CN102717969A - Packaging layer, method for manufacturing packaging pressure plate and packaging container produced therefrom - Google Patents

Abstract

The invention relates to a non-foil pressure plate used for liquid food packaging. The non-foil pressure plate comprises a core layer of paper or paperboard, a liquid-tight and heat-sealable outermost layer of polyolefin, and an oxygen barrier layer which is formed by liquid film coating of a liquid gas barrier composition and subsequent drying and is applied onto the inner side of the core layer of paper or paperboard, the liquid composition containing a polymer binder dispersed or dissolved in a liquid medium. The invention also relates to a method for manufacturing the packaging pressure plate and a packaging container from the packaging pressure plate.

Description

Wrapper, prepare packaging laminate method with and the packing container produced

Technical field

The present invention relates to a kind of non-foil laminate that is used for liquid food packing, this non-foil laminate comprises: paper or back flow liner; Fluid-tight, heat-sealing polyolefin outermost layer and be coated in paper or back flow liner on, forms the also oxygen barrier layer of subsequent drying by liquid gas barrier compsns liquid film coating; This fluid composition comprises the polymer adhesive that is dispersed or dissolved in aqueous medium or SOL MEDIA.This invention also relates to a kind of method for preparing this packaging laminate and made packing container by this packaging laminate.Background technology

The packing container that is used for the disposable use type of food liquid is often made by the packaging laminate based on cardboard or carton.A kind of packing container that Tetrapack aseptic

trade mark appears on the market that has commonly used; Be mainly used in the aseptic packaging of long-term normal temperature storage food liquid for sale, like milk, fruit juice etc.The packing of this known package container are generally and comprise paper or cardboard core body layer and the outer field ply wood of thermoplastic material fluid-tight.For the packing container air-tightness is provided, oxygen air-tightness particularly, for example in order to realize the packing of aseptic packaging and milk or fruit juice, the ply wood of these packing containers generally includes at least one extra play, and aluminium foil is the most common.

In the inboard of ply wood, promptly a side of the vessel filling food contents that makes towards ply wood of predetermined face has an innermost layer that is applied on the aluminium foil of innermost layer, and nexine can be by comprising that heat-sealing adhesive poly-mer and/or polyolefinic one or more layers layering form.Simultaneously, in the sandwich layer outside heat seal polymer outermost layer is arranged.

Usually utilization means modern, high-revolving packaging machine are produced packing container, and such packaging machine can be from plate or prefabricated blank formation, filling and the sealed package of packing.Heat-sealing thermoplastic polymer through weld layer pressing plate packing timber flitch becomes overlapped joint with outermost in layer by layer, and two longitudinal edges of plate are bonding each other, and plate is transformed into pipe, thereby processes packing container.Be packed into the predetermined liquid food products in the pipe, repeat horizontal sealing through the predetermined space under the weighting material horizon in pipe subsequently, thereby pipe is divided into independent packaging.Along the across seal cutting, separate packing from managing, and along the fold line folding forming of preparing in the packing, the geometric shape of giving to expect is generally parallelohedron.

Plate was sustainable aseptic before the major advantage of this lasting one-tenth pipe, filling and seal packing method notion mainly was to manage moulding; Thereby the possibility of aseptic packaging method is provided; Promptly wherein liquid contents packing are the same fills with self; Reduced bacterium, and the packing container of being filled makes feasible packing of filling even at room temperature long-term storage and the risk that do not have germ in institute's filling product, to breed under cleaning condition.Another important advantage of Tetrapack

type of package method is; Foregoing; Continue the possibility of high-speed packaging, the appreciable impact cost benefit.

Aluminium foil layer in the packaging laminate provides the gas barrier characteristic to be superior to the most polymers gas barrier material far away.Being used for the conventional aluminium foil type packaging laminate of liquid food aseptic packaging, is to have the most cost-effective aseptic packaging material on its performance level on the market now.With regard to raw material, any other competitive materials must have more cost-benefit, has comparable food storage characteristic, and the comparable low-complexity that changes the laminated board finished product into.

Say from cost benefit, compare with the aluminium foil layer pressing plate that surpasses 3 months food preservation characteristics that non-Foilpac ply wood so far, almost has no the aseptic packaging of business-like paper or cardboard type to can be used for long-term normal temperature storage with barrier properties with reliable level.There are some polymeric materials that the high-barrier characteristic can be provided; But they or the mechanical properties of ply wood, or be difficult in the thin layer in changing ply wood into handling, for example; Need expensive co-extrusion bonding coat; Or etc. feasible thickness more more expensive than aluminium, therefore, not cost-effective for packing like milk or fruit juice.

Have more cost-benefit packing and reduce in the effort of preparation packing raw MAT'L consumption the performed thin film with multiple barriers function of the alternative aluminium foil of encourage growth as far as possible in development.Previously known combines the embodiment of a plurality of layers film, and every layer provides additional barrier properties for final film, for example has the vapor deposition barrier layer and the film of further coated polymer barrier layer on same substrate film.But this film is applied twice by different cladding process, and often raw MAT'L and preparation cost all become expensive, simultaneously owing in most cases need an additional encryption seal, the quality of substrate film is had very high request, like resistance to effect of heat and processing durability.

The polymer gas barrier layer that a kind of expensive benefit is arranged promptly is coated on the substrate and subsequent drying becomes to intercept the barrier polymer of shallow layer to be dispersed or dissolved in form in liquid or the solvent.Yet uniform and stable dispersion or solution are extremely important for the coating that formation has even barrier properties.The poly-mer that is applicable to water composition has the ethylene-vinyl alcohol (EVOH) of polyvinyl alcohol (PVOH), aqueous dispersion or based on the aqueous dispersion or the dissolved polymers of polysaccharide.Scatter coated or so-called liquid film apply (LFC) layer and can be produced extremely thinly, less than 0.1g/m ², uniform and stable in dispersion or solution, promptly under the condition of preparation and mixing high-quality even layer can be provided fully.For example, PVOH has the high oxygen barrier properties under drying condition, and this is by for many years known.PVOH also provides high peculiar smell barrier properties, i.e. the ability that prevention gets into packing container like smell substance in the surrounding environment of refrigerator or normal temperature condition storage room, and this ability is extremely important for the packing long-term storage.And this liquid film coated polymer layer that is derived from aqueous dispersion or dissolved polymers often provides the high inner binding force with adjacent layer, helps the high integrality of final packaging container.For packing, integraty typically refers to package durability, that is, and and the resistibility of packing container seepage.The major defect of this water-soluble layer of barrier polymer is that they are to humidity sensitive, and the oxygen obstruction characteristic is degenerated rapidly in the humidity in the high water capacity relatively of packaging laminate.Therefore, the dispersion scumbling coating of PVOH or EVOH or similar poly-mer is applicable to the packing of the dry products in dry environment, is packaged under the wet or moist condition and stores but seldom be used for liquid and wet product.

And visible high oxygen barrier properties (comparing with aluminium foil) with plane packaging ply wood of dispersion coating layer of barrier polymer seriously reduces when changing and being transformed into packing container.

In addition, attempt to add other material, promptly through cross-linked polymer, for humidity-sensitive polymer layer provides better initial stage oxygen obstruction characteristic and makes its more moisture-resistant through polymer modification or in polymer composition before.Yet this modification or increase material often make the liquid film coating procedure more be difficult to control, it is also important that, and be expensive more.In view of the existing food security rules legislation of packaging for foodstuff, these materials also possibly need careful screening.For example, also attempt to realize the heat cure that combines with its drying through more than the heating PVOH dispersion coat to 100 ℃ before.Yet such heat can damage and apply paperboard substrates and negative effect coating quality, for example through inducing the oxygen obstruction Coating defect like bubble or crackle.Therefore; Still need a kind of cost-effective and firm; Identically under i.e. preparation and the treatment conditions change still that the non-In Aluminium Foil Packing material of failure-free is used for the sterile liquid packaging for foodstuff like milk or Other Drinks, this material is that the packing container that is used for the aseptic storage of long-term normal temperature provides sufficient barrier properties.The term relevant with the present invention " long-term storage " is meant that packing container can preserve the quality of the food product packed at normal temperature condition, and promptly nutritive value, safe and sanitary, local flavor are at least 3 months, longer better.Summary of the invention

Therefore, the objective of the invention is to overcome or alleviate the above-mentioned non-foil paper of liquid or the long-term aseptic packaging of wet provision or the problem of carton package laminated board production of being used for.

