CN104953034A - Degradable substrate for flexible optoelectronic device and manufacture method thereof - Google Patents

Degradable substrate for flexible optoelectronic device and manufacture method thereof Download PDF

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Publication number
CN104953034A
CN104953034A CN201510194269.2A CN201510194269A CN104953034A CN 104953034 A CN104953034 A CN 104953034A CN 201510194269 A CN201510194269 A CN 201510194269A CN 104953034 A CN104953034 A CN 104953034A
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Prior art keywords
flexible
flexible substrate
base board
ultraviolet sensitivity
ultraviolet
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CN104953034B (en
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于军胜
王煦
周殿力
韩世蛟
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • 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

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Abstract

The invention discloses a degradable substrate for a flexible optoelectronic device and a manufacture method thereof. The substrate comprises a flexible substrate and a conducting layer on the flexible substrate. The flexible substrate is made of shellac which is doped with ultraviolet-sensitive adhesive with the mass ratio of 0.3-6.5%. The ultraviolet-sensitive adhesive is a mixture of free-radical type ultraviolet-sensitive adhesive and cationic-type ultraviolet-sensitive adhesive. According to the invention, the light transmission performance of the substrate is improved through cross-linking reaction of the ultraviolet-sensitive adhesive, therefore increasing the performance of the optoelectronic device. Meanwhile, the flexibility and the water- and oxygen-resistant performance of the substrate are also greatly enhanced, and the conducting layer and the substrate are combined quite firmly. Furthermore, the shellac has the biodegradability which solves the problem of ecological environment pollution caused by electronic wastes, and can be widely applied in the environment-friendly flexible optoelectronic field in future.

Description

Degradable base board for flexible optoelectronic part and preparation method thereof
Technical field
The invention belongs to organic optoelectronic technical field, be specifically related to a kind of degradable base board for flexible optoelectronic part and preparation method thereof.
Background technology
Photoelectron technology is the industry of the high-tech content developed rapidly after microelectric technique.Along with the fast development of photoelectron technology, the O-E Products such as solar cell, optical image sensor, electricity slurry flat-panel screens, electroluminescent display, thin-film transistor and panel of LCD, full-fledged all gradually, they substantially improve the life of the mankind.Meanwhile, opto-electronic information technology, in the extensive use of social life every field, also creates growing great market.Developed country all using optoelectronic information industry as one of field given priority to, the competition of the field of opto-electronic information just launches at world wide.
Organic material extensive use is in optoelectronic devices that the development of photoelectron technology serves the effect of adding fuel to the flames.From 1987, after the people such as Kodak Deng high official position have invented the ultra-thin organic electroluminescence device of sandwich structure on the basis of summing up forefathers, organic optoelectronic device entered the period of high speed development.Organic material is widely used in the fields such as photodetection, solar cell, display device.By the application of organic material, the production cost of opto-electronic device significantly reduces, and performance has had large increase.
At present, organic optoelectronic device is mostly be prepared in rigid substrate (as on glass or silicon chip).Though they have excellent device performance, anti-vibration, shock proof ability are more weak, and weight is relatively heavier, and it is very not convenient to carry, and is very restricted in the application of some occasion.People start to attempt by organic optoelectronic device deposition on flexible substrates instead of in glass substrate.Perhaps in the near future, we can be involved in computer display in a pen and carry with; Solar cell can be produced on wearable mobile phone and palmtop PC, utilize sunlight for powering portable devices; Flexible TFT can be made into 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 gentlier, not easily broken, institute take up space little and be more convenient for carrying.But although there are these advantages, replace rigid substrate also to there is many restrictions by flexible substrate, the preparation of flexible device still has many underlying issues to need to solve.Such as, first, due to compared with rigid substrate, the surface energy of flexible substrate is low, so the film tack that relatively will deposit is poor, and 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, thus cause the decline of device performance; Organic material is all very responsive to impurity, oxygen, water, is easy to contaminated thus reduces device efficiency.In addition, most of flexible substrate non-degradable or have certain toxicity, therefore, the ecological environmental pollution that electronic waste causes also is the problem being present in flexible optoelectronic field.
Summary of the invention
The present invention is in order to solve the problem, and a kind of degradable base board for flexible optoelectronic part and preparation method thereof is provided, significantly improve conductive layer adhesive force on flexible substrates, smooth flexible substrate surface, improve the pliability of flexible base, board, strengthen the water oxygen obstructing capacity of flexible substrate, improve the light transmission rate of flexible substrate.In addition, flexible substrate has biodegradable characteristics, to environment without destruction.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is:
A kind of degradable base board for flexible optoelectronic part, comprise flexible substrate and conductive layer, described conductive layer is positioned at the top of flexible substrate, it is characterized in that, described flexible substrate is shellac, be mixed with the ultraviolet sensitivity glue that mass ratio is 0.3-6.5% in described shellac, described ultraviolet sensitivity glue is by the mixed system comprising free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue.
Component and the mass ratio of described free radical type ultraviolet sensitivity glue are:
Component and the mass ratio of described cationic ultraviolet sensitivity glue are:
Cationic monomer 88-98%
Diluent 1.2-9%
Cation light initiator 0.8-4%.
Described base resin is one or more in unsaturated polyester resin, acrylic resin or polythiol-polyene systems; Described monomer is one or more in Styrene and its derivatives, simple function group or multi-functional acrylate; Described light trigger is styrax or Benzoin derivative, and described Benzoin derivative is one or more in benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or acetophenone derivative; Described sensitising agent is one or more in benzophenone, thia anthraquinone or Michler's keton; Described auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant and coupling agent; Described cationic monomer is one or more in epoxy resin, modified epoxy, fluorine-containing and not fluorine-containing hybrid resin or aliphat or bis-phenol D-type blending epoxy; Described diluent is one or more in reactive epoxies diluent, cyclic ethers, cyclic lactone or vinyl ether monomers; Described cation light initiator is one or more in diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts or triaryl selenium salt.
Described acrylic resin is one or more in polyester-acrylate, epoxy-acrylate, urethane acrylates or polyethers-acrylate.
Described polythiol-polyene systems is the material of following structural:
Described mixed system raw material comprises epoxy resin E-51, diaryl group iodized salt and diisopropyl thiazolone.
Described mixed system raw material comprises bisphenol A epoxide resin, sulphion hexafluorophosphate and sulphion hexafluoro antimonate, butyl glycidyl ether, Long carbon chain glycidol ether, carboxylic monomer, the polycaprolactone polyol of two senses and trifunctional.
Described mixed system raw material comprises tetraethylene-glycol dimethylacrylate, 3,4-epoxycyclohexyl-methyl-3', 4'-epoxycyclohexane carboxylate, Alpha-hydroxy cyclohexyl benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, dimethoxybenzoin and hexafluorophosphoric acid diphenyl iodnium.
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 and 2-hydroxy-2-methyl propiophenone.
The preparation method of degradable base board for flexible optoelectronic part, is characterized in that, comprises the following steps,
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. roller coat, LB embrane method, blade coating, spin coating, a painting, spraying, czochralski method, the tape casting, dip-coating, inkjet printing, self assembly or silk screen printing is adopted to prepare flexible substrate on the rigid substrate, described flexible substrate is shellac, be mixed with ultraviolet sensitivity glue in described shellac, described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue;
3. roller coat, LB embrane method, a painting, spraying, czochralski method, inkjet printing or silk screen print method is adopted to prepare conductive layer on flexible substrate surface;
4. treatment with ultraviolet light is carried out to the flexible substrate that 3. step obtains;
5. the flexible substrate after the step 4. process of medium ultraviolet light is peeled off from rigid substrates, form base board for flexible optoelectronic part.
After having prepared, test the degradation characteristic of base board for flexible optoelectronic part, sheet resistance, surface topography, water oxygen permeability and light transmission rate.
Compared with prior art, the present invention has following beneficial effect:
(1) mix the shellac of ultraviolet sensitivity glue by after ultraviolet process, in shellac, molecular resin degree of crystallinity reduces, thus reduces the scattering of light, improves light transmission rate, and then improves the performance of device.
(2) in shellac, mix appropriate ultraviolet sensitivity glue, by being cross-linked with each other between molecule after treatment with ultraviolet light, molecules align is finer and close, thus improves the mechanical strength of flexible substrate, too increases the water resistant oxygen ability of flexible base, board simultaneously.
(3) conductive layer adhesion is on flexible substrates effectively increased.
