CN104379464B - It is thermally fused to the packaging material of package - Google Patents

It is thermally fused to the packaging material of package Download PDF

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Publication number
CN104379464B
CN104379464B CN201380032226.3A CN201380032226A CN104379464B CN 104379464 B CN104379464 B CN 104379464B CN 201380032226 A CN201380032226 A CN 201380032226A CN 104379464 B CN104379464 B CN 104379464B
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China
Prior art keywords
layer
gas barrier
packaging material
barrier film
organic layer
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Expired - Fee Related
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CN201380032226.3A
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Chinese (zh)
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CN104379464A (en
Inventor
岩濑英二郎
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Fujifilm Corp
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Fujifilm Corp
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • A61J1/10—Bag-type containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging

Abstract

The present invention provides a kind of packaging material, it is the packaging material being thermally fused to package, it is characterized in that, there is gas barrier film (12), utilize the intermediate layer (16) of the first adhesive phase (14) and the bonding of described gas barrier film, with the hot welding layer (20) utilizing the second adhesive phase (18) and described interlayer adhesion, described gas barrier film has the combination of the organic layer (26) at the upper inorganic layer (28) with gas barrier property and the basal layer becoming this inorganic layer forming more than 1 of supporter (24), and the stepped construction that the superiors are organic layer (26), in addition, the glass transition temperature of described organic layer is than the support height of described intermediate layer and gas barrier film, the glass transition temperature of the supporter of described intermediate layer and gas barrier film is than described thermal welding floor height.

Description

It is thermally fused to the packaging material of package
Technical field
The present invention relates to the packagings such as a kind of flexible pipe being thermally fused to therapeutic medical transfusion bag or food The packaging material of part, in particular to one by being thermally fused to these packages and to packaging Part gives the packaging material of high gas barrier property.
Background technology
For accommodating the transfusion bag of the medicament rotten because of moisture or oxygen or accommodating similarly because of moisture Or oxygen and the flexible pipe of food that deteriorates or packaging bag, it is desirable to gas barrier property is high.
Additionally, it is known that there is following transfusion bag, i.e. in a side of 2 rooms utilizing next door to separate Accommodate water, the opposing party accommodates medicament, soon by next door opening by water and medicament Mixing.In this kind of transfusion bag, in order to carry out appropriate disposal, it is important that by water with medicament reliably Mixing, preferably can utilize and visually confirm.Said, in the packaging of the confirmation needing content In container, also require to guarantee the observability of inside.
In response to this kind of requirement, various scheme was proposed.
Such as, in patent documentation 1, record following package body, i.e. by periphery, there are rule 2 thin film of fixed adhesion area are constituted, and at the adhesion area of the thin film of at least one party, bonding has The gas barrier film (gas occluding film) of the metal level of oxygen barrier.
This package body utilizes gas barrier film to block oxygen when not in use, prevents the rotten of content, makes Used time, by peeling off gas barrier film from week genesis, guarantee the observability within package body.
It addition, in patent documentation 2, record following container, it it is the fracture having and utilizing next door The container of multiple Room 2 of connection, utilizes a wherein Room to accommodate easily and produces rotten product because of oxygen Product, utilize gas barrier film (gas barrier property wrapping film) closely sealed packaging, in the inner side of wrapping film by this room It is provided with oxygen and absorbs resin bed.
Described in patent documentation 3, there is powder body accommodating chamber and the liquid of the fracture connection utilizing next door In the container of body accommodating chamber, bonding can be peeled off in powder body accommodating chamber gas barrier film (for moisture and Oxygen is the backplate of impermeability), utilize gas barrier film to protect powder body.
Additionally, described in patent documentation 4, surpass in the application with internal layer, intermediate layer and outer layer In the composite soft tube stacked film of sonic seal, described internal layer is by with fusing point, density and melt flows speed Rate meets the first resin bed and the second resin bed composition of the polyethylene-based resin formation of the relation of regulation, Described intermediate layer is made up of nylon layer and PET (polyethylene terephthalate) layer, described outside Layer is formed by polyethylene-based resin, as required, arranges gas barrier film (resistance between outer layer and intermediate layer Gear property substrate layer), thus give gas barrier property to this stacked film.
But, as the gas barrier film with the highest gas barrier property, it is known to by organic layer and inorganic layer The gas barrier film of organic/inorganic cascade type obtained by stacking (hereinafter also referred to as " cascade type ").
The gas barrier film of so-called cascade type, is the thin film with following composition, i.e. make with PET film etc. For supporter, it is formed into the organic layer of basal layer on the surface of supporter, this organic layer is formed The inorganic layers such as the silicon nitride of performance gas barrier property.It addition, the most also have on inorganic layer for protecting nothing The organic layer of machine layer.
In the gas barrier film of cascade type, by having the organic layer of substrate, and can be in whole shape of thin film Become and do not rupture or the suitable inorganic layer of crackle etc..Thus, it is possible to given play to nothing fully The gas barrier film with high-gas resistance of the high-gas resistance that machine layer is had.
It addition, by having organic layer in the superiors, be possible to prevent in hard and crisp inorganic layer to produce and break Split or crackle etc., stably obtain high-gas resistance.
It is known that situation about being used in packing container by the gas barrier film of this kind of cascade type.
Such as, in patent documentation 5, record containing polyethylene and/or polyacrylic resin bag In be provided with the transfusion bag on the barrier layer with the first organic layer, inorganic layer and the second organic layer.
It addition, this barrier layer is substantially using plastic foil as supporter stacking on this supporter First organic layer, inorganic layer and the second organic layer and constitute.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 10-277135 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-201818 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2003-230618 publication
Patent documentation 4: International Publication 2003-099557 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2012-75716 publication
Summary of the invention
Invent problem to be solved
As it was previously stated, the gas barrier film of cascade type has the gas barrier property of excellence.
Thus, by therapeutic medical transfusion bag as shown in patent documentation 1～4, food The gas barrier film of utilization cascade type as shown in patent documentation 5 in flexible pipe etc., can expect to obtain choke The packing container that property is more excellent.
Herein, as shown in patent documentation 5, when the gas barrier film of cascade type is used in packing container, The surface (one side contrary with the plastic foil becoming supporter) at gas barrier film can be considered, utilize viscous Mixture attaches the hot welding layer being made up of plastic foil, by this hot welding layer and packing container thermal welding (heat Envelope (heat seal)).
But, according to the research of the present inventor, if by the gas barrier film of cascade type and packing container hot melt Connect, then can often produce the feelings that cannot obtain the excellent gas barrier property that the gas barrier film of cascade type is had Condition.
It is an object of the invention to, the problem solving described conventional art, it is provided that a kind of packaging material, It is defeated with therapeutic medical by the gas barrier film of the organic/inorganic cascade type of the gas barrier properties by having excellence The package thermal weldings such as liquid bag, the flexible pipe of food or packaging bag, and organic/inorganic layer can be played The excellent gas barrier property that the gas barrier film of stack-type is had, gives excellent gas barrier property to these packages.
For the method solving problem
In order to solve the problems referred to above, the present invention provides a kind of packaging material, it is characterised in that by hot It is fused to the packaging material of package,
There is gas barrier film, the intermediate layer utilizing the first adhesive phase to bond with gas barrier film and utilize second Adhesive phase and the hot welding layer of interlayer adhesion,
Gas barrier film has the inorganic layer with gas barrier property forming more than 1 on supporter and becomes The combination of the organic layer of the basal layer of this inorganic layer and the superiors are the stepped construction of organic layer,
Additionally, the glass transition temperature of organic layer is than the support height of intermediate layer and gas barrier film, middle The glass transition temperature of the supporter of layer and gas barrier film is than thermal welding floor height.
