CN101119844A - Multilayer polyolefin film for use in paper container for liquids, material for use in paper container for liquids comprising the same, and paper container for liquids using the same - Google Patents

Abstract

Disclosed are a multilayer polyolefin film which has a such specified layer structure that, when used as a sealant layer to be provided on the innermost surface of a paper container for liquids, can prevent the deterioration in flavor, taste or smack of a content in the container; a material for a paper container for liquids comprising the film; and a paper container for liquids using the film. A multilayer polyolefin film for use in a paper container for liquids comprising at least a surface layer (layer a), an opposite surface layer (layer c) and a middle layer (layer b), the layers a, b and c having the following properties: layer a: a layer comprising a propylene homopolymer or a propylene copolymer; layer b: a layer comprising a propylene copolymer and an ethylene-a-olefin copolymer; and layer c: a layer comprising an ethylene-a-olefin copolymer and having a melting point ranging from 60 to 140 DEG C and a thickness ranging from 1 to 20 [mu]m; a material for use in a paper container for liquids comprising the film; and a paper container for liquids using the film.

Description

The liquid paper container is with multi-layer polyolefin film, the liquid paper container material that uses this film and liquid paper container

Technical field

The present invention relates to a kind of taste of content and the polyolefin film that the sense of taste, local flavor change, the liquid paper container material that uses this film and liquid paper container of as the sealant of the inner face of liquid paper container the time, not making.

Background technology

All the time, as the liquid paper container that milk, fruit juice or other beverage are used, various types of containers such as shape top, known room type, flat-head type, brick type.These liquid paper containers use at the two sides of paper base material outermost layer lamination to be had as the liquid paper container material of the thermoplasticity synthetic resin of sealant and moulding, and, when this moulding, must comprise outermost layer of this liquid paper container material (for example, becoming the most inboard sealant when the liquid paper container formation) and the thermosealed operation of another outermost layer (becoming identical outermost sealant).In this case, as the thermoplasticity synthetic resin that constitutes above-mentioned sealant,, be extensive use of polyethylene from the viewpoint of heat seal and cost.

But if use the resin of polyethylene as the sealant that constitutes the inner face of liquid paper container, wherein contained low molecular weight compositions will shift to the content in the liquid paper container, makes it easily to produce that resin is smelly, resinous odour or foreign odor, peculiar smell.Particularly have under the automatic selling-machine of heating function or the situation that heater heats the liquid paper container beverage in use, through the time ground smelly commodity value of this liquid paper container beverage that makes of resin that takes place significantly descend.In addition, when the content of liquid paper container is fruit juice etc., polyethylene absorption taste component.Therefore, use the liquid paper container of polyethylene, in it is preserved, the taste of content and the sense of taste, local flavor are changed as the resin that constitutes inner face sealant.

In order to address this is that, thermoplasticity synthetic resin as the sealant that constitutes the inner face of liquid paper container has been proposed, replace polyethylene, use the scheme as the liquid paper container material such as ethene-alpha-olefin copolymer (patent documentation 1) or use polyester (patent documentation 2), but do not obtain the material of abundant performance as yet.

Patent documentation 1: TOHKEMY 2001-199433 communique

Patent documentation 2: Japanese kokai publication hei 11-216821 communique

Summary of the invention

In view of above-mentioned prior art problems, the objective of the invention is to, provide a kind of liquid paper container with multi-layer polyolefin film, the liquid paper container material that uses this film and liquid paper container, this liquid paper container with multi-layer polyolefin film as the sealant of the inner face of liquid paper container the time, taste, the sense of taste and the local flavor of content are changed, and and can access excellent heat-seal strength between the polyethylene as the resin of the sealant that constitutes liquid paper container outermost side all the time.

The inventor etc. carry out deep research repeatedly in order to address the above problem, as a result, find to adopt and use the liquid paper container material of specific liquid paper container, make the liquid paper container formation with the multi-layer polyolefin film, can solve above-mentioned problem, so far finish the present invention.

Promptly, liquid paper container multi-layer polyolefin film of the present invention, it is characterized in that, it is the liquid paper container multi-layer polyolefin film that has a superficial layer (a layer), another superficial layer (c layer) and intermediate layer (b layer) at least, this a layer, b layer and c layer have following characteristic, a layer: by being selected from the layer that a kind of in Noblen, propylene series copolymer, the ethene-alpha-olefin copolymer or their mixture constitute; The b layer: by propylene series copolymer and ethene-alpha-olefin copolymer constitute the layer; The c layer: the fusing point that is made of ethene-alpha-olefin copolymer is that 60～140 ℃ and thickness are the layer of 1～20 μ m.

In addition, this liquid paper container is characterised in that with the multi-layer polyolefin film propylene series copolymer that constitutes a layer is propylene-ethylene-1-butene terpolymers or propylene-ethylene random copolymer.And this liquid paper container is characterised in that with the multi-layer polyolefin film ethene-alpha-olefin copolymer that constitutes a layer is ethene-butene-1 copolymer or ethene-1-hexene copolymer.

In addition, this liquid paper container is characterised in that with the multi-layer polyolefin film propylene series copolymer that constitutes the b layer is the propylene-ethylene random copolymer.This liquid paper container is characterised in that with the multi-layer polyolefin film ethene-alpha-olefin copolymer that constitutes the b layer equally is ethene-butene-1 copolymer.

In addition, this liquid paper container is characterised in that with the multi-layer polyolefin film ethene-alpha-olefin copolymer that constitutes the c layer is ethene-butene-1 copolymer.

And, preferred these liquid paper containers with multi-layer polyolefin at least lamination form as an outermost sealant B layer that constitutes by thermoplasticity synthetic resin, ply of paper with as another outermost sealant A layer, sealant A layer as the liquid paper container material, use its a layer to the inside, use the c layer laterally.And preferably this liquid paper container material is as the moulding material of liquid paper container.

Description of drawings

Fig. 1 is the stereogram of brick type liquid paper container of the present invention.

Fig. 2 is the layer structure chart of the liquid paper container that comprises the suction pipe patchhole of embodiment 1.

Fig. 3 is the layer structure chart of the liquid paper container that comprises the suction pipe patchhole of comparative example 1.

Fig. 4 is the layer structure chart of the liquid paper container that comprises the suction pipe patchhole of comparative example 2.

Fig. 5 is the layer structure chart of the liquid paper container that comprises the suction pipe patchhole of embodiment 2～4.

Fig. 6 is the layer structure chart of the liquid paper container that comprises the suction pipe patchhole of comparative example 3.

Symbol description

1: low density polyethylene layer; 2: printed layers; 3: ply of paper; 4: aluminium foil layer; 5: biaxial stretch-formed lamination polyolefm film layer; 6: three layers of no drawing polyolefin thin layer; 7: the low-density polyethylene film layer; 8: suction pipe inserts oral area; 9: individual layer does not have stretching straight chain shape low-density polyethylene film.

The invention effect

Liquid paper container of the present invention with the multi-layer polyolefin film as the sealant of the inner face of liquid paper container the time, can make hardly that content produces that resin is smelly, resinous odour or foreign odor, peculiar smell etc., or the taste component of absorption content, so, taste, the sense of taste and the local flavor of content are changed.And, carry out under the thermosealed situation at the polyethylene as the resin of the sealant of the outermost side that constitutes the liquid paper container all the time, can access excellent heat-seal strength.

The specific embodiment

At first, liquid paper container multi-layer polyolefin film of the present invention is described.

Liquid paper container of the present invention is with a layer of multi-layer polyolefin film, by being selected from a kind of in Noblen, propylene series copolymer, the ethene-alpha-olefin copolymer or their mixture constitutes.Its thickness is not particularly limited, and is generally about 1～10 μ m.

As mentioned above, the liquid paper container of the present invention a layer of multi-layer polyolefin film, by being selected from a kind of in Noblen, propylene series copolymer, the ethene-alpha-olefin copolymer or their mixture constitutes, wherein, preferred use is independent by propylene series copolymer, by the mixture of propylene series copolymer and ethene-alpha-olefin copolymer or the resin that is made of ethene-alpha-olefin copolymer separately.More preferably use separately separately or the resin that constitutes by the mixture of propylene series copolymer and ethene-alpha-olefin copolymer by propylene series copolymer.In addition, mixture as propylene series copolymer and ethene-alpha-olefin copolymer, from the viewpoint of the adhesive strength when polyethylene-based resin described later carries out the interlayer lamination, be preferably the mixture that in propylene series copolymer, contains the ethene-alpha-olefin copolymer more than the 30 weight %.

When making liquid paper container material of the present invention, liquid paper container of the present invention is constituted raw material with a aspect of multi-layer polyolefin film and other, and for example the face of other thermoplasticity synthetic resin layer, aluminium foil layer or ply of paper etc. is bonding, makes liquid paper container of the present invention constitute the raw material lamination with multi-layer polyolefin film and other.Other constitutes the method for raw material as lamination, can use dry lamination method or interlayer laminating etc.

Liquid paper container of the present invention with a layer of multi-layer polyolefin film by Noblen or when constituting by the resin of propylene series copolymer separately, viewpoint from adhesive strength, preferably a laminar surface is carried out surface treatments such as sided corona treatment, using biliquid curing type ester is bonding agents such as bonding agent, adopts dry lamination method and other formation raw material to carry out lamination.In addition, as the resin that constitutes a layer, when selecting, also can adopt interlayer lamination across polyethylene-based resin by the mixture of propylene series copolymer and ethene-alpha-olefin copolymer or the independent resin that constitutes by ethene-alpha-olefin copolymer.In this case, even a laminar surface is not implemented sided corona treatment, in a layer contained ethene-alpha-olefin copolymer also can with for example low density polyethylene (LDPE), straight chain shape low density polyethylene (LDPE) or their weldings securely such as modified poly ethylene of polyethylene-based resin of fusion, obtain having the laminated body of high-adhesive-strength.

