CN104379805A

CN104379805A - Deposition of ultra-thin inorganic oxide coatings on packaging

Info

Publication number: CN104379805A
Application number: CN201380033270.6A
Authority: CN
Inventors: 罗伯特·戈德弗瓦; 格伦·乔丹; 安东尼·罗伯特·克诺尔泽; 肯尼思·斯科特·拉弗杜里; 埃尔德里奇·M.·芒特
Original assignee: Frito Lay North America Inc
Current assignee: Frito Lay North America Inc
Priority date: 2012-06-23
Filing date: 2013-06-21
Publication date: 2015-02-25
Also published as: WO2013192560A2; US20130340673A1; MX2014015675A; CA2872318A1; WO2013192560A3; BR112014029940A2

Abstract

An apparatus and method for depositing an ultra-thin inorganic coating on to a packaging film substrate is disclosed. Flame pretreatment enhances the quality of the inorganic coating. Multiple coating layers may be deposited onto the substrate by passing the substrate over various one or more flame head configurations in either a stand-alone or in-line manufacturing environment.

Description

Ultra-thin inorganic oxide coating deposition on the packaging

Background of invention

Description of Related Art

In the occasion needing to possess favourable obstruct, the characteristic such as sealing and impression ability, often can adopt the multi-layer type package base be made up of petroleum chemicals, polymkeric substance, multipolymer, biological polymer and/or paper structure.Barrier property in the one or more layers comprising package base is important, to protect product in packaging from the invasion and attack of illumination, oxygen and/or moisture.Just there is this demand in the protection of such as food, if do not have enough barrier properties to prevent Transmission light, oxygen or moisture from entering or packaging of overflowing, these food just have generation loss of flavor, spoiled or rotten risk.Also may need impression ability, to enable human consumer identify its product that will buy fast, this also provides means for food manufacturer, to indicate the information such as the such as interior food nutrition content of packaging, and have such as, to be placed to product works as pricing information, barcode.

In package food article industry, protection food embodies in many aspects from the importance of moisture and oxygen impact, comprises health, security and Consumer acceptance's (i.e. retaining food product freshness and taste) etc.Protect the ordinary method of in-built food to be included in special-purpose coat on the inner or surface of package base or thin layer, it is as the barrier that cannot permeate, and stops propagation and the migration of light, water, water vapour, liquid and foreign matter.Be stored in the level of the barrier property required for quality of the product in wrapping body according to protection, these coatings can be made up of co-extrusion polymkeric substance (such as ethyl vinyl alcohol (ethyl vinylalcohol), polyvinyl alcohol, polyimide, polymeric amide (i.e. nylon and polyvinyl acetate)) and/or the thin layer of metal or metal oxide.

It is known that the coating generated by chemical vapour deposition the substrate accompanying by it can provide certain barrier properties.Such as, the organic coating such as decolorizing carbon can stop the propagation comprising the compositions such as water, oxygen and carbonic acid gas.Correspondingly, there is people that carbon coating is applied to substrate, such as polymeric film, to improve the barrier properties that substrate presents.Another is applied in substrate, in order to improve the example of the coating of barrier adhesion property is the coating be made up of inorganic materials such as such as inorganic, metal oxides.Ethylene-vinyl alcohol copolymer and other polymeric surface layers are widely used in film substrate primer coating or improve its wetting properties, and to apply a barrier layer, this barrier layer is in this article also referred to as " metallization priming paint ".Metallic aluminium, aluminum oxide and silicon oxide are widely used in directly applying barrier layer in substrate, thisly operate in herein also referred to as " metallization ".

Above-mentioned inorganic coating by various deposition techniques known in the art in substrate.These technology comprise physical vapor deposition (PVD) or chemical vapour deposition (CVD) technique.The example of PVD comprises ion beam sputtering and thermal evaporation.The example of CVD comprises glow discharge, combustion chemical vapor deposition (CCVD) and by generating the plasma enhanced chemical vapor deposition (PECVD) that flame plasma or the mode that is placed in highfield are carried out.

When metallizing, for the most known of deposited barrier layers in package base and method requirement employing vacuum chamber of the most often using, for the deposition of inorganic atoms/ion on film substrate surface provides vacuum environment.This known technology used at food packaging industry comprises: in vacuum metallization processes chamber to width being less than between 1m to 3m, length between 500 to 150,000m, industry park plan speed is that the package base of 60-600m/min and higher travelling speed involves in row processing.This device height is specialized, needs a large amount of electricity consumption, and will have very large capital outlay.At present for thin film metallized vacuum chamber technique inefficiency in many aspects, this be due to higher running cost and with this type of device-dependent limited throughput of use.In addition, for obtaining required barrier property, usually must adopt the film substrate of better quality, this just requires extra fund expenditure.

Combustion chemical vapor deposition (CCVD) and plasma enhanced chemical vapor deposition (PECVD) apparatus and method are known in the art, as 5, and 997,996 and 7, disclosed in 351, No. 449 United States Patent (USP)s, its disclosure is by reference to being merged in herein.Usually, environment required for the required coating of deposition (steam or gas by burning or plasma generation) is provided in substrate by combustion flame or argon-arc plasma field.Key element precursor (such as organometallic compound) can be vapor permeability, or is dissolved in and also can serves as in the solvent of explosive fuel.Then, deposition that is organic and inorganic oxide can be carried out under standard and/or open atmosphere pressure and temperature, and does not need vacuum chamber, smelting furnace and/or pressure chamber.

As mentioned above, need to apply barrier layer to food product pack, to protect food and food article from the impact of moisture and oxygen.Water vapour and oxygen will be made to reduce about 3 orders of magnitude to the penetration of film special it is well known that to metallize based on the polyolefine of oil to OPP or PET etc. in the industry.The inorganic layer of what routine techniques adopted is metal on particular polymers film or pottery.Inorganic layer can be aluminium, silicon, zinc or exist with metal or oxide form other needed for element.But, it scribbles priming paint usually by the substrate surface being applied in barrier layer, to improve its surface energy, with be convenient to receive will be deposited thereon metal barrier, and/or carry out " smoothly " process to needing metallized surface, need the planometer change degree of metallized film or surfaceness to reduce." wetting properties " one word be defined as in this article comprise surface energy, metal adhesion intensity and other anyly improve the correlation properties of thin-film surface to the receiving degree of inorganic superthin layer deposition described herein.

Such as, the low surface energy plastics such as such as Biaxially oriented polypropylene film (BOPP) (BOPP) film adopt metallic aluminium as barrier layer, require metallization priming paint to reduce the thickness deviation on film substrate surface, and/or the sticking power improved between metal and film substrate or bonding force.Existing number of chemical method is used to apply priming paint to substrate surface layer, to improve substrate surface and/or to improve the bonding force of metal barrier and film substrate.For polymer film base, method substrate being applied for metallized priming paint is coextrusion specialty polymer, as the top layer on substrate film.These top layers may comprise ethyl vinyl alcohol (EVOH), polyvinyl alcohol (PVOH), and polyvinyl acetate (PVA), ethylene-vinyl acetate (EVA), polyethylene terephthalate glycol (PETG), amorphous polyethylene terephthalate (aPET), and other polymkeric substance of industrial use.Unfortunately, these materials are quite expensive, can to the production of metallized film increasing extra cost.Plastics film core, such as oriented polypropylene (OPP), polystyrene (PS) and polyethylene terephthalate (PET), will adopt corona discharge or flame to process usually.But, these process are tending towards producing the negative impact of not wishing to produce to film substrate characteristic, such as form the chemical degradation that surface occurs because of chain rupture in crosslinked or molecule for pin hole, surface, these impacts can have a negative impact to follow-up metallization and hot sealing process.

Thus, need a kind of apparatus and method of improvement, for depositing a ultra-thin inorganic oxide layer in package base, to be applied for metallized priming paint to substrate.Similarly, this area also needs a kind of apparatus and method of improvement, for depositing multiple ultra-thin inorganic oxide layer in package base, to strengthen package base barrier property, described apparatus and method are more cheap and have higher efficiency than traditional metallization, can realize again and keep high-quality barrier properties simultaneously.

