CN102431239A - Polymer lithium ion battery core outer package forming material - Google Patents

Abstract

The invention provides a polymer lithium ion battery core outer package forming material, and aims at providing a battery core outer package forming material with the advantages that the blocking performance is very high, the cold punching forming performance is good, and puncture resistance, electrolyte resistance stability and organic solvent and high-volatile substance resistance can be realized. An outer resistance layer lamination layer body is formed by at least one layer of heat resistance resin film: any one material from polyethylene glycol terephthalate (PET), biaxially oriented polyamide (BOPA) and polyethylene naphthalate (PEN) or coexistence of two materials from PET, BOPA and PEN through co-extrusion compounding, aluminum foils in a resistance permeation layer lamination body at least comprise 0.9 weight percent to 1.5 weight percent of Fe, a high-resistance layer lamination body comprises a base layer, a function layer and a hot sealing layer, the base layer is a co-polymer film formed by paired compounding or the combination of at least two kinds of film substrates in polystyrene (PP), chlorinated polypropylene (CPP), polyurethane (PE), PET, polyamide (PA) or metaxylylene diamine (MPE) elastic body polymer blends, polyvinyl dichloride (PVDC), ethylene vinyl silane (EVOH), PEN and transpeptidase (GT), and a high-resistance water-resistance modified polyvinyl acetate (PVA) coating film is respectively coated on the co-polymer film substrate. The polymer lithium ion battery core outer package forming material revolutionarily solves the electrolyte resistance stability problem.

Description

Polymer Li-ion battery core external packing moulding material

Technical field

The present invention relates to a kind ofly be mainly used in battery, particularly can generally be applied to mobile phone, palm PC; Laptop computer; Portable military instrument; Hand-held camera, DVD player, electric motor car (electric bicycle, motorcycle and automobile), electric wheelchair, electrocar and electric motor coach, the composition structure of the plastic-aluminum combined Soft Roll membrane material of polymer ions battery in military aerospace field.In country packing generic term (GB4122-83), being defined as of flexible package: flexible package is meant after filling or taking out content, the packing that container shapes can change.Be flexible package with paper, aluminium foil, fiber, plastic sheeting and their compound made various bags, box, overlap, seal etc.Generally the slice plastic of thickness below 0.25mm is called film.In the world will be to OTR oxygen transmission rate less than 3.8Cm ³.mm/24b.m ².MPa polymer is called separating polymer.The high-barrier standard of high barrier packaging material is: O ₂Transit dose is 5ml/m ², below the d, vapor transfer rate is 2g/m ², below the d.

Background technology

Its positive pole of polymer Li-ion electric power storage, negative pole, polymer film (also claiming barrier film), conflux body (copper mesh and aluminium net), electrolyte and positive and negative electrode (aluminium and copper or al and ni; Also claim lug) etc. be the content of battery, they with flexible packing material through the heat-sealing after constitute battery.In general because single thin-film material is not ideal enough to the protectiveness of content, so adopt with two or more films compound be the laminated film of one deck.The cladding material multiselect of laminated film is used and is difficult for scuffing, sanding, excellent optical performance, and the material section that printing performance is good, as: paper, glassine paper, oriented polypropylene, polyester etc.; The intermediate layer is a separating polymer, like: aluminium foil, AM aluminum metallization, nontoxic, tasteless thermoplastic resins such as polyethylene.Internal layer is: EVOH, and MXD6, PVDC etc. need add and cohere resin.High gas barrier resin is selected EVOH usually for use, and MXD6, PVDC, PAN etc. need not add and cohere resin.Generally can be divided into basic unit, functional layer and hot sealing layer.Effects such as that basic unit mainly plays is attractive in appearance, printing, resistance are wet.Like BOPP, BOPET, BOPA, MT, KOP, KPET etc.; Functional layer mainly plays effects such as obstruct, lucifuge, like VMPET, AL, EVOH, PVDC etc.; Hot sealing layer directly contacts with connection with wrapping of piece, plays adaptability, osmotic-pressure-tolerant, good heat sealability, and function such as the transparency, like LDPE, LLDPE, MLLDPE, CPP, VMCPP, EVA, EAA, E-MAA, EMA, EBA etc.

More general gas barrier complex method is both at home and abroad, and is external: PE//TIE//EVOH//TIE//PE, PE (EVA) TIE/PA/EVOH/PA/TIE/PE; Domestic: PP/TIE/PA/TIE/PP, LDPE/TIE/PA/TIE/LDPE, MLLDPE/TIE/EVOH/TIE/MLLDPE, MLLDPE/TIE/PA/TIE/MLLDPE or the like.

With the film that individual layer LDPE or LDPE and other resin alloy are produced, performance is single, can't satisfy the requirement of modern article development to packing, and therefore three layers, the nylon co-extrusion film of five-layer structure, five layers, seven layers EVOH, PVDC high-resistant diaphragm are also in continuous development.The development of composite soft packaging material inner layer film from LDPE, LLDPE, CPP, MLLDPE, develops into a large amount of uses of present co-extrusion film, realizes packaging functionization, personalization basically, has satisfied that package contents is guaranteed the quality, processing characteristics, transportation, storage requirement.But for polymer Li-ion battery, it is insignificant but to seem, because polymer Li-ion battery is that technology content is the highest in the battery industry, and up-to-date kind.It is a positive pole with cobalt acid lithium material, and material with carbon element is a negative pole, and electrolyte adopts solid-state or gel state organic conductive film is formed, and adopts aluminum plastic film to do the latest generation chargeable lithium ion battery of external packing.It is liquid renewal product from battery, not only has the characteristics such as high voltage, long circulation life, discharging voltage balance and cleanliness without any pollution of liquid lithium ionic cell; And eliminated the potential safety hazard of the blast that liquid lithium ionic cell exists, have a higher energy density; Profile is more flexible, convenient simultaneously, and weight is light and handy; Properties of product all meet or exceed the technical indicator of liquid lithium ion, have more security.Therefore be described as the Green Chemistry energy of 21st century.

The polymer Li-ion battery product can not break away from packing and have the service life of packing and the stock of product and the same period in service life.Packing has become an indispensable important component part of product, and in fact the life cycle of product is exactly the process that packing lost efficacy gradually, and packing does not just have product, and packing lost efficacy in other words, and product is scrapped thereupon.

Succeeding in developing of polymer Li-ion battery depends primarily on the solution of masking technique, lamination and soft package technology three big technical barriers.Soft package technology is one of three big technical barriers that will solve in this top hi-tech industry of polymer Li-ion battery; It is placed in consequence like this, the technology content that this product is described in design, make and use on and common compound package material qualitative difference is all arranged on performance.Up to the present, still there is not this project product of a company can satisfy the complex art requirement of polymer Li-ion battery fully in the world to this product.Therefore, the polymer Li-ion battery in-core is packaged into the packaging Problems that type material is not only a polymer Li-ion battery, and is an indispensable important component part that constitutes polymer Li-ion battery.

Polymer Li-ion battery is the mid-90 development in laboratory success, and mass production three quinquenniads only, the development of packaging film is than battery more a little later.A little indexs in the relation between aluminum foil thickness changes before and after the cold stamping shaped degree of depth of the cold stamping shaped flexible packing material that difficulty is maximum, aluminium foil percentage elongation and the cold stamping can quantitative description; Can detect through suitable method, what have but can not detect with advanced person's method.Some requirement can only qualitative description, can not find suitable method and detects.Therefore also do not form international standard, the domestic producer that furthers investigate is very little, does not more have standard to follow.Multi layer coex composite membranes structure on the ordinary meaning can't satisfy the extremely harsh requirement of polymer Li-ion battery external packing at all.

At first; The flexible packing material of polymer Li-ion battery can not react with electrolyte, can not be dissolved by electrolyte, can not play swelling action with electrolyte; If flexible packing material is dissolved by electrolyte, electrochemical reaction will take place and produce gas in the composition that is dissolved; If the flexible packing material swelling electrolyte, the concentration that changes electrolyte is influenced battery performance.Secondly, flexible packing material must have high block water, oxygen resistance, and the barrier of flexible packing material (like moisture, oxygen) is higher 10000 times than the barrier of common aluminum-plastic composite membrane, high barrier like this has exceeded the accuracy of detection of instrument.And must have good electrolyte resistance immersion ability, the seepage phenomenon can not take place in electrolyte, must have than high-flexibility and mechanical strength, also must have fabulous heat sealing property.Polymer Li-ion battery is very responsive to high temperature, and serviceability temperature is lower than 60 ℃, and heat-sealing temperature generally can not be higher than 150 ℃.

The use of polymer Li-ion battery is a charge and discharge process constantly, also is a dynamic electrochemical reaction process, and flexible packing material itself is wanted effectively to resist swelling, dissolving, infiltration, absorption and the electrochemical reaction of electrolyte inside to it.

Electrolyte in the battery is the lithium salts that can be produced severe corrosive hydrofluoric acid by multiple organic solvent and chance moisture rapidly.This electrolyte is made up of about 18 kinds of organic solvent high volatile volatile materials and lithium salts, and main component has ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC), dimethoxy-ethane (DME), monomethyl carbonic ester (DMC), lithium hexafluoro phosphate (LiPF ₆), hexafluoroarsenate lithium (LiASF ₆) cobalt acid lithium (j, Lic ∞ 2) etc.Conflux body copper mesh and aluminium net are arranged in the middle of the monolithic battery.Electrolyte and positive and negative electrode (aluminium and copper or al and ni are also claimed lug) etc. are the contents of battery, and they constitute battery with flexible packing material after sealing.Because multiple high volatile volatile material of cell contents and organic solvent are like moisture; Can produce severe corrosive hydrofluoric acid rapidly, and multiple organic solvent is understood swelling, dissolving, absorption flexible packing material usually; They are again the good solvents of flexible package composite material adhesive; Can destroy bond effect between composite bed, change the concentration of each component in the electrolyte, and then influence the electrical property of battery.The composition of organic solvent is seen from electrolyte, and they singly are not the solvents that polarity is strong, permeability is strong, and according to the principle of organic matter " polarity similar compatibility ", they are the good organic solvent of aluminium plastic composite packaging material typical binders just.In fact; It is ethyl acetate that the multiple platform packaging material of plastic-aluminum stick with glue solvent the most frequently used in the agent; They belong to the ester class, and are fine to the dissolubility of adhesive, that is to say cementation between their ability heavy damage (swelling, dissolving or reaction) composite films; Adhesive strength is reduced or delamination, thereby lose the excellent obstruct protective value of compound package material.Very easily hydrolysis of lithium salts in the electrolyte. meet water and just produce hydrofluoric acid rapidly with severe corrosive. and hydrofluoric acid is in case be penetrated into the middle aluminium foil layer of aluminum-plastic composite membrane with solvent; With the very fast aluminium foil surface that is connected with adhesive layer that destroys, inner membrance is separated with aluminium foil, even more serious is will accelerate electrochemical corrosion speed can aluminium foil corrosion be worn; Severe corrosive hydrofluoric acid is with the heavy corrosion aluminium foil; Underlying membrane is separated with aluminium foil, and then bore a hole aluminium foil corrosion, thereby destroy whole packing.Secondly; Polymer Li-ion battery core periphery has the burr of copper mesh and aluminium net, the insulating properties of aluminium foil in metal electrode and the flexible packing material when puncture of all burrs of the necessary anti-battery battery core of flexible packing material inner membrance of contact poly-lithium battery electrolyte innermost layer and high temperature and pressure effect seal down.When vacuumizing contraction, burr can be jabbed the barrier layer inner membrance, may pierce through the aluminium foil of barrier layer inner membrance until barrier layer; The hydrofluoric acid of so electric in-core will lead directly to barrier layer, quicken electrochemical corrosion, make aluminium foil produce pit corrosion; And then the composition of change electrolyte; When serious aluminium foil corrosion is worn and leakage, also can be caused short circuit simultaneously, cause battery to be scrapped.Because about metal electrode film thickness 100u; When sealing under heat-sealing temperature about 190 ℃ and the pressure about 3kg/cm2; If there is not resistant to elevated temperatures insulating barrier to exist in the barrier layer inner membrance, metal electrode usually is forced on the packaging foil, causes short circuit; Battery is scrapped, and yield rate reduces.