Accompanying drawing explanation
Fig. 1 is the structural representation of degradable base board for flexible optoelectronic part of the present invention;
Mark in figure: 1, conductive layer, 2, flexible substrate.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and described embodiment is only the present invention's part embodiment, is not whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments used obtained under creative work prerequisite, belongs to protection scope of the present invention.
By reference to the accompanying drawings, degradable base board for flexible optoelectronic part provided by the invention, comprise flexible substrate 2 and conductive layer 1, conductive layer 1 is positioned at the upper surface of flexible substrate 2, flexible substrate 2 is the support of conductive layer 1, and flexible substrate 2 has certain bending performance, has the ability of certain anti-steam and oxygen infiltration, there is good planarization, have good light transmission.
In the present invention, conductive layer 1 requires to have good filming performance, good conductivity, usually adopt in Graphene, carbon nano-tube, metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction nano wire, zinc oxide, titanium oxide, tin indium oxide or polymer electrode material one or more.Wherein, metal simple-substance nano wire comprises Fe nanowire, copper nano-wire, nano silver wire, nanowires of gold, aluminium nano wire, nickel nano wire, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires and Pt nanowires.Metal alloy nanowires comprises copper-iron alloy nano wire, silver ferroalloy nano wire, bule gold nano wire, alfer nano wire, dilval nano wire, ferro-cobalt nano wire, manganeisen nano wire, cadmium ferroalloy nano wire, indium ferroalloy nano wire, tin ferroalloy nano wire, ferro-tungsten nano wire, pt-fe alloy nano wire, yellow gold nano wire, gold copper nano wire, aluminium copper nano wire, monel nano wire, cobalt-copper alloy nano wire, manganin nano wire, cadmium copper alloy nano wire, gun-metal nano wire, tungsten-copper alloy nano wire, Mock gold nano wire, electrum nano wire, aluminium silver alloy nanowires, bazar metal nano wire, cobalt silver alloy nanowires, manganese silver alloy nanowires, cadmium silver nano wire, indium silver alloy nanowires, sn-ag alloy nano wire, tungsten silver alloy nanowires, platinum-silver alloys nano wire, aluminium gold alloy nano-wire, nickel billon nano wire, cobalt billon nano wire, manganese billon nano wire, cadmium billon nano wire, indium billon nano wire, Sillim's alloy nano-wire, tungsten billon nano wire, cobalt-nickel alloy nano wire, manganese-nickel nano wire, cadmium-nickel alloy nano wire, indium nickel alloy nano wire, tin-nickel alloy nano wire, tungsten nickel nano wire, platinum-nickel alloy nano wire, cadmium manganese alloy nano wire, indium manganese alloy nano wire, tin manganese alloy nano wire, tungsten manganese alloy nano wire, platinum manganese alloy nano wire, indium cadmium alloy nano wire, tin cadmium alloy nano wire, tungsten cadmium alloy nano wire, platinum cadmium alloy nano wire, tin-indium alloy nano wire, tungsten indium alloy nano wire, platinum indium alloy nano wire, tungsten ashbury metal nano wire, platinum ashbury metal nano wire, platinum-tungsten alloys nano wire.Metal hetero-junction nano wire comprises copper iron heterojunction nano-wire, silver iron heterojunction nano-wire, gold iron heterojunction nano-wire, ferro-aluminum heterojunction nano-wire, ferronickel heterojunction nano-wire, ferro-cobalt heterojunction nano-wire, ferromanganese heterojunction nano-wire, cadmium iron heterojunction nano-wire, indium iron heterojunction nano-wire, tin iron heterojunction nano-wire, ferrotungsten heterojunction nano-wire, platinum iron heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, gold copper heterojunction nano-wire, aluminum copper dissimilar junction nanowire, ambrose alloy heterojunction nano-wire, cobalt copper heterojunction nano-wire, copper-manganese heterojunction nano-wire, cadmium copper heterojunction nano-wire, tin copper heterojunction nano-wire, tungsten copper heterojunction nano-wire, platinoid heterojunction nano-wire, gold and silver heterojunction nano-wire, aluminium silver heterojunction nano-wire, nickeline heterojunction nano-wire, cobalt silver heterojunction nano-wire, manganese silver heterojunction nano-wire, cadmium silver heterojunction nano-wire, indium silver heterojunction nano-wire, tin silver heterojunction nano-wire, tungsten silver heterojunction nano-wire, platinum silver heterojunction nano-wire, aluminium gold heterojunction nano-wire, nickel gold heterojunction nano-wire, cobalt gold heterojunction nano-wire, manganese gold heterojunction nano-wire, cadmium gold heterojunction nano-wire, indium gold heterojunction nano-wire, Sillim's heterojunction nano-wire, tungsten gold heterojunction nano-wire, cobalt nickel heterojunction nano-wire, manganese nickel heterojunction nano-wire, cadmium nickel heterojunction nano-wire, indium nickel heterojunction nano-wire, tin nickel heterojunction nano-wire, tungsten nickel heterojunction nano-wire, platinum nickel heterojunction nano-wire, cadmium manganese heterojunction nano-wire, indium manganese heterojunction nano-wire, tin manganese heterojunction nano-wire, tungsten manganese heterojunction nano-wire, platinum manganese heterojunction nano-wire, indium cadmium heterojunction nano-wire, tin cadmium heterojunction nano-wire, tungsten cadmium heterojunction nano-wire, platinum cadmium heterojunction nano-wire, tin indium heterojunction nano-wire, tungsten indium heterojunction nano-wire, platinum indium heterojunction nano-wire, tungsten tin heterojunction nano-wire, platinum tin heterojunction nano-wire, platinum tungsten heterojunction nano-wire.Polymer electrode material comprises poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) or 3,4-polyethylene dioxythiophene.
Shellac is a kind of natural resin, has unique good characteristic, be widely used in food, medicine, plastics, military affairs, electrically, the industry such as rubber, ink, leather, coating, dyestuff and adhesive.Shellac is nontoxic, is mainly used in the capsule etc. of nutrients that the moistureproof sugar-coat of pill tablet, medication containment, glazing, enteric cartridge bag clothing and developed recently get up and cosmetics at present in medical industry.Shellac coating can be used for a lot of aspects of food industry equally, can be absorbed by the body, can natural degradation, such as, after candy and cake have been coated with shellac coating, can become very attractive in appearance, bright, can protection against the tide, anti-caking, anti-metamorphic and prolongation period of storage etc.Fruit, with after shellac coating film, can suppress moisture to evaporate over a period to come, keep fresh, reduces and rots, improve outward appearance, produces the effect of increasing economic efficiency.Shellac product has good tensile strength, resistance to wear, resilience and hardness, has desirable mechanical performance.Electric property aspect, the dielectric strength of shellac is high, and dielectric constant is low, and after arranging by electric arc, without conductivity, adds that it has good adherence and thermoplasticity, electrical apparatus insulation has special purposes.In addition, the film that the film that the shellac be hydrolyzed is formed is formed than natural shellac is more soft, and this is relevant with the increase of barras in shellac.But the steam impregnability of hydrolysis shellac film is than lower with natural shellac film, so need to carry out the water oxygen obstructing capacity that some process ensure shellac.
Component and the mass ratio of described free radical type ultraviolet sensitivity glue are:
Base resin 88-98%, monomer 0.5-4%, light trigger 1-4%, sensitising agent and auxiliary agent 0.5-6%; Component and the mass ratio of described cationic ultraviolet sensitivity glue are: cationic monomer 88-98%, diluent 1.2-9%, cation light initiator 0.8-4%.
Base resin comprises unsaturated polyester resin, acrylic resin and polythiol-polyene systems; Described monomer comprises Styrene and its derivatives, simple function group or multi-functional acrylate.
Unsaturated polyester resin: unsaturated polyester (UP) to react under the effect of initator the linear polyesters made with fractional saturation binary acid (or acid anhydrides) and dihydroxylic alcohols by undersaturated binary acid (or acid anhydrides) is mixed.In its molecular structure, there is undersaturated vinyl monomer to exist, if with active vinyl monomer and this kind of undersaturated vinyl monomer copolymerization, then crosslinking curing and become three-dimensional-structure.In general, the adhesive obtained by this resin-made due to volume contraction in solidification process comparatively large, the internal stress of gluded joint is very large.Easily there is micro-crack in the inside of glue-line and cause splicing power to diminish; Meanwhile, due in macromolecular chain containing ester bond, meet acid, alkali be easily hydrolyzed, thus resistance to medium and resistance to water poor, be easily out of shape under the environment of high temperature and humidity; In addition, its curing rate is comparatively slow, therefore, shows poor combination property, therefore mostly uses as non-structural glue.By reducing unsatisfied chemical bond content, adopting the low monomer of polymerization shrinkage, adding the means such as inorganic filler and thermal plastic high polymer, its overall performance can be improved.
