CN102329594A - 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 that is used for polymer Li-ion battery packing film adhesive linkage.
Background technology
In the prior art, the sizing agent of soft packaging sector application has monocomponent polyurethane adhesive, dual-component polyurethane adhesive, acrylic acid or the like sizing agent, does not have the agent of appearance sizing agent, pure dissolubility, aqurous ployurethane tackiness agent etc.And performances such as the water-fast solvent resistance of present most of aqueous polyurethane, thermotolerance and bonding force are still waiting to improve, and therefore in recent years the modification of aqueous polyurethane have been become the focus in this field.But up to the present, adopt the dual-component aqueous polyurethane sizing agent to replace two-pack solvent borne polyurethane sizing agent not make a breakthrough both at home and abroad.
The weak point that is used for the aqurous ployurethane sizing agent of bonding plastics film soft packaging at present is:
(1) general tackiness agent resistance to elevated temperatures is not enough, and hydrolytic resistance is relatively poor, and viscosity is little.The viscosity of aqurous ployurethane generally can be regulated through water-soluble thickener and water, and in addition, the important factor that influences aqurous ployurethane sizing agent viscosity also has ionic charge, micellar structure and particle diameter etc.Ion on the polymer molecule and gegenion are many more, and viscosity is big more, and the viscosity of identical solids content, water-soluble gluing agent is little than the solvent-based adhesive viscosity.
(2) rate of drying is slow.Because the volatility of water is than organic solvent difference; So aqurous ployurethane sizing agent rate of drying is slow; And it is,, poor to the wetting ability of surperficial hydrophobic substrates for 3 times of common organic solvent because the surface tension of water is approximately 7.3 * 10-4N/cm; When most of moisture not from adhesive linkage, evaporate into the air or absorbed just suddenly dryly by porous substrate, then be difficult to obtain successional glue-line.
(3) water-fast, thermotolerance is relatively poor.Great majority are linear thermoplastic's urethane in the commercial aqurous ployurethane; And the ionic group that contains hydrophilic radical or side joint in the molecular structure; Sometimes also contain water-soluble thickener; Can not form to a certain degree crosslinked after the glued membrane drying, thereby performance such as it is water-fast, thermotolerance, anti-solvent, chemical-resistant and glued membrane intensity is all not good enough.
Aqurous ployurethane is main with anionic, self-emulsifying at present.Anion-type water-thinned polyurethane divides two types of sulfonate type and carboxylic acid types again.What application was more now is carboxylic acid type.Carboxylic hydrophilic chain extender generally has dihydroxyl half ester and 2, the two hydroxymethyl propionic acids (DMPA) of 2-.The DMPA relative molecular mass is little, and less consumption just can provide enough hydroxyl equivalents, but because DMPA is a solid; And fusing point is higher; In reaction process, can produce non-uniform phenomenon, and half acid is how good with the polyvalent alcohol consistency, but consumption is greatly and the aqurous ployurethane glued membrane stickness that obtains. the disadvantage of aqurous ployurethane dispersion liquid is; The required activation temperature of activation adhesive layer is too high, damages to such an extent as to make continually by sticking base material.For reducing activation temperature, normal employing adds the way of solvent, softening agent or other resin, but these methods can be cost with the thermotolerance of loss adhesive for polyurethane usually again.
The barrier property of polymer Li-ion battery barrier layer flexible packaging film is main relevant with aluminium foil barrier films and tackiness agent.And and barrier layer aluminium foil and ectonexine between bonding strength and plastic deformation ability closely bound up because polymer lithium ion battery electric separate the liquid content can swelling, dissolving absorbs internal layer composite package, particularly tackiness agent or binding resin between rete.