The metal electrode film of 100u left and right thickness, heat-sealing temperature about 170 ℃ and 3kg/cm ²About pressure down during heat-sealing, if there is not resistant to elevated temperatures insulating barrier to exist in the inner membrance, metal electrode usually is forced on the packaging foil, causes short circuit, and battery is scrapped, yield rate reduces.On barrier, steam permeable amount＜10 ^-4G/m ²D.1atm, oxygen transit dose＜0.1cm ³/ m ²D.1atm.The thickness deviation of film, dimensional discrepancy, heat-sealing folding are peeled off, initial bonding strength between former rete, fracture strength (＞100N), elongation at break (＞35%) etc.

Flexible packing material is participated in electrochemical reaction, and is very complicated to the mechanism of lithium ion battery battery performance impact.The specification requirement of wrapping film is very harsh, such as:

Outward appearance: do not allow pin hole, foreign matter, adhesion, coating is inhomogeneous, compound separates between leading and defectives such as obvious damage, bubble, wrinkle, foul.Thickness: composite membrane moulding gross thickness must be in 150u on the thickness, and non-moulding must be in 120u.

Cold stamping shaped property; The cold stamping degree of depth is 3-8mm, does not allow layering, breaks, the pin hole light leak, shape retention, degree of deformation a＜5 °

Heat seal strength: inner membrance is soaked by electrolyte and is penetrated into three when sealing (at about 12 days), sealing-strength＞40u/15mm.

Water-fast bubble performance: the finished product battery is placed on normal-temperature water and dash soaks and to seal tightly in 20 days, does not produce the air-blowing phenomenon.

Electrical insulating property: the resistivity between electrode and composite membrane aluminium foil, heat-sealing pole piece resistivity＞1 * 10 ⁷s ²Cm ^-1,

Inner membrance puncture performance: when inner membrance can stand burr puncture of electric core week and heat-sealing metal electrode not with film in the middle of the short circuit of AL paper tinsel.Finished product pit corrosion rate and short circuit ratio＜1 ‰.

Electrolyte resistance stability: owing to electrolyte meeting swelling, dissolving absorb the internal layer composite membrane; Particularly adhesive or binding resin between rete, the HF that wherein produces can corrode the AL paper tinsel in the middle of the composite membrane, causes separating of AL paper tinsel and inner membrance; Thereby produce leakage or inflatable, battery is scrapped.Three when sealing, and the AL paper tinsel could guarantee the tight fastness of sealing with interior each interlaminar strength＞2.5N/15mm.

Electrical property: among electrical performance indexes was further being groped to inquire into, manufacturer temporarily maintained secrecy, and is reluctant to reveal in detail.To be packaging film charge and discharge the influence of rate to battery to the essence of electrical property, and this influence comprises electrical insulating property, to the influence of electrolyte component balance, and composite membrane electrical insulating property after particularly the AL paper tinsel is soaked by electrolyte with inner membrance or the like.

Other: the thickness deviation of film, dimensional discrepancy, heat-sealing folding are peeled off, initial bonding strength between former rete, fracture strength (＞100N), elongation at break (＞35%) etc.

In a word, the desired index of flexible packing material film is a lot, and wherein most important index also is that the place different with common composite membrane is 1. high barrier; 2. good cold stamping shaped property; 3. paracentesis resistance; 4. electrolyte resistance is stable; 5. electrical property (comprising insulating properties)

Because these special high performance requirements, make the flexible packing material film become one of three big technical barriers of polymer Li-ion battery industry, also be the challenging problem of tool of current poly-lithium battery.

It is reported; Polymer Li-ion battery core external packing moulding material is monopolized by Japan at present fully; The America and Europe once developed the non-moulding flexible packaging film of the first generation, was eliminated basically, and Korea S is once with Japan's occupying inter-national market at present; As if but the sign that withdraws from is arranged in recent years, and the reason that Korea S withdraws from the market is that the wrapping film properties of product do not have competitiveness.The sharpest edges of Japan are the electrolyte resistance good stabilities, thereby cause barrier, and service life is longer, and its maximum weakness is that paracentesis resistance is poor, and yield rate is low and electrical property is bad.Domestic Xia Men Baolong of the producer industry of really going deep into the research and development of this lithium ion battery wrapping film, Huizhou TCL all can, Dongguan new forms of energy ATL, Shuande electronics etc. that progresses greatly; Because input is big; The difficulty of the difficulty of subject study; Nearly 2 years achievement in research is few, and almost stays cool.Higher at barrier; Cold stamping shaped property better (dash darker, to satisfy the requirement of laptop computer and electric bicycle lithium battery), paracentesis resistance are more excellent, and heat seal strength is higher; The electrical property influence is littler; And how thoroughly to solve on this difficult problem of stability of electrolyte resistance, domestic manufacturers almost are at a loss what to do, can not put forward series of solutions.The composite soft packaging material that the inner core of polymer lithium ion secondary flexible packing material is made up of aluminium foil, multiple plastics and multiple bonding agent (comprising adhering resin).Its design, manufacturing and application technology thereof (abbreviation soft package technology) are the difficult problems of the polymer lithium-ion battery industry three big technical barriers that will solve.In the prior art, be generally used for the outer flexible package of barrier polymer lithium battery content, if do not comprise adhesive linkage; Be generally three layers, the Al paper tinsel is middle barrier layer, and NY and PET beyond the AI paper tinsel are outer protective layer; The Al paper tinsel with interior be internal layer, be multi-functional high-obstruction again.The multi-layer co-extruded laminated film that this three-decker mainly is made up of extrernal resistance layer, barrier layer (intermediate layer aluminium foil) and high-obstruction (internal layer), i.e. skin/aluminium foil/internal layer.Skin is meant external protection or printed layers, and internal layer then is meant composite bed and hot sealing layer.

Skin requires high temperature resistant, and heat-sealing temperature is in (160 ± 15) ℃, and wear-resisting wiping property, paracentesis resistance and folding resistance are good.Skin mainly is that the intermediate layer is played good protective action and is fit to the requirement of cold stamping shaped property, and special also requires printing good.Except that requiring to possess the performance of non-cold stamping shaped cladding material, also require suitable percentage elongation, higher impact strength, tearing strength and fracture strength.Prior art adopts the PUR bonding layer of thermoplastic and inboard bonding aluminium foil to form on skin usually.The thermoplastic resin membrane of, stream court of a feudal ruler polypropylene film thin, polyamine polymer film or nylon (PA) single face such as the polypropylene screen (CPP) of single face coating hot-melt adhesive or co-extrusion polypropylene apply hot melt and the aluminium foil of coating hot-melt adhesive glue.The PUR that applies is generally vinyl or EVA hot melt adhesive, polyolefin polyhydric alcohol, multi-functional isocyanide acid alcohol curing agent, has added thermoplastic elastomer (TPE), has added tackifier etc., and thickness is generally 0.001-0.01MM.Nylon poor impact resistance on the skin scratches easily, leaks gas, and hydrophily is arranged again, easy moisture absorption gas, and oxygen gas barrier reduces.

And be used for the aluminium foil (intermediate layer) of barrier layer; Usually adopting iron-holder is the aluminum foil material below 0.9; And on aluminum foil inner layer one side surperficial, form at least a phosphate layer, complex acid salt film, fluoride films, the antiacid film of triazine thiol compound film; The tensile strength of its generation, percentage elongation and Erichsen number generally are difficult to reach the right angle and dash dark value requirement, also are difficult to the requirement that reaches higher about 10000 times than the barrier of conventional aluminium plastic composite materials.Prior art is employed in the two sides of aluminium foil usually and selects the modifier of mylar, vistanex or these resins and a kind of next bonding ectonexine nonmetal film of mixture for use.The PUR that applies is vinyl or EVA hot melt adhesive, polyolefin polyhydric alcohol, multi-functional isocyanide acid alcohol curing agent, and added thermoplastic elastomer (TPE), added tackifier etc., thickness is generally 0.001-0.01MM.And employing applies the two sides of aluminium foil with a kind of bonding agent.The experiment proof; No matter be to adopt dry type to be coated with that organic solvent cement is compound, wet type coating inorganic bond is compound; Still hot melt agent coating is compound, and this two sides adopts the weak point with a kind of glue bond layer to be, can not effectively intercept the infiltration of cell contents.Because aluminium plastic composite material is metal and nonmetallic combination, aluminium foil and nonmetallic adhesive bond dynamics are generally all smaller.In forming process, aluminium foil and other nonmetallic composite comprise that bonding agent extends jointly, flows, and aluminium foil can attenuation in the process of extending, and the strand of the bonding agent after dry and hard ruptures easily, forms stealthy crack broken belt.In general, the aluminium foil moulding degree of depth that 40 μ m are thick generally can not surpass 4mm, and the thickness of aluminium foil can not be less than 30 μ m after the moulding.The finished product battery is exposed in the atmospheric environment of certain humidity, and the moisture of air has the effect of seeing through to packaging material.Because lithium-ions battery is very harsh to the requirement of non-water condition, moisture can directly influence battery cycle life, so the barrier property of each composite bed of packaging material is very important.And the key that plays iris action in the layers of material is aluminium foil.Aluminium foil ductility is very important, and the R place of its percentage elongation deficiency around then when drawing and forming is prone to generation gauffer and pin hole, can reduce the barrier property of material.

High-obstruction (internal layer) inner membrance is the special multi-functional layer that designs and produces to the property of electrolyte in the lithium ion, and these functions mainly contain:

(1) electrolyte resistance soaks and when using in the process of electrochemical reaction. and inner layer sheet reveals good chemical stability, as by swelling, dissolving or chemical reaction takes place and do not destroyed.

(2) hot sealing layer must possess higher anti-electric core periphery copper mesh, the performance of aluminium net burr puncture when vacuumizing powerful the contraction, thus avoid pit corrosion and short circuit phenomenon.

(3) also must possess anti-175 ℃ (heat-sealing temperatures) above heat-resisting quantity material in the middle of the bottom, produce short circuit or poor contact phenomenon when avoiding the electrode banding.

(4) moisture that contains in the primer, and react and the oxygen fluoric acid of generation, hydrofluoric acid can not be penetrated into produce corrosion on the aluminium foil of intermediate layer.Therefore must be able to fix in the middle of the internal layer, can absorb the moisture of electric in-core in the manufacturing process, airborne moisture.