The general objects of this invention is to provide non-foil paper or carton package ply wood, and it has high gas barrier characteristic and the high inner binding force of interlayer that is fit to long-term aseptic packaging, the high integrality that provides ply wood to make packing container,

Especially, purpose also is to provide to compare with aluminium foil has cost-benefit non-foil paper or carton package ply wood, and it provides high inner binding force between high packing container gas barrier characteristic, high package integrity properties and ply wood.

Further purpose of the present invention is to provide to compare with aluminium foil has cost-benefit non-foil paper or carton package ply wood; It has high gas barrier characteristic, high water vapor barrier properties and the high inner binding force that is used to prepare aseptic, airtight and the close packing container of aqueous vapor, has high package integrity properties.

Further aim of the present invention also is to provide has the cost-benefit firm non-foil paper or the heat sealed package ply wood of cardboard type; It has high gas barrier characteristic, high water vapor barrier properties and the high inner binding force of the long-term storage sterile packaging container that is used to prepare room-temperature extender body food value.

According at least some embodiments of the present invention; More detailed purpose is that provide to have cost-benefit non-foil paper or cardboard type liquid package container, it has high gas and aqueous vapor barrier properties; High peculiar smell barrier properties, and the aseptic high package integrity properties that is used for long-term normal temperature storage milk.

Through liking the preparation method of the described ply wood packing of claim, packing container and packing enclosed, these purposes have all reached according to the present invention.

According to a first aspect of the invention, realize that the general objects packaging laminate comprises: paper or back flow liner; First fluid-tight, heat-sealing polyolefin outermost layer; Second fluid-tight heat, fluid-tight polyolefin innermost layer and be coated in paper or the ply of board inboard on forms the also oxygen barrier layer of subsequent drying by liquid gas barrier compsns liquid film coating; This fluid composition comprises the polymer adhesive that is dispersed or dissolved in aqueous medium or SOL MEDIA; Wherein packaging laminate further comprises the vapor deposition barrier layer that is coated on the polymer substrate film; This vapor deposition applies film between said oxygen barrier layer and polyolefin heat-sealing innermost layer, applies film in this this vapor deposition and is adhered to the coating sandwich layer through intermediate polymer layer.

Therefore, be expected to pass through new tool or some known method of modifying in order to reach the required oxygen obstruction characteristic levels of the packing container finished product that is used for aseptic long-term storage; Promptly increase cross-linked material, or heat cure, liquid film coating type gas barrier polymer adhesive improved; For example, PVOH.However, whether the improvement of oxygen obstruction is strong enough to the long-term normal temperature storage that can be used for aseptic packaging, still is not sure of.

The packaging laminate that is used for aseptic long-term storage packing container also need strengthen the aqueous vapor barrier properties.

Be meant the barrier properties that lets aqueous vapor slowly move material with the aqueous vapor barrier properties, promptly non-is not instant liquid barrier characteristic.For example, be liquid barrier like the heat-sealing polyolefin of preferred low density polyethylene (LDPE) (LDPE ' S or LLDPE ' S), be applicable to that outermost layer separates the liquid product of filling with the inboard cardboard of protective cover pressing plate or separates the wet condition of outer package, as under the high humidity or refrigeration.Yet low density polyethylene (LDPE) has lower aqueous vapor barrier properties, promptly in fact Rational Thickness tool can not bear transportation and the long-term slowly migration of when storage aqueous vapor through the ability of ply wood.The aqueous vapor barrier properties is extremely important when long-term storage; The humidity of the liquid food product that also can prevent to be packed because of them is run out from packing container, avoids the content of liquid food product when the customer finally unpacks container to be lower than each packing container expection.In addition, run out of packing container and get into paper or ply of board through preventing the aqueous vapor migration, packaging laminate can keep its stiffness characteristics in a long time.Therefore, to have the aseptic packaging aqueous vapor barrier properties that is applicable to liquid product fully also be very important to packing.

The aluminum metallization thin layer, promptly the vapor deposition layer of aluminum metal is considered to provide aqueous vapor to intercept.Yet when the expensive benefit of preparation, when comprising the paper mold packaging laminate of these layers of finding, the oxygen obstruction characteristic is also insufficient.

Be used in traditional aluminium foil of sterile liquid food container now, have aqueous vapor barrier properties and oxygen obstruction characteristic simultaneously.Reliable oxygen obstruction that almost has no material substitution article suitable, that have economic benefit to provide simultaneously to compare favourably with aluminium foil and aqueous vapor intercept.

Yet be unexpectedly; When through the independently different each other barrier materials of two kinds of laminations when coming together the Production and Packaging container; Be a kind of liquid film coating PVOH barrier layer that has, another kind has the vapor deposition barrier layer, finds not only to have reached sufficient aqueous vapor barrier properties; And the laminated board finished product particularly the oxygen obstruction characteristic of final packaging all of a sudden strengthened, and become good especially.According to the oxygen transmission value of independent measurement on each barrier layer, the vapor deposition composite bed should be also insufficient to the contribution of laminated board finished product oxygen obstruction characteristic, but far above expection and estimation.In fact, with the corresponding package laminate that does not contain the gas phase deposit film, contain the film inclusion of gas phase depositing metal layers, the transmission of self oxygen is high, and the oxygen obstruction of laminated board finished product has improved 2 times.

In addition, after transformation and formation packing container are thick, obtained the unexpected oxygen obstruction characteristic that further strengthens.Although for example the inclusion of metal layer is unexpected to the contribution of total oxygen obstruction of laminated board finished product, to compare with the packing container of the equivalent layer pressing plate that does not contain the gas phase deposit film, the oxygen obstruction of laminated board finished product has further improved 20 times.

Also found can to cause in the dispersion coat to contain the impaired defective of oxygen obstruction characteristic of planar sample of the packaging laminate of scatter coated layer afterwards, can be by the vapor deposition compound with unexpected mode " repairing " or " reparation ".

For example, according to the present invention, when using different board quality to come packaging laminate, visible this repairing or repairing effect.Some board grades seem not to be suitable for the liquid film coating of oxygen isolation layer, because measured oxygen obstruction is widely different at different stage on the plane packaging ply wood.Yet the inboard additional vapor deposition of liquid film coat intercepts thin layer and has proofreaied and correct these difference.Generate the defective as aperture or type tiny crack when applying subquality cardboard in the liquid film coating film, when lamination had the vapor deposition thin layer of some barrier properties, these defectives were not influenced the characteristic of final packaging very much by reparation.

The poly-mer that the used polymer adhesive that disperses or dissolves of the present invention preferably self has the gas barrier characteristic.

Vinyl alcohol type poly-mer, acrylic or methacrylic acid-based polymer (PAA, PMAA), polysaccharide, shitosan or other cellulose derivatives, aqueous dispersion polyvinyl dichloride (PVDC) or the polynary fat of aqueous dispersion of preferred PVOH freely of this poly-mer or aqueous dispersion EVOH, or the group that forms of two or more combination wherein like starch or starch derivative.

Polymer adhesive is more preferably from PVOH, aqueous dispersion EVOH, acrylic or methacrylic acid-based polymer (PAA, PMAA), polysaccharide, shitosan or other cellulose derivatives like starch or starch derivative, or the group that forms of two or more combination wherein.

Compare with aluminium foil, PVOH has many ideal behaviores as liquid film coating barrier polymer, causes being used as in many cases first-selected barrier material.Wherein, depend on high one-tenth film characteristics, with the compatibility of food and economic value, together with its high oxygen barrier properties.Particularly, PVOH provides the packaging laminate with high peculiar smell barrier properties, and is particularly important for milk pack.

In application; Other many available barrier polymer of picture starch or starch derivative etc.; Through the means that the liquid film coating is handled, promptly water or solvent type dispersion or solution form is using polythene alcohol suitably, on substrate, launches to form even thin layer and subsequent drying.Yet we have found a shortcoming of this technology, and the liquid polymers dispersion or the polymer solution that are applied on paper or the back flow liner possibly penetrate into sandwich layer liquid-absorbent fiber.Along with the drying of application barrier layer has been removed water or solvent,,, there is the risk that forms aperture according to the cardboard characteristic if institute's application layer is too thin.

Water system has certain environmental advantage usually.Liquid gas intercepts complex preferred water type, because such cmpd has better working environment than solvent-borne type system usually.

Briefly mention as top, known adding contains function perssad carboxylate's poly-mer or aqueous vapor and the oxygen obstruction characteristic that compound improves the PVOH coating.The poly-mer that contains the function perssad carboxylate suitably is selected from ethylene acrylic acid co polymer (EAA) and ethylene acrylic acid co polymer (EMAA) or their compound.A kind of known preferred especially barrier layer compound is made up of PVOH, EAA and inorganic layer compound.Based on the coating dry weight, EAA copolymer content in barrier layer is about 1-20%.

