CN101970225B - Laminate, cover member for hermetically sealed container using same, and hermetically sealed container - Google Patents

Laminate, cover member for hermetically sealed container using same, and hermetically sealed container Download PDF

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Publication number
CN101970225B
CN101970225B CN2009801084514A CN200980108451A CN101970225B CN 101970225 B CN101970225 B CN 101970225B CN 2009801084514 A CN2009801084514 A CN 2009801084514A CN 200980108451 A CN200980108451 A CN 200980108451A CN 101970225 B CN101970225 B CN 101970225B
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China
Prior art keywords
mentioned
resin
laminated body
layer
superficial layer
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Expired - Fee Related
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CN2009801084514A
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Chinese (zh)
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CN101970225A (en
Inventor
高木康行
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Sumika Plastech Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • B32B2435/00—Closures, end caps, stoppers
    • B32B2435/02—Closures, end caps, stoppers for 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Landscapes

  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

Disclosed is a laminate having a surface layer, a base layer, and an adhesive layer arranged between the surface layer and the base layer. On side of the adhesive layer is bonded with the surface layer, and the other side of the adhesive layer is bonded with the base layer. The surface layer is composed of a resin material containing a thermoplastic resin, and forms one surface of the laminate. The base layer is composed of a resin material containing not less than 40% by mass of an amorphous thermoplastic resin having a glass transition temperature within the range of 50-150 DEG C, and has a thickness of 30-200 [mu]m. The laminate has a thickness of 60-250 [mu]m. A cover member for a hermetically sealed container using the laminate, and a hermetically sealed container are also disclosed.

Description

Laminated body and the closed container that uses this laminated body are with cap member and closed container
Technical field
The present invention relates to conformality (the particularly retentivity of buckling deformation and bending distortion) excellent, be suitable for use as closed container with cap member (Cover material), do not have the laminated body of aluminium foil layer, also relate to this laminated body in the application (typically, relating to closed container cap member and the closed container that has used this laminated body) of packaging field.
Background technology
At present, accommodate in the closed container of the food such as yoghourt, pudding, use to comprise the laminated body of aluminium foil base material and hot sealing layer as cap member.But in recent years, has the cap member (with reference to TOHKEMY 2003-267422 communique) that replaces aluminium foil base material base material in order to adapt to the packaging material that to use as the requirement that industrial materials recycle, to have researched and developed.
For example in patent documentation 1, put down in writing substrate layer by resin combination form without aluminium lid body member, described resin combination comprises the copolymer resin (A) of specific composition ratio of styrenic monomers (a) and conjugated diene monomer (b) and the copolymer resin (B) of polystyrene or acrylic monomer (c) and styrenic monomers (d).
For the existing laminated body of using without aluminium lid body member, be improved the requirement of conformality, in addition, for the stability of sealing intensity and the easily requirement that also is improved of fissility.
Summary of the invention
In view of above problem, the object of the present invention is to provide excellent shape retention property, be suitable as closed container with the materials'use of cap member without the aluminium laminated body, also provide be suitable as sealing intensity stability or easily the improved cap member of fissility materials'use without the aluminium laminated body, the closed container that the sealing property excellence further is provided is with cap member and closed container.
The invention provides laminated body, it has superficial layer, substrate layer and tack coat, described tack coat is configured between this superficial layer and the substrate layer, on the one surface with above-mentioned superficial layer bonding, on another side with above-mentioned substrate layer bonding, it is characterized in that,
Above-mentioned superficial layer is formed by the resin material that contains thermoplastic resin, and consists of a surface of this laminated body,
Above-mentioned substrate layer is formed by resin material, and this resin material contains the above amorphism thermoplastic resin of glass transition temperature in 50～150 ℃ of scopes of 40 quality %,
The thickness of above-mentioned substrate layer is 30 μ m～200 μ m, and the thickness of above-mentioned laminated body is 60 μ m～250 μ m.
The present invention also provides the closed container of being made by above-mentioned laminated body cap member, and the closed container with this cap member and container body.