In the packaging material of this kind of present invention, excellent from first adhesive phase thickness to hot welding layer Elect below 100 μm as.
Additionally, it is preferred that the supporter of intermediate layer and gas barrier film is formed from the same material.
Additionally, it is preferred that all of organic layer is formed from the same material.
It addition, the thickness of hot welding layer is preferably below 60 μm.
It addition, the thickness in intermediate layer is preferably below 20 μm.
It is made up of it addition, organic layer is preferably at least one party of acrylic resin and methacrylic resin Layer.
It addition, inorganic layer preferably comprises the layer of silicon nitride.
It addition, hot welding layer preferably comprises polyethylene or polyacrylic layer.
Additionally, intermediate layer preferably comprises the layer of polyethylene terephthalate.
Invention effect
Used with therapeutic medical transfusion bag, food by the packaging material of the present invention by having above-mentioned composition Flexible pipe or the package thermal welding such as packaging bag, it is possible to give organic/inorganic to these packages etc. The excellent gas barrier property that the gas barrier film of cascade type is had.
Accompanying drawing explanation
Fig. 1 is the figure of an example of the packaging material schematically showing the present invention.
Fig. 2 is an example of the gas barrier film utilized in the packaging material schematically showing the present invention Figure.
Detailed description of the invention
Hereinafter, based on the preferred embodiment shown in accompanying drawing, the packaging material of the present invention are carried out in detail Explanation.
In Fig. 1, it is schematically indicated go out an example of the packaging material of the present invention.
Packaging material 10 shown in Fig. 1 substantially have gas barrier film the 12, first adhesive phase 14, Intermediate layer the 16, second adhesive phase 18 and hot welding layer 20 and constitute.
It addition, in the present invention, gas barrier film 12 is to form the performance of more than 1 on supporter 24 The organic layer 26 of the inorganic layer 28 of gas barrier property and the basal layer (priming coat) becoming this inorganic layer 28 Combination and the superiors (surface) formed as protective layer organic layer 26, aforesaid The gas barrier film of organic/inorganic cascade type (hereinafter also referred to as " cascade type ").
In the packaging material 10 of illustrated example, gas barrier film 12 has organic layer 26 on supporter 24, There is inorganic layer 28 thereon, there is organic layer 26 thereon, be organic layer and inorganic layer has 3 3 layer stackup of layer are constituted.
That is, in gas barrier film 12, the organic layer 26 on supporter 24 is the basal layer of inorganic layer 28, Organic layer 26 on inorganic layer 28 is the protective layer of protection inorganic layer 28.
By by the packaging material 10 of this kind of present invention and therapeutic medical transfusion bag, the flexible pipe of food Or the thermal welding such as packaging bag, and packing container is given such as moisture-vapor transmission less than 1 × 10-4[g/ (m2Day) high-gas resistance].
And, in the packing material of the present invention, the package being heating-fusion bonded is not limited to aforesaid Transfusion bag, the flexible pipe of food or packaging bag.That is, the packaging material of the present invention may be used for accommodating medicine Flexible pipe or the packaging bag of the article beyond the bag of the liquid beyond agent etc. are medical, receiving food (accommodate Bag), the wrapping tablet such as packaging film, the housing (shell) accommodating article or package body Deng packaging or the various packagings of article that accommodate various article, particularly deteriorate because of moisture or oxygen etc. They (are the most also concentrated and be referred to as " package ") by part.
It addition, in the packing material of the present invention, gas barrier film is not limited to 3 as shown in Figure 1 Layer is constituted.That is, in order to obtain higher gas barrier property, it is possible to have multiple inorganic layers 28 with become The combination of the organic layer 26 of the basal layer of this inorganic layer 28.
As an example, as shown in Figure 2, it is also possible to the choke that the stacking that the tool being following is of five storeys is constituted Film, i.e. on supporter 24, has the organic layer 26 as basal layer, has inorganic thereon Layer 28, has the organic layer 26 as basal layer thereon, has inorganic layer 28 thereon, at it On the superiors there is the organic layer 26 as protective layer.That is, the gas barrier film shown in Fig. 2 has 2 The combination of the organic layer 26 of individual inorganic layer 28 and substrate.
It addition, in order to obtain higher gas barrier property, it is also possible to be that there is the inorganic layer 28 of more than 3 The gas barrier film of the combination with the organic layer 26 of substrate.
In the packaging material 10 of the present invention, gas barrier film 12 is by organic layer 26 on supporter 24 The thin film being alternately laminated with inorganic layer 28.
In this kind of gas barrier film 12, supporter 24 is not limited, however it is not limited to the resistance of cascade type Air film, it is possible to use the various known tablets utilized by the supporter as various gas barrier films.
As supporter 24 (substrate (base material)), specifically, can exemplify suitably by Polyethylene terephthalate (PET), PEN (PEN), polyethylene, Polypropylene, polystyrene, polyamide, polrvinyl chloride, Merlon, polyacrylonitrile, polyimides, The plastic foil that the various plastics such as polyacrylate, polymethacrylates (macromolecular material) are constituted.
It addition, in the present invention, it is also possible to the surface at this kind of plastic foil is formed protective layer, glues Close layer, reflection layer, anti-reflection layer, light shield layer, planarization layer, cushion, stress relief layer etc. Use as supporter 24 for obtaining the material of the layer (film) of various function.
And, although describe in detail below, but in the packing material of the present invention, this supporter 24 Glass transition temperature (vitrifying point Tg) lower than organic layer 26, higher than hot welding layer 20.
Herein, the glass transition temperature in intermediate layer 16 described later is also low than organic layer 26, compares hot melt Connect layer 20 high.Furthermore it is preferred that the glass transition temperature of supporter 24 is identical with intermediate layer 16, Or it is roughly the same.Wherein particularly preferably supporter 24 and intermediate layer 16 are formed from the same material.
In gas barrier film 12, as it was previously stated, on supporter 24, have as inorganic layer 28 The organic layer 26 of basal layer.Additionally, in the superiors of gas barrier film 12, there is having as protective layer Machine layer 26.
Organic layer 26 is that the layer being made up of organic compound is (using organic compound as main component Layer (film)), substantially monomer and/or oligomer are cross-linked layer obtained by (polymerization).
Organic layer 26 on supporter 24 is as forming the inorganic layer playing gas barrier property rightly The basal layer of 28 plays a role.
By having the organic layer 26 of this kind of substrate, it is possible to by the surface of supporter 24 concavo-convex, The foreign body etc. being attached to the surface of supporter 24 embeds, and the film forming face of inorganic layer 28 is made and is suitable for The state of the film forming of inorganic layer 28.Thus, it is possible to eliminate surface concavo-convex or different of supporter 24 The inorganic compound making to become inorganic layer 28 of the image of thing etc is difficult to the region of film, at base Whole of the surface of plate forms suitable inorganic layer 28 very close to each otherly.
It addition, the organic layer 26 of the superiors is the protective layer of protection inorganic layer 28.
Inorganic layer 28 is the layer being made up of inorganic compound such as silicon nitrides, the hardest and crisp.Thus, meeting Rupture or crackle etc. damages because contacting with other component or easily being produced by certain impact etc. Wound.