As constitute the propylene series copolymer of liquid paper container of the present invention, can list with a layer of multi-layer polyolefin film be derived from the alpha-olefin beyond the propylene monomeric unit less than the propylene-alpha-olefin copolymers of 10 weight % or their mixture.As above-mentioned alpha-olefin, for example, can list ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.And above-mentioned copolymer can be any one in random copolymer, block copolymer, the graft copolymer.Wherein, as constituting Noblen or the propylene series copolymer of liquid paper container of the present invention with a layer of multi-layer polyolefin film, the surface-treated effect that is produced by corona discharge is very big, with the liquid paper container of the present invention formation raw material of multi-layer polyolefin film as this liquid paper container material, adopting the dry lamination method with the formation raw material of itself and other liquid paper container material other thermoplasticity synthetic resin layer for example, aluminium foil layer or ply of paper etc. carry out under the situation of lamination, preferably can access the propylene-ethylene-1-butene terpolymers or the propylene-ethylene random copolymer of excellent dry lamination adhesive strength.

As constituting the ethene-alpha-olefin copolymer of liquid paper container of the present invention with a layer of multi-layer polyolefin film, can list the monomeric unit that is derived from ethene alpha-olefin in addition is the ethene-alpha-olefin copolymer of 5～20 weight % or the mixture of these copolymers.As above-mentioned alpha-olefin, for example, can list propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.And above-mentioned copolymer can be any one in random copolymer, block copolymer, the graft copolymer.Wherein, as the ethene-alpha-olefin copolymer that constitutes multi-layer polyolefin film a layer of the present invention, with the liquid paper container of the present invention formation raw material of multi-layer polyolefin film as the liquid paper container material, adopt the interlayer laminating with the formation raw material of itself and other liquid paper container material other thermoplasticity synthetic resin layer for example, aluminium foil layer or ply of paper etc. carry out lamination across polyethylene-based resin, in this case, even preferably do not implement ethene-butene-1 copolymer that Corona discharge Treatment also can access excellent interlayer lamination adhesive strength, ethene-1-hexene copolymer.

In addition, liquid paper container of the present invention is made of propylene series copolymer and ethene-alpha-olefin copolymer with the b layer of multi-layer polyolefin film.There is no particular limitation for the thickness of this b layer, usually can be for about 10～20 μ m.

In this case, as propylene series copolymer, can list the monomeric unit that is derived from propylene alpha-olefin in addition is the propylene-alpha-olefin copolymers of 2.5～6.0 weight % or the mixture of these copolymers.As above-mentioned alpha-olefin, for example, can list ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.

And above-mentioned copolymer can be any one in random copolymer, block copolymer, the graft copolymer.Wherein, as constituting the propylene series copolymer of liquid paper container of the present invention with the b layer of multi-layer polyolefin film, when considering more firm bonding of above-mentioned a layer and this b layer, preferred propylene-ethylene random copolymer.The propylene-ethylene random copolymer is when cooperating Noblen or propylene series copolymer, with the intermiscibility height of these resins, so as the resin that constitutes the b layer, can access more firm bonding of a layer and b layer in a layer.

On the other hand, as ethene-alpha-olefin copolymer, can list the monomeric unit that is derived from ethene alpha-olefin in addition is the ethene-alpha-olefin copolymer of 5～20 weight % or the mixture of these copolymers.As above-mentioned alpha-olefin, for example, can list propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.And above-mentioned copolymer can be any one in random copolymer, block copolymer, the graft copolymer.Wherein, as the ethene-alpha-olefin copolymer that constitutes multi-layer polyolefin film b layer of the present invention, when considering more firm bonding of this b layer and c layer and b layer and a layer, be preferably ethene-butene-1 copolymer.Ethene-butene-1 copolymer, with the intermiscibility height of ethene-alpha-olefin copolymer, so, when in a layer, cooperating ethene-alpha-olefin copolymer,, can access the more firm bonding of b layer and c layer and b layer and a layer as the resin that constitutes the b layer.

Wherein, so-called propylene series copolymer and the ethene-alpha-olefin copolymer that in the b layer, uses, preferably with propylene series copolymer: ethene-alpha-olefin copolymer=50～75 weight %: the ratio of 25～50 weight % cooperates.

The resin that constitutes the b layer contains the propylene series copolymer of 50～75 weight % and the ethene-alpha-olefin copolymer of 25～50 weight %, the intermiscibility of the intermiscibility of the resin that constitutes a layer thus and the resin that constitutes the b layer and resin that constitutes the c layer and the resin that constitutes the b layer increases, the interlaminar strength of the interlaminar strength of a layer and b layer and b layer and c layer becomes firm, so this liquid paper container is used for the multi-layer polyolefin film can access the higher paper container of heat-seal strength under the situation of sealant of the inner face of liquid paper container.And so, a layer, b layer, c layer interlaminar strength separately become firmly, the result, even attenuate c layer, the thickness of a layer, b layer is also brought into play the effect that remedies the c layer thickness, can access higher heat-seal strength.

In addition, the liquid paper container multi-layer polyolefin film that propylene series copolymer that uses in the b layer and ethene-alpha-olefin copolymer cooperate with aforementioned proportion, under the situation of the sealant of inner face as the liquid paper container,, resinous odour smelly or foreign odor, peculiar smell etc. for the resin that prevents content, and then prevent taste, the sense of taste and local flavor rotten of content, can bring into play more excellent effect.Can think, this be because, the resin that constitutes the b layer contains the propylene series copolymer of 50～75 weight %, although stop for a small amount of but still be adsorbed on soaking into of taste component in the c layer, realization will stop at minimal function with the absorption of multi-layer polyolefin film to liquid paper container of the present invention, on the other hand, the ratio that cooperates that constitutes the ethene-alpha-olefin copolymer of b layer with this propylene series copolymer jointly is below the 50 weight %, vinylite content in the b layer is few, so it is smelly that the distinctive resin of vinylite takes place, resinous odour or foreign odor, the absorption of the taste component of peculiar smell and content is also few.

In addition, liquid paper container of the present invention is made of ethene-alpha-olefin copolymer with the c layer of multi-layer polyolefin film.

In this case, as ethene-alpha-olefin copolymer, can list the monomeric unit that is derived from ethene alpha-olefin in addition is the ethene-alpha-olefin copolymer of 5～20 weight % or the mixture of these copolymers.As above-mentioned alpha-olefin, for example, can list propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.And above-mentioned copolymer can be any one in random copolymer, block copolymer, the graft copolymer.Wherein, when liquid paper container of the present invention is made the liquid paper container formation with the multi-layer polyolefin film as the sealant of inner face, the sealant direct heat sealing of this c layer and outermost side, and, become with content directly contact layer.

Therefore, as the ethene-alpha-olefin copolymer that constitutes this c layer, and be widely used as between the polyethylene of sealant of liquid paper container outermost side, can access excellent heat-seal strength, and to content be difficult to take place that resin is smelly, resinous odour or foreign odor, peculiar smell, also be difficult to cause taste component absorption etc., be preferably ethene-butene-1 copolymer, wherein, the preferred low ethene-butene-1 copolymer of crystallinity.Particularly, the density of optimal ethylene-butene-1 copolymer is 0.880g/cm ³More than, less than 0.900g/cm ³More preferably the peak temperature (Tp) that is produced by intensification wash-out partition method (TREF) of ethene-butene-1 copolymer is below 55 ℃, and the branch rate of ethylene-vinyl-ethene (EEE) chain during the chain according to 3 continuous chain links of the molecular structure parsing of NMR of ethene-butene-1 copolymer distributes is below 0.80.Like this, even in ethene-butene-1 copolymer, be difficult to make by adopting the low material of crystallinity, also can accessing that content generation resin is smelly, resinous odour or foreign odor, peculiar smell, also be difficult to cause the copolymer of the absorption etc. of taste component.

In addition, requiring the fusing point of above-mentioned c layer is 60～140 ℃.If fusing point is lower than 60 ℃, when liquid paper container of the present invention is taken care of for the roller shape with the circumvolution of multi-layer polyolefin film, causes adhesion (blocking) or hinder sliding between the film etc., handling and after this processing brings obstacle.On the other hand, if fusing point is above 140 ℃, the difficulty because the heat seal between this c layer and other raw material becomes, so when using liquid paper container material of the present invention to make the liquid paper container formation (c layer become with the heat sealing layer of outermost side by direct thermosealed layer time), between the sealant of the sealant of liquid paper container outermost side and inner face side, can't obtain the heat-seal strength of needs.

And the thickness that requires this c layer is 1～20 μ m.If thickness is less than 1 μ m, when using liquid paper container material of the present invention to make the liquid paper container formation, still between the sealant of the sealant of liquid paper container outermost side and inner face side, can't obtain the heat-seal strength of needs.Can think at thickness during, because the pressure during heat seal and make the c damage layer easily less than 1 μ m.On the other hand, if thickness greater than 20 μ m, when using liquid paper container material of the present invention to make the liquid paper container formation, will cause take place that resin is smelly, resinous odour or taste components such as foreign odor, peculiar smell and/or fruit juice are to the absorption of inner face sealant etc.

