CN101511585A - Multilayer body - Google Patents
Multilayer body Download PDFInfo
- Publication number
- CN101511585A CN101511585A CNA2007800331407A CN200780033140A CN101511585A CN 101511585 A CN101511585 A CN 101511585A CN A2007800331407 A CNA2007800331407 A CN A2007800331407A CN 200780033140 A CN200780033140 A CN 200780033140A CN 101511585 A CN101511585 A CN 101511585A
- Authority
- CN
- China
- Prior art keywords
- base material
- ray
- duplexer according
- rete
- gas barrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
A laminate prepared by pretreating at least one side of a substrate of a plastic film by plasma treatment and then directly laminating a thermoplastic resin on a surface treated by pretreatment.
Description
Technical field
The present invention relates to plastic sheeting or comprise the base material of plastic sheeting and thermoplastic resin is realized the duplexer of firm interlayer adaptation when carrying out extruded lamination.More specifically, relate to and not be used in coating cementation smears (anchor coating agent), binding agent etc. on plastic sheeting or the base material, when noting be used in extruded lamination in addition thermoplastic resin is implemented ozone treatment etc., and by directly plastic sheeting or base material being carried out the duplexer that extruded lamination just can realize firm adaptation.
Background technology
The multi-layer laminate that uses in the packing etc. uses in modes such as applying plastic sheeting, metal forming, paper according to desired rerum natura.For example because polyester film has favorable mechanical characteristic, dimensional stability, obdurability etc., therefore adopt it as base material, laminated metal paper tinsel or inorganic matter evaporated film thereon in order to give gas barrier property are in order to give as the heat sealability of packaging material and stacked heat sealability resin bed.
As in the folded manufacture method that the laminate film of heat sealability resin bed is arranged of such layers on substrates, can list dry lamination method, wet type laminating, extruded layer platen press etc., but extensively adopt extruded layer platen press favourable aspect cost, efficient.
The general thermoplastic resins such as polyethylene, polypropylene, vinyl copolymer that use in the extruded layer platen press., if with the direct extruded lamination of these thermoplastic resins on the plastic sheeting of base material, then because of the adaptation difference is coated with cementation coating (AC) agent usually in advance on plastic sheeting, extruded lamination thermoplastic resin thereon then.
; because the AC agent adopts organic solvents such as ethyl acetate or toluene to be coated with as retarder thinner, therefore general exist need corresponding with the regulation of fire service law, operating environment worsens, coating agent than higher price makes that manufacturing cost rises because of using, residual organic solvent produces problems such as foul smell in the end article.
Moreover, with plastic sheeting as the intermediate layer, then under the situation of the described thermoplastic resin of two sides extruded lamination, sometimes need be in the two sided coatings AC of plastic sheeting agent., can the while be special at the equipment of the two sided coatings AC of plastic sheeting agent.On the other hand, as using the duplexer of making formation like this at the conventional equipment of the one side extruded lamination thermoplastic resin of base material, then there is the problem that must increase the operation passage.
For this reason, carried out multiple test to not using the AC agent in the method for the two sides of base material extruded lamination thermoplastic resin so far.Example as these methods, known have an employing ethylene-methacrylic acid copolymer, and the effect by sour composition makes technology that itself and aluminium foil bond securely, and improves the technology etc. of dhering strength by extruding on the evaporation base material forms unsaturated carboxylic acid graft on acrylic resin modified resin., because spendable resin and base material are restricted in these methods, thereby can not adopt the combination of thermoplastic resins such as common plastic basis material and polyvinyl resin.
Recently, specially permit No. 2895917 communique, No. 3385663 communique of special permission and specially permit as shown in No. 3716006 communique as Japan, disclose by the molten resin face being carried out ozone treatment when the extruded lamination, thereby also can obtain method with the good adaptation of base material without the AC agent.Improve caking property by in resin, being blown into ozone in the method, but have the foul smell severity of ozone and have toxicity, need to consider security, and be difficult to confirm to have carried out whether equably the problem of ozone treatment.
For addressing the above problem, in TOHKEMY 2000-238195 communique, disclose printed layers has been set on base material, utilize ultraviolet ray that printed layers is implemented surface treatment, carry out the method for extruded lamination then., printed layers is essential in the method, thereby is difficult to use in the formation that printed layers is not set.If even if do not need the formation of printed layers, then there is the problem that increases operation and cost in the online stacked and surface treatment procedure that carries out printed layers.
Moreover, in recent years, as film for packaging and widely used transparent gas barrier film in the one or both sides of film stacked gas barrier property coating., when making this gas barrier property coating realize adaptation with the resin of extruded lamination, identical problem when also existing with above-mentioned base material.
Summary of the invention
The object of the present invention is to provide a kind of duplexer, it not be used in coating cementation smears, binding agent etc. on the plastic basis material, when also noting be used in extruded lamination in addition thermoplastic resin is implemented ozone treatment, to base material extruded lamination thermoplastic resin, just can obtain the good adaptation of base material and thermoplastic resin by directly.
Duplexer of the present invention is by at least one surface of the base material that formed by plastic sheeting being implemented preliminary treatment of plasma treatment, through on the pretreated treated side directly the extruded lamination thermoplastic resin form.
In the present invention, also the preliminary treatment of plasma treatment is implemented on the surface of not establishing the evaporation layer of the base material that can constitute the plastic sheeting that is provided with the evaporation layer by single face, direct extruded lamination thermoplastic resin on the pretreated treated side of process.
In the present invention, also can on described evaporation layer, gas barrier property further be set by rete.
In the present invention, while the treated side of preferred described base material when described base material of water saturates and thermoplastic resin are peeled off, is peeled off by destroying cohesion.
Described plasma treatment for example is to utilize the processing of reactive ion etching (RIE), be utilize be set in its automatic bias value more than the 200V and below the 2000V, will be set in 100Wm with the Ed value that Ed=(plasma density) * (processing time) defines
-2Above and the 10000Wm of sec
-2The processing of the low temperature plasma that sec is following.
Described thermoplastic resin contains and is selected from ldpe resin, high-density polyethylene resin, medium density polyethylene resin, ethylene-vinyl acetate copolymer, ethene-alpha-olefin copolymer, ethene-α, the resin more than a kind or 2 kinds among beta-unsaturated carboxylic acid copolymer and carboxylate thereof or ionomer thing, acrylic resin, propylene-alpha-olefin copolymers, anhydride modified polyolefin and the epoxide modified polyolefin.
Preferably, described base material is formed by polyethylene terephthalate thin film, surface after the preliminary treatment that this polyethylene terephthalate thin film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and elemental ratio (O/C) is below 0.49.
Preferably, described base material is for example formed by polyethylene terephthalate thin film, surface after the preliminary treatment that this polyethylene terephthalate thin film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, is below 0.33 from functional group's ratio (COO/C-C) that the analysis of Cls waveform is obtained.
Preferably, described base material is for example formed by polyethylene terephthalate thin film, surface after the preliminary treatment that this polyethylene terephthalate thin film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and the half-breadth value of the C-C key of obtaining from the analysis of Cls waveform is 1.340～1.560eV.