(5) lug of battery will seal through two-layer aluminum-plastic composite membrane; This just requires packaging material internal layer heat sealability good; Make primer and lug (Copper Foil, nickel foil, aluminium foil) that good affinity adhesion property and sealing property arranged; Enough peel strengths are arranged, will guarantee that simultaneously lug and not short circuit of packaging material and battery electrolyte inside do not leak outside for a long time.Peel strength that heat sealability is good and chemical resistance equally also are the key properties of lithium ion battery applications packaging material.The heat-sealing effect of CPP film is mainly controlled through heat-sealing temperature, time, pressure.The heat sealability quality of heat-sealing PP layer is directly related with battery inflatable problem.CPP film heat-sealing effect receives the influence of many-sided factor, comprises temperature, time and pressure and material self character (density, melt flow rate (MFR), thickness, manufacture craft, surface property and structure composition etc.).Evaluation plastic sheeting heat-sealing effect quality is mainly carried out from sticking two aspects of intensity of heat seal strength and heat, considers the planarization after film seals simultaneously, fold or tiny defectives such as micropore whether occur.Improve performance of composites, except that adopting better aluminium foil, other composite bed also will adopt barrier property and mechanical and physical performance better material.After electric core packing finishes, carry out final grading and turn over the heat-sealing limit (when general heat-sealable area width is 3～5mm); Require polyester (PET), nylon films such as (BOPA) that the favorable mechanical physical property is arranged equally, otherwise problems such as fracture, bounce-back can occur at the broken line place of flanging.Behind stretched cuboid die cavity on the packaging material, can put into battery and carry out heat sealed package, this technology is called packaging material cold moudling.This just requires flexible package composite material integral body that good ductility will be arranged.

One of best barrier layer inner membrane material known today is a kind of novel special barrier layer flexible packaging film material that Japanology goes out, and this special barrier layer flexible packing material is called as X100. and posts protective layer on it, when producing, will it be torn.Why this material of Japanology is called X100 barrier layer flexible packing material.

The weak point of the glue bond layer that the hot melt agent coating that above-mentioned prior art adopts is compound is; Can not effectively intercept the infiltration of cell contents; Anti-strong acid-base is not enough with the performance of 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 electrolyte to it.

Summary of the invention

Task of the present invention is to propose a kind of superpower barrier that has, good cold stamping shaped property, paracentesis resistance, electrolyte resistance stability, anti-organic solvent of ability and high volatile volatile material, the polymer Li-ion battery core external packing moulding material that heat seal strength is high.

The object of the invention can reach through following measure; A kind of polymer Li-ion battery core external packing moulding material; Comprise that the multi-layer co-extruded THIN COMPOSITE rete that extrernal resistance layer, barrier layer and high-obstruction laminated body are formed is characterized in that; Described extrernal resistance layer laminate body is by one deck heat-resistant resin film: PET, BOPA at least; PEN chooses one of which wantonly, perhaps wherein both and deposit that coextru-lamination constitutes, the aluminium foil in the said barrier layer laminated body contains the Fe that content is 0.9wt%～1.5wt% at least; Described high-obstruction laminated body comprises basic unit, functional layer and hot sealing layer; Said basic unit is by polypropylene (PP), chlorinated polypropylene or cast polypropylene (CPP), polyethylene (PE), polyethylene terephthalate (PET), nylon (PA) or aromatic nylon (MXD6), MPE elastomer blend; Polyvinylidene chloride (PVDC), ethylene-vinyl alcohol copolymer (EVOH); PEN (PEN); At least two kinds of film substrates combination in the high barrier transparent packaging film (GT) or the EVA film of compound composition in twos all are coated with the water-fast modified polyvinylalcohol of high-barrier (PVA) coated film on said EVA film substrate.

The present invention has following beneficial effect than prior art.

Extrernal resistance layer laminate body of the present invention is selected PET, BOPA for use, PEN heat-resistant resin film, and the screening ability of the micro-molecular gas of environment, liquid, water vapour and smell is big to external world, gas barrier property is high.Adopt the interaction bonding compatibility of dual-component polyurethane resin glue stick and metal aluminum foil splendid, adhesive force is good: adhesive coating is incrust, does not influence its barrier and compound peel strength; Adventitia and binder molecule chain be in dark process, and interactive extensibility of plasticity and compound firmness are excellent, and it is not stratified not rupture, and toughness is high temperature resistant, and be shock-resistant, peel resistant strength is high, anti-external environment infiltration, free of pinholes light leak and breaking almost.

Because PEN surface smoothing gloss.In wider temperature range, have excellent physical and mechanical properties, electrical insulating property is good, even under the high temperature high frequency, its electrical property is still better, creep resistance, and fatigue durability, rub resistance, dimensional stability are all fine.As packaging material the good mechanical performance is arranged, impact strength is 3～5 times of other films.Folding resistance is good, oil resistant, anti-fat, anti-diluted acid, diluted alkaline, anti-most of solvents.Have good high-and low-temperature resistance performance, can be in 120 ℃ of temperature ranges use for a long time, short-term is used can anti-150 ℃ of high temperature, can anti--70 ℃ of low temperature, and very little to its influence during high and low temperature.Gas and vapor permeability are low, and good choke, water, oil and peculiar smell performance are arranged.

Because the naphthalene ring of PEN makes PEN have performances such as higher physical and mechanical properties, gas barrier property, chemical stability and heat-resisting, UV resistant, radiation hardness than PET.Resistance to water is 4 times of PET.PEN to the barrier of water be PET 3-4 doubly, be 4-5 times of PET to the barrier of oxygen and carbon dioxide, be 3.5 times of PET to the barrier of water, its barrier can be compared with PVDC, does not receive the influence of wet environment.

The present invention is through increasing grafting flexibilizer, and the BOPA film is except that easy formation crystalline texture. and also have and do not get wet, be difficult for suction, characteristics such as acid and alkali resistance.Organic solvent and multiple other chemicals had favorable chemical resistance, excellent toughness and paracentesis resistance, shock-resistant, anti-explosion, mar proof etc.Its excellent oil resistivity, grease resistance and chemical solvent resistance, fabulous gas (oxygen, nitrogen, carbon dioxide), fragrance and smell barrier, hear resistance are strong, and Applicable temperature (60 ℃-150 ℃) in extensive range can be convenient to other base material compound.Too extend in forming process but also solved BOPA, the BOPA layer shrinks after heat-sealing, when convergent force layering occurs during greater than the adhesive strength of BOPA layer and AL layer, understands at a certain turning or the difficult problem of flanging gassing or lamination once heat-sealing.Nylon obturator that adds or plasticizer intermingling material form impact resistance, cold resistance, processing and forming property that graft copolymer can improve nylon, reduce water absorption rate, in addition, toughness reinforcing after, can remove the trouble that nylon products needs poach usually from.Nylon 6/ polyolefin blends has improved impact strength, has reduced water absorption rate.

Nylon 6 elastomeric addings can increase substantially the system impact strength, have tangible toughening effect.When elastomer content reached 20%, the system impact strength improved 12 times.Suitable shear strength can be regulated and control the microscopic pattern structure of co-mixing system, and the elastomer particle phase farmland size that obtains is little, uniformity coefficient is high, is easy to make co-mixing system generation brittle-ductile transition.The result shows that micron order and nanoscale CaCO particle all have the coordination plasticizing effect with the elastomer particle.But micron order calcium carbonate does not have humidification.DMA analyzes and shows, the adding of POE reduces the secondary transition temperature T gg of PA6, has improved the black brittleness of PA6.The hybrid mode of two step method helps improving toughness of material, and the intensity of material is improved.

DMA analyzes and shows that the adding of POE makes PA6/n-CaCO.The tan6 peak value of system significantly increases, and secondary transition temperature T gg reduces.Explain that POE can significantly improve PA6/n-CaCO.Toughness, improve black brittleness.Simultaneously, the adding of POE, to PA6/n-CaCO, little to the influence of system modulus.The toughness reinforcing mechanism and enhancement mechanism of particles filled PA6 binary system is the toughness reinforcing and coefficient result of matrix shear yielding of microcavities.

Can also obviously improve the water imbibition of using PA66 and dry state, low temperature impact properties through adding grafting flexibilizer.

The aluminium foil that the present invention constitutes barrier layer has overcome the prejudice of prior art so-called " when the aluminium foil iron-holder surpassed 0.9 weight %, the flexibility of aluminium was damaged, as its bag property variation of lamilated body ".And the Fe/Si that has overcome commercial-purity aluminium Al-Fe-Si alloy is controlled at 0.25% than generally, and Fe/Si can cause the prejudice of work hardening rate raising than greater than 5% o'clock.Through a large amount of experiments, the physical characteristic and the mechanical performance of the final aluminium foil that forms of the present invention: O state, tensile strength be greater than more than 80～98Mpa, percentage elongation＞21%, and Erichsen number >=more than 6.10, yield strength 455Mpa, springform E/Gpa:71.Transmitance is≤1ml, hot strength is>=and 30Mpa, fracture extension rate>=40, peeling force>=1, heat sealing strength>=40, light penetration≤0.4, towards dark 4mm-12mm, 25 (kpa) ne-leakage that keep-ups pressure, crack-free.

The bonding aluminum foil outer layer of dual-component polyurethane resin glue stick that adopts, splendid towards dark interactive bonding compatibility with metal aluminum foil, adhesive force 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 peel strength; Adopt polyester polyols alcohols adhesive glue aluminum foil inner layer, viscosity is high, anti-organic solvent, and anti-strong acid-base, anti-high corrosion volatile materials, and toughness is high temperature resistant, shock-resistant, peel resistant strength is high, anti-infiltration, bonding free of pinholes, strand is complete not to rupture.

The present invention preferably adopts the basic unit of multiple base material coating such as CPP, PE, BOPP, PET, PA, MXD6, PEN, PVDC, GT high-barrier PVA as high-obstruction, does not change the original performance of base material, increase barrier at double.And have extraordinary barrier with excellent choke, block water, performance such as corrosion-resistant, antiultraviolet, barrier property obviously is superior to existing PVF polyvinylidenechloride coated film in market and ethylene-vinyl alcohol copolymer EVOH co-extrusion film.After being coated with on the films such as CPP, PE, finished film is the color printing bag directly, greatly reduces packing cost, also can be widely used in packaging fields such as food, fine chemistry industry, precision electronic device instrument and medical pesticide intermediate.Being also advantageous in that of the modified PVA of coating:

1. solvent resistance is good: organic solvent property such as oil resistant, fat are good, can effectively intercept its seepage.

2. ultraviolet resistance is good: can prevent preferably because of UV-induced rotten.

3. moisture resistance is good: PVA is through after the water-fast modification, and under wet condition, the barrier of packing material does not descend, and still has good protective effect, and this characteristic is that PVDC and EVOH co-extrusion film are incomparable.

4. excellent in stability: even directly receive solar radiation, coating is stable, non-yellowing, be difficult for aging.

5. adhesive force is good: coating is incrust, can not influence its barrier and compound peel strength.

6. have good temperature resistance and superpower gas barrier property, have the anti-puncture resistance of superelevation and the structure that heat-sealing temperature is wide, the oil rub resistance sealing property is good simultaneously.Aspect oxygen resistance, the average 2cm of water-fast modified PVA coated film oxygen transit dose ³That (m224h0.1MPa), test value is minimum is 0.27cm ³/ (m224h0.1MPa), and be coated with twice PVDC coated film oxygen transit dose at 15cm ³/ (m224h0.1MPa) about; When having good oxygen resistance; Having excellent water tolerance can; Coating is returned glutinous, swelling phenomenon having can not produce under water or the super-humid conditions, and the packaging material that the base material that has a heat sealability through the PE after the coating, CPP etc. can be used as high barrier directly use.Adhesive force is good, at PE, PET, BOPA, BOPP, CPP is last is coated with, and does not need any pre-coating and adhesive.Coating is incrust, can not influence its barrier and compound peel strength.The modified PVA coated film is compared with unmodified PVA coated film, and cohesive force, hygrometric state barrier and resistance to water are significantly improved.