Liquid paper container multi-layer polyolefin film of the present invention, at least possess as the above-mentioned a layer of two superficial layers and c layer and as the above-mentioned b layer in intermediate layer, under the situation of the sealant of inner face as the liquid paper container, taste, the sense of taste and the local flavor of content are changed, and, can bring into play and obtain between the thermoplasticity synthetic resin such as polyethylene as the resin of the sealant that constitutes liquid paper container outermost side all the time the effect of excellent heat-seal strength.

Promptly, use liquid paper container multi-layer polyolefin film of the present invention, at least lamination has as an outermost sealant B layer that is made of thermoplasticity synthetic resin, ply of paper and as another outermost sealant A layer that constitutes with the multi-layer polyolefin film by inventive aspect 1 described liquid paper container and form, and, in sealing layer A layer, liquid paper container of the present invention with polyolefin film with its a layer towards the inboard, c layer mode lamination toward the outer side, make liquid paper container material of the present invention, in this case, because the function of a layer, this multi-layer polyolefin film with other of the liquid paper container material of its lamination constituted for example other thermoplasticity synthetic resin layer of raw material, between aluminium foil layer or the ply of paper etc., can access excellent dry lamination and/or interlayer lamination adhesive strength.In addition, use this liquid paper container material, so that the sealant A layer inner face that is the liquid paper container, sealant B layer are the outmost mode of liquid paper container when making the liquid paper container formation, because the function of c layer, at the sealant A layer that becomes the inner face of liquid paper container and become between the outmost sealant B of the liquid paper container layer, can access excellent heat-seal strength.

On the other hand, in aforesaid liquid paper container, liquid paper container of the present invention is with in the multi-layer polyolefin film, and the c layer that constitutes as the ethene-alpha-olefin copolymer of vinylite directly contacts with content.In the liquid paper container, when layer that content directly contacts uses the layer that is made of vinylite, may take place in this content usually that resin is smelly, resinous odour or foreign odor, peculiar smell, or adsorb taste component.But, liquid paper container of the present invention adopts sandwich construction with the multi-layer polyolefin film, by lamination a layer, b layer successively and the c layer that constitutes by ethene-alpha-olefin copolymer, the characteristic that can keep the heat-seal strength excellence, simultaneously can make this c layer is extremely thin thickness 1～20 μ m, so, can bring pernicious influence to content hardly, needn't worry to cause this problem.

In addition, when using liquid paper container of the present invention to make liquid paper container material of the present invention, implement the lamination of this liquid paper container with other formation raw material of multi-layer polyolefin film and liquid paper container material with the multi-layer polyolefin film.Form a layer of liquid paper container of the present invention with a superficial layer of multi-layer polyolefin film, by Noblen or when constituting by the propylene series copolymer resin separately, as above-mentioned laminating method, the preferred dry laminating, at this moment, in order to improve the lamination adhesive strength, a layer is implemented Corona discharge Treatment, improve cementability.Liquid paper container multi-layer polyolefin film of the present invention is made of ethene-alpha-olefin copolymer owing to form the c layer of another superficial layer, so even so improve the cementability of a superficial layer a layer, also is difficult to stick together with the keeping of roller shape the time.Can think that when using plural layers with roller shape keeping liquid paper container, directly contact between the different resins is so because the anti-stick effect that connects that the difference of resin causes can reduce adhesion.

In addition, when in the resin of a superficial layer a layer that constitutes liquid paper container usefulness multi-layer polyolefin film of the present invention, cooperating ethene-alpha-olefin copolymer, as above-mentioned laminating method, by adopting interlayer laminating across polyethylene-based resin, can access firm lamination adhesive strength, so needn't implement Corona discharge Treatment to a laminar surface.Therefore, can think that liquid paper container multi-layer polyolefin film of the present invention even cooperate and formation another superficial layer c layer ethene-alpha-olefin copolymer of the same race, also is difficult to produce adhesion in one surface layer a layer with the keeping of roller shape the time.

And, can think the b layer of liquid paper container of the present invention in the multi-layer polyolefin film, as mentioned above, bonding securely a layer and c layer, although and stop seldom but still be adsorbed on soaking into of taste component in the c layer, bringing into play that this absorption is stopped at minimal function.

There is no particular limitation with the thickness of multi-layer polyolefin film itself for liquid paper container of the present invention, usually, is suitable for selecting use in thickness is the scope of 15～60 μ m.

As the manufacture method of liquid paper container of the present invention with the multi-layer polyolefin film, there is no particular limitation, can adopt known method.For example, be suitable for adopting feed zone (feed block) mode of using multilayer film or individual layer mould, utilize the roller that to regulate temperature to carry out the method that cooling curing twines continuously then respectively from different extruder fusion coextrusion a layer, b layer, c layer resin; After the fusion coextrusion, utilize air chamber or air knife to carry out the method that the air cooling curing twines continuously; Or after the fusion coextrusion, use can be adjusted the tank of temperature, utilizes water cooling to carry out the method that cooling curing twines continuously; Or the employing aeration, while utilize air-cooling or water cooling to carry out the method that cooling curing twines continuously.Behind the cooling curing, as required, also can implement known surface treatments such as Corona discharge Treatment, flame treatment to film surface.As mentioned above, liquid paper container multi-layer polyolefin film of the present invention, can adopt dry lamination method or interlayer laminating, other that is stacked in the liquid paper container material constitutes raw material for example on paper, aluminium foil, polyolefin film, the polyolefin resin layer, in addition, adopt the feed zone mode of using above-mentioned multilayer film and individual layer mould, on one side fusion coextrusion resin, on other formation raw material of these liquid paper container materials, directly extrude lamination on one side, also without any problem.

Below, liquid paper container material of the present invention is described.

In liquid paper container material of the present invention, the thermoplasticity synthetic resin as constituting sealant B layer is suitable for using low density polyethylene (LDPE).But, be not limited to this, also be suitable for using polymer and their mixtures such as straight chain shape low density polyethylene (LDPE), high density polyethylene (HDPE), ethylene-propylene copolymer, ethylene-butene copolymer, propene-1-butene copolymer, Noblen, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer.

As the thermoplasticity synthetic resin that constitutes sealant B layer, can select with the same resin of the resin that in the c layer of liquid paper container that constitutes sealant A layer, uses with the multi-layer polyolefin film or with the resin of the heat seal adaptability excellence of c layer.In addition, the thickness of sealant B layer is preferably 10～50 μ m.

In liquid paper container material of the present invention, also there is no particular limitation for the paper of formation ply of paper.Usually being suitable for using by weight per unit area is 150～400g/m ²Coniferous tree and the former paper pulp of broad leaf tree copy the cardboard of system.

Liquid paper container material of the present invention, at least the lamination ply of paper, as an outermost sealant B layer that constitutes by thermoplasticity synthetic resin with as another outermost sealant A layer that constitutes with the multi-layer polyolefin film by aforesaid liquid paper container and form, and, in sealing layer A layer, the liquid paper container carries out lamination with its a layer towards inboard, c layer mode toward the outer side with the multi-layer polyolefin film.Promptly, as long as take an outermost layer: the sealant B layer that constitutes by thermoplasticity synthetic resin/... / ply of paper/... / another outermost layer: the laminated construction of the sealant A layer (a layer/b layer/c layer) that constitutes with the multi-layer polyolefin film paper by liquid paper container of the present invention, all can with other any layer of any order lamination.

For example, in aforesaid liquid paper container material, airbond (gas barrier) layer can be set between sealant A layer that constitutes with the multi-layer polyolefin film by liquid paper container of the present invention and ply of paper.This airbond layer can be made of known raw material.Wherein, the most representative is aluminium foil.The layer that is made of aluminium foil not only possesses function as the airbond layer, also has both the function as light shield layer, prevents the content oxidation, also plays a part to prevent the deterioration that is caused by light simultaneously., when the raw material beyond using aluminium foil constitutes the airbond layer,, also can prevent the deterioration that content is caused by light by light shield layer is set in addition.In addition, say when the deterioration that content is not vulnerable to be caused by light, this light shield layer is not essential especially.Thickness as the aluminium foil layer of airbond layer is not particularly limited.Usually, be suitable for the layer that used thickness is 7～12 μ m.

In addition, between sealant A layer that constitutes with the multi-layer polyolefin film by liquid paper container of the present invention and above-mentioned airbond layer, can be provided with to improve the layer that the paper vessel strength is a purpose.

As the raw material that constitutes this layer (below be also referred to as " paying the intensity layer "), for example, the fusing point that can be illustrated in fusing point by 75～100 weight % and be 130～145 ℃ polyolefin (hereinafter referred to as " Resin A ") and 0～25 weight % is at least one face of the polyolefin film I layer that constitutes of 154～164 ℃ polyolefin (hereinafter referred to as " resin B "), lamination is that the fusing point of 154～164 ℃ polyolefin (hereinafter referred to as " resin C ") and 20～50 weight % is the oriented polyolefin film II layer of the biaxial orientation that constitutes of 105～145 ℃ polyolefin (hereinafter referred to as " resin D ") by the fusing point of 50～80 weight %, and the planar orientation index that obtains is the biaxial stretch-formed lamination polyolefin film below 0.6.This biaxial stretch-formed lamination polyolefin film, as increasing substantially, has very favorable characteristic by the buckling strength of the liquid paper container of the liquid paper container material moulding of its lamination etc. and suction pipe are inserted the also very excellent raw material of paying the intensity layer that constitutes the liquid paper container material of property.As this thickness of paying the biaxial stretch-formed lamination polyolefm film layer of intensity layer, preferably in the scope of 10～80 μ m.