Prior art adopts modifier and mixture a kind of of polyolefin resin or these resins to come bonding polymer lithium ion battery ectonexine flexible packaging film usually.Perhaps with having added thermoplastic elastomer and tackifier vinyl or EVA hot melt adhesive; Polyolefin polyhydric alcohol, multi-functional isocyanide acid alcohol stiffening agent, and polyester-ammonia ester resin, polyethers-ammonia ester resin, isocyanic ester, unsaturated acid graft polyolefin resin a kind of caking agent wherein.The weak point of these hot melt agent coating compound glue bond layers is; Can not effectively 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 swelling, dissolving, infiltration, absorption and the electrochemical reaction of inside battery electrolytic solution it.In moulding process, aluminium foil and other nonmetallic composite comprise that caking agent extends jointly, flows, and in the process of extending, and the molecular chain of the caking agent after dry and hard ruptures easily, forms stealthy crack broken belt.
Summary of the invention
The objective of the invention is weak point, provide a kind of bonding strength high, anti-peeling off to above-mentioned prior art; Barrier property is excellent; Shock-resistant, good with nonmetal film or aluminium foil bonding consistency, electrolyte resistance organic solvent and high volatile volatile material swelling, dissolving, infiltration, absorption; Strong acid-base resistance, dry and hard back molecular chain is the dual-component polyurethane resin glue stick of easy fracture not.
Above-mentioned purpose of the present invention can reach through following measure; A kind of dual-component polyurethane resin glue stick that is used for polymer lithium from the battery flexible packaging film; Form by two kinds of components; First component (A) is that the polyethers of polyester and isocyanic ester/contain phenyl ring carries out composite with 75/25～55/45 mass ratio; And add the emulsified water based polyurethane performed polymer (PU) that the auxiliary agent reaction obtains, and second kind of component (B) is that a kind of oxirane value is 0.25～0.45 the glycidyl ether based epoxy resin and the compsn of melamine formaldehyde resin additional crosslink agent, wherein the weight ratio of first component and second component is 10/1～10/2; In the PU emulsion, add a certain amount of above-mentioned additional crosslink agent, mix and promptly get bi-component waterborne PU sizing agent emulsion by mass ratio.
The method for preparing dual-component polyurethane resin glue stick is with the polyester polyol of sloughing moisture, polyether glycol, carries out composite joining in the reactor drum by polyester and polyether with 75/25～55/45 mass ratio; Add the dihydroxyphenyl propane chainextender simultaneously, stir and be warmed up to 80 ℃, add appropriate amount of catalysts and POLYMETHYLENE POLYPHENYLISOCYANATE; Insulation reaction 4h; Be cooled to 30 ℃ then and add coupling agent A, add a certain amount of acetone simultaneously and reduce viscosity, add trihexylamine (TEA) again behind the continuation reaction 1h and carry out neutralization reaction; Under high-speed stirring, drip deionized water behind the 15min, de-bubbled 30min obtains emulsified water based polyurethane performed polymer (PU).
The present invention has following beneficial effect than prior art.
Adopt hydrolytic resistance contain the polyethers of phenyl ring preferably, with polyester and isocyanic ester and with the preparation polyurethane adhesive, improved the thermotolerance of polyurethane adhesive.In the dual-component aqueous polyurethane sizing agent; Crosslinking reaction has taken place in aqueous polyurethane and linking agent; Two kinds of additional crosslink agents can both increase the degree of crosslinking and the viscosity of aqueous polyurethane sizing agent, improve the T type stripping strength and the solvent resistance that strengthens made glued membrane of sizing agent.Can make urethane form reticulated structure through crosslinking reaction, its force of cohesion is improved, multiple film T stripping strength also rises thereupon.And when being heating and curing, autohemagglutination can take place in isocyanic ester, forms crosslinking structure, makes its T type stripping strength become big.Use epoxy resin 6360 and the aqueous polyurethane sizing agent adherent film of terpolycyantoamino-formaldehyde resin respectively, in the T of 50 ℃ of following thermal treatment 1h type stripping strength as linking agent.The adding of epoxy resin and melamine formaldehyde resin makes the degree of crosslinking of aqueous polyurethane sizing agent improve the corresponding