The present invention carries out appropriately crosslinked modified PVA with melamine resin modification liquid to PVA; PVA is when high-isolation film is keeping dry state barrier property, transparent, pliable and tough advantage; Also improved cementability with base material; Saved pre-coating and binding agent, especially outstanding is to compare the hygrometric state barrier property with unmodified PVA obviously to improve.Compare with unmodified PVA technology, the PVA of modification has saved pre-coating and the operation of using binding agent, has cancelled and has covered technology, can reduce equipment investment and reduce product cost.The PVA hydrosol after the modification has solved the difficult problem that viscosity rises under static lower surface skinning and the working condition.

Performance and unmodified PVA relatively, the modified PVA coating layer soaks after 24 hours coating in water do not have swelling and obscission, key index oxygen transit dose is reached advanced world standards.

Oil resistant, organic solvent resistance are good, all are insoluble to animal oil, vegetable oil, mineral oil, alcohols, ethers, ketone, ester class.

Have good barrier properties for gases, extremely low oxygen permeability is particularly arranged, the packing that is suitable for various article is sealed up for safekeeping.

The present invention organically combines thin-film materials such as MA-PVDC, PE, EVA, PP, PA, and performance complement becomes the splendid high-barrier flexible packing material of a kind of combination property.Because the high barrier of MA-PVDC, oxygen flow can be controlled in＜1cm ³/ m ²0.1MPad (GB/T1038-2000), passing through the vapour amount is controlled at＜0.7g/m ³D (GB/T1037-1987).

The present invention combines evoh layer and typical PA layer or aromatic nylon MXD6, can protect the puncture resistance of PA, has increased the intensity of EVOH again, has improved the anti-fragility of EVOH.The EVOH ethylene-vinyl alcohol copolymer of selecting for use, outstanding feature is that fabulous gas barrier property is arranged, the infiltration of blocking oxygen, carbon dioxide and other gases effectively; It also has the good transparency, glossiness, mechanical strength and heat endurance simultaneously.Test shows that external packing PA layer hot strength MpaMD of the present invention can reach 252.38 (standard value >=180), and TD can reach 312.04 (standard value >=180).Fracture extensibility %, MD can reach 163.74 (standard value≤180), and TD can reach 121.33 (standard value≤180).Tear-resistant power mN, MD can reach 245.3 (standard value >=60), and TD can reach 238.1 (standard value >=60).

The PVF polyvinylidenechloride of selecting for use has very high degree of crystallinity, and its maximum characteristics are that splendid materials with high barrier property is arranged, but since its quality hard, softening point is high, to thermally labile, cause machine-shaping quite the difficulty.If with monomer whose vinylidene chloride class (VDC) and other monomer, like copolymerization such as vinyl chloride, methyl acrylate, acrylonitrile, then copolymer can address the above problem preferably.

The PEN PEN that selects for use and the difference of PET molecular structure are to have replaced the phenyl ring in the PET molecule with naphthalene nucleus, and the starting monomer of polymer replaces terephthalic acid (TPA) with 2,6 naphthalenedicarboxylic acids, and it constitutes with PET similar.Therefore, PEN is outstanding person in the polyester material, and it almost all is superior to PET in all respects, has excellent barrier, to ultraviolet absorbability, hear resistance and chemical stability.

The GT film of selecting for use not only can reach the barrier property of aluminium plastic composite material, and also has many outstanding features, can not change because of the variation of temperature and humidity like barrier property; Can stop extraneous peculiar smell to infiltrate;

Propylene and ethene semi-crystalline co-polymers propylene-based elastomeric (propylene-based elastomer that functional layer adopts; PBE) the BOPP film is the extraordinary olefin elastomer that adopts the manufacturing of the TM of ExxonMobil Chemical (Exxpol) metallocene catalysis proprietary technology to form; Unique propylene and ethene semi-crystalline co-polymers (second third elastomer), they and other copolymer have the compatibility of excellence, and can in a lot of flexible film terminal uses, reach and have outstanding film heat sealability; With various polyolefin excellent adhesion strength is arranged all; Excellent adhesive property, high resiliency and pliability, outstanding target properties such as toughness.

In hot sealing layer, because polybutene at polyethylene (PE) and polypropylene (PP) intermiscibility, seals integrality, surface smoothing is with clean, and average peel force is the 5-6N/15 millimeter.

Select for use POE to make hot sealing layer; Be that this polymer has extremely low degree of crystallinity because POE is a kind of ethene--a olefin copolymer of producing with metallocene catalyst, density is very low; Narrow molecular weight distribution; Characteristics such as the glass catalytic temperature is low, and have good resilience and pliability etc., and its hardness is very low.These specialty polymers have remarkable adhesion to ethene and acrylic polymers.Compare with the random copolymerization PP resin of standard and the AFFINITY POP that is widely known by the people, propylene-based elastomeric (VERSIFY) plastic body and elastomer also have splendid adhesion to LLDPE (LLDPE) and HOPP (PP).This high adhesion makes the VERSIFY plastic body and elastomer can be total to structure with polyethylene (PE) and PP resin or combination (multilayer or blending) produces film.The degree of crystallinity scope that VERSIFY plastic body and elastomer are wide makes heat-seal temperature wider range, and it is lower to play envelope temperature (SIT), can be applied in the blowing and cast film that needs higher heat-sealing speed.In BOPP used, VERSIFY plastic body and elastomer can be made had excellent transparency and jewelly fexible film, had suitable modulus and the excellent properties balance of having hanged down the envelope temperature simultaneously, and this is the combination of properties that in the BOPP hot sealing layer, is difficult to realization.Another interesting characteristic of VERSIFY plastic body and elastomer is the ability that after carrying out corona or flame treatment, still keeps heat seal strength.Compare with similar plastics, can not cause the obvious decline of heat sealing strength when VERSIFY plastic body and elastomer use as hot sealing layer or play the rising of envelope temperature.

The battery external packing aluminum-plastic composite membrane of the present invention and a of offshore company and the b of company has carried out multiple performance contrast experiment under equal environmental condition.

1. aluminum-plastic composite membrane is high temperature resistant, corrosion-resistant, the performance test of organic solvent-resistant and high volatile volatile material.

With infusion method its above-mentioned aluminum-plastic composite membrane resistive formation (innermost layer) is got its PP rete wherein; The poly-lithium battery electrolyte solution package encapsulation of 20mg is good; Be placed in 85 ℃ of high temperature experimental boxs 4 hours, let molecule accelerated motion, survey that it is high temperature resistant, corrosion-resistant; The performance of organic solvent-resistant and high volatile volatile material, weighing is taken out in the back.Result after the taking-up is that above-mentioned two companies electrolyte solution wherein all volatilizees no residue.The present invention is after 4 hours, and electrolyte solution also remains 10-12mg.Test proof, the present invention is high temperature resistant, corrosion-resistant, and the performance of organic solvent-resistant and high volatile volatile material is superior to above-mentioned two tame foreign corporations.

2. the corrosion failure of the anti-battery electrolyte of finished product packaging film test.

The composite membrane outsourcing finished film that packing is had battery; And injection 20mg poly-lithium battery electrolyte solution encapsulates; Be placed in 85 ℃ of high temperature experimental boxs; The result is that the battery external packing of a company was moulded the aluminium film and is corroded and breaks after 23 days, and the battery external packing of b company was moulded the aluminium film and is corroded and breaks after 25 days, and the present invention moulded the aluminium film and is corroded and breaks after 28 days.

3. the test of the anti-battery electrolyte of finished product packaging film and water reaction back generation strong acid and swelling.

With the external packing moulding material diaphragm of processing finished product; Put into the poly-lithium battery electrolyte solution that is added with 3%-5% water, and good seal, in 85 ℃ of high temperature experimental boxs, let its molecule accelerated motion; The result shows; The battery wrapping film of b company broke in 24 hours, and the battery wrapping film of a company broke in 28 hours, and the present invention was broken at 48 hours.

4. heat seal strength test.

Under 3Mpa/ 3 seconds time of heat-sealing, heat-sealing pressure newton N/15mm condition,

A company: 40N-50N/15mm

B company: 43N-55N/15mm

The present invention: 55N-68N/15mm.

In acupuncture overtesting journey, the external packing aluminum plastic film of battery of the present invention changes hardly, and the battery profile is complete basically.

The specific embodiment

In following examples; The said heat-resistant resin film of extrernal resistance layer laminate body is wherein a kind of of polyethylene terephthalate (PET), nylon (BOPA), PEN (PEN); Wherein thin with the PEN/PET copolyesters, contain 0.1% (mass fraction)～0.4% (mass fraction) SiO ₂Particulate; And carry out ester exchange reaction synthetic intermediate 2 through naphthalene diformic acid dimethyl ester (NDC) and ethylene glycol (EG); 6-(ethylene naphthalate) (BHEN); And BHEN content is 8% (molar fraction), and what on the medial surface of above-mentioned heat-resistant resin film, be coated with is dual-component polyurethane resin glue stick.Extrernal resistance layer laminate body is selected PET, BOPA for use, PEN heat-resistant resin film.

The PEN chemical constitution is similar with PET, and difference is that PEN has replaced the phenyl ring among the PET by the bigger naphthalene nucleus of rigidity in the strand.The fusing point of PEN is that 265 degree are close with PET, and its vitrification point exceeds about 50 degree than PET more than 120 degree.PEN also has excellent mechanical property, and Young's modulus and the tensile modulus of elasticity of PEN all exceed 50% than PET.And, the stable mechanical property of PEN, even under the HTHP situation, its elastic modelling quantity, intensity, creep and life-span still can keep suitable stability.Select BOPA; Then the BOPA transverse tensile strength (>=250MPa) greater than prior art (180MPa) 70Mpa; Vertical amount hot strength (>=310MPa) greater than prior art (180MPa) 130, laterally vertically tear-resistant (245M/N) is greater than prior art (60M/N) 180M/N.

Under the situation of selecting the PEN/PET copolyesters, under identical draw ratio, because 2,6-naphthalene two formyl construction units are along with in the copolyesters 2, and the introducing of 6-naphthalene nucleus unit has increased the rigidity of copolyesters macromolecular chain.This is because in the thin film fabrication process; Naphthalene nucleus has bigger conjugated structure than phenyl ring, and the strand rigidity is high, tends to generate extended-chain configuration; Although and molecularly oriented also takes place in PET; But be folded-chain structure, thus sound wave when PEN/PET copolyesters film stretching differently-oriented directivity is propagated, its direction of propagation together the polyester macromolecule chain than more parallel with the PET macromolecular chain.Along with the increase of draw ratio, explain that the performance of copolyesters film helps strand along the direction arrangement parallel with draw direction.The PEN/PET of same stretch multiple slightly increases than PET fracture strength, but extension at break significantly diminishes.

This is because the naphthalene nucleus of introducing has the bigger structure of gripping altogether, make the strand rigidity high, so the copolyesters after the modification is not because the symmetry of strand is destroyed and does not make intensity decline with regularity.The PEN/PET copolyesters of same composition is but with the increase of draw ratio, and intensity increases gradually, and elongation reduces gradually.This be because the anisotropy of the intensity of polymer with degree of orientation increase and the result that increases.

