CN102329594B - Two-component urethane resin adhesive for polymer lithium ion battery flexible package film - Google Patents
Two-component urethane resin adhesive for polymer lithium ion battery flexible package film Download PDFInfo
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Abstract
The invention provides a two-component urethane resin adhesive for a polymer lithium ion battery flexible package film, and aims to provide an adhesive which has the advantages of high bonding strength, stripping resistance, excellent barrier property, impact resistance, high bonding compatibility with a nonmetallic film or an aluminum foil, resistance to swelling, dissolving, permeation and absorption of electrolyte organic solvents and high-volatility substances, resistance to strong acid and strong alkali and difficulty in breaking a molecular chain after becoming dry and hard. The two-component urethane resin adhesive consists of components, wherein a first component (A) is an emulsion waterborne Poly Urethane (PU) performed polymer which is obtained by compounding polyester and isocyanate/benzene ring-containing polyether in the mass ratio 75/25-55/45 and adding an aid for reacting; a second component (B) is a composition consisting of glycidyl ether epoxy resin with the epoxy resin 0.25-0.45 and a melamine-formaldehyde resin additional crosslinking agent; the weight ratio of the first component to the second component is 10/1-10/2; and a certain amount of additional crosslinking agent is added into a PU emulsion in a certain mass ratio.
Description
Technical field
The present invention relates to a kind of dual-component polyurethane resin glue stick for polymer Li-ion battery packing film adhesive linkage.
Background technology
In prior art, the sizing agent of Flexible-Packaging Industry application has monocomponent polyurethane adhesive, dual-component polyurethane adhesive, acrylic acid or the like sizing agent, without holding agent sizing agent, alcohol dissolubility, aqurous ployurethane tackiness agent etc.And the performances such as the water-fast solvent resistance of current most of aqueous polyurethane, thermotolerance and bonding force need to improve, therefore in recent years the modification of aqueous polyurethane is become to the focus in this field.But up to the present, adopt dual-component aqueous polyurethane sizing agent to replace two part solvent type polyurethane sizing agent not make a breakthrough both at home and abroad.
Weak point at present for the aqurous ployurethane sizing agent of bonding plastics film soft packaging is:
(1) general tackiness agent resistance to elevated temperatures is not enough, and hydrolytic resistance is poor, and viscosity is little.The viscosity of aqurous ployurethane generally regulates by water-soluble thickener and water, and in addition, the important factor affecting aqurous ployurethane sizing agent viscosity also has ionic charge, micellar structure and particle diameter etc.Ion on polymer molecule and gegenion more, viscosity is larger, and identical solids content, the viscosity of Water-soluble adhesive are little compared with solvent-based adhesive viscosity.
(2) rate of drying is slow.Because the volatility of water is poorer than organic solvent, therefore aqurous ployurethane sizing agent rate of drying is slow, and because the surface tension of water is approximately 7.3 × 10-4N/cm, for 3 times of usual organic solvent, the wetting ability of effects on surface hydrophobic substrates is poor, when most of moisture not from adhesive linkage, evaporate into air or absorbed by porous substrate just suddenly dry, be then difficult to obtain successional glue-line.
(3) water-fast, thermotolerance is poor.In commercial aqurous ployurethane, great majority are linear thermoplastic's urethane, and in molecular structure, contain the ionic group of hydrophilic radical or side joint, sometimes also containing water-soluble thickener, what can not be formed to a certain degree after glued membrane drying is crosslinked, and the performances such as thus it is water-fast, thermotolerance, solvent resistant, chemical-resistant and glued membrane intensity are all not good enough.
Current aqurous ployurethane is based on anionic, self-emulsifying.Anion-type water-thinned polyurethane divides again sulfonate type and carboxylic acid type two class.What present application was more is carboxylic acid type.Carboxylic hydrophilic chain extender generally has dihydroxyl half ester and the two hydroxymethyl propionic acid (DMPA) of 2,2-.DMPA relative molecular mass is little, less consumption just can provide enough hydroxyl equivalents, but because DMPA is solid, and fusing point is higher, can produce non-uniform phenomenon in reaction process, and half acid is how good with polyol phase capacitive, but consumption is greatly and the aqurous ployurethane glued membrane stickness obtained. the disadvantage of aqurous ployurethane dispersion liquid is, the activation temperature of activation needed for adhesive layer is too high, to such an extent as to makes continually to be glued substrate damage.For reducing activation temperature, normal employing adds the way of solvent, softening agent or other resin, but these methods again usually can to lose the thermotolerance of adhesive for polyurethane for cost.