Inorganic layer 28 is the layer mainly playing gas barrier property in gas barrier film 12.Thus, once inorganic layer 28 damage, and moisture or oxygen etc. are possible to pass through from damage location, and gas barrier property is greatly lowered.
In contrast, by there is the organic layer 26 played a role as protective layer in the superiors, just It is possible to prevent by the damage contacting or impacting the inorganic layer 28 caused.
That is, the gas barrier film of (organic/inorganic) cascade type used in the packaging material 10 of the present invention In 12, by there is the organic layer 26 of the basal layer becoming inorganic layer 28 and becoming inorganic layer 28 The organic layer 26 of protective layer, suitable inorganic layer 28 can be formed at whole very close to each otherly, and And prevent the damage of this inorganic layer 28.
Thus, the gas barrier film 12 of cascade type can stably obtain following high performance gas barrier film, I.e., it is possible to play the excellent gas barrier property that inorganic layer 28 is had, such as, there is moisture-vapor transmission Less than 1 × 10-4[g/(m2Day) high-gas resistance].
In gas barrier film 12 used in the packaging material 10 of the present invention, for the shape of organic layer 26 Material is become not limit, it is possible to use various known organic compound (resin/macromolecular compound).
Specifically, can exemplify suitably polyester, acrylic resin, methacrylic resin, Methacrylic acid-maleic acid, polystyrene, transparent fluororesin, polyimides, fluorination gather Acid imide, polyamide, polyamidoimide, Polyetherimide, cellulose acylate, polyurethane, Polyether-ether-ketone, Merlon, ester ring type polyolefin, polyarylate, polyether sulfone, polysulfones, fluorenes ring are modified The thermoplasticity such as Merlon, alicyclic modified Merlon, fluorenes ring modified poly ester, acryl compound Resin or polysiloxanes, other the film of organo-silicon compound.They can also and with multiple.
Wherein, from the standpoint of glass transition temperature, excellent strength etc., it is suitably for by radical polymerization Conjunction property compound and/or there is in functional group the polymer structure of cationically polymerizable compound of ether The organic layer 26 become.
Wherein, particularly from the most above-mentioned glass transition temperature, excellent strength and also refractive index is low, The transparency high and from the standpoint of optical characteristics excellence etc., can exemplify suitably as organic layer 26 Using the polymer of acrylate and/or the monomer of methacrylate or oligomer as main component Acrylic resin or methacrylic resin.
Wherein, can exemplify suitably especially with dipropyl glycol two (methyl) acrylate (DPGDA), trimethylolpropane tris (methyl) acrylate (TMPTA), two seasons penta 4 2 officials such as alcohol six (methyl) acrylate (DPHA) can above, particularly 3 officials can above third The polymer of olefin(e) acid ester and/or the monomer of methacrylate or oligomer is as the propylene of main component Acid resin or methacrylic resin.Alternatively, it is also possible to use these multiple acrylic resins or first Base acrylic resin.
Herein, although describe in detail below, but in the packaging material 10 of the present invention, organic layer 26 Glass transition temperature higher than supporter 24 and intermediate layer 16.Specifically, organic layer 26 Glass transition temperature is preferably high than the glass transition temperature of supporter 24 and intermediate layer 16 70 DEG C Above.It addition, as it was previously stated, the glass transition temperature in supporter 24 and intermediate layer 16 compares hot melt Connect layer 20 high.Specifically, the glass transition temperature in supporter 24 and intermediate layer 16 preferably than The glass transition temperature of hot welding layer 20 is high more than 70 DEG C.Thus, in packaging material 10, Remove the glass transition temperature (glass transition temperature forming material of each layer of each layer of adhesive phase Degree) be:
Hot welding layer 20 ＜ supporter 24 and intermediate layer 16 ＜ organic layer 26.
That is, in the packaging material 10 of the present invention, (multiple have having centered by inorganic layer 28 In the case of the repetition of machine layer/inorganic layer, count from the organic layer 26 of outermost), along with towards foreign side To, the glass transition temperature step-down of each layer.
And, the glass transition temperature of organic layer 26 is certainly less than as comprising inorganic compound The inorganic layer 28 of layer.
The packaging material 10 of the present invention utilize hot welding layer 20 and transfusion bag, the packaging bag etc. of food Package thermal welding (heat bonding).
The packaging material 10 of the present invention are said, have centered by inorganic layer 28, along with towards Outer direction and make the composition of the glass transition temperature step-down of each layer, the most just can carry out thermal welding Time, prevent because hot welding layer 20 is heated the damage of inorganic layer 28 caused by softening transform, stable Ground plays the gas barrier property as target.
In terms of above, will be described in more detail below.
The thickness of organic layer 26 does not limit, but is preferably set to 0.5～5 μm.
By the thickness of organic layer 26 is set to more than 0.5 μm, it is possible to by the table of supporter 24 The foreign body concavo-convex, the surface that is attached to supporter 24 in face embeds, rightly by the table of organic layer 26 The film forming face planarization of the i.e. inorganic layer 28 in face.
It addition, by the thickness of organic layer 26 is set to below 5 μm, it is possible to suppress suitably because of The product of the problems such as organic layer 26 is blocked up and causes the be full of cracks of organic layer 26, the curling of gas barrier film 12 Raw.
If it is considered that above aspect, then the thickness of organic layer 26 is more preferably set to 1～3 μm.
And, in the present invention, gas barrier film 12 has multiple organic layer 26, and each organic layer 26 Thickness both can be identical, it is also possible to different.
It addition, the formation material of each organic layer 26 both can be identical, it is also possible to different.But, In the packaging material 10 of the present invention, from preventing the viewpoints such as the damage of inorganic layer 28 described later, productivity Consider, preferably all of organic layer 26 is all formed with identical material.
As long as this kind of organic layer 26 utilizes known method to carry out film forming (formation).
For example, it is possible to utilize following so-called rubbing method to carry out film forming, i.e. preparation containing organic solvent, Become the coating of the organic compound of organic layer 26, surfactant etc., be coated with this coating and be dried After, cross-link.
Inorganic layer 28 is that the layer comprising inorganic compound is (using inorganic compound as the layer of main component (film)).
In gas barrier film 12 used in the packaging material 10 of the present invention, inorganic layer 28 is main sending out Wave the layer of the gas barrier property as target.
Formation material for inorganic layer 28 does not limit, it is possible to use the bag of various performance gas barrier properties The layer of inorganic-containing compound.
Specifically, can exemplify suitably comprise aluminium oxide, magnesium oxide, tantalum oxide, zirconium oxide, The metal-oxides such as titanium oxide, tin indium oxide (ITO)；The metal nitrides such as aluminium nitride；Aluminium carbide Deng metal carbides；The silica such as silicon oxide, oxidized silicon nitride, siloxicon, oxidation nitridation carborundum Compound；The silicon nitrides such as silicon nitride, carbonitride SiClx；The silicon carbides such as carborundum；Their hydrogenation Thing；They mixture of more than two kinds；And the film of the inorganic compound such as their hydrogeneous thing.
The particularly transparency height of silicon nitride, silicon oxide, silicon oxynitride, aluminium oxide, and can send out Wave the gas barrier property of excellence, consider from this point, be suitable in gas barrier film.The most particularly silicon nitride In addition to excellent gas barrier property, the transparency is the highest, thus can utilize suitably.
In the present invention, the thickness for inorganic layer 28 does not limit.That is, the thickness of inorganic layer 28 As long as determine the thickness that can play the gas barrier property as target rightly according to formation material.And And, according to the research of the present inventor, the thickness of inorganic layer 28 is preferably set to 10～200nm.