Preferably, described base material is for example formed by polyamide film, surface after the preliminary treatment that this polyamide film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and elemental ratio (O/ (C+N)) is more than 0.2.
Preferably, described base material is for example formed by polyamide film, surface after the preliminary treatment that this polyamide film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and the half-breadth value of the C-C key of obtaining from the analysis of Cls waveform is 1.380～1.560eV.
Preferably, described base material is for example formed by polypropylene film, surface after the preliminary treatment that this polypropylene film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and elemental ratio (O/C) is 0.03～0.135.
Preferably, described base material is for example formed by polypropylene film, surface after the preliminary treatment that this polypropylene film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and the half-breadth value of the C-C key of obtaining from the analysis of Cls waveform is 1.320～1.600eV.
In the present invention, also can be implemented the preliminary treatment of plasma treatment to described gas barrier property by the surface of rete.
Described gas barrier property by rete for example be contain water soluble polymer or contain water soluble polymer and the gas barrier property of inorganic compound by rete.
Preferably, when adopting X ray photoelectricity optical spectroscopy (XPS) to measure described gas barrier property by rete surperficial, the functional group of the carbon-carbon bond of water soluble polymer (C-C) and carbon-hydroxyl bond (C-OH) is more than 0.25 and below 0.87 than D (C-OH/C-C).
Described water soluble polymer for example is a polyvinyl alcohol.
Described inorganic compound for example is the hydrolysate of particulates such as silicon dioxide granule or the metal alkoxide more than a kind.
The inorganic oxide evaporation layer of thick 5～100nm also can be set between described material main body and described gas barrier property are by rete.
By rete, the functional group after the preferred pretreatment compares D than the functional group before D and the preliminary treatment about described gas barrier property
0Ratio D/D
0Be more than 0.30 and below 0.92.
Description of drawings
Fig. 1 is the cutaway view of the duplexer of one embodiment of the present invention.
Fig. 2 is the Cls waveform compartment analysis wave spectrum that the XPS by the PET film that is untreated obtains.
Fig. 3 is the Cls waveform compartment analysis wave spectrum that the XPS by the Ny film that is untreated obtains.
Fig. 4 is the Cls waveform compartment analysis wave spectrum that the XPS by the PP film that is untreated obtains.
Fig. 5 is the cutaway view of the duplexer of other embodiments of the present invention.
Fig. 6 is the Cls waveform compartment analysis wave spectrum that is obtained by the XPS of rete by the gas barrier property that contains PVA.
The specific embodiment
Below, the embodiment of the best of the present invention is described.
In the present invention, for plastic sheeting, so long as generally can be used as the just qualification especially of material that the base material of duplexer uses as base material.For example can list: polyolefin films such as PET (PET) or PEN mylar such as (PEN), polyethylene or polypropylene, polystyrene film, polyamide film, polycarbonate film, polyacrylonitrile film, Kapton etc.Base material also can be any in stretching, stretching, but preferably has mechanical strength and dimensional stability.In addition, also can implement processing such as sided corona treatment to film surface.In above-mentioned, preferably adopt polyethylene terephthalate thin film, polyamide film and polypropylene film.
The one side with being provided with thermoplastic resin at base material becomes on the surface of opposition side, also can use well-known various additive or stabilizing agent, and for example antistatic agent, ultraviolet ray prevent agent, plasticizer, lubricant etc.In addition, also can pass through processing such as this surface enforcement sided corona treatment, plasma treatment, or inorganic oxide evaporation layer, metal evaporation layer, overlay, printed layers etc. are set on this surface.These layers are not limited to 1 layer, also can be stacked more than 2 layers.For example, also can base material be formed gas-barrier films by the evaporation layer is set.In addition, also can be in advance with laminations such as base material and various plastic sheeting, metal forming, thermoplastic resins.Laminating method as constituting base material can list: several different methods such as dry lamination, extruded lamination.
Thickness for base material does not limit especially.In addition, consider applicability, not only can use monomer film, and can adopt the stacked film that film of different nature forms that has as base film as packaging material.Have, if consider processability when forming thermoplastic resin by extruded lamination, the thickness of base material is preferably the scope of 3～200 μ m, the scope of 6～30 μ m more preferably in the practicality again.
In the present invention, in order to strengthen the driving fit of base material and thermoplastic resin, utilize plasma or reactive ion etching (RIE) that substrate surface is implemented preliminary treatment.Can obtain two kinds of effects simultaneously by the processing that utilizes RIE, that is: free radical that utilize to produce or ion increase plastic basis material the surface amount of functional groups chemical result and make the physical effect of its noncrystallineization by the ion etching substrate surface.Be squeezed in by thermoplastic resin like this and implemented to utilize on the pretreated base material of RIE, can make the adaptation of base material and thermoplastic resin firm fusion.Also can utilize the preliminary treatment of this RIE to the two sides of base material as required.
Treatment conditions by the RIE of expression such as process velocity, energy level can be according to suitable settings such as base material kind, purposes, electric discharge device characteristics.But, in the present invention, preferred utilize automatic bias value with plasma to be set in more than the 200V and below the 2000V, will be set in 100Wm with the Ed value that Ed=(plasma density) * (processing time) defines
-2Above and the 10000W of sec.m
-2The following low temperature plasma of sec is handled.Even the value that automatic bias value and Ed value are lower slightly than above-mentioned lower limit is also found adaptation to a certain degree, but compares with the product of being untreated that dominance is low.If automatic bias value and Ed value are the values higher than above-mentioned higher limit, then make the substrate surface deterioration because of too implementing strong processing, become the reason that adaptation descends.Gas of using about plasma and mixing ratio thereof etc., owing to, make flow different with the actual effect deal by importing deal according to pump performance or installation site etc., therefore can be, equipment energy characteristic is suitable sets according to purposes, base material.
About extruded lamination at the thermoplastic resin of having implemented on the pretreated base material, so long as thermoplastic resin that can be stacked does not just limit especially.For example can list: ldpe resin, high-density polyethylene resin, medium density polyethylene resin, ethylene-vinyl acetate copolymer, ethene-alpha-olefin copolymer, ethene-α, resins such as beta-unsaturated carboxylic acid copolymer and carboxylate thereof or ionomer thing, acrylic resin, propylene-alpha-olefin copolymers, anhydride modified polyolefin and epoxide modified polyolefin.They can use monomer, also can use and mix the mixture that forms more than 2 kinds.
Can be by on base material, carrying out above-mentioned thermoplastic resin extruded lamination stacked.Extrusion temperature during for lamination does not limit especially, can determine according to the resin that uses is suitable.The thickness of thermoplastic resin is preferably 5～200 μ m, more preferably 5～100 μ m.If the thinner thickness of thermoplastic resin is lower than 5 μ m, then be difficult to push equably, the thickness of layer becomes inhomogeneous.If the thickness of thermoplastic resin is thicker, greater than 200 μ m, for example when thermoplastic resin was sealed, heat seal strength died down etc., and the possibility of decline is arranged as the rerum natura of duplexer.
Also can in the scope that does not hinder with the adaptation of base material, in thermoplastic resin, add additives such as antiseize paste, antistatic agent, antifoggant, ultra-violet absorber, antioxidant, and inorganic fillers such as silica, titanium oxide etc.