Technical field

The present invention relates to a kind of key element layer in package base and the method and apparatus for applying key element layer.More specifically, invention disclosed herein relates to a kind of ultra-thin inorganic metal oxide, when it is applied to package base, as oxygen and vapor water barriers layer and/or the interface being used as follow-up functionalization.This layer can be formed in the production of package base, also in the process segment after this, can generate by using known chemical vapor deposition unit and method in commercial package base manufacturing environment.

Summary of the invention

Innovative embodiments disclosed herein comprises and a kind ofly has the package base of ultra-thin barrier layer and apply the apparatus and method of ultra-thin inorganic, metal oxide barrier layer on a thin film substrate.In one embodiment, apparatus and method disclosed herein adopt the mode of the liquid containing precursor or reactant, gas and/or steam being carried out to directly burning, and described precursor or reactant can be created in open atmosphere the inorganic oxide deposited on film substrate surface.Precursor, such as tetraethyl orthosilicate, tetramethyl disiloxane, silicon tetrachloride, silane, trimethyl aluminium, triethyl aluminum, methylaluminum dichloride-ether, trimethyl aluminium-ether, ethyl aluminum dichloride-ether, dimethylamino diethyl aluminum-, aluminum chloride and other aluminum halides, can spray in oxygenant or be atomized, and burnt by one or more flame front, produce steam and/or gas, described steam and/or gas are directed to substrate surface by one or more flame front, for forming required coating or multiple coating thereon.By making substrate pass system in unit or inline process type manufacturing environment, or by making the mode of substrate above one or more different flame fronts configuration in unit as herein described or inline process type manufacturing environment, substrate deposits multiple coating.

One embodiment of the present of invention comprise a kind of package base, and it has the inorganic metal oxide that thickness is less than 50nm on the surface, and these series of strata are by being formed in the mode of the multiple inorganic, metal oxide superthin layer of the surface deposition of package base.In various embodiments, can package base complete on the surface inorganic oxide layer deposition selection process be CCVD or PECVD in open atmosphere, it will adopt novel flame front component design and direction, to realize and to adjust deposition various precursor concentration on a thin film substrate and coat-thickness.

In one embodiment of the invention, a kind of method applying at least one deck inorganic oxide layer on a thin film substrate comprises carries out pre-treatment to described substrate, described pre-treatment is make described substrate through at least one the flame treating flame front assembly not being provided precursors of inorganic oxides, after described pre-treatment step, by making described substrate through the mode of the one or more deposition flame fronts at least one deposition flame front assembly, wherein at least one deposition flame front assembly is provided with at least one precursors of inorganic oxides, deposit one or more inorganic oxide layer on the substrate, wherein said pre-treatment and deposition step carry out in open atmosphere.

In another embodiment, at least one precursors of inorganic oxides comprises at least one in tetraethoxy, tetramethyl disiloxane, silicon tetrachloride, silane, trimethyl aluminium, triethyl aluminum, methylaluminum dichloride-ether, trimethyl aluminium-ether, ethyl aluminum dichloride-ether, dimethylamino diethyl aluminum (diethylaluminium-dimethylamide), aluminum chloride and aluminum halide.

In one embodiment, pre-treatment step makes described substrate through the top of a part at least one cooling roller.In another embodiment, pre-treatment step makes described substrate through the top of a part for multiple cooling roller.The temperature of cooling roller can between 40 DEG C to 80 DEG C.

In one embodiment, deposition step makes described substrate continue to pass through two or more deposition flame fronts, deposits multiple inorganic oxide layer on the substrate thus.In another embodiment, pre-treatment and deposition step launch in described film substrate from a volume and carry out in the process of rolling up to another.In the production of described film substrate, pre-treatment and deposition step can onlinely carry out.

In one embodiment, by spraying the mode of cooling fluid in described film substrate, the cooling of film substrate in described pre-treatment step is realized.

In one embodiment of the invention, a kind of system for coating inorganic oxide skin in packaging film substrate comprises the flame treating flame front assembly that at least one is not provided precursors of inorganic oxides, described flame front assembly is provided with the one or more deposition flame fronts being provided with at least one precursors of inorganic oxides be arranged in order at least one deposition flame front assembly, wherein said substrate is first through described flame treating flame front assembly, described substrate is subsequently again through described deposition flame front assembly, and at least one flame treating flame front assembly wherein said and described one or more deposition flame front are in open atmosphere.

In another embodiment, at least one flame treating flame front assembly or at least one deposition flame front assembly described comprise with the multiple flame front assemblies arranged perpendicular to basement movement direction parallel rows.

In one embodiment, at least one flame treating flame front assembly or at least one deposition flame front assembly described comprise square or rectangle flame front assembly.In another embodiment, at least one flame treating flame front assembly or at least one deposition flame front assembly described comprise being parallel to the multiple flame front assemblies in a row arranged in basement movement direction.In another embodiment, at least one flame treating flame front assembly or at least one deposition flame front assembly described comprise bending flame front assembly.

In one embodiment, at least one flame treating flame front assembly or at least one deposition flame front assembly described be oriented to relative to described substrate surface at angle.In another embodiment, substrate its by above a part at least one cooling roller described time, through described flame front assembly.

In one embodiment, inorganic precursor is first admitted to the flame furl pipe of described deposition flame front, subsequently with the air mixed from blast main, and in the burning of described flame front place, or be first admitted to the blast main of described deposition flame front, subsequently with the fuel mix from fuel tube, and in the burning of described flame front place, or be first admitted to blast main and the fuel tube of described deposition flame front, mixed at described flame front place subsequently and burn, or after mixing with air/fuel mixture, then be sent to described deposition flame front.In another embodiment, inorganic precursor is injected in the flame that described deposition flame front produces.

Innovative embodiments as herein described can realize in the stand-alone configuration transformed based on existing film line, also can be installed in the manufacture of inline process type film substrate and/or system of processing.Base material to be coated does not need heating or process in smelting furnace or reaction chamber, deposits under not needing to be placed in vacuum or non-standard atmospheric condition to realize coating yet.The heat that burning produces provides the condition needed for precursor reaction.Coated base material is heated by combustion flame too, and it produces and/or enhance the dynamic environment that surface reaction, wetting properties, diffusion, film (coating) forming core and film (coating) grow.Precursor used needs to have suitable activity, to generate required coating.Although inorganic, metal oxide is the preferred material of the coating being applied to package base, also other simple substance coating and compounds can be adopted as required, such as metal, nitride, carbide and carbonate.

By following detailed description of the present invention, and by reference to the accompanying drawings, can obviously know other aspects of the present invention, embodiment and feature.Accompanying drawing is illustrative nature, not draws in proportion.For the purpose of distinct, those skilled in the art can be made to understand place of the present invention without the need to illustrating, not in every width figure, indicating each assembly, also not each assembly of each embodiment of the present invention illustrated all in the drawings.All be incorporated to herein by reference to entirety by reference to all patent applications and patent that are incorporated to this paper.In the situation where there is a conflict, should be as the criterion with this specification sheets comprising definition.

Brief Description Of Drawings

The features of novelty being regarded as feature of the present invention is set forth in the following claims.But, when reading by reference to the accompanying drawings, by referring to the following detailed description to example embodiment, better understanding can be had to the present invention itself and preferred use-pattern, more objects and advantage.Wherein:

Figure 1 shows that a cross-sectional view typically adopting the food product packing film substrate of prior art;

Fig. 2 A-2I shows the various embodiments of the apparatus and method adopted in the present invention disclosed herein;

Fig. 3 A-3E shows and to be integrated into inline process type package base according to one embodiment of the present of invention disclosed herein and to manufacture and apparatus and method in processing units;

Fig. 4 shows according to one embodiment of the present of invention disclosed herein, the cross-sectional view with the film substrate of multiple coated with nano layer;

Fig. 5 A-5I shows the embodiment of the various devices that can adopt in the present invention disclosed herein;

Fig. 6 shows in the one single deposition stroke of silicon-dioxide, by the graphic representation of the amount of determined the deposited silicon-dioxide of strength of signal formed by the information collected by XPS;

Fig. 7 shows strength of signal (CPS) in Multiple through then out stroke and the combination that draws from XPS can graph of a relation between (eV);

Fig. 8 shows the atomic percent of the Siliciumatom on film surface, WVTR and OTR value and the silica deposit graph of a relation by the number of times of stroke.