Acrylic resin: this resin system curing rate is fast.Acrylic resin is one or more in polyester-acrylate, epoxy-acrylate, urethane acrylates or polyethers-acrylate.
Polythiol-polyene systems is the material of following structural:
Monomer usually and resin complex use, one side, as diluent, makes glue have the viscosity of constructability; Again there is reactivity on the other hand, enter resin web network after solidification, to the final performance of solidfied material, there is certain improvement.Monomer is one or more the combination in styrene, styrene derivative, monofunctional acrylates's ester or multi-functional acrylate; Simple function group or multi-functional acrylate be such as: methyl methacrylate, ethyl acrylate, acrylic acid propylene glycol ester, n-butyl acrylate etc.
To the requirement of monomer mainly: the respond of low viscosity, highly diluted effect and height, also to take into account volatility, toxicity and peculiar smell little simultaneously, good etc. to the compatibility of resin.
As the preferred mode of one, in order to regulate various performance parameter, adopt mix monomer, mix monomer is as follows: free radical activity diluent and cation activity diluent.
Free radical activity diluent comprises first generation polyfunctional acrylate monomer, second generation polyfunctional acrylate monomer and more excellent third generation acrylic monomers.
Monofunctional reactive diluent has: styrene, NVP, Isooctyl acrylate monomer, hydroxy-ethyl acrylate and isobornyl acrylate, methacrylate phosphate and isobornyl methacrylate.
Difunctional reactive diluents has: triethylene glycol diacrylate, tripropylene glycol diacrylate, glycol diacrylate, polyethylene glycol diacrylate alcohol ester, neopentylglycol diacrylate and propoxyl group neopentylglycol diacrylate, acrylate functional monomers has: 1,6-hexanediyl ester (HDDA), BDO diacrylate (BDDA), propylene glycol diacrylate (DPGDA), glycerol diacrylate (TPGDA), the trihydroxy methyl propane triacrylate (TMPTA) of trifunctional, pentaerythritol triacrylate (PETA), trihydroxy methyl propane triol triacrylate (TMPTMA), trimethylolpropane triacrylate, propoxylation trihydroxy methyl propane triacrylate, pentaerythrite three propylene alcohol ester, pentaerythritol propoxylate propylene alcohol ester, N, N-dihydroxy ethyl-3 amido methyl propionate, triethylene glycolbismethyl-acrylate, double pentaerythritol C5 methacrylate, tri (propylene glycol) diacrylate, phthalic acid diethanol diacrylate (PDDA).They instead of active little first generation acrylic acid monofunctional monomer.
Second generation polyfunctional acrylate monomer mainly introduces ethyoxyl or propoxyl group in the molecule, have excitant little, also there is 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), propoxylated glycerine triacrylate (G (PO) TA).
Third generation acrylic monomers is mainly the acrylate containing methoxyl group, preferably resolves the contradiction of high curing rate and shrinkage, low state of cure.This kind of 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 molecule, the viscosity of monomer can be reduced, reduce the excitant of monomer simultaneously.
The compatibility of introducing to diluent monomer of alkoxyl also improves a lot, and vinyltriethoxysilane (A15I), gamma-methyl allyl acyloxypropyl trimethoxysilane (A174) can be used as monomer.
Cruel in various reactive epoxies diluent and various cyclic ethers, ring, vinyl ether monomers etc. can as cation activity diluent.Wherein fast, the modest viscosity of vinyl ethers compound and oligomer curing rate, tasteless, nontoxic, can with epoxy resin with the use of.Vinyl ether monomers has: triethyleneglycol divinylether (DVE-3), 1, 4-butanediol vinyl ethers (HBVE), cyclohexyl vinyl ether (CHVE), perfluoro methyl vinyl ether (PMVE), perfluoropropylvinylether, IVE, hydroxy butyl vinyl ether, vinyl ethyl ether, ethyl vinyl ether, ethyl vinyl ether propylene, ethylene glycol monoallyl ether, hydroxy butyl vinyl ether, butyl vinyl ether, chlorotrifluoroethylene (CTFE), triethylene glycol divinyl ether, methoxy ethylene, vinyl butyl ether, dodecyl vinyl (DDVE), cyclohexyl vinyl ether, tribenzyl-benzene phenol polyethenoxy base ether, tetrafluoroethylene-perfluoro propyl vinyl ether, tetrafluoroethylene-perfluoro propyl vinyl ether, tert-Butyl vinyl ether:
Epoxy compounds monomer has: 3,4-expoxycyclohexyl formic acid-3 ', 4 '-expoxycyclohexyl methyl esters (ERL-4221), bisphenol A type epoxy resin (EP), epoxy acrylate, epoxy vinyl ester, acrylic acid epoxy ester, epoxymethacrylate, water-soluble itaconic acid epoxy ester resin:
Light trigger: in ultraviolet photo-curing cementing agent, often needs to add Photoactive compounds, to cause or the carrying out of accelerated reaction.Light trigger and sensitising agent can be divided into by the difference of its mechanism of action.Difference is that light trigger is when reacting beginning, absorbs the luminous energy of suitable wavelength and intensity, photophysical process occurs and reaches its a certain excitation state, if this excited energy is greater than the energy required for breaking bonds, then produce free radical polymerization; And after sensitiser absorption luminous energy to its a certain excitation state, just by energy in molecule or intermolecularly to shift, produce free radical polymerization by another molecule obtaining energy.Compared with light trigger, sensitising agent itself does not consume or change structure, and it can be regarded as photochemically reactive catalyst.Its mechanism of action roughly has three kinds: one to be energy transfer mechanism, and two is take hydrogen mechanism by force, and three is the photosensitive mechanism through generating Charger transfer.The light trigger with practical value developed has benzoin and its derivatives and acetophenone derivative, and sensitising agent has benzophenone, thia anthraquinone and Michler's keton.The stability of various initator, yellowing resistance, trigger rate are different, and in different resin systems, efficiency of initiation is also different, should need reasonable selection according to different occasion.As cyanacrylate and C (CH 2oCCH 2cH 2sH) system, use benzoin methyl ether, benzoin ethyl ether respectively, benzoin isopropyl ether causes, curing time is respectively 18s, 20s and 25s, and when causing with benzophenone, curing time is only 15s, and simultaneously the light transmittance of solidfied material also can difference be comparatively large because wavelength is different, and this will according to actual conditions reasonable selection.
The effect of light trigger is after it absorbs UV energy, produces free radical through decomposing, thus the unsaturated bond polymerization in initiator system, crosslinking curing becomes an entirety.Conventional radical photoinitiator has cracking type and puies forward the large class of Hydrogen two.
Crack type photoinitiator: crack type photoinitiator mainly contains benzoin ethers (styrax ethers), benzil ketals and acetophenone etc.Crack type photoinitiator is chapped after absorption ultraviolet light, produces two free radicals, and free radical causes unsaturated group polymerization.Benzoin ethers (styrax ethers) comprising: styrax (Benzoin), benzoin methyl ether, benzoin ethyl ether (Benzoin ethyl ether), benzoin isobutyl ether (Benzoin butyl ether), styrax lose (Benzoin oxime), benzoin isopropyl ether, acylphosphine oxide comprises: 2, 4, 6 trimethylbenzoyl diphenyl phosphine oxides (TPO) and (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide [BAPO phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide], phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide (819), tetramethylpiperidone oxide (TMPO), triethyl phosphate (TEPO), they are more satisfactory light triggers, there is very high space charge force, absorption is had to long wave near ultraviolet ray, be applicable to whitewash and the thicker situation of film, and there is good stability, can not variable color or fade.
Carry Hydrogen initator: carry Hydrogen initator and mainly contain benzophenone and thioxanthones etc.Wherein thioxanthone photoinitiator is at the maximum absorption wavelength in black light district at 380-420nm, and absorbability and hydrogen-taking capacity are strong, have higher efficiency of initiation.Carry Hydrogen initator and must have hydrogen donor as collaborative composition, otherwise efficiency of initiation is too low, so that application can not be put to.Triplet state carbonyl free radical more likely extracts hydrogen than on secondary carbon or on methyl from the tertiary carbon of hydrogen donor molecule, and the hydrogen be connected on the hetero-atom such as oxygen or nitrogen more easily extracts than the hydrogen on carbon atom.This kind of hydrogen donor has amine, hydramine (triethanolamine, methyl diethanolamine, triisopropanolamine etc.), mercaptan, N, N-diethyl-and to dimethylamino benzamide.