In addition, in above-mentioned biaxial stretch-formed lamination polyolefin film, as Resin A, can list the monomeric unit that is derived from the alpha-olefin beyond the propylene and be 2.5 weight % above, less than propylene-alpha-olefin copolymers or these mixture of polymers of 10 weight %.As above-mentioned alpha-olefin, for example, can list ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.And above-mentioned copolymer can be any one in random copolymer, block copolymer, the graft copolymer.Wherein, preferred propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-ethylene-butene copolymer.

As resin B, can list Noblen or be derived from propylene-alpha-olefin copolymers or these mixture of polymers of the monomeric unit of propylene alpha-olefin in addition less than 3 weight %.As above-mentioned alpha-olefin, for example, can list ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.Wherein, preferred Noblen or the monomeric unit that is derived from ethene are the following propylene-ethylene random copolymer of 1 weight %.

As resin C, can list Noblen or be derived from propylene-alpha-olefin copolymers or these mixture of polymers of the monomeric unit of propylene alpha-olefin in addition less than 3 weight %.As above-mentioned alpha-olefin, for example, can list ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.Wherein, preferred Noblen or the monomeric unit that is derived from ethene are the following propylene-ethylene random copolymer of 1 weight %.

As resin D, can list the monomeric unit that is derived from the alpha-olefin beyond the propylene and be 3 weight % above, less than propylene-alpha-olefin copolymers or these mixture of polymers of 30 weight %.As above-mentioned alpha-olefin, for example, can list ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.And above-mentioned copolymer can be any one in random copolymer, block copolymer, the graft copolymer.Wherein, preferably propylene-ethylene-butene copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, propene-1-butene copolymer are mixed.

Above-mentioned biaxial stretch-formed lamination polyolefin film is suitable for adopting method manufacturing shown below.At first, use the multilayer film more than at least 2 layers, obtain by polyolefin film I layer with resin constitute the layer single face or the two sides lamination have by polyolefin film II layer with resin constitute the layer sheet material, after MD direction (length direction of film) is carried out uniaxial tension to this sheet material, carry out biaxial stretch-formed in TD direction (direction vertical) with the length direction of film.At this moment, in carrying out biaxial stretch-formed stenter, make formation polyolefin film I the layer Resin A of resin and the Resin A fusion in the resin B by stenter heat treatment, polyolefin film I layer is in does not have the state that is orientated or a little orientation is arranged in fact.

On the other hand, at this moment, constituting polyolefin film II layer with among the resin C and resin D of resin, resin D orientation relaxes and by partial melting, but the orientation of resin C is residual, as a result, the orientation of polyolefin film II layer is residual, and obtaining has biaxial stretch-formed lamination polyolefin film through the oriented polyolefin film II layer of biaxial orientation at the single face of polyolefin film I layer or two sides superimposed layer.At this moment, stretching ratio has no particular limits, usually can be from being 4～8 times at MD, selecting in TD is 6～13 times scope.

Wherein, so-called planar orientation index is the index of expression to the planar orientation degree of the face of the laminate film face that is parallel to 010 of the crystalling propylene obtained by X-ray diffraction method.Specifically, making above-mentioned biaxial stretch-formed lamination polyolefin film on one side is that the center rotates at a high speed with the axle perpendicular to pellicular front, make X ray from direction incident on one side perpendicular to pellicular front, measure diffracted intensity, the X-ray diffraction intensity curve that obtains is carried out the separation at peak, be separated into amorphous mass peak, crystallization mass peak and each crystallization mass peak, the peak intensity that reflects (2 θ=17.1 °) by 111 reflections (2 θ=21.4 °) and 040 by crystalling propylene (α crystallization) is than obtaining with following formula (1).

Planar orientation indices P 010=log{1.508 * I (111)/I (040) } (1)

Wherein,

I (111): 111 reflection peak intensity (counts)

I (040): 040 reflection peak intensity (counts)

Wherein, the coefficient 1.508 of formula (1) is, by Z.Mencik (Z.Mencik, Journal ofMacromoleculer Science, Physics B6,101 (1972)), the I (040) during the complete random orientation of crystalling propylene and strength ratio I (040)/I (111)=116.9/77.5=1.508 of I (111) (inverse of I (111)/I (040) value).For example, if 010 of the crystalling propylene of the sample of measuring fully randomly is orientated with respect to pellicular front, the value of [P010] just is 0,010 of crystalling propylene is parallel-oriented more with respect to pellicular front, the value of [P010] is just big more, on the contrary, if this 010 perpendicular to pellicular front orientation, [P010] is negative value just.

In addition, in liquid paper container material of the present invention, can between above-mentioned ply of paper and sealant B layer, printed layers be set.Printed layers for be used for making by demonstrations such as printings by the name of an article of the attractive pattern of commodity value of the content of the liquid paper container filling of this liquid paper container material moulding or this content, raw material, amount, other legal sign etc. layer.This printed layers can be provided with by directly printing on ply of paper, but the ply of paper superimposed layer by thermoplasticity synthetic resin constitute the layer, the method of on this thermoplasticity synthetic resin layer, implementing printing and being provided with, can implement the dark more shallow printing of version simply, implement extremely fine and close printings such as intaglio printing, so typographical aspect is good, thus preferred.But, printing process is not particularly limited, except that above-mentioned intaglio printing, can also carry out letterpress, hectographic printing etc.

In these cases, the ply of paper superimposed layer by thermoplasticity synthetic resin constitute the layer thickness be preferably 5～30 μ m.As thermoplasticity synthetic resin, can list low density polyethylene (LDPE), straight chain shape low density polyethylene (LDPE), high density polyethylene (HDPE), ethylene-propylene copolymer, ethylene-butene copolymer, propene-1-butene copolymer, Noblen, the propylene-ethylene random copolymer, propylene-ethylene block copolymer, the propylene-ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, polymer and their mixtures such as ethylene-methyl methacrylate methyl terpolymer.

And, in liquid paper container material of the present invention, beyond above explanation, as required, for bonding this each layer securely and/or other layer, for example also can be provided with by cementability vistanex such as low density polyethylene (LDPE), straight chain shape low density polyethylene (LDPE) or their modifier or biliquid curing type ester at its interlayer is the adhesive linkage that bonding agent etc. constitutes.

In constituting all layers of liquid paper container material of the present invention, as required, can cooperate various additives such as antistatic agent, anti-adhesive agent, lubricant, antioxidant, chlorine replenishers, nucleating agent.But, the aforesaid liquid paper container c layer of multi-layer polyolefin film, when making the liquid paper container by liquid paper container material of the present invention, for with the liquid paper container contents directly contact the layer, so preferred the interpolation in this layer may bring the additive of pernicious influence to content, even it is perhaps add, also a small amount of as far as possible.But, in this multi-layer polyolefin film, in the time of can not in the c layer, adding additive, instead for example add this additive in a layer at other layer, also can obtain, keep or improve the performance that needs.For example, when liquid paper container of the present invention is made the roller shape with the multi-layer polyolefin film, the purpose of the generation fold when preventing to twine, in order to give a laminar surface and c laminar surface lubricity with appropriateness, can make with lubricator, but this moment, lubricant mainly was added in a layer, by regulating its addition, the amounts of lubrication of adding in the c layer also can reach this purpose for seldom or not adding.

Liquid paper container material of the present invention can adopt any method to obtain.For example, from another outermost layer side of an outermost layer side direction, successively lamination the sealant B layer that is made of thermoplasticity synthetic resin, printed layers, thermoplasticity synthetic resin layer, ply of paper are arranged, as the aluminium foil layer of barrier layer, as the above-mentioned biaxial stretch-formed lamination polyolefin film of paying the intensity layer with as the liquid paper container material of the multi-layer polyolefin film of the present invention (a layer/b layer/c layer) of sealant A layer, can be as described below and obtain.

At first, behind coating adhesive on the face of above-mentioned biaxial stretch-formed lamination polyolefin film, adopt the dry lamination method lamination liquid paper container multi-layer polyolefin film of the present invention of processing and forming in advance, make the adhesive side adjacency of its a layer and this biaxial stretch-formed lamination polyolefin film.Perhaps on a face of above-mentioned biaxial stretch-formed lamination polyolefin film, across polyethylene-based resin, adopt the interlayer laminating lamination liquid paper container multi-layer polyolefin film of the present invention of processing and forming in advance, make its a layer and this biaxial stretch-formed lamination polyolefin film adjacency.Perhaps at this moment, also can be after coating cementation coating (anchor coat) agent on the face of above-mentioned biaxial stretch-formed lamination polyolefin film, use multilayer film, utilization melt extrudes the machine coextrusion and constitutes the resin of liquid paper container of the present invention with a layer, b layer and the c layer of multi-layer polyolefin film, carry out lamination, make the cementation coat side adjacency of a layer and this biaxial stretch-formed lamination polyolefin film.So, after lamination liquid paper container of the present invention was with multi-layer polyolefin film and above-mentioned biaxial stretch-formed lamination polyolefin film, another face superimposed layer aluminium foil layer at this biaxial stretch-formed lamination polyolefin film obtained laminate 1.