Embodiment Figure 1 shows that one typically, at present by the example cross-section of the food packaging multilayer that uses or laminated film substrate 10.Film 10 is made up of multiple middle layer, and these middle layers synergy is to make film 10 possess desired properties feature.Such as, graph layer 14 makes figure be printed or deposited thereon, and provides protection by the transparent outside basic unit 12 that may be made up of oriented polypropylene (OPP) or polyethylene terephthalate (PET).Be generally the tackiness agent of polyethylene extrusion or laminate layers 16 for outside basic unit 12 being bonded together with the basic unit 18 of inner product side.Method for metallising known in the art depositing metal layers on inner base layer 18 can be adopted.Sealant layer 20 is deposited on OPP or PET inner base layer 18, to realize forming gas-tight seal at the temperature in the temperature of fusion lower than inner basic unit 18.Described each layer is all formed a volume film, and film rolling is unfolded subsequently, and is again laminated on together, to generate laminated film.Each film is laminated on and generates laminated film together, and laminated film is when being extruded at first or make, the membrane structure formed by multiple layers.

Other the alternative materials used in packaging film substrate generative process may comprise the biofilms such as polyester, polyolefin extrusions, cellulose polymer compound, cellulose acetate polymkeric substance, adhesive coating compressing tablet, such as poly(lactic acid) (PLA) film and polyhydroxyalkanoate (PHA) film, these materials are produced with various array mode, thus obtain the multilayer film structure of compound.Film substrate is formed by typical coextrusion as known in the art, lamination or extruding coating technology.Film substrate also can be made up of polyimide, liquid crystal, polyethylene or the other materials usually used in electronics, optics or specialized package or multilayer are applied.

In PECVD and CCVD technique as herein described, the local environment realized needed for coating deposition is provided by flame, plasma body or other energy mode.Adopting CCVD and PECVD, without the need to using smelting furnace, boosting or reaction chamber, reaction being occurred.In addition, CCVD and PECVD also can carry out under open atmosphere condition.The kinetic energy of material that plasma body or flame occur and the form of radiation provide the energy needed for coating deposition.This energy is that forming reactions material creates suitable thermal environment, heats substrate simultaneously, thus for occurring that surface reaction, diffusion, nucleation and growth provide dynamic condition.When using combustible solution, solvent plays two kinds of effects.First, coating reaction thing feeding will carry out, near the substrate of coating deposition, can using the use of low cost soluble precursor thus by solvent.Only need the concentration of reactant in change solution and solution flow rate easily can realize the even conveying of any reactant dosage.Secondly, the burning of solvent can produce the flame needed for CCVD and PECVD.

Generally speaking, depositing operation as herein described carries out under tying up to the envrionment conditions of open atmosphere, to generate inorganic thin film in a substrate.Film is preferably amorphous, but also can be polycrystalline, specifically depends on reactant and mode of deposition.Reactant or have chemically active compound to be dissolved or be carried in a solvent, solvent is generally liguid organic solvent, such as alkene, aikylide or ethanol.The solution formed to be sprayed as propelling gas by oxygen-rich air and is lighted from a nozzle.Substrate be placed in flame end or its near.Use the heating units such as such as pilot lamp can prevent flame blow-off situation.Reactant burns in flame, and the ion that burning produces or atomic group are deposited as coating in substrate.For the present invention, the formation of inorganic oxide layer and sedimentation velocity are important for formed coating quality, and the various embodiment of the equipment and process to this type of quality coating of formation and example are introduced by the present invention disclosed herein.

Be provide the lower and method that efficiency is higher of energy-intensive degree for the surface treatment of the film substrate of various application occasions for performing the method and apparatus of innovative approach disclosed herein.Such as, usually need to be applied for metallized priming paint to substrate, to strengthen the wetting properties needed for substrate surface receiving metal layer.As previously mentioned, the existing method being applied for metallized priming paint to substrate needs applied by coextrusion or with the solution of the chemical additives such as such as EVOH and/or add top layer by the mode of flame or Corona discharge Treatment before metallization usually.Apparatus and method as herein described provide an innovative approach, this method is usually by increasing inorganic bottom nanometer layer, make the surface energy of film substrate improve 1 to 10 dyne, strengthen the wetting properties of substrate surface thus, thus strengthen the adhesivity be deposited between metal barrier coat and substrate.

It is equally important that inorganic oxide layer also wants to realize the vapor deposition of follow-up barrier layer, the printing or the adhesion layer that enable to put on film substrate adhere to well, and heat-seal process still will play a role by expection.A composition aspect of the present invention comprises film substrate applying inorganic oxide layer, to improve the surface wettability of substrate surface, for follow-up application.

By using different inorganic materials, extra character can be produced, to improve the use of film under various application scenario.Such as, silver is used can to provide antibacterial or sterilization character.In other embodiments, can adopt can the inorganics of shielding of ultraviolet radiation, comprises and can use zinc oxide and tin-oxide, to form transparent UV-light and gas-barrier layer.Other transparent materials, such as silicon-dioxide, can be used for being formed and/or serving as ultra-thin barrier layer.

The economic traits based on of product of polymkeric substance is crucial are adopted to be to keep low cost.Consequently, the inorganic materials as nanolayered coating is selected usually from low cost inorganic elements.Equally, the problem for the healthy aspect generating the material of packaging film is also extremely important, because polymeric film is most commonly used to comprise in the consuming product of food and medical package.Therefore, to healthy and safe material, such as, based on the inorganics of silicon-dioxide, can use in various embodiments.Silicon-dioxide is modal oxide compound in the earth's crust of the earth and soil, deposits medium as in health of human body requirement is safe and efficient, and the long-term storage in Glass Containers has had extensively and through the history of checking.

In thin film fabrication, adopt current surface modification material can form the significant volume and weight part of the finished product, thus reduce its returnability.Present invention substantially reduces the material for the formation of required obstruct thickness, make the returnability of product and/or compostability higher.In one embodiment, the thickness of inorganic oxide layer is less than 10nm usually, and preferred situation is that mean thickness is less than 5nm.Because the thickness of this layer is little, inorganic oxide layer can more easily be broken for less fragment, makes the grade of recyclable material higher.In fact, silicon-dioxide through being often used as the enhancement additive of polymkeric substance, to improve intensity and weather resistance.One embodiment of the present of invention comprise a kind of inorganic oxide layer, and it can make the globality physical properties of thin film based polymkeric substance, and compared with the reprocessing to clean polymkeric substance, change is less than 1%.

Such as, for biodegradable polymkeric substance, PLA and PHA, being applied to may in the degradable ability of the expectation of the wrapping material formed by it that in fact detract containing the barrier layer in the film substrate of PLA and/or PHA or other biological polymkeric substance.This barrier layer can reduce moisture or oxygen through, this can affect the degradation process of film packaging.Multiple barrier layer can form non-degradable packaging, because core film base material (all there is barrier layer both sides) always can not be exposed in the environment being suitable for decomposing.One embodiment of the present of invention comprise a kind of inorganic oxide coating of formation, this coating itself does not provide the barrier that cannot permeate, but enable follow-up printing, adhesion layer or high quality barrier layer in online production environment or subsequent downstream equipment, be deposited on this inorganic oxide coating.In one embodiment, inorganic oxide layer can be deposited on the two sides of package base, for the final application of multiple conception.

One of critical applications of smooth inorganic superthin layer will form barrier layer thereon subsequently.Thin film metallized or oxide barrier layers can attach better and implement on the smooth surface that defect is less.Polymeric film can form this surface easily aborning, and the mode of the interpolation anti-hard caking agent of this area use at present can cause the roughness of film surface and defect to increase, and its surface Root Mean Square roughness (RMS) is usually more than 100nm.A critical aspects of the present invention be the surface Root Mean Square roughness of the package base making formation lower than 30nm, more preferably situation is lower than 10nm, is then less than 5nm especially in some cases.

In another embodiment, the present invention disclosed herein can keep lower surface roughness rms, simultaneously control surface humidifying character.Surface tension can be controlled jointly by the terminal material on the surfaceness of inorganic superthin layer and surface.For improving the adhesivity of inorganic barrier layer material and substrate, substrate surface preferably should be able to receive metal or inorganic oxide ionic bonding or covalent bonding.Inorganic oxide surface can be metal and oxide skin provides outstanding bonding place, provides the top coat that smooth simultaneously.Have been found that smooth surface can contribute to barrier layer in suprabasil generation.For barrier layer deposition applications occasion, substrate surface to be coated preferably should have be surface that is smooth, low texture in nanometer and micron dimension.