Benzophenone light initiation system, benzophenone needs with alcohol, ether or amine also with vinyl monomer just can be made to carry out photopolymerization.Mainly comprise: benzophenone, thia anthraquinone, Michler's keton, dimethoxy benezene phenyl ketone (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-morpholinopropanone (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 the oxygen in glued membrane can be eliminated initiator system is coordinated to the benzophenone of the inhibition of Raolical polymerizable and tertiary ammonia; Michler's keton and benzophenone with the use of, more cheap and effectively initiator system can be obtained.
Cationic photoinitiator: aromatic sulfonium salts and salt compounded of iodine class initator have excellent high-temperature stability, also have stability, so be widely used in Cationic curing systems with epoxy resin after coordinating.But their the longest absorbing wavelength does not absorb near ultraviolet band in 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), the two detergent alkylate iodine hexafluoro antimonate of 4,4-, xylyl salt compounded of iodine, diphenyl hexafluoroarsenate salt compounded of iodine, [4-(2-hydroxyl-3-butoxy-1-propoxyl group) phenyl] iodo-hexafluoro antimonate of benzene, [4-(to benzoylphenylsulfanyl) benzene] phenyl-iodide hexafluorophosphate, [4-(4-benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate, 4-(to benzoylphenylsulfanyl) benzene] phenyl-iodide hexafluorophosphate, 4,4 '-dimethyl diphenyl salt compounded of iodine hexafluorophosphate (IHT-PI 820), 4,4' 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, tetrafluoro boric acid diaryl group iodized salt, 3,3'-dinitro diphenyl salt compounded of iodine, 3,3'-dinitro diphenyl salt compounded of iodine and several 2,2'-bis-replaces (iodine, bromine, chlorine)-5,5'-dinitrophenyl salt compounded of iodine, iodate 2-[2-(3-indolizine) vinyl]-1-methylquinoline salt, iodate 4-(2-benzoxazole)-N-picoline salt, 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate, triaryl phosphine glyoxalidine salt, triaryl phosphine 1,1'-dinaphthalene glyoxalidine ring salt, 3,7-dinitro dibenzo bromine five rings salt, p-methyl benzenesulfonic acid triphenyl sulfosalt, bromination triphenyl sulfosalt, (4-Phenylsulfanyl-phenyl) diphenyl sulphur hexafluorophosphate, 4-(thiophenyl) triphenyl sulphur hexafluorophosphate, 3,3 '-dinitro diphenyl iodine hexafluorophosphate, 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate, triphenyl sulfosalt, 4-chlorphenyl diphenyl sulphur hexafluorophosphate, 3-nitrobenzophenone diphenyl sulphur hexafluorophosphate, 4-acetamidophenyl diphenyl sulphur hexafluorophosphate, 3-benzoylphenyl diphenyl sulphur hexafluorophosphate, triphenyl sulphur borofluoride, triphenyl sulphur hexafluorophosphate, triphenyl sulphur hexafluoro antimonate, 4-tolyl diphenyl sulphur hexafluorophosphate, phosphorus hexafluoride triaryl sulfonium salts, antimony hexafluoride triaryl sulfonium salts, [4-(to benzoylphenylsulfanyl) benzene] phenyl-iodide hexafluorophosphate, 1-(the bromo-2'-luorobenzyl of 4'-) pyridiniujm, [4-(to benzoylphenylsulfanyl) benzene] phenyl-iodide hexafluorophosphate, { 4-[4-(p-nitrophenyl formoxyl) thiophenyl] benzene } phenyl-iodide hexafluorophosphate, { 4-[4-(to methyl benzoyl) thiophenyl] benzene } phenyl-iodide hexafluorophosphate, { 4-[4-(to methyl benzoyl) phenoxy group] benzene } phenyl-iodide hexafluorophosphate, [4-(to benzoyl phenoxy group) benzene] phenyl-iodide hexafluorophosphate, the two detergent alkylate iodine hexafluoro antimonate of 4,4-.
Luxuriant molysite class: luxuriant molysite class light initiation system is the new cation light initiator of one developed after two aromatic iodonium salt and three aromatic sulfonium salts, first luxuriant molysite ion forms aromatic radical ligand under light illumination, produce the complex compound with the unsaturated iron of an epoxy compounds molecular complexes simultaneously, the lewis acidic feature of this complex compound tool also then forms the complex compound with three epoxy compounds molecular complexes, one of them epoxy compounds open loop can form 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, therefore under the condition that need heat in the external world, to improve polymerization speed.
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, ferrocene tetrafluoroborate, the luxuriant iron tetrafluoroborate of toluene, cyclopentadienyl group-iron-methyl phenyl ethers anisole salt, cyclopentadienyl group-iron-diphenyl ether salt, cyclopentadienyl group-iron-Isosorbide-5-Nitrae-diethoxybenzene salt, cyclopentadienyl group-iron-chlorobenzene salt, cyclopentadienyl group-iron-(Isosorbide-5-Nitrae-diethoxybenzene) hexafluorophosphate, cyclopentadienyl group-iron-diphenyl ether hexafluorophosphate, 1,10-phenanthrolene ferrous perchlorate salt, 1,10-phenanthrolene ferrous sulfate cyclopentadienyl group-iron-methyl phenyl ethers anisole salt, cyclopentadienyl group-iron-diphenyl ether salt, [two (diphenylphosphine) ferrocene of 1,1'-] Nickel Chloride, vinyl ferrocene, N, N'-di-ferrocene methylene butanediamine quaternary ammonium salt, ferrocene formamide, ferrocene acyl propionic acid, ferrocenyl methyl ketone, ethyl dicyclopentadienyl iron, Butyrylferrocene, butyl ferrocene, N, N-dimethyl-amine methyl ferrocene, 1,1'-dibenzoyl ferrocene, (3-carboxyl propionyl group) ferrocene, 1,1'-dibromof errocene, Aminoferrocene.
The light trigger of macromolecule loading: in photocuring system, light trigger is not often exhaust completely in Light Curing, and the part of non-photodissociation can move to coating surface, makes coating yellowing and aging, affects the quality of product; On the other hand, some initators and system is incompatible or compatibility is bad, make it apply and are restricted.For addressing these problems, people are by light trigger producing high-molecular.The initator tool of the initator low relative molecular of producing high-molecular has the following advantages: A, in polymer chain, energy transfer and intermolecular reaction become and be more prone to, and make Polymeric photoinitiators have higher activity.B, by with nonactive group copolymerization, regulates and design the distance of photosensitive group, or changing the distance of optical active group and main chain, thus acquisition has different photoactive initator.C, different optical active groups can be introduced at same macromolecular chain, utilize their cooperative effect to improve light sensitive effect.The producing high-molecular of D, initator, limits the migration of initator, prevent coating turn yellow and aging.E, because most of photolysis debris is still connected on macromolecule matrix, therefore, smell and the toxicity of system can be reduced.
Initator can directly be connected on the chain of macromolecule or oligomer by the producing high-molecular of initator, as introduced on macromolecular chain by thioxanthone or acidic group phosphine oxide etc.; Also can introduce the functional group that can occur to be polymerized in initator, make it in Light Curing, realize producing high-molecular, as introduced in tetraacrylate by benzophenone structural.
The compatibility of various light trigger is also a research direction in recent years, re-uses, both can reduce costs, can expand again the region of absorbing wavelength after compatibility, improves the absorption of ultraviolet radiation energy, thus the solidification effect obtained.The compatibility of light trigger both can be between same type, as being both free radical type, the Irgacure-1700 that such as Ciba newly releases is exactly by 25% (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (BAPO) and 75% alpha-hydroxy-2,2 dimethyl acetophenones (1173) form, and Irgacure-1800 is made up of the Alpha-hydroxy cyclohexyl-phenyl ketone (184) of the BAPO of 25% and 75%; Also can be made up of dissimilar initator, as free radical type with cationic light trigger compatibility, such as, triaryl thiaxanthene salt and benzophenone are coordinated, the curing rate of epoxy compounds can be made to be improved.