raising of adhesiveproperties.In polyester polyol, add polyether glycol; Suitable proportioning with polyester and polyether; Preparation feedback type polyurethane hot melt adhesive; Not only bonding strength is high, also can overcome owing to the too fast defective that causes internal stress of crystallization, also can pass through setting time and the curing speed of the ratio control PUR of change polyester and polyether.Because it does not contain organic solvent, solids content is absolutely, has changed the characteristic of the volatile obnoxious flavour of traditional tackiness agent, can not damage human body.Having 120 ℃ of melt viscosities is that 3000～4000cps, surface drying time are 60s, resin added 20～40g/m
2, final stripping strength reaches the above performance of 40N/25mm.The performed polymer that is made by polyether glycol has good stability to hydrolysis, snappiness and extensibility preferably, and resistance to low temperature is good; And polyester polyol type performed polymer force of cohesion is big, and bonding strength is high.It forms 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 surpass the tackiness agent of all other types.In addition, polyurethane adhesive also has easy, splendid resistance to low temperature of toughness adjustable, adhesion technique and advantages of excellent stability or the like characteristic.That the high-performance water-based polyurethane tackiness agent has is water-fast, resistance to medium good, bonding strength is high, and initial bonding strength is big, freeze-thawing resistant, and anti-comparatively high temps, rate of drying are very fast, and film-forming properties is good under the low ambient temperature.
Along with the increase of the add-on of linking agent, T type stripping strength all appears and increases earlier the trend that afterwards reduces.It is convenient to solidify.Select various solidifying agent for use, epoxy-resin systems almost can solidify in 0～180 ℃ of TR.
Because melamine formaldehyde resin is easy to and the polymer reaction that has primary and secondary hydroxyl, carboxyl and carboxamido-group, forms a 3 D stereo reticulated structure through crosslinking reaction.Melamine formaldehyde resin itself has higher thermostability and water-fast preferably solvent resistance, adds in the aqueous polyurethane to significantly improve its performance.Epoxy resin is because it be a polyol, with polyurethane reaction in can branch point be introduced polyurethane backbone, make it part formation reticulated structure and performance is more excellent.The rigidity of epoxy resin and strong adhesion.The existence of inherent polarity hydroxyl and ehter bond in the epoxy resin molecular chain makes it have very high adhesive power to various materials.Shrinkability during epoxy resin cure is low, and the internal stress of generation is little, and this also helps to improve adhesion strength.The reaction of epoxy resin and used solidifying agent is that the ring-opening polymerization through epoxy group(ing) in direct addition reaction or the molecular resin carries out, and does not have water or other volatile byproducts to emit.They are compared with unsaturated polyester resin, resol, in solidification process, demonstrate very low shrinkability (less than 2%).Epoxy-resin systems after the curing has excellent mechanical property.Epoxy-resin systems after the curing is a kind of superior isolation material with high dielectric property, anti-surface leakage, anti-electric arc.Usually, the epoxy-resin systems after the curing has good alkali resistance, acid resistance and solvent resistance.With infrared spectrum and dsc analysis revealed, in the dual-component aqueous polyurethane sizing agent, crosslinking reaction has taken place in aqueous polyurethane and linking agent.Additional crosslink agent can increase the degree of crosslinking and the viscosity of aqueous polyurethane sizing agent, thereby effectively improves the T type 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, splendid towards dark interactive bonding consistency with metal aluminum foil, sticking power is good.Adventitia and binder molecule chain are in dark process, and interactive extensibility of plasticity and compound firmness are excellent, and it is not stratified not rupture, and adhesive coating is incrust, does not influence its barrier and compound stripping strength; Viscosity is high, anti-organic solvent, and anti-strong acid-base, anti-high corrosion volatile matter, and toughness is high temperature resistant, shock-resistant, peel resistant strength is high, anti-infiltration, bonding free of pinholes, molecular chain is complete not to rupture.