The barrier property of barrier layer soft package film of polymer lithium ion battery is main relevant with tackiness agent with aluminium foil barrier films.And and bonding strength between barrier layer aluminium foil and ectonexine and plastic deformation ability closely bound up because polymer lithium ion battery electric solution liquid content can swelling, solution absorption internal layer composite membrane, particularly film interlaminated adhesive or binding resin.
Prior art adopts the modifier of polyolefin resin or these resins and the one of mixture to carry out bonding polymer lithium ion battery ectonexine flexible packaging film usually.Or with the addition of thermoplastic elastomer and tackifier vinyl or EVA hot melt adhesive, polyolefin polyhydric alcohol, multi-functional isocyanide acid alcohol stiffening agent, and polyester-urethane resin, polyethers-ammonia ester resin, isocyanic ester, unsaturated acid grafted polyolefin resins a kind of caking agent wherein.The weak point of the glue bonding layer of these hot solvents coating compound is, effectively can not intercept the infiltration of cell contents, do not possess the performance of anti-strong acid-base and high corrosion and anti-organic solvent and high volatile volatile material, can not effectively resist inside battery electrolytic solution to it swelling, dissolve, infiltration, to absorb and electrochemical reaction.In moulding process, aluminium foil and other nonmetallic composite, comprise caking agent and jointly extend, flow, and in the process extended, the molecular chain of the caking agent after dry and hard easily ruptures, and forms stealthy crack broken belt.
Summary of the invention
The object of the invention is for above-mentioned the deficiencies in the prior art part, there is provided a kind of bonding strength high, resistance to stripping, barrier property is excellent, shock-resistant, with nonmetal film or aluminium foil Binder Phase capacitive good, electrolyte resistance organic solvent and high volatile volatile material is swelling, dissolve, infiltration, absorb, strong acid-base resistance, the dual-component polyurethane resin glue stick of dry and hard rear molecular chain not easy fracture.
Above-mentioned purpose of the present invention can be reached by following measures, a kind of for the dual-component polyurethane resin glue stick of polymer lithium from battery flexible packaging film, be made up of two kinds of components, first component (A) be polyester and isocyanic ester/containing phenyl ring polyethers with 75/25 ~ 55/45 mass ratio carry out composite, and add the emulsus Waterborne Polyurethane Prepolymer (PU) that auxiliary agent is obtained by reacting, the second component (B) is a kind of oxirane value is the glycidyl ether type epoxy resin of 0.25 ~ 0.45 and the composition of melamine formaldehyde resin additional crosslink agent, wherein the weight ratio of the first component and second component is 10/1 ~ 10/2, a certain amount of above-mentioned additional crosslink agent is added in mass ratio in PU emulsion, mix and obtain bi-component waterborne PU sizing agent emulsion.
Prepare the method for dual-component polyurethane resin glue stick, to slough the polyester polyol of moisture, polyether glycol, by polyester and polyether with 75/25 ~ 55/45 mass ratio carry out compositely joining in reactor, add dihydroxyphenyl propane chainextender simultaneously, stirring is warmed up to 80 DEG C, add appropriate catalyzer and polyisocyanates, insulation reaction 4h, then be cooled to 30 DEG C and add coupling agent A, add a certain amount of acetone simultaneously and reduce viscosity, add trihexylamine (TEA) again after continuing reaction 1h and carry out neutralization reaction, deionized water is dripped under high velocity agitation after 15min, de-bubbled 30min obtains emulsus Waterborne Polyurethane Prepolymer (PU).
The present invention has following beneficial effect compared to prior art.