This heat-resistant resin film can be selected: any the extrernal resistance layer as polymer Li-ion battery in polyethylene terephthalate (PET), nylon (BOPA), the PEN (PEN).Preferably can also select the PEN/PET copolyesters thin.Thin 0.1% (mass fraction)～0.4% (mass fraction) SiO that contains of PEN/PET copolyesters ₂Particulate, and carry out ester exchange reaction synthetic intermediate 2 through naphthalene diformic acid dimethyl ester (NDC) and ethylene glycol (EG), 6-(ethylene naphthalate) (BHEN), and BHEN content is 8% (molar fraction).The PEN/PET copolyesters is thin to be catalyst with the zinc acetate, is antioxidant with sterically hindered phenol 1010, and reaction temperature is 295 ℃; It is 4 * 10 that every mole of BHEN uses the amount of catalyst ^-4Mol, the reaction time is 180min; It is 1 * 10 that every mole of BHEN uses the amount of antioxidant ^-5Mol.With the PEN/PET copolyesters of above-mentioned acquisition through the biaxial stretch-formed film of processing excellent performance.The result shows: SiO ₂The batten section that particle content is different, particle disperse relatively evenly, and particle diameter all below 0.4 μ m, does not have excessive particulate and exists; Work as SiO ₂When fraction of particle increases, do not flocculate into the excessive particle of particle.

In the thin film fabrication process, the membrane of PEN/PET copolyesters adopts LSJ20 plastics extrusion device to extrude, screw diameter 20mm, and the spiro rod length diameter is 25 than L/D, rotating speed 60r/min.Adopt the twin shaft elongator to stretch.Earlier be extruded into sheet in 275 ℃ at LSJ20 plastics extrusion device, again on the twin shaft elongator in 130 ℃ to 3-4 doubly with identical multiple biaxial tension.In the thin film fabrication process, because naphthalene nucleus has bigger conjugated structure than phenyl ring, the strand rigidity is high. tend to generate extended-chain configuration, although and molecularly oriented also takes place PET.The biaxial orientation polymer film is along its plane two directions stretchings in length and breadth, and macromolecular chain tends to the direction parallel with thin film planar and arranges, but the orientation of strand is random in this plane.When sound wave was propagated in PEN/PET copolyesters film stretching differently-oriented directivity, the polyester macromolecule chain was than more parallel with the PET macromolecular chain together in its direction of propagation that is folded-chain structure, and the velocity of sound is bigger.Therefore, the velocity of sound orientation factor of calculating increases.The copolyesters of each composition, along with the increase of draw ratio, velocity of sound modulus and velocity of sound orientation factor increase, and this explanation more helps strand and arranges along the direction parallel with draw direction along with the increase of draw ratio.

In the thin film fabrication process, the PEN/PET copolyesters is along with in the copolyesters 2, the introducing of 6-naphthalene nucleus unit and the increase of content; Dry-hot shrinkage obviously reduces, and this is that the introducing of 6-naphthalene two formyl unit has increased the rigidity of copolyesters macromolecular chain owing to 2; Thereby make the PEN/PET copolyesters show the thermal stability more better than PET; And 2,6-naphthalene nucleus unit content is big more, and thermal stability is good more.Eminency is the enhancing that orientation produces anisotropy and differently-oriented directivity.

No matter selecting PET, BOPA, PEN still is that the PEN/PET copolyesters is thin; On the medial surface of these heat-resistant resin films or what be coated with on the aluminium foil outer surface is a kind of shock-resistant, high temperature high voltage resistant, big with metal aluminum foil firm binding force degree, the dual-component polyurethane resin glue stick of extension good toughness.This dual-component polyurethane resin glue stick is made up of two kinds of components; First component (A) can be polyester and isocyanates/the contain polyethers blend of phenyl ring; The polyethers of polyester and isocyanates/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 dihydroxylic alcohols, 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 carbodiimides, epoxide etc., also can adopt long-chain biatomic acid and dihydroxylic alcohols raw material, like decanedioic acid, 1, and 6-hexylene glycol etc.The dihydroxylic alcohols of side chain such as the hydrolytic resistance that the neopentyl glycol raw material improves polyester are arranged.

For improving the hydrolytic resistance adhesive of adhesive layer, improve the hear resistance 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 coupler 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 catalyst 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 adhesive strength with water.

Above-mentioned polyisocyanates can be: vulcabond; The polyisocyanates, diisocyanate monomer, methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), the 3-isocyanates methylene-3 that contain isocyanurate ring; 5,5-3-methyl cyclohexanol based isocyanate (IPDI), hydrogenation methylenebis phenyl isocyanate (H ₁₂MDI), IPDI, dicyclohexyl methyl hydride diisocyanate, PPDI, cyclohexane diisocyanate, XDI, cyclohexanedimethyleterephthalate vulcabond, tetramethyl m-phenylenedimethylim-vulcabond, norbornene alkyl diisocyanate, dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate etc.The isocyanates raw material is main with toluene di-isocyanate(TDI) (TDI).Vulcabond is divided into two types of aromatic series and aliphatic (or alicyclic).The performed polymer synthetic by aromatic diisocyanate has higher intensity, 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 product is a polyurethane-urea, and the existence of urea key makes the glued membrane hardening, and modulus increases.Amine commonly used has ethylenediamine, diethylenetriamine, triethylene tetramine etc.Amine chain extender generally adds in performed polymer emulsification, limit emulsification, limit chain extension.Making chain extender with the mixing amine, to make aqueous polyurethane urea dispersions adhesive property good, and vitrification point is higher.The alcohols chain extender has 1,4-butanediol, ethylene glycol, diglycol etc.Make the resistance to water that chain extender can improve glued membrane with the three-functionality-degree alcohols.It is one of committed step of preparation aqueous polyurethane that the hydrophily chain extender is incorporated in the performed polymer molecule.

Base polyurethane prepolymer for use as can be that by a certain percentage PPG and the mixture of PEPA 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 PPG and PEPAs usually.The performed polymer that is made by PPG has good hydrolytic stability, pliability and extensibility preferably, and resistance to low temperature is good.PEPA type performed polymer cohesive force is big, and adhesive strength is high.The molecular weight of oligomer polyol and degree of 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 resistance to water of aqueous polyurethane.

Base polyurethane prepolymer for use as can also be by a certain percentage, makes with base stocks such as PPG, toluene di-isocyanate(TDI), dihydromethyl propionic acid and triethylamines.Above-mentioned a certain proportion of numerical value is that this area can be known.

Second kind of component (B) is that a kind of epoxide number is that glycidol ether based epoxy resin and the melamine formaldehyde resin of 0.25-0.45 is the composition 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 adhesive emulsion by mass ratio.

The glycidol ether based epoxy resin that second kind of component (B) adds is to be formed by the phenols that contains active hydrogen or alcohols and epoxychloropropane polycondensation.Mainly comprise,

(1) propane type epoxy resin of di phenolic group, propane type epoxy resin of di phenolic group is formed by diphenol propane and epoxychloropropane polycondensation.

Epoxide number is meant the amount of substance number of contained epoxy radicals in every 100g resin.The inverse of epoxide number multiply by 100 and is referred to as epoxide equivalent.The implication of epoxide equivalent is: the gram number that contains the epoxy resin of 1mol epoxy radicals.

(2) the many epoxy resin of phenolic aldehyde.The many epoxy resin of phenolic aldehyde include phenol formaldehyde type, the many epoxy resin of orthoresol formaldehyde type; It is compared with propane type epoxy resin of di phenolic group; In linear molecule, contain plural epoxy radicals; Therefore the crosslink density of solidified after-product is big, has good heat endurance, mechanical property, electrical insulating property, resistance to water and corrosion resistance.By the many epoxy resin of phenolic aldehyde that linear phenol-aldehyde resin and epoxychloropropane polycondensation form, be most preferred embodiment of the present invention.

(3) other polyhydroxy phenols glycidol 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 hydroxyphenyl methane type epoxy resin; Have high heat distortion temperature and rigidity behind these polyfunctional glycidyl ether's resin solidifications, can be independent.

(4) aliphatic polyol glycidol ether type epoxy.Contain two or more epoxy radicals in the aliphatic polyol glycidol ether molecule, the most viscosity of this resinoid are very low; Great majority are long-chain linear molecules, therefore are rich in pliability.

Epoxy resin can be 6360,6101,634 in second kind of component (B).The catalyst quality mark is generally 0.04%.

The A component (host) of being synthesized, B component (crosslinking agent) bin 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 bi-component adhesive, 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 adhesive is 100% reaction system, and no any solvent or volatile matter discharge in the curing.Good to most of plastics and bonding foil property, peel strength is up to 4.4kNm ²-1 hot strength 7.9MPa, percentage elongation are greater than 125%, and serviceability temperature reaches 121 ℃.Also have high electric insulation property and chemical-resistant resistance and good heat-resisting and impact resistance.

During preparation.Can PEPA that slough moisture, PPG, dihydromethyl propionic acid (DMPA) and toluene di-isocyanate(TDI) (TDI) be carried out composite joining in the reactor by polyester and polyether with 75/25～55/45 mass ratio; Add the bisphenol-A chain extender 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 stirred, drip deionized water behind the 15min, de-bubbled 30min obtains emulsified water based polyurethane performed polymer (PU).The addition of catalyst is 0.05%～0.2%, at 70 ℃ of polyisocyanates that add metering, the preferred methyl diphenylene diisocyanate of polyisocyanates (MDI)/toluene di-isocyanate(TDI) (TDI); Or adding dihydromethyl propionic acid (DMPA); Reaction temperature is 95～100 ℃, when temperature reaches 85 ℃, at the uniform velocity stirs, and mixing speed is 400r/min; Be 95～100 ℃ of following insulation reaction 2h in temperature then, the Compound Fabric and the PET that can obtain function admirable use reaction type polyurethane hot-melt adhesive.Can effectively prevent implode and gel accident at 70 ℃ of MDI/TDI that add metering.The PU adhesive emulsion that makes evenly is applied to (6～7g/m through the plastic sheeting surface of corona treatment ²), the epoxy resin optimum amount is about 5% (mass fraction) 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, peel strength is all greater than 3N/15mm.Aqueous polyurethane (PU) is with the new polyurethane system of water to replace organic solvent as decentralized medium, is suitably handled a period of time under higher temperature by the PET/PE film that the dual-component aqueous polyurethane adhesive binds, and the bonding effect is better.

The catalyst that adds can be organic tin and aliphatic, alicyclic tertiary amine compounds.The organic tin compound all has catalytic action to positive reaction and the back 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 ethylether is made catalyst,

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 performance; So for initial viscosity, the shortening that improves adhesive produces the required time of certain adhesive strength; Usually polyethers or PEPA 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 coupler be added in the performed polymer of monocomponent moisture cure as curing agent, the adhesive adhesive strength and heat-resisting, the anti-boiling ability that make all are improved.As the silane coupler that will hold the NCO group joins in the performed polymer of end NCO.Even can also be with the silane coupler that contains the NCO end group and micromolecular polyalcohol or amine reaction.Introducing contains active end group-OH in the performed polymer of end NCO group, the silane coupler of-NH2, or in the performed polymer of end OH, add the silane coupler that contains the NCO group, the performed polymer of synthetic end siloxy group.Or make oligomer with silane coupler and the oligomeric isocyanate reaction of end amido and join in the prepolymer of end NCO as curing agent.Such as with 66 parts of the product of 100 parts of isocyanate terminated performed polymers, 100 parts of carbon blacks, polycaprolactam trihydroxylic alcohol and end NCO base substituted propyl trihydroxy methyl silane, and HDI110 part makes oligomer and joins in the prepolymer of end NCO as curing agent.Above-mentioned isocyanate terminated performed polymer can be by 500 parts of PPOX dihydroxylic alcohols, 750 parts of PPOX trihydroxylic alcohols and 4, and 4 '-benzhydryl vulcabond makes for 214 parts.