By the thickness of inorganic layer 28 is set to more than 10nm, it is possible to formed to play consistently and fill The inorganic layer 28 of the gas barrier properties divided.It addition, inorganic layer 28 is the most crisp, if blocked up, just have May produce rupture or crackle, stripping etc., and by the thickness of inorganic layer 28 is set to 200nm with Under, it is possible to prevent to rupture.
It addition, if it is considered that this point, then the thickness of inorganic layer 28 is preferably set to 15～100nm, Particularly preferably it is set to 20～75nm.
It addition, example is such as shown in Figure 2, there are at gas barrier film the feelings of multiple inorganic layer 28 Under condition, the thickness of each inorganic layer 28 both can be identical, it is also possible to different.
And, in the present invention, in the case of gas barrier film 12 has multiple inorganic layer 28, each nothing The thickness of machine layer 28 both can be identical, it is also possible to different.
It addition, in the case of gas barrier film 12 has multiple inorganic layer 28, the shape of each inorganic layer 28 Becoming material is also both can be identical, it is also possible to different.
In the packaging material 10 (gas barrier film 12) of the present invention, for the film build method of inorganic layer 28 Do not limit, various known inorganic layer can be utilized (inorganic according to inorganic layer 28 to be formed Film) film build method.
Specifically, the plasmas such as CCP-CVD or ICP-CVD can be exemplified suitably The gas phase membrane formation process such as sputtering, vacuum evaporation such as CVD, magnetron sputtering or reactive sputtering.
In the packaging material 10 of the present invention, on gas barrier film 12, utilize the first adhesive phase 14 Bonding intermediate layer 16.
Intermediate layer 16 is for by package thermal weldings such as the packaging material 10 of the present invention and transfusion bag Time prevent the layer that inorganic layer 28 damages.
As it was previously stated, in the packaging material 10 of the present invention, intermediate layer 16 and described supporter 24 Identical, glass transition temperature is lower than organic layer 26, and higher than hot welding layer 20.In additionally, The glass transition temperature of interbed 16 is preferably same or about with supporter 24, in more preferably inciting somebody to action Interbed 16 and supporter 24 utilize identical material to be formed.
About this intermediate layer 16, will be described in more detail below.
It addition, in the packaging material 10 of the present invention, on intermediate layer 16, utilize the second binding agent Layer 18 bonding hot welding layer 20.
As it was previously stated, the packaging material 10 of the present invention are heating-fusion bonded (heat-sealing/heat seal) in packaging The surface of material.Hot welding layer 20 is for carrying out the layer of this thermal welding (sealant layer).
Thus, hot welding layer 20 is substantially by the transfusion bag with the packaging material 10 of the thermal welding present invention The material identical Deng the formation material (the formation material on the surface of package) of package is formed.That is, In the case of package is polyethylene (PE) system, as long as using PE system as hot welding layer 20 Tablet (membranoid substance), package be polypropylene (PP) system in the case of, as As long as hot welding layer 20 uses the tablet of PP.
In the packaging material 10 of the present invention, gas barrier film 12 is as the inorganic layer playing gas barrier property The basal layer of 28 has organic layer 26 and has protective layer as inorganic layer 28 in the superiors The gas barrier film of the cascade type of organic layer 26.The gas barrier film 12 of this cascade type has the highest gas barrier property, Such as there is moisture-vapor transmission less than 1 × 10-4[g/(m2Day) high-gas resistance].
Thus it is believed that by the gas barrier film 12 of this cascade type being used for transfusion bag or food In the packages such as packaging bag, it is possible to obtain the package that gas barrier property is high, can prevent significantly by Medicament that moisture or oxygen cause or the deterioration of food.
Herein, also as shown in patent documentation 5, the gas barrier film 12 of cascade type is being used for package In the case of in, it may be considered that following method, i.e. on the surface of the organic layer 26 of the superiors, As hot welding layer utilize binding agent bond material identical with package tablet (thin film), with By gas barrier film 12 and package stacking, propping up from gas barrier film 12 under the state of hot welding layer contact Support body 24 side pushes while heating, by the surface of package and hot welding layer thermal welding.
But, according to the research of the present inventor, in this kind of method, if merely by the resistance of cascade type Air film 12 and package thermal welding, then often produce cannot obtain that gas barrier film 12 had excellent The situation of gas barrier property.
Present inventor has performed further investigation, it was found that this gas barrier property reduce reason be based on by The deformation (shrink/expanded) of the hot welding layer that heating causes.
Specifically, find when package is with the thermal welding of gas barrier film 12, owing to hot welding layer becomes Shape, power that therefore inorganic layer 28 of gas barrier film 12 is deformed by this and damage, thus, gas barrier film The gas barrier property of 12 is greatly lowered.
Gas barrier film 12 has organic layer 26 in the superiors.
By having the organic layer 26 of these the superiors, at disposal or the use gas barrier film of gas barrier film 12 During 12 grades, it is possible to prevent the inorganic layer 28 mainly playing gas barrier property from damaging.
That is, by making gas barrier film 12 have the organic layer 26 of these the superiors, it is possible to play consistently Aforesaid moisture-vapor transmission is less than 1 × 10-4[g/(m2Day) high-gas resistance performance].
In other words, in the gas barrier film of organic layer 26 without the superiors, wait meeting to exist in use Inorganic layer 28 cracks or ruptures equivalent damage, moisture or gas pass through from pars affecta, gas barrier property It is greatly lowered.That is, in the gas barrier film of organic layer 26 without the superiors, it is difficult to guarantee as High-gas resistance described in before.
Herein, according to the research of the present inventor, at the gas barrier film 12 by (organic/inorganic) cascade type In the case of package thermal welding, the organic layer 26 of the superiors has height the most to a certain extent Glass transition temperature.
Particularly, the organic layer 26 of the superiors preferably has the glass transition temperature of more than 120 DEG C.
That is, as it was previously stated, by be used for the hot welding layer of package thermal welding utilize adhesive phase with The organic layer 26 on upper strata bonds.Herein, if the glass transition temperature of the organic layer of the superiors 26 Low, then can be because the heat during solvent seasoning of adhesive phase be softened, as the protection of inorganic layer 28 Layer can not play sufficient function.
It addition, when by hot welding layer with package thermal welding, require heat to high temperature, and need Pressurize.Particularly, it is contemplated that productivity, in order to carry out the thermal welding in the short time, preferably exist Heat far above at a temperature of the melt temperature of hot welding layer.Now, if the superiors organic The glass transition temperature of layer 26 is low, then between hot welding layer and inorganic layer 28, and organic layer 26 Can expand because of heat, two-layer be extruded, thus becomes the reason of the damage causing inorganic layer 28.
Additionally, in the gas barrier film 12 of cascade type, inorganic layer 28 generally utilizes plasma CVD Or sputtering etc. is formed.Organic layer 26 accordingly, for the basal layer becoming inorganic layer 28, it is desirable to tool There is plasma resistance, there is high glass-transition temperature the most to a certain extent.Herein, resistance Air film 12 has multiple organic layer 26.If it is considered that productivity, the most preferably by all of organic layer 26 All using identical material to be formed, therefore the organic layer 26 of the superiors is it is also preferred that have to a certain extent High glass-transition temperature.
