CN101465408A - Substrate for flexible organic optoelectronic device and preparation method thereof - Google Patents

Substrate for flexible organic optoelectronic device and preparation method thereof Download PDF

Info

Publication number
CN101465408A
CN101465408A CN 200810148117 CN200810148117A CN101465408A CN 101465408 A CN101465408 A CN 101465408A CN 200810148117 CN200810148117 CN 200810148117 CN 200810148117 A CN200810148117 A CN 200810148117A CN 101465408 A CN101465408 A CN 101465408A
Authority
CN
China
Prior art keywords
ether
resin
salt
flexible
agent
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.)
Granted
Application number
CN 200810148117
Other languages
Chinese (zh)
Other versions
CN101465408B (en
Inventor
于军胜
李璐
蒋亚东
王娜娜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Electronic Science and Technology of China
Original Assignee
University of Electronic Science and Technology of China
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Electronic Science and Technology of China filed Critical University of Electronic Science and Technology of China
Priority to CN 200810148117 priority Critical patent/CN101465408B/en
Publication of CN101465408A publication Critical patent/CN101465408A/en
Application granted granted Critical
Publication of CN101465408B publication Critical patent/CN101465408B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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 flexible substrate used for optoelectronic devices and comprises a flexible substrate; the invention is characterized in that a bonding layer and a conductive thin film are arranged on the surface of the flexible substrate; the conductive thin film is deposited on the surface of the bonding layer; the bonding layer is made of UV-curable adhesive; and the adhesive is the mixture of free radical type UV-curable adhesive and cationic type UV-curable adhesive. The cationic-type and free radical-type UV-curable adhesives are united in one to make full use of light energy and achieve mutual modification; the curing product concentrates the advantages of epoxy resin and acrylic resin and overcomes certain shortcomings, thereby creating a brand-new system.