The key point that success applies this type of interfacial layer was formed in substrate before the winding or winding of film and applies priming paint and barrier layer.Film is made by kinds of processes, comprises injection moulding and film blowing.These techniques are carried out usually under ambient atmosphere and pressure, in large-scale production line.This type of production line adopt the vacuum sediment equipment of prior art these techniques will be made infeasible economically.Therefore, under normal pressure, on low-temperature polymer, the online method with the film of inorganic superthin layer that formed is the better approach obtaining this innovative superthin layer.How to adopt the techniques such as such as CCVD to realize the problem of this object open in 5,652, No. 021 United States Patent (USP) people such as () Hunt and 5,863, No. 604 United States Patent (USP)s people such as () Hunt, its disclosure is by reference to being incorporated herein.

In order to form effective barrier layer in follow-up processing, film substrate surface smooth very important.Thin-film barrier requires that substrate surface is smooth, does not have to block or to stop thin-film material to be deposited to feature on the overwhelming majority on whole surface.Preferable case is, the substrate surface of at least 90% is coated, and more preferably vaporizing material can be coated on the surface more than 99%, and does not have to cause to block or the surface irregularity situation of film defects.It is equally important that inorganic bottom enamelled coating wants unusual light, the densification of the additional inorganic oxide layer it can not being affected be deposited thereon, evenly and continuous print growth, to form effective thin-film barrier layers.Columnar growth on inorganic bottom enamelled coating will have a negative impact to the growth of the thin-film barrier layers that follow-up vacuum deposited layer or other are applied on it.Final effect is, first deposits in the substrate of inorganic bottom enamelled coating before deposited barrier layers, and the growth of follow-up barrier layer can obtain and be less than 10cc/m under 23 DEG C and 0% relative humidity ²the OTR oxygen transmission rate (OTR) in/sky and be less than 2g/m under 38 DEG C and 90% relative humidity ²the water vapor transmission rate (WVTR) (WVTR) in/sky, preferred index is OTR<2cc/m under 23 DEG C and 0% relative humidity ²/ sky, WVTR<1g/m under 38 DEG C and 90% relative humidity ²/ sky, preferred index is OTR<1cc/m under 23 DEG C and 0% relative humidity ²/ sky, WVTR<0.2g/m under 38 DEG C and 90% relative humidity ²/ sky.In one embodiment, priming paint and/or barrier layer are to the optical transparency in visible spectrum.In alternate embodiments, for enabling coated substrate effectively use in flexible package or the final application of other conceptions, follow-up priming paint and/or barrier layer can be translucent or opaque.

Owing to decreasing the quantity of the organic chemicals be mixed in polymer film base, environmental influence also can be down to minimum by the present invention, and obtains safer wrapping material.Examples of such additives may cause health problem, or can reduce the quality of recyclable material.Silicon oxide, aluminum oxide and other principles of the present invention are very common in the earth's crust, and through being commonly used for foodstuff additive, by for many years safely for Glass Containers.Thus, the inorganic materials rich reserves that the present invention disclosed herein adopts, nontoxic, substantially unharmful environmental influence.

By applying one or more ultra-thin inorganic oxide layer as herein described, the multi-layer packaging substrate possessing outstanding adhesion characteristics can be produced.In various embodiments, moisture, oxygen and light can penetrate inorganic oxide layer, and the structured polymer film of compost still can be decomposed under common envrionment conditions.By suitably selecting metalloid or metallic element, such as silicon or aluminium, inorganic oxide coating can be formed and can not stop film substrate compost and reach minimum shallow layer to environmental influence.

In an embodiment disclosed herein, in open atmosphere environment, adopt a PECVD or CCVD device to deposit one or more superthin layers of one or more Si oxide (SiOx) and/or other inorganic oxides on the surface of the substrate, improve substrate surface energy thus, and improve the adhesivity of metal barrier and substrate, effectively to substrate " applying priming paint ", to metallize.In an embodiment disclosed herein, PECVD or CCVD device and a package base production line " inline process type " integrated, for substrate winding before to its apply metallization priming paint.

Various embodiment of the present invention disclosed herein also comprises the apparatus and method for applying barrier layer in open atmosphere on the surface of package base.Apparatus and method disclosed herein achieve the direct burning of liquid and/or steam, contain the precursor or reactant that will deposit in open atmosphere on substrate material surface in described liquid and/or steam.The metal oxides such as aluminum oxide are formed by the burning of the materials such as such as organo-aluminium compound and oxygenant, and burn in open atmosphere, and form steam and/or gas, described steam and/or gas are directed to substrate surface, realize required coating deposition thereon.

According to one embodiment of the present of invention disclosed herein, Fig. 2 A shows a flame CCVD device, and it is provided with flammable precursor, for inorganic oxide coating is deposited to substrate.The effect of this system is the drop in combustion zone, precursor being broken for micron order and submicron order, to apply ultra-thin coating processes as herein described.

Going to Fig. 2 A, being wherein depicted as the general illustration of the device 40 for performing coating depositing operation.Precursor 42 may comprise solvent-reactant solution that flammable or non-combustible solvent and liquid, steam or gas reactant mix, and it is sent to flame front assembly 44 or other produce the device of flames.Term " flame front assembly " is generally used for referring to describe any device that can be produced flame by feed fuel, comprises flame treating device, flame-thrower nozzle and flame front device as herein described, and can buy from Duo Jia manufacturers.Precursor 42 is lighted when oxygenant 46 exists, and forms flame 48.When precursor 42 solution or mixture burns, reactant reacts, and forms Inorganic Vapor, leaves flame 48 and other hot gas 50 and combustion prodes.Want coated substrate 52 to be positioned near flame 48, be in the region of gas 50.In one embodiment, substrate 52 is positioned in the tangential direction of flame 48, or as shown in Figure 2 B, it is directed that substrate 52 favours flame 48, or at any angle in the face of the flame end 54 of flame 48, make the hot gas 50 containing reactant steam can touch substrate surface 56 to be coated.In various embodiments, substrate 52 may be made up of film or laminated film, containing known at the bottom of the oriented polypropylene (OPP) of form existence alone or in combination, polyethylene (PE), poly(lactic acid) (PLA), polyhydroxyalkanoate (PHA), polyethylene terephthalate (PETP), other polyester or other known polymkeric substance, biological polymer, papery or other cellulosic baseds in the prior art in it.

Device in Fig. 2 B and Fig. 2 A shown device 40 similar, but it is configured to for non-turbulent flow flame method, is applicable to the precursor comprising gaseous precursors 42 and non-combustible carrier soln 46.The flame characteristics that the flame 48 produced by flame front assembly 44a possesses usually is, internal flame 48a limits reduction zone, the most of oxidizing gas provided together with reactant burns at this, flame envelope 48b then limits oxidation zone, and any oxidizing gas in the fuel and air of this surplus is oxidized at this.In this example embodiment, substrate is oriented to closely face with the flame end 54 of angle of inclination and flame 48, makes the hot gas containing reactant steam and/or steam 50 can contact the substrate surface 56 of substrate 52.

Again see Fig. 2 A, precursor mixture 46 is sent to flame front assembly 44.Oxygenant 46 also delivers to flame front assembly 44 by independent transfer lime in some manner, or be present in processing atmosphere, or oxygenant may be delivered to processing atmosphere or flame ignition point by independent transfer lime, or oxygenant may be present in reaction-ure mixture.In the illustrated embodiment, chemical precursor solution 42 is lighted when there being oxygenant 46 to exist, and burns in flame 48, causes generating heat, the generation of gas and/or steam 50.Any liquid reactants solution evaporation that heating can make this place exist, and improve the temperature of substrate 52, to make the surface diffusion situation of coating improve, thus obtain the more uniform coating be deposited on substrate surface 56.