As it has been described above, in the case of by the gas barrier film 12 of cascade type and package thermal welding, preferably Hot welding layer and the organic layer 26 to a certain extent with high glass-transition temperature are bonded.
Herein, it is contemplated that productivity, in order to the thermal welding in the short time, preferably thermal welding can be realized Layer melts at low temperatures.
When thermal welding, hot welding layer deforms.But, have high glass-transition temperature has Although machine layer 26 thermostability is strong, yet with hard, therefore stress toleration is weak.It addition, hot melt Connect layer to bond securely by binding agent with organic layer 26.Thus, due to the deformation of hot welding layer, have Machine layer 26 also deforms, thus damages further.
The deformation of this organic layer 26 and damage are also delivered to adjacent and the most closely sealed inorganic Layer 28.Inorganic layer 28 is the layer comprising the inorganic compound such as silicon nitride, has higher than organic layer 26 Glass transition temperature, thus more firmly more crisp.
As a result of which it is, the inorganic layer 28 of the deformation and destruction for being passed organic layer 26, also execute Add the excessive power being intended to be allowed to deformation, thus produce in inorganic layer 28 and rupture or crackle equivalent damage.
Once inorganic layer 28 damages, and moisture or oxygen just can pass through from there, therefore gas barrier property fall Low.Particularly, in the gas barrier film 12 of cascade type, it is less than owing to having moisture-vapor transmission 1×10-4[g/(m2Day) high-gas resistance], so even the most slightly damage inorganic layer 28, Will also result in the reduction of the biggest performance.
In contrast, the packaging material 10 of the present invention have between hot welding layer 20 and gas barrier film 12 There is intermediate layer 16.It addition, the glass transition temperature of the supporter 24 of intermediate layer 16 and gas barrier film 12 Spend lower than organic layer 26 and higher than hot welding layer 20.
Thus, the vitrification of each layer (removing each layer of adhesive phase) constituting packaging material 10 turns Temperature is:
Hot welding layer 20 ＜ supporter 24 and intermediate layer 16 ＜ organic layer 26.
That is, in the packaging material 10 of the present invention, centered by inorganic layer 28, along with towards foreign side To, the glass transition temperature of each layer reduces.In other words, in the packaging material 10 of the present invention, Centered by inorganic layer 28, along with towards outward direction, heating the property of softening caused of each layer uprises.
Constitute by making the packaging material 10 of the present invention have this kind, it is possible to carry out rightly and bag The thermal welding of piece installing, even and if when thermal welding hot welding layer 20 (go up most organic layer 26) become Shape, it is also possible to prevent the damage of inorganic layer 28.
That is, between hot welding layer 20 and organic layer 26, there is glass transition temperature and compare thermal welding High and lower than organic layer 26 intermediate layer 16 of layer 20.Thus, by packaging material 10 and bag During piece installing thermal welding, even if hot welding layer 20 significantly deforms because of heating, intermediate layer 16 also can be made Cushion for the deformation of buffering hot welding layer 20 plays a role.As a result, it is possible to significantly drop The deformation of the low hot welding layer 20 being delivered to organic layer 26 from hot welding layer 20 and power.And, by In organic layer 26, there is the glass transition temperature higher than intermediate layer 16, therefore can also significantly drop The deformation of the low hot welding layer 20 being delivered to inorganic layer 28 from organic layer 26 and power.
Thus, even if the contraction of hot welding layer 20 is delivered to inorganic layer 28, the deflection transmitted is also Little, and its power is faint, is therefore possible to prevent crack in inorganic layer 28 or rupture equivalent damage.
Additionally, due to hot welding layer 20 has minimum glass transition temperature, therefore will pack When material 10 and package thermal welding, it is also possible to prevent the layer beyond hot welding layer 20 from damaging because of heat.
It addition, in the packing material of the present invention, it is not only intermediate layer 16, and gas barrier film 12 The glass transition temperature of supporter 24 is also low than organic layer 26 and higher than hot welding layer 20. That is, intermediate layer 16 and supporter 24 are in the middle of each layer constituting packaging material 10, have equal Glass transition temperature.
The thermal welding of packaging material 10 typically by by closely sealed to hot welding layer 20 and package and Heat support 24 and carry out.Now, if the glass transition temperature in intermediate layer 16 significantly Higher than supporter 24, then when carrying out thermal welding, relative to the deformation of gas barrier film 12, intermediate layer 16 Can play a role along the direction of suppression deformation.That is, intermediate layer 16 becomes the organic layer keeping the superiors 26 and the shape of inorganic layer 28.As a result of which it is, the organic layer 26 of substrate and inorganic layer 28 cannot chase after With the deformation of supporter 24, still cause the result damaging inorganic layer 28.
In contrast, by making intermediate layer 16 and supporter 24 have equal glass transition temperature, Intermediate layer 16 will be made also to deform in the same manner as supporter, and the best the most above-mentioned situation all can eliminate, The damage of inorganic layer 28 can be prevented more suitably.
If it is considered that above aspect, then the glass transition temperature of intermediate layer 16 and supporter 24 is excellent Select same or about.
Particularly, in the case of supporter 24 is PET, more preferably phase is also used in intermediate layer 16 Same PET is formed, and is formed with identical material with supporter 24 in intermediate layer 16.
Herein, it is also possible to consider by supporter 24 and the organic layer 26 becoming substrate are all used glass Changing transition temperature is to be formed with contour material, the deformation of the supporter 24 when preventing thermal welding.
However, it is possible to play the plasma-resistant that the organic layer 26 becoming substrate is required fully Property, the glass transition temperature of expansion when additionally can fully suppress welding are about 200 DEG C. This kind have high glass-transition temperature and have the transparency plastic foil be defined as transparent polyamides Imines etc., price is the highest.Thus, this selection is the most real.
And, the deformation of the hot welding layer 20 during this thermal welding the damage of the inorganic layer 28 caused Problem is that the superiors are organic layer 26 and have moisture-vapor transmission less than 1 × 10-4[g/(m2· Distinctive problem in the gas barrier film 12 of the cascade type of high-gas resistance day)].
The gas barrier film directly forming inorganic layer 28 on supporter as shown in patent documentation 4 Not there is high-gas resistance as the gas barrier film 12 of the cascade type that image surface is organic layer 26.
On the other hand, even if as it was previously stated, have the organic layer 26 of basal layer, not having as guarantor The gas barrier film of the cascade type of the organic layer 26 of sheath is inorganic layer 28 due to surface, therefore dispose time, Or when carrying out various process, it is also difficult to avoid the damage of inorganic layer 28.Thus, as a result of which it is, be somebody's turn to do Gas barrier film does not the most have high resistant as the gas barrier film 12 of the cascade type that image surface is organic layer 26 Gas.
Thus, in these gas barrier films, even if because of the deformation of hot welding layer, how many of inorganic layer 28 Raw damage, the reduction of gas barrier property is also few, does not results in the problem in performance.That is, at these gas barrier films Surface be provided with in the packaging material of hot welding layer, the most do not produce and caused by the deformation of hot welding layer Performance reduce, do not result in problem.Thus, in these gas barrier films, even if in hot welding layer The lower floor of 20 arranges intermediate layer 16 as representative of the present invention, the most nonsensical, increase by 1 layer unnecessary Layer, only can make cost raise, and with the heat sealability reduction of package.
In contrast, be organic layer 26 in the superiors and there is moisture-vapor transmission be less than 1×10-4[g/(m2In the gas barrier film 12 of the cascade type of high-gas resistance day)], as it was previously stated, i.e. Making is the damage of slight inorganic layer 28, will also result in the big gas barrier property i.e. reduction of performance.Thus, The effect with intermediate layer 16 is the biggest.