Description

A kind of substrate for flexible organic opto-electronic device and preparation method thereof
Technical field
The present invention relates to the organic optoelectronic device technical field, be specifically related to a kind of substrate for flexible organic opto-electronic device and preparation method thereof.
Background technology
Photoelectron technology is the industry of the high-tech content that develops rapidly after microelectric technique.Fast development along with photoelectron technology, photoelectron products such as solar cell, optical image sensor, electricity slurry flat-panel screens, electroluminescent display, thin-film transistor and panel of LCD, all full-fledged gradually, they have improved human life greatly.Simultaneously, opto-electronic information technology has also been created growing great market in the extensive use of social life every field.Developed country all the optoelectronic information industry as one of field of giving priority to, the competition of the field of opto-electronic information just launches at world wide.
The extensive use of organic material in opto-electronic device is that the effect of adding fuel to the flames has been played in the development of photoelectron technology.From 1987, people such as Deng of Kodak high official position were after having invented the ultra-thin organic electroluminescence device of sandwich structure on the basis of summing up forefathers, and organic optoelectronic device enters the period of high speed development.Organic material is widely used in fields such as photodetection, solar cell, display device.By the application of organic material, the production cost of opto-electronic device reduces significantly, and performance has had large increase.
At present, organic optoelectronic device mostly is that preparation is at rigid substrate (on glass or silicon chip).Though they have good device performance, anti-vibration, shock proof ability a little less than, weight is heavier relatively, 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 substrate rather than on the glass substrate.Perhaps in the near future, we can be involved in computer display in the pen and carry; Can be produced on solar cell on wearable mobile phone and the palmtop PC, utilize sunlight to be powering portable devices; Can be made into flexible TFT the plastic label of radio frequency identification identification technology, detect the content of gas with various, solution system ion.
With flexible substrate replace the benefit of rigid substrate 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 substrate also to have many restrictions with flexible substrate, the preparation of flexible device still has many underlying issues to need to solve.For example, at first, owing to compare with rigid substrate, the surface energy of flexible substrate is low, so the film tack that will deposit relatively is relatively poor, the profile pattern of flexible substrate is also far away from glass substrate in addition.And the electrode material of organic optoelectronic device is very easily oxidized in oxygen containing environment, thereby causes the decline of device performance; Organic material is all very responsive to impurity, oxygen, water, thereby is easy to contaminated reduction device efficiency.The performance that flexible base, board intercepts water oxygen just seems very important.
Usually, in order to obtain the good substrate for flexible organic opto-electronic device of tack, meeting is made conductive film after adopting the method for routines such as mechanical polishing, electrochemical polish or deposition compact inorganic thin film that flexible substrate is handled again, these methods need special equipment and technology difficulty bigger, have improved substrate production cost; On the other hand, utilize the compliant conductive substrate of conventional method preparation, engaging force is low between the electrode of conductive film or patterning and the substrate, is easy to peel off.
Summary of the invention
Technical problem to be solved by this invention is how a kind of substrate for flexible organic opto-electronic device and preparation method thereof is provided, this substrate has solved the problem of the tack difference that causes the film that deposits and substrate owing to the flexible substrate surface energy is low, improved the barrier property of substrate, simultaneously substrate surface has been played good smoothing effect water oxygen.
Technical problem proposed by the invention is to solve like this: construct a kind of base board for flexible optoelectronic part, comprise flexible substrate, it is characterized in that, described flexible substrate surface is provided with tack coat and conductive film, described conductive film is deposited on the surface of tack coat, described bonding layer material is the adhesive that needs ultraviolet light polymerization, and described adhesive is the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent.
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that described free radical type ultraviolet photo-curing cementing agent raw material comprises 90～99.5% base resin, 0.2～3% monomer, 0.1～3% light trigger and 0.2～6% sensitising agent and auxiliary agent; Described cation type ultraviolet photo-curing cementing agent raw material comprises 90～99.5% cationic monomer, 0.4～8% diluent and 0.1～3% cation light initiator.
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that described base resin comprises unsaturated polyester resin, acrylic resin and polythiol-polyenoid system; Described monomer comprises styrene and derivative, simple function group or multi-functional acrylate; Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and acetophenone derivative; Sensitising agent comprises benzophenone, thia anthraquinone and Michler's keton, and auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant and coupling agent; Described cationic monomer comprises various epoxy resin or modified epoxy or fluorine-containing and not fluorine-containing hybrid resin or aliphat and bis-phenol D-type blending epoxy; Described diluent comprises various active epoxy diluent resins and various cyclic ethers, cyclic lactone, the vinyl ether monomers diluent as light-cured resin; Described cation light initiator has diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts, triaryl selenium salt.
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that described acrylic resin comprises polyester-acrylate, epoxy-acrylate, carbamate-acrylate and polyethers-acrylate.
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that described polythiol-polyenoid system comprises the material of following structural formula:
Figure A200810148117D00071
HS(CH 2CH 2O) nCH 2CH 2SH?
Figure A200810148117D00072
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that described flexible substrate is a kind of in metal forming, ultra-thin glass and the thin polymer film.
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that, described mixed system raw material comprises epoxy resin E-51 (bisphenol-A (2, and the epoxychloropropane linear polymer that polycondensation is synthesized in alkaline medium two (4-hydroxy phenyl) propane of 2-)), (51 represent the representative fraction 50% of epoxy), diaryl group iodized salt (CD-1012), the ultra-violet curing adhesive that sensitising agent diisopropyl thiazolone (ITX) is formed.
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that, described mixed system raw material comprises bisphenol A epoxide resin (epoxy resin 128), cationic initiator sulphion hexafluorophosphate (6992) and sulphion hexafluoro antimonate (6976), reactive diluent butyl glycidyl ether (669), long carbochain glycidol ether (114), carboxylic monomer (0200), the polycaprolactone polyol of two senses and trifunctional (0301).
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that, described mixed system raw material comprises the tetraethylene-glycol dimethylacrylate, 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, Alpha-hydroxy cyclohexyl benzophenone (Irgacure184), 2,2-dimethoxy-2-phenyl acetophenone (Irgacure651), styrax dimethyl ether, hexafluorophosphoric acid diphenyl iodnium.
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that, described mixed system raw material comprises 2-ethylene glycol allyl ether and epoxy acrylic resin (CG602) mixture, cationic photoinitiator xylyl salt compounded of iodine or radical photoinitiator 2,2-dimethoxy-2-phenyl acetophenone (Irgacure 651) or 2-hydroxy-2-methyl propiophenone (Darocur 1173).
According to base board for flexible optoelectronic part provided by the present invention, it is characterized in that described tack coat is single layer structure or double-decker or sandwich construction; Double-decker comprises: the ultra-violet curing adhesive that bottom adopts, be spun on the flexible substrate, the ultra-violet curing adhesive that top layer adopts, be spun on the bottom ultra-violet curing adhesive, and bottom ultra-violet curing adhesive concentration is identical or different with top layer ultra-violet curing adhesive concentration, bottom ultra-violet curing adhesive component is identical or different with top layer ultra-violet curing adhesive component, and the adhesive layer thickness that bottom ultra-violet curing adhesive forms is identical or different with the adhesive layer thickness that top layer ultra-violet curing adhesive forms; Sandwich construction is double-deck the repetition for M time or N repetition of single layer structure, wherein 100〉M〉1,200〉N〉1.
A kind of preparation method of base board for flexible optoelectronic part may further comprise the steps:
1. earlier flexible substrate is cleaned completely, it is dry to clean the back;
2. with flexible substrate surface-coated bonding layer material;
3. on substrate, prepare conductive film;
4. parameters such as the transmitance of test base, conductivity, surface topography;
For the ultraviolet light polymerization of ultraviolet photo-curing cementing agent respectively step 2. and/or step implement when 4. finishing.
Preparation method according to base board for flexible optoelectronic part provided by the present invention is characterized in that, step 2. in, tack coat directly is spun on the flexible substrate, perhaps through being spun on the flexible substrate behind the organic solvent diluting; Described tack coat and conductive film are by vacuum evaporation, ion cluster bundle deposition, ion plating, dc sputtering deposition, the RF sputter coating, ion beam sputtering deposition, ion beam assisted depositing, (wherein the plasma generator in the plasma reinforced chemical vapour deposition is a radio-frequency drive to plasma reinforced chemical vapour deposition, direct-current discharge, a kind of in microwave plasma and the electron cyclotron resonace), high density inductance coupling high formula plasma source chemical vapor deposition (HD-ICP-CVD), catalyst chemical vapour deposition (CVD) (Cat-CVD), magnetron sputtering, electroplate, spin coating, dip-coating, inkjet printing, roller coat, one or several modes in the LB film and forming.
Beneficial effect of the present invention is: 1) adopt tack coat, improve the evenness on flexible substrate surface, obtain the more desirable conductive film of surface property; 2) adhesive property of tack coat has improved the adhesive ability between flexible substrate and the conductive film, thereby improves the etching performance of conductive film, reaches the purpose of improving the organic optoelectronic device performance; 3) behind the preparation conductive film, substrate is carried out suitable cured, make tack coat form compact texture, intercept water oxygen and enter device inside, improved the performance and the life-span of device; 4) adopt various preferred proportions and the technological parameter that provides among the present invention, can obtain more excellent realization effect; 5) adopt the preparation method who provides among the present invention can reduce substrate production cost and technology difficulty greatly; 6) cationic and free radical type ultra-violet curing adhesive are unified in one, both reached the purpose that makes full use of luminous energy, reached the purpose of mutual modification again, its cured product has been concentrated epoxy resin and acrylate advantage separately, simultaneously overcome some defective again, started a brand-new system.
Description of drawings
Fig. 1 is substrate for flexible organic opto-electronic device provided by the present invention and preparation structural representation thereof;
Fig. 2 is the transmission measurement curve of substrate described in the embodiment 1 provided by the present invention;
Fig. 3 is the structural representation of embodiment 5 provided by the present invention;
Wherein, 1, flexible substrate, 2, tack coat, 3, conductive film, 21, first tack coat, 22, second tack coat.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and embodiment.
Technical scheme of the present invention provides a kind of substrate for flexible organic opto-electronic device, and as shown in Figure 1, the structure of device comprises flexible substrate 1, tack coat 2, and conductive film 3, wherein tack coat 2 is positioned at flexible substrate 1 surface, and conductive film 3 is positioned at tack coat 2 surfaces.
Flexible substrate 1 is the support of tack coat and conductive film among the present invention, and it has bending performance preferably, and the ability of certain anti-steam and oxygen infiltration is arranged, and good chemical stability and thermal stability are arranged.It can be ultra-thin glass, thin polymer film or metal forming, and thin polymer film adopts a kind of material in polyesters, the polyalkenes compound, and metal forming adopts stainless steel or some other Alloy Foil material.
Tack coat 2 is as the intermediate layer of flexible substrate and conductive film among the present invention, it requires to have planarization, visible light permeability and good tack preferably, raw material has adopted the mechanical mixture system of free radical type and cation type ultraviolet photo-curing adhesive, mixed proportion can change according to the difference of purposes, mixed process is the mixing of free radical type and the various compositions of cation type ultraviolet photo-curing adhesive, treat that all the components mixes the back and adds various light triggers, re-use UV-irradiation and solidify.Various components in proportions can be with reference to the component ratio of free radical type and cation type ultraviolet photo-curing adhesive in the mixed system.