On the other hand,, this thermoplasticity synthetic resin layer is implemented printing, obtain printed article 1 at ply of paper superimposed layer thermoplasticity synthetic resin layer.At this moment, as required, insert mouthful or the content inlet, can implement the processing of opening circular hole printed article 1 as suction pipe.Then, adopt the interlayer lamination, across the cementability vistanex, the ply of paper side of superimposition printing thing 1 and the aluminium foil layer side of above-mentioned laminate 1 are extruded the thermoplasticity synthetic resin that constitutes sealant B layer in this printed layers side again, carry out lamination and are accomplished.But this is an example only.In the present invention,, use other any means, also can obtain as long as the result can access purpose liquid paper container material.

At last, liquid paper container of the present invention is described.

Liquid paper container material of the present invention can be used as the material of the liquid paper container of any kind.For example, when using this liquid paper container material in the moulding of the sterile type liquid paper container that obtains carrying out aseptic packaging, on the liquid paper container material that is banded continuous state that obtains as described above, extrude rip out stitches with crimper, use for example UP-FUJI filling machine of four countries' chemical industry machine production of aseptic filling machine, this liquid paper container material that has rip out stitches is carried out sterilization with aquae hydrogenii dioxidi continuously, after the aquae hydrogenii dioxidi sterilization, indoor at aseptic cavity, implement longitudinal sealing along its length, be shaped to tubulose, filling is filled with thing (content) in being shaped to the liquid paper container material of tubulose, transverse direction along tubulose liquid paper container material, every predetermined distance is implemented the horizontal line sealing, and cut off the liquid paper container material along the horizontal line sealing, fold along crease, be shaped to net shape, obtain the liquid paper container.The shape of liquid paper container is not particularly limited.For example,,, can make polygon column or asymmetric, also can make its upper and lower warpage as long as in above-mentioned filling machine can the scope of moulding, be not limited to the brick type even make above-mentioned sterile type liquid paper container.In addition, as required, can be on the liquid paper container that obtains, sipper pore or Kaifeng mouthful are set in position, perhaps installing port bolt and draw back label, striping etc.Can also have suction pipe.

Embodiment

Below, in order to specifically describe the present invention, enumerate embodiment, but the invention is not restricted to these embodiment.Wherein, adopt following assay method to carry out at following embodiment and the film evaluation of physical property in the comparative example.

The rerum natura of the biaxial stretch-formed lamination polyolefin film that in embodiment and comparative example, uses, after manufacturing 40 ℃ of following slakings 2 days, be sampled as each size up then, under 23 ℃ of temperature, humidity 50%RH, carry out 24 hours status adjustment, under this similarity condition, measure.

By the laminated body that each lamination operation obtains as the centre product, behind lamination,, under 23 ℃ of temperature, humidity 50%RH, carry out 24 hours status adjustment then 40 ℃ of following slakings 3 days, under this similarity condition, measure.

(1) thickness:

Use mechanical thickness meter (micrometerOMV-25DM that the ITUTOYO of M Co., Ltd. produces) to measure thickness.

(2) fusing point of resin:

Use differential scanning calorimeter (DSC6200R that Seiko electronics industry Co., Ltd. produces), at 235 ℃ of following molten resins and film, keep cooling to 30 ℃ with 10 ℃/minute of cooling rates after 10 minutes, fusing point when then, mensuration is warmed up to 235 ℃ with 10 ℃/minute of programming rates.

(3) copolymerization composition and EEE chain divide rate:

Use nuclear magnetic resonance light-dividing device (JNM-GSX-270 that Jeol Ltd. produces), with o-dichlorohenzene/heavy benzol (capacity 90/10) as solvent, from what measure down at 120 ℃ ¹³The C-NMR spectrum is calculated.The ownership at each peak in the spectrum and copolymerization are formed and the EEE chain divides the computational methods of rate, carry out according to the method (Eric T.Hsieh and James C.RandallMacromolecules 1982,15.365) of J.C.Randall etc.The EEE chain branch rate of ethene-butene-1 copolymer is the 6 kind whole branch rates of EEE chain with respect to 3 continuous chain link EEE, BEE, BEB, EBE, BBE, BBB (ethene (E), 1-butylene (B)), the ratio of the structure that the expression ethylene unit is continuous.Usually, have that EEE chain branch rate is high more, the high more trend of crystallization degree of ethene-butene-1 copolymer.

(4) planar orientation index:

The X-ray diffraction device JDX-3500 that uses society of NEC to produce measures under the following conditions.

Target: copper (Cu-K alpha ray)

Tube voltage-tube current: 40kV-400mA

X ray incident method: perpendicular fasciculus penetrant method

Monochromatization: graphite monochromator

Disperse otch: 0.2mm

Be subjected to light otch: 0.4mm

Detector: scintillation counter is measured

Angular range: 9.0 °～31.0 °

Stepping angle: 0.04 °

Gate time: 3.0 seconds

Sample rotating speed: 120rpm

In this case, will be cut into 20mm * 20mm, and, make thickness be about 3mm, and rotate on the sample bench in the penetrant method that is installed in the wide-angle goniometer mensuration is installed its overlapping tens for the examination film.The peak is separated in to be removed in the scope of 9 °～31 ° of the angles of diffraction (2 θ) owing to after the substrate that air scattering etc. cause, by adopting the common peak partition method of Gaussian function and Lorentzian, be separated into noncrystalline mass peak and each crystallization mass peak.

The planar orientation index by the peak intensity ratio of 040 reflection with 111 reflections, uses following formula (1) to calculate with said method.

Planar orientation indices P 010=log{1.508 * I (111)/I (040) } (1)

Wherein,

I (111): 111 reflection peak intensity (counts)

I (040): 040 reflection peak intensity (counts)

(5) melt quality turnover rate:

According to JIS-K7210, measure melt quality turnover rate (being designated hereinafter simply as MFR).Wherein, the MFR of Noblen, propylene series copolymer, ethene-butene-1 copolymer measures under 230 ℃.And the MFR of ethene-1-hexene copolymer, low-density polyethylene film (AJ-5) measures under 190 ℃.

(6) the suction pipe property inserted:

Use plastic suction pipe, in the sipper pore of the brick type liquid paper container that obtains in embodiment and comparative example, the property inserted of the suction pipe when 10 estimators insert with hand is actual is estimated with following 3 grades.

Zero ... insert simply.

△ ... resistance sense is arranged but can insert.

* ... can not insert, perhaps brick type liquid paper container deforms.

(7) lamination adhesive strength:

From implementing the laminated body behind the lamination, with the MD direction is the sample that the mode of length direction cuts out wide 15mm, long 150mm respectively, the interface of desire being measured the lamination adhesive strength is after the MD direction is peeled off 50mm length, use cupping machine (AG500 that Shimadzu Seisakusho Ltd. produces), adopting 90 °, to peel off with the draw speed be to carry out disbonded test in 20mm/ minute, measures the lamination adhesive strength.

(8) wetting index:

Measure according to JIS-Z1712.

(9) buckling strength of liquid paper container:

The brick type liquid paper container that obtains in embodiment and the comparative example vertically is installed on the suction pipe figure testing machine (the M2 type that smart machine society of Toyo Co., Ltd. produces), make and be provided with the top of sipper pore for last, the bottom surface of its opposition side is following (state shown in Figure 1), at force cell is that 1.96kN, compression speed are to make a strength test under 200mm/ minute the condition, with initial peak value as buckling strength (N).

(10) resin is smelly:

The brick type liquid paper vessel insulation that will obtain in embodiment and comparative example with heater is at 60 ℃, undertaken estimating resin is smelly with 5 following grades through after 5 days, through the sense evaluation after 10 days by 10 estimators respectively.

1 ... almost imperceptible resin is smelly.

2 ... feel that a little resin is smelly.

3 ... feel that resin is smelly.

4 ... feel that consumingly resin is smelly.

5 ... feel that very consumingly resin is smelly.

(11) crystallinity

The automatic TREF device SSC-7300ATREF that uses the Senshu scientific company to produce measures the peak temperature (Tp) that is obtained by intensification wash-out partition method under the following conditions.

Solvent: o-dichlorohenzene

Flow velocity: 1ml/ minute

Programming rate: 40 ℃/h

Detector: infrared detector

Measure frequency: 3.41 μ m

Post: internal diameter 4.6mm * 150mm

Filler: Chromosorb P (Chromosorb P)

Concentration: 5mg/ml

Injection rate: 100ml

In this case, after in post, importing sample solution under 145 ℃, speed with 40 ℃/h slowly is cooled to 10 ℃, make sample polymer be adsorbed on the filler surface, column temperature then under these conditions raises, be determined at the polymer concentration of separating out at each temperature with infrared detector, the peak temperature with the amount of separating out when maximum as the TREF temperature (℃).At this moment, when crystallinity is high, TREF temperature height; Otherwise when crystallinity was low, the TREF temperature reduced.

(12) density:

Measure according to ASTM, D1505.

Embodiment 1

At first, as described below making as the biaxial stretch-formed lamination polyolefin film of paying the intensity layer.

Making propylene-ethylene random copolymer as the Resin A that constitutes polyolefin film I layer (monomeric unit that is derived from ethene is that 4.6 weight %, fusing point are that 135 ℃, MFR are 2.1g/10 minute) is 95 weight %, as the propylene-ethylene random copolymer of the resin B that constitutes polyolefin film I layer (monomeric unit that is derived from ethene is that 0.4 weight %, fusing point are that 156 ℃, MFR are 2.3g/10 minute) is 5 weight %, hybrid resin A and resin B are made the resin of polyolefin film I layer.