Hydrolytic resistance is adopted with preparing polyurethane adhesive, to improve the thermotolerance of polyurethane adhesive containing the polyethers of phenyl ring, with polyester and isocyanic ester preferably.In dual-component aqueous polyurethane sizing agent, aqueous polyurethane and linking agent there occurs crosslinking reaction, two kinds of additional crosslink agents can increase degree of crosslinking and the viscosity of Aqueous Polyurethane Adhesives, improve the T-shaped stripping strength of sizing agent and strengthen the solvent resistance of made glued membrane.Urethane can be made to form reticulated structure by crosslinking reaction, its force of cohesion is improved, multiple film T stripping strength also rises thereupon.And when being heating and curing, isocyanic ester autohemagglutination can occur, form crosslinking structure, make its T-shaped stripping strength become large.Use the film that the Aqueous Polyurethane Adhesives that epoxy resin 6360 and terpolycyantoamino-formaldehyde resin are linking agent bonds respectively, the T-shaped stripping strength of thermal treatment 1h at 50 DEG C.Adding of epoxy resin and melamine formaldehyde resin, the degree of crosslinking of Aqueous Polyurethane Adhesives is improved, the corresponding raising of adhesiveproperties.Polyether glycol is added in polyester polyol, with the suitable proportioning of polyester and polyether, preparation feedback type polyurethane hot melt adhesive, not only bonding strength is high, also can overcome the defect causing internal stress because crystallization is too fast, also can by changing setting time and the curing speed of the ratio control PUR of polyester and polyether.Because it is not containing organic solvent, solids content is absolutely, changes the characteristic of the volatile obnoxious flavour of traditional tackiness agent, can not damage human body.Have that 120 DEG C of melt viscosities are 3000 ~ 4000cps, surface drying time is 60s, resin added 20 ~ 40g/m
2, final stripping strength reaches more than 40N/25mm performance.The performed polymer obtained by polyether glycol has good stability to hydrolysis, good snappiness and extensibility, and resistance to low temperature is good; And polyester polyols alcohol type performed polymer force of cohesion is large, bonding strength is high.It is formed between base material has soft-hard transition layer, and not only bonding force is strong, also has excellent buffering, shock-absorbing function simultaneously.The low temperature of the gluing stick of urethane and very low temperature performance exceed the tackiness agent of other types all.In addition, polyurethane adhesive also has resistance to low temperature and excellent stability etc. the characteristic that toughness is adjustable, adhesion technique is easy, splendid.High performance water-borne polyurethane adhesive have water-fast, resistance to medium good, bonding strength is high, initial bonding strength is large, freeze-thawing resistant, and higher temperature resistant, rate of drying are very fast, and under low ambient temperature, film-forming properties is good.
Along with the increase of the add-on of linking agent, T-shaped stripping strength all presents the trend of first increases and then decreases.Solidification is convenient.Select various different solidifying agent, epoxy-resin systems almost can solidify in 0 ~ 180 DEG C of temperature range.
Because melamine formaldehyde resin is easy to and the polymer reaction with primary and secondary hydroxyl, carboxyl and amide group, form a 3 D stereo reticulated structure by crosslinking reaction.Melamine formaldehyde resin itself has higher thermostability and good water-fast solvent resistance, adds in aqueous polyurethane and can significantly improve its performance.Epoxy resin is polyol due to it, with polyurethane reaction in branch point can be introduced polyurethane backbone, make it part and form reticulated structure and performance is more excellent.The rigidity of epoxy resin and strong adhesion.Polar hydroxyl groups intrinsic in epoxy molecule chain and the existence of ehter bond, make it have very high adhesive power to various material.Shrinkability during epoxy resin cure is low, and the internal stress of generation is little, and this also contributes to improving adhesion strength.The reaction of epoxy resin and solidifying agent used is undertaken by the ring-opening polymerization of direct addition reaction or molecular resin epoxy group, do not have water or other volatile byproducts to release.They are compared with unsaturated polyester resin, resol, demonstrate very low shrinkability (being less than 2%) in the curing process.Epoxy-resin systems after solidification has excellent mechanical property.Epoxy-resin systems after solidification is a kind of superior isolation material with high dielectric property, resistance to surface leakage, resistance to electric arc.Usually, the epoxy-resin systems after solidification has excellent alkali resistance, acid resistance and solvent resistance.Show with infrared spectrum and dsc analysis, in dual-component aqueous polyurethane sizing agent, aqueous polyurethane and linking agent there occurs crosslinking reaction.Additional crosslink agent can increase degree of crosslinking and the viscosity of Aqueous Polyurethane Adhesives, thus effectively improves T-shaped stripping strength and the solvent resistance of sizing agent.