Conductive film 3 adopts metal oxide (as tin indium oxide ITO, zinc oxide ZnO etc.), organic conductive polymer (as PEDOT:PSS, PANI etc.) or some other metallic conduction material (as gold, copper, silver, platinum etc.) usually among the present invention.
As shown in Figure 3, tack coat 21 among the present invention adopts the ultra-violet curing adhesive, be spun on the flexible substrate, tack coat 22 among the present invention adopts the ultra-violet curing adhesive, be spun on first tack coat 21, but first tack coat 21 is identical or different with the ultra-violet curing adhesive component that second tack coat 22 uses, and concentration is identical or different, and the adhesive layer thickness of formation is identical or different.
Each composition is described as follows among the present invention:
Unsaturated polyester resin: unsaturated polyester (UP) is to mix the linear polyesters that reacts and make with fractional saturation binary acid (or acid anhydrides) and dihydroxylic alcohols by undersaturated binary acid (or acid anhydrides) under action of evocating.In its molecular structure, there is undersaturated vinyl monomer to exist, if with active vinyl monomer and the undersaturated vinyl monomer copolymerization of this class, crosslinking curing and become three-dimensional-structure then.In general, the adhesive that makes by this resin since in the solidification process volume contraction bigger, the internal stress of gluded joint is very big.Micro-crack occurs easily and cause splicing power to diminish in the inside of glue-line; Simultaneously,, meet acid, the easy hydrolysis of alkali, thereby resistance to medium and resistance to water are relatively poor, easy deformation under the how wet environment of high temperature owing to contain ester bond in the macromolecular chain; In addition, its curing rate is slower, therefore, shows relatively poor combination property, so mostly use as non-structure glue.By reducing unsatisfied chemical bond content, adopt the low monomer of polymerization shrinkage, adding means such as inorganic filler and thermal plastic high polymer, can improve its overall performance.
Acrylic resin: this resin system curing rate is fast, studies morely at present.
Monomer (styrene and derivative thereof etc.) usually and resin be used, one side is as diluent, the viscosity that glue is had be convenient to construct; Have reactivity on the other hand again, solidify the laggard resin network of going into, the final performance of solidfied material is had certain improvement.The early stage monomer that uses is styrene and derivative thereof, and this class diluent crosslinking rate is slow, volatility is big and poisonous, poor heat resistance.Now, simple function group or polyfunctional group (methyl) acrylate of adopting more, as methyl methacrylate, ethyl acrylate, acrylic acid propylene glycol ester, n-butyl acrylate etc., the relatively poor problem of adhesive ubiquity thermal endurance of these ester preparations, and also there is the big defective of volatility in the lower ester of some molecular weight.If introduce aromatic rings in the molecular structure, then can improve the intensity and the resistance to water of glue, prolong the storage period of glue.Requirement to monomer mainly is: the respond of low viscosity, highly diluted effect and height, it is little also will to take into account volatility, toxicity and peculiar smell simultaneously, good etc. to the compatibility of resin.In order to regulate various performance parameters, often adopt mix monomer, mix monomer is as follows: free radical activity diluent and cation activity diluent.
The free radical activity diluent is divided into exploitation first generation acrylic acid polyfunctional monomer, the second generation acrylic acid polyfunctional monomer of recent development and more excellent third generation acrylic monomers early.
The simple function reactive diluent has: styrene, N-vinyl pyrrolidone, Isooctyl acrylate monomer, hydroxy-ethyl acrylate and isobornyl acrylate, methacrylate phosphate and isobornyl methacrylate, latter two is the good toughness reinforcing monomer of plasticising.
The difunctionality reactive diluent has: triethylene glycol diacrylate, tripropylene glycol diacrylate, glycol diacrylate, polyethylene glycol diacrylate alcohol ester, neopentylglycol diacrylate and propoxyl group neopentylglycol diacrylate, the acrylate-functional monomer mainly contains 1,6-hexanediyl ester (HDDA), 1,4-butanediol diacrylate (BDDA), propylene glycol diacrylate (DPGDA), glycerol diacrylate (TPGDA), the trihydroxy methyl propane triacrylate (TMPTA) of trifunctional, pentaerythritol triacrylate (PETA), trihydroxy methyl propane triol triacrylate (TMPTMA), trimethylolpropane triacrylate, propoxylation trihydroxy methyl propane triacrylate, pentaerythrite three propylene alcohol esters, pentaerythritol propoxylate propylene alcohol ester, N, N-dihydroxy ethyl-3 amido methyl propionate, triethylene glycolbismethyl-acrylate, long-chain fat hydrocarbon glycidol ether acrylic acid, the resorcinol bisglycidyl ether, double pentaerythritol C5 methacrylate, tri (propylene glycol) diacrylate, phthalic acid diethanol diacrylate (PDDA).They have replaced active little first generation acrylic acid monofunctional monomer.But along with the develop rapidly of ultra-violet curing technology, they reveal the big shortcoming of the excitant of skin.
Second generation acrylic acid polyfunctional monomer mainly is to introduce ethyoxyl or propoxyl group in molecule, has overcome the big shortcoming of excitant, also should have higher activity and state of cure.As ethoxylation trihydroxy methyl propane triol triacrylate [TMP (EO) TMA], propoxylation trihydroxy methyl propane triol triacrylate [TMP (PO) TMA], propoxylation glycerol triacrylate [G (PO) TA].Third generation acrylic monomers is mainly the acrylate that contains methoxyl group, preferably resolves the contradiction of high curing rate and shrinkage, low state of cure.This class material has 1,6-hexylene glycol methoxyl group mono acrylic ester (HDOMEMA), ethoxylation neopentyl glycol methoxyl group mono acrylic ester [TMP (PO) MEDA].After introducing alkoxyl in the molecule, can reduce the viscosity of monomer, reduce the excitant of monomer simultaneously.
The introducing of alkoxyl is also improved a lot to the compatibility of diluent monomer, and vinyltriethoxysilane (A15I), gamma-methyl allyl acyloxypropyl trimethoxysilane (A174) can be used as monomer.
Cruel in various active epoxy diluent resins and various cyclic ethers, the ring, vinyl ether monomers etc. can be as the diluent of cation photocuring resin.Therein ethylene pyridyl ethers compound and oligomer curing rate are fast, modest viscosity, tasteless, nontoxic, can be used with epoxy resin.Vinyl ether monomers has: 1,2,3-propanetriol-diglycidyl-ether (EPON-812), triethylene glycol divinyl ether (DVE-3), 1,4-butanediol vinyl ethers (HBVE), cyclohexyl vinyl ether (CHVE), perfluoro methyl vinyl ether (PMVE), the perfluor n-propyl vinyl ether, IVE, hydroxy butyl vinyl ether, vinyl ethyl ether, ethyl vinyl ether, the ethyl vinyl ether propylene, ethylene glycol monoallyl ether, hydroxy butyl vinyl ether, butyl vinyl ether, chlorotrifluoroethylene (CTFE), triethylene glycol divinyl ether, methoxy ethylene, the vinyl n-butyl ether, dodecyl vinyl (DDVE), cyclohexyl vinyl ether, tribenzyl-benzene phenol polyethenoxy base ether, tetrafluoroethene-perfluoro propyl vinyl ether, tetrafluoroethene-perfluoro propyl vinyl ether, tert-Butyl vinyl ether:
The epoxy compounds monomer has: 3,4-epoxy radicals hexahydrobenzoid acid-3 ', 4 '-epoxy radicals cyclohexyl methyl esters (ERL-4221), bisphenol A type epoxy resin (EP), epoxy acrylate, epoxy vinyl ester, acrylic acid epoxy ester, methacrylic acid epoxy-ester, water-soluble itaconic acid epoxy ester resin:
Figure A200810148117D00132
Light trigger: in the ultraviolet photo-curing cementing agent, often need to add Photoactive compounds, with the carrying out of initiation or accelerated reaction.Difference by its mechanism of action can be divided into light trigger and sensitising agent.Difference is that light trigger when the reaction beginning, absorbs the luminous energy of suitable wavelength and intensity, photophysical process takes place reach its a certain excitation state, if this excited energy greater than the breaking bonds energy needed, then produces free radical polymerization; And sensitiser absorption luminous energy is to its a certain excitation state, just with energy in molecule or intermolecular the transfer, produce free radical polymerization by another molecule that obtains energy.Compare with light trigger, sensitising agent itself does not consume or changes structure, and it can be regarded as photochemically reactive catalyst.Its mechanism of action roughly has three kinds: the one, and the energy transfer mechanism, the 2nd, take hydrogen mechanism by force, the 3rd, through generating the photosensitive mechanism that electric charge shifts.The light trigger of having developed with practical value has styrax and derivative and acetophenone derivative, and sensitising agent has benzophenone, thia anthraquinone and Michler's keton.The stability of various initators, yellowing resistance, trigger rate have nothing in common with each other, and in different resin systems, efficiency of initiation is also different, should rationally select for use according to the needs of different occasions.As cyanacrylate and C (CH 2OCCH 2CH 2SH) system, use benzoin methyl ether, benzoin ethyl ether respectively, benzoin isopropyl ether causes, be respectively 18s, 20s and 25s curing time, and when causing with benzophenone, only be 15s curing time, and simultaneously the light transmittance of solidfied material also can difference be bigger owing to the wavelength difference, and this will rationally select for use according to actual conditions.
The effect of light trigger is after it absorbs the ultraviolet light energy, produces free radical through decomposing, thus the unsaturated bond polymerization in the initiator system, and crosslinking curing becomes an integral body.Radical photoinitiator commonly used has the cracking type and puies forward Hydrogen two big classes.
Crack type photoinitiator: crack type photoinitiator mainly contains benzoin ethers (styrax ethers), benzil ketals and acetophenone etc.Crack type photoinitiator is chapped after absorbing ultraviolet light, produces two free radicals, and free radical causes the unsaturated group polymerization.Benzoin ethers (styrax ethers) comprising: styrax (Benzoin), benzoin methyl ether, benzoin ethyl ether (Benzoin ethyl ether), benzoin isobutyl ether (Benzoin butyl ether), styrax lose (Benzoin oxime), benzoin isopropyl ether; Acylphosphine oxide comprises: 2; 4; 6 trimethylbenzene formyl diphenyl phosphine oxides (TPO) and (2; 4; 6-trimethylbenzene formyl) phenyl phosphine oxide [BAPO 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 situation that whitewash and film are thicker; and have good stability, can variable color or fade.
Carry the Hydrogen initator: carry the Hydrogen initator and mainly contain benzophenone and thioxanthones etc.Wherein at 380-420nm, and absorbability and hydrogen-taking capacity are strong, have higher efficiency of initiation at the maximum absorption wavelength in black light district for thioxanthone photoinitiator.Carrying the Hydrogen initator must have hydrogen donor as collaborative composition, otherwise efficiency of initiation is too low, so that can not be put to use.Triplet state carbonyl free radical than more likely extracting hydrogen on the secondary carbon or on the methyl, is connected on hydrogen on the hetero-atoms such as oxygen or nitrogen than the easier extraction of the hydrogen on the carbon atom from the tertiary carbon of hydrogen donor molecule.This class hydrogen donor has amine, hydramine (triethanolamine, methyl diethanolamine, triisopropanolamine etc.), mercaptan, N, the N-diethyl-and to the dimethylamino benzamide.
The benzophenone light initiation system, benzophenone need be with alcohol, ether or amine and with just making vinyl monomer carry out photopolymerization.Mainly comprise: benzophenone, the thia anthraquinone, Michler's keton, dimethoxy benzene acetophenone (DMPA), alpha-hydroxy-2,2 dimethyl acetophenones (1173), Alpha-hydroxy cyclohexyl-phenyl ketone (184), α-amine alkyl phenones, 2-methyl isophthalic acid (4-first coloured glaze base phenyl)-2-morpholinyl acetone (MMMP), 2 ' 2-dibenzamidodiphenyl disulfide (DBMD), (4-dimethylamino phenyl)-(1-piperidyl)-ketone, isopropyl thioxanthone (ITX), (4-dimethylamino phenyl)-(4-morpholinyl)-ketone, 2-hydroxy-2-methyl-1-phenyl-1-phenyl-1-acetone, two phenoxy group benzophenone, hydroxy-2-methyl phenyl-propane-1-ketone.And mixed system, as eliminating oxygen in the glued membrane to the benzophenone of the inhibition of Raolical polymerizable and the initiator system that cooperates of uncle's ammonia; Michler's keton and benzophenone are used, and can obtain more cheap and effectively initiator system.
Cationic photoinitiator: aromatic sulfonium salts and salt compounded of iodine class initator have excellent high-temperature stability, and also have stability after epoxy resin cooperates, so be widely used in the cationic curing system.But their the most apneusis receipts wavelength does not absorb in the near ultraviolet band in the far-ultraviolet region, generally will add light sensitizer, as: radical initiator or light-sensitive coloring agent carry out sensitizing.