(monomeric unit that is derived from ethene is 0.4 weight % to make propylene-ethylene random copolymer as the resin C of the oriented polyolefin film II layer that constitutes biaxial orientation, fusing point is 156 ℃, MFR is 2.3g/10 minute) be 60 weight %, (monomeric unit that is derived from ethene is 6.2 weight % as propylene-ethylene-1-butene terpolymers of the resin D of the oriented polyolefin film II layer that constitutes biaxial orientation, the monomeric unit that is derived from the 1-butylene is 5.1 weight %, fusing point is 130 ℃, MFR is 5.0g/10 minute) be 40 weight %, hybrid resin C and resin D make the resin of the oriented polyolefin film II layer of biaxial orientation.

Use multilayer film to carry out coextrusion, make two sides lamination that the resin of the oriented polyolefin film II layer of biaxial orientation be arranged, obtain not stretched sheet at the resin of polyolefin film I layer.

This sheet material is stretched after 5.8 times along the MD direction, be stretched as 10 times along the TD direction again, in 167 ℃ of following heat treatments of stenter heat treatment temperature after 15 seconds, sided corona treatment is implemented on the two sides, and the thickness that obtains polyolefin film I layer is 15 μ m, respectively be that 2.5 μ m, planar orientation index are the biaxial stretch-formed lamination polyolefin films of-0.361 20 μ m at the thickness of the biaxial stretch-formed oriented polyolefin film II layer of two sides lamination.Wherein, the wetting index of this biaxial stretch-formed lamination polyolefin film is 41mN/m on the two sides.

Then, as described belowly make liquid paper container material of the present invention.

As sealant A layer, use is three layers of no drawing polyolefin film of 30 μ m by the three-layer co-extruded gross thickness with the order lamination of a/b/c that goes out to obtain, wherein, the thickness that a) is made of propylene-ethylene-1-butene terpolymers (monomeric unit that the monomeric unit that is derived from ethene is 2.3 weight %, be derived from the 1-butylene is that 1.3 weight %, fusing point are that 137 ℃, MFR are 7.0g/10 minute) is the layer of 6 μ m; B) thickness that is made of the resin that is mixed with 70 weight % propylene-ethylene random copolymers (monomeric unit that is derived from ethene is that 3.6 weight %, fusing point are that 146 ℃, MFR are 7.0g/10 minute) and 30 weight % ethene-butene-1 copolymers (monomeric unit that is derived from the 1-butylene is that 15 weight %, fusing point are that 69 ℃, MFR are 6.7g/10 minute) is the layer of 20 μ m; And c) (monomeric unit that is derived from the 1-butylene is that 15 weight %, fusing point are that 69 ℃, MFR are that 6.7g/10 minute, TREF temperature are that 45.1 ℃, density are 0.885g/cm by ethene-butene-1 copolymer ³, EEE chain branch rate is 0.67) thickness that constitutes is the layer of 4 μ m.A laminar surface to these three layers of no drawing polyolefin films is implemented Corona discharge Treatment, on the single face of above-mentioned biaxial stretch-formed lamination polyolefin film, using biliquid curing type ester is bonding agent, adopt the dry lamination method under 80 ℃ of baking temperatures, this Corona discharge Treatment face to be carried out lamination, obtain the plural layers that thickness is 52 μ m.The wetting index of the biaxial stretch-formed lamination polyolefin film side of these plural layers is 39mN/m.

Then, biaxial stretch-formed lamination polyolefin film side at these plural layers, same use biliquid curing type ester is a bonding agent, with the dried aluminium foil that shows laminating laminated thickness 7 μ m, obtaining successively lamination, the thickness of the three-decker of three layers of no drawing polyolefin film, biaxial stretch-formed lamination polyolefin film, aluminium foil is arranged is the laminate 1 of 61 μ m under 80 ℃ of baking temperatures.With this laminate 1 slaking 3 days, measure the lamination strength between each layer.The three layers of no drawing polyolefin film of slaking laminate 1 after 3 days and the interlayer lamination adhesive strength of biaxial stretch-formed lamination polyolefin film are 4.61N/15mm.On the other hand, the interlayer lamination adhesive strength of aluminium foil and biaxial stretch-formed lamination polyolefin film is 3.39N/15mm.

On the other hand, at weight per unit area 200g/m ²Cardboard on melt extrude low density polyethylene (LDPE), carry out lamination, the low density polyethylene layer that thickness is 15 μ m is set, on this low density polyethylene layer, implement printing again, obtain printed article 1.

Then, the processing that circular hole is opened in enforcement on printed article 1, form suction pipe and insert oral area, utilize the interlayer lamination again, across the paperboard side of low density polyethylene (LDPE) superimposition printing thing 1 and the aluminium foil side of above-mentioned laminate 1, obtain the laminate 2 that lamination successively has printed layers, low density polyethylene layer, ply of paper, low density polyethylene layer, aluminium foil layer, biaxial stretch-formed lamination polyolefin film, three layers of no drawing polyolefin film.Again on the printed layers of laminate 2, as sealant, extrude low density polyethylene (LDPE), adopt lamination to carry out lamination, obtain from outermost layer side lamination successively low density polyethylene layer (thickness is 15 μ m), printed layers, low density polyethylene layer (thickness is 15 μ m) are arranged, (weight per unit area is 200g/m to ply of paper ²Cardboard), the liquid paper container material of low density polyethylene layer (thickness is 30 μ m), aluminium foil layer (thickness is 7 μ m), biaxial stretch-formed lamination polyolefin film (thickness is 20 μ m), three layers of no drawing polyolefin film (thickness is 30 μ m).

The material of above-mentioned biaxial stretch-formed lamination polyolefin film and three layers of no drawing polyolefin films use this moment in addition is as described below.

The MIRASON 16P that low density polyethylene (LDPE) all uses Mitsui Chemicals, Inc to produce, cardboard use the weight per unit area of copying system from the former paper pulp of coniferous tree and broad leaf tree to be 200g/m ²Cardboard, aluminium foil uses JIS specification standards product 1N30.

After the liquid paper container material that obtains is cut into the band shape of Rack, the UP-FUJI-MA80 machine that uses shikoku Chemical Engineering Material Co., Ltd to produce carries out aseptic packaging, in content, add the activated carbon filtration water that to estimate water as the official, obtain the brick type liquid paper container of inner capacities 250ml.

The brick type liquid paper container that obtains is carried out mensuration, the suction pipe property inserted and the smelly evaluation of resin of buckling strength, ecbatic in table 1.

＜comparative example 1 〉

The liquid paper container material of making as described below.

The single face of the biaxial stretch-formed lamination polyolefin film of in embodiment 1, making, using biliquid curing type ester is bonding agent, and adopting the dry lamination laminated thickness down 80 ℃ of baking temperatures is that (LDPE, fusing point are that 106 ℃, MFR are that 7.5g/10 minute, TREF temperature are that 72.5 ℃, density are 0.917g/cm for the low-density polyethylene film of 20 μ m ³), obtain the plural layers that thickness is 42 μ m.The wetting index of the biaxial stretch-formed lamination polyolefin film side of these plural layers is 40mN/m.

Then, biaxial stretch-formed lamination polyolefin film side at these plural layers, same use biliquid curing type ester is a bonding agent, adopt the aluminium foils of dry lamination laminated thickness 7 μ m down 80 ℃ of baking temperatures, obtaining successively lamination, the thickness of the three-decker of low-density polyethylene film, biaxial stretch-formed lamination polyolefin film, aluminium foil is arranged is the laminate 1 of 50 μ m.With this laminate 1 slaking 3 days, measure the lamination strength between each layer.The interlayer lamination strength of the low-density polyethylene film of laminate 1 and biaxial stretch-formed lamination polyolefin film is 4.88N/15mm.On the other hand, the interlayer lamination adhesive strength of aluminium foil and biaxial stretch-formed lamination polyolefin film is 3.51N/15mm.

On the other hand, at weight per unit area 200g/m ²Cardboard on melt extrude low density polyethylene (LDPE), carry out lamination, the low density polyethylene layer that thickness is 15 μ m is set, on this low density polyethylene layer, implement printing again, obtain printed article 1.

Then, the processing that circular hole is opened in enforcement on printed article 1, form suction pipe and insert oral area, utilize the interlayer lamination again, across the paperboard side of low density polyethylene (LDPE) superimposition printing thing 1 and the aluminium foil side of above-mentioned laminate 1, obtain the laminate 2 that lamination successively has printed layers, low density polyethylene layer, ply of paper, low density polyethylene layer, aluminium foil layer, biaxial stretch-formed lamination polyolefin film, low-density polyethylene film.On the printed layers of laminate 2, extrude low density polyethylene (LDPE) again, adopt lamination to carry out lamination, obtain from outermost layer side lamination successively low density polyethylene layer (thickness is 15 μ m), printed layers, low density polyethylene layer (thickness is 15 μ m) are arranged, (weight per unit area is 200g/m to ply of paper ²Cardboard), the liquid paper container material of low density polyethylene layer (thickness is 30 μ m), aluminium foil layer (thickness is 7 μ m), biaxial stretch-formed lamination polyolefin film (thickness is 20 μ m), low-density polyethylene film (thickness is 20 μ m).

The material that use this moment beyond the above-mentioned biaxial stretch-formed lamination polyolefin film is as described below.