The specific embodiment
(laminated body)
Laminated body of the present invention has superficial layer, substrate layer and tack coat, and described tack coat is configured between this superficial layer and the substrate layer, is boning with above-mentioned superficial layer on the one surface, boning with above-mentioned substrate layer on another side.The thickness of this laminated body is in the scope of 30 μ m～200 μ m, preferably in the scope of 80 μ m～240 μ m, more preferably in the scope of 100 μ m～230 μ m.
＜substrate layer 〉
Substrate layer of the present invention refers to the thickest layer that comprises in the laminated body of the present invention.
This substrate layer is the layer that is formed by resin material, and described resin material contains the above amorphism thermoplastic resin of glass transition temperature in 50 ℃～150 ℃ scopes of 40 quality %.The base material that is formed by following resin material can make laminated body of the present invention have high rigidity, can form the laminated body of the retentivity excellence of conformality, particularly buckling deformation and bending distortion, described resin material contains the amorphism thermoplastic resin of glass transition temperature in above-mentioned scope.The glass transition temperature of the above-mentioned amorphism thermoplastic resin that contains in the substrate layer is preferably in 60 ℃～140 ℃ scope, more preferably in 70 ℃～120 ℃ scope.The resin material of formation substrate layer also can contain the amorphism thermoplastic resin with this glass transition temperature more than 2 kinds.And " the amorphism thermoplastic resin " among the present invention refers to not observe the thermoplastic resin of endothermic peak in the mensuration of utilizing differential scanning calorimeter (DSC) to carry out.In addition, " glass transition temperature " of the present invention refers to the method according to JIS K7121 regulation, the numerical value that utilizes DSC to measure.
As the amorphism thermoplastic resin that in consisting of the resin material of substrate layer, comprises, can enumerate phenylethylene resin series, ester is resin etc.Phenylethylene resin series can be enumerated polystyrene, rubber modified polystyrene etc.Rubber modified polystyrene refers to that the soft composition particle that is obtained by styrenic and rubber-like polymer disperses to be present in the resin in the matrix that is formed by styrenic, and known have so-called " resistance to impact styrene (High Impact Polystyrene: be abbreviated as HIPS) ".Formation generally has styrene as the styrenic monomers of the styrene polymer of the matrix in the rubber modified polystyrene, also can be the phenylethylene that the alkyl such as o-methyl styrene, a methyl styrene, p-methylstyrene replace.The rubber-like polymer that contains in the soft composition particle can use butadiene polymer, SB, isoprene copolymer, styrene-isoprene copolymer etc.Also SB and butadiene polymer can be share.It is any one of about 35% what is called " middle cis polybutadiene " that butadiene polymer can use the high what is called of cis-content " high-cis polybutadiene " or cis containing ratio.
Ester is that resin is binary acid and polyalcohol to be carried out polycondensation and the product for preparing.Binary acid can be enumerated the aliphatic dicarboxylic acids such as the aromatic dicarboxylic acids such as terephthalic acid (TPA), M-phthalic acid, NDA or adipic acid.Polyalcohol can be enumerated ethylene glycol, BDO, 1,4-CHDM, five glycol, 2,2-dimethyl propylene glycol, 1, the glycol such as 6-hexylene glycol, neopentyl glycol.Be in the resin at ester, can be with arbitrarily binary acid and arbitrarily polyalcohol combination.Ester is that the example of resin can be enumerated terephthalic acid (TPA)/glycol copolymer, terephthalic acid (TPA)/ethylene glycol/1,4-CHDM terpolymer, NDA/glycol copolymer, terephthalic acid (TPA)/BDO copolymer.Consider from the angle of the conformality of extruding processability, gained laminated body, the amorphism thermoplastic resin that contains in the substrate layer is rubber modified polystyrene and terephthalic acid (TPA)/ethylene glycol/1 preferably, 4-cyclohexanedimethanol terpolymer, more preferably rubber modified polystyrene.