This type of initator comprises: xylyl iodine hexafluorophosphate (PI810); hydroxy phenyl salt compounded of iodine (HTIB); 4; the two detergent alkylate iodine hexafluoro antimonates of 4-; the xylyl salt compounded of iodine; diphenyl hexafluoroarsenate salt compounded of iodine; [4-(2-hydroxyl-3-butoxy-1-propoxyl group) phenyl] benzene iodo-hexafluoro antimonate; [4-(to the benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate; [4-(4-benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate; 4-(to the benzoyl thiophenyl) benzene] the phenyl-iodide hexafluorophosphate; 4; 4 '-dimethyl diphenyl salt compounded of iodine hexafluorophosphate (IHT-PI 820); 4; 4 '-the diacetylamino diphenyl iodine hexafluorophosphate; 3; 7 one dinitro dibenzo ring-type salt compounded of iodine and 3; 7 one dinitro dibenzo ring-type bromine salt; the tetrafluoro boric acid diaryl group iodized salt; 3; 3 '-the dinitro diphenyl salt compounded of iodine; 3; 3 '-dinitro diphenyl salt compounded of iodine and several 2; 2 '-two replace (iodine; bromine; chlorine)-5; 5 '-the dinitrophenyl salt compounded of iodine; iodate 2-[2-(3-indolizine) vinyl]-1-methylquinoline salt; iodate 4-(2-benzoxazole)-N-picoline salt; 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate; triaryl phosphine glyoxalidine salt; triaryl phosphine 1; 1 '-dinaphthalene glyoxalidine ring salt; 3; 7-dinitro dibenzo bromine five rings salt; p-methyl benzenesulfonic acid triphenyl sulfosalt; bromination triphenyl sulfosalt; (4-thiophenyl-phenyl) diphenyl sulphur hexafluorophosphate; 4-(thiophenyl) triphenyl sulphur hexafluorophosphate; 3; 3 '-dinitro diphenyl iodine hexafluorophosphate; 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate; the triphenyl sulfosalt; 4-chlorphenyl diphenyl sulphur hexafluorophosphate; 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate; 4-acetamido phenyl diphenyl sulphur hexafluorophosphate; 3-benzoyl phenyl diphenyl sulphur hexafluorophosphate; triphenyl sulphur borofluoride; triphenyl sulphur hexafluorophosphate; triphenyl sulphur hexafluoro antimonate; 4-tolyl diphenyl sulphur hexafluorophosphate; the phosphorus hexafluoride triaryl sulfonium salts; the antimony hexafluoride triaryl sulfonium salts; [4-(to the benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate; 1-(4 '-bromo-2 '-luorobenzyl) pyridiniujm; [4-(to the benzoyl thiophenyl) benzene] phenyl-iodide hexafluorophosphate; 4-[4-(p-nitrophenyl formoxyl) thiophenyl] and benzene } the phenyl-iodide hexafluorophosphate; 4-[4-(to methyl benzoyl) thiophenyl] and benzene } the phenyl-iodide hexafluorophosphate; 4-[4-(to methyl benzoyl) phenoxy group] and benzene } the phenyl-iodide hexafluorophosphate; [4-(to the benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate; 4, the two detergent alkylate iodine hexafluoro antimonates of 4-.
Luxuriant molysite class: luxuriant molysite class light initiation system is a kind of new cation light initiator that develops after two fragrant salt compounded of iodine and three aromatic sulfonium salts, luxuriant molysite ion at first forms the aromatic radical ligand under illumination, produce complex compound simultaneously with the unsaturated iron of epoxy compounds molecule coordination, the lewis acidic characteristics of this complex compound tool are also followed the complex compound that forms with the coordination of three epoxy compounds molecules, but one of them epoxy compounds open loop forms cation, it can cause cationic ring-opening polymerization, forms polymer.At normal temperatures because the formation of ferrocene salt-epoxy radicals complex, epoxy compounds cationic species needs the time, so under the condition that needs to heat, to improve polymerization speed in the external world.
This type of salt comprises: cyclopentadienyl group-iron-benzene salt; cyclopentadienyl group-iron-toluene salt; cyclopentadienyl group-iron-paraxylene salt; cyclopentadienyl group-iron-naphthalene salts; cyclopentadienyl group-iron-biphenyl salt; cyclopentadienyl group-iron-2; 4-dimethyl acetophenone salt; acetyl group-cyclopentadienyl group-iron-paraxylene salt; cyclopentadienyl group-iron-methyl phenyl ethers anisole salt; cyclopentadienyl group-iron-diphenyl ether salt; cyclopentadienyl group-iron-2; 4-diethoxybenzene salt; the ferrocene tetrafluoroborate; the luxuriant iron tetrafluoroborate of toluene; cyclopentadienyl group-iron-methyl phenyl ethers anisole salt; cyclopentadienyl group-iron-diphenyl ether salt; cyclopentadienyl group-iron-1; 4-diethoxybenzene salt; cyclopentadienyl group-iron-chlorobenzene salt; cyclopentadienyl group-iron-(1; the 4-diethoxybenzene) hexafluorophosphate; cyclopentadienyl group-iron-diphenyl ether hexafluorophosphate; 1; 10-phenanthrolene ferrous perchlorate salt; 1; 10-phenanthrolene ferrous sulfate cyclopentadienyl group-iron-methyl phenyl ethers anisole salt; cyclopentadienyl group-iron-diphenyl ether salt; [1; 1 '-two (diphenylphosphine) ferrocene] Nickel Chloride; vinyl ferrocene; N; N '-di-ferrocene methylene butanediamine quaternary ammonium salt; ferrocene formamide; ferrocene acyl propionic acid; ferrocenyl methyl ketone; ethyl dicyclopentadienyl iron; Butyrylferrocene; butyl ferrocene; N; N-dimethyl-amine methyl ferrocene; 1; 1 '-the dibenzoyl ferrocene; (3-carboxyl propionyl group) ferrocene; 1,1 '-the dibromo ferrocene; amino ferrocene.
The light trigger of macromolecule loading: in the photocuring system, light trigger often is not to exhaust fully in the photocuring process, and the part of photodissociation can not moved to coating surface, makes coating yellowing and aging, influences the quality of product; On the other hand, some initators and system are incompatible or compatibility is bad, and its application is restricted.For addressing these problems, people are with the light trigger producing high-molecular.The low molecular relatively initator of the initator of producing high-molecular has following advantage: A, energy transfer and intermolecular reaction become and be more prone in polymer chain, make the high-molecular optical initator have higher activity.B, by with nonactive group copolymerization, regulates and the distance of design photosensitive group, or change the distance of optical active group and main chain, thereby acquisition has different photoactive initators.C, can introduce different optical active groups, utilize their cooperative effect to improve light sensitive effect at same macromolecular chain.The producing high-molecular of D, initator has limited the migration of initator, prevents coating flavescence and aging.E, since most of photolysis debris still be connected on the macromolecule matrix, therefore, can reduce the smell and the toxicity of system.
The producing high-molecular of initator can directly be connected in initator on the chain of macromolecule or oligomer, as thioxanthone or acidic group phosphine oxide etc. are introduced on the macromolecular chain; Also can in initator, introduce the functional group that polymerization can take place, make it in the photocuring process, realize producing high-molecular, as benzophenone structural is introduced in the tetraacrylate.
The compatibility of various light triggers also is a research direction in recent years, re-uses through behind the compatibility, both can reduce cost, and can enlarge the zone of absorbing wavelength again, improves the absorption of ultraviolet radiation energy, thereby obtains good solidification effect.The compatibility of light trigger both can be between the same type, as be both free radical type, for example the new Irgacure-1700 that releases of Ciba be exactly by 25% (2,4,6-trimethylbenzene formyl) phenyl phosphine oxide (BAPO) and 75% alpha-hydroxy-2,2 dimethyl acetophenones (1173) are formed, and Irgacure-1800 is made up of 25% BAPO and 75% Alpha-hydroxy cyclohexyl-phenyl ketone (184) etc.; Also can form,, for example, triaryl thiaxanthene salt and benzophenone be cooperated, the curing rate of epoxy compounds is improved as light trigger compatibility free radical type and cationic by dissimilar initators.
Auxiliary agent: in general,, also need to add various auxiliary agents in the ultraviolet photo-curing cementing agent, as plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent etc. for adapting to the bonding requirement of varying environment.Though their shared components in adhesive are few, processing characteristics or the adhesive property to glue produces crucial effects sometimes.As cyanacrylate and C (CH 2OCCH 2CH 2SH) under the initiation of benzophenone, if the silicone couplet CH of adding 1% 2=CHSi (OCH 2CH 2OCH 3) 3, behind ultraviolet light polymerization, place under the environment of 80～100% humidity, find after 1 year to change, and if do not add coupling agent, under the same terms, white erosion just to take place in the bonded part after 2 days, glue-line strips down fully after the week.
Plasticizer comprises: diisooctyl azelate (DIOZ), dioctyl azelate (DOZ), phthalic acid two is ester (DHP), separate two dioctyl phthalates (DOS), hexanedioic acid dioctyl ester (DOA), diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), dibutyl phthalate (DBP), dipropyl phthalate (DAP), three vinyl butyl ether base phosphates, polyvinyl butyral resin, tributyl 2-acetylcitrate, repefral (DMP), diethyl phthalate (DEP), hexanedioic acid two (butoxy ethyoxyl) ethyl ester, isopropyl titanate, tetrabutyl titanate, triethyl citrate, tributyl citrate, tributyl 2-acetylcitrate, tri trimellitate (2-ethyl) own ester (TOTM), the own ester of phthalic acid two (2-ethyl), decanedioic acid two (2-ethyl) own ester (DOS), diglycol dibenzoate (DEDB), phthalic anhydride, dipropylene glycol dibenzoate, separate diacid dibenzyl ester (DBS), BS (BS), chlorosulfonated polyethylene (toughening elastic body), triphenyl phosphate (TPP), tricresyl phosphate (dimethylbenzene) ester (TXP), poly-hexanedioic acid propylidene ester (PPA), epoxidized soybean oil (ESO), octyl epoxy stearate (OES2), chlorinated paraffin-42 (CP-42), chlorinated paraffin wax-48 (CP-48), chlorinated paraffin-52 (CP-52), distearyl acid diethylene glycol (DEG) (DEDR), tricresyl phosphate benzene methyl (TCP), diphenyl octyl phosphate (DPO), poly-hexanedioic acid butylidene ester (PBA), butyl epoxy stearate (BES), askarel (CDP), dimethylbenzene methylal resin (plasticizer FH), pumice wax pattern base oil (PROCESS OIL637), soybean oil, naphthenic processing oil (310), W150 softening oil (petroleum hydrocarbon, hydrogenation artificial oil), zirconium aluminium is coupling agent, WB215 (aliphatic acid 18%; Fatty acid ester 52%; Calcium carbonate 20%).
Coupling agent is the material that a class has the both sexes structure, and a part of group in their molecules can react with the chemical group on inorganic matter surface, forms strong chemical bonding; Another part group then has close organic character, can twine with reactive organic molecule or physics, thus the material strong bonded that two kinds of character are varied in size.The coupling agent of present industrial use is divided into silanes, acyl esters of gallic acid, zirconium class and Organic Chromium complex compound four big classes by chemical constitution.Wherein using more in adhesive is silanes, as the methyl ethylene dichlorosilane, methyl hydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-An Bingjisanjiayangjiguiwan, dimethyl silicone polymer, poly-hydrogen methylsiloxane, poly-methyl methoxy radical siloxane, γ-methacrylic acid third vinegar base trimethoxy silane (KH-570), gamma-aminopropyl-triethoxy-silane (KH-550), γ-glycidol ether propyl trimethoxy silicane, the aminopropyl silsesquioxane, γ-methacryloxypropyl trimethoxy silane, the chain alkyl trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-chloropropyl triethoxysilane, two-(the silica-based propyl group of γ-triethoxy), anilinomethyl triethoxysilane, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane.
Levelling agent is the flow leveling that is used for improving resin, prevent the generation of coating disadvantages such as shrinkage cavity and pinprick, make smooth coating, and can improve glossiness, comprise mixed solvent, organosilicon, polyacrylate, acetate butyrate fiber, nitrocellulose and polyvinyl butyral resin.Wherein silicone based, comprise diphenyl polysiloxanes, methyl phenyl silicone, organic group modified polyorganosiloxane, polyethers organosilicon.
Stabilizer is to be used for reducing polymerization takes place when depositing, and improves the storage stability of resin.Stabilizer commonly used has hydroquinones, p methoxy phenol, 1,4-benzoquinone, 2,6 one di-t-butyl cresols, phenothiazine, anthraquinone etc.
Defoamer is to be used for preventing and to eliminate coating producing bubble in manufacturing and use, prevents that coating from producing disadvantages such as pinprick.Phosphate, fatty acid ester and organosilicon etc. can be made defoamer.Tributyl phosphate is specifically arranged, dibutylphosphoric acid ester, phosphate foam inhibitor (AD-14L), froth breaking king (FAG470), defoamer (FAG470), defoamer (BYK-141), defoamer (BYK 037), three (butoxyethyl group) phosphate, triethyl phosphate, the Tributyl phosphate ester, triethyl phosphate, tricresyl phosphate chloro isopropyl ester, three butoxy ethyl ester of phosphoric acid, the mixture of polyoxyethylene polyoxypropylene and glycol or three alcohol ethers (light yellow) to the water white transparency thick liquid, dimethyl silicone polymer, glycerine polyethenoxy ether (GP330), laureth, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polyoxypropylene glycerin ether and polyoxypropylene, polyethers, cithrol, metallic soap of stearic acid, polyureas, the fatty acid ester compounded thing of higher alcohols; Silicone defoaming agent has organic silicon modified by polyether oxygen alkane, organopolysiloxane mixture, silicone emulsion.
Polymerization inhibitor is to be used for reducing polymerization takes place when depositing, and improves the storage stability of resin.Polymerization inhibitor commonly used generally is divided into molecule-type polymerization inhibitor and stabilized free fundamental mode polymerization inhibitor, the former mainly contains: hydroquinones, 1,4-benzoquinone, phenothiazine, the beta-phenyl naphthylamines, p-tert-butyl catechol, methylene blue, three (N-nitroso-N-Phenylhydroxylamine) aluminium salt, stannous chloride, inorganic matters such as ferric trichloride and Sulfur etc. also can be made polymerization inhibitor stabilized free fundamental mode polymerization inhibitor and mainly contain 1, the bitter hydrazine (DPPH) of 1-diphenyl-2-, 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical (TMP), hydroquinones, allyl acetate, MEHQ (MEHQ), NO free radical piperidines alcohol, phosphorous acid (2,2,6, the 6-tetramethyl piperidine nitrogen oxygen free radical) mixed ester, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen radical (TMHPHA), 8% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt: 92% 2-phenolic group ethoxy propylene acid esters, 4% 3 (N-nitroso N-Phenylhydroxylamine) aluminium salt, 96% ethyoxyl list oil triacrylate, MEHQ hydroquinone monomethyl ether, the polymerization inhibitor mantoquita, adjacent methyl hydroquinone, 2,6-di-t-butyl cresols, the dimethyl hydroquinones, p-tert-butyl catechol (TBC), catechol, p methoxy phenol, 2.6-BHT, 2.5-di-tert-butyl hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, 1.4-naphthoquinones, phenthazine, TBHQ (TBHQ), o-sec-butyl-4,6 dinitrophenol (DNBP), ethylene glycol ether, the benzene sulfonamide amine acid salt, right-t-butyl catechol, methyl methacrylate (MMA), 2,4,6-trinitrophenol (TNP), 2,4-dimethyl-6-tert-butyl phenol (TBX), N, N-diethyl hydroxylamine (DEHA), to t-butyl catechol, 2, the 5-ditert-butylhydro quinone, adjacent methyl is to benzene two adjacent methyl 1,4-benzoquinone, 3-tertiary butyl-4-hydroxyanisol (BHA), 2,6-dinitro-p-cresol (DNPC), polyvinyl acetal, NO free radical piperidines alcohol, 4,6-dinitro o sec-butyl phenol, DMSS (DMSS), propilolic alcohol.