Adopt the bonding aluminum foil outer layer of dual-component polyurethane resin glue stick of the present invention, to rush dark interactive Binder Phase capacitive splendid with metal aluminum foil, and sticking power is good.Adventitia and binder molecule chain are rushing in dark process, the interactive extensibility of plasticity and compound firmness excellence, and do not rupture not stratified, adhesive coating is incrust, does not affect the stripping strength of its barrier and compound; Viscosity is high, anti-organic solvent, anti-strong acid-base, anti-height corrosion volatile matter, and toughness is high temperature resistant, shock-resistant, peel resistant strength is high, resistance to infiltration, bonding free of pinholes, and molecular chain is complete not to rupture.
Embodiment
The present invention is further illustrated below by embodiment.Be made up of two kinds of components for the dual-component polyurethane resin glue stick of polymer lithium from battery flexible packaging film, first component (A) can be polyester and isocyanic ester/containing the polyethers blend of phenyl ring, polyester and isocyanic ester/containing phenyl ring polyethers with 75/25 ~ 55/45 mass ratio carry out composite, and add the emulsus Waterborne Polyurethane Prepolymer (PU) that auxiliary agent is obtained by reacting, add auxiliary agent and comprise hydrolysis stabilizer, long-chain biatomic acid and have at least one in the dibasic alcohol of side chain, organo-silicon coupling agent.Add the hydrolytic resistance that auxiliary agent can improve polyester itself.The hydrolysis stabilizer added can be carbodiimide, epoxy compounds etc., also can adopt long-chain biatomic acid and dibasic alcohol raw material, as sebacic acid, 1,6-hexylene glycol etc.The dibasic alcohol of side chain such as neopentyl glycol raw material is had to improve the hydrolytic resistance of polyester.
For improving the hydrolytic resistance tackiness agent of adhesive layer, improve the thermotolerance of polyurethane adhesive, can add a small amount of organo-silicon coupling agent in formula, organo-silicon coupling agent very weight can be 0.5-5%.The hydrolytic resistance that a small amount of organo-silicon coupling agent can improve adhesive layer is added in adhesive formulation.Silane coupling agent is an organosilyl important branch, and general formula can be expressed as: Y-R-SiX3, X with Y are the different active groups of two class response characteristics.End silica group, under catalyzer existent condition, is solidified into silanol by the moisture silane group hydrolysis in air, and then reticulates structure with another silanol or silane group cross-linking reaction, produce bonding.Can avoid like this NCO group directly and water react and produce too much bubble, cause too much bonding defect, affect the drawback of bonding strength.
Polyisocyanates has, vulcabond, containing polyisocyanates, diisocyanate monomer, diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), the 3-isocyanic ester methylene-3 of isocyanurate ring, 5,5-trimethylcyclohexylisocyanate (IPDI), hydrogenation of benzene dicyclohexylmethane diisocyanate (H
12mDI), isophorone diisocyanate, dicyclohexyl methane diisocyanate, PPDI, cyclohexyl diisocyanate, xylylene diisocyanate, cyclohexanedimethyleterephthalate vulcabond, tetramethyl-m-xylylene diisocyanate, norbornene alkyl diisocyanate, dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate etc.Isocyanic ester raw material is based on tolylene diisocyanate (TDI).Vulcabond is divided into aromatic series and aliphatics (or alicyclic) two class.The performed polymer synthesized by aromatic diisocyanate has higher intensity, but not color inhibition, and aliphatic diisocyanate due in molecular structure containing unsaturated double-bond, the performed polymer anti-yellowing property obtained by it is excellent.Except oligomer polyol and vulcabond, in synthesis performed polymer raw material, small molecule chain extender can be used.Small molecule chain extender generally has amine and alcohols two kinds.Amine chain extender and isocyanate reaction activity high, resultant is polyurethane-urea, and the existence of urea key makes glued membrane hardening, modulus increase.Conventional amine has quadrol, diethylenetriamine, triethylene tetramine etc.Amine chain extender generally adds while performed polymer emulsification, limit emulsification, limit chain extension.Making chainextender with mixing amine, to obtain aqueous polyurethane urea dispersions adhesiveproperties excellent, and second-order transition temperature is higher.Alcohols chainextender has BDO, ethylene glycol, glycol ether etc.The water tolerance that chainextender can improve glued membrane is made with three-functionality-degree alcohols.It is one of committed step preparing aqueous polyurethane that hydrophilic chain extender is incorporated in performed polymer molecule.