In the packaging material 10 of the present invention, the formation material for intermediate layer 16 does not limit, can To utilize various glass transition temperature to be higher than hot welding layer 20 and the material higher than organic layer 26 (tablet (thin film)).
As an example, the supporter 24 at gas barrier film 12 is PET or PEN (poly-naphthalenedicarboxylic acid second Diol ester), organic layer 26 be the resin of (methyl) acrylic acid series, inorganic layer 28 be silicon nitride In the case of silicon compound, the formation material of package are PE or PP, as intermediate layer 16, suitable Close and use PET film, pen film, nylon membrane etc..
And, the reason that intermediate layer 16 is preferably formed with the material identical with supporter 24 is as previously mentioned. Thus, in this example embodiment, in the case of supporter 24 is PET, preferably as intermediate layer 16 Use PET film, in the case of supporter 24 is PEN, use PEN preferably as intermediate layer 16 Film.
As it was previously stated, the glass transition temperature of the packaging material 10 of the present invention meets " hot welding layer 20 ＜ supporters 24 and intermediate layer 16 ＜ organic layer 26 " relation.
Herein, different according to the material (constituting the composition of the material of layer) constituting layer, do not have Glass transition temperature (cannot define glass transition temperature) sometimes.
In the packaging material 10 of the present invention, in intermediate layer 16, hot welding layer 20, supporter 24, And in the case of more than 1 of organic layer 26 uses this kind of material, replace glass transition temperature Degree, and use softening temperature (softening point Ts) or fusing point (Tm).And, soft defining In the case of changing temperature and fusing point both sides, use softening temperature.
It addition, the thickness for intermediate layer 16 does not the most limit, as long as according to the formation in intermediate layer 16 Material, properly selects to play and alleviates shrinking or the effect of movement of aforesaid hot welding layer 20 Thickness.
Herein, although describe in detail below, if but from the first adhesive phase 14 to hot welding layer 20 Thickness excessive, then the gas barrier property of the packaging material 10 of the present invention will reduce.
If it is considered that this point, then the thickness in intermediate layer 16 is preferably below 20 μm, particularly preferably It is 15～8 μm.
The first adhesive phase 14 intermediate layer 16 and gas barrier film 12 bonded is to comprise known bonding The layer of agent, it is possible to use all intermediate layer 16 and gas barrier film 12 (organic layer 26) can be bonded Binding agent.And, if it is considered that the optical characteristics of packaging material 10, then excellent preferably by the transparency Different binding agent.
It addition, the thickness for the first adhesive phase 14 does not limit, can as long as properly selecting The thickness that intermediate layer 16 and gas barrier film 12 are reliably bonded.
Herein, if as it was previously stated, blocked up to hot welding layer 20 from the first adhesive phase 14, then this The gas barrier property of the packaging material 10 of invention will reduce.Thus, the first adhesive phase 14 more Bao Yuehao, Particularly preferably it is set to below 10 μm.
As it was previously stated, the material that formed of hot welding layer 20 substantially uses and is heating-fusion bonded the present invention's The packages such as the transfusion bag of packaging material 10 form the identical material of material.
That is, if hot melt is connected to the package of packaging material 10 is PE system, then hot welding layer 20 Formed with the thin film of PE, if it is PP system that hot melt is connected to the package of packaging material 10, As long as then hot welding layer 20 film of PP is formed.
It addition, the thickness for hot welding layer 20 does not the most limit, as long as according to hot welding layer 20 Formation material, be connected to shape or the state of the package of the packaging material 10 of the present invention according to hot melt Deng, properly selecting can the thickness of reliably thermal welding.
Herein, if as it was previously stated, excessive to the thickness of hot welding layer 20 from the first adhesive phase 14, Then the gas barrier property of the packaging material of the present invention will reduce.If it is considered that this point, then hot welding layer The thickness of 20 is preferably below 60 μm, particularly preferably 50～10 μm.
The second adhesive phase 18 bonded in hot welding layer 20 and intermediate layer 16 can utilize all energy Enough binding agents that hot welding layer 20 is bonded with intermediate layer 16, it addition, with the first adhesive phase 14 Identical, preferably by the binding agent that the transparency is excellent.
It addition, the thickness for the second adhesive phase 18 does not limit, as long as properly selecting permissible The thickness that hot welding layer 20 and intermediate layer 16 are reliably bonded.
If it is it addition, as it was previously stated, blocked up to hot welding layer 20 from the first adhesive phase 14, then originally The gas barrier property of the packaging material of invention will reduce.Thus, the second adhesive phase 18 more Bao Yuehao, Particularly preferably it is set to below 10 μm.
If as it was previously stated, blocked up to hot welding layer 20 from the first adhesive phase 14, then the present invention The gas barrier property of packaging material 10 will reduce.
That is, each layer from the first adhesive phase 14 to hot welding layer 20 does not the most have gas barrier property. Thus, moisture or oxygen can invade from the end face of these each layer, and the moisture of intrusion etc. can invade welding There is the inside of the package of the packaging material 10 of the present invention.Thus, if from the first adhesive phase 14 Blocked up to hot welding layer 20, then the moisture invaded from this end face or the amount of oxygen will increase, packaging The gas barrier property of material 10 is greatly lowered.
In other words, if blocked up to hot welding layer 20 from the first adhesive phase 14, then 1 is being increased Before the intermediate layer 16 that layer gas barrier film etc. shown in patent documentation 4 grade is not usually required to, can lose Go to use the meaning of the gas barrier film 12 of the cascade type of gas barrier property excellence.
Herein, if from the thickness of the first adhesive phase 14 to hot welding layer 20 more than 100 μm, The reduction of the gas barrier property then caused by the moisture etc. invaded from end face will become very large.
Thus, in the packaging material 10 of the present invention, from the first adhesive phase 14 to hot welding layer The thickness of 20 is preferably below 100 μm, below more preferably 80 μm, and particularly preferably 60 μm Below.
Above the packaging material of the present invention are described in detail, but on the present invention is not limited to State embodiment, naturally it is also possible to carry out in the scope without departing from the purport of the present invention various improvement or Change.
Embodiment
Hereinafter enumerating the specific embodiment of the present invention, the present invention will be described in more detail.
[embodiment 1]
Produce have on supporter 24 organic layer 26 as basal layer, inorganic layer 28 and The gas barrier film 12 of the organic layer 26 as protective layer of the superiors.
Supporter 24 employs the PET film of the long size of thick 100 μm of wide 1000mm, and (Japan is spun Company Cosmoshine A4300).
DSC (means of differential scanning calorimetry mensuration) is utilized to measure the glass transition temperature of this supporter 24, Its result is 69 DEG C.
In MEK (butanone), add TMPTA (DAICEL CYTEC company system), Modified bisphenol A diacrylate (DAICEL CYTEC company EBECRYL150), surface Activating agent (BYK Chemie Japan company BYK378) and Photoepolymerizationinitiater initiater (Ciba Chemicals company Irg184), prepare the coating forming organic layer 26.
The addition of surfactant is set in terms of the concentration (solid component concentration) removing organic solvent 1 mass %, the addition of Photoepolymerizationinitiater initiater is set to 2 mass % with the densitometer removing organic solvent (i.e. organic compound in solid constituent is 97 mass %).It addition, modified bisphenol A two propylene The addition of acid esters is set to the 10% of TMPTA, and the solid component concentration of coating is set to 15 mass %.