Auxiliary agent: in general, for adapting to the bonding requirement of varying environment, also needs in ultraviolet photo-curing cementing agent to add various auxiliary agent, as plasticizer, thixotropic agent, filler, antistatic agent, fire retardant, coupling agent etc.Although their components shared in adhesive are few, sometimes vital effect is produced to the processing characteristics of glue or adhesive property.As cyanacrylate and C (CH 2oCCH 2cH 2sH) under the initiation of benzophenone, if add the silicone couplet CH of l% 2=CHSi (OCH 2cH 2oCH 3) 3, after ultraviolet light polymerization, under being placed in the environment of 80-100% humidity, after 1 year, do not find change, and if do not add coupling agent, under the same terms, after 2 days just there is white erosion in bonded part, one week afterwards glue-line strip down completely.
Plasticizer comprises: diisooctyl azelate (DIOZ), dioctyl azelate (DOZ), phthalic acid two is ester (DHP), separate adipate (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 (Butoxyethoxy) ethyl ester, isopropyl titanate, tetrabutyl titanate, triethyl citrate, tributyl citrate, tributyl 2-acetylcitrate, tri trimellitate (2-ethyl) own ester (TOTM), phthalic acid two (2-ethyl) own ester, decanedioic acid two (2-ethyl) own ester (DOS), Diethylene Glycol 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 system coupling agent, WB215 (aliphatic acid 18%, fatty acid ester 52%, calcium carbonate 20%).
Coupling agent is the material that a class has both sexes structure, and a part of group in their molecules can react with the chemical group of mineral surfaces, forms strong chemical bonding; Another part group then has close organic character, can with reactive organic molecule or physical entanglement, thus the material strong bonded that two kinds of character vary in size.The coupling agent of current industrial use is divided into the large class of silanes, acyl esters of gallic acid, zirconium class and organochromium complexes four by chemical constitution.Wherein applying more in adhesive is silanes, as methylvinyldichlorosilane, methyl hydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-aminopropyltrimethoxysilane, 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, aminopropyl silsesquioxane, γ-methacryloxypropyl trimethoxy silane, chain alkyl trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-chloropropyl triethoxysilane, two-(the silica-based propyl group of γ-triethoxy), anilinomethyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ mercaptopropyitrimethoxy silane, γ-Mercaptopropyltriethoxysilane.
Levelling agent is used to the flow leveling improving resin, prevent the generation of the defects of coatings such as shrinkage cavity and pinprick, make smooth coating, and can glossiness be improved, comprise mixed solvent, organosilicon, polyacrylate, acetate butyrate fiber, nitrocellulose and polyvinyl butyral resin.Wherein silicone based, comprise diphenylpolysiloxane, methyl phenyl silicone, Organo-modified polysiloxanes, polyether silicones.
Stabilizer is used to be polymerized when minimizing is deposited, and improves the storage stability of resin.Conventional stabilizer has hydroquinones, p methoxy phenol, 1,4-benzoquinone, 2,6 one di-t-butyl cresols, phenothiazine, anthraquinone etc.
Defoamer is used to prevent and eliminate coating and produces bubble in manufacture and use procedure, prevents coating from producing the disadvantages such as pinprick.Phosphate, fatty acid ester and organosilicon etc. can make defoamer.Specifically there is tributyl phosphate, 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, Tributyl phosphate ester, triethyl phosphate, tricresyl phosphate chloro isopropyl ester, three butoxy ethyl ester of phosphoric acid, the mixture (light yellow to water white transparency thick liquid) of polyoxyethylene polyoxypropylene and glycol or three alcohol ethers, dimethyl silicone polymer, glycerine polyethenoxy ether (GP330), laureth, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether 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 used to be polymerized when minimizing is deposited, and improves the storage stability of resin.Conventional polymerization inhibitor is generally divided into molecule-type polymerization inhibitor and stabilized free fundamental mode polymerization inhibitor, and the former mainly contains: hydroquinones, 1,4-benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-tert-butyl catechol, methylene blue, three (N-nitroso-N-Phenylhydroxylamine) aluminium salt, stannous chloride, inorganic matter and the Sulfurs etc. such as ferric trichloride also can be made polymerization inhibitor stabilized free fundamental mode polymerization inhibitor and mainly contain the bitter hydrazine (DPPH) of 1,1-diphenyl-2-, TEMPO (TMP), hydroquinones, allyl acetate, MEHQ (MEHQ), NO free radical piperidine alcohols, phosphorous acid (TEMPO) mixed ester, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen radical (TMHPHA), 8% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt: the 2-phenolic group ethoxy acrylate of 92%, 4% 3 (N-nitroso-N-Phenylhydroxylamine) aluminium salt, 96% ethyoxyl list oil triacrylate, MEHQ hydroquinone monomethyl ether, polymerization inhibitor mantoquita, adjacent methyl hydroquinone, 2,6-di-t-butyl cresols, 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, alkylbenzenesulfonate amine salt, p-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, 2,5-ditert-butylhydro quinone, adjacent methyl is to the adjacent methyl-p-benzoquinone of benzene two, 3-tertiary butyl-4-hydroxyanisol (BHA), 2,6-dinitro-p-cresol (DNPC), polyvinyl acetal, NO free radical piperidine alcohols, 4,6-dinitro o sec-butyl phenol, DMSS (DMSS), propilolic alcohol.
Thixotropic agent adds in resin, can make resin adhesive liquid when static, have higher denseness, becomes again the material of low denseness fluid under external force.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 2composition, and containing a 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 in water-based system, polyvinyl alcohol, polyacrylic acid, poly(ethylene oxide), polymethylacrylic acid, Lauxite, melamine resin, resol, phenolic resins water-soluble resin are thickener.
The effect of filler is that part replaces binding agent, reduces the consumption of binding agent, with the effect reaching filling, reinforcement, anti-attrition and reduce costs.Filler require particle thin and even, can be scattered in slurries equably, to binding agent and other component associativities good.The consumption of filler should be suitable, otherwise also can affect 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 polymers, butyl polyacrylate, polyurethane.
Dispersant impels material particles to be dispersed in medium, forms the reagent of stable suspension.Dispersant is generally divided into inorganic dispersant and the large class of organic dispersing agent two.Conventional inorganic dispersant has silicates (such as waterglass) and alkali metal phosphonates (Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium, Amino Trimethylene Phosphonic Acid potassium, HEDP sodium, HEDP disodium, HEDP four sodium, HEDP potassium, ethylene diamine tetra methylene phosphonic acid five sodium, diethylene triamine pentamethylene phosphonic five sodium, diethylenetriamine penta seven sodium, diethylene triamine pentamethylene phosphonic sodium, 2-phosphonobutane-1, 2, 4-tricarboxylic acids four sodium, hexapotassium sylvite, two 1, 6 hexamethylene triamine five methylenephosphonic acid sodium, 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-phosphonobutane-1,2,4-tricarboxylic acids (PBTCA), PAPE (PAPE), 2-HPAA (HPAA), hexapotassium (HDTMPA), polyamino polyether base methylenephosphonic acid (PAPEMP), two 1,6 hexamethylene 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 copolymer (AA/AMPS), acrylic acid-acrylic acid hydroxypropyl acrylate copolymer, acrylic acid-acrylic ester-phosphonic acids-sulfonate quadripolymer, acrylic acid-acrylic ester-sulfonate terpolymer, copolymer of phosphono carboxylic acid (POCA), polyacrylate, carboxylate-sulfonate-nonionic terpolymer, polyepoxy sodium succinate (PESA), poly (sodium aspartate) (PASP), base amylalcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester etc.
Antioxidant, with the auxiliary agent suppressing fluoropolymer resin thermal oxidative degradation to be major function, 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, to catch polymer peroxy radical for major function, has again the title of " peroxy radical capturing agent " and " chain termination type antioxidant ", relates to aromatic amine compounds and the large series of products of hindered phenol compound two.Aromatic amine antioxidant has: diphenylamines, p-phenylenediamine (PPD), N, N-be two-and [3-(3,5-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), 2,6-tri-grades of butyl-4-methylphenols, two (3,5-tri-grades of butyl-4-hydroxy phenyls) thioether, four [β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) 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) ester, the dimer of many alkyl bisphenol A phosphite ester and trimerical compound, 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, 1,3,5-trimethyl-2,4,6-tri-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene.Auxiliary antioxidant has the effect of decomposing copolymer per-compound, also claims " peroxide decomposer ", comprises sulfo-dicarboxylic ester class and bi-ester of phosphite, usually and primary antioxidant with the use of.The two lauryl of the two octadecyl ester (DSTP) of two Lauryl Alcohol ester, two ten four carbon alcohols esters, thio-2 acid, thio-2 acid dibasic acid esters, two octadecanol ester, thio-2 acid, three monooctyl esters, three the last of the ten Heavenly stems ester, three (Lauryl Alcohol) esters and three (16 carbon alcohol) ester, 3,6,9-trioxa decane-1,11-glycol-bis--n-dodecane mercaptopropionic acid ester, triphenyl phosphate TPP, trisnonyl phenyl phosphite, phosphorous acid octyl diphenyl.