From considering with the angle of material recovery the purposes of cap member at closed container, when forming container body with the amorphism thermoplastic resin, the amorphism thermoplastic resin that further preferably uses the resin identical with this amorphism thermoplastic resin to use as substrate layer.For example when container body contained rubber modified polystyrene, more preferably the substrate layer of laminated body of the present invention contained rubber modified polystyrene as the amorphism thermoplastic resin.
Form the resin material of substrate layer except above-mentioned amorphism thermoplastic resin, can also further contain polyamide-based resin, polyester based resin, polycarbonate resin, polyolefin-based resins, ionomer and be other the thermoplastic resin such as resin, Biodegradable resin.
Polyamide-based resin can be enumerated nylon 6, nylon 66, nylon 666, poly hexamethylene adipamide metaphenylene dimethylamine, poly-heptanedioyl metaphenylene dimethylamine, poly-nonanedioyl metaphenylene dimethylamine, poly-nonanedioyl is to the phenylene dimethylamine, poly-decanedioyl is to the phenylene dimethylamine, adipyl metaphenylene dimethylamine/adipyl is to phenylene dimethylamine copolymer, heptanedioyl metaphenylene dimethylamine/heptanedioyl is to phenylene dimethylamine copolymer, nonanedioyl metaphenylene dimethylamine/nonanedioyl is to phenylene dimethylamine copolymer, decanedioyl metaphenylene dimethylamine/decanedioyl is to phenylene dimethylamine copolymer etc.
Polyester based resin can be enumerated PETG, PTT, polybutylene terephthalate (PBT), polyethylene glycol isophthalate, PEN, PBN, PETG/ethylene isophthalate copolymer etc.
Polyolefin-based resins can be enumerated the polyethylene-based resins such as ultra-low density polyethylene (VLDPE), wire low density polyethylene (LDPE) (LLDPE), low density polyethylene (LDPE) (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) (HDPE).
In addition, said polyolefins is that resin can also be enumerated vinyl-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate methyl terpolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA), ethane-acetic acid ethyenyl ester-glycidyl methacrylate copolymer (E-VA-GMA), ethene-copolymer-maleic anhydride (E-MAH), ethylene-propylene acetoacetic ester-copolymer-maleic anhydride (E-EA-MAH), Noblen, the polyolefin-based resins such as copolymer of propylene and other alpha-olefins, the random copolymer of the cyclic olefins such as ethene and ENB or tetracyclododecane class and derivative thereof, the ring opening copolymer thing of cyclic olefin, the hydride of the ring opening copolymer thing of cyclic olefin, and the annular ethylene series resin such as graft modification thing of these copolymers.
Ionomer is the resin metal corrective that can enumerate ethylene-acrylic acid copolymer, metal corrective of ethylene-methacrylic acid copolymer etc.
Biodegradable resin can be enumerated PLA (such as Mitsui Chemicals society system " LACEA "), cellulose acetate (such as ダ イ セ Le chemistry society's system " セ Le グ リ one Application PCA "), chemical starch (such as Japanese コ one Application ス タ one チ society " コ one Application Port one Le ") etc.
In the resin material that forms substrate layer, the content of above-mentioned amorphism thermoplastic resin is in the scope of 40 quality %～100 quality %, preferably in the scope of 50 quality %～100 quality %, further in the scope of preferred 55 quality %～100 quality %.
The resin material that consists of substrate layer also can contain the additives such as lubricant, antistatic additive, antioxidant, heat stabilizer, ultra-violet absorber, antiseptic, antifoggant.
The thickness of substrate layer is in the scope of 30 μ m～200 μ m, and is preferably in the scope of 40 μ m～180 μ m, further preferred in the scope of 50 μ m～160 μ m.Thickness by making substrate layer can be given the conformality of lamination height in above-mentioned scope.