The MIRASON 16P that low density polyethylene (LDPE) all uses Mitsui Chemicals, Inc to produce, the AJ-5 that low-density polyethylene film uses tamapoly Co., Ltd. to produce, cardboard use the weight per unit area of copying system from the former paper pulp of coniferous tree and broad leaf tree to be 200g/m ²Cardboard, aluminium foil uses JIS specification standards product 1N30.

After the liquid paper container material that obtains is cut into the band shape of Rack, the UP-FUJI-MA80 machine that uses shikoku Chemical Engineering Material Co., Ltd to produce carries out aseptic packaging, in content, add the activated carbon filtration water that to estimate water as the official, obtain the brick type liquid paper container of inner capacities 250ml.The brick type liquid paper container that obtains is carried out mensuration, the suction pipe property inserted and the smelly evaluation of resin of buckling strength, ecbatic in table 1.

＜comparative example 2 〉

To thickness is that (LDPE, fusing point are that 106 ℃, MFR are that 7.5g/10 minute, TREF temperature are that 72.5 ℃, density are 0.917g/cm for the low-density polyethylene film of 40 μ m ³) enforcement single face sided corona treatment, its wetting index is 38mN/m, in this sided corona treatment face side, using biliquid curing type ester is bonding agent, adopting the dry lamination laminated thickness down 75 ℃ of baking temperatures is the aluminium foil of 7 μ m, obtains the laminate 1 that 2 layers of thickness of structure of low-density polyethylene film, aluminium foil are arranged is 49 μ m of lamination successively.With this laminate 1 slaking 3 days, measure the interlayer lamination adhesive strength of aluminium foil and low-density polyethylene film.At this moment, the interlayer lamination adhesive strength of aluminium foil and low-density polyethylene film is 2.54N/15mm.

On the other hand, at weight per unit area 200g/m ²Cardboard on melt extrude low density polyethylene (LDPE), carry out lamination, the low density polyethylene layer that thickness is 15 μ m is set, on this low density polyethylene layer, implement printing again, obtain printed article 1.

Then, the processing that circular hole is opened in enforcement on printed article 1, form suction pipe and insert oral area, utilize the interlayer lamination again, across the paperboard side of low density polyethylene (LDPE) superimposition printing thing 1 and the aluminium foil side of above-mentioned laminate 1, obtain the laminate 2 that lamination successively has printed layers, low density polyethylene layer, ply of paper, low density polyethylene layer, aluminium foil layer, low-density polyethylene film.

On the printed layers of laminate 2, extrude low density polyethylene (LDPE) again, adopt lamination to carry out lamination, obtain from outermost layer side lamination successively low density polyethylene layer (thickness is 15 μ m), printed layers, low density polyethylene layer (thickness is 15 μ m) are arranged, (weight per unit area is 200g/m to ply of paper ²Cardboard), the liquid paper container material of low density polyethylene layer (thickness is 30 μ m), aluminium foil layer (thickness is 7 μ m), low-density polyethylene film (thickness is 40 μ m).

The material that use this moment is as described below.

The MIRASON 16P that low density polyethylene (LDPE) all uses Mitsui Chemicals, Inc to produce, the AJ-5 that low-density polyethylene film uses tamapoly Co., Ltd. to produce, cardboard use the weight per unit area of copying system from the former paper pulp of coniferous tree and broad leaf tree to be 200g/m ²Cardboard, aluminium foil uses JIS specification standards product 1N30.

After the liquid paper container material that obtains is cut into the band shape of Rack, the UP-FUJI-MA80 machine that uses shikoku Chemical Engineering Material Co., Ltd to produce carries out aseptic packaging, in content, add the activated carbon filtration water that to estimate water as the official, obtain the brick type liquid paper container of inner capacities 250ml.The brick type liquid paper container that obtains is carried out mensuration, the suction pipe property inserted and the smelly evaluation of resin of buckling strength, ecbatic in table 1.

＜embodiment 2 〉

The following stated is made liquid paper container material of the present invention.

As sealant A layer, go out by three-layer co-extruded, the gross thickness made from the order lamination of a/b/c is three layers of no drawing polyolefin film of 30 μ m, wherein, the thickness that a) is made of the resin that is mixed with 50 weight % propylene-ethylene random copolymers (monomeric unit that is derived from ethene is that 3.6 weight %, fusing point are that 146 ℃, MFR are 7.0g/10 minute) and 50 weight % ethene-butene-1 copolymers (monomeric unit that is derived from the 1-butylene is that 17 weight %, fusing point are that 63 ℃, MFR are 4.9g/10 minute) is the layer of 6 μ m; B) thickness that is made of the resin that is mixed with 70 weight % propylene-ethylene random copolymers (monomeric unit that is derived from ethene is 3.6 weight %, and fusing point is that 146 ℃, MFR are 7.0g/10 minute) and 30 weight % ethene-butene-1 copolymers (monomeric unit that is derived from the 1-butylene is that 17 weight %, fusing point are that 63 ℃, MFR are 4.9g/10 minute) is the layer of 20 μ m; And c) (monomeric unit that is derived from the 1-butylene is that 17 weight %, fusing point are that 63 ℃, MFR are that 4.9g/10 minute, TREF temperature are that 36.1 ℃, density are 0.885g/cm by ethene-butene-1 copolymer ³, EEE chain branch rate is 0.67) thickness that constitutes is the layer of 4 μ m.

On the other hand, at weight per unit area 200g/m ²Cardboard on melt extrude low density polyethylene (LDPE), carry out lamination, the low density polyethylene layer that thickness is 15 μ m is set, on this low density polyethylene layer, implement printing again, obtain printed article 1.Then, the processing that circular hole is opened in enforcement on printed article 1, form suction pipe and insert oral area, paperboard side at printed article 1 is the aluminium foil of 7 μ m while melt extruding low density polyethylene (LDPE), utilizing interlayer laminated stack thickness again, obtains the laminate 2 that lamination successively has printed layers, low density polyethylene layer, ply of paper, low density polyethylene layer, aluminium foil layer.On the printed layers of laminate 2,, melt extrude low density polyethylene (LDPE) again, carry out lamination and lamination as sealant B layer.Then, have at lamination on the aluminium foil layer of laminate 2 of sealant B layer, melt extrude low density polyethylene (LDPE) on one side, on one side as sealant A layer, adopt the above-mentioned three layers of no drawing polyolefin film of interlayer laminated stack, make its a layer side to the aluminium foil layer side, obtain from outermost layer side lamination successively low density polyethylene layer (thickness is 15 μ m), printed layers, low density polyethylene layer (thickness is 15 μ m) are arranged, (weight per unit area is 200g/m to ply of paper ²Cardboard), the liquid paper container material of low density polyethylene layer (thickness is 30 μ m), aluminium foil layer (thickness is 7 μ m), low-density polyethylene film (thickness is 15 μ m), three layers of no drawing polyolefin film (thickness is 30 μ m).

The material of three layers of no drawing polyolefin films use this moment in addition is as described below.

The MIRASON 16P that low density polyethylene (LDPE) all uses Mitsui Chemicals, Inc to produce, cardboard use the weight per unit area of copying system from the former paper pulp of coniferous tree and broad leaf tree to be 200g/m ²Cardboard, aluminium foil uses JIS specification standards product 1N30.

After the liquid paper container material that obtains is cut into the band shape of Rack, the UP-FUJI-MA80 machine that uses shikoku Chemical Engineering Material Co., Ltd to produce carries out aseptic packaging, in content, add the activated carbon filtration water that to estimate water as the official, obtain the brick type liquid paper container of inner capacities 250ml.

The brick type liquid paper container that obtains is carried out mensuration, the suction pipe property inserted and the smelly evaluation of resin of buckling strength, ecbatic in table 2.

＜embodiment 3 〉

As described belowly make liquid paper container material of the present invention.

As sealant A layer, go out by three-layer co-extruded, the gross thickness made from the order lamination of a/b/c is three layers of no drawing polyolefin film of 30 μ m, wherein, a) (monomeric unit that is derived from ethene is 3.6 weight % by being mixed with 40 weight % propylene-ethylene random copolymers, fusing point is 146 ℃, and MFR is 7.0g/10 minute) and the thickness that constitutes of the resin of 60 weight % ethene-1-hexene copolymers (monomeric unit that is derived from the 1-hexene is that 11 weight %, fusing point are that 100 ℃, MFR are 8.0g/10 minute) be the layer of 6 μ m; B) thickness that is made of the resin that is mixed with 70 weight % propylene-ethylene random copolymers (monomeric unit that is derived from ethene is that 3.6 weight %, fusing point are that 146 ℃, MFR are 7.0g/10 minute) and 30 weight % ethene-butene-1 copolymers (monomeric unit that is derived from the 1-butylene is that 16 weight %, fusing point are that 66 ℃, MFR are 4.0g/10 minute) is the layer of 21 μ m; And c) (monomeric unit that is derived from the 1-butylene is that 16 weight %, fusing point are that 66 ℃, MFR are that 4.0g/10 minute, TREF temperature are that 39.2 ℃, density are 0.885g/cm by ethene-butene-1 copolymer ³, EEE chain branch rate is 0.67) thickness that constitutes is the layer of 3 μ m.

As the A layer, beyond three layers of no drawing polyolefin film that use is made, similarly to Example 2 the operation, obtain from outermost layer side lamination successively low density polyethylene layer (thickness is 15 μ m), printed layers, low density polyethylene layer (thickness is 15 μ m) are arranged, (weight per unit area is 200g/m to ply of paper ²Cardboard), the liquid paper container material of low density polyethylene layer (thickness is 30 μ m), aluminium foil layer (thickness is 7 μ m), low-density polyethylene film (thickness is 15 μ m), three layers of no drawing polyolefin film (thickness is 30 μ m).