Also can be with the thermoplastic resin of mode lamination more than 2 kinds of co-extrusion pressure.In addition, also can be on thermoplastic resin stacked other plastic sheeting.
Fig. 1 is the cutaway view of the duplexer 10 of one embodiment of the present invention.As shown in Figure 1, base material 11 is formed with on a face at least and has implemented the pretreated processing region 11a of RIE.In the enforcement of this base material 11 on the processing region 11a of pretreated of RIE extruded layer be pressed with thermoplastic resin 12.
If duplexer of the present invention while making water saturates implement to peel off between pretreated base material 11 of RIE and the thermoplastic resin 12, is then produced cohesion destruction by 11 of base materials in processing region 11a place and peels off.It is because base material 11 is good with the driving fit of thermoplastic resin 12 that generation is so peeled off, and can obtain strong lamination strength between base material and thermoplastic resin.On the other hand,, then peel off, can only obtain very weak lamination strength at the interlayer of base material 11 and thermoplastic resin 12 if base material 11 is not implemented the RIE preliminary treatment.
Base material about duplexer of the present invention, by adopting the mensuration (XPS mensuration) of X ray photoelectricity optical spectroscopy, can analyze by measured matter be the surface of base material to the kind of the kind of the atom in the dark zone of several nm and concentration, the atom that combines with this atom, their bonding state, can obtain elemental ratio, functional group's ratio etc.
Fig. 2 is when using PET (PET) film as the plastic film substrate of duplexer of the present invention, an example of the peak compartment analysis wave spectrum of the Cls waveform that obtains from the X ray photoelectricity spectral photometry (x-ray source is that MgK alpha ray, power are 100W) on the surface of PET film.The Cls waveform can be separated into C-C key (1), C-O key (2) and COO key (3).The value of bond energy separately is 285.0eV (C-C key), 286.6～286.7eV (C-O key) and 288.9～289.0eV (COO key).
In the present invention, when the surface of the pretreated PET film that carried out utilizing RIE was measured, be preferably formed following surface state: elemental ratio (O/C) was below 0.49, is preferably 0.20～0.49; And/or functional group's ratio (COO/C-C) of obtaining from the separation of Cls waveform is below 0.33, is preferably 0.05～0.33; And/or the half-breadth value of C-C key is 1.340～1.560eV.If the PET that uses as base material forms such surface state, then when carrying out the extruded lamination of thermoplastic resin, can realize extraordinary adaptation.If the numerical value of presentation surface state exceeds above-mentioned scope, then can not fully obtain utilizing above-mentioned RIE to handle and the chemical result and the physical effect that bring, poor with the adaptation of thermoplastic resin, thereby be difficult to use.
Fig. 3 is when using polyamide (Ny) film as the plastic film substrate of duplexer of the present invention, an example of the peak compartment analysis wave spectrum of the Cls waveform that obtains from the X ray photoelectricity spectral photometry (x-ray source is that MgK alpha ray, power are 100W) on the surface of Ny film.The Cls waveform can be separated into C-C key (1), C-N key (4) and NHC=O key (5).The value of bond energy separately is 285.0eV (C-C key), 286.6～286.7eV (C-O key) and 288.0eV (NHC=O key).
In the present invention, when the surface of pretreated polyamide (Ny) film that carried out utilizing RIE was measured, being preferably formed elemental ratio (O/ (C+N)) was more than 0.2 and/or the half-breadth value of C-C key is the surface state of 1.380～1.560eV.If the numerical value of presentation surface state exceeds above-mentioned scope, then be difficult to use because of adaptation difference with thermoplastic resin.
Fig. 4 is when using polypropylene (PP) film as the plastic film substrate of duplexer of the present invention, an example of the peak compartment analysis wave spectrum of the Cls waveform that obtains from the X ray photoelectricity spectral photometry (x-ray source is that MgK alpha ray, power are 100W) on the surface of PP film.The Cls waveform has only C-C key (1).The value of its bond energy is 285.0eV.
In the present invention, when the surface of pretreated polypropylene (PP) film that carried out utilizing RIE is measured, be preferably formed elemental ratio (O/C) and be 0.03～0.135 and/or the half-breadth value of C-C key be the surface state of 1.320～1.600eV.If the numerical value of presentation surface state exceeds above-mentioned scope, then be difficult to use because of adaptation difference with thermoplastic resin.
Duplexer of the present invention can be made as outermost layer or middle and use as various packaging material.4 examples of the formation of packaging material below are shown.Particularly, as following (II) or (III), in that duplexer of the present invention is used is under the situation of intermediate layer and then the thermoplastic resin that extruded lamination is set in the both sides of this duplexer, because as long as form described treated side in the one side of base material, that cementation coating (AC) layer is set is just passable on another side, even therefore special equipment is not set also can implement lamination, can simplify working process thereby have, reduce the cost of packaging material.
(I) base material (RIE treated side)/thermoplastic resin/straight chain shape low density polyethylene (LDPE) (LLDPE) layer
(II) PET/AC/ thermoplastic resin/(RIE treated side) base material/AC/ thermoplastic resin/straight chain shape low density polyethylene (LDPE) (LLDPE) layer
(III) OPP/AC/ thermoplastic resin/(RIE treated side) base material/AC/ thermoplastic resin/low density polypropylene (CPP) layer
(IV) PET/ printing ink/AC/ maleic anhydride inoculated polypropylene/(treated side) PET/ evaporation layer/gas barrier property is by rete (treated side)/maleic anhydride inoculated polypropylene/CPP
Duplexer as other embodiments of the present invention, also can be that base material has the substrate body that is formed by plastic sheeting and is located at its at least one lip-deep and gas barrier property of containing water soluble polymer by rete, by described gas barrier property is implemented the preliminary treatment of plasma treatment by the surface of rete, carrying out the duplexer that stacked above-mentioned thermoplastic resin forms on pretreated.
About this duplexer, for example, preferably in the gas barrier property that adopts X ray photoelectricity optical spectroscopy (XPS) to measure to contain water soluble polymer during by rete surperficial, the functional group of the carbon-carbon bond of water soluble polymer (C-C) and carbon-hydroxyl bond (C-OH) is more than 0.25 and below 0.87 than D (C-OH/C-C).
The inorganic oxide evaporation layer of thick 5～100nm also can be set between substrate body and gas barrier property are by rete in addition.
The cutaway view of the duplexer 20 of other embodiments of the present invention has been shown among Fig. 5.As shown in Figure 5, at least one surface of substrate body 21, form inorganic oxide evaporation layer 22 and gas barrier property successively, constitute base material (gas-barrier films) by rete 23.Form in gas barrier property and to have implemented pretreated processing region 23a by plasma treatment or Corona discharge Treatment by the surface of rete 23.Be laminated with thermoplastic resin 24 in gas barrier property on by the processing region 23a of rete 23.Above-mentioned each layer also can be formed on the two sides of substrate body 21.In addition, above-mentioned each layer also can form multilayer.
About substrate body 21, can directly adopt explanation to the base material that forms by the plastic sheeting of having stated.