Thixotropic agent adds in the resin, can make resin adhesive liquid that higher denseness is arranged when static, becomes the material of low denseness fluid under external force again.Organobentonite acrylonitrile-butadiene rubber (NBR), montmorillonite (Na x(H 2O) 4{ (Al 2-xMg 0.33) [Si 4O 10] (OH) 2), bentonite [(Na x(H 2O) 4(Al 2-xMg 0.83) Si 4O 10) (OH) 2], diatomite (unbodied SiO 2Form, and contain small amount of Fe 2O 3, CaO, MgO, Al 2O 3And organic impurities), asbestos, wollastonite (CaSiO 3), muscovite (KAl 2(AlSi 3O 10) (OH) 2), phlogopite (KMg 3(AlSi 3O 10) (F, OH) 2), magnesium silicon muscovite [K 2((Fe 2+ Mg) (Fe 3+ Al) 3(Si 7AlO 20) (OH) 4)], montmorillonite [Na x(H 2O) 4{ (Al 2-xMg 0.33) [Si 4O 10] (OH) 2], bentonite [Na x(H 2O) 4(Al 2-xMg 0.83) (Si 4O 10) (OH) 2], rilanit special, fumed silica, metallic soap (lead stearate, barium, cadmium, calcium, zinc, magnesium, aluminium, rare earth).Then with cellulose derivatives such as hydroxyethylcelluloses, polyvinyl alcohol, polyacrylic acid, poly(ethylene oxide), polymethylacrylic acid, Lauxite, melamine resin, resol, phenolic resins water-soluble resin are thickener in water-based system.
The effect of filler is that part replaces binding agent, reduces the consumption of binding agent, with the effect that reaches filling, reinforcement, anti-attrition and reduce cost.Filler requires particle carefully to spare, and can be scattered in equably in the slurries, and is good to binding agent and other component associativities.The consumption of filler should be suitable, otherwise also can influence the serous coat quality.Comprise inorganic mineral bentonite acrylonitrile-butadiene rubber (NBR), potassium aluminosilicate sodium (nepheline), calcium carbonate, moisture Petimin [Mg 3[Si 4O 10] (OH) 2], wollastonite (CaSiO 3), muscovite [KAl 2(AlSi 3O 10) (OH) 2], phlogopite [KMg 3(AlSi 3O 10) (FOH) 2], magnesium silicon muscovite [K 2((Fe 2+ Mg) (Fe 3+ Al) 3(Si 7AlO 20) (OH) 4)], montmorillonite [Na x(H 2O) 4{ (Al 2-xMg 0.33) [Si 4O 10] (OH) 2], bentonite [Na x(H 2O) 4(Al 2-xMg 0.83) (Si 4O 10) (OH) 2], kaolin, red mud (Al 1-xO x), calcium sulfate, acrylate high polymer, butyl polyacrylate, polyurethane.
Dispersant impels material particles to be dispersed in the medium, forms the reagent of stable suspension.Dispersant generally is divided into inorganic dispersant and organic dispersing agent two big classes.Inorganic dispersant commonly used has silicates (for example waterglass) and alkali metal phosphonates (Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium, Amino Trimethylene Phosphonic Acid potassium, HEDP sodium, the HEDP disodium, HEDP four sodium, HEDP potassium, ethylene diamine tetra methylene phosphonic acid five sodium, diethylene triamine pentamethylene phosphonic five sodium, diethylenetriamine pentamethylene phosphonic acids seven sodium, diethylene triamine pentamethylene phosphonic sodium, 2-phosphonic acids butane-1,2,4-tricarboxylic acids four sodium, hexamethylene diamine tetramethyl fork phosphonic acids sylvite, two 1,6 hexylidene triamine, five methylenephosphonic acid sodium, the trimerization Alendronate, calgon and sodium pyrophosphate etc.).Organic dispersing agent comprises triethyl group hexyl phosphonic acids; Amino Trimethylene Phosphonic Acid; HEDP (HEDP); ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS); ethylene diamine tetra methylene phosphonic acid (EDTMPA); diethylene triamine pentamethylene phosphonic (DTPMP); 2-phosphonic acids butane-1; 2; 4-tricarboxylic acids (PBTCA); PAPE (PAPE); 2-HPAA (HPAA); hexamethylene diamine tetramethyl fork phosphonic acids (HDTMPA); polyamino polyether base methylenephosphonic acid (PAPEMP); two 1,6 hexylidene triamine, five methylenephosphonic acids (BHMTPMPA); lauryl sodium sulfate; polyacrylic acid (PAA); Sodium Polyacrylate (PAAS); HPMA (HPMA); maleic acid-acrylic acid copolymer (MA-AA); acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer (AA/AMPS); acrylic acid-hydroxypropyl acrylate copolymer; acrylic acid-acrylate-phosphonic acids-sulfonate quadripolymer; acrylic acid-acrylate-sulfonate terpolymer; phosphono-carboxylic acids copolymer (POCA); polyacrylate; carboxylate-sulfonate-nonionic terpolymer; polyepoxy sodium succinate (PESA); poly (sodium aspartate) (PASP); the base amylalcohol; cellulose derivative; polyacrylamide; guar gum; fatty acid polyethylene glycol ester etc.
Antioxidant is the auxiliary agent of major function to suppress the fluoropolymer resin thermal oxidative degradation, belongs to the category of anti-oxidant reagent.Antioxidant is the topmost type of plastics stabilizing additive, and nearly all fluoropolymer resin all relates to the application of antioxidant.According to the mechanism of action, traditional antioxidant systems generally comprises primary antioxidant, auxiliary antioxidant and heavy metal ion passivator etc.Primary antioxidant is a major function to catch the polymer peroxy radical, and the title of " peroxy radical trapping agent " and " chain termination type antioxidant " is arranged again, relates to aromatic amine compounds and hindered phenol compound two big series of products.Aromatic amine antioxidant has: diphenylamines, p-phenylenediamine (PPD), N, N-pair-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propiono] hexamethylene diamine, dihydroquinoline; Hinered phenols antioxidant has: 2,5-ditert-butylhydro quinone, 2,6-di-tert-butyl-4-methy phenol, TBHQ, 2,5-ditert-butylhydro quinone (DBHQ), 2, three grades of butyl of 6--4-methylphenol, two (3, three grades of butyl of 5--4-hydroxy phenyl) thioether, four [β-(3, three grades of butyl of 5--4-hydroxy phenyl) propionic acid] pentaerythritol ester; Triphenyl phosphite (TPPi), phosphite ester three (2,4-di-tert-butyl phenyl) ester, pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) dimer and the trimerical compound, 3 of ester, many alkyl bisphenol-A phosphite ester, 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, β-(4-hydroxy phenyl-3, the 5-di-t-butyl) the positive octadecanol ester of propionic acid, 1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-hydroxy benzenes methyl) benzene.Auxiliary antioxidant has the effect of decomposing copolymer per-compound, also claims " peroxide decomposer " to comprise sulfo-dicarboxylic ester class and bi-ester of phosphite, and common and primary antioxidant is used.The two octadecyl esters (DSTP) of two 12 carbon alcohol esters, two ten four carbon alcohols esters, thio-2 acid, thio-2 acid dibasic acid esters, two octadecanol ester, the two lauryls of thio-2 acid, three monooctyl esters, three the last of the ten Heavenly stems ester, three (12 carbon alcohol) ester and three (16 carbon alcohol) ester, 3,6,9-trioxa decane-1,11-glycol-two-n-dodecane mercaptopropionic acid ester, triphenyl phosphate TPP, trisnonyl phenyl phosphite, phosphorous acid octyl group diphenyl.
Heavy metal ion passivator is commonly called as " copper resistant agent ", can the complexing transition metal ions, prevent the oxidative degradation of its catalytic polymerization resin, typical structure such as hydrazide kind compound etc.Recent years, along with going deep into of polymer antioxygen theoretical research, certain variation has also taken place in the classification of antioxidant, and the most outstanding feature is a notion of having introduced " carbon radicals trapping agent ".This radical scavenger is different from traditional primary antioxidant, and they can catch the polymer alkyl diradical, is equivalent to set up one in traditional antioxidant system the defence line.This type of stabilizing additive mainly comprises 2-ethyl benzofuran ketone, 2-methyl benzofuranone, Dihydrobenzofuranes ketone, benzofuranone, dibenzopyrone, 3-aryl-benzofuran-2-ones, 3-aryl benzofuranone, 2-aryl Dihydrobenzofuranes ketone, 2-aryl benzofuranone, 5-cyano group-1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 5-replaces 1-(4-fluorophenyl)-1,3-dihydroisobenzofuran ketone, 2,3-dihydroxy-2,2-dimethyl-7-benzofuran phenol, 3-(2-acyloxyethoxyphenyl) benzofuran-2-ones, isobenzofuranone, 5-[(imidazo [4,5-b] pyridin-3-yl) methyl] benzofuranone, 1,2,3,4-tetrahydrochysene-benzofuranone, 2,3-dihydro-2-methyl-2-alkyl and furanone, 4-ethyoxyl bisphenol-A-diacrylate, (2-10)-ethoxyquin bisphenol-A-dimethylacrylate, 2-[1-(2-hydroxyl-3,5-two tertiary amyl phenyl)-and ethyl]-4,6-two tertiary amyl phenyl acrylate, bisphenol-A-glycerol double methyl methacrylate, bisphenol-A-dimethylacrylate, 4-ethyoxyl bisphenol-A-dimethylacrylate, N, the N-dibenzyl hydroxylamine, N-ethyl-N-aminoethyle alcohol, N, the N-diethyl hydroxylamine, IPD acrylamide HAS, isopropylhydroxyla, hydroxylamine hydrochloride, the chlorination hydroxylammonium, hydrogen chlorine azanol, N-methyl-azanol, acetohydroxamic acid, the N-hydroxyl acetamide.
Modifier is intended to improve plasticizing capacity, improves the modified additive of resin melt viscoelasticity and promotion resin melt-flow, and this analog assistant is based on acrylic acid esters co-polymer (ACR).
Anti-impact modifier improves the auxiliary agent of rigid polymer goods shock resistance.Mainly comprise haloflex (CPE), acrylate copolymer (ACR), methacrylate-diene-ethylene copolymer (MBS), ethene-thiazolinyl acetate copolymer (EVA) and acrylonitrile-diene-ethylene copolymer (ABS) etc.The ethylene propylene diene rubber (EPDM) that uses in polypropylene toughness-increasing modified also belongs to rubber toughened scope.
The function of antistatic agent is to reduce the sheet resistance of polymer product, eliminates the electrostatic hazard that accumulation of static electricity may cause, and mainly is included as cationic surfactant and anion surfactant.Cationic surfactant has: the alkyl phosphate diethanolamine salt, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, stearmide, stearoyl dimethyl-penten ammonium chloride, N, two (2-ethoxy)-N-(3 '-dodecyloxy-2 '-hydroxypropyl) the first ammonium Methylsulfate salt of N-, trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, stearamide propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, N, N-cetyl ethyl morpholine ethyl-sulfate salt, (dodecanamide propyl trimethyl ammonium) Methylsulfate salt dibrominated N, N-two (octadecyl dimethyl)-3-oxa--1,5-penta 2 ammoniums, styrene polymer type quaternary ammonium salt, the palmitate quaternary ammonium salt, the alkylphenol-polyethenoxy based quaternary ammonium salt, dialkyl quaternary ammonium salt, the polyacrylamide quaternary ammonium salt, octadecyl dimethyl ethoxy quaternary ammonium nitrate, ammonium polystyrene sulphonate salt, propyl-dimethyl-beta-hydroxyethyl nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, 2,2 '-nitrilo-di-methylcarbinol and the poly-(oxygen-1 of α-three decyls-ω-hydroxyl, 2-second two bases) polymer of phosphate, the polyethylene glycol tridecyl ether phosphate, diethanolamine salt, the oleic acid diethanolamine salt, triethanol amine oleate, ethoxylated amine, N, N-dihydroxy ethyl octadecylamine, N, the N-dihydroxyethyl p-toluidine, the alkylphenol-polyethenoxy based quaternary ammonium salt, ethoxyl quaternary ammonium salt, the fluorine-containing quaternary ammonium salt of oxa-; Anion surfactant has: fatty alcohol ether phosphate, phenolic ether phosphate (TXP-4), phenolic ether phosphate (TXP-10), different tridecanol phosphate, Tryfac 5573 (MA24P), fatty alcohol ether phosphate potassium (MOA-3PK), phenolic ether phosphate kalium salt (NP-4PK), phenolic ether phosphate kalium salt (NP-10PK), different tridecanol ether phosphate sylvite, Tryfac 5573 sylvite (MA24PK), fatty alcohol phosphate sylvite, ALS; Non-ionic surface active agent: the condensation product of alkylamine and oxirane, alkanolamide, AEO, aliphatic acid polyethenoxy ether, two (beta-hydroxyethyl) coco amine, two (beta-hydroxyethyl) stearylamine, two (beta-hydroxyethyl) beef tallow amine, HMPA, perfluoroalkyl ethanol APEO.
Figure A200810148117D00241
The negative and positive amphoteric surfactant comprises: dodecyl-dimethyl quaternary ammonium second inner salt, dodecyl dimethyl quaternary ammonium second inner salt, alkyl dihydroxy ethyl ammonium second inner salt, the N-alkylaminoacid salts, epoxy tripolymer acid inner salt, carboxybetaine, tridecyl dimethyl (2-sulfurous acid) ethyl ammonium second inner salt, N-dodecyl alanine, the 3-chloro propyl amine hydrochloric acid salt, N-tertbutyloxycarbonyl-D-3-(2-naphthyl)-alanine, N-tert-butoxycarbonyl-D-2-naphthylalanine, tertbutyloxycarbonyl-D-2-naphthylalanine, tertbutyloxycarbonyl-D-3-(2-naphthyl)-alanine, N-tertbutyloxycarbonyl-L-2-trifluoromethyl-phenylalanine, glyphosate isopropyl amine salt.
The polymer electrolyte antistatic agent comprises: the amphipathic copolymer that poly(ethylene oxide) (PEO), polyether ester acid imide, polyethylene glycol methacrylic acid copolymer, polyether ester amides (PEEA), polyether ester acetamide (PEAI), polyethylene glycol oxide, epoxy propane copolymer (PEO-ECH), polyethylene glycol methacrylate-styrene polymer (PEGMA), methacrylic acid (MAA), methacrylic acid stearyl (SMA)+polyethylene glycol methacrylate-styrene polymer (PEGMA) are formed.
Inorganic combustion inhibitor comprises antimonous oxide, zinc molybdate, zinc oxide, iron oxide, tin oxide, aluminium hydroxide, magnesium hydroxide, antimony oxide, Firebrake ZB and red phosphorus in the fire retardant; Organic fire-retardant comprises deca-BDE, three (2, the 3-dibromopropyl) phosphate, HBCD, poly-2, the 6-dibromobenzene aether, chlorinated paraffin wax, polyphosphate, red phosphorus, two (tetrabromo phthalimide) ethane, the Dowspray 9 homopolymers, melamine, cyanurate, the isodecyl diphenyl phosphoester, ethylhexyl diphenyl phosphate, tricresyl phosphate isopropylbenzene ester, two (2 chloroethyl) vinylphosphonate, ethylene two [three (2 cyanoethyl) bromination microcosmic salt], N, two (2 ethoxy) the aminomethyl diethyl phosphonates of N, polyphenylene phosphonic acids diphenyl sulphone (DPS) ester, polyphenylene phosphonic acids hexichol azo ester, polyphenylene phosphonic acids bisphenol-A ester.