BOPA can select nylon BOPA6 or nylon BOPA66.Nylon BOPA6 or nylon BOPA66 are to be the rete of master's nylon resin matrix formation with PA6 or PA66.Contain enhancing, increasing tougheness nylon obturator or plasticizer intermingling material in the nylon resin matrix of said BOPA and form graft copolymer; The toughening nylon agent that wherein adds in the nylon resin is the grafting elastomer, and the elastomeric addition of this grafting is 3wt%-18wt%.The toughening nylon agent mainly comprises: with maleic anhydride grafted polyethylene and ethylene propylene diene rubber is the macromolecular coupling agent of interfacial compatibilizer, mineral and glass fibre filled nylon; Nano-calcium carbonate (n-CaCO_3) particle, nano-calcium carbonate, epoxy resin, N-butylbenzenesulfonamide, silane surface conditioning agent, POE or EPDM.

Nylon resin with polyamide PA6 or PA66 is raw material; By weight percentage; In 80%-97% (wt) nylon resin and 3wt%-20wt% nylon obturator or plasticizer, value is filled in the nylon matrix arbitrarily, and blend forms graft copolymer; Adopt aqua-solution method, directly be sent to nylon factory with saline solution and carry out polycondensation.The PA66 technological process is adopted usually: PA66 resin drying-raw material mixing-extruding pelletization-injection moulding is drawn a design-check and analysis.Process conditions: extrusion temperature 250--280 ℃, 300 rev/mins of screw speeds, injection temperature 230-260 ℃.

The enhancing that contains in the above-mentioned nylon resin matrix, increasing tougheness nylon obturator or plasticizer can be that the toughening nylon agent that adds in the nylon resin is the grafting elastomer, the elastomeric addition of grafting can be in the 3wt%-20wt% scope value arbitrarily.

Preferably, the elastomeric addition of grafting can be in the 6wt%-18wt% scope value arbitrarily.The intervention of the elastomer particles of different modulus not only makes the PA-6 material become two phase structure, and makes its crystallization behavior that change take place.

The toughening nylon agent mainly comprises: with maleic anhydride grafted polyethylene and ethylene propylene diene rubber is the macromolecular coupling agent of interfacial compatibilizer, mineral and glass fibre filled nylon; Nano-calcium carbonate (n-CaCO_3) particle, nano-calcium carbonate, epoxy resin, N-butylbenzenesulfonamide, silane surface conditioning agent, POE or EPDM any.

(n-CaCO_3) particle-filled polyamide-6 not only has heterogeneous nucleation agent effect, and can cause the new crystal formation of PA-6 generation.The result shows that inorganic nano-particle is prone to disperse in the bigger PA-6 of matrix viscosity, is difficult for reuniting, and the degree that is uniformly dispersed height, toughening effect is stronger.Suitably increase loading within the specific limits, can lure more how high molecular orientation movement more fully into, the fracture strength of PA-6 is reduced and the elongation at break increase, be of value to the malleableize of PA-6.The melt of compound system is a pseudoplastic fluid, and its apparent viscosity increases with the increase of n-CaCO_3 loading, reduces along with the increase of shear rate, and simultaneously, apparent viscosity has temperature dependency, and melt viscosity reduces along with the raising of probe temperature.With the elastic body toughening modification PA-6 of the different modulus with two phase structure, the result shows: the size of phase farmland size is very approaching with distribution.The toughening effect of low modulus elastomer is good slightly.The epoxy chain extender can carry out chain extending reaction to nylon in extruder, and epoxy resin is higher to the chain extending reaction activity of nylon 1010, and the chain extension effect is apparent in view; N-butylbenzenesulfonamide is the good plasticizer of nylon, through plasticising, after toughness reinforcing nylon pliability behind chain extension is significantly improved.

The silane surface conditioning agent has a lot.Select three kinds of representative silicon, 18 (1989) 4-33-alkane coupling agents for use; Promptly 7 one amino radon propyl-triethoxysilicanes (KH55O) of band are with a glycidol ether time j methoxy silane (KH56O) of epoxy radicals and the r propyl methacrylate base trimethoxy silane (KH57O) of the two keys of band.Carry out surface-treated wollastonite system with KH55O, its hot strength, impact flexibility are all good than other two kinds of surface conditioning agents, and this is because amino and the nylon branch in the KH55O molecular structure gives is used in the structure ending up.Nylon infill system mixed physical performance data in single screw rod and double screw extruder shows; Because the shear effect of double screw extruder is better; The percentage elongation of gained composite, impact strength, notched Izod impact strength are all higher, and particularly unnotched impact strength numerical value is the twice of single screw extrusion machine approximately.This explanation is through double screw extruder composite material mixed homogeneous more.Can reduce the loss of infill system impact strength and notched Izod impact strength with the mineral filler of silane treatment.Be the best with the combination property of wollastonite infill system especially wherein.Fill the nylon compound system of 40% wollastonite (KH55O coupling agent treatment), its hot strength can reach 63.0MPa, and impact strength is 102.4KJ/1TI, and notched Izod impact strength is 12.0KJ/m.

The present embodiment two sided coatings has the aluminium foil barrier layer of adhesive linkage, contains silicon Si, iron Fe, copper Cu, manganese Mn and aluminium Al at least.Aluminium foil is that main chemical compositions is carried out component with aluminium Al, iron Fe, silicon Si, copper Cu, manganese Mn and/or magnesium Mg; Wherein, The content sum of silicon Si:0.09wt%～0.9wt%, iron Fe:0.9wt%～1.5wt%, Fe+Si is 0.99%～2.4% (wt), copper Cu:0.006wt%～0.03wt%, manganese Mn and magnesium Mg:0.04%～0.05% (wt) or manganese Mn:0.03wt%～0.05wt%; Or magnesium Mg:0.005wt%～0.010wt%; Aluminium Al is a surplus, and usually the Fe/Si of Al-Fe-Si alloy ratio is 10.0%～1.67%.Aluminium Al surplus can for 99.0% or more than.By any value of above-mentioned scope.Other adds the alloy micronutrient levels and adds up to little 0.15% (wt).Aluminium foil goes the metal surface greasy dirt to handle and forms the metal passivation layer processing; And the surfaces externally and internally of aluminium foil has one side at least through corona treatment; What be coated with on the surface of bonding extrernal resistance layer is dual-component polyurethane resin glue stick, and what on the surface of bonding internal resistance layer, be coated with is one pack system polyester polyols alcohols adhesive.

The surfaces externally and internally of aluminium foil can a corona, also can the two sides corona.-10 KW can be used three kilowatts or more corona high power foil, the greater the power, the more the ozone generated, and the higher the temperature, to reduce the temperature of the device, the need to install a powerful exhaust system excluded ozone.Utilize high frequency or intermediate frequency high voltage source and ozone concentration can reach the ozone tubular type discharge of 80-120mg/L, produce a kind of corona in the gap of discharge knife rest and blade and discharge, aluminium foil is carried out electron bombardment or electric discharge surface processing; Through discharge; Make the oxygen ionization between the two poles of the earth, produce strong oxidizer ozone high power and be generally 3 kilowatts, peak power is 10 kilowatts; Can make aluminium foil surface form special ozone layer, the alumina foil surface molecular.After adopting the high power corona treatment, at the surface coated Nano titanium dioxide of aluminium foil, nanoscale zinc oxide and calcium carbonate or nanometer grade silica, the aluminium foil top layer forms anti-oxidant, anti-strong acid, the special protection rete of anti-deep-etching.When aluminum foil metal contacts with macromolecule gluing agent nonmetallic materials closely; Metal loses electronics easily, nonmetally obtains electronics easily, so that electronics can be shifted to from metal is nonmetal; Make the both sides, interface produce contact potential; And form electric double layer and produce electrostatic attraction, adhesive is full of the slit or the concavo-convex part on adherend surface, solidifies the back and produces engagement force in the boundary zone.

The base film layer of forming high-obstruction; Can be at following film: polypropylene (PP), chlorinated polypropylene or cast polypropylene (CPP), polyethylene (PE), polyethylene terephthalate (PET), nylon (PA) or aromatic nylon (MXD6), MPE elastomer blend, polyvinylidene chloride (PVDC), ethylene-vinyl alcohol copolymer (EVOH), PEN (PEN); Any two kinds of film combinations in the GT film; Such as: can select PP and CPP, PP and PE, PET and CPP, PA and CPP, BOPP and MPE elastomer blend, PVDC and PEN, EVOH and PA or MXD6; EVOH and PEN; GT and CPP, films such as GT and sarin resin are combined into the high-barrier base film layer in twos, and perhaps above-mentioned any three kinds of film combinations are compound to be one deck substrate film.On the EVA thin film based tunic of forming by above-mentioned two kinds of films or three kinds of film combinations, all can be coated with the water-fast modified PVA coated film of high-barrier.Above-mentioned various film can also adopt methods such as blend, coating surface, surface coated, MULTILAYER COMPOSITE, stretch orientation further to strengthen barrier as the case may be.Behind the water-fast modified PVA film of coating high-barrier, the version of said base film layer can be the high-isolation film of specific (special) requirements such as BOPP/ modified PVA/PE, BOPA/ modified PVA/PE, modified PVA/PE, PET/ modified PVA/PE, modified PVA/CPP, BOPA/ modified PVA/CPP, PET/ modified PVA/CPP, BOPP/ modified PVA/MPE, BIOET/ modified PVA/MPE, BOPE/MPE, BOPET/MPE.

PVA is a kind of water-soluble poly zoarium that contains hydroxyl, and why not water-fast polyvinyl alcohol is, is because it has hydrophilic hydroxyl (OH), if can hydroxyl suitably be sealed, connects the resistance to water group, just can improve the resistance to water of PVA film.It is base-material that modified PVA can adopt polyvinyl alcohol (PVA), with nano silicon it is carried out modification, also can through add plasticizer, filler, solvation, gel, precipitating reagent, antifoaming agent, wetting agent etc. do not carry out modification.

Plasticizer mainly is water miscible acid amides or the amino organic compound that has hydroxyl, like glycerine, ethylene glycol, formamide, moisture etc.

Filler mainly adopts fillers such as starch, dextrin, casein, urea, water soluble amino formaldehyde resin or phenolic resins and clay, calcium carbonate.Purpose is to reduce product cost and improve some performance.

Solvation not.Add not that PVA to be lost behind the solvation water-soluble, improve the resistance to water of PVA film or coating.Commonly used is the water-soluble amine formaldehyde condensation products, like dimethyl urea, trimethyl melamine, dimethyl ethyl urea, dialdehyde, multivalent metal salt or complex compound; Metallic compound mainly contains bichromate, chromic nitrate etc.Gel.The purpose that adds gel is to control PVA solution to many also internal penetrations of property material, prevents the sagging of dip-coating.Its principal item has: two kinds of dyestuff and aromatic hydroxy compound (resorcinol, catechol, resorcinol, gallic acid, 2,4 dihydroxy-benzoic acids etc.) and inorganic complex.The former can form the reversible gel of heat, and the latter forms heat-staple gel.Borax is very effective PVA gel, and forms irreversible gel.Precipitating reagent sodium carbonate is the precipitating reagent that is used for precipitating PVA in the PVA aqueous solution.Sodium sulphate and potassium sulfate can use under quite low concentration.Antifoaming agent mainly adopts Tributyl phosphate salt, polyglycol ether etc., and purpose is to reduce the foam of PVA solution, addition is the 0.1%-0.5% of PVA solution.Any wetting agent of wetting agent can use as the wetting agent of PVA solution, and its consumption is 0.05%-0.2%.Pigment and dyestuff mainly contain clay, chalk powder, titanium white, calcium sulfate etc., but will add the dispersant-sodium pyrophosphate of amount of pigment 30%, to promote to disperse and reduce viscosity.Other lithopone, zinc oxide, carbon black, antimony oxide and iron oxide and finely divided silica also can use.