It is believed that the esterification result between the PVOH and EAA when oxygen and barrier properties after the improvement increases from baking temperature, thereby hydrophobic EAA polymer chain and crosslinked PVOH are gone into the structure of PVOH by structure.Yet because the additive-treated oil cost, this compound is quite expensive.In addition, in view of the risk that on paperboard substrates, forms crack and bubble in the barrier coat, preferably at high temperature dry and reparation.Also can induce crosslinked through appearance like the versatile compound of metal composite.Yet the liquid film after this improvement applies gas-barrier layer still can not provide the easy-formation packing container abundant oxygen obstruction characteristic, cost-effective with the aseptic packaging of the long-term normal temperature storage of failure-free voluntarily.

The extraordinary water-soluble EVOH of research and development can be used as oxygen obstruction liquid coating composite according to the present invention recently.Yet traditional E VOH poly-mer is generally used for extruding, and can't generate 5g/m in the aqueous medium dispersed/dissolved ²Or following liquid film applies barrier film, preferred 3.5g/m ²Or below.It is believed that EVOH should comprise that large quantity of moisture looses or the vinyl alcohol monomer of dissolving, and its characteristic is as far as possible near the characteristic of liquid film coating grade PVOH.Evoh layer after extruding can not substitute liquid film and apply EVOH, because compared with the EVOH kind that is used for extruding coating, its intrinsic property is not so near PVOH, and because its impassabitity extruding coating or extruding layer pressing plate realize being lower than 5g/m ²Cost-effective individual layer consumption, promptly it need be generally the co-extrusion bonding coat of quite expensive poly-mer.In addition, the thin layer cooling after extruding is too fast, does not have the laminate adhesive that enough heat energy is kept adjacent layer.

Other provide the oxygen obstruction characteristic also to use and the polymer adhesive embodiment of liquid film coating is polysaccharide, especially starch or starch derivative, preferably oxidized starch, cationic starch and hydroxypropyl starch.The embodiment of this modified starch is hypochlorite oxidation farina (Raisamyl 306 from Raisio), hydroxypropylation cornstarch (Cerestar 05773) etc.But, also have other known starch form and derivants that the gas barrier characteristic is provided to a certain extent.

The further embodiment of polymer adhesive is a gas barrier coating; Comprise containing carboxylic acid polyalcohol and, in the embodiment of EP-A-608808, EP-A-1086981 and WO2005/037535, describe like the acrylic or methacrylic acid polymer like the compound of the polyhydric alcohol polymer of PVOH or starch.As stated, preferably the cross-linking reaction of these polymer adhesives is used for anti-high humidity.

The compound that said components is mixed with small scale and the combination of one-component, the oxygen obstruction characteristic is not provided in the aqueous coating composite.

Yet most preferred gas barrier poly-mer is PVOH1 because it has above-described all superperformances, film characteristics, gas barrier characteristic, cost-effective, food is compatible and the peculiar smell barrier properties.

Although the PVOH of low saponification degree also can provide the oxygen obstruction characteristic, when PVOH had at least 98% saponification degree, the performance of PVOH type gas barrier composite was best, preferably at least 99%.

According to preferred implementation, the liquid constituent comprises also that in addition inorganic particles further improves the oxygen obstruction characteristic.

For example, polymeric adhesive material can preferably be mixed with sheet or lepidiod inorganic composite.Through the layering mechanism of flakey inorganic particles, oxygen molecule passes through oxygen barrier layer via zigzag path, than moving longer road through common straight line path through barrier layer.

When adopting inorganic sheet particulate, can use and not have or the polymer adhesive of low oxygen barrier properties.These other non-obstruct adhesives is other the high hydrogen bond poly-mers with a large amount of hydrogen bond groups, these a large amount of hydrogen bond groups such as oh group, amino group, carboxylic group, sulfonic acid group, carboxylate group, azochlorosulfonate acid ion group and ammonium group etc.The specific embodiment of these non-barrier polymer adhesivess is promptly like the cellulosic cellulose derivative of methylol (or ethyl), amylopectin and other polysaccharide derivates, polyethyleneimine, PAH etc.

Preferred inorganic sheet-like composite is so-called nanoparticle compound, and this nanoparticle compound is separated into the state of coming off through the means of liquid medium, and promptly the thin slice of layered inorganic compound is separated from each other.Therefore, preferably through polymer dispersed or dissolving, the electrodeless compound of stratiform of inflatable, division, the laminar texture of infiltration inorganic material when disperseing.Before being added to polymer dissolution or polymer dispersed, it also can pass through solvent expansion.Therefore, inorganic sheet-like composite is separated into stratification state in the liquid gas barrier compsns He in the dried barrier layer.The clay mineral term comprises kaolin, antigorite, smectite, vermiculite, bentonite or mica type mineral respectively.Specifically; Lithium algae soil, kaolin, dickite, carnat, halloysite, antigorite, chrysotile, pyrophillite, polynite, hectorite, saponite, sauconite, four silicon mica sodium (sodium tetrasilicic mica), taincolite sodium, muscovite (commonmica), emerylite, vermiculite, phlogopite and green emerald green mica etc. can be carried and are suitable clay mineral.Preferred especially montmorillonite-based nano particulate, the polynite of first-selected purifying or sodium-based montmorillonite (Na-MMT).Nano grade inorganic sheet-like composite or clay mineral preferably come off, and aspect ratio is 50-5000 in the state, and granularity is up to about 5um.

Preferred is the inorganic particles that the sheet bentonite particulate of 50-5000 is formed by aspect ratio mainly.

Preferred inorganic sheet-like composite accounts for the coating barrier layer of coating dry weight weight about 1% to about 40%, and more preferably from about 1% to about 30%, and first-selected about 5% to 30%.Compare and do not use inorganic sheet-like composite, if content is too low, the gas barrier characteristic that applies dry barrier layer can not significantly improve.If content is too high, fluid composition will more be difficult to use as coating, more be difficult in the storage tank of applicator system and conduit, handle.Preferred polymers accounts for the coating barrier layer of coating dry weight weight about 99% to about 60%, and more preferably from about 99% to about 70%, and first-selected about 95% to 80%.The gas barrier composite can comprise the additive like dispersion stabilizer or analogue, preferably accounts for coating dry weight weight and is less than or equal to about 1%.The total dried content of preferred composition accounts for about 5% to about 15% coating barrier layer, and more preferably from about 7% to about 12%.

According to different preferred implementations, preferred is the inorganic particles that the platy talc particulate of 10-500 is formed by aspect ratio mainly.Preferably talc powder particulate accounts for the composite of dry weight weight about 10% to about 50%, and more preferably from about 20% to about 40%.Proportion is lower than at 20% o'clock, and the gas barrier characteristic does not have obvious increase, and is higher than at 50% o'clock, because internal cohesion reduction between particulate in the layer, it is fragile, frangible that coat becomes.Polymer adhesive seem content too low and can not be in layer around making their mutual lamination with disperse particles.This total dried content proportion that is derived from the liquid barrier composite of polyvinyl alcohol and french talc particulate can be between 5% and 25%.

Appended WO03/031720 can know by list of references, and it is special to utilize cataloid can reach unexpected good oxygen obstruction, and the displaying granularity is 3-150nm, preferred 4-100nm, more preferably 5-70nm, preferably amorphous or spherical particle.And along with dry by force requirement has reduced, the use of colloidal silica particles has the liquid barrier composite can be at dried content proportion 15-40%, preferred 20-35%, the advantage of more preferably using during 24-31%.

According to the present invention, the low preferred substitute of inorganic particles is particulates such as kaolin, mica, calcium carbonate.

When adopting inorganic particles that the oxygen obstruction characteristic is provided, the preferred polymers adhesives is PVOH, and major cause is its above-mentioned advantageous characteristic.In addition, from the viewpoint of mixing point, the advantage of PVOH is that it disperses or shed particles easily usually, forms the stable PVOH and the compound of particulate in the PVOH aqueous system, and height is evenly formed and the coated film of form thereby formation has.