Embodiment
Further specify the present invention through embodiment below.Being used for polymer lithium is made up of two kinds of components from the dual-component polyurethane resin glue stick of battery flexible packaging film; First component (A) can be polyester and isocyanic ester/the contain polyethers blend of phenyl ring; The polyethers of polyester and isocyanic ester/contain phenyl ring carries out composite with 75/25～55/45 mass ratio; And add the emulsified water based polyurethane performed polymer (PU) that the auxiliary agent reaction obtains, add auxiliary agent and comprise hydrolysis stabilizer, long-chain biatomic acid and at least a in the divalent alcohol, organo-silicon coupling agent of side chain arranged.The adding auxiliary agent can improve the hydrolytic resistance of polyester itself.The hydrolysis stabilizer that adds can be carbodiimide, epoxy compounds etc., also can adopt long-chain biatomic acid and divalent alcohol raw material, like sebacic acid, 1, and 6-pinakon etc.The divalent alcohol of side chain such as the hydrolytic resistance that the NSC 6366 raw material improves polyester are arranged.
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 the prescription, organo-silicon coupling agent very weight can be 0.5-5%.In adhesive formulation, add the hydrolytic resistance that a small amount of organo-silicon coupling agent can improve adhesive layer.Silane coupling agent is an organosilyl important branch, and general formula can be expressed as: Y-R-SiX3, X and Y are two types of response characteristic different activity groups.End silica group is under the condition that catalyzer exists, and hydrolysis is solidified into silanol by airborne moisture silane group, and then reticulates structure with another silanol or silane group cross-linking reaction, produces bonding.Can avoid the NCO group directly to react like this and produce too much bubble, cause too much bonding defect, influence the drawback of bonding strength with water.
POLYMETHYLENE POLYPHENYLISOCYANATE has; Vulcabond; The POLYMETHYLENE POLYPHENYLISOCYANATE, diisocyanate monomer, diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), the 3-isocyanic ester methylene-3 that contain isocyanurate ring; 5,5-3-methyl cyclohexanol based isocyanate (IPDI), hydrogenation methylenebis phenyl isocyanate (H
12MDI), isophorone diisocyanate, dicyclohexyl methane diisocyanate, PPDI, cyclohexyl diisocyanate, xylylene diisocyanate, cyclohexanedimethyleterephthalate vulcabond, tetramethyl-mphenylenedimethylim-vulcabond, norbornene alkyl diisocyanate, dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate etc.The isocyanic ester raw material is main with tolylene diisocyanate (TDI).Vulcabond is divided into two types of aromatic series and aliphatics (or alicyclic).By aromatic diisocyanate synthetic performed polymer higher intensity is arranged, but not anti-xanthochromia, and aliphatic diisocyanate does not contain unsaturated double-bond owing in the molecular structure, good by its performed polymer anti-yellowing property that makes.Except oligomer polyol and vulcabond, can use small molecule chain extender in the synthetic performed polymer raw material.Small molecule chain extender generally has two kinds of amine and alcohols.Amine chain extender and isocyanate reaction are active high, and resultant is a polyurethane-urea, and the existence of urea key makes the glued membrane hardening, and modulus increases.Amine commonly used has quadrol, diethylenetriamine, triethylene tetramine etc.Amine chain extender generally adds at the performed polymer emulsive simultaneously, limit emulsification, limit chain extension.Making chainextender with the mixing amine, to make aqueous polyurethane urea dispersions adhesiveproperties good, and second-order transition temperature is higher.The alcohols chainextender has 1,4-butyleneglycol, terepthaloyl moietie, glycol ether etc.Make the water tolerance that chainextender can improve glued membrane with the three-functionality-degree alcohols.It is one of committed step of preparation aqueous polyurethane that the wetting ability chainextender is incorporated in the performed polymer molecule.