Base polyurethane prepolymer for use as can be the mixture of polyether glycol by a certain percentage and polyester polyol is that raw material obtains.Synthesis material mainly oligomer polyol and the vulcabond of base polyurethane prepolymer for use as.Oligomer polyol is divided into polyether glycol and polyester polyol two class usually.The performed polymer obtained by polyether glycol has good stability to hydrolysis, good snappiness and extensibility, and resistance to low temperature is good.Polyester polyols alcohol type performed polymer force of cohesion is large, and bonding strength is high.The molecular weight of oligomer polyol and the performance of functionality to performed polymer have a significant impact, and the three-functionality-degree polyethers that introducing portion molecular weight is appropriate in the molecule of performed polymer can increase the molecule crosslinked degree of performed polymer, improve the water tolerance of aqueous polyurethane.
Base polyurethane prepolymer for use as can also be by a certain percentage, obtains with basic raw materials such as polyether glycol, tolylene diisocyanate, dimethylol propionic acid and triethylamines.
Glycidyl ether type epoxy resin and the melamine formaldehyde resin of the second component (B) to be a kind of oxirane value be 0.25-0.45 are the composition of additional crosslink agent, the weight ratio of the first component and second component is 10/1 ~ 10/2, in PU emulsion, add a certain amount of above-mentioned additional crosslink agent in mass ratio, mix and obtain bi-component waterborne PU sizing agent emulsion.
The glycidyl ether type epoxy resin that the second component (B) adds is by containing the phenols of reactive hydrogen or alcohols and epoxy chloropropane polycondensation.Mainly comprise,
(1) propane type epoxy resin of di phenolic group, propane type epoxy resin of di phenolic group is formed by diphenylol propane and epoxy chloropropane polycondensation.
Oxirane value refers to the amount of substance number of contained epoxy group(ing) in every 100g resin.The inverse of oxirane value is multiplied by 100 and is referred to as epoxy equivalent (weight).The implication of epoxy equivalent (weight) is: the grams of the epoxy resin containing 1mol epoxy group(ing).
(2) phenolic aldehyde multi-epoxy resin.Phenolic aldehyde multi-epoxy resin includes phenol formaldehyde type, ortho-cresol formaldehyde type multi-epoxy resin, it is compared with propane type epoxy resin of di phenolic group, containing plural epoxy group(ing) in thread-like molecule, therefore the cross-linking density of solidified after-product is large, has excellent thermostability, mechanical property, electrical insulating property, water tolerance and erosion resistance.By the phenolic aldehyde multi-epoxy resin of lacquer resins and epoxy chloropropane polycondensation, it is most preferred embodiment of the present invention.
(3) other poly-hydroxy phenols diglycidyl ether type epoxy resin.The representative in this resinoid with practicality has: Resorcinol type epoxy resin, resorcinol-formaldehyde type epoxy resin, four phenolic group ethane type epoxy resin and three hydroxyphenyl methane type epoxy resin, after these polyfunctional glycidyl ether's resin solidifications, there is high heat-drawn wire and rigidity, can be independent.
(4) aliphatic polyol diglycidyl ether type epoxy resin.Containing two or more epoxy group(ing) in aliphatic polyol glycidyl ether molecule, the most viscosity of this resinoid is very low; Great majority are long-chain thread-like molecules, are therefore rich in snappiness.
Can be 6360,6101,634 in the second component (B) epoxy resin.Catalyst quality mark is generally 0.04%.
Synthesized component A (host), B component (linking agent) package stability are all good.B component can also take part TDI and IPDI to be combined in synthesis, to reduce costs and to improve performance.Field pilot application proves, this technical matters is stablized, and existing solvent-borne type coating machine directly applies two-pack sizing agent, can make qualified laminated film goods.There is the feature such as high-flexibility, quick solidifying.Mixing match 1: 1, room temperature/(30 ~ 40) min solidifies.This sizing agent is 100% reaction system, without any solvent or volatile matter release in solidification.Good to most of plastics and bonding foil, stripping strength is up to 4.4kNm^-1 tensile strength 7.9MPa, and elongation is greater than 125%, and use temperature reaches 121 DEG C.Also there is high electrical insulating properties and chemical-resistant resistance and excellent heat-resisting and impact resistance.