The material of three layers of no drawing polyolefin films use this moment in addition is as described below.

The MIRASON 16P that low density polyethylene (LDPE) all uses Mitsui Chemicals, Inc to produce, cardboard use the weight per unit area of copying system from the former paper pulp of coniferous tree and broad leaf tree to be 200g/m ²Cardboard, aluminium foil uses JIS specification standards product 1N30.

After the liquid paper container material that obtains is cut into the band shape of Rack, the UP-FUJI-MA80 machine that uses shikoku Chemical Engineering Material Co., Ltd to produce carries out aseptic packaging, in content, add the activated carbon filtration water that to estimate water as the official, obtain the brick type liquid paper container of inner capacities 250ml.

The brick type liquid paper container that obtains is carried out mensuration, the suction pipe property inserted and the smelly evaluation of resin of buckling strength, ecbatic in table 1.

＜embodiment 4 〉

As described belowly make liquid paper container material of the present invention.

As sealant A layer, go out by three-layer co-extruded, the gross thickness made from the order lamination of a/b/c is three layers of no drawing polyolefin film of 30 μ m, wherein, a) (monomeric unit that is derived from ethene is 2.3 weight % by being mixed with 60 weight % propylene-ethylene-1-butene terpolymers, the monomeric unit that is derived from the 1-butylene is 1.3 weight %, fusing point is 137 ℃, MFR is 7.0g/10 minute) and 40 weight % ethene-butene-1 copolymers (monomeric unit that is derived from the 1-butylene is 13 weight %, fusing point is 83 ℃, MFR is 6.8g/10 minute) the thickness that constitutes of resin be the layer of 6 μ m; B) thickness that is made of the resin that is mixed with 70 weight % propylene-ethylene random copolymers (monomeric unit that is derived from ethene is that 3.6 weight %, fusing point are that 146 ℃, MFR are 7.0g/10 minute) and 30 weight % ethene-butene-1 copolymers (monomeric unit that is derived from the 1-butylene is that 13 weight %, fusing point are that 83 ℃, MFR are 6.8g/10 minute) is the layer of 20 μ m; And c) (monomeric unit that is derived from the 1-butylene is that 13 weight %, fusing point are that 83 ℃, MFR are that 6.8g/10 minute, TREF temperature are that 53 ℃, density are 0.890g/cm by ethene-butene-1 copolymer ³, EEE chain branch rate is 0.77) thickness that constitutes is the layer of 4 μ m.

As the A layer, beyond three layers of no drawing polyolefin film that use is made, similarly to Example 2 the operation, obtain from outermost layer side lamination successively low density polyethylene layer (thickness is 15 μ m), printed layers, low density polyethylene layer (thickness is 15 μ m) are arranged, (weight per unit area is 200g/m to ply of paper ²Cardboard), the liquid paper container material of low density polyethylene layer (thickness is 30 μ m), aluminium foil layer (thickness is 7 μ m), low-density polyethylene film (thickness is 15 μ m), three layers of no drawing polyolefin film (thickness is 30 μ m).

The material of three layers of no drawing polyolefin films use this moment in addition is as described below.

The MIRASON 16P that low density polyethylene (LDPE) all uses Mitsui Chemicals, Inc to produce, cardboard use the weight per unit area of copying system from the former paper pulp of coniferous tree and broad leaf tree to be 200g/m ²Cardboard, aluminium foil uses JIS specification standards product 1N30.

After the liquid paper container material that obtains is cut into the band shape of Rack, the UP-FUJI-MA80 machine that uses shikoku Chemical Engineering Material Co., Ltd to produce carries out aseptic packaging, in content, add the activated carbon filtration water that to estimate water as the official, obtain the brick type liquid paper container of inner capacities 250ml.

The brick type liquid paper container that obtains is carried out mensuration, the suction pipe property inserted and the smelly evaluation of resin of buckling strength, ecbatic in table 1.

＜comparative example 3 〉

As described belowly make liquid paper container material of the present invention.

As sealant A layer, (straight chain shape low density polyethylene (LDPE) (hereinafter referred to as LLDPE), the monomeric unit that is derived from the 1-hexene are that 11 weight %, fusing point are that 100 ℃, MFR are that 8.0g/10 minute, TREF temperature are that 73.3 ℃, density are 0.912g/cm to extrude ethene-1-hexene copolymer by the T mould ³, EEE chain branch rate is 0.92, wherein, ethene-EEE the chain of 1-hexene copolymer divides the computational methods of rate, method (Eric T.Hsieh and JamesC.Randall Macromolecules 1982 according to people such as J.C.Randall, 15.1402)), the individual layer of making thickness and be 40 μ m does not have stretching LLDPE film.

As the A layer, the individual layer that use is made does not have beyond the stretching LLDPE film, similarly to Example 2 the operation, obtain from outermost layer side lamination successively low density polyethylene layer (thickness is 15 μ m), printed layers, low density polyethylene layer (thickness is 15 μ m) are arranged, (weight per unit area is 200g/m to ply of paper ²Cardboard), low density polyethylene layer (thickness is 30 μ m), aluminium foil layer (thickness is 7 μ m), low-density polyethylene film (thickness is 15 μ m), individual layer do not have the liquid paper container material of stretching LLDPE film (thickness is 40 μ m).

It is as follows that individual layer does not have the material that uses this moment beyond the stretching LLDPE film.

The MIRASON 16P that low density polyethylene (LDPE) all uses Mitsui Chemicals, Inc to produce, cardboard use the weight per unit area of copying system from the former paper pulp of coniferous tree and broad leaf tree to be 200g/m ²Cardboard, aluminium foil uses JIS specification standards product 1N30.

After the liquid paper container material that obtains is cut into the band shape of Rack, the UP-FUJI-MA80 machine that uses shikoku Chemical Engineering Material Co., Ltd to produce carries out aseptic packaging, in content, add the activated carbon filtration water that to estimate water as the official, obtain the brick type liquid paper container of inner capacities 250ml.

The brick type liquid paper container that obtains is carried out mensuration, the suction pipe property inserted and the smelly evaluation of resin of buckling strength, ecbatic in table 1.

[table 1]

	Buckling strength	The suction pipe property inserted	The smelly evaluation of resin
					(unit: N)	3 grade evaluations	5 grade evaluations
	After 5 days	After 10 days
			Embodiment
1	184	○		1	2
			Comparative example 1			181	○	4	4
Comparative example 2	163	○		5	5
			Embodiment 2			178	○	1	2
Embodiment 3	181	○		1	2
			Embodiment 4			182	○	1	2
Comparative example 3	172	○		3	4

Utilize the field on the industry

Multi-layer polyolefin film of the present invention, as the sealant of the inner face of liquid paper container the time, can not produce in content that resin is smelly, resinous odour, foreign odor, peculiar smell etc., and the taste component that can adsorb hardly content, so utilize possibility high as the constituent material of multi-ply paper container.

Claims (9)

1. a liquid paper container multi-layer polyolefin film is characterized in that, it is the multi-layer polyolefin film that has a superficial layer a layer, another superficial layer c layer and intermediate layer b layer at least, and this a layer, b layer and c layer have following characteristic,

A layer: by being selected from the layer that a kind of in Noblen, propylene series copolymer, the ethene-alpha-olefin copolymer or their mixture constitute;

The b layer: by propylene series copolymer and ethene-alpha-olefin copolymer constitute the layer;

The c layer: the fusing point that is made of ethene-alpha-olefin copolymer is that 60～140 ℃ and thickness are the layer of 1～20 μ m.

2. liquid paper container multi-layer polyolefin film as claimed in claim 1 is characterized in that, a layer be separately by propylene series copolymer or by the mixture of propylene series copolymer and ethene-alpha-olefin copolymer constitute layer.

3. liquid paper container multi-layer polyolefin film as claimed in claim 1 or 2 is characterized in that, the propylene series copolymer that constitutes a layer is propylene-ethylene-1-butene terpolymers or propylene-ethylene random copolymer.

4. liquid paper container multi-layer polyolefin film as claimed in claim 1 or 2 is characterized in that, the ethene-alpha-olefin copolymer that constitutes a layer is ethene-butene-1 copolymer or ethene-1-hexene copolymer.

5. as each described liquid paper container multi-layer polyolefin film in the claim 1～4, it is characterized in that the propylene series copolymer that constitutes the b layer is the propylene-ethylene random copolymer.

6. as each described liquid paper container multi-layer polyolefin film in the claim 1～5, it is characterized in that the ethene-alpha-olefin copolymer that constitutes the b layer is ethene-butene-1 copolymer.

7. as each described liquid paper container multi-layer polyolefin film in the claim 1～5, it is characterized in that the ethene-alpha-olefin copolymer that constitutes the c layer is ethene-butene-1 copolymer.

8. liquid paper container material, it is characterized in that, at least lamination is as an outermost sealant B layer that is made of thermoplasticity synthetic resin, ply of paper with as another outermost sealant A layer that is made of with the multi-layer polyolefin film the described liquid paper container of claim 1 and form, and, in the sealing layer A layer, the described liquid paper container of claim 1 carries out lamination with its a layer towards inboard, c layer mode toward the outer side with the multi-layer polyolefin film.

9. a liquid paper container is characterized in that, is the mode moulding of inner face with its sealant A layer with the described liquid paper container material of claim 8.

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