Base polyurethane prepolymer for use as can be that by a certain percentage polyether glycol and the mixture of polyester polyol is that raw material makes.The synthesis material of base polyurethane prepolymer for use as mainly is oligomer polyol and vulcabond.Oligomer polyol is divided into two types of polyether glycol and polyester polyols usually.The performed polymer that is made by polyether glycol has good stability to hydrolysis, snappiness and extensibility preferably, and resistance to low temperature is good.Polyester polyol type performed polymer force of cohesion is big, and bonding strength is high.The molecular weight of oligomer polyol and functionality have very big influence to the performance of performed polymer, in the molecule of performed polymer, introduce an amount of three-functionality-degree polyethers of part molecular weight, 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, makes with basic raw materials such as polyether glycol, tolylene diisocyanate, dimethylol propionic acid and triethylamines.
Second kind of component (B) is that a kind of oxirane value is that glycidyl ether based epoxy resin and the melamine formaldehyde resin of 0.25-0.45 is the compsn of additional crosslink agent; The weight ratio of first component and second component is 10/1～10/2; In the PU emulsion, add a certain amount of above-mentioned additional crosslink agent, mix and promptly get bi-component waterborne PU sizing agent emulsion by mass ratio.
The glycidyl ether based epoxy resin that second kind of component (B) adds is to be formed by the phenols that contains 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 is meant the amount of substance number of contained epoxy group(ing) in every 100g resin.The inverse of oxirane value multiply by 100 and is referred to as epoxy equivalent (weight).The implication of epoxy equivalent (weight) is: the gram number that contains the epoxy resin of 1mol epoxy group(ing).
(2) the many epoxy resin of phenolic aldehyde.The many epoxy resin of phenolic aldehyde include phenol formaldehyde type, the many epoxy resin of ortho-cresol formaldehyde type; It is compared with propane type epoxy resin of di phenolic group; In thread-like molecule, contain plural epoxy group(ing); Therefore the cross-linking density of solidified after-product is big, has good thermostability, mechanical property, electrical insulating property, water tolerance and erosion resistance.By the many epoxy resin of phenolic aldehyde that lacquer resins and epoxy chloropropane polycondensation form, be most preferred embodiment of the present invention.
(3) other poly-hydroxy phenols glycidyl ether type epoxy resin.The representative that has practicality in this resinoid has: Resorcinol type epoxy resin, Resorcinol-formaldehyde type epoxy resin, four phenolic group ethane type epoxy resin and three phenylor methane type epoxy resin; Have high heat-drawn wire and rigidity behind these polyfunctional glycidyl ether's resin solidifications, can be independent.
(4) aliphatic polyol Racemic glycidol ether type epoxy.Contain two or more epoxy group(ing) in the aliphatic polyol glycidyl ether molecule, the most viscosity of this resinoid are very low; Great majority are long-chain thread-like molecules, therefore are rich in snappiness.
Epoxy resin can be 6360,6101,634 in second kind of component (B).The catalyst quality mark is generally 0.04%.
The synthetic A of institute component (host), B component (linking agent) package stability are all good.The B component can also take part TDI to be used in combination with IPDI in synthetic, to reduce cost and to improve performance.Proof is used in pilot scale, the present technique process stabilizing, existing solvent-borne type be coated with answer a pager's call on direct application two-pack sizing agent, can make qualified laminated film goods.Have characteristics such as high-flexibility, quick solidifying.Mixing match 1: 1, room temperature/(30～40) min solidifies.This sizing agent is 100% reaction system, and no any solvent or volatile matter discharge in the curing.Good to most of plastics and bonding foil property, stripping strength is up to 4.4kNm^-1 tensile strength 7.9MPa, and elongation is greater than 125%, and use temperature reaches 121 ℃.Also have high electric insulation property and chemical-resistant resistance and good heat-resisting and impact resistance.