When carrying out CCVD or PECVD coating deposition to film substrate, preferably adopt some mode of deposition.First, substrate needs to be positioned in certain region, and it is heated by the hot gas that flame radiation energy and flame produce, fully to realize surface diffusion.This temperature province is present in a distance in the middle part of flame outside flame end.By changing the proportioning of oxygenant and fuel and adding non-active gas to institute's supplied gas or add the mode of non-flammable miscible liquid to supplied solution, to the control that the temperature of flame is carried out to a certain degree.Secondly, the precursor based on metal needs to be vaporized, and chemically changes required state into.For oxide compound, if there is sufficient oxygen, this will occur in flame.The high temperature of flame, radiating capacity (infrared rays, ultraviolet and other radiating capacity) and plasma body also can assist the response capacity of precursor.Finally, for monocrystal thin films, the material be deposited should be in gas phase, is not almost with or without stable particle deposition.By keeping lower strength of solution, and reduce the distance between reactant reaction part and substrate whereabouts to greatest extent, thus its required time is minimized, suppress particle to be formed.These different combined factors can be doped, best deposition region is positioned near flame tip together.If sprayed to solution, the substrate of hypertelorism may be struck flame nearby by drop, and this may form some spray pyrolysis characteristic in formed film.In fact, adopt large drop at some or have in the configuration of some reactant, possibly some spray pyrolysis cannot be made to occur.

In various embodiment of the present invention disclosed herein, plasmatorch also can be adopted to realize similar effect by the mode being similar to flame attachment.Precursor is sprayed by a plasmatorch, and is deposited in substrate.Reactant and other materials fed by plasmatorch are heated, and then heat substrate surface, and type of heating is identical to a great extent with flame embodiment as herein described.In plasma enhanced chemical vapor deposition, the plasma temperature lower than Conventional plasma spray body can be adopted, because need lower heat to make precursor react.Consequently, precursor reaction occurs at a lower temperature, and the substrate enabling fusing point lower thus utilizes pecvd process.Coating comes from suprabasil deposition guides the plasma gas steam containing charged ion into substrate direction.Such as, precursor gaseous mixture or solution are sent in plasma flame, cause forming chemical vapors.Chemical precursor solution may comprise the inorganic, metal oxide such as aluminum oxide or silicon oxide.Once oxidation, generate be substantially in vapor form generate ion and be drawn towards substrate surface, cause and form solid-state coating on the surface of the substrate, its common thickness is in 1 to 50nm scope.

Generally speaking, as long as generate flame, the carrying out of CCVD or PECVD just has nothing to do with flame temperature or substrate surface temperatures.Flame temperature depends on type and the quantity of reactant used, solvent, fuel and oxygenant, and shapes of substrates and material, when possessing the specific reactants for depositing, solvent, fuel, oxygenant and other assemblies and condition, these can be determined by those skilled in the art.Preferred flame temperature near deposition surface on movable wire netting twine about 800 DEG C to 1300 DEG C between.Because flame may be present in a wider pressure range, CCVD can complete under the pressure of about 10torr to about thousands of torr, but preferably carries out under ambient pressure, to make its application on polymeric film machining production line more easy.Similarly, generate if plasma body is deposited coatings, then the temperature range of plasma body can between about 400 DEG C to about 1200 DEG C.The temperature of substrate in CCVD process also may change with required types of coatings, base material and flame characteristics.Generally speaking, for thermally sensitive polymeric film, preferably adopt the substrate surface temperatures of about 40 DEG C to 80 DEG C.

Coating may have very large difference in suprabasil sedimentation velocity, and concrete depended on some of them factor comprises coating quality, coat-thickness, reactant, base material and flame characteristics.Such as, vacation is oriented in the supply rate relative constancy providing precursor of the flame that flame-thrower nozzle place generates, then the open-assembly time increased under the vapour stream that film substrate produces at flame front can make the coating being deposited on film substrate thicker.If at flame-thrower nozzle place to generate the supply rate of flame relatively low, the coating that hole is less can be formed, and if at flame-thrower nozzle place to generate the supply rate of flame relatively high, then can form the coating compared with porous.Equally, if need high-quality coating, may need to take longer open-assembly time under lower precursor supply flow velocity, and adopt higher precursor supply flow velocity, can relative to comparatively fast being formed coarse or having the coating of texture.Those skilled in the art can determine to generate the precursor supply flow velocity needed for desired coating and open-assembly time on a thin film substrate.Adopt typical deposition rate on the product manufactured by apparatus and method disclosed herein within the scope of about 10nm/min to about 1000nm/min, the film surface time be exposed in flame is 0.1 to 10 second.As mentioned above, the chemical precursor solution in an embodiment is the liquid reactants be dissolved in liquid solvent.But also can adopt solid, liquid, steam and gas reactant, use together with liquid or gas-solvent, as long as the precursor delivering to flame place possesses the character of liquid or gas usually.

See Fig. 2 C, there is shown one embodiment of the present of invention disclosed herein, there is shown a kind of flame and turn to source.This flame steering technique adopts and with flame 48 angled air knife 49, the gas in technique and/or steam 50 is turned to.Airflow imports from the vapour stream 50 of flame 48 by air knife 49.Vapour stream 50 can be directed to direction needed for substrate surface 56 effectively again like this, meanwhile, the hot-fluid be associated with flame 48 be turned to, so as not to make the substrate 52 coated by steam 50 overheated or fusing.The heat being directed to substrate 52 made from flame 48 hot-fluid is dissipated by this method, thus realizes the deposition of required coating on substrate surface 56 at a lower temperature.

This flame turns to embodiment also can disperse the gas sent from flame 48 and/or vapour stream 50, forms the wider deposition flow stream 50 on directed toward substrate surface 56, and expands the coated area on it.In an alternative embodiment, can adopt electromagnetism or " electricity turns to " method that the deposition of the ion sent from flame and/or plasma source and/or particle is redirect to substrate surface.In such an embodiment, flame and/or plasma source are at first by ion and/or particle flux and all relevant heats guiding direction substantially parallel with film substrate to be coated.Generate the field with electromotive force by manner known in the art, this is through a part for film substrate, and the ion that flame or plasma source are sent and/or particle flux turn to and/or accelerate, and arrives on film surface.Chemical bond in polymer molecule more easily ruptures, and this can cause the quick formation of free radical.This makes required microthin coating deposit on film surface, and the heat be associated can not be delivered to film surface, thus prevents film substrate contingent fusing in deposition process.

See Fig. 2 D, there is shown the one embodiment of the present of invention disclosed herein adopting many flame fronts system 60.In this embodiment, system 60 comprises flame front assembly 62, and flame front assembly 62 comprises the pipe with spaced apart hole or nozzle for sending flame, and hole or nozzle are called as flame front 64, is formed with pipe entirety.In various embodiments, this type of flame front assembly 62 may comprise the flame head can purchased by the market of New York Flynn Burner Corporation of New Rochelle company manufacture.The precursor 61 that also may comprise oxygenant is sent to flame front assembly 62, when being lighted, makes flame front 64 send flame, forms hot gas and/or steam 66.Substrate 52 to be coated is placed in flame front 64 side, is in the region of hot gas and/or steam 66, makes the hot gas containing reactant steam and/or steam 66 contact substrate surface 56, forms deposited coatings thereon.Owing to making hot gas and/or Steam area 66 expand by the multiple flame source of use, bull flame front depositing system 60 can improve continuity and the thickness of the coating deposition on whole substrate surface 56.Show system 60 in figure 2d, wherein flame front assembly 62 aligns with the multiple flame fronts being positioned at a plane and/or linear direction.But, also it is conceivable that going out other embodiments, wherein one or more flame front devices can be designed to have the multiple two dimension or 3 dimensional coil geometry that possibility is formed, such as square, rhombus, cylindrical, it can position relative to processed film according to the needs of user, as shown in Fig. 2 E, 2F, 2G, 2H and 2I.In the constructed embodiment that these are substituting, one or multiple precursor can be provided, to select flame front in single flame front assembly, user be changed be deposited on the type of suprabasil coating, characteristic and thickness.Can see easily in these figures, by apparatus and method as herein described, the shape of single flame front and flame front assembly and can be configured to realize the microthin coating of dissimilar, concentration and/or thickness in suprabasil deposition relative to the direction of substrate.

Such as, Fig. 2 E discloses with the multiple flame front assemblies 68 arranged perpendicular to the direction of motion parallel rows of package base 52.By arranging the direction of flame front assembly 68 in this way, can along shown substrate 52 direct of travel once by stroke, substrate 52 deposits multiple coating.In one embodiment, various concentration, precursor concentration variable gradient or different types of precursor can be sent to each single flame front assembly 68, or be sent in each single flame front that is integrated in each flame front assembly 68, deposit to types of coatings in substrate 52 and/or coating concentration and/or coat-thickness to change.In one embodiment, one or more flame front assembly 68 sends flame, to be primed to film substrate 52 by flame treating.By after flame treating flame front assembly, substrate runs into that location is posterior may be provided with one or more flame front assemblies 68 of one or multiple different precursor, according to the needs of user, the substrate 52 through flame treating to apply microthin coating.