Mould inhibitor claims microbial inhibitor again, is growth of microorganism such as a class mould fungus inhibition, prevents the stabilizing additive that fluoropolymer resin is degraded by microbial attack.Most polymeric materials are to mould and insensitive, but have mould sensitivity owing to its goods work in-process has added the material that plasticizer, lubricant, fatty acid soaps class etc. can grow der Pilz.Plastics are a lot of with the chemical substance that mould inhibitor comprised, and more common kind comprises organo-metallic compound (as organic mercury, organotin, organic copper, organo-arsenic etc.), organic compounds containing nitrogen, organic compounds containing sulfur, organic halogen compound and phenol derivatives etc.Comprising phenol, pentachlorophenol, phenyl mercury oleate, copper 8-quinolinolate, chlorination three second or tributyl tin, copper sulphate, mercury chloride, sodium fluoride.
Sensitizer is to the dimethylamino benzamide; Aminopropyl silsesquioxane and Versamid mass ratio are 3:1 in the promoter.
Cationic photocuring system mainly utilizes the photodissociation under ultraviolet irradiation of aromatic series diazol, aromatic series salt compounded of iodine, aromatic series sulfonium salt to produce Bronsted acid, and Bronsted acid trigger monomer again carries out cationic polymerization.Compare with the radically curing system, it has, and cure shrinkage is little, the inhibition that is not subjected to various oxygen and if there is not nucleophilic impurity to exist, in case cause polymerization advantage such as will continue for a long time.But the Bronsted acid that light trigger discharges when rayed can produce corrosiveness to glued matrix.In theory, all monomers that can carry out cationic polymerization may be used to cationic curing, and still, at present the most frequently used is various epoxy resin or modified epoxy.Various active epoxy diluent resins and various cyclic ethers, cyclic lactone, vinyl ether monomers etc. can be as the diluents of light-cured resin, and cation light initiator has diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts, triaryl selenium salt etc.At present, more and more round the research of this system, for example there is report to utilize fluorine-containing and not fluorine-containing hybrid resin to cause at above-mentioned cationic initiator, made the adjustable accurate adhesive of low-shrinkage and refractive index; In disc making, the adhesive that the epoxy resin that utilizes cation to cause makes is that 96h does not have erosion to be taken place under 95% the experiment condition at 85 ℃, relative humidity; When the assembling of hollow devices, the aliphat and the bis-phenol D-type blending epoxy that utilize sulfonium salt to cause can make low linear expansion coefficient and have the adhesive of good moisture resistance.
2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide (TPO); the luxuriant molysite of virtue, organic aluminium compound/silane systems, dialkyl benzene acid methyl sulphur father-in-law salt; the reaction of the cation photocuring of triaryl sulphur hexafluorophosphate cation light initiator-tung oil-modified novolac epoxy resin (TMPE) and E-44 epoxy resin compound system. studied of the influence of various conditions by the mensuration of gel fraction to laser curing velocity, and coating structure before and after this reaction system photocuring reaction that utilized infrared spectrum analysis.The result shows that the kind of light trigger and concentration can change laser curing velocity effectively, and the initiating activity of Omnicat 550 is better than Omnicat 432 and proportional with its concentration; The punishment of photoactivate such as anthracene, BPO has certain sensibilization to system, and the phenthazine effect is not obvious; Different types of epoxy and vinyl ethers reactive diluent have considerable influence to laser curing velocity; Increase laser curing velocity increase along with epoxide group concentration in the resin proportioning; This diagram of system reveals " solidify the back " phenomenon.
Because light-initiated IONENE G cording has light-initiated not ideal enough, defectives such as curing rate is slow, cost height, limited it in industrial popularization, someone is unified in one with the cationic polymerization of epoxy resin and the radical polymerization of acrylate, both reached the purpose that makes full use of luminous energy, reached the purpose of mutual modification again, its cured product has been concentrated epoxy resin and acrylate advantage separately, has overcome some defective again simultaneously, has started a brand-new system.With benzhydryl iodine hexafluorophosphate (DPI.PF 6) make light trigger, cause bisphenol A epoxide resin E 51Made low viscosity, curing time weak point, bonding layer shear strength height, the good adhesive of water-fast boiling property with the hybrid resin of acrylic ester prepolymer AE, the advantage of epoxy resin and acrylate is all shown up.Below enumerated the composition of several mixed systems:
1, epoxy resin E-51 (bisphenol-A (2, and the epoxychloropropane linear polymer that polycondensation is synthesized in alkaline medium two (4-hydroxy phenyl) propane of 2-)), (51 represent the representative fraction 50% of epoxy), diaryl group iodized salt (CD-1012), the cationic photopolymerization initiator system that sensitising agent diisopropyl thiazolone (ITX) is formed.
2, bisphenol A epoxide resin (epoxy resin 128), cationic initiator sulphion hexafluorophosphate (6992) and sulphion hexafluoro antimonate (6976) are sulfosalt, reactive diluent butyl glycidyl ether (669), long carbochain glycidol ether (114), carboxylic monomer (0200), the polycaprolactone polyol of two senses and trifunctional (0301).
3, one methacrylate/glycidyl methacrylate copolymer is grafted on the polyurethane, in amine and after make self-emulsifying type acrylic resin grafted polyurethane, strengthened the compatibility of polyurethane and acrylic resin, improved the cost performance of resin.
4, tetraethylene-glycol dimethylacrylate, tetraethylene-glycol dimethylacrylate are respectively with 3,4-epoxycyclohexyl methyl-3 ', 4 '-the epoxycyclohexane carboxylate mixing, light trigger is an Alpha-hydroxy cyclohexyl benzophenone (Irgacure 184), 2,2-dimethoxy-2-phenyl acetophenone (Irgacure 651), styrax dimethyl ether, hexafluorophosphoric acid diphenyl iodnium.
5,2-ethylene glycol allyl ether and epoxy acrylic resin (CG602) mixture, cationic photoinitiator xylyl salt compounded of iodine or radical photoinitiator 2,2-dimethoxy-2-phenyl acetophenone (Irgacure651) or 2-hydroxy-2-methyl propiophenone (Darocur 1173).
6,4-epoxycyclohexyl formic acid-3,4-epoxycyclohexyl methyl ester (CY179), caprolactone trihydroxy alcohol, triaryl sulfonium salts, benzophenone and acrylate monomer.
7, vinyl ethers compound have that curing rate is fast, viscosity is low, be not afraid of oxygen inhibition, tasteless, nontoxic advantage.The photocuring system of forming with acrylic ester oligomer, triethylene Glycol divinyl ether, xylyl salt compounded of iodine, Alpha-hydroxy cyclohexyl benzophenone (Irgacure 184) that mixes has that curing rate is fast, solvent resistance good, need not " solidify the back " and to characteristics such as polyester base material adhesive force are good.
Adopt the substrate for flexible organic opto-electronic device structure of the present invention's preparation, be exemplified below:
1. flexible polymer film/ultra-violet curing adhesive/ITO
2. flexible metal foil/ultra-violet curing adhesive/ITO;
3. flexible ultra-thin glass/ultra-violet curing adhesive/ITO;
4. flexible polymer film/ultra-violet curing adhesive/ZnO;
5. flexible metal foil/ultra-violet curing adhesive/PEDOT:PSS;
6. flexible ultra-thin glass/ultra-violet curing adhesive/silver;
7. flexible polymer film/ultra-violet curing adhesive/copper;
8. flexible polymer film/ground floor ultra-violet curing adhesive/second layer ultra-violet curing adhesive/copper.Below be specific embodiments of the invention:
Embodiment 1
Board structure as shown in Figure 1, flexible substrate 1 adopts flexible polyethylene terephthalate polymer (PET) substrate, and tack coat 2 adopts individual layer ultra-violet curing adhesive, and conductive film 3 is the ITO transparent conductive film of DC magnetron sputtering.The transmission measurement curve as shown in Figure 2.
The preparation method is as follows:
1. utilize washing agent, acetone soln, ethanolic solution and deionized water that the PET substrate is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen;
2. after will stirring 20 hours with the ultra-violet curing adhesive that ethanol carries out 1:10 dilution, be spin-coated on the pet sheet face, rotating speed is 2000 revolutions per seconds, duration one minute, and thickness is about 100 nanometers;
3. substrate surface being carried out ultra-violet curing handled 30 seconds;
4. substrate is put into vacuum chamber, at ambient temperature, by the means of DC magnetron sputtering, under 100 watts of power condition at the ITO transparent conductive film of pet substrate surface sputtering 100 nanometer thickness;
The substrate that 5. will be coated with conductive film carries out ultraviolet light polymerization once more to be handled 60 seconds;
6. parameters such as the transmitance of test base, surface topography.
Embodiment 2
Board structure as shown in Figure 1, flexible substrate 1 adopts flexible metal foil, and tack coat 2 adopts individual layer ultra-violet curing adhesive, and conductive film 3 is the ITO transparent conductive film of DC magnetron sputtering.
The preparation method is as follows:
1. utilize washing agent, acetone soln, ethanolic solution and deionized water that flexible metal foil is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen;
2. after will stirring 30 hours with the ultra-violet curing adhesive that ethanol carries out 1:1 dilution, be spin-coated on the flexible metal foil surface, rotating speed is 3000 revolutions per seconds, duration 1 minute, and thickness is about 200 nanometers;
3. substrate surface being carried out ultra-violet curing handled 30 seconds;
4. substrate is put into vacuum chamber, at ambient temperature, by the means of DC magnetron sputtering, under 100 watts of power condition at the ITO transparent conductive film of flexible metal foil surface sputtering 200 nanometer thickness;
The substrate that 5. will be coated with conductive film carries out ultra-violet curing once more to be handled 180 seconds.
Embodiment 3
Board structure as shown in Figure 1, flexible substrate 1 adopts the PET substrate, and tack coat 2 adopts individual layer ultra-violet curing adhesive, the conductive metal film that conductive film 3 prepares for thermal evaporation method.
1. utilize washing agent, acetone soln, ethanolic solution and deionized water that the PET substrate surface is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen;
2. after will stirring 20 hours with the ultra-violet curing adhesive that ethanol carries out 1:10 dilution, be spun on the pet sheet face, rotating speed is 2000 revolutions per seconds, duration one minute, and thickness is about 100 nanometers;
3. substrate surface was carried out UV-irradiation 30 seconds;
4. substrate is put into vacuum chamber, at ambient temperature, with the method for thermal evaporation, at the conductive metal film of pet substrate surface evaporation 100 nanometer thickness;
5. after substrate being taken out from vacuum chamber, made the ultraviolet glue of coating further solidify in 60 seconds with UV-irradiation.
Embodiment 4
Board structure as shown in Figure 1, flexible substrate 1 adopts the PET substrate, and tack coat 2 adopts individual layer ultra-violet curing adhesive, and conductive film 3 is a polymer P EDOT:PSS conductive film.
1. utilize washing agent, acetone soln, ethanolic solution and deionized water that the PET substrate surface is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen;
2. after will stirring 20 hours with the ultra-violet curing adhesive that ethanol carries out 1:1 dilution, be spun on the pet sheet face, rotating speed is 2000 revolutions per seconds, duration one minute, and thickness is about 100 nanometers;
3. substrate surface was carried out the ultraviolet glue cured 30 seconds;
4. at the polymer P EDOT:PSS of substrate surface spin coating 100 nanometer thickness conductive film;
5. substrate is put into baking oven 60 degrees centigrade of following bakings 30 minutes;
6. made the ultraviolet glue of coating solidify once more in 60 seconds with the UV-irradiation substrate.
Embodiment 5
Board structure as shown in Figure 3, flexible substrate 1 adopts the PET substrate, and tack coat 2 adopts double-deck ultra-violet curing adhesive, and conductive film 3 is the ITO transparent conductive film of DC magnetron sputtering.
1. utilize washing agent, acetone soln, ethanolic solution and deionized water that the PET substrate surface is carried out ultrasonic cleaning, clean the back and dry up with drying nitrogen;
2. after will stirring 30 hours with the ultra-violet curing adhesive that ethanol carries out 1:1 dilution, be spun on the pet sheet face, rotating speed is 4000 revolutions per seconds, duration one minute, and thickness is about 100 nanometers, and is bonding as ground floor;
3. substrate surface was carried out the ultraviolet glue cured 60 seconds;
4. after will stirring 20 hours with the ultra-violet curing adhesive that ethanol carries out 1:10 dilution, be spun on on the bonding PET flexible substrate surface of one deck, rotating speed is 2000 revolutions per seconds, duration one minute, and thickness is about 100 nanometers, and is bonding as the second layer;
5. substrate surface was carried out UV-irradiation 30 seconds;
6. substrate is put into vacuum chamber, at ambient temperature, by the means of DC magnetron sputtering, under 100 watts of power condition at the ITO transparent conductive film of pet substrate surface sputtering 100 nanometer thickness;
The substrate that 7. will be coated with conductive film carries out ultra-violet curing once more to be handled 60 seconds.