During preparation.Can polyester polyol that slough moisture, polyether glycol, dimethylol propionic acid (DMPA) and tolylene diisocyanate (TDI) be carried out composite joining in the reactor drum by polyester and polyether with 75/25～55/45 mass ratio; Add the dihydroxyphenyl propane chainextender simultaneously, stir and be warmed up to 80 ℃, add appropriate amount of catalysts; Insulation reaction 4h; Be cooled to 30 ℃ then and add coupling agent A, add a certain amount of acetone simultaneously and reduce viscosity, add trihexylamine (TEA) again behind the continuation reaction 1h and carry out neutralization reaction; Under high-speed stirring, drip deionized water behind the 15min, de-bubbled 30min obtains emulsified water based polyurethane performed polymer (PU).The addition of catalyzer is 0.05%～0.2%, at 70 ℃ of POLYMETHYLENE POLYPHENYLISOCYANATE that add metering, the preferred diphenylmethanediisocyanate of POLYMETHYLENE POLYPHENYLISOCYANATE (MDI)/tolylene diisocyanate (TDI); Or adding dimethylol propionic acid (DMPA); Temperature of reaction is 95～100 ℃, when temperature reaches 85 ℃, at the uniform velocity stirs, and stirring velocity is 400r/min; Be 95～100 ℃ of following insulation reaction 2h in temperature then, the Compound Fabric and the PET that can obtain excellent property use reaction type polyurethane hot-melt adhesive.Can effectively prevent implode and gel accident at 70 ℃ of MDI/TDI that add metering.The PU sizing agent emulsion that makes is applied to evenly through the plastics film of corona treatment surface that (6～7g/m2), the epoxy resin optimum amount is about 5% (massfraction) and the optimum amount of melamine formaldehyde resin is about 10%.Airing or oven dry back pressing make laminated film.Cohering base material is PET/PE, BOPA/PP, BOPA/CPP, BOPP/PE, BOPP/PP, BOPA/AL, PET/AL etc.Be positioned over 45 ℃ of-60 ℃ of drying room matured 48h--72h after film is compound.Through test, stripping strength is all greater than 3N/15mm.Aqueous polyurethane (PU) is with the new polyurethane system of water to replace organic solvent as dispersion medium, is suitably handled for some time under comparatively high temps by dual-component aqueous polyurethane sizing agent adherent PET/PE film, and the bonding effect is better.
The catalyzer that adds can be organic tin and aliphatics, alicyclic tertiary amine compounds.The organic tin compound all has katalysis to positive reaction and the reversed reaction of NCO/OH, and tertiary amines is commonly used has triethylenediamine, N-alkyl diamine, N-alkyl morphine quinoline, 2,2 '-N,N-Dibenzylamine or 2, and 6-morpholine methyl ethyl ether is made catalyzer,
Because the molecular weight of most of oligomer polyol is lower; And TDI volatilization toxicity is big, and MDI normal temperature is down for solid-state, and it is relatively poor directly to be made into the glue general property; So for initial viscosity, the shortening that improves tackiness agent produces the required time of certain bonding strength; Usually polyethers or polyester polyol and TDI or MDI monomer reaction, process 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 and heat-resisting, the anti-boiling ability that make all are improved.As the silane coupling agent that will hold the NCO group joins in the performed polymer of end NCO.Even can also be with the silane coupling agent that contains the NCO end group and micromolecular polyvalent alcohol or amine reaction.Introducing contains active end group-OH in the performed polymer of end NCO group, the silane coupling agent of-NH2, or in the performed polymer of end OH, add the silane coupling agent that contains the NCO group, the performed polymer of synthetic end siloxanes.Or make oligopolymer with silane coupling agent and the oligomeric isocyanate reaction of end amido and join in the prepolymer of end NCO as solidifying agent.Such as with 66 parts of the reaction product of 100 parts of isocyanate terminated performed polymers, 100 parts of carbon blacks, polycaprolactam trivalent alcohol and end NCO base substituted propyl trishydroxymethyl silane, and HDI110 part makes oligopolymer and joins in the prepolymer of end NCO as solidifying agent.Above-mentioned isocyanate terminated performed polymer can be by 500 parts of polyoxytrimethylene divalent alcohol, 750 parts of polyoxytrimethylene trivalent alcohols and 4, and 4 '-benzhydryl vulcabond makes for 214 parts.