On the surface of supporter 24, utilize the coating prepared by the coating of die coating machine, after hot air drying, Irradiation ultraviolet radiation, forms the organic layer 26 that thickness is 2 μm.
Utilize the method identical with supporter 24, determine the glass transition temperature of organic layer 26, Its result is 250 DEG C.
On this organic layer 26, utilize CCP-CVD formed 50nm as inorganic layer 28 Silicon nitride layer.
Unstrpped gas employs silane gas (SiH4), ammonia (NH3), nitrogen (N2) and hydrogen Gas (H2).Quantity delivered is set to, and silane gas is 100sccm, and ammonia is 200sccm, and nitrogen is 500sccm, hydrogen is 500sccm.It addition, become film pressure to be set to 50Pa.
Plasma exciatiaon power is set to 3000W under frequency 13.5MHz.It addition, at inorganic layer In the film forming of 28, supply the substrate bias power of 500W from the rear side of supporter 24, by supporter 24 Homoiothermic is-20 DEG C.
On this inorganic layer 28, and previously it was identically formed the organic layer 26 that thickness is 2 μm, system It is made in and there is on supporter 24 the organic of the organic layer 26 of substrate, inorganic layer 28 and the superiors The gas barrier film 12 of layer 26.
Calcium etch (method described in Japanese Unexamined Patent Publication 2005-283561 publication) is utilized to measure Go out the moisture-vapor transmission [g/ (m of produced gas barrier film 122·day)].As a result of which it is, water steams Vapor permeability is 8 × 10-5[g/(m2·day)]。
On the surface (organic layer 26 on surface) of gas barrier film 12, bar coater coating is utilized to be dissolved in second Binding agent (Mitsui Chemicals, Inc. TAKELAC and TAKENATE) in acetoacetic ester, at 80 DEG C Lower dry, form the first adhesive phase 14 of thick 4 μm.
On the first adhesive phase 14, as intermediate layer 16, the PET film (Toray of thick 12 μm of stacking Company LUMIRROR), transport while by niproll pressurization and/or heating and bond.
Utilize the method identical with supporter 24, determine the glass transition temperature in intermediate layer 16, Its result is 69 DEG C.
On the surface in intermediate layer 16, with the first adhesive phase 14 identical ground coating adhesive, form thickness Second adhesive phase 18 of 4 μm.
Thereon as PE film (the Tohcello company FC of thick 40 μm of hot welding layer 20 stacking -S40), transport while by niproll pressurization and/or heating and bond, produce such as Fig. 1 institute The packaging material 10 shown.
Utilize the method identical with supporter 24, determine the glass transition temperature of hot welding layer 20, Its result is-25 DEG C.
Produced packaging material 10 are cut into 100 × 100mm, are layered in same size On the PE film of thick 40 μm.Then, whole peripheral end portion to packaging material 10 from supporter 24 side 10mm carries out heating, pressing, by packaging material 10 and PE film thermal welding.
With the most identical the packaging material 10 determining thermal welding and the water of the duplexer of PE film Vapor transmission rates, its result is 1.0 × 10-4[g/(m2·day)]。
[embodiment 2]
Do not change the solid component concentration (15 mass %) of coating, for forming organic layer 26 In coating, the addition of modified bisphenol A diacrylate is set to the 20% of TMPTA, except this In addition, produce gas barrier film 12 same as in Example 1ly, and then produce packaging material 10.
Determining the glass transition temperature of organic layer 26, its result is same as in Example 1ly 140℃.It addition, the steam determining produced gas barrier film 12 is saturating same as in Example 1ly Crossing rate, its result is 1.8 × 10-4[g/(m2·day)]。
By same as in Example 1 for produced packaging material 10 with PE film thermal welding, measure Going out the moisture-vapor transmission of duplexer, its result is 1.9 × 10-4[g/(m2·day)]。
[embodiment 3]
Except hot welding layer 20 being replaced with PE film (the Tohcello company FC of thick 100 μm -S100) beyond, produce packaging material 10 same as in Example 1ly.
Determining the glass transition temperature of hot welding layer 20, its result is same as in Example 1ly -25℃。
By same as in Example 1 for produced packaging material 10 with PE film thermal welding, measure Going out the moisture-vapor transmission of duplexer, its result is 1.7 × 10-4[g/(m2·day)]。
[embodiment 4]
Except intermediate layer 16 replaces with the PET film of thick 100 μm, (company's system is spun by Japan Cosmoshine A4300) beyond, produce packaging material 10 same as in Example 1ly.
Determining the glass transition temperature in intermediate layer 16, its result is same as in Example 1ly 69℃。
By same as in Example 1 for produced packaging material 10 with PE film thermal welding, measure Going out the moisture-vapor transmission of duplexer, its result is 4.9 × 10-4[g/(m2·day)]。
[embodiment 5]
Except hot welding layer 20 being replaced with PE film (the Tohcello company FC of thick 25 μm -S25) beyond, produce packaging material 10 same as in Example 1ly.
Determining the glass transition temperature of hot welding layer 20, its result is same as in Example 1ly -25℃。
By same as in Example 1 for produced packaging material 10 with PE film thermal welding, measure Going out the moisture-vapor transmission of duplexer, its result is 9.8 × 10-5[g/(m2·day)]。
[comparative example 1]
Except intermediate layer 16 replaces with the PE film of thick 12 μm, (Chu Guang Unitech company makes Light NEW IP Stretch) beyond, produce packaging material 10 same as in Example 1ly.
Determining the glass transition temperature in intermediate layer 16 same as in Example 1ly, its result is- 25℃。
By same as in Example 1 for produced packaging material 10 with PE film thermal welding, measure Going out the moisture-vapor transmission of duplexer, its result is 1.5 × 10-3[g/(m2·day)]。
[comparative example 2]
Except intermediate layer 16 being replaced with polyimide film (the Toray-Dupont company of thick 12 μm CAPTON 50H processed) beyond, produce packaging material 10 same as in Example 1ly.
Determining the glass transition temperature in intermediate layer 16, its result is super same as in Example 1ly Cross determination limit (about 260 DEG C).I.e., it is possible to think the glass transition temperature of this polyimide film Far above 250 DEG C.
By same as in Example 1 for produced packaging material 10 with PE film thermal welding, measure Going out the moisture-vapor transmission of duplexer, its result is 1.2 × 10-3[g/(m2·day)]。
[comparative example 3]
Replace TMPTA, and use fatty acid modified epoxy acrylate (DAICEL CYTEC Company EBECRYL3702) preparation is for forming the coating of organic layer 26, with embodiment 1 Produce gas barrier film 12 in the same manner, and then produce packaging material 10.
Determining the glass transition temperature of organic layer 26, its result is same as in Example 1ly 56℃.It addition, the steam determining made gas barrier film 12 passes through same as in Example 1ly Rate, its result is 5 × 10-3[g/(m2·day)]。
By same as in Example 1 for produced packaging material 10 with PE film thermal welding, measure Going out the moisture-vapor transmission of duplexer, its result is 6.5 × 10-3[g/(m2·day)]。
[comparative example 4]
2 layers of composition of organic layer 26 with inorganic layer 28 except gas barrier film is set to substrate (do not have The organic layer 26 on upper strata) beyond, produce gas barrier film same as in Example 1ly, and then produce Packaging material 10.