Fig. 2 F discloses a bending-type flame front assembly 70, its can its above a part for cooling roller 72 time in substrate 52 depositing ultrathin inorganic oxide layer, and by arrange niproll 74, make it keep relative with cooling roller 72 and contact.In one embodiment, the variable gradient of various concentration, precursor concentration or different types of precursor can be sent to bending-type flame front assembly 70, or be sent to each single flame front be integrated in bending-type flame front assembly 70, deposit to types of coatings in substrate 52 and/or coating concentration and/or coat-thickness to change.

Fig. 2 G shows a square or rectangle flame front assembly 76, and it can deposit a ultra-thin inorganic oxide layer in substrate 52.In one embodiment, various concentration, precursor concentration variable gradient or different types of precursor can be sent to flame front assembly 76, or be sent to each single flame front be integrated in flame front assembly 76, deposit to types of coatings in substrate 52 and/or coating concentration and/or coat-thickness to change.

Fig. 2 H discloses and is integrated in flame front assembly 68, to be parallel to multiple flame fronts of the layout in a row of package base 52 direct of travel.In one embodiment, various concentration, precursor concentration variable gradient or different types of precursor can be sent to each single flame front assembly 68, or be sent to each single flame front be integrated in each flame front assembly 68, deposit to types of coatings in substrate 52 and/or coating concentration and/or coat-thickness to change.

Go to Fig. 2 I, one embodiment of the present of invention disclosed herein show a kind of relative to substrate 52 surface flame front assembly 78 at angle.In this configuration, in substrate 52 along when being parallel to the longitudinal motion of flame front assembly 78, one end of flame front assembly 78 is more close to substrate surface.In one embodiment, the D score end of flame front assembly 78 is placed in roughly 20mm place, substrate 52 surface, for carrying out pre-treatment to substrate 52, because it can provide more concentrated thermal treatment when substrate 52 is sent near flame front assembly 78, and by for removing dirt, dust and other pollutents that substrate surface may exist.Along with the motion of substrate 52, flame front assembly 78 " on " end is placed in roughly 40mm place, substrate 52 surface, due to substrate 52 surface and the increase of the spacing of flame front assembly 78, thus the more low intensive thermal treatment that formation is applied in substrate 52.Thus, the precursor of various concentration can be sent into, so that select can part or all of residue flame front in flame front assembly 78, make, when substrate 52 is moved along the length direction of flame front assembly 78, to form the differentiation coating of inorganic oxide layer on the surface in substrate 52.In one embodiment, part is contacted at first with substrate 52 surface in flamelplasma, flame front assembly 78 is positioned in the distance surperficial 2mm place of substrate 52, and flame front assembly 78 one-tenth one location, angle of inclination, to form the distance of 4mm between last flame front in substrate 52 and flame front assembly 78, as shown in FIG..In alternative embodiments, flame front assembly 78 is oriented to the direction perpendicular to substrate 52 or tilts at an angle along a radial arc relative to substrate 52 direction, to realize the deposition of required flame pre-treatment or the diversified organic oxidation nitride layer in substrate 52.

These configurations and shape can be increased in the film surface area that film substrate is exposed to flame in the once-through stroke of burner.Then, these geometric configuration can increase the residence time of flame or plasma body and film substrate surface contact, thus change the coating performance giving film substrate.Therefore, embodiment as herein described is not intended to be limited to disclosure herein.

Go to Fig. 3 A, an embodiment of CCVD and/or PECVD coating unit as herein described be shown in a typical production environment reel with a Reel-to-reel type/coating unit 80 " online " arranges.In the embodiment shown, film 88 launches from roller 96 by unwind unit 86, and film 88 is then wound up on winding core 94 by winder unit 84.The flame chamber 82 that inside accommodates CCVD and/or PECVD coating unit 92 described herein is online integrated with unwinding/winder unit 86 and 84.Flame chamber 82 forms a non-pressurised enclosed space, at least accommodates a CCVD and/or PECVD flame front assembly 92, to guarantee the safety of user and surrounding devices and material in it.In uncoiling/winding process, film substrate 88 is extracted out from unwinder unit 86 via multiple roller, and delivers on cylinder 90.In receiving coating after walking out from flame chamber 82, film substrate 88 is reeled by around winding core 94.Cylinder 90 rotates, the hot gas that winding and/or traction substrate 88 produce close to flame front assembly 92 and/or steam.In the embodiment shown, cylinder 90 is placed in above flame front assembly 92, to increase the hot gas of the rising produced by flame front assembly 92 and/or the contact area between steam and surface to greatest extent, thus the coated material entrained by hot gas and/or steam is deposited in substrate 88 expeditiously.In the embodiment of various conception, cylinder 90 may comprise a temperature control roller or " cooling roller ", with the temperature making substrate have heat, and form difference between the heat produced in substrate 88 to be coated and flame front assembly 92, it contributes to employing and applies in the substrate of low melting point according to innovative approach disclosed herein and device, and does not cause pyrolytic damage to substrate.In the embodiment shown in fig. 3b, multiple flame attachment 82 is online integrated, to provide multiple coating to substrate 88.In this configuration, according to the needs of user and configuration, each flame front assembly 82 platform can apply the different ultra-thin inorganic coating of multiple type, concentration and/or thickness possibility to substrate.

With reference to Fig. 3 A and 3B and not by theoretical limitation, have been found that, in order to form thicker settled layer, substrate film is made repeatedly to adopt the mode of lower concentration precursor through flame treatment system or through multiple flame front and/or flame front assembly, pass with making substrate single and adopt compared with high concentration of precursor flame treatment system, higher-quality deposited coatings (namely have better coating to cover uniformity coefficient on the surface of the substrate, the rootmean-square slickness of institute's deposited coatings is higher) can be realized.In an example embodiment, a free-standing volume to volume coating machine is equipped with single afterburner plasma flame treatment system.A flammable inorganic precursor, tetraethoxy (TEOS), adopts instrument measurement, sends in flow in fuel with in check speed.Be unfolded along with film and pass through above plasma flame, the silicon-dioxide of lower concentration level is deposited on the surface of film substrate.The data presentation of collecting, SiO ₂deposition quality in TEOS concentration higher than poor when 22mg/min, when TEOS concentration is lower than 11mg/min, SiO ₂deposition quality is assessed as well, and when TEOS concentration level is lower than 2mg/min, SiO ₂deposition quality is rated as outstanding.Along with film is repeatedly through being provided with above the plasma flame of lower concentration TEOS, multilayer SiO ₂be deposited in film substrate, making it to form thickness is the barrier layer of 50nm, shows as OTR<10cc/m ²/ sky, WVTR<0.5g/m ²/ sky.

Metallization priming paint technique as herein described can during thin film fabrication (" inline process type ") or carry out afterwards.Inline process type film surface finished product are usually clean, do not have pollutent, make it thus to be applicable to primer surface process, and this stems from the problem of the maintenance film surface cleaning existed after manufacturing processed completes.Such as, the additive in dust, anti-clogging plug particle or polymeric film may in environment after fabrication " diffusion " on the surface of film substrate.These situations may make at film manufactured and be difficult to obtain uniform primer coating in priming paint coating processes that is that carry out after depositing for some time.The additive of diffusion also may move on inorganic nano layer, because itself is not barrier layer, therefore in film, does not preferably have these additives.

Go to Fig. 3 C, one embodiment of the present of invention disclosed herein are illustrated, one of them flame CCVD or PECVD unit and the online installation of biaxial films substrate production line 100.In the embodiment shown, biaxial films substrate 102 is formed by extruding unit 104.Film substrate 102 is through cooling unit 106 subsequently, and is laterally being stretched in machine (longitudinal direction) direction, in cross directional stretch unit 110 in machine draw unit 108.Film substrate is through flame front assembly 112 subsequently, is coated with meets inorganic priming paint needed for device described herein and process and/or barrier coat this its.Film substrate through coating is wound into transportable volume subsequently in winder unit 114, for further processing or dispensing.