According to the present invention, preferred said oxygen barrier layer is at gross dry weight amount 0.1g/m ²To 5g/m ²Shi Yingyong, preferred 0.5g/m ²To 3.5g/m ², more preferably 0.5g/m ²To 2g/m ²Be lower than 0.1g/m ²The time, do not have the gas barrier characteristic, and be higher than 5g/m ²The time, coat can not provide cost benefit for packaging laminate, and this is because the highly energy-consuming of the expensive and liquid of barrier polymer evaporation usually.At 0.5g/m ²Higher, PVOH can reach the oxygen obstruction level that can know, and 0.5g/m ²To 1g/m ²The time can reach the balance between barrier properties and the cost.

According to preferred implementation of the present invention, oxygen barrier layer is applied to two consecutive steps and drying therebetween as two layerings.When as two layerings, each layer is at 0.1g/m ²To 2.5g/m ²Be suitable for preferred 0.5g/m between consumption ²To 1g/m ², and have from the total layer of the higher quality of low liquid gas barrier compsns consumption.More preferably two layerings are respectively at 0.5g/m ²To 2g/m ²Consumption between use preferred 0.5g/m ²To 1g/m ²

Direct or continuous being coated on paper or the back flow liner of preferred oxygen barrier layer according to the present invention.Ply of paper guarantees, is not trapped in humidity sensitive liquid film coating oxygen barrier layer through laminate wrapping material to the humidity of external migration, and further outwards transports through ply of paper.Ply of paper is inhaled the humidity of removing adjacent barrier layer, and keeps the moisture in the barrier layer to be in low-level for a long time always.

Used paper of the present invention and back flow liner have the thickness of about 100um to about 600um usually, and surface weight is near 100-500g/m ², preferred 200-300g/m ², be the conventional paper or the cardboard of suitable package quality.

For the low-cost long-term aseptic packaging of liquid food, used to have the thinner packaging laminate of thin paper sandwich layer.The packing container that is made by this packaging laminate is not what be folded to form, more near with pincushion elasticity parcel.The paper that is applicable to this resilient packing has about 50g/m usually ²To 140g/m ²Weight, preferred 70g/m ²To 120g/m ², more preferably 50g/m ²To 110g/m ².

Being suitable for outermost layer with the thermoplastic plastic that seals the fluid-tight innermost layer does, polyolefin, and preferably polyethylene, first-selection is the low density polyethylene (LDPE) of LDPE, linear LDPE (LLDPE), metallocene PE single-site catalysts (m-LLDPE) or its compound for example.

Through the means of physical vapor deposition (PVD) or chemical vapor deposition (CVD), the vapor phase deposition barrier layer can be used on the polymer substrate film.

According to the present invention, the vapor phase deposition thin layer is a nano thickness, and promptly they have with nanometer counting, 5nm to 500nm for example, preferred 5nm to 200nm, more preferably 5nm to 100nm, first-selected 5nm to 50nm.

Generally, barrier properties is too low and inoperative when being lower than 5nm, and when being higher than 200nm, coating elasticity is relatively poor, easy of crack when being applied to elastic substrate.

As a rule, this vapour deposition coating with barrier properties is made by metal composite or inorganic metal compound.According to the present invention, also just like the organic vapor phase deposition barrier coat of carbon type vapour deposition coating, for example amorphous carbon layer or so-called diamond-like are bored carbon coating, have the advantage that is used for packaging laminate and packing container.

The vapor deposition thin layer of preferably forming by aluminum metal.In the corresponding conventional thickness aluminium foil less than 1%, i.e. 6.3um, the preferred 5nm of this vapor deposited metal thin layer is to 50nm thickness, more preferably 5-30nm.

Preferably,, particularly before the metallized substrates film, implement substrate film surface-treated step in the vapor phase deposition coating through the surface ion bombardment.

Preferred optical density (OD) (OD) is 1.8 to 3.0 metal layer, preferred 2.0 to 2.7.When being lower than 1.8 optional density, the barrier properties of metallized film is too low.On the other hand, be higher than at 3.0 o'clock, it is too frangible that metal layer becomes, and during metalized heat stability too poor be because the higher thermal load during long-time metallized substrates film.Coating quality and binding force obviously receive negative effect.Finding between these values that optimum value is between 2.0 to 2.7.

Further preferred coatings is the aluminum oxide coating layer with formula AIOx, and wherein x changes between 1.0 to 1.5, preferred AI2O3.The thickness of preferred this coating is 5nm to 300nm, more preferably 5nm to 100nm, first-selected 5nm to 50nm.

Under the normal circumstances, because the character of employed metalized coated processing, aluminum metallization layers has aluminium oxide and forms intrinsic sake part.

The means application of coatings metallization thin layer or the inorganic metal composite layer of preferred vacuum vapor deposition, but low preferred through other lower general known methods of production efficiency in this area, as electroplating and spraying.According to the present invention, first-selected metal is an aluminium, although can use any other metallo-vacuum moulding machine, plating or spray characteristics according to the present invention.Therefore, also can imagine, be the low recommendation and the metal that is of little use like Au, A, Cr, Zn, Ti or Cu.Usually, the shallow layer of metal or metal mixture or metallic oxide provides the barrier properties to aqueous vapor, is used to prevent aqueous vapor migration entering and passes through multilayer film or packaging laminate.Metal in first-selected metallization or the inorganic metal coating is aluminium (Al).The further embodiment of aluminium inorganic composite is oxidation, aluminium nitride and aluminium carbide or these compound.

Though preferred aluminium or alumina metals layer or its compound according to the present invention, other vapor deposition inorganic metal compounds also are applicable to embodiment of the present invention.Being derived from semimetallic similar compound, like silicon, needing only their cost-effective and at least some low-level oxygen barrier properties, is that the term inorganic metal composite is included applicable to the present invention also.

Some this inorganic coatings can be realized through the means of plasma enhanced chemical vapor deposition method (PECVD) using, and wherein metal or metal composite vapour are deposited on the substrate under more or less oxidation situation.For example, can handle the application silica coating through PECVD.

According to another embodiment of the present invention, vapour deposition coating can be the carbon type and intercepts thin layer.Can apply this carbon type layer through the means that plasma coating is handled, thereby generate the hydrocarbon polymer coating, bore carbon (DLC) coating referring to agraphitic carbon or diamond-like.

The substrate polymers film can comprise any thin polymer film from the poly-mer that is used for vapour deposition coating, any thickness, as long as it can be packing container in handling and distributing high-barrier characteristic and integraty is provided.Yet the selection of substrate film influences the cost of packing and packing container so preferably polyethylene type substrate film to a certain extent.But, comprise the for example film of poly terephthalic acid ethanediol (PET), polyamide (PA) or other thermoplastic polymers, also be contained in scope of the present invention, this depends on price.This commercialization can get film, and normally twin shaft is to guiding.These films have constituted more expensive alternatives, this also since they self seal, Yi Bian means that often need be through extruding coating when lamination entering packaging laminate are in the fact of using the additional heat seal.According to the selection of poly-mer, substrate film can be guiding or non-guiding, can be by making through the means of extruding the blown film preparation method or extruding the casting film preparation method.

According to preferred implementation of the present invention, vapor deposition applies barrier applications on the substrate polymers film that comprises said heat seal polymer innermost layer.

Preferred polyolefm type substrate polymers film.The preferred heat seal polymer innermost layer of mainly forming by low density polyethylene (LDPE), preferred linear low density polyethylene (LLDPE).

More preferably the substrate polymers film is the unidirectional film that comprises said innermost layer heat seal polymer.Through unidirectional film, obtain Young's modulus increase in the film, elongation at break descends.But this makes vapor deposition apply extremely thin film and in lamination treatment, handles this film.In addition, although this film is extremely thin, still help the rigidity of laminated material.

Even more preferably unidirectional film comprises most dissimilar low density polyethylene (LDPE)s, preferred linear low density polyethylene (LLDPE).

Preferred unidirectional film thickness is 20um or thinner, more preferably 15um or thinner.

Preferably, implement the step of single shaft to the stereospecific polymer substrate film through combining directed with lax method means; Directed with the lax method means of this combination relate at least 10 guide roller jaws, and wherein, first comprises the idle roller of drive roller and non-driving therebetween with last jaw.Through this method, under the help that idle rod operation is stretched, need not to destroy plate, stretch and loosen and occur in the film internal tension and allow and need in its processing.Through this method, the speed that also can increase directional process further increases the cost benefit of unidirectional film-substrate.

It is 2-7 that the preferred polymers substrate film is directed to ratio, preferred 2-4, and more preferably 2-3, and preferred polymers substrate film elongation at break is lower than 400%, preferably is lower than 300%, more preferably less than 200%.