Claims (10)

1, a kind of base board for flexible optoelectronic part, comprise flexible substrate, it is characterized in that, described flexible substrate surface is provided with tack coat and conductive film, described conductive film is deposited on the surface of tack coat, described bonding layer material is the adhesive that needs ultraviolet light polymerization, and described adhesive is the mixed system of free radical type ultraviolet photo-curing cementing agent and cation type ultraviolet photo-curing cementing agent.
2, base board for flexible optoelectronic part according to claim 1, it is characterized in that described free radical type ultraviolet photo-curing cementing agent raw material comprises 90～99.5% base resin, 0.2～3% monomer, 0.1～3% light trigger and 0.2～6% sensitising agent and auxiliary agent; Described cation type ultraviolet photo-curing cementing agent raw material comprises 90～99.5% cationic monomer, 0.4～8% diluent and 0.1～3% cation light initiator.
3, base board for flexible optoelectronic part according to claim 2 is characterized in that, described base resin comprises unsaturated polyester resin, acrylic resin and polythiol-polyenoid system; Described monomer comprises styrene and derivative, simple function group or multi-functional acrylate; Described light trigger comprises styrax and derivative benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and acetophenone derivative; Sensitising agent comprises benzophenone, thia anthraquinone and Michler's keton, and auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant and coupling agent; Described cationic monomer comprises various epoxy resin or modified epoxy or fluorine-containing and not fluorine-containing hybrid resin or aliphat and bis-phenol D-type blending epoxy; Described diluent comprises various active epoxy diluent resins and various cyclic ethers, cyclic lactone, the vinyl ether monomers diluent as light-cured resin; Described cation light initiator has diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts, triaryl selenium salt.
4, base board for flexible optoelectronic part according to claim 3 is characterized in that, described acrylic resin comprises polyester-acrylate, epoxy-acrylate, carbamate-acrylate and polyethers-acrylate.
5, base board for flexible optoelectronic part according to claim 3 is characterized in that, described polythiol-polyenoid system comprises the material of following structural formula:
HS(CH 2CH 2O) nCH 2CH 2SH
Figure A200810148117C00032
6, base board for flexible optoelectronic part according to claim 1 is characterized in that, described mixed system raw material comprises epoxy resin E-51, diaryl group iodized salt, diisopropyl thiazolone.
7, base board for flexible optoelectronic part according to claim 1, it is characterized in that, described mixed system raw material comprises bisphenol A epoxide resin, sulphion hexafluorophosphate and sulphion hexafluoro antimonate, butyl glycidyl ether, long carbochain glycidol ether, carboxylic monomer, the polycaprolactone polyol of two senses and trifunctional.
8, base board for flexible optoelectronic part according to claim 1, it is characterized in that, described mixed system raw material comprises the tetraethylene-glycol dimethylacrylate, 3, and 4-epoxycyclohexyl methyl-3 ＇, 4 ＇-epoxycyclohexane carboxylate, Alpha-hydroxy cyclohexyl benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, the styrax dimethyl ether, the hexafluorophosphoric acid diphenyl iodnium.
9, base board for flexible optoelectronic part according to claim 1 is characterized in that, described mixed system raw material comprises 2-ethylene glycol allyl ether, epoxy acrylic resin, xylyl salt compounded of iodine, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl propiophenone.
10, a kind of preparation method of base board for flexible optoelectronic part may further comprise the steps:
1. earlier flexible substrate is cleaned completely, it is dry to clean the back;
2. with flexible substrate surface-coated bonding layer material;
3. on substrate, prepare conductive film;
4. the transmitance of test base, conductivity, surface topography parameters;
For the ultraviolet light polymerization of ultraviolet photo-curing cementing agent respectively step 2. and/or step implement when 4. finishing, step 2. in, tack coat directly is spun on the flexible substrate, perhaps is spun on the flexible substrate through behind the organic solvent diluting; Described tack coat and conductive film are to form by one or several modes in vacuum evaporation, ion cluster bundle deposition, ion plating, dc sputtering deposition, RF sputter coating, ion beam sputtering deposition, ion beam assisted depositing, plasma reinforced chemical vapour deposition, magnetron sputtering, plating, spin coating, dip-coating, inkjet printing, roller coat, the LB film.
CN 200810148117 2008-12-31 2008-12-31 Substrate for flexible organic optoelectronic device and preparation method thereof Expired - Fee Related CN101465408B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200810148117 CN101465408B (en) 2008-12-31 2008-12-31 Substrate for flexible organic optoelectronic device and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200810148117 CN101465408B (en) 2008-12-31 2008-12-31 Substrate for flexible organic optoelectronic device and preparation method thereof