See Fig. 3 D, it illustrates one embodiment of the present of invention disclosed herein, its Flame CCVD or PECVD applies tower unit 118 and the online installation of biaxial films substrate production line 100 being similar to production line shown in Fig. 3 C.In such an embodiment, multiple flame front assembly 120 is by arranged in series, and when substrate 102 is during once-through system, pass production line through each cooling roller and niproll, each flame front assembly 120 all provides the inorganic precursor of lower concentration.The geometrical shape of flame front assembly, substrate line speed, chill-roll temperature and precursor-type and concentration can be configured, in a variety of contexts to deposit the ultra-thin inorganic coating with required type, concentration and/or thickness in specific package base.Typical processing condition are as follows: line speed is between 200 to 1500ft/min (60m/min to 450m/min); Chill-roll temperature 40 to 80 DEG C; The pretreated burner of flame and film pitch are 5mm, and the fuel of flame treating step and air ratio are the Sweet natural gas flow velocity of 0.90 to 0.95,1m wide production line is 100l/min; In deposition step, burner and film pitch are 5 to 45mm, and fuel and air ratio are the Sweet natural gas flow velocity of the wide production line of 1.0,1m is 70 to 105l/min, and the concentration of precursor is 0.0001 % by mole to 0.01 % by mole (molecular fraction) of air-flow.Plasma temperature presents good result at 1200 DEG C, and temperature range is 650 DEG C to 1450 DEG C.Above-mentioned condition will generate WVTR<0.2g/m ²/ sky, OTR<20cc/m ²the coating in/sky.

Being managed the accumulation of heat produced because being exposed to PECVD or CCVD flame front in substrate is a problem extremely attracted people's attention, because this accumulation of heat will make coated substrate distortion or fusing.As shown here go out with described in disclosed various embodiment, adopt cooling roller technology to dissipate the heat of accumulation in substrate.But due to the size in production environment or space constraint, the quantity obtaining cooling roller diameter needed for specific coating or multiple cooling roller cannot may realize at cost or spatially.Alternatively, when adopt in the environment of limited space meet apparatus and method as herein described substrate is processed time, spray cooling agent can be adopted to the heat of the accumulation in substrate that dissipates.As shown in FIGURE 3 E, one embodiment of the present of invention disclosed herein show " off-line " formula inorganic coating deposition apparatus that can be used for applying the substrate of producing in a different facility.Such as, in one embodiment, the equipment de-sign shown in Fig. 3 E can be included in free-standing processing step at a transmodulator place.In such an embodiment, package base 102 is launched by from withdrawal roller 96, above a series of flame front assembly 82, its using flame processes and/or deposits a microthin coating on the exposed surface of substrate 102, use the exposed surface of spray cooling agent to the opposite side of substrate 102 from coolant jet 130 to cool simultaneously, with heat dissipation, control or prevent degeneration or the fusing of substrate 102.In this embodiment, do not need to adopt cooling roller or other hot applicators to avoid because being exposed to burner 82, obtaining heat input and degeneration or overheated occurring to make substrate 102.The geometrical shape of flame front assembly, substrate flow process speed, refrigerant vapo(u)rizing temperature and precursor concentration can be configured, in a variety of contexts to deposit the microthin coating with desired thickness in specific package base.The technical spray refrigerant that can use in the present embodiment may comprise aromatics, silicon ester (COOLANOL 25R), fatty compounds (PAO), silicone (SYLTHERM XLT) or other materials known in the art.Typical processing condition are as follows: line speed is between 200 to 1500ft/min (60m/min to 450m/min); Chill-roll temperature 40 to 80 DEG C; The pretreated burner of flame and film pitch are 5mm, and the fuel of flame treating step and air ratio are the Sweet natural gas flow velocity of 0.90 to 0.95,1m wide production line is 100l/min; In deposition step, burner and film pitch are 5 to 45mm, and fuel and air ratio are the Sweet natural gas flow velocity of the wide production line of 1.0,1m is 70 to 105l/min, and the concentration of precursor is 0.0001 % by mole of air-flow to 0.01 % by mole.Plasma temperature presents good result at 1200 DEG C, and temperature range is 650 DEG C to 1450 DEG C.Above-mentioned condition will generate WVTR<0.2g/m ²/ sky, OTR<20cc/m ²the coating in/sky.

It should be noted that, the embodiment shown in Fig. 2 A-3E and Fig. 5 A-5I using plasma enhanced chemical vapor deposition (PECVD) apparatus and method can complete coating processes as herein described.Thus, illustrated embodiment is not intended to be limited to flame CCVD method.Use the place of term " flame " or its synonym (as " flame front " or " flame front assembly ") in this article, be understood to include " plasma body " and cognate thereof, and the laser ablation equipment of equivalence.Plasma body can be controlled by the electromagnetic field near plasma source, with the substrate surface that ion guide plasma reaction produced is to be coated.Therefore CCVD is not limited to made product, and a kind of implementation method just for completing the manufacture of described product on film line.As mentioned before, the device disclosed in Fig. 2 A-3E and the alternate embodiments of system can be configured independently carries out flame treating to substrate, when substrate is moved along production line, in open atmosphere, applies primer coating and/or barrier coat to it.

Fig. 4 is the structure diagram of the embodiment that coated substrate 120 is shown.In the embodiment shown, film or paper substrates 122 are coated with silicon-dioxide bottom 124 that is pure or substantially pure.Be coated with the coated additional oxide skin 126 of substrate 122 of silicon dioxide layer 124 and follow-up metal or oxide skin 128 subsequently.Oxide skin 126,128 may be made up of the silicon-dioxide being mixed with additional chemical additive or " doping agent ", for improving the response capacity on the surface 124 being covered with priming paint with additional required coating.In one embodiment, the thickness of the metal barrier deposited by apparatus and method described herein is between 5 to 50nm, and optical density(OD) is more than 30%.Other metals that metal barrier may comprise aluminium, copper, iron, manganese, zinc and/or determine according to customer need.In other embodiments, layer 128 is the oxide skin deposited by CCVD, and layer 128 is the metal level deposited by conventional vacuum metallization technology.

Fig. 5 A-5I is depicted as the various devices in the present invention, and it, in various embodiment of the present invention disclosed herein, can be configured by user as required.Disclosed in Fig. 5 A configuration in, precursor 504 is first sent to flame furl pipeline 502, subsequently again with the air mixed from air line 506, and as shown in the figure flame front 508 place burning.In the configuration shown in Fig. 5 B, precursor 504 is first sent to air line 506, subsequently again with the fuel mix (fuel in the present embodiment is Sweet natural gas) from burning line 502, and as shown in the figure flame front 508 place burning.In configuration disclosed in Fig. 5 C, precursor 504 is first sent in air line 506 and burning line 502, subsequently again in the mixing of fuel/air mixture mixing tank 510 place, and in flame front 508 place burning as shown in the figure.In such an embodiment, different precursors can be adopted, after first delivering to air line and burning line, then mix at fuel/air mixture mixing tank place.In configuration disclosed in Fig. 5 D, at fuel and air constituent after fuel/air mixture mixing tank place mixes, introduce precursor.The mixture formed burns at flame front place as herein described subsequently.In configuration disclosed in Fig. 5 E, one or number of chemical precursor first in the mixing of fuel/air mixture mixing tank place, can introduce additional precursor in downstream subsequently again, then in flame front place burning as shown in the figure.In configuration disclosed in Fig. 5 F, precursor is introduced at fuel and air mixed place.The mixture formed burns at flame front place as herein described subsequently.In configuration disclosed in Fig. 5 G, precursor is injected or be otherwise injected in the existing flame of flame front generation.In configuration disclosed in Fig. 5 H, precursor is in flame front burner combustion as shown in the figure.In configuration disclosed in Fig. 5 I, adopt ablative device 512 to produce steam and/or ionic current 514, steam and/or ionic current 514 are directed to substrate, for implementing coating thereon.In Fig. 5 A-5I the disclosed embodiments, those of ordinary skill in the art should understand, as described herein, pass through in the process near flame front in film substrate with the required degree of approach, various fuel, air and precursor can be adopted, to produce required coating thereon.Various embodiments shown in Fig. 5 A-5I can be integrated into disclosed herein various online with in free-standing film substrate manufacture and processing environment.