Heavy metal ion passivator, is commonly called as " copper resistant agent ", can complexed transition metal ion, and prevent the oxidative degradation of its catalytic polymerization resin, typical structure is as hydrazide kind compound etc.Recent years, along with going deep into of polymer antioxygen theoretical research, the classification of antioxidant also there occurs certain change, and the most outstanding feature is the introduction of the concept of " carbon free radical trapers ".This radical scavenger is different from traditional primary antioxidant, and they can catch polymer alkyl diradical, is equivalent to set up one defence line in traditional antioxidant system.This type of stabilizing additive mainly comprises 2-ethyl benzofuran ketone, 2-methyl benzofuran ketone, Dihydrobenzofuranes ketone, benzofuranone, dibenzopyrone, 3-aryl-benzofuran-2-ones, 3-arylben-zofuranone, 2-aryl Dihydrobenzofuranes ketone, 2-arylben-zofuranone, 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 furanone, 4-ethoxylated bisphenol-A-diacrylate, (2-10)-ethoxylated bisphenol-A-dimethylacrylate, 2-[1-(2-hydroxyl-3,5-bis-tertiary amyl phenyl)-ethyl]-4,6-bis-tertiary amyl phenyl acrylates, bisphenol-A-glycerol double methyl methacrylate, bisphenol-A-dimethylacrylate, 4-ethoxylated bisphenol-A-dimethylacrylate, N, N-dibenzyl hydroxylamine, N-ethyl-N-hvdroxv ethamine, N, N-diethyl hydroxylamine, IPD acrylamide HAS, isopropylhydroxyla, hydroxylamine hydrochloride, hydroxylammonium chloride, hydrogen chlorine azanol, N-methyl-hydroxylamine, acetohydroxamic acid, N-hydroxyl acetamide.
Modifier is intended to improve plasticizing capacity, improves resin melt viscoelasticity and promotes the modified additive that resin melting flows, and this analog assistant is based on acrylic acid esters co-polymer (ACR).
Anti-impact modifier improves the auxiliary agent of hard polymer article 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) of polypropylene toughness-increasing modified middle use also belongs to rubber toughened scope.
The function of antistatic agent is the sheet resistance reducing polymer product, eliminates the electrostatic hazard that accumulation of static electricity may cause, mainly comprises for cationic surfactant and anion surfactant.Cationic surfactant has: alkyl phosphate diethanolamine salt, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, stearmide, stearoyl dimethyl-penten ammonium chloride, two (2-the ethoxy)-N-of N, N-(3 '-dodecyloxy-2 '-hydroxypropyl) first ammonium Methylsulfate salt, trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, N, N-cetyl ethyl morpholine ethyl-sulfate salt, (dodecanamide propyl trimethyl ammonium) Methylsulfate salt dibrominated N, N-bis-(octadecyldimethyl)-3-oxa--1,5-penta 2 ammonium, styrene polymer type quaternary ammonium salt, palmitate quaternary ammonium salt, alkylphenol-polyethenoxy based quaternary ammonium salt, dialkyl quaternary ammonium salt, polyacrylamide quaternary ammonium salt, octadecyldimethyl ethoxy quaternary ammonium nitrate, ammonium polystyrene sulphonate salt, propyl-dimethyl-beta-hydroxyethyl nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, the polymer of 2,2'-nitrilo-di-methylcarbinol and poly-(oxygen-1, the 2-second two base) phosphate of α-three decyl-ω-hydroxyl, polyethylene glycol tridecyl ether phosphate, diethanolamine salt, oleic acid diethanolamine salt, triethanol amine oleate, ethoxylated amine, N, N-dihydroxy ethyl octadecylamine, N, N-dihydroxyethyl p-toluidine, 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 tridecyl alcohol phosphate ester, 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.
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, N-alkylaminoacid salts, epoxy tripolymer acid inner salt, carboxybetaine, tridecyl dimethyl (2-sulfurous acid) ethyl ammonium second inner salt, N-dodecyl alanine, 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.
Polymer Antistatic Agent comprises: poly(ethylene oxide) (PEO), polyether ester acid imide, polyethylene glycol methacrylic acid copolymer body, 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), the amphipathic copolymer that octadecyl methacrylate (SMA)+polyethylene glycol methacrylate-styrene polymer (PEGMA) forms.
In fire retardant, 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, organic fire-retardant comprises deca-BDE, three (2, 3-dibromopropyl) phosphate, HBCD, poly-2, 6-dibromobenzene aether, chlorinated paraffin wax, polyphosphate, red phosphorus, two (tetrabromo phthalimide) ethane, Dowspray 9 homopolymers, melamine, cyanurate, isodecyl diphenyl phosphate, ethylhexyl diphenyl phosphate, tricresyl phosphate isopropyl phenyl ester, two (2 chloroethyl) vinylphosphonate, ethylene two [three (2 cyanoethyl) bromination microcosmic salt], N, two (2 ethoxy) the AminomethylphosphoniAcid Acid diethylester of N, polyphenylene phosphonic acids diphenyl sulphone (DPS) ester, polyazodiphenylene phenyiphosphonate, polyphenylene phosphonic acids bisphenol-A ester.
Mould inhibitor, also known as microbial inhibitor, is the growth of microorganism such as a class mould fungus inhibition, prevents the stabilizing additive that fluoropolymer resin is degraded by microbial attack.Most polymeric material is insensitive to mould, but due to its goods work in-process with the addition of plasticizer, lubricant, fatty acid soaps class etc. can mould growth class material and there is mould sensitivity.The chemical substance that plastics mould inhibitor comprises is a lot, 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 dimethylamino benzamide; In promoter, aminopropyl silsesquioxane and Versamid mass ratio are 3:1.
Cationic photocuring system mainly utilizes the photodissociation under Ultraviolet radiation of aromatic diazonium salt, aromatic iodonium salts, aromatic series sulfonium salt to produce Bronsted acid, and Bronsted acid again trigger monomer carries out cationic polymerization.Compared with radically curing system, if it have cure shrinkage little, not by various oxygen inhibition and there is no nucleophilic impurity, once cause, polymerization such as will to continue for a long time at the advantage.But the Bronsted acid that light trigger discharges when illumination is penetrated, can produce corrosiveness to cementing matrix.In theory, all monomers that can carry out cationic polymerization may be used to cationic curing, but the most frequently used is various epoxy resin or modified epoxy at present.Various reactive epoxies diluent and various cyclic ethers, cyclic lactone, vinyl ether monomers etc. can 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, the research round this system gets more and more, such as, have report to utilize fluorine-containing and not fluorine-containing hybrid resin to cause at above-mentioned cationic initiator, has obtained low-shrinkage and the adjustable accurate adhesive of refractive index; In disc making, the adhesive that the epoxy resin utilizing cation to cause obtains 85 DEG C, under relative humidity is the experiment condition of 95%, the non-corrosive phenomenon of 96h occurs; When the assembling of hollow devices, the aliphat utilizing sulfonium salt to cause and bis-phenol D-type blending epoxy, can obtain low linear expansion coefficient and have the adhesive of good moisture resistance.
2; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide (TPO); iron arene complexes, organic aluminium compound/silane systems, dialkyl benzene acid methyl sulphur father-in-law salt; the cation photocuring reaction of triaryl sulphur hexafluorophosphate cation light initiator-tung oil-modified novolac epoxy resin (TMPE) and E-44 epoxy resin compound system. have studied the impact of various condition on laser curing velocity by the mensuration of gel fraction, and utilize coating structure before and after this reaction system photocuring reaction of infrared spectrum analysis.Result shows, 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 the photoactivate such as anthracene, BPO has certain sensibilization to system, and phenthazine effect is not obvious; Different types of epoxy and vinyl ethers reactive diluent have considerable influence to laser curing velocity; Along with the increase laser curing velocity of resin proportioning epoxy group group concentration increases; This diagram of system reveals " Post RDBMS " phenomenon.
