester, triethylene Glycol double methyl methacrylate, ethyleneglycol dimethyacrylate, hydroxyethyl methacrylate or hydroxypropyl acrylate, methoxylated polyethylene glycol methacrylate, phthalic acid Triethylene Glycol, β-hydroxyethyl methacry-late, triethylene Glycol double methyl methacrylate, Dimethacryloylethylthioether, phthalic acid two (diethylene glycol (DEG) acrylate), ethoxylation bisphenol a dimethacrylate, dimethacrylate bisphenol-A ethylene glycol fat, second diester methacrylate, triethylene-glycol dimethylacrylate, triethlene glycol bismethylacrylate, glycol methacrylate, one diethyl acetal double methyl methacrylate, epoxy resin methacrylate, methacrylate diglycol ester, described electronic beam curing adhesive comprises: triphenol methylmethane tetraglycidel ether epoxy resin, bicyclopentadiene bisphenol-type epoxy resin, 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, methylolation bisphenol A type epoxy resin, bisphenol-A acrylate, urethane acrylate, bisphenol-A epoxide vinylester resin, bisphenol A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, bisphenol-a epoxy acrylate resin, bisphenol A diglycidyl ether or bisphenol-A epoxy chloropropene acid esters resin.
6. substrate used in luminescent device according to claim 1, it is characterized in that, described light trigger comprises benzoin and its derivatives benzoin methyl ether, benzoin ethyl ether, 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 and coupling agent.
7. substrate used in luminescent device according to claim 6, 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 or chlorosulfonated polyethylene, described coupling agent comprises 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, aminopropyl silsesquioxane, γ-methacryloxypropyl trimethoxy silane, 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.
8. a preparation method for substrate used in luminescent device, is characterized in that, comprises the following steps:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and after cleaning, with drying nitrogen, dries up;
2. adopt the method for chemical vapour deposition (CVD) to prepare graphene film on clean rigid substrates;
3. the adhesive layer that needs dual cure of spin coating or spraying doping inorganic light-emitting nano particle on graphene layer, described dual cure by two independently cure stage complete, 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 adopting is to be first heating and curing or microwave curing, then carry out ultraviolet light polymerization, be heating and curing again or microwave curing, or first carry out ultraviolet light polymerization, be then heating and curing or microwave curing, then carry out ultraviolet light polymerization,
4. the adhesive layer that needs dual cure of the doping inorganic light-emitting nano particle by graphene layer and after solidifying is peeled off rigid substrates surface, forms compliant conductive substrate;
5. test the parameters of transmitance, conductivity and the surface topography of compliant conductive substrate.
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| EP2833428A4 (en) * | 2012-03-31 | 2015-11-25 | Oceans King Lighting Science | Organic electroluminescence device and method for manufacture thereof |
| WO2017103640A1 (en) | 2015-12-18 | 2017-06-22 | Essilor International (Compagnie Generale D'optique) | Liquid polymerizable composition comprising chain-growth and step-growth polymerization monomers and inorganic nanoparticles dispersed therein, and its use to manufacture an optical article |
| EP3417032A1 (en) * | 2016-02-16 | 2018-12-26 | Henkel IP & Holding GmbH | Nanocrystal epoxy thiol (meth)acrylate composite material and nanocrystal epoxy thiol (methacrylate) composite film |
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