In order to make substrate body 21 have gas barrier property, also can form inorganic oxide evaporation layer 22 as required.As inorganic oxide evaporation layer, so long as form by the evaporation layer of aluminium oxide, silica, tin oxide, magnesia or their inorganic oxides such as mixture, have the transparency and oxygen, water vapour etc. had a layer of gas barrier property just passable.If consider anti-pasteurization, wherein more preferably adopt aluminium oxide and silica especially.But evaporation layer of the present invention is not limited to above-mentioned inorganic oxide, just can use so long as be fit to the material of above-mentioned condition.
About the thickness of inorganic oxide evaporation layer 22, because of the kind and the formation of the inorganic oxide that adopted, its optimum value is different, but generally is preferably in the scope of 5～300nm, can suit to select in this scope.If thickness is lower than 5nm, then can not obtain uniform film or thickness deficiency sometimes, can not give full play to function sometimes as the choke material.If thickness surpasses 300nm, have then that film is had is flexible, the possibility that film is cracked because of external cause such as bending, stretching after the film forming.More preferably the thickness of inorganic oxide evaporation layer 22 is the scope of 10～150nm.
The method that forms inorganic oxide evaporation layer 22 on plastic basis material main body 21 has multiple.For example, can adopt common vacuum vapour deposition.In addition, also can adopt other film formation method is sputtering method, ion plating method, plasma vapor phase deposition (CVD) etc.But, consider productivity, present, vacuum vapour deposition is best.As the heater means of vacuum vapour deposition, preferably adopt any mode in electron beam mode of heating, resistance heated mode, the induction heating mode, if but consider the selectivity wide ranges of evaporating materials, more preferably adopt the electron beam mode of heating.In addition, for the adaptation that improves evaporation layer and base material and the compactness of evaporation layer, also can adopt plasma auxiliary law or ion beam-assisted method to carry out evaporation.In addition, in order to improve the transparency of evaporation layer, also can adopt the evaporation reaction of all gases such as when evaporation, being blown into oxygen etc.
In order to strengthen the driving fit of substrate body 21 and inorganic oxide evaporation layer 22, also can carry out surface treatments such as plasma treatment, sided corona treatment, also can between substrate body 21 and inorganic oxide evaporation layer 22, the cementation coating layer be set the surface of substrate body 21.By these layers are set, can make duplexer as gas-barrier films have the anti-heating property of distillation being handled, boiling processing etc., can enlarge the scope of application of film.
Can go up in substrate body 21 (or inorganic oxide evaporation layer 22) and form gas barrier property by rete 23.As described gas barrier property by rete 23, so long as contain just like macromolecule resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyester or acrylic resins or to contain the formation of the such macromolecule resin of the macromolecule resin of other compound just passable.Described gas barrier property generally is to form by these macromolecule resins being dissolved in the solvent, being coated with then by rete.
Specifically, preferred gas barrier property is contained water soluble polymer by rete 23, as water soluble polymer, can list: polyvinyl alcohol, polyvinylpyrrolidone, starch, methylcellulose, carboxymethyl cellulose, mosanom etc.Especially under the situation that adopts polyvinyl alcohol (being designated hereinafter simply as PVA), can obtain best gas barrier property, be preferred therefore.
Gas barrier property also can be contained inorganic compound by rete 23.As this inorganic compound, can list the material that obtains by the metal alkoxide of hydrolysis more than a kind.Metal alkoxide is with formula M (OR)
n(metal, R:CH such as M:Si, Ti, Al, Zr
3, C
2H
5In alkyl) expression compound.Tetraethoxysilane [Si (OC wherein
2H
5)
4], and aluminium isopropoxide [Al (O-iso-C
3H
7)
3] more stable in water solvent after the hydrolysis, be preferred therefore.
About gas barrier property by rete 23, specifically, can by modulation water soluble polymer is dissolved in the solution that forms in water or the water/alcohol mixed solvent or in above-mentioned solution direct mixed metal alkoxide or make metal alkoxide hydrolysis etc. handle the solution that mix the back in advance, then this solution is coated in substrate body 21 (or inorganic oxide evaporation layer 22) upward and carry out heat drying and form.In above-mentioned solution, also can in the scope that does not diminish gas barrier property, add known additives such as isocyanate compound, silane coupler, dispersant, stabilizing agent, viscosity modifier, colouring agent as required.
When adopting PVA as water soluble polymer, the ratio of PVA by weight the ratio meter to be preferably the 20wt% of the solid constituent total amount in the mixed solution above and below the 50wt%, the more preferably scope that 25wt% is above and 45wt% is following.If PVA is lower than 20wt%, then be difficult to form gas barrier property by rete because of the flexibility of film is impaired.If therefore PVA greater than 50wt%, can not be not preferred to giving sufficient gas barrier property as the duplexer of gas-barrier films then.
If add silane coupler in by the mixed solution of rete 23 forming gas barrier property, then can improve gas barrier property by the resistance to water of rete 23, to give better anti-heating property as the duplexer of gas-barrier films, can prevent the deterioration of the gas barrier property under hot and humid better.As silane coupler, have the silane coupler that is selected from the organo-functional group among vinyl, epoxy radicals, methacryloxy, urea groups, the NCO if adopt, then, functional group further improves resistance to water because of having hydrophobicity.
Preferably convert by the weight ratio after the hydrolysis, silane coupler is below the 12wt% of the solid constituent total amount in the mixed solution.In addition, preferably more than the 20wt% that adds up to the solid constituent total amount of PVA and silane coupler and below the 50wt%.If the amount of silane coupler is many, then can not obtain as gas barrier property by the function of rete, be not preferred therefore.
Be provided with under the situation of thermoplastic resin in evaporation layer side,, form processing region 23a from the teeth outwards by carrying out plasma treatment to forming the surface of gas barrier property after by rete 23.By carrying out so surface treatment, can be imported new functional group by the processing region 23a on the surface of rete 23 to gas barrier property, thereby can improve the driving fit with thermoplastic resin.As plasma treatment, can list atmospheric plasma treatment, Low Temperature Plasma Treating is multiple modes such as reactive ion etching processing, ionic bombardment processing, but, processing method is not just limited especially so long as can form the processing of surface state shown below.In addition, various treatment conditions can suit to set according to the method for dealing with separately.
Fig. 6 is when adopting PVA as water soluble polymer, an example of the peak compartment analysis wave spectrum of the Cls waveform that obtains from gas barrier property is measured by the X ray photoelectricity optical spectroscopy (XPS) on the surface of rete.About condition determination, adopt the MgK alpha ray as x-ray source, be 100W with power setting.The Cls waveform can be separated into C-C key peak (6) and C-OH key peak (7).The value of bond energy separately be near (C-C key) 285.0eV, and 286.5eV near (C-OH key).Can obtain the ratio D of functional group (C-OH/C-C) by the peak intensity of C-C key and C-OH key.In the duplexer as gas-barrier films of the present invention, preferred gas barrier property is more than 0.25 and below 0.87 by functional group ratio D (C-OH/C-C) of the C-C key of the water soluble polymer of rete and C-OH key.If the ratio D of functional group is lower than 0.25, then too carry out because of surface treatment, adaptation is descended, and damage as gas barrier property by the function of rete.If the ratio D of functional group is greater than 0.87, then because of poor processing effect, can not import functional group, and can not obtain sufficient dhering strength.