Because photoinitiated cationic polymerization system has, light-initiated not ideal enough, curing rate is slow, high in cost of production defect, limit its popularization industrially, the cationic polymerization of epoxy resin and the radical polymerization of acrylate are unified in one by someone, both the object making full use of luminous energy had been reached, reach again the object of mutual modification, its cured product has concentrated epoxy resin and acrylate advantage separately, simultaneously overcomes again some defect, has started a brand-new system.With benzhydryl iodine hexafluorophosphate (DPI.PF 6) make light trigger, cause bisphenol A epoxide resin E 51obtain low viscosity, curing time is short, high, water-fast the boiling property of bonding layer shear strength is good adhesive with the hybrid resin of acrylic ester prepolymer AE, made the advantage of epoxy resin and acrylate all show out.Below list the composition of several mixed system:
1, epoxy resin E-51 (bisphenol-A (2, two (4-hydroxy phenyl) propane of 2-)) and the epoxychloropropane linear polymer that polycondensation is synthesized in alkaline medium, the representative fraction 50% of epoxy (51 represent), diaryl group iodized salt (CD-1012), the cationic photopolymerization initiator system that sensitising agent diisopropyl thiazolone (ITX) forms.
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 carbon chain glycidol ether (114), carboxylic monomer (0200), the polycaprolactone polyol (0301) of two senses and trifunctional.
3, one methacrylate/glycidyl methacrylate copolymer is grafted on polyurethane, through in amine and after obtained self-emulsifying type acrylic resin grafted polyurethane, enhance the compatibility of polyurethane and acrylic resin, improve the cost performance of resin.
4, tetraethylene-glycol dimethylacrylate, tetraethylene-glycol dimethylacrylate are respectively with 3,4-epoxycyclohexyl-methyl-3', 4'-epoxycyclohexane carboxylate mixes, light trigger is Alpha-hydroxy cyclohexyl benzophenone (Irgacure184), 2,2-dimethoxy-2-phenyl acetophenone (Irgacure 651), dimethoxybenzoin, 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 (Irgacure 651) 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 hybrid UV curable paint formed with acrylic ester oligomer, triethylene Glycol divinyl ether, xylyl salt compounded of iodine, Alpha-hydroxy cyclohexyl benzophenone (Irgacure184) has that curing rate is fast, solvent resistance good, without the need to " Post RDBMS " and to features such as polyester base material adhesive force are good.
Below specific embodiments of the invention:
Embodiment 1
Board structure as shown in Figure 1, flexible substrate 2 is for being mixed with the shellac of ultraviolet sensitivity glue, and conductive layer 1 is Graphene.Preparation method is as follows:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. spin coating is adopted to prepare flexible substrate on the rigid substrate, described flexible substrate is shellac, the ultraviolet sensitivity glue that mass ratio is 0.3% is mixed with in described shellac, thickness is 100 μm, described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue, the mass ratio of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue is 1:10, described free radical type ultraviolet sensitivity collagen material comprise 88% base resin, the monomer of 4%, the light trigger of 4% and 4% sensitising agent and auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprise the cationic monomer of 98%, the diluent of 1.2% and 0.8% cation light initiator;
3. adopt spraying process to prepare graphene conductive layer on flexible substrate surface, height 20cm, spraying air pressure 0.3MPa, spray rate 0.3mL/min, conductive layer thickness is 80nm;
4. treatment with ultraviolet light is carried out to the flexible substrate that 3. step obtains;
5. the flexible substrate after the step 4. process of medium ultraviolet light is peeled off from rigid substrates, form base board for flexible optoelectronic part;
6. the degradation characteristic of base board for flexible optoelectronic part, sheet resistance, surface topography, water oxygen permeability and light transmission rate is tested.Test gained, prepared base board for flexible optoelectronic part square resistance is 106 Ω/.
Embodiment 2
Board structure as shown in Figure 1, flexible substrate 2 is for being mixed with the shellac of ultraviolet sensitivity glue, and conductive layer 1 is carbon nano-tube.Preparation method is as follows:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. spin coating is adopted to prepare flexible substrate on the rigid substrate, described flexible substrate is shellac, the ultraviolet sensitivity glue that mass ratio is 0.5% is mixed with in described shellac, thickness is 150 μm, described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue, the mass ratio of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue is 1:8, described free radical type ultraviolet sensitivity collagen material comprise 90% base resin, the monomer of 3.5%, the light trigger of 1% and 5.5% sensitising agent and auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprise the cationic monomer of 95%, the diluent of 2% and 3% cation light initiator;
3. adopt spraying process to prepare carbon nanotube conducting layer on flexible substrate surface, height 20cm, spraying air pressure 0.3MPa, spray rate 0.3mL/min, conductive layer thickness is 90nm;
4. treatment with ultraviolet light is carried out to the flexible substrate that 3. step obtains;
5. the flexible substrate after the step 4. process of medium ultraviolet light is peeled off from rigid substrates, form base board for flexible optoelectronic part;
6. the degradation characteristic of base board for flexible optoelectronic part, sheet resistance, surface topography, water oxygen permeability and light transmission rate is tested.Test gained, prepared base board for flexible optoelectronic part square resistance is 146 Ω/.
Embodiment 3
Board structure as shown in Figure 1, flexible substrate 2 is for being mixed with the shellac of ultraviolet sensitivity glue, and conductive layer 1 is nano silver wire.Preparation method is as follows:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. spin coating is adopted to prepare flexible substrate on the rigid substrate, described flexible substrate is shellac, the ultraviolet sensitivity glue that mass ratio is 0.9% is mixed with in described shellac, thickness is 200 μm, described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue, the mass ratio of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue is 1:5, described free radical type ultraviolet sensitivity collagen material comprise 92% base resin, the monomer of 3%, the light trigger of 2% and 3% sensitising agent and auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprise the cationic monomer of 93%, the diluent of 3% and 4% cation light initiator;
3. adopt spraying process to prepare nano silver wire conductive layer on flexible substrate surface, height 20cm, spraying air pressure 0.3MPa, spray rate 0.3mL/min, conductive layer thickness is 100nm;
4. treatment with ultraviolet light is carried out to the flexible substrate that 3. step obtains;
5. the flexible substrate after the step 4. process of medium ultraviolet light is peeled off from rigid substrates, form base board for flexible optoelectronic part;
6. the degradation characteristic of base board for flexible optoelectronic part, sheet resistance, surface topography, water oxygen permeability and light transmission rate is tested.Test gained, prepared base board for flexible optoelectronic part square resistance is 87 Ω/.
Embodiment 4
Board structure as shown in Figure 1, flexible substrate 2 is for being mixed with the shellac of ultraviolet sensitivity glue, and conductive layer 1 is nickel billon nano wire.Preparation method is as follows:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. spin coating is adopted to prepare flexible substrate on the rigid substrate, described flexible substrate is shellac, the ultraviolet sensitivity glue that mass ratio is 1.5% is mixed with in described shellac, thickness is 250 μm, described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue, the mass ratio of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue is 1:2, described free radical type ultraviolet sensitivity collagen material comprise 94% base resin, the monomer of 2%, the light trigger of 3% and 1% sensitising agent and auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprise the cationic monomer of 91%, the diluent of 6% and 3% cation light initiator;
3. adopt spraying process to prepare nickel billon nano wire conductive layer on flexible substrate surface, height 20cm, spraying air pressure 0.3MPa, spray rate 0.3mL/min, conductive layer thickness is 120nm;
4. treatment with ultraviolet light is carried out to the flexible substrate that 3. step obtains;
5. the flexible substrate after the step 4. process of medium ultraviolet light is peeled off from rigid substrates, form base board for flexible optoelectronic part;
6. the degradation characteristic of base board for flexible optoelectronic part, sheet resistance, surface topography, water oxygen permeability and light transmission rate is tested.Test gained, prepared base board for flexible optoelectronic part square resistance is 86 Ω/.