Therefore, Young's modulus is the 700-800MPa that 2 250-300MPa changes to the about 6-7 of orientation ratio from orientation ratio.Ratio increases at 7 o'clock from 2, and elongation at break is reduced to from about 400% and is lower than 100%

In general, Young's modulus increases with orientation ratio, and elongation at break reduces with the orientation ratio increase.Developed orientation ratio and be about 3 good film, be comprise its prepared packing container of packaging laminate of inboard film possess better elastic, intensity and integraty.Use the low density polyethylene (LDPE) of other types and grade, in addition can preferred higher orientation ratio.

According to preferred implementation; Unidirectional film comprises the top layer or the so-called binder polymer of improved polyalkene, the top layer vapor deposition of metal composite, electrodeless metal composite or carbon type compound apply the barrier layer vapor deposition this top layer or should the what is called binder polymer on.

The embodiment of these improved polyalkenes is based on LDPE or LLDPE copolymer or preferably contains the graft copolymer of monomer functional group, like carboxyl or glycidyl functional group, (methyl) acrylic monomers or maleic anhydride (MAH) monomer, (being ethylene acrylic acid co polymer (EAA)), ethene-epoxy (methyl) acrylic copolymer (EG (M) A) or MAH-grafted polyethylene (MAH-g-PE).These another embodiment polymer-modified or binder copolymer are so-called from aggressiveness or ionomer.Preferred improved polyalkene is ethylene acrylic acid co polymer (EAA) or ethylene methacrylic acid copolymer (EMAA).

Preferred vapor deposition film is adhered to paper or ply of board through intermediate polymer layer, and the preferred thermoplastic polymeric layer is more preferably from the polyolefin and the polyolefin-type copolymer that are considered to binder polymer usually.

According to the present invention, separated for the photoresistance that further improves packaging laminate, in case of necessity, in intermediate heat plastic-bonded layer, incorporate extinction particulate or pigment.The preferred embodiment of this extinction particulate is a carbon black.The inboard metal layer of outside ply of board and ply wood, for example aluminium helps the black color of hiding inboard intermediate adhesion layer.

In order to have the thin low cost section packaging laminate than the thin paper sandwich layer, the preferred further bag of intermediate heat plastic-bonded layer inorganic particles is drawn together the separated characteristic of photoresistance that increases packaging laminate with reflective, white form.Simultaneously or in addition, the substrate polymers film that is used for vapor deposition further comprises photoresistance that inorganic particles increases packaging laminate with the form of extinction, black at a distance from characteristic, preferred carbon black.Outside metal layer and/or white intermediate adhesion layer help the black of hiding innermost layer extinction film.

For High Performance packaging laminate more, for example be used for the longer aseptic shelf-life than sensitive product, need further to increase barrier layer certainly.For example, a kind of plain mode of oxygen obstruction characteristic of further increase packaging laminate contains the thermoplastic bonded layer that melt extrudes barrier layer with use and realizes that vapor deposition applies inner membrance and liquid film obstruct coating cardboard is bonding each other.Like this, producing High Performance packaging laminate more, unique what need to change is in the conversion process of lamination stages, to add additional melt extruded polymer layer (for example, further barrier layer with maybe one deck or two-layer melt coextrusion bonding coat).Other all things about raw material and conversion process are constant.

According to a further aspect in the invention; Provide by the prepared packing container of packaging laminate of the present invention; Compare those and be used for the commercialization conventional aluminum Foilpac container of liquid food packing now, have hypoxemia and the aqueous vapor inside binding force between infiltration rate, package integrity properties and laminate layers mutually.

The preparation method of the packaging laminate that is limited like independent claims 28 also is provided according to a further aspect in the invention.

Therefore, this method may further comprise the steps: paper or ply of board are provided; The fluid composition that contains the polymer adhesive that is dispersed or dissolved in liquid, water or SOL MEDIA is provided; Contain said polymer adhesive oxygen obstruction thin layer through using fluid composition on said paper or ply of board and subsequent drying evaporating liquid medium, forming; Vapor deposition intercepts thin layer, preferable alloy compound, electrodeless metal composite or carbon type compound on the polymeric liner counterdie; And the means through interlayer, the lamination vapor deposition applies the inboard of film to oxygen barrier layer; In the vapor deposition layer inboard heat seal polymer innermost layer is provided; And the heat seal polymer outermost layer is provided in the vapor deposition layer outside.

In a preferred method of the invention, the liquid gas barrier compsns directly is coated on the inboard of paper or cardboard.Because the packaged food product is liquid or contains liquid, there is a certain amount of aqueous vapor transportation from the inboard to the outside, therefore, outwards rapidly through ply of paper, preferably make aqueous vapor outwards continue to escape through the fluid film coat compared with aqueous vapor.If ply of paper is applied by polymeric layer, the aqueous vapor that can keep for a long time bottling up is inboard at ply of paper, and the relevant humidity that liquid film applies in the barrier layer increases.Therefore, preferably with the liquid film coat of ply of paper direct neighbor.

According to method for optimizing of the present invention, oxygen barrier layer is applied to have two subsequent steps of dry run therebetween as two layerings.When as two layerings, each layer is at 0.1g/m ²To 2.5g/m ²Use preferred 0.5g/m between consumption ²To 1g/m ²

In general, the polymer substrate film that is used for vapor deposition is a thermoplastic polymer film, preferred polyolefm type film.

According to the preferred implementation of the inventive method, the polymer substrate film that is used for vapour deposition coating is the film that comprises the innermost layer hot sealing layer, and more preferably this film mainly is made up of hot sealing layer.According to the present invention, this film preferably through extruding the blown film preparation, comes from this processing reliability and cost benefit.Yet, prepare film through casting film and also fall into scope of the present invention.

According to the more preferably embodiment of the inventive method, this method further comprises the unilateralization step of the polymer substrate film that is used for the metal composite vapour deposition coating, and this polymer substrate film comprises most low density polyethylene (LDPE)s.

Preferably include the polymer substrate film of most low density polyethylene (LDPE)s, unidirectional thickness 20um or thinner, more preferably 15um or thinner.

According to preferred implementation, the polymer substrate film comprises carboxylic group modified poly ethylene or the graft copolymer top layer with acrylic or methacrylic acid monomers, and like ethylene copolymer, metal or the vapor deposition of inorganic metal compound are on this top layer.More preferably improved polyalkene is ethylene acrylic acid co polymer (EAA).Preferred thin, promptly 0.5um is to 5um, more preferably 1um to 3um.

Preferred vapor deposition composite layer has 5nm to 500nm thickness (from 50A to 5000A).

Preferred the inventive method further comprises the means through the intermediate polymer bonding coat, the extruding layer step of phase deposited polymer substrate film to the oxygen barrier layer nexine of calming the anger.When liquid film coating oxygen barrier layer was coated or is laminated to preferred thermoplastic poly-mer adjacent layer, its oxygen barrier property significantly improved, and such layer also helps to improve overall package ply wood durability.Under the situation of the long-term storage of aseptic packaging and transportation, it is extremely important that packing container has the durability of full intensity and transportation and disposition.Preferred this intermediate heat plastic-bonded layer is in polyolefin and polyolefin-type poly-mer.Under the situation of extruding lamination of aluminum metal or alumina coated substrate, intermediate adhesion layer is preferably traditional LDPE.This intermediate adhesion layer also helps the inboard volume Heat forming of heat seal polymer material, thereby helps packing container leak free high leakproofness conversely.The preferred amounts of finding the intermediate polymer bonding coat is 7um to 20um, preferred 10um to 18um.

According to the embodiment that substitutes; Alternative method comprises that liquid film applies the step on the applied oxygen barrier layer on the middle preferred thermoplastic polymeric adhesive layer; Drying steps, and the hot pressing lamination is coated with the step of the polymer substrate film of vapor deposited metal compound to the intermediate polymer bonding coat subsequently.For this hot pressing lamination, middle liquid film applies the binder polymer that bonding coat is preferably like the polyolefin-type copolymer or contains the graft copolymer of (methyl) acrylic acid or maleic anhydride monomer.The latter's embodiment can be preferred for the low and so not high situation of durability requirement of thickness of intermediate polymer bonding coat, for example, and preferred 2um to 12um, preferred 5um to 10um.Embodiment and preferred implementation explanation

Next, preferred implementation of the present invention is described in conjunction with accompanying drawing, wherein:

Fig. 1 a and 1b symmetry illustrate the cross-sectional view of first and second embodiment of the packaging laminate that makes according to the present invention;

Fig. 2 a and 2b illustrate the preparation method of Fig. 1 a and the said packaging laminate of 1b;

Fig. 3 illustrates the coextrusion of the preferred substrate poly-mer according to the present invention and the scheme drawing of unidirectional orientation subsequently.