Publications (2)

Publication Number Publication Date
CN101465408A true CN101465408A (en) 2009-06-24
CN101465408B CN101465408B (en) 2010-12-29

Family

ID=40805855

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200810148117 Expired - Fee Related CN101465408B (en) 2008-12-31 2008-12-31 Substrate for flexible organic optoelectronic device and preparation method thereof

Country Status (1)

Country Link
CN (1) CN101465408B (en)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101916815A (en) * 2010-07-09 2010-12-15 电子科技大学 Light-emitting diode and preparation method thereof
CN101916812A (en) * 2010-07-09 2010-12-15 电子科技大学 Light-emitting diode and preparation method thereof
CN101916813A (en) * 2010-07-09 2010-12-15 电子科技大学 Light-emitting diode (LED) and preparation method thereof
CN102208562A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible luminescent device and preparation method thereof
CN102208544A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible optoelectronic device and preparation method thereof
CN102208541A (en) * 2011-04-18 2011-10-05 电子科技大学 Flexible substrate used in opto electronic device and preparation method thereof
CN102208566A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate used in luminescent device and preparation method thereof
CN102208540A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible photoelectronic device and preparation method thereof
CN102208557A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible luminescent device and preparation method thereof
CN102208558A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible luminescent device and preparation method thereof
CN102208537A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible photoelectronic device and preparation method thereof
CN102208568A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate used by flexible light-emitting device and preparation method thereof
CN102391715A (en) * 2010-07-13 2012-03-28 松下电器产业株式会社 Ink composition for ink-jetting and method for manufacturing organic film using the same
CN102516501A (en) * 2011-11-22 2012-06-27 中国科学院上海有机化学研究所 Photo-curing material for manufacturing light-emitting diode (LED) lens
CN103131226A (en) * 2013-01-23 2013-06-05 长兴化学工业股份有限公司 Coating composition and uses thereof
CN103459453A (en) * 2011-04-14 2013-12-18 迪睿合电子材料有限公司 Anisotropic conductive film
CN103890126A (en) * 2011-10-18 2014-06-25 乐金华奥斯有限公司 Composition for forming electronic paper without particle freezing, and adhesive film prepared thereby
CN107431020A (en) * 2015-03-27 2017-12-01 东丽株式会社 The effective photosensitive polymer combination of film crystal, cured film, thin film transistor (TFT), liquid crystal display device or organic el display, the manufacture method of cured film, the manufacture method of thin film transistor (TFT) and the manufacture method of liquid crystal display device or organic el display
CN108841235A (en) * 2018-06-05 2018-11-20 深圳市容大感光科技股份有限公司 Antioxygen hinders and improves composition and the application of light-curable ink surface cure degree
CN110003807A (en) * 2018-12-05 2019-07-12 高鼐 A kind of water based emulsion xenogenesis graft materials and preparation method thereof and its application in soft pvc film pressure sensitive adhesive tape
CN110831335A (en) * 2019-11-05 2020-02-21 东莞市科佳电路有限公司 Drilling deslagging electroplating process for FPC board
CN112837844A (en) * 2021-03-01 2021-05-25 佛山市瑞纳新材科技有限公司 HJT low-temperature curing silver paste with dual curing properties and preparation method thereof
CN113773682A (en) * 2021-08-25 2021-12-10 佛山市思博睿科技有限公司 Hydrophobic material for low-temperature plasma chemical vapor deposition and method for preparing nano-film by using same
CN114141830A (en) * 2021-11-22 2022-03-04 深圳市华星光电半导体显示技术有限公司 Display panel and display device

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI465534B (en) * 2010-12-31 2014-12-21 Eternal Materials Co Ltd Photocurable adhesive composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6896967B2 (en) * 2000-09-16 2005-05-24 Goo Chemical Co., Ltd. Ultraviolet-curable resin composition and photosolder resist ink containing the composition
CN101034687A (en) * 2007-04-18 2007-09-12 电子科技大学 Base board for flexible optoelectronic part and its making method

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101916812A (en) * 2010-07-09 2010-12-15 电子科技大学 Light-emitting diode and preparation method thereof
CN101916813A (en) * 2010-07-09 2010-12-15 电子科技大学 Light-emitting diode (LED) and preparation method thereof
CN101916815A (en) * 2010-07-09 2010-12-15 电子科技大学 Light-emitting diode and preparation method thereof
CN102391715A (en) * 2010-07-13 2012-03-28 松下电器产业株式会社 Ink composition for ink-jetting and method for manufacturing organic film using the same
CN102391715B (en) * 2010-07-13 2014-04-02 松下电器产业株式会社 Ink composition for ink-jetting and method for manufacturing organic film using the same
CN103459453A (en) * 2011-04-14 2013-12-18 迪睿合电子材料有限公司 Anisotropic conductive film
CN102208568B (en) * 2011-04-18 2013-03-27 电子科技大学 Substrate used by flexible light-emitting device and preparation method thereof
CN102208540A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible photoelectronic device and preparation method thereof
CN102208557A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible luminescent device and preparation method thereof
CN102208558A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible luminescent device and preparation method thereof
CN102208537A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible photoelectronic device and preparation method thereof
CN102208568A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate used by flexible light-emitting device and preparation method thereof
CN102208566A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate used in luminescent device and preparation method thereof
CN102208544B (en) * 2011-04-18 2014-03-26 电子科技大学 Substrate for flexible optoelectronic device and preparation method thereof
CN102208540B (en) * 2011-04-18 2013-03-06 电子科技大学 Substrate for flexible photoelectronic device and preparation method thereof
CN102208557B (en) * 2011-04-18 2013-03-27 电子科技大学 Substrate for flexible luminescent device and preparation method thereof
CN102208541A (en) * 2011-04-18 2011-10-05 电子科技大学 Flexible substrate used in opto electronic device and preparation method thereof
CN102208562A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible luminescent device and preparation method thereof
CN102208541B (en) * 2011-04-18 2013-07-10 电子科技大学 Flexible substrate used in opto electronic device and preparation method thereof
CN102208558B (en) * 2011-04-18 2013-07-10 电子科技大学 Substrate for flexible luminescent device and preparation method thereof
CN102208537B (en) * 2011-04-18 2013-09-25 电子科技大学 Substrate for flexible photoelectronic device and preparation method thereof
CN102208544A (en) * 2011-04-18 2011-10-05 电子科技大学 Substrate for flexible optoelectronic device and preparation method thereof
US9139757B2 (en) 2011-10-18 2015-09-22 Lg Hausys, Ltd. Composition for forming electronic paper without particle freezing, and adhesive film prepared thereby
CN103890126A (en) * 2011-10-18 2014-06-25 乐金华奥斯有限公司 Composition for forming electronic paper without particle freezing, and adhesive film prepared thereby
CN102516501A (en) * 2011-11-22 2012-06-27 中国科学院上海有机化学研究所 Photo-curing material for manufacturing light-emitting diode (LED) lens
CN103131226A (en) * 2013-01-23 2013-06-05 长兴化学工业股份有限公司 Coating composition and uses thereof
CN107431020A (en) * 2015-03-27 2017-12-01 东丽株式会社 The effective photosensitive polymer combination of film crystal, cured film, thin film transistor (TFT), liquid crystal display device or organic el display, the manufacture method of cured film, the manufacture method of thin film transistor (TFT) and the manufacture method of liquid crystal display device or organic el display
CN108841235A (en) * 2018-06-05 2018-11-20 深圳市容大感光科技股份有限公司 Antioxygen hinders and improves composition and the application of light-curable ink surface cure degree
CN110003807A (en) * 2018-12-05 2019-07-12 高鼐 A kind of water based emulsion xenogenesis graft materials and preparation method thereof and its application in soft pvc film pressure sensitive adhesive tape
CN110831335A (en) * 2019-11-05 2020-02-21 东莞市科佳电路有限公司 Drilling deslagging electroplating process for FPC board
CN112837844A (en) * 2021-03-01 2021-05-25 佛山市瑞纳新材科技有限公司 HJT low-temperature curing silver paste with dual curing properties and preparation method thereof
CN112837844B (en) * 2021-03-01 2022-07-15 佛山市瑞纳新材科技有限公司 HJT low-temperature curing silver paste with dual curing properties and preparation method thereof
CN113773682A (en) * 2021-08-25 2021-12-10 佛山市思博睿科技有限公司 Hydrophobic material for low-temperature plasma chemical vapor deposition and method for preparing nano-film by using same
CN114141830A (en) * 2021-11-22 2022-03-04 深圳市华星光电半导体显示技术有限公司 Display panel and display device

Also Published As

Publication number Publication date
CN101465408B (en) 2010-12-29

Similar Documents

Publication Publication Date Title
CN101465408B (en) Substrate for flexible organic optoelectronic device and preparation method thereof
CN101425560B (en) Substrate for flexible organic optoelectric device and preparation thereof
CN101465410B (en) Substrate for flexible organic optoelectronic device and preparation method thereof
CN101436644B (en) Substrate for flexible organic optoelectronic device and preparation method thereof
CN102208563B (en) Substrate for flexible luminescent device and preparation method thereof
CN102214803A (en) Packaging method of photoelectronic device
CN103594628A (en) Organic thin-film solar battery and manufacturing method thereof
CN102208559B (en) Substrate for flexible luminescent device and preparation method thereof
CN101930991A (en) Active driving organic electroluminescence device and preparation method thereof
CN102208540B (en) Substrate for flexible photoelectronic device and preparation method thereof
CN101916815A (en) Light-emitting diode and preparation method thereof
CN102208541B (en) Flexible substrate used in opto electronic device and preparation method thereof
CN102208555B (en) Substrate used in luminescent device and preparation method thereof
CN101887908B (en) Active drive organic electroluminescent device and preparation method thereof
CN102208539B (en) Substrate for flexible photoelectronic device and preparation method thereof
CN102208567A (en) Substrate for flexible luminous device and preparation method thereof
CN102074646A (en) Light-emitting diode (LED) and manufacturing method thereof
CN102208537B (en) Substrate for flexible photoelectronic device and preparation method thereof
CN102208544B (en) Substrate for flexible optoelectronic device and preparation method thereof
CN101894859A (en) Actively-driven organic electroluminescent device and preparation method thereof
CN102208564B (en) Flexible substrate used in luminescent device and preparation method thereof
CN102208566A (en) Substrate used in luminescent device and preparation method thereof
CN102208565B (en) Substrate for flexible luminous device and preparation method thereof
CN102208570B (en) Substrate for flexible luminescent device and preparation method thereof
CN102208557B (en) Substrate for flexible luminescent 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
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20101229

Termination date: 20131231