In addition, about gas barrier property by rete 23, if pretreated functional group compares D than the functional group before D and the preliminary treatment
0Ratio D/D
0Be more than 0.30 and below 0.92, then gas barrier property is more firm with the driving fit of thermoplastic resin by rete 23.If D/D
0Exceed above-mentioned scope, because of can not the improve effect of adaptation of reason same as described above.
If utilize the extruded layer platen press the gas barrier property with above-mentioned surface by rete 23 on stacked thermoplastic resin 24, then can improve gas barrier property by rete 23 adaptation with thermoplastic resin 24.For thermoplastic resin, as long as can stackedly just not limit especially, as mentioned above, for example can list: ldpe resin, high-density polyethylene resin, medium density polyethylene resin, ethylene-vinyl acetate copolymer, ethene-alpha-olefin copolymer, ethene-α, resins such as beta-unsaturated carboxylic acid copolymer and carboxylate thereof or ionomer thing, acrylic resin, propylene-alpha-olefin copolymers, anhydride modified polyolefin and epoxide modified polyolefin.They can use monomer, also can use and mix the mixture that forms more than 2 kinds.
The extrusion temperature during about lamination and the thickness of thermoplastic resin are all as mentioned above.Additive also as mentioned above.In addition, also can use the thermoplastic resin of co-extrusion pressure mode lamination more than 2 kinds, also other plastic sheeting can be layered on the thermoplastic resin.
(embodiment)
Below, the embodiment to duplexer of the present invention describes particularly.Have, the present invention is not limited to these embodiment again.
(example 1)
On the face that is untreated of PET (PET) film of thick 12 μ m, implement to have utilized the preliminary treatment of reactive ion etching (RIE) by following condition.As electrode, adopting frequency is the high frequency electric source of 13.56MHz.
[plasma process conditions]
Add electric power: 120W
Processing time: 0.1sec
Handle gas: argon gas
Processing unit pressure: 2.0Pa.
The automatic bias value is that 450V, Ed value are 210Wm
-2Sec.On this treated side, under 320 ℃ extrusion temperature,,, obtain duplexer by the thick system film of 15 μ m by extruded lamination low density polyethylene (LDPE) (LDPE).And then thereon as the interlayer base material stacked thick straight chain shape low density polyethylene (LDPE) (LLDPE) films of 60 μ m.
(example 2)
Processing time except with the RIE preliminary treatment in the above-mentioned example 1 time is set at the 0.5sec, uses the method identical with example 1 to make duplexer.The automatic bias value is 450V, and the Ed value is 430Wm
-2Sec.
(example 3)
The electric power that adds except with the RIE preliminary treatment in the above-mentioned example 1 time is set at the 500W, uses the method identical with example 1 to make duplexer.The automatic bias value is 900V, and the Ed value is 900Wm
-2Sec.
(example 4)
Except in above-mentioned example 1, outside extruded lamination polypropylene (PP) resin under 290 ℃ the extrusion temperature, use the method identical to make duplexer with example 1.
(example 5)
Except in above-mentioned example 1, the PET film not being carried out the preliminary treatment, use the method identical to make duplexer with example 1.
(example 6)
RIE preliminary treatment in substituting above-mentioned the example 1 and PET film is carried out the sided corona treatment uses the method identical with example 1 to make duplexer.
(example 7)
On the face that is untreated of polyamide (Ny) film of thick 15 μ m, implement to have utilized the preliminary treatment of reactive ion etching (RIE) by following condition.As electrode, adopting frequency is the high frequency electric source of 13.56MHz.
[plasma process conditions]
Add electric power: 120W
Processing time: 0.1sec
Handle gas: argon gas
Processing unit pressure: 2.0Pa.
The automatic bias value is that 450V, Ed value are 210Wm
-2Sec.On this treated side, under 320 ℃ extrusion temperature,,, obtain duplexer by the thick system film of 15 μ m by extruded lamination low density polyethylene (LDPE) (LDPE).And then thereon as the interlayer base material stacked thick straight chain shape low density polyethylene (LDPE) (LLDPE) films of 60 μ m.
(example 8)
Processing time except with the RIE preliminary treatment in the above-mentioned example 7 time is set at the 0.5sec, uses the method identical with example 7 to make duplexer.The automatic bias value is 450V, and the Ed value is 430Wm
-2Sec.
(example 9)
Except in above-mentioned example 7, outside extruded lamination polypropylene (PP) resin under 290 ℃ the extrusion temperature, use the method identical to make duplexer with example 7.
(example 10)
Except in above-mentioned example 7, the Ny film not being carried out the preliminary treatment, use the method identical to make duplexer with example 7.
(example 11)
RIE preliminary treatment in substituting above-mentioned the example 7 and Ny film is carried out the sided corona treatment uses the method identical with example 7 to make duplexer.
(example 12)
On the face that is untreated of polypropylene (PP) film of thick 20 μ m, implement to have utilized the preliminary treatment of reactive ion etching (RIE) by following condition.As electrode, adopting frequency is the high frequency electric source of 13.56MHz.
[plasma process conditions]
Add electric power: 200W
Processing time: 0.2sec
Handle gas: argon gas
Processing unit pressure: 2.0Pa.
The automatic bias value is that 550V, Ed value are 700Wm
-2Sec.On this treated side, under 320 ℃ extrusion temperature,,, obtain duplexer by the thick system film of 15 μ m by extruded lamination low density polyethylene (LDPE) (LDPE).And then thereon as the interlayer base material stacked thick straight chain shape low density polyethylene (LDPE) (LLDPE) films of 60 μ m.
(example 13)
Processing time except with the RIE preliminary treatment in the above-mentioned example 12 time is set at the 0.5sec, uses the method identical with example 12 to make duplexer.The automatic bias value is 550V, and the Ed value is 1800Wm
- 2Sec.
(example 14)
Except in above-mentioned example 12, the PP film not being carried out the preliminary treatment, use the method identical to make duplexer with example 12.
(example 15)
RIE preliminary treatment in substituting above-mentioned the example 12 and PP film is carried out the sided corona treatment uses the method identical with example 12 to make duplexer.
[surface state analytical method]
In example 1～15, before extruded lamination thermoplastic resin on the base material, carried out utilizing the surface analysis of the preliminary treatment face of RIE by the spectral photometry of X ray photoelectricity.Used X ray photoelectricity light-dividing device is the JPS-90MXV that Jeol Ltd. makes in the mensuration, as the MgK alpha ray (1253.6eV) of x-ray source employing polyenergeticization, presses power 100W (10kV-10mA) and measures.It is 2.28 in Ols that quantitative analysis is adopted, in Cls, be 1.00, be that 1.61 the relative sensitivity factor is calculated in Nls, obtain O than (O/C or O/ (C+N)) as elemental ratio.Use the mixed function of Gaussian function and this function of long-range navigation in the waveform compartment analysis of Cls waveform, the C-C key peak that charged correction has carried out being derived from phenyl ring is made as the correction of 285.0eV.