Modified PVA also can be selected a kind of condensation polymer to the human non-toxic side effect for use; Carry out molecule crosslinked like the OH among melamine resin modification liquid and the PVA; Under the little situation of addition, just can hand over sign with the hydroxyl appropriateness among the PVA, make PVA form a kind of tough three-dimensional structure coating; Stablize the air-tightness under the PVA hygrometric state condition, improve water-resistant capacity.

PVA glue after the modification, skinning not at normal temperatures, normal temperature is joined glue, the normal temperature coating.The modified PVA coating process: can be directly in the coating of film surfaces such as PE, BOPP, BOPA, BOPET, formation modified PVA/PE, modified PVA/BOPP are coated with composite membrane.Can also further be processed into BOPP/ modified PVA/PE film with the modified PVA coating is compound.Technological process: PE uncoiling → modified PVA coating → drying → rolling → slaking → cut → check → put in storage.

Described GT film is to be base material with the PET film, a kind of high barrier transparent packaging film that forms at its surface deposition SiOx steam (being called for short the GT film).Wherein the production technology of SiOx Coating Materials and method mainly contain two kinds of physical vapor deposition and chemical vapor deposition methods.

Physical vapor deposition is under high vacuum, to make raw material with silicon monoxide (SiO), makes it distillation through heat, and through controlling the import volume of oxygen, forms the different SiOx thin layer of x value on plastic film substrates such as PET, OPPL, LDPE, BON surface.

The physical vapor deposition heating has multiple mode.A kind of is to use the resistance wire mode of heating, generally uses the silicon monoxide raw material of sheet; Another kind method is to adopt the great-power electronic rifle to launch strong electron beam, and electron beam is concentrated the bombardment silicon monoxide a bit, and moment produces high temperature, makes it distillation, and then is deposited on the base material.

The chemical vapor deposition method is that the silane of mellitene diether (HMDSO), tetramethyl disilane organo-silicon compound such as (TMDSO) or gaseous state with liquid state is raw material, in vacuum chamber, feeds helium and the oxygen or the nitrous oxide (N that play oxidation as carrier ₂O), make particle ionization, activation with frequency electromagnetic waves (generally adopting 13.56MHz) or microwave (generally adopting 2.45GHz), the form with SiOx is deposited on the plastic film substrate surface then.Because utilize the activation of plasma gas,, this kind method strengthens vapour deposition method or plasma chemical vapor deposition so being also referred to as plasma gas.Also can, be raw material with mellitene two silicon ethers, adopt frequency electromagnetic waves high-temperature plasma method.

In order further to improve the barrier property of product; Also have a kind of two step chemical methods; This method is a raw material with organo-silicon compound such as mellitene diether; Make the evaporation particle plasma with the low-temperature plasma method, on plastic basis material, be formed with the film of organic silicon compound, and then it is oxidized into Si oxide.The Si oxide laminar surface is more bright and clean, can make barrier property improve about 1 times.

In these two kinds of methods, the required vacuum of physical vapor deposition is higher, is 10-2～10-3Pa, and temperature is higher, and coating layer thickness can reach 40～50nm, and color is pale yellow, and utilization rate of raw materials is about 25%, and the speed of present this technology can reach 500m/min; The required vacuum of chemical vapor deposition method is about 2Pa, coating layer thickness 15～30nm, and bright transparent, utilization rate of raw materials is more than or equal to 5%, and barrier property is higher than physical vapor deposition, and speed of production is slower, can only reach 90～300m/min.

Chemical action between plastic film substrate and the SiOx rete normally at the formation-Si-O-C-at the interface of rete and base material and-Si-N-C-, thereby forms stable chemical bond.So the active atomic oxygen on plastic basis material surface, the content of nitrogen have determined the density that this chemical bond forms, and have influence on the adhesive strength between base material and the SiOx film material, have changed the barrier property of material.

The preliminary treatment on plastic film substrate surface.The raising of SiOx Coating Materials barrier property depends on the improvement of substrate surface performance, so film must carry out preliminary treatment before vapor deposition production, promptly to macromolecule material surface modification.Generally adopt corona discharge, spark discharge, low-voltage direct glow discharge, microwave plasma gas etc. aborning.Electron energy in the corona discharge can reach 10eV; In time less than 0.1s; Can form one deck oxide layer as thin as a wafer at film surface, promptly, oxygen, nitrogen-atoms and functional group thereof introduced film surface through the reaction of multiple complicacies such as crosslinked, ozonisation, hydroxylating, carboxylated, nitration.The chemical composition on surface and the change of structure can make the adhesion between rete and the base material strengthen greatly.

Connected mode between plastic film substrate and the rete.Generally bonding in two ways between base material and the SiOx rete, i.e. suction-operated and chemical bond effect.Suction-operated comes from the body surface ability, and two kinds of object surfaces are bonding each other, and its trend is the total surface ability that reduces the two, thereby produces suction-operated.Suction-operated has two kinds, i.e. physical absorption and chemisorbed.Physical absorption is irreversible, under certain condition can desorption, i.e. desorption; Chemisorbed is irreversible, and its adsorption strength is bigger.The chemical bond effect is to produce powerful bond strength through chemical reaction takes place between molecule, the atom.

Bonding between SiOx Coating Materials and the plastic film substrate includes above-mentioned two kinds of combinations, but along with the difference of process conditions, substrate surface performance, its main bonding way also changes thereupon.For commaterial, general physisorption is occupied an leading position in physical vapor deposition, and along with the difference of the surface property of material, the chemical bond effect also has variation in various degree.Strengthen the chemical vapor deposition method for plasma gas, join with suitable surface treatment, can make chemical bond effect dominates status, thereby improve its adhesive strength and barrier property greatly.

Selected aborning after production technology, base material, the preprocess method, the concrete controlled condition parameter in the production process also has direct influence to properties of product.

The rete degree that oxygen feeding speed, vapor deposition time and power are controlled in the shape of the power of the temperature of the height of vacuum, base material, electron gun, raw material (SiO), the vacuum chamber in physical vapor deposition technology all can influence the performance of final products.The electron gun need of work is vacuum as much as possible, and vacuum is high more to be beneficial to electron gun work more; The temperature control of base material is high more, is beneficial to hydatogenesis more and becomes fine and close film, improves adhesive strength; Electron gun bombards the block SiO material of appropriate to the occasion employing, and pulverous material can be applicable to the resistance wire evaporation process, because the bombardment of electron gun will make the dusty material sputter; The feeding speed of oxygen can be controlled the content of the oxygen element in the SiOx rete; Usually the value of x is controlled at 1.5～1.8 among the SiOx; Barrier property reduces along with the increase of x value; The color of the rete water white transparency more that becomes along with the increase of x simultaneously, barrier property is the poorest when the x value reaches 2, but rete is colourless fully.When the thickness of vapor deposition rete was lower than 50nm, along with the increase of thickness, the barrier property of Coating Materials significantly increased, and the barrier property that surpasses the 50nm rear film remains unchanged basically.

In chemical vapor deposition; The selection of frequency electromagnetic waves or microwave frequency is according to particle energy in the plasma gas and deposition material ionization energy needed matching principle; Frequency electromagnetic waves is generally 13.56MHz; The frequency of microwave is 2.45GHz, and vacuum can obtain excellent results about 2Pa.

Because through the film that SiOx handles, the surface has fabulous wetability, therefore in producing the GT thin-film process, want careful processing list surface layer, it is very important that coating is sustained damage.Generally speaking, 40～45dym/cm compares with the common PET film, and it can reach 70～72dyn/cm.Wherein adhesive is the most desirable with the polyurethanes adhesive.

Yet, plating SiOx film unlike aluminizer such easy extrude with polyethylene compound because with this film of PET film as base material; When its SiOx surface directly is coated with or compound tense with polyethylene high temperature; Be prone to trend towards elongation, thereby destroy the SiOx superficial layer, cause barrier property to descend.Simultaneously, under present circumstances, because the problem on the technical matters, the PET film is curled in plating SiOx process sometimes, thereby influences the quality of this film.It is conspicuous that but the PECVD technology is made the advance of SiOx coating packaging material technology.The oxygen resistance of SiOx/PET composite membrane that like coating thickness is 40nm is higher 100 times than the PET film that is not coated with SiOx, and moisture barrier property is high 40～50 times.Owing to can apply continuously, its linear velocity can change in the scope of 90～300m/min.Factors such as low temperature, low vacuum operation descend the coating cost greatly, and simultaneously, coating is extremely thin, and combines very firmly with the PET material.

Plating silastomer film is to be base material with the plastic sheeting, uses the method for vacuum coating above that, plates the silicon oxide film that a layer thickness is tens nanometers.This layer Si oxide is non-crystal SiO ₂This layer Si oxide is very thin, and the transparency is fine, with the bonding extremely jail of plastic sheeting, so the boiling resistance and the bending resistance folding endurance of plating silastomer film are all good.Silicon oxide film is very thin, and microwave can see through with being absorbed hardly.Film is very fine and close, and resistance oxygen, moisture barrier property are all very good, makes plating silastomer film all be superior to the plastic foil of aluminizing.

The aluminium oxide evaporated film is the plastic sheeting of the high gas barrier property of producing in recent years, has excellent gas barrier property, and is very good to the gas barrier property of oxygen and steam; Temperature tolerance is good, the serviceability temperature wide ranges, and can see through electromagnetic wave; Outstanding resistance to acids and bases; The good transparency; Non-environmental-pollution, discarded back is recyclable, and incineration residue is few, and is very little for the transmitance of oxygen and steam, is good passing through property of the transparency high film of balance gas barrier property of generally acknowledging at present.

In the above-described embodiments, PA membrane laminated film, polyamide are a kind of important barrier materials of multilayer complex films, and it and polyolefin are compound.The structure of making PA6 nanocomposite films nano complexes material can be divided into two types: sandwich type and sheet stratotype.Sandwich type is through inserting the composite that each layer of people's silicon salt centre can obtain the multilayer phase clamping structure of marshalling to the macromolecular chain of single stretching, extension; In lamella or laminated devices composite; Coincide between each layer and also can separate, and single silicate layer is to disperse to exist in polymeric matrix.Polymer/silicate nanometer composite material can be made by the multiple polymers material.Nano material is used for film, can make material have very high intensity and gas barrier property, has prolonged the evolving path, has slowed down diffusion velocity, has just improved gas barrier property.The heat resisting temperature of material also increases significantly simultaneously.Nano combined PA6 film compare with pure PA6 have high strength, high-modulus, high-fire resistance, high gas barrier property, and processing and forming and environmental protection conformability, particularly gas barrier property, hot strength and heat distortion temperature are greatly improved.

The special nylon of MxD6 is semi-crystalline polymer by the polycondensation of m-xylene diamine and adipic acid, and its hear resistance is high, and water absorption rate is very low; Dimensional stability is good, and the high strength barrier has good high gas barrier property and puncture resistance; Have outstanding gas barrier property, and its gas barrier property is not with the increase Er Shi of humidity.PET/MXD6 polyester co-extrusion can obtain nano composite material.