During preparation.The polyester polyol of moisture can be sloughed, polyether glycol, dimethylol propionic acid (DMPA) and tolylene diisocyanate (TDI) by polyester and polyether with 75/25 ~ 55/45 mass ratio carry out compositely joining in reactor, add dihydroxyphenyl propane chainextender simultaneously, stirring is warmed up to 80 DEG C, add appropriate catalyzer, insulation reaction 4h, then be cooled to 30 DEG C and add coupling agent A, add a certain amount of acetone simultaneously and reduce viscosity, add trihexylamine (TEA) again after continuing reaction 1h and carry out neutralization reaction, deionized water is dripped under high velocity agitation after 15min, de-bubbled 30min obtains emulsus Waterborne Polyurethane Prepolymer (PU).The addition of catalyzer is 0.05% ~ 0.2%, the polyisocyanates of metering is added at 70 DEG C, the preferred diphenylmethanediisocyanate of polyisocyanates (MDI)/tolylene diisocyanate (TDI), or add dimethylol propionic acid (DMPA), temperature of reaction is 95 ~ 100 DEG C, at the uniform velocity stir when temperature reaches 85 DEG C, stirring velocity is 400r/min, then insulation reaction 2h at temperature is 95 ~ 100 DEG C, available can excellent Compound Fabric and PET reaction type polyurethane hot-melt adhesive.The MDI/TDI adding metering at 70 DEG C can prevent implode and gel accident effectively.Obtained PU sizing agent emulsion is evenly applied to the Plastic film surface (6 ~ 7g/m2) through corona treatment, and epoxy resin optimum amount is about 5% (massfraction) and the optimum amount of melamine formaldehyde resin is about 10%.Airing or pressing after drying, obtained laminated film.Cohering base material is PET/PE, BOPA/PP, BOPA/CPP, BOPP/PE, BOPP/PP, BOPA/AL, PET/AL etc.Slaking 48h--72h in 45 DEG C of-60 DEG C of drying rooms is positioned over after Film laminated.After tested, stripping strength is all greater than 3N/15mm.Aqueous polyurethane (PU) is the new polyurethane system using water to replace organic solvent as dispersion medium, and the PET/PE film binded by dual-component aqueous polyurethane sizing agent suitably processes for some time at relatively high temperatures, and bonding effect is better.
The catalyzer added can be organic tin and aliphatics, cycloaliphatic amines compounds.Organic tin compound has katalysis to the positive reaction of NCO/OH and reversed reaction, and what tertiary amines was conventional has triethylenediamine, N-alkyl diamine, N-alkyl morpholine, 2, and 2 '-N,N-Dibenzylamine or 2,6-morpholine methyl ethyl ether make catalyzer,
Because the molecular weight of most of oligomer polyol is lower, and TDI volatilizees, toxicity is large, be solid-state under MDI normal temperature, directly be made into glue general property poor, therefore in order to improve tackiness agent initial viscosity, shorten the time produced needed for certain bonding strength, usually polyethers or polyester polyol and TDI or MDI monomer reaction, make the carbamate prepolymer of end NCO base or OH base, use as NCO composition or OH composition.Can also silane coupling agent be added in the performed polymer of monocomponent moisture cure as solidifying agent, the tackiness agent bonding strength that obtains and heat-resisting, resistance to boiling ability are all improved.As the silane coupling agent of end NCO group is joined in the performed polymer of end NCO.Even can also by containing the silane coupling agent of NCO end group and micromolecular polyvalent alcohol or amine reaction.In the performed polymer of end NCO group, introduce the silane coupling agent containing active end group-OH ,-NH2, or in the performed polymer of end OH, add the silane coupling agent containing NCO group, the performed polymer of synthesis end siloxanes.Or obtain oligopolymer with the end silane coupling agent of amido and oligomeric isocyanate reaction and join in the prepolymer of end NCO as solidifying agent.Such as by the reaction product 66 parts of isocyanate terminated performed polymer 100 parts, carbon black 100 parts, polycaprolactam trivalent alcohol and end NCO base substituted propyl trishydroxymethyl silane, and HDI110 part obtains oligopolymer and joins in the prepolymer of end NCO as solidifying agent.Above-mentioned isocyanate terminated performed polymer can by Polyoxypropylene diol 500 parts, polyoxytrimethylene trivalent alcohol 750 parts and 4, and 4 '-benzhydryl vulcabond 214 parts obtains.