[lamination strength]
In the duplexer of example 1～15, adopt the TENSILON universal testing machine RTC-1250 of ORIENTEC company to measure lamination strength (according to JIS Z1707) between the thermoplastic resin of film substrate and lamination.When this is measured, while use water-wet determination part position to peel off.Peel angle is 180 degree.The results are shown in Table 1.In addition, confirmed that by the spectral photometry of X ray photoelectricity the release surface of the sample after this lamination strength is measured is base material or interlayer.
Table 1
| Automatic bias value (V) | Ed value (Wm -2·sec) | Elemental ratio | COO/ C-C | C-C half-breadth value (eV) | Wetting lamination strength (N/15mm) | Release surface * | |
| Example 1 | 450 | 210 | 0.46 | 0.32 | 1.38 | 3.0 | Base material |
| Example 2 | 450 | 430 | 0.47 | 0.30 | 1.49 | 3.5 | Base material |
| Example 3 | 900 | 900 | 0.46 | 0.24 | 1.56 | 3.8 | Base material |
| Example 4 | 450 | 210 | 0.46 | 0.32 | 1.38 | 4.2 | Base material |
| Example 5 | 450 | 0 | 0.51 | 0.34 | 1.25 | 0.5 | Interlayer |
| Example 6 | 450 | 0 | 0.56 | 0.38 | 1.30 | 0.7 | Interlayer |
| Example 7 | 450 | 210 | 0.22 | — | 1.40 | 2.5 | Base material |
| Example 8 | 450 | 430 | 0.23 | — | 1.43 | 3.2 | Base material |
| Example 9 | 450 | 210 | 0.22 | — | 1.40 | 3.8 | Base material |
| Example 10 | 450 | 0 | 0.16 | — | 1.35 | 0.3 | Interlayer |
| Example 11 | 450 | 0 | 0.18 | — | 1.35 | 0.4 | Interlayer |
| Example 12 | 550 | 700 | 0.11 | — | 1.55 | 5.5 | Base material |
| Example 13 | 550 | 1800 | 0.05 | — | 1.52 | 6.0 | Base material |
| Example 14 | 550 | 0 | 0.005 | — | 1.10 | 0.1 | Interlayer |
| Example 15 | 550 | 0 | 0.14 | — | 1.30 | 0.3 | Interlayer |
*Release surface base material: peel off of generation by the cohesion destruction of base material
Interlayer: peeling off of the interlayer of base material/thermoplastic resin
As can be known, example 1～4 is compared with the example 5,6 that is used for comparison, and the dhering strength between base material/thermoplastic resin is good.Equally, as can be known, example 7～9 is compared with the example 10,11 that is used for comparison, and the dhering strength between base material/thermoplastic resin is good, and example 12,13 is compared with the example 14,15 that is used for comparison, and the dhering strength between base material/thermoplastic resin is good.Like this, according to the present invention, even do not carry out the coating of the cementation smears on base material or when extruding to the ozone treatment of thermoplastic resin etc., the good duplexer of adaptation of plastic basis material and thermoplastic resin also can be provided.
(example 21)
On a face of PET (PET) film of thick 12 μ m, utilize the vacuum deposition apparatus evaporation metal aluminium that adopts the electron beam mode of heating, to wherein importing oxygen, form the thick aluminium oxide of 15nm.The solution that on this aluminium oxide, utilizes A liquid that gravure coating method coating will show down and B liquid to mix by match ratio (wt%) 60/40, dry then, form the thick gas barrier property of 0.3 μ m by rete, made gas-barrier films.
A liquid: in the tetraethoxysilane of 10.4g, add the hydrochloric acid (0.1N) of 89.6g, stirred 30 minutes and the solid constituent that is hydrolyzed is that 3wt% (presses SiO
2Conversion) hydrating solution;
B liquid: the 3wt% water/aqueous isopropanol of polyvinyl alcohol (water: the weight ratio of isopropyl alcohol is 90: 10).
Then, adding electric power outside is 120W, plasma density E=400Wsec/m
2Condition under gas barrier property is implemented to utilize the plasma treatment of reactive ion etching (RIE) by rete.Adopt argon/oxygen gas mixture as handling gas, processing unit pressure is set at 2.0Pa, the automatic bias value is 450V.
Under 320 ℃ extrusion temperature, carry out extruded lamination in this gas barrier property on by rete, form the thick low density polyethylene (LDPE) (LDPE) of 15 μ m, obtain duplexer.Then, thereon as thick straight chain shape low density polyethylene (LDPE) (LLDPE) film of the stacked 60 μ m of interlayer base material.
(example 22)
In above-mentioned example 21, adding electric power outside is 1200W, plasma density E=1700Wsec/m
2Condition under gas barrier property is implemented to utilize the plasma treatment of ionic bombardment by rete.Adopt argon gas as handling gas, processing unit pressure is set at 0.4Pa.In addition, use the method identical to make duplexer with example 21.
(example 23)
With example 21 similarly, on a face of PET (PET) film of thick 12 μ m, utilize the vacuum deposition apparatus evaporation metal aluminium that adopts the electron beam mode of heating, to wherein importing oxygen, form the thick aluminium oxide of 15nm.Utilizing gravure coating method coating to mix the solution that A liquid, B liquid and the C liquid shown in the note down forms by match ratio (wt%) 70/25/5 on this aluminium oxide, drying forms the thick gas barrier property of 0.3 μ m by rete then, makes gas-barrier films.
A liquid: in the tetraethoxysilane of 10.4g, add the hydrochloric acid (0.1N) of 89.6g, stirred 30 minutes and the solid constituent that is hydrolyzed is that 3wt% (presses SiO
2Conversion) hydrating solution;
B liquid: the 3wt% water/aqueous isopropanol of polyvinyl alcohol (water: the weight ratio of isopropyl alcohol is 90: 10);
C liquid: slowly add hydrochloric acid (1N) in β-(3, the 4-epoxycyclohexyl) trimethoxy silane and isopropyl alcohol (IPA solution), after stirring made its hydrolysis in 30 minutes, water/IPA=1/1 solution was hydrolyzed, and being adjusted to solid constituent is that 5wt% (presses R
2Si (OH)
3Conversion) hydrating solution.
Then, adding electric power outside is 1200W, plasma density E=1700Wsec/m
2Condition under gas barrier property is implemented to utilize the plasma treatment of ionic bombardment by rete.Adopt argon gas as handling gas, processing unit pressure is set at 0.4Pa.
This gas barrier property by rete on, under 320 ℃ extrusion temperature, carry out extruded lamination, form the thick low density polyethylene (LDPE) (LDPE) of 15 μ m, obtain duplexer.And then, thereon as thick straight chain shape low density polyethylene (LDPE) (LLDPE) film of the stacked 60 μ m of interlayer base material.
(example 24)
In above-mentioned example 23, adding electric power outside is 350W, plasma density E=600Wsec/m
2Condition under gas barrier property is implemented to utilize the plasma treatment of reactive ion etching (RIE) by rete.Adopt oxygen as handling gas, processing unit pressure is set at 2.0Pa, the automatic bias value is 650V.In addition, use the method identical to make duplexer with example 23.
(example 25)
Except in above-mentioned example 21, gas barrier property not being implemented the plasma treatment by rete, use the method identical to make duplexer with example 21.