Claims (9)
1. one kind is used for the dual-component polyurethane resin glue stick that polymer lithium leaves the battery flexible packaging film; Form by two kinds of components; First component (A) is that the polyethers of polyester and isocyanic ester/contain phenyl ring carries out composite with 75/25～55/45 mass ratio; And the adding auxiliary agent reacts the emulsified water based polyurethane performed polymer (PU) that obtains; Second kind of component (B) is that a kind of oxirane value is 0.25～0.45 the glycidyl ether based epoxy resin and the compsn of melamine formaldehyde resin additional crosslink agent; Wherein the weight ratio of first component and second component is 10/1～10/2, in the PU emulsion, adds a certain amount of above-mentioned additional crosslink agent by mass ratio, mixes and promptly gets bi-component waterborne PU sizing agent emulsion.
2. dual-component polyurethane resin glue stick as claimed in claim 1 is characterized in that, adds auxiliary agent and comprises hydrolysis stabilizer, long-chain biatomic acid and at least a in divalent alcohol and the organo-silicon coupling agent of side chain arranged.
3. dual-component polyurethane resin glue stick as claimed in claim 2 is characterized in that described hydrolysis stabilizer is carbodiimide, epoxy compounds.
4. dual-component polyurethane resin glue stick as claimed in claim 2 is characterized in that described long-chain biatomic acid and divalent alcohol are sebacic acid, 1,6-pinakon or the divalent alcohol of side chain is arranged, NSC 6366.
5. dual-component polyurethane resin glue stick as claimed in claim 1 is characterized in that, described glycidyl ether based epoxy resin is to be formed by the phenols that contains reactive hydrogen or alcohols and epoxy chloropropane polycondensation.
6. dual-component polyurethane resin glue stick as claimed in claim 5 is characterized in that, described glycidyl ether based epoxy resin is the many epoxy resin of phenolic aldehyde that formed by lacquer resins and epoxy chloropropane polycondensation.
7. a method for preparing dual-component polyurethane resin glue stick as claimed in claim 1 is with the polyester polyol of sloughing moisture, polyether glycol, carries out composite joining in the reactor drum by polyester and polyether with 75/25～55/45 mass ratio; Add the dihydroxyphenyl propane chainextender simultaneously, stir and be warmed up to 80 ℃, add appropriate amount of catalysts and POLYMETHYLENE POLYPHENYLISOCYANATE; Insulation reaction 4h; Be cooled to 30 ℃ then and add coupling agent, add a certain amount of acetone simultaneously and reduce viscosity, add trihexylamine (TEA) again behind the continuation reaction 1h and carry out neutralization reaction; Under high-speed stirring, drip deionized water behind the 15min, de-bubbled 30min obtains emulsified water based polyurethane performed polymer (PU).
8. the method for preparing dual-component polyurethane resin glue stick as claimed in claim 8; It is characterized in that, are diphenylmethanediisocyanate (MDI)/tolylene diisocyanates (TDI) at 70 ℃ of POLYMETHYLENE POLYPHENYLISOCYANATE that add metering, or add dimethylol propionic acid (DMPA); Temperature of reaction is 95～100 ℃; When temperature reaches 85 ℃, at the uniform velocity stir, stirring velocity is 400r/min, is 95～100 ℃ of following insulation reaction 2h in temperature then.
9. the method for preparing dual-component polyurethane resin glue stick as claimed in claim 8 is characterized in that, described coupling agent is the machine silicone couplet.
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| CN115181500A (en) * | 2015-01-17 | 2022-10-14 | 重庆利尔达科技开发有限公司 | Application of coupling agent in water glass polyurethane environment-friendly two-component glue solution |
| CN106189996A (en) * | 2016-07-14 | 2016-12-07 | 瑞安市智造科技有限公司 | A kind of timber environment-protecting asepsis monocomponent polyurethane adhesive and preparation method thereof |
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| CN111087963A (en) * | 2019-12-27 | 2020-05-01 | 江苏乘鹰新材料股份有限公司 | Single-component solvent-free moisture-curing adhesive for compounding cigarette paperboard |
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