For introducing the specific embodiment of innovative device disclosed herein and method, provide following example.After understanding example described herein, apparatus and method disclosed herein should be able to be applied to other chemical depositions by those of ordinary skill in the art, and this type of application is regarded as belonging in scope disclosed herein.Following example is only used as to illustrate, and does not mean that and limited scope of the present invention.In these examples, primer coating adopts CCVD to deposit in open atmosphere environment.Unless otherwise specified outside place, the precursor be made up of the TEOS be in methane-air (precursor concentration) is carried through film flame treating device, and flame temperature is between 800 DEG C to 1200 DEG C.

Example 1 roller coating machine carries out SiO on OPP polymkeric substance ₂deposition

Exemplarily and for comparison purposes, first on the internal surface of volume, flame treating is carried out to the OPP polymer film base of diaxial orientation.The condition of film flame treating comprises: line speed is about 184ft/min, and burner and film distance are about 5mm, and fuel and air ratio are about 1.0.After flame treating step, film second time passes through roller coating machine, with deposited silicon dioxide layer.The mode of deposition of silicon dioxide layer comprises: for flame treating and silica deposit stroke, line speed is about 184ft/min, and burner and film distance are about 5mm, and the concentration that fuel and air ratio are about 1.0, TEOS is about 0.00379 % by mole.

By by the flame treating step before silica treatment, the deposition of silicon-dioxide is improved greatly.This effect is in figure 6 by by being illustrated the information collected by the one single deposition stroke of silicon-dioxide by XPS.In deposited silicon-dioxide, the silica volume determined by strength of signal has the increase of 70%.Be 290 countings (CPS) per second without the pretreated signal of flame place's intensity when peak-peak, and after the flame treatment, the maximum signal of silicon-dioxide once-through stroke is that 500 countings are per second.In other words, the atomic percent of the dioxide-containing silica never pretreated silicon of flame is the atomic percent that 0.18% silicon is increased to silicon is 0.23% silicon.

Pre-treatment is very successful, and make after the pre-treatment of employing flame, multi-layer silica dioxide is deposited.Strength of signal (CPS) from XPS and the relation combining energy (eV) have been shown in Fig. 7.Can clearly find out, each by stroke, silica volume has increase.In the atomic percent of formed silicon, by stroke, 1,2 and 3 deposition of silicon-dioxide show that the atomic percent of silicon is respectively 0.23%, 0.26% and 0.44%.

It is the barrier of deposited silicon dioxide layer to the final decision factor of validity.In this example, aforementioned all samples is all metallized optical density(OD) under standard vacuum metallization condition is 2.3.Atomic percent, WVTR and the OTR value of the Siliciumatom on film surface are shown in Figure 8, and depict itself and the silica deposit relation by the number of times of stroke.All samples silica deposit by before stroke all through flame treating, only with first sample exception of Black oval mark, its before single silica deposit not through flame pre-treatment.Flame treating and silicon-dioxide make WVTR and OTR reduce by the increase of the number of times of stroke, namely improve barrier property.The raising of this barrier property comes from the more high quality or more effective aluminum metal layer that deposit on silicon-dioxide prime treatment film.

High speed deposition on example 2 OPP film

This example is for Biaxially oriented polypropylene film (BOPP) (BOPP) film be arranged on volume to volume roller coating machine as disclosed herein, for once-through flame treating with at the individual layer silica dioxide coating once by middle deposition.Typical processing condition are as follows: line speed is about 900ft/min (275m/min); Chill-roll temperature is about 54 DEG C; The pretreated burner of flame and film pitch are about 5mm, and the Sweet natural gas flow velocity that the fuel of flame pre-treatment step and air ratio are about the wide production line of 0.95,1m is about 100l/min; In silica deposit step, burner and film pitch are about 5 to 10mm, and the Sweet natural gas flow velocity that fuel and air ratio are about the wide production line of 1.0,1m is about 75 to 100l/min, the concentration range of precursor is about 0.0001 % by mole to 0.01 % by mole of air-flow, and plasma temperature is 1200 DEG C.It is 2.5 that film sample is metallized optical density(OD) subsequently at the standard conditions.Aforesaid operations condition generates WVTR<0.2g/m ²/ sky, OTR<20cc/m ²the film substrate in/sky.WVTR and the OTR data under multiple operating distance (flame burner and film substrate spacing), gas flow rate and precursor concentration (TEOS) are given in table 1.

Table 1

Data presentation in table 1 robustness of silica deposit and priming paint technique.Line speed in the speed adopted in this example and typical thin film substrate production technique is same or similar.

Multi-layer silica dioxide deposition on example 3 OPP film

Experiment is carried out repeatedly, to produce the pure silicon dioxide coating of 10 to 50nm on a film.The formation condition of coating is as follows: line speed is about 600 to 900FPM (180m/min to 275m/min), the spacing of flame treating step Flame burner and film substrate is about 5mm, the Sweet natural gas flow velocity that fuel and air ratio are about the wide production line of 0.95,0.3m is about 100l/min.For deposition step, flame burner and film substrate spacing are about 5 to 15mm, the gas flow rate that fuel and air ratio are about the wide production line of 1.0,0.3m is about 75 to 100l/min, and the concentration of precursor is in 0.0001 % by mole of gas stream within the scope of 0.01 % by mole.Plasma temperature is about 1250 DEG C.Silica deposit number of times is between about 36 to 72.

Except as otherwise noted, the amount of the expression composition used in the specification and in the claims and all numerical value of the such as character such as molecular weight, reaction conditions all should be understood in all cases " approximately " one word modify.Correspondingly, unless indicated to the contrary, the numerical parameter provided in the following description and appended dependent claims is approximation, its may according to the present invention be intended to obtain character and change.To each numerical parameter should at least according to reported significant figure figure place and apply the common method of rounding up and understood, and at least this and do not mean that and will limit right application doctrine of equivalents.Although specifically show the present invention with reference to preferred embodiment and illustrate herein, those skilled in the art should understand, and under the conditions without departing from the spirit and scope of the present invention, can do multiple change in form and details.

Claims

1., for the system to packaging film substrate coating inorganic oxide skin, comprising:

At least one flame treating flame front assembly, it is not provided precursors of inorganic oxides;

One or more deposition flame front, it is provided with at least one precursors of inorganic oxides, and is arranged at least one deposition flame front assembly in order;

Wherein said substrate, through before described deposition flame front assembly, first pass described flame treating flame front assembly, and at least one flame treating flame front assembly wherein said and described one or more deposition flame front is in open atmosphere.

2. the system as claimed in claim 1, at least one flame treating flame front assembly wherein said or at least one deposition flame front assembly described comprise the multiple flame front assemblies arranged with the parallel rows of the direction of motion perpendicular to described substrate.

3. the system as claimed in claim 1, at least one flame treating flame front assembly wherein said or at least one deposition flame front assembly described comprise square or rectangle flame front assembly.

4. the system as claimed in claim 1, at least one flame treating flame front assembly wherein said or at least one deposition flame front assembly described comprise multiple flame front assemblies that the direction of motion that is parallel to described substrate is in a row arranged.

5. the system as claimed in claim 1, at least one flame treating flame front assembly wherein said or at least one deposition flame front assembly described comprise bending-type flame front assembly.

6. the system as claimed in claim 1, the surface that at least one flame treating flame front assembly wherein said or at least one deposition flame front assembly described are oriented to relatively described substrate is angled.

7. the system as claimed in claim 1, when wherein said substrate is above the part passing through at least one cooling roller, through described flame front assembly.

8. the system as claimed in claim 1, wherein said inorganic precursor is first sent to the flame furl pipeline of described deposition flame front, subsequently again with the air mixed from air line, and in the burning of described flame front place.

9. the system as claimed in claim 1, wherein said inorganic precursor is first sent in the air line of described deposition flame front, subsequently again with the fuel mix from burning line, and in the burning of described flame front place.

10. the system as claimed in claim 1, in the air line that wherein said inorganic precursor is first sent to described deposition flame front and burning line, mixes subsequently again, and in the burning of described flame front place.

11. the system as claimed in claim 1, wherein said inorganic precursor first mixes with air/fuel mixture, is sent to described deposition flame front subsequently again.

12. the system as claimed in claim 1, wherein said inorganic precursor is injected in the flame produced by described deposition flame front.

13. the system as claimed in claim 1, also comprise the air knife of guiding into for flame.