(example 26)
In above-mentioned example 21, adding electric power outside is 1000W, discharge capacity 500Wmin/m
2Condition under gas barrier property has been carried out Corona discharge Treatment by rete.In addition, use the method identical to make duplexer with example 21.
(example 27)
Except in above-mentioned example 23, gas barrier property not being undertaken the plasma treatment by rete, use the method identical to make duplexer with example 23.
(example 28)
Substituting the plasma treatment in the above-mentioned example 23, is 10W, plasma density E=15Wsec/m and add electric power outside
2Condition under gas barrier property is implemented to utilize the plasma treatment of reactive ion etching (RIE) by rete.Adopt argon/oxygen gas mixture as handling gas, processing unit pressure is set at 2.0Pa, the automatic bias value is 100V.In addition, use the method identical to make duplexer with example 23.
(example 29)
Substituting the plasma treatment in the above-mentioned example 28, is 250W, plasma density E=1300Wsec/m and add electric power outside
2Condition under gas barrier property is implemented to utilize the plasma treatment of reactive ion etching (RIE) by rete.Adopt argon/oxygen gas mixture as handling gas, processing unit pressure is set at 2.0Pa, the automatic bias value is 650V.In addition, use the method identical to make duplexer with example 28.
[surface state analytical method]
In example 21～29, before and after the preliminary treatment that gas barrier property is implemented by rete, carried out gas barrier property by the surface analysis of rete by the spectral photometry of X ray photoelectricity.Used X ray photoelectricity light-dividing device is the JPS-90MXV that Jeol Ltd. makes in the mensuration, as the MgK alpha ray (1253.6eV) of x-ray source employing polyenergeticization, presses power 100W (10kV-10mA) and measures.Use the mixed function of Gaussian function and this function of long-range navigation in the waveform compartment analysis of Cls waveform, charged correction has carried out C-C key peak is set at the correction of 285.0eV.Obtained the peak intensity of C-C key and C-OH key by the waveform compartment analysis.Obtain the preceding functional group of preliminary treatment and compared D
0(C-OH/C-C) and pretreated functional group than D (C-OH/C-C).In addition, obtained D/D
0
[lamination strength]
In the duplexer of example 21～29, according to the determination of test method of regulation among the JIS K6854-3:1999 of Japanese Industrial Standards " 3 ones of binding agents-peel adhesion strength test method-Di: the T type is peeled off " lamination strength.Adopted in the mensuration that ORIENTEC company makes TENSILON universal testing machine RTC-1250.
Table 2
| D(C-OH/C-C) | D/D 0 | Lamination strength (N/15mm) | Driving fit is judged | |
| Example 21 | 0.73 | 0.75 | 1.5 | ○ |
| Example 22 | 0.55 | 0.58 | 2.0 | ○ |
| Example 23 | 0.45 | 0.50 | 1.0 | ○ |
| Example 24 | 0.26 | 0.32 | 1.1 | ○ |
| Example 25 | 0.98 | 1.0 | 0.05 | × |
| Example 26 | 0.23 | 0.26 | 0.2 | △ |
| Example 27 | 0.89 | 1.0 | 0.02 | × |
| Example 28 | 0.88 | 0.94 | 0.3 | △ |
| Example 29 | 0.23 | 0.28 | 0.05 | × |
As can be known, example 21～24 is compared with the example 25～29 that is used for comparison, and gas barrier property is good by the dhering strength between rete/thermoplastic resin.Like this, according to the present invention, even do not carry out gas barrier property by the coating of the cementation smears on the rete or when extruding to the ozone treatment of thermoplastic resin etc., also can provide gas barrier property by the good duplexer of the adaptation of rete and thermoplastic resin.
(example 30)
Gas barrier property to the gas-barrier films of example 23 is similarly implemented plasma treatment by rete, and then the PET face of base material has also been carried out the plasma treatment identical with example 1.
Having prepared with carbamate in addition is the polyethylene terephthalate thin film that the printing ink of 2 liquid-solidization has been implemented printing.Film by extruded lamination maleic anhydride inoculated polypropylene (MAH-graftedPP), has been made by thick 20 μ m in the cementation smears of coating carbamate 2 liquid-solidization on the printing surface of this polyethylene terephthalate thin film.Employing has been implemented the gas-barrier films of above-mentioned plasma treatment as the interlayer base material to the two sides, passing through the above-mentioned maleic anhydride inoculated polypropylene of directly fitting on the PET face of plasma treatment, and then, not gas barrier property by face on coating cementation smears and directly make film by thick 20 μ m by the extruded lamination maleic anhydride inoculated polypropylene.On the maleic anhydride inoculated polypropylene face, as the 2nd interlayer base material, the polypropylene film that does not stretch that extruding is prepared in addition comes stacked.
PET/ printing ink/AC/ maleic anhydride inoculated polypropylene/(treated side) PET/ evaporation layer/gas barrier property is by rete (treated side)/maleic anhydride inoculated polypropylene/CPP
Adopt two these duplexers, CPP is faced put and seal perimeter portion, make pouch, fill water therein, distill sterilization processing.Distillation condition is the steam-type distillation, carries out under 120 ℃ 120 minutes.
Lamination strength is as follows:
Between maleic anhydride inoculated polypropylene/(treated side) PET,
Before the distillation: 2.4N/15mm, distillation back: 1.5N/15mm;
Between gas barrier property is by rete (treated side)/maleic anhydride inoculated polypropylene,
Before the distillation: 1.0N/15mm, distillation back: 4.1N/15mm.
This mensuration utilizes the disbonded test of T type to carry out under drying regime.
Oxygen permeability is for before distilling: 0.38cc/m
2My god, distillation back: 0.45cc/m
2My god.This mensuration is analyzer (the instrument title: OXTRAN) carry out that adopts MOCON company to make under 30 ℃, the condition of 70%RH.
According to the present invention, by adopting pretreated plastic basis material, even direct extruded lamination thermoplastic resin on base material also can provide the good duplexer of driving fit of base material and thermoplastic resin through plasma treatment.In addition, because without limits to thermoplastic resin, therefore can use common thermoplastic resin, when carrying out extruded lamination, need on base material, not be coated with the cementation smears or thermoplastic resin is carried out ozone treatment etc., thereby can obtain to adapt to the outstanding advantage of various packaging material.
Claims (20)
1, a kind of duplexer is characterized in that: preliminary treatment of plasma treatment is implemented at least one surface of the base material that formed by plastic sheeting, through direct stacked thermoplastic resin on the pretreated treated side.
2, duplexer according to claim 1 is characterized in that: described base material is formed by the plastic sheeting that is provided with the evaporation layer at single face.
3, duplexer according to claim 1 is characterized in that: gas barrier property further is set by rete on the surface of described base material.
4, duplexer according to claim 1 is characterized in that: while when described base material of water saturates and thermoplastic resin were peeled off, the treated side of described base material was peeled off by destroying cohesion.
5, duplexer according to claim 1, it is characterized in that: described plasma treatment is to utilize the processing of reactive ion etching (RIE), be utilize be set in its automatic bias value more than the 200V and below the 2000V, will be set in 100Wm with the Ed value that Ed=(plasma density) * (processing time) defines
-2Above and the 10000Wm of sec
-2The processing of the low temperature plasma that sec is following.