Embodiment 5
Board structure as shown in Figure 1, flexible substrate (2) is for being mixed with the shellac of ultraviolet sensitivity glue, and conductive layer (1) is tin indium oxide.Preparation method is as follows:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. spin coating is adopted to prepare flexible substrate on the rigid substrate, described flexible substrate is shellac, the ultraviolet sensitivity glue that mass ratio is 2% is mixed with in described shellac, thickness is 300 μm, described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue, the mass ratio of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue is 1:1, described free radical type ultraviolet sensitivity collagen material comprise 96% base resin, the monomer of 0.5%, the light trigger of 2% and 1.5% sensitising agent and auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprise the cationic monomer of 90%, the diluent of 8.5% and 1.5% cation light initiator;
3. 2. surface screen-printed legal system is for conductive indium-tin oxide layer, conductive layer thickness is 100nm;
4. treatment with ultraviolet light is carried out to the flexible substrate that 3. step obtains;
5. the flexible substrate after the step 4. process of medium ultraviolet light is peeled off from rigid substrates, form base board for flexible optoelectronic part; 6. the degradation characteristic of base board for flexible optoelectronic part, sheet resistance, surface topography, water oxygen permeability and light transmission rate is tested.Test gained, prepared base board for flexible optoelectronic part square resistance is 27 Ω/.
Embodiment 6
Board structure as shown in Figure 1, flexible substrate is the shellac being mixed with ultraviolet sensitivity glue, and conductive layer is poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) (PEDOT:PSS).Preparation method is as follows:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. spin coating is adopted to prepare flexible substrate on the rigid substrate, described flexible substrate is shellac, the ultraviolet sensitivity glue that mass ratio is 4% is mixed with in described shellac, thickness is 500 μm, described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue, the mass ratio of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue is 3:1, described free radical type ultraviolet sensitivity collagen material comprise 97% base resin, the monomer of 1%, the light trigger of 1% and 1% sensitising agent and auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprise the cationic monomer of 89%, the diluent of 9% and 2% cation light initiator;
3. prepare PEDOT:PSS conductive layer at 2. surperficial ink-jet printing process, conductive layer thickness is 150nm;
4. treatment with ultraviolet light is carried out to the flexible substrate that 3. step obtains;
5. the flexible substrate after the step 4. process of medium ultraviolet light is peeled off from rigid substrates, form base board for flexible optoelectronic part; 6. the degradation characteristic of base board for flexible optoelectronic part, sheet resistance, surface topography, water oxygen permeability and light transmission rate is tested.Test gained, prepared base board for flexible optoelectronic part square resistance is 66 Ω/.
Embodiment 7
Board structure as shown in Figure 1, flexible substrate 1 is for being mixed with the shellac of ultraviolet sensitivity glue, and conductive layer 2 is golden copper heterojunction nano-wire.Preparation method is as follows:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. spin coating is adopted to prepare flexible substrate on the rigid substrate, described flexible substrate is shellac, the ultraviolet sensitivity glue that mass ratio is 6.5% is mixed with in described shellac, thickness is 1000 μm, described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue, the mass ratio of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue is 8:1, described free radical type ultraviolet sensitivity collagen material comprise 98% base resin, the monomer of 0.5%, the light trigger of 1% and 0.5% sensitising agent and auxiliary agent; Described cationic ultraviolet sensitivity collagen material comprise the cationic monomer of 88%, the diluent of 8% and 4% cation light initiator;
3. prepare golden copper heterojunction nano-wire conductive layer at 2. surperficial ink-jet printing process, conductive layer thickness is 100nm;
4. treatment with ultraviolet light is carried out to the flexible substrate that 3. step obtains;
5. the flexible substrate after the step 4. process of medium ultraviolet light is peeled off from rigid substrates, form base board for flexible optoelectronic part;
6. the degradation characteristic of base board for flexible optoelectronic part, sheet resistance, surface topography, water oxygen permeability and light transmission rate is tested.Test gained, prepared base board for flexible optoelectronic part square resistance is 19 Ω/.
Table 1 is the light transmission rate test result of embodiment 1-7 flexible substrate, and a kind of is the shellac being mixed with a certain amount of ultraviolet sensitivity glue, and another kind is the shellac not mixing ultraviolet sensitivity glue.
Embodiment Mix the light transmittance after ultraviolet sensitivity glue Do not mix the light transmittance of ultraviolet sensitivity glue
1 86％ 70％
2 79％ 68％
3 77％ 61％
[0160]
4 78％ 64％
5 82％ 73％
6 82％ 66％
7 79％ 64％

Claims (10)

1. degradable base board for flexible optoelectronic part, comprise flexible substrate and conductive layer, described conductive layer is positioned at the top of flexible substrate, it is characterized in that, described flexible substrate is the shellac being mixed with ultraviolet sensitivity glue, the mass ratio of described ultraviolet sensitivity glue in shellac is 0.3-6.5%, and described ultraviolet sensitivity glue is made up of the mixed system comprising free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue.
2. degradable base board for flexible optoelectronic part according to claim 1, is characterized in that, component and the mass ratio of described free radical type ultraviolet sensitivity glue are:
Component and the mass ratio of described cationic ultraviolet sensitivity glue are:
Cationic monomer 88-98%
Diluent 1.2-9%
Cation light initiator 0.8-4%.
3. degradable base board for flexible optoelectronic part according to claim 2, is characterized in that, described base resin is one or more in unsaturated polyester resin, acrylic resin or polythiol-polyene systems; Described monomer is one or more in Styrene and its derivatives, simple function group or multi-functional acrylate; Described light trigger is styrax or Benzoin derivative, and described Benzoin derivative is one or more in benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or acetophenone derivative; Described sensitising agent is one or more in benzophenone, thia anthraquinone or Michler's keton; Described auxiliary agent comprises plasticizer, thixotropic agent, filler, antistatic agent, fire retardant and coupling agent; Described cationic monomer is one or more in epoxy resin, modified epoxy, fluorine-containing and not fluorine-containing hybrid resin or aliphat or bis-phenol D-type blending epoxy; Described diluent is one or more in reactive epoxies diluent, cyclic ethers, cyclic lactone or vinyl ether monomers; Described cation light initiator is one or more in diaryl group iodized salt, triaryl salt compounded of iodine, triaryl sulfonium salts or triaryl selenium salt.
4. degradable base board for flexible optoelectronic part according to claim 3, is characterized in that, described acrylic resin is one or more in polyester-acrylate, epoxy-acrylate, urethane acrylates or polyethers-acrylate.
5. degradable base board for flexible optoelectronic part according to claim 3, is characterized in that, described polythiol-polyene systems is one or more in the material of following structural:
6. degradable 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 and diisopropyl thiazolone.
7. degradable 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 carbon chain glycidol ether, carboxylic monomer, the polycaprolactone polyol of two senses and trifunctional.
8. degradable base board for flexible optoelectronic part according to claim 1, it is characterized in that, described mixed system raw material comprises tetraethylene-glycol dimethylacrylate, 3,4-epoxycyclohexyl-methyl-3', 4'-epoxycyclohexane carboxylate, Alpha-hydroxy cyclohexyl benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, dimethoxybenzoin and hexafluorophosphoric acid diphenyl iodnium.
9. degradable 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 and 2-hydroxy-2-methyl propiophenone.
10., according to the preparation method of the arbitrary described degradable base board for flexible optoelectronic part of claim 1-9, it is characterized in that, comprise the following steps:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. roller coat, LB embrane method, blade coating, spin coating, a painting, spraying, czochralski method, the tape casting, dip-coating, inkjet printing, self assembly or silk screen printing is adopted to prepare flexible substrate on the rigid substrate, described flexible substrate is shellac, be mixed with ultraviolet sensitivity glue in described shellac, described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue;
3. roller coat, LB embrane method, a painting, spraying, czochralski method, inkjet printing or silk screen print method is adopted to prepare conductive layer on flexible substrate surface;
4. treatment with ultraviolet light is carried out to the flexible substrate that 3. step obtains;
5. the flexible substrate after the step 4. process of medium ultraviolet light is peeled off from rigid substrates, form base board for flexible optoelectronic part.
After having prepared, test the degradation characteristic of base board for flexible optoelectronic part, sheet resistance, surface topography, water oxygen permeability and light transmission rate.
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CN111430550A (en) * 2020-03-26 2020-07-17 杭州纤纳光电科技有限公司 Perovskite battery component with ultraviolet protection layer and preparation method thereof
TWI768791B (en) * 2021-03-26 2022-06-21 中國鋼鐵股份有限公司 Cleaning agent compositions for solar panel glass and cleaning method using the same
CN115141297A (en) * 2022-07-07 2022-10-04 李旭东 Degradable polystyrene synthesis method based on nitrobenzyl disulfide and pyridinium ester block macromolecular azo initiator
CN115141297B (en) * 2022-07-07 2024-02-20 广东蓝海包装新技术有限公司 Degradable polystyrene synthesis method based on nitrobenzyl disulfide and pyridinium ester block macromolecular azo initiator

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