Determining the moisture-vapor transmission of made gas barrier film, its result is same as in Example 1ly 1.8×10-3[g/(m2·day)]。
By same as in Example 1 for produced packaging material 10 with PE film thermal welding, measure Going out the moisture-vapor transmission of duplexer, its result is 8.5 × 10-3[g/(m2·day)]。
[comparative example 5]
2 layers of composition of organic layer 26 with inorganic layer 28 except gas barrier film is set to substrate (do not have The organic layer 26 on upper strata) beyond, produce gas barrier film (that is, gas barrier film same as in Example 1ly Identical with comparative example 4).
In addition to using this gas barrier film and not there is intermediate layer 16, make same as in Example 1ly Make packaging material.
By same as in Example 1 for produced packaging material 10 with PE film thermal welding, measure Going out the moisture-vapor transmission of duplexer, its result is 9.0 × 10-2[g/(m2·day)]。
[comparative example 6]
In addition to not there is intermediate layer 16, produce packaging material same as in Example 1ly.
By same as in Example 1 for produced packaging material 10 with PE film thermal welding, measure Going out the moisture-vapor transmission of duplexer, its result is 7.0 × 10-4[g/(m2·day)]。
Above result set will be shown in following table.
And, in following table, moisture-vapor transmission (block) is evaluated as follows, i.e.
Will be less than 1 × 10-4[g/(m2Day)] be evaluated as " outstanding "；
By 1 × 10-4[g/(m2Day) more than] and less than 2 × 10-4[g/(m2Being evaluated as day)] " well "；
By 2 × 10-4[g/(m2Day) more than] and less than 1 × 10-3[g/(m2Being evaluated as day)] " still can "；
By 1 × 10-3[g/(m2Day) it is evaluated as " bad " more than].
[table 1]
Also described above shown in table, the glass transition temperature of each layer is satisfied, and " hot welding layer 20 ＜ props up Support body 24 and intermediate layer 16 ＜ organic layer 26 " the present invention packaging material 10 with PE film heat After welding, also can give play to less than 2.0 × 10-4[g/(m2Day) high-gas resistance].
Wherein, the embodiment 5 that the thickness of hot welding layer 20 is thinner compared with other has and is less than 1×10-4[g/(m2Day) the highest gas barrier properties].
And it is believed that owing to the glass transition temperature of the organic layer 26 of embodiment 2 is low, real The hot welding layer 20 executing example 3 is thick, and the intermediate layer 16 of embodiment 4 is thick, the most compared with Example 1, Gas barrier properties slightly reduces.
In contrast, due to the glass transition temperature in intermediate layer 16 of comparative example 1 and hot welding layer 20 is identical, and the glass transition temperature in the intermediate layer 16 of comparative example 2 is higher than organic layer 26, and also Significantly higher than supporter 24, the glass transition temperature in the intermediate layer 16 of comparative example 3 is higher than organic Layer 26, and the glass transition temperature of organic layer 26 is low, the most all can be by supporter 24 or heat The displacement transfer of welding layer 20 grade is to inorganic layer 28, thus damages inorganic layer 28, with the bag of the present invention Package material is compared, and gas barrier property is low.Additionally, not there is the comparative example 6 in intermediate layer 16 because of identical yet Reason, compared with the packaging material of the present invention, gas barrier property is low.
Embodiment 1,3,4 and 5 and comparative example 1,2 and 6 are all the use of identical resistance Air film 12.I.e. it is believed that in comparative example, when with the thermal welding of PE film, inorganic layer 28 damages, Gas barrier property reduces.In contrast, packaging material according to the invention 10, it is possible to prevent and package Thermal welding time the damage of inorganic layer 28.
It addition, gas barrier film is organic layer/inorganic layer 2 layers of comparative example 4 and 5 constituted are owing to disposing Deng time the reason of damage of inorganic layer, the gas barrier properties of gas barrier film self is low, therefore cannot obtain and fill The gas barrier properties divided.
According to above result, the effect of the present invention is apparent.
Industrial applicability
Can be suitably employed in therapeutic medical transfusion bag or the flexible pipe of food or packaging bag etc..
Symbol description
10 packaging material
12 gas barrier films
14 first adhesive phases
16 intermediate layers
18 second adhesive phases
20 hot welding layer
24 supporters
26 organic layers
28 inorganic layers

Claims (13)

1. packaging material, are the packaging material being thermally fused to package,
There is gas barrier film, the intermediate layer utilizing the first adhesive phase to bond with described gas barrier film and utilize Second adhesive phase and the hot welding layer of described interlayer adhesion, it is characterised in that
Described gas barrier film have on supporter formed more than 1 the inorganic layer with gas barrier property and Become combination and stacking that the superiors the are organic layer knot of the organic layer of the basal layer of this inorganic layer Structure,
And, the glass transition temperature of described organic layer is than described intermediate layer and the supporter of gas barrier film Height, the glass transition temperature of the supporter of described intermediate layer and gas barrier film is than described thermal welding floor height.
Packaging material the most according to claim 1, wherein,
It is below 100 μm from described first adhesive phase thickness to hot welding layer.
Packaging material the most according to claim 1, wherein,
Described intermediate layer is formed from the same material with the supporter of described gas barrier film.
Packaging material the most according to claim 2, wherein,
Described intermediate layer is formed from the same material with the supporter of described gas barrier film.
5. according to the packaging material according to any one of Claims 1 to 4, wherein,
All of described organic layer is formed from the same material.
6. according to the packaging material according to any one of Claims 1 to 4, wherein,
The thickness of described hot welding layer is below 60 μm.
7. according to the packaging material according to any one of Claims 1 to 4, wherein,
The thickness in described intermediate layer is below 20 μm.
Packaging material the most according to claim 6, wherein,
The thickness in described intermediate layer is below 20 μm.
9. according to the packaging material according to any one of Claims 1 to 4, wherein,
Described organic layer is to comprise the layer of at least one party in acrylic resin and methacrylic resin.
Packaging material the most according to claim 5, wherein,
Described organic layer is to comprise the layer of at least one party in acrylic resin and methacrylic resin.
11. according to the packaging material according to any one of Claims 1 to 4, wherein,
Described inorganic layer is the layer comprising silicon nitride.
12. according to the packaging material according to any one of Claims 1 to 4, wherein,
Described hot welding layer is to comprise polyethylene or polyacrylic layer.
13. according to the packaging material according to any one of Claims 1 to 4, wherein,
Described intermediate layer is the layer comprising polyethylene terephthalate.
CN201380032226.3A 2012-08-10 2013-07-01 It is thermally fused to the packaging material of package Expired - Fee Related CN104379464B (en)

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JP2012-178115 2012-08-10
JP2012178115 2012-08-10
PCT/JP2013/068026 WO2014024602A1 (en) 2012-08-10 2013-07-01 Packaging material to be thermally welded to package

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JP6457371B2 (en) * 2015-10-09 2019-01-23 富士フイルム株式会社 Gas barrier film, organic electronic device, substrate for organic electroluminescent device, organic electroluminescent device
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JP3835198B2 (en) * 2001-04-11 2006-10-18 東洋製罐株式会社 Method for producing oxygen-absorbing multilayer film
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US7297414B2 (en) * 2003-09-30 2007-11-20 Fujifilm Corporation Gas barrier film and method for producing the same
US20050214556A1 (en) * 2004-02-20 2005-09-29 Fuji Photo Film Co., Ltd Organic-inorganic composite composition, plastic substrate, gas barrier laminate film, and image display device
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