6, duplexer according to claim 1, it is characterized in that: described thermoplastic resin contains and is selected from ldpe resin, high-density polyethylene resin, medium density polyethylene resin, ethylene-vinyl acetate copolymer, ethene-alpha-olefin copolymer, ethene-α, the resin more than a kind or 2 kinds among beta-unsaturated carboxylic acid copolymer and carboxylate thereof or ionomer thing, acrylic resin, propylene-alpha-olefin copolymers, anhydride modified polyolefin and the epoxide modified polyolefin.
7, duplexer according to claim 1, it is characterized in that: described base material is formed by polyethylene terephthalate thin film, surface after the preliminary treatment that this polyethylene terephthalate thin film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and elemental ratio O/C is below 0.49.
8, duplexer according to claim 1, it is characterized in that: described base material is formed by polyethylene terephthalate thin film, surface after the preliminary treatment that this polyethylene terephthalate thin film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, is below 0.33 from the ratio COO/C-C of functional group that the analysis of Cls waveform is obtained.
9, duplexer according to claim 1, it is characterized in that: described base material is formed by polyethylene terephthalate thin film, surface after the preliminary treatment that this polyethylene terephthalate thin film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and the half-breadth value of the C-C key of obtaining from the analysis of Cls waveform is 1.340～1.560eV.
10, duplexer according to claim 1, it is characterized in that: described base material is formed by polyamide film, surface after the preliminary treatment that this polyamide film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and elemental ratio O/ (C+N) is more than 0.2.
11, duplexer according to claim 1, it is characterized in that: described base material is formed by polyamide film, surface after the preliminary treatment that this polyamide film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and the half-breadth value of the C-C key of obtaining from the analysis of Cls waveform is 1.380～1.560eV.
12, duplexer according to claim 1, it is characterized in that: described base material is formed by polypropylene film, surface after the preliminary treatment that this polypropylene film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and elemental ratio O/C is 0.03～0.135.
13, duplexer according to claim 1, it is characterized in that: described base material is formed by polypropylene film, surface after the preliminary treatment that this polypropylene film is utilized reactive ion etching, adopt X ray photoelectricity optical spectroscopy, at x-ray source is that MgK alpha ray, power are when measuring under the condition of 100W, and the half-breadth value of the C-C key of obtaining from the analysis of Cls waveform is 1.320～1.600eV.
14, duplexer according to claim 3 is characterized in that: described gas barrier property has been implemented the preliminary treatment of plasma treatment by the surface of rete.
15, duplexer according to claim 14 is characterized in that: described gas barrier property by rete be contain water soluble polymer or contain water soluble polymer and the gas barrier property of inorganic compound by rete.
16, duplexer according to claim 14, it is characterized in that: when adopting X ray photoelectricity optical spectroscopy (XPS) to measure described gas barrier property by rete surperficial, the functional group of the carbon-carbon bond of water soluble polymer (C-C) and carbon-hydroxyl bond (C-OH) is that C-OH/C-C is more than 0.25 and below 0.87 than D.
17, duplexer according to claim 15 is characterized in that: described water soluble polymer is a polyvinyl alcohol.
18, duplexer according to claim 15 is characterized in that: described inorganic compound is the hydrolysate of the metal alkoxide more than a kind.
19, duplexer according to claim 14 is characterized in that: the inorganic oxide evaporation layer that is provided with thick 5～100nm between described material main body and described gas barrier property are by rete.
20, duplexer according to claim 14 is characterized in that: by rete, pretreated functional group compares D than the functional group before D and the preliminary treatment about described gas barrier property
0Ratio D/D
0Be more than 0.30 and below 0.92.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006244513 | 2006-09-08 | ||
| JP244513/2006 | 2006-09-08 | ||
| JP094833/2007 | 2007-03-30 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110359351.8A Division CN102514336B (en) | 2006-09-08 | 2007-08-31 | Multilayer body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101511585A true CN101511585A (en) | 2009-08-19 |
Family
ID=41003429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800331407A Pending CN101511585A (en) | 2006-09-08 | 2007-08-31 | Multilayer body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101511585A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110022992A (en) * | 2016-12-01 | 2019-07-16 | 凸版印刷株式会社 | Choke laminated body and its manufacturing method |
| CN111655487A (en) * | 2018-01-31 | 2020-09-11 | 凸版印刷株式会社 | Laminate and method for producing laminate |
| CN113677604A (en) * | 2019-01-17 | 2021-11-19 | 凸版印刷株式会社 | Package, gas barrier laminate, and packaging material |
-
2007
- 2007-08-31 CN CNA2007800331407A patent/CN101511585A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110022992A (en) * | 2016-12-01 | 2019-07-16 | 凸版印刷株式会社 | Choke laminated body and its manufacturing method |
| CN111655487A (en) * | 2018-01-31 | 2020-09-11 | 凸版印刷株式会社 | Laminate and method for producing laminate |
| CN111655487B (en) * | 2018-01-31 | 2023-03-31 | 凸版印刷株式会社 | Laminate and method for producing laminate |
| CN113677604A (en) * | 2019-01-17 | 2021-11-19 | 凸版印刷株式会社 | Package, gas barrier laminate, and packaging material |
| CN113677604B (en) * | 2019-01-17 | 2023-06-09 | 凸版印刷株式会社 | Package, gas barrier laminate, and packaging material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102514336B (en) | Multilayer body | |
| CN101039801B (en) | Gas barrier laminated film and manufacture method thereof | |
| JP5051494B2 (en) | Gas barrier laminate film and method for producing the same | |
| TW201002527A (en) | Gas barrier laminated film for organic devices | |
| JP2018122562A (en) | Gas barrier film laminate | |
| JP4923837B2 (en) | Boil / retort container lid | |
| JP2006168340A (en) | Transparent gas barrier layered product | |
| JP2008143103A (en) | Gas barrier laminated film | |
| JP2008073986A (en) | Gas barrier laminated film | |
| CN101511585A (en) | Multilayer body | |
| JP5092541B2 (en) | Gas barrier film and gas barrier laminate | |
| JP4402412B2 (en) | Laminate and packaging bag using the same | |
| JP2010221595A (en) | Gas-barrier film and manufacturing method thereof | |
| JP2005324361A (en) | Barrier film and laminated material using it | |
| JP4978066B2 (en) | Method for evaluating manufacturing conditions of gas barrier film laminate | |
| JP2023052209A (en) | Gas barrier vapor-deposited film | |
| JP2020131676A (en) | High interlaminar adhesive gas barrier vapor-deposited film | |
| JP2008143585A (en) | Paper container for liquid | |
| WO2016133038A1 (en) | Transparent barrier film | |
| JP2006116703A (en) | Barrier film and laminated material using it | |
| JP2005297376A (en) | Strong adhesive vapor depositioin film and packaging material for retorting using this film | |
| JP2010221596A (en) | Gas-barrier laminated film and gas-barrier packaging material | |
| JP2008265853A (en) | Paper container for retort processing, and packaging body for retort processing using same | |
| CN114456429B (en) | Air-blocking and water-blocking laminated film, preparation method and application thereof in packaging | |
| JP2009248455A (en) | High gas-barrier laminate and packaging container |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090819 |