Claims (4)
1. the dual-component polyurethane resin glue stick for polymer Li-ion battery flexible packaging film, be made up of two kinds of components, first component (A) is emulsus Waterborne Polyurethane Prepolymer (PU), described emulsus Waterborne Polyurethane Prepolymer (PU) prepares in accordance with the following steps: will slough the polyester polyol of moisture, polyether glycol, by polyester and polyether with 75/25 ~ 55/45 mass ratio carry out compositely joining in reactor, add dihydroxyphenyl propane chainextender simultaneously, stirring is warmed up to 80 DEG C, add appropriate catalyzer and polyisocyanates, insulation reaction 4h, then the organo-silicon coupling agent that 30 DEG C add 0.5-5wt% is cooled to, add a certain amount of acetone simultaneously and reduce viscosity, continue reaction 1h after add again three amine (THA) carry out neutralization reaction, deionized water is dripped under high velocity agitation after 15min, de-bubbled 30min obtains emulsus Waterborne Polyurethane Prepolymer (PU), the second component (B) is a kind of oxirane value is the glycidyl ether type epoxy resin of 0.25 ~ 0.45 and the composition of melamine formaldehyde resin additional crosslink agent, wherein the weight ratio of the first component and second component is 10/1 ~ 10/2, in PU emulsion, add a certain amount of above-mentioned additional crosslink agent in mass ratio, mix and obtain bi-component waterborne PU sizing agent emulsion.
2. dual-component polyurethane resin glue stick as claimed in claim 1, is characterized in that, described glycidyl ether type epoxy resin is by containing the phenols of reactive hydrogen or alcohols and epoxy chloropropane polycondensation.
3. dual-component polyurethane resin glue stick as claimed in claim 1, it is characterized in that, described glycidyl ether type epoxy resin is the phenolic aldehyde multi-epoxy resin by lacquer resins and epoxy chloropropane polycondensation.
4. prepare the method for dual-component polyurethane resin glue stick as claimed in claim 1 for one kind, to slough the polyester polyol of moisture, polyether glycol, by polyester and polyether with 75/25 ~ 55/45 mass ratio carry out compositely joining in reactor, add dihydroxyphenyl propane chainextender simultaneously, stirring is warmed up to 80 DEG C, add appropriate catalyzer and polyisocyanates, insulation reaction 4h, then the organo-silicon coupling agent that 30 DEG C add 0.5-5wt% is cooled to, add a certain amount of acetone simultaneously and reduce viscosity, continue reaction 1h after add again three amine (THA) carry out neutralization reaction, deionized water is dripped under high velocity agitation after 15min, de-bubbled 30min obtains emulsus Waterborne Polyurethane Prepolymer (PU), a certain amount of additional crosslink agent is added in mass ratio in the PU emulsion prepared, mix and obtain bi-component waterborne PU sizing agent emulsion, described additional crosslink agent is a kind of oxirane value is the glycidyl ether type epoxy resin of 0.25 ~ 0.45 and the composition of melamine formaldehyde resin additional crosslink agent, and wherein the weight ratio of the composition of PU emulsion and additional crosslink agent is 10/1 ~ 10/2.
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|---|---|---|---|---|
| CN101007934A (en) * | 2007-01-25 | 2007-08-01 | 南京工业大学 | Waterborne polyurethane adhesive for composite film and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007934A (en) * | 2007-01-25 | 2007-08-01 | 南京工业大学 | Waterborne polyurethane adhesive for composite film and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181621A (en) * | 2018-09-11 | 2019-01-11 | 浙江奔富新能源股份有限公司 | A kind of dual-component polyurethane Resin adhesive and preparation method thereof for polymer Li-ion battery flexible packaging film |
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| CN102329594A (en) | 2012-01-25 |
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