Fig. 4 illustrates among Fig. 3 the scheme drawing of the equipment of on the substrate polymers that makes vapor deposition preferable alloy or metal inorganic compound.

Fig. 5 a and 5b illustrate according to the present invention from the embodiment of laminated board production packing container.

How Fig. 6 illustrates in continuing moulding, filling and encapsulation process the key element for preparing packing container from packaging laminate;

How the metallized film that Fig. 7 illustrates on the packaging laminate inboard influences the oxygen transmission in plane packaging ply wood and packing container finished product;

Fig. 8 illustrates the oxygen the transmission how weather with high humidity influences the plane packaging ply wood;

Fig. 9 illustrates according to the present invention, and the packaging laminate that does not have the vapor deposited metal film in the inboard is compared in the oxygen transportation of the packaging laminate of the metallized film that has on the inboard, how in the different brackets cardboard, to change.Embodiment 1

Through in two consecutive steps and therebetween drying, through from

320mN CLC/C cardboard on liquid film apply 2x1g/m ²The aqueous vapor barrier compsns makes packaging laminate, calculates according to dry, and this aqueous vapor barrier compsns is for dissolving and disperse the diffusing PVOH and the amargosite of proportion 20%.

This water vapor rejection preparation of compositions: the aqueous dispersion (from the Kunipia F of Kunimine Kogyo Co.) from the sheet polynite particulate that comes off of the about 1-5% of proportion has the aspect ratio of about 50-5000; Mixed 1-8 hour at 60-90 ℃ with the PVOH aqueous system of proportion about 10% (Mowiol 15-99, have be higher than 99% saponification degree).Can stablize this sheet mineral microparticle that comes off through stabilization additives.In addition, in PVOH solution, placed 1-8 hour for 60-90 ℃, the sheet mineral microparticle directly comes off.

Use coating at 100-150 ℃ of drying plate of plate surface temperature.

The cardboard that contains the obstruct of liquid film coating gas is made folding line, and half of materials is inboard to apply with 25g/m ²The low density polyethylene (LDPE) that LDPE forms, the innermost layer is 15g/m ²The m-LLDPE layer.Half of materials is in addition extruded the means of LDPE laminate layers through melt, with the unidirectional ldpe film lamination of aluminum metallization.The thick 18um of this unidirectional film.The about 15um of this LDPE laminate layers thickness.Be about 400cc/m at 23 ℃, the oxygen transmission of measuring the unidirectional film of metallization during 80%RH ²Day, barometric pressure, corresponding 23 ℃, approximately be about 100cc/m during 50%RH ²Day, barometric pressure.

On plane laminate wrapping material and packing container Cheng Ping, measure the oxygen transmission, unit is (cc/m ²Day, barometric pressure 100% oxygen), according to 1 liter of dress Tetrapack

The observed reading of type packing is calculated.The numerical value that is obtained is as shown in table 1, and the result is shown in Fig. 7 histogram.

Conclusion is that two kinds of increments between packaging laminate are higher than expection.The quite low oxygen obstruction level of metal layer is the same with good PVOH oxygen barrier layer unexpectedly useful.The oxygen obstruction effect is unexpectedly good on the plane packaging ply wood.Yet real pleasantly surprised with the effect of packed products.Almost completely lose the oxygen obstruction characteristic (oxygen transmits near 800cc/m and contain packing container finished product that the inboard Structural layer pressing plate of PE makes ²Day, barometric pressure), as if although the inboard metallized film of packing container can be repaired and the influence that greatly reduces oxygen barrier layer harm in the wrinkle packaging laminate, the packing of the inboard structure of other containing metals PE-film has only increased the oxygen transmission of controlled level.

When 23 ℃ of standard testing weathers, 50%RH, the oxygen obstruction characteristic has cooperative effect.Yet after packing is filled filled with product preservation certain hour, barrier layer will finally reach higher RH (relative humidity), and usually near 80%RH, this moment, the performance of humidity sensitive barrier polymer received negative effect usually.

Table 2 and Fig. 8 (OTR-cc/m ²Day, barometric pressure, 100% oxygen) shown in the result show that between 50%RH and 80%RH, the oxygen of no wrinkle plane packaging ply wood transmits difference and is about 10cc/m in the time of 23 ℃ ²Day, barometric pressure.Although we know the oxygen transmission that on wrinkle plane packaging ply wood, still has wrinkle damages relevant, through or without " reparations " of metallized film, increased initial oxygen and transmitted, between 50%RH and 80%RH, can be observed 10cc/m ²Day, atmospheric identical approximation difference.According to this fact, we can infer that when RH increased, the oxygen transmission difference that comes from initial oxygen transmission had also increased greatly, and this difference is not recording on the corrugated layer pressing plate.The RH susceptibility of the initial oxygen transmission that records on this increase and the packing container is relevant.The oxygen transmission difference relevant with reparation with damage changes insensitive to RH.According to following result, this means on the packing container are when 80%RH, consistent when containing the inboard ply wood of PE-and containing oxygen transmission quantity difference between the inboard ply wood of met-PE almost with 50%RH.As a result, during 80%RH, cooperative effect is equal to effectively.Carry out the oxygen test transmission because can't obtain the high humidity laboratory, this conclusion can not verify that still the fact that the test of long-term normal temperature storage has successfully been kept out in the high-quality aseptic packaging of still being produced has confirmed it through actual measurement.

Need not further to improve liquid film to apply the quality that intercepts opposite with the oxygen obstruction characteristic with thinking at first.Through combine applying film with thin vapor deposited metal or inorganic metal compound, may reduce the oxygen obstruction characteristic of liquid film coat, but still can in the packing container finished product, obtain reliable level oxygen obstruction.Two kinds of first thin and fragiles the layer that is not durable, can mutually combine to gnotobasis packing provides the durable packaging laminate that can compare with the characteristic of aluminium foil type packaging laminate, keep at least 3 months time at least.

And, through applying thicker gas barrier composition layer or improving the consumption of filling PVOH layer inorganic particles, can also further improve the gas barrier characteristic slightly.Yet,, can significantly improve the peculiar smell barrier properties through applying thicker and fine and close blanketing gas barrier layer composition.The representative type example has, and contains the barrier compsns of PVOH and proportion 10% to 50% french talc particulate, preferably talc powder particles specific weight 20% to 40%.

Through the oxygen transmission value on the Mocon Oxtran 2/20 device measuring packing.Use air as test gas, the packing structure comprises cardboard.All central enterprise's transmission values all multiply by the factor 4.76.Pretreatment (23 ℃, 50%RH in the laboratory, indoor 23 ℃ of artificial climate, 80%RH) is after the week, further through the equipment test constantly up to reaching stationary value.For statistical estimation, six samples have been measured.Table 1 shows the average of three methods in Table 1?

Table 2?

× valuation Example 2

In different tests,, obtain the oxygen transmission of quite big variation when applying identical liquid gas barrier compsns to the different brackets cardboard the time.Different cardboards provide different oxygen obstruction results' reason and are not also understood fully.As stated, different cardboards apply with above-mentioned 2x1g/m ²The race of montmorillonoid-containing is respectively with PE inboard or the inboard lamination of metallization PE-film.23 ℃, oxygen transmission during 50%RH on the measurement plane packaging laminate.The following coated paperboard (numbered from 1 to 8): 1.?

? 280mN2.?

? 320mN3.?

? 260mN4.?

? 150mN5.?

? 80mN6.Stora? Enso? 260mN7.International? Paper? 260mN8.Klabin? 260mN

As illustrate shown in Figure 9, through increasing metallized film to packaging laminate (LDPE is inboard for the inboard contrast of Met-PE-), the difference of correction oxygen transmission value.As a result, as if in this case,, can also proofread and correct and repair the oxygen obstruction defective that some kind is derived from the cardboard different qualities by the film of metal composite institute vapor deposition.