The EVOH composite membrane has the barrier properties for gases of poly workability and polyvinyl alcohol concurrently, and performance depends on the content of ethene, and ethylene contents increases, and barrier properties for gases descends, but the processing characteristics of resin improves.EVOH has good barrier properties for gases; The excellent transparency, glossiness, mechanical strength, retractility, wearability, cold resistance and surface strength are arranged, excellent antistatic behaviour is particularly arranged.The film that EVOH is processed is as the intermediate interlayer of composite membrane,

Because PVDC is a kind of crystalline polymer, the processing of PVDC film is difficulty relatively.In process, the time that film at high temperature exposes is long more, and percent crystallization in massecuite is high more; And the glass transition temperature of PVDC is lower than normal temperature, even also crystalline polamer might take place at normal temperatures.Add man-hour PVDC in addition and always have a bit and decompose, the chloride of generation has certain influence to equipment.In order to improve the production method Using P VDC laminated film of PVDC film.The PVDC laminated film combines the excellent properties of multiple material.PVDC laminated film barrier property is excellent, and is all very low to the transmitance of all gases, and especially gas barrier properties is excellent under the condition of humidity, oil resistant, chemical-resistant resistance, anti-boiling, and PVDC composite membrane barrier property is good, and anti-110 ℃ of hot water.PVDC can obtain compound PVDC film with synthetic resin such as PE, PP are multi-layer co-extruded.This composite membrane tensile property is good.Composite membrane or sheet material that PVDC and PE, PVC etc. make, good barrier property.PVDC also can latex form apply and do on other film, process composite membrane.Coating at the PVDC latex improves a lot barrier property; The coating consumption of PVDC seldom, and the process technology of PVDC composite membrane than the process technology difficulty of pure PVDC film with require lowly, good environmental protection can reclaim granulation and make injection moulding usefulness, is a kind of good high barrier packaging film.PVDC is considered to the safety non-toxic material, meets the FDA standard; It is irrelevant to have confirmed that PVDC burns with the generation dioxin.The content of PVDC is about 10% in the PVDC co-extrusion film, compares with EVOH, PVA and PA co-extrusion film, and better vapor barrier property ability is arranged, and the high barrier of oxygen is not received humidity effect.

Functional layer after the base film layer can be to be made up of monocrystal or EVA after propylene and the ethene modification, also can be propylene and ethene semi-crystalline co-polymers cast polypropylene film and/or BOPP film.Basic unit is the layer base material that directly contacts with aluminium foil, and the intermediate layer is a functional layer, and bottom is thermal synthesis layer (being substrate layer/functional layer/thermal synthesis layer).Functional layer is between base film layer and hot sealing layer, and is bonding each other through heat-seal adhesive between each layer.Heat-seal adhesive can be a polyester polyols alcohols adhesive.The alcohols gluing of polyester polyols is to have anti-strong acid-base, and the glue of high corrosion and anti-organic solvent and high volatile volatile material is like EVA or A Dema (maleic acid bar) or modified POE resin.

Hot sealing layer is polybutene (PB-1) TM metallocene PE (mPE) and/or POE film, can also be modified polypropene (PP), i.e. TM metallocene PE (mPE) or title ^TMMPE and POE film can be chosen one of which wantonly, perhaps both and deposit.POE has good resilience and pliability, and its hardness is very low, and cold resistance is splendid, so the POE elastomer is widely used in the toughness reinforcing of PP, improves the normal temperature of PP and the impact strength under the low temperature.

^TMMPE is a kind of novel metallocene PE; Has long-chain branch component (LCB) and narrow component distribution (CD); LDPE is a primary monolayer, and the TM metallocene PE is multi-layer co-extruded, LDPE-major ingredient (75%LDPE+25%LLDPE) LLDPE-major ingredient (25%LDPE+75%LLDPE).Mainly by the balance quality decision of single resin property or compounding resin, be mainly LDPE/LLDPE compounding (75: 25)-LDPE: base resin is used to provide melt strength, shrinkage and raising extrusion capacity-LLDPE to film performance: be used to provide toughness, anti-pore-creating character, sealing intensity and puncture resistance.Mixing material (for example, 75%LDPE-25%C4LLDPE).Add alhpa olefin among the 75%LLDPE/25%LDPE (like the 1-butylene; 1-hexene and 1-octene) to polymeric chain, introduce short-chain branch (SCB), very little to melt rheology influence, significantly change crystallization, solid-state structure and respective performances; Long-chain branch (LCB) refers to that a chain length surpasses about 250 carbon atoms; Melt rheology, shearing and tensile viscosity there are considerable influence, very little to the crystallization influence, the crystallization that the shearing in the appreciable impact film production process causes and the generation of orientation; Even bubble stability also can keep high level under higher temperature, even and than melt fracture also be difficult for to take place under the low processing temperature.Has heat-sealing faster, the sticking scope of heat that production operation is wideer, excellent heat seal strength, not lost heat sealing property.Experiment showed, metallocene PE ( ^TMMPE) vertical yield tensile strength＞35 (MPa); Longitudinal fracture hot strength＞350Mpa; Horizontal Elmendorf tear strength＞4000 (g) creep-resistant property＞1.3kg50C5hr (%); Vertical Elmendorf tear strength＞1200 (g), the sticking intensity＞25N/30mm of heat, puncture power 150N-1100N.

VERSIFY plastic body and elastomer are the special propylene-ethylene copolymers that is used for the new series of flexible package.It has adopted revolutionary catalyst technology, is the breakthrough achievement of propylene and ethene combination technology.Propylene-ethylene copolymers (VERSIFY) plastic body and elastomeric has comprised polyfunctional implication.Utilize its unique modulus, heat sealability and splendid optical characteristics.Cast polypropylene film, the propylene-based elastomeric in the BOPP film (VERSIFY), plastic body and elastomer are made up of a series of multiduty olefin polymers, and therein ethylene content is 9%～16%, has the excellent balance of various performances.Adopt revolutionary catalyst technology and liquid phase method explained hereafter propylene-ethylene bond, can produce the comonomer distribution that to make surely of narrow molecular-weight.Its uniformity makes VERSIFY plastic body and elastomer have physics and mechanical property excellent and that can fully predict.Because the height balance of modulus and excellent optical property.

Attractive instance comprised during VERSIFY plastic body and elastomer were used: the hot sealing layer of Biaially oriented polypropylene (BOPP) hot sealing layer, composite membrane, co-extrusion PP film and calendering and extrusion molding flexible film and sheet material.Distribute through its wide degree of crystallinity.

Explanation of nouns: EVOH: (EVAL) ethylene-vinyl alcohol copolymer, PA6-666: polyamide (nylon), MXD6: aramid, the inclined to one side polymers of m-xylene diamine and adipic acid; PVDC: polyvinylidene chloride, PAN: polypropylene is fine, PEN: poly-naphthalene dicarboxylic acid glycol ester, PET: polyethylene terephthalate; PP: polypropylene, PE: polyethylene, HDPE: high density polyethylene (HDPE), LDPE low density polyethylene (LDPE); The LLDPE LLDPE, MLLDPE: metallocene linear-low density polyethylene, IONOMER: iolon, EVA: ethane-acetic acid ethyenyl resin copolymer; The TIE titanium, resin binder, AC: polymine.

Claims (11)

1. polymer Li-ion battery core external packing moulding material; Comprise that the multi-layer co-extruded THIN COMPOSITE rete that extrernal resistance layer, barrier layer and high-obstruction laminated body are formed is characterized in that; Described extrernal resistance layer laminate body is by one deck heat-resistant resin film: PET, BOPA at least; PEN chooses one of which wantonly, perhaps wherein both and deposit that coextru-lamination constitutes, the aluminium foil in the said barrier layer laminated body contains the Fe that content is 0.9wt%～1.5wt% at least; Described high-obstruction laminated body comprises basic unit, functional layer and hot sealing layer; Said basic unit is by polypropylene (PP), chlorinated polypropylene or cast polypropylene (CPP), polyethylene (PE), polyethylene terephthalate (PET), nylon (PA) or aromatic nylon (MXD6), MPE elastomer blend; Polyvinylidene chloride (PVDC), ethylene-vinyl alcohol copolymer (EVOH); PEN (PEN); At least two kinds of film substrates combination in the high barrier transparent packaging film (GT) or the EVA film of compound composition in twos all are coated with the water-fast modified polyvinylalcohol of high-barrier (PVA) coated film on said EVA film substrate.

2. polymer Li-ion battery core external packing moulding material as claimed in claim 1; It is characterized in that; The heat-resistant resin film that constitutes extrernal resistance layer laminate body is; Wherein at least a of polyethylene terephthalate (PET), nylon (BOPA), PEN (PEN), wherein thin with the PEN/PET copolyesters, contain 0.1% (mass fraction)～0.4% (mass fraction) SiO ₂Grain; And carry out ester exchange reaction synthetic intermediate 2 through naphthalene diformic acid dimethyl ester (NDC) and ethylene glycol (EG); 6-(ethylene naphthalate) (BHEN); And BHEN content is 8% (molar fraction), and what on the medial surface of above-mentioned heat-resistant resin film, be coated with is dual-component polyurethane resin glue stick.

3. polymer Li-ion battery core external packing moulding material as claimed in claim 1; It is characterized in that; Described dual-component polyurethane resin glue stick is made up of two kinds of components; First component (A) is that the polyethers of polyester and isocyanates/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 epoxide number is 0.25～0.45 the glycidol ether based epoxy resin and the composition 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 adhesive emulsion by mass ratio.

4. polymer Li-ion battery core external packing moulding material as claimed in claim 3 is characterized in that, the auxiliary agent of said adding comprises hydrolysis stabilizer, long-chain biatomic acid and at least a in dihydroxylic alcohols and the organo-silicon coupling agent of side chain arranged; Described glycidol ether based epoxy resin is the many epoxy resin of phenolic aldehyde that formed by linear phenol-aldehyde resin and epoxychloropropane polycondensation; Described coupling agent is an organo-silicon coupling agent.

5. polymer Li-ion battery core external packing moulding material as claimed in claim 1; It is characterized in that; Aluminium foil in the said barrier layer laminated body contains silicon Si, iron Fe, copper Cu, manganese Mn and aluminium Al at least, and the Fe/Si ratio is 10.0%～1.67%, and the surfaces externally and internally of aluminium foil has one side at least through corona treatment; What be coated with on the surface of bonding extrernal resistance layer is dual-component polyurethane resin glue stick, and what on the surface of bonding internal resistance layer, be coated with is polyester polyols alcohols adhesive.

6. polymer Li-ion battery core external packing moulding material as claimed in claim 1 is characterized in that, is furnished with Nano titanium dioxide, nanoscale zinc oxide, nanoscale SiO in the surfaces coated of aluminium foil ₂And at least a top layer in the calcium carbonate form anti-oxidant, anti-strong acid, the protective film of anti-deep-etching.

7. polymer Li-ion battery core external packing moulding material as claimed in claim 1; It is characterized in that; Said functional layer in the described high-obstruction laminated body is to be made up of monocrystal or EVA after propylene and the ethene modification; Said hot sealing layer is by polybutene (PB-1), TM metallocene PE (mPE) and/or POE, or modified polypropene (PP) film formation.

8. polymer Li-ion battery core external packing moulding material as claimed in claim 1 is characterized in that, described GT film is to be base material with the PET film, a kind of high barrier transparent packaging film that forms at its surface deposition SiOx steam.

9. polymer Li-ion battery core external packing moulding material as claimed in claim 1; It is characterized in that; What be coated with on the surface of the bonding extrernal resistance layer of said barrier layer is dual-component polyurethane resin glue stick, and what be coated with on the surface of bonding said high-obstruction laminated body is one pack system polyester polyols alcohols adhesive.

10. polymer Li-ion battery core external packing moulding material as claimed in claim 1; It is characterized in that; Contain propylene-based elastomeric (VERSIFY) in the said cast polypropylene film BOPP film, this VERSIFY is made up of a series of olefin polymers, and therein ethylene content is 9%～16%.

11. polymer Li-ion battery core external packing moulding material as claimed in claim 8 is characterized in that the value of x is 1.5～1.8 in said SiOx.