Fig. 1 a cross-sectional plane illustrates, and makes first embodiment that is used for the aseptic packaging and the packaging laminate 10a of long-term normal temperature storage according to the present invention.This ply wood comprises the back flow liner 11 with 320mN binding power, and on back flow liner, form and the oxygen obstruction thin layer 12 of subsequent drying by the liquid film coating of liquid gas barrier compsns.This oxygen barrier composition comprises the dispersion of the PVOH aqueous system and lamination inorganic particles; Especially account for the amargosite of dry weight quality 20%; Therefore after drying, the included PVOH of this coat has flakey or the sheet particulate that is distributed in PVOH matrix or continuous phase with the layering form.This packaging laminate further comprises by the coated polymer substrate film 15 of aluminum metal vapor deposition thin layer of thickness 10nm to 30nm.Through polyolefin-type Polymer interlayers 13, preferred low density polyethylene (LDPE) (LDPE), this vapor deposition applies film 15-14 and is laminated to liquid film coating sandwich layer 11-12.Preferably press oxygen obstruction to apply the means of the gentle phase deposited polymer of sandwich layer substrate film, form this intermediate adhesion layer 13 through mutual extruding layer.The thickness of preferred intermediate adhesion layer 13 is 7um to 20um, more preferably 12-18um.Use polyolefin fluid-tight heat-sealing in sandwich layer 11 outsides outer 16, the outside of the packing container that is promptly made by packaging laminate.The polyolefin of this skin 16 is the conventional low density polyethylene (LDPE) (LDPE) with heat sealability.Fluid-tight heat-sealing innermost layer is positioned at vapor deposition layer 14 inboards, the inboard of the packing container that promptly makes by packaging laminate, and layer 15 directly contacts with the institute packaged products.This seals the included linear low density polyethylene in innermost layer (LLDPE), preferably also is included in vinyl monomer and C4-C8 under the metallocene catalyst effect, the preferred LLDPE of C6-C8 alpha-olefin alkene monomer polymerization, promptly so-called metallocene-LLDPE (m-LLDPE).This heat-sealing innermost layer 15 can be made up of two-layer or several layers of identical or different kind of LLDPE layering, thereby forms polymer substrate film 15.This polymer substrate film 15 is unidirectional thickness 20um or thinner, preferred 15um or thinner, and have ethylene acrylic acid co polymer (EAA) metal reception thin.This metal is married and is searched the thick 1um to 3um of being in layer back.Although do not recommend in the cost angle, at the thicker hot sealing layer of some demands in particular cases, can further use the heat-sealing polyethylene layer to the innermost layer 15 inboard.

Similar shown in packaging laminate shown in Fig. 1 b and Fig. 1 a, difference is that refill layer 11 is 11g/m ²More tissue layers.Because ply of paper is thinner,, this packaging laminate intercepts thereby need adding the pigment additional optical in the thermoplastic layer.Therefore, in intermediate adhesion layer 13, add like titanium dioxide (TiO ₂) wait reflective antholeucin.In addition, in the polymer substrate film, can add extinction melanin.

Fig. 2 a character property is illustrated in the method that liquid film on paper or the ply of board applies liquid oxygen barrier composition.Be coated with stop 22a supply ply of paper 21a from memory disc to liquid film, here, using the amount that a certain amount of liquid gas barrier compsns makes paper after applying apply drying layer during 22b through the super-dry station is about 1-2g/m ²Preferably implement the liquid film coating operation in two steps, promptly through applying for the first time 0.5-1g/m ², dry through intermediate steps, apply 0.5-1g/m then for the second time ², the total liquid film coat of final drying obtains oxygen obstruction and applies ply of paper 21b.

Fig. 2 b illustrates lamination treatment 20b; Wherein through extrude LDPE interlayer 24 and pinched together by rod jaw 25 from extrusion station 24a, oxygen obstruction coat 21b is laminated to and is containing on the vapor deposition substrate polymers film 23 of gas phase deposit thin 23a in the face of the ply of paper side.Under the situation of metallization vapour deposition coating, before these layers are pinched together by jaw, through the contact surface of surface treatment (not shown) pre-processed substrate film or receiving layer.Subsequently, the lamination carton membrane is through second extruder 27 and lamination jaw 28, and here, LDPE heat-sealing outermost layer 26 is applied to the ply of paper skin.Last packaging laminate 29 is wound on the unshowned memory disc.

Fig. 3 is for being used for by (being total to) extrusion blow intermediate film, i.e. the equipment scheme drawing of substrate polymers film before metal or the electrodeless metal composite vapor deposition coating.Extruder 30 is extruded the film 34 that one or more layers substrate polymers film forms high relatively thickness with air blower 32.Then, when film 34 still receives single shaft between roller heat the time to directed 36, thereby reduce this film thickness 34a, the substrate polymers film becomes unidirectional and obtains certain rigidity, and this is because it has higher crystallinity relatively than omnidirectional thin polymer film.Result's intermediate film shows selective thermal stability in the additional heating steps before being wound onto roller 38.Thereby optimizing temperature curve through the adjustment roller avoids curling of plate with the concrete structure of orientation film or breaks.Film 34 leaves and extrudes-during air blower 32, can open before being directed.If necessary, class uses two parallel orienters 36 in this case.Can also break away from the film air blower and implement directional operation.

Fig. 4 is the embodiment scheme drawing of equipment that is used for the vapour deposition coating of the intermediate film that Fig. 3 makes.At the coating receiving end, receive the lasting evaporating deposition 40 of aluminium (can mix) metal layer from the orientation film 44a among Fig. 3 with aluminium oxide, given this coat thickness is 5-100nm, preferred 5-50nm, thus form coated film 14-15 of the present invention.This aluminum vapor is from solid members evaporation source 41.

Fig. 5 a illustrates according to the present invention, by the preferred embodiment of the prepared packing container 50a of packaging laminate 10a.This packing container is particularly useful for beverage, soy sauce, soup or analogue.Usually, this packing has the capacity of 100mL to 1000mL.It can be any form, but preferably has the brick shape of vertical envelope 51 and horizontal sealing 52, and opener 53 optionally.In unshowned another embodiment, packing container can be wedge shape.This in order to obtain " wedge shape ", only wrapped bottom is folded, thereby is hidden within the bottom transverse heat-sealing under the triangle flap, and this triangle flap is folded and is pasting the package base sealing.Not folding top horizontal sealing.Through like this, when this half-lap packing container is placed on food supply retail shop's shelf or desk or the analogue, still be easy to take dimensionally stable.

Fig. 5 b is illustrated a kind of possible selection of packing container 50b according to the present invention by the preferred embodiment of the prepared packing container 50b of packaging laminate 10b.Because packaging laminate 10b has thin refill layer, so it is thinner, size is stable inadequately folding to form parallelohedron or wedge shaped packages container, and is folding at horizontal sealing 52b rear portion.Therefore, it still is a pillow pouch class packing, and with this form dispensing and sale.

Fig. 6 illustrates the key element shown in the application explanation, and promptly the packing timber flitch leads to that ' mutual bonding formation overlapped joint 63 forms pipe 61 crossing in the class longitudinal edge 62,62.This pipe warp 64 is packed into the predetermined liquid food product, and repeats horizontal sealing 65 through the predetermined space under the weighting material horizon in pipe, thereby pipe is divided into independent packaging.Along across seal cutting and separating packing 66, and along the crease line folding forming of preparing in the material, the geometric shape of giving to expect.

The present invention is not limited by above-mentioned embodiment, but changes within the scope of the claims." OTR after the different disposal step " legend 1a:C97 (no wrinkle) 1b:C107 (no wrinkle) 1c:C121 (no wrinkle) 2a:C97 among Fig. 7 and Fig. 8 (wrinkle, PE-is inboard) 2b:C107 (wrinkle, PE-is inboard) 2c:C121 be (wrinkle; PE-is inboard) 3a:C97 (wrinkle, met PE-is inboard) 3b:C107 (wrinkle, met PE-is inboard) 3c:C121 (wrinkle; Met PE-is inboard) 4a:C97 (packing, PE-is inboard) 4b:C107 (packing, PE-is inboard) 4c:C121 (packing; PE-is inboard) 5a:C97 (packing; Met PE-is inboard) 5b:C107 (packing, met PE-is inboard) 5c:C121 (packing, met PE-is inboard).

Claims (41)

1. packaging laminate (the 10a that is used for the liquid food packing of product that has the gas barrier characteristic; 10b) comprising: the sandwich layer of paper or cardboard; First fluid-tight, heat-sealing polyolefin outermost be (16) layer by layer; Second fluid-tight, heat-sealing polyolefin innermost layer (15); Form the also oxygen barrier layer (12) of subsequent drying by liquid gas barrier compsns liquid film coating, be coated on paper or the ply of board inboard; This fluid composition comprises the polymer adhesive that is dispersed or dissolved in aqueous medium or solvent medium; It is characterized in that packaging laminate further comprises the vapor deposition barrier layer (14) that is coated on the polymer substrate film; This vapor deposition applies film and is positioned between said oxygen barrier layer (12) and the heat-sealing polyolefin innermost layer (15), and its characteristic is that also this vapor deposition applies film and is adhered to the coating sandwich layer through intermediate polymer layer (13).

2. the packaging laminate that is used for liquid food packing according to claim 1 is characterized in that said polymer adhesive is the poly-mer with gas barrier characteristic.

3. the packaging laminate that is used for liquid food packing according to claim 1 is characterized in that said polymer adhesive is selected from vinyl alcohol type poly-mer like preferred PVOH or aqueous dispersion EVOH, acrylic or methacrylic acid-based polymer, polysaccharide, polysaccharide derivates and the group that forms of two or more combination wherein.

4. the packaging laminate that is used for liquid food packing according to claim 1 is characterized in that said polymer adhesive is PVOH, preferably has at least 98% saponification degree, more preferably at least 99%.

5. according to each described packaging laminate among the claim 1-4, it is characterized in that said fluid composition further comprises inorganic particles.

6. according to the packaging laminate described in the claim 5, it is characterized in that said inorganic particles is sheet or flakey.

7. according to the packaging laminate described in the claim 6, it is characterized in that said inorganic particles is that the flake nano level small bits of clay of 50-5000 is formed by aspect ratio mainly.

8. according to the packaging laminate described in the claim 6, it is characterized in that said inorganic particles is that the platy talc particulate of 10-500 is formed by aspect ratio mainly.

9. according to each described packaging laminate among the claim 1-8, it is characterized in that said oxygen barrier layer (12) is at gross dry weight amount 0.1g/m ²To 5g/m ²Shi Yingyong, preferred 0.5g/m ²To 3.5g/m ², more preferably 0.5g/m ²To 2g/m ²

10. according to each described packaging laminate in the aforementioned claim, it is characterized in that said oxygen barrier layer (12) is dry in two or more subsequent steps and centre as two or more hierarchical application, each layer consumption 0.5g/m ²To 2g/m ², preferred 0.5g/m ²To 1g/m ²

11., it is characterized in that said oxygen barrier layer (12) and said paper or back flow liner direct neighbor according to each described packaging laminate of 1-10 in the claim.

12., it is characterized in that the layer of said vapor deposition coat (14) for forming by aluminium or aluminium oxide in fact according to each described packaging laminate in the aforementioned claim.

13., it is characterized in that said vapor deposition coat (14) is a metal layer according to each described packaging laminate in the aforementioned claim.

14., it is characterized in that said vapor deposition coat (14) is a carbon type layer according to each described packaging laminate in the aforementioned claim.。

15., it is characterized in that said vapor deposition coat (14) uses when thickness 5nm to 500nm (from 50A to 5000A) according to each described packaging laminate in the aforementioned claim.

16. according to each described packaging laminate in the aforementioned claim, the said substrate polymers film that it is characterized in that being used for vapor deposition is the polyolefin-type film.

17., it is characterized in that the said substrate polymers film that is used for vapor deposition also comprises said heat seal polymer innermost layer (15) according to each described packaging laminate in the aforementioned claim.

18. according to each described packaging laminate in the aforementioned claim, it is characterized in that said heat seal polymer innermost layer (15) mainly is made up of low density polyethylene (LDPE), preferably mainly form by linear low density polyethylene (LLDPE).

19., it is characterized in that said substrate polymers film is the unidirectional film that said innermost layer heat seal polymer (15) is formed according to each described packaging laminate among the claim 16-18.

20. according to each described packaging laminate in the claim 19, it is characterized in that said unidirectional film (15) comprises most low density polyethylene (LDPE)s, preferred linear low density polyethylene.

21. according to each described packaging laminate among the claim 19-20, it is characterized in that said unidirectional film (15) thickness is 20um or thinner, preferred 15um or thinner.

22. according to each described packaging laminate among the claim 19-21, it is characterized in that said unidirectional film (15) further comprises the polyolefin top layer of functional groups modification, said vapour deposition coating is applied on this top layer.

23. according to the packaging laminate described in the claim 22, it is characterized by said improved polyalkene is ethene (methyl) acrylic copolymer (EAA or EMAA).

24., it is characterized in that said vapor deposition film (14-15) is bonding with paper or ply of board through the intermediate polymer layer (13) that is selected from polyolefin or polyolefin-type binder polymer according to each described packaging laminate in the aforementioned claim.

25. according to the packaging laminate described in the claim 24, it is characterized in that inorganic particles that intermediate polymer bonding coat (13) further comprises the melanin form with the photoresistance that strengthens packaging laminate at a distance from characteristic.

26. according to the packaging laminate described in the claim 24, it is characterized in that inorganic particles that said intermediate polymer bonding coat (13) further comprises the antholeucin form with the photoresistance that strengthens packaging laminate at a distance from characteristic.

27. according to the packaging laminate described in the claim 26, it is characterized in that said vapor deposition apply inorganic particles that substrate polymers thin layer (14-15) further comprises the melanin form with the photoresistance that strengthens said packaging laminate at a distance from characteristic, preferred carbon black.

28. the packaging laminate (10a according to claim 1-27 in arbitrary; Preparation method 10b) comprises that step is following:

Prepare paper or ply of board (21a);

Preparation contains the liquid gas barrier compsns of the polymer adhesive that is dispersed or dissolved in aqueous medium or solvent-borne type liquid dielectric;

Comprise that through applying (22a) fluid composition first, forming the oxygen barrier layer of said polymer adhesive and subsequent drying (22b) evaporate liquid to said paper or ply of board;

Prepare polymer substrate film (23);

Vapor deposition barrier layer (14 on said substrate polymers film; 23a);

Said vapor deposition film (23) is laminated to the inboard of said vapor deposition layer (21b) through said intermediate polymer layer (13);

In the inboard preparation of said vapor deposition layer (14) heat seal polymer innermost layer (15);

At said sandwich layer (11) outside preparation heat seal polymer outermost layer (16).

29. according to the method described in the claim 28, wherein said oxygen barrier layer (12) directly is coated in the inboard of said paper or back flow liner (11).

30. according to each described method among the claim 28-39, wherein said liquid gas barrier compsns further comprises inorganic particles.

31. according to each described method among the claim 28-30, the said oxygen obstruction poly-mer in the wherein said fluid composition is selected from by PVOH, water-soluble EVOH, acrylic or methacrylic acid polymer, polysaccharide, polysaccharide derivates and the group that forms of two or more combination wherein.

32. according to each described method among the claim 28-31, wherein said oxygen barrier layer (12) gross dry weight amount when using is 0.1g/m ²To 5g/m ², preferred 0.5g/m ²To 3.5g/m ², more preferably 0.5g/m ²To 2g/m ²

33. according to each described method among the claim 28-32, wherein oxygen barrier layer (12) is dry in two or more subsequent steps and centre as two or more hierarchical application, each layer consumption 0.5g/m ²To 2g/m ², preferred 0.5g/m ²To 1g/m ²

34. according to each described method among the claim 28-33, the said polymer substrate film 34a that wherein is used for vapor phase deposition is made by the blown film of extruding that comprises the heat seal polymer innermost layer.

35. according to the method described in the claim 34, further be included in the step of the polymer substrate film of preceding unidirectional orientation (36) blowing of vapor phase deposition coating, this polymer substrate film comprises most linear low density polyethylenes.

36. according to the method described in the claim 35, comprising the polymer substrate film (23 of most linear low density polyethylenes; 34a) unidirectional (36) thickness 20um or thinner, preferred 15um or thinner.

37. according to each described method among the claim 28-36, wherein at substrate polymers film (23; 34a; 44a) go up vapor deposition aluminum metal or alumina layer (14; 23a).

38. according to each described method among the claim 28-37, wherein said vapor deposition coat (14; 23a) when thickness 5nm to 200nm (from 50A to 2000A), use.

39. according to each described method among the claim 28-38, wherein through with intermediate polymer bonding coat (13; 24) extrude the means of lamination, with said vapor deposition film (23; 23a) be pressed onto said oxygen barrier layer (12; 21b) inboard.

40. according to each described method among the claim 28-38, further be included in applied oxygen barrier layer (12) go up liquid film apply intermediate polymer layer (13), dry and subsequently the hot pressing lamination by the coated polymer substrate film of vapor deposited metal compound (14-15; 23-23a) to the step of intermediate heat plastic-bonded layer (13).

41. packaging laminate (10a according to each elaboration among the claim 1-27; 10b) the packing container (50 of preparation; 50b).

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