＜superficial layer 〉
Superficial layer in the laminated body of the present invention refers to that one surface consists of the layer on a surface of above-mentioned laminated body.This superficial layer is formed by the resin material that contains thermoplastic resin.The composition that consists of the resin material of superficial layer suitably determines according to the purposes of laminated body.For example for the laminated body as the design of the cap member of closed container, consider that this superficial layer forms the layer that is fitted on the container body, can select and container body between show the composition of appropriate sealing intensity.In a preferred scheme, it is 50～120 ℃ the amorphism thermoplastic resin more than a kind that this resin material preferably contains glass transition temperature.
As the example of the amorphism thermoplastic resin that contains in the superficial layer, same with the amorphism thermoplastic resin that uses in the substrate layer, can enumerate phenylethylene resin series, ester is resin etc.In addition, consider from the angle of material recovery that preferably the amorphism thermoplastic resin of use and substrate layer is amorphism thermoplastic resin of the same race in superficial layer.As closed container with in the purposes of cap member, when forming container body with the amorphism thermoplastic resin, in laminated body of the present invention, preferably using respectively with this amorphism thermoplastic resin in substrate layer and superficial layer is resin of the same race.For example, when container body contained rubber modified polystyrene, in the laminated body that the cap member as this container designs, more preferably the amorphism thermoplastic resin of the amorphism thermoplastic resin of substrate layer and superficial layer used rubber modified polystyrene separately.
The above-mentioned resin material that superficial layer is used also can contain the additives such as lubricant, antiblocking agent, antistatic additive, antioxidant, heat stabilizer, ultra-violet absorber, antiseptic, antifoggant.
The thickness of superficial layer is preferably in the scope of 1 μ m～15 μ m, more preferably in the scope of 3 μ m～10 μ m, further preferably in the scope of 3 μ m～8 μ m.If the thickness of superficial layer in above-mentioned scope, is then used in the purposes of cap member at closed container, when peeling off cap member from airtight container, superficial layer destroys, and can make thus tack coat and superficial layer carry out splitting.By producing this splitting, no matter for the seal temperature of container body how cap member can show roughly certain peel strength, the Kaifeng of container becomes easy simultaneously.
In laminated body of the present invention, the thickness of superficial layer with respect to the ratio of substrate layer thickness preferably in 1/6～1/50 scope, more preferably in 1/6～1/30 scope.Thickness by making superficial layer in such scope, can make laminated body show conformality with respect to the ratio of substrate layer thickness.
＜tack coat 〉
Tack coat in the laminated body of the present invention is layer as described below: it is configured between above-mentioned superficial layer and the substrate layer, is boning with above-mentioned superficial layer on the one surface, boning with above-mentioned substrate layer on another side.
Tack coat can be the individual layer tack coat, also can be the multi-layered bonded layer that comprises the layer more than 2 layers.The multi-layered bonded layer is mainly using the individual layer tack coat can not realize using in the situation of balance desired between the adhesion strength of the adhesion strength of tack coat and superficial layer and tack coat and substrate layer.Tack coat can be enumerated the resin combination that contains styrene series elastomer and/or ethene-unsaturated carboxylic acid ester copolymer.Wherein preferably use ethene-unsaturated carboxylic acid ester copolymer.
Here, styrene series elastomer can be enumerated hydrogenation styrene-butadiene block copolymer (SEBS), styrene-ethylene-propylene-based block copolymer (SEP, SEPS), hydrogenation SBR styrene butadiene rubbers (HSBR) etc.In addition, ethene-unsaturated carboxylic acid ester copolymer can be enumerated ethylene/methyl acrylate copolymer, ethylene/methacrylic acid methyl terpolymer, ethylene/ethyl acrylate copolymer, ethylene/methacrylic acid ethyl ester copolymer, the positive butyl ester copolymer of ethylene/acrylic acid, the positive butyl ester copolymer of ethylene/methacrylic acid etc.The content that comes from the construction unit of ethene in ethene/unsaturated carboxylic acid ester copolymer is preferably 60 quality %～80 quality %.
Form the above-mentioned resin combination of tack coat except styrene series elastomer and ethene-unsaturated carboxylic acid ester copolymer, can also contain vinylite, propylene resin, ester is the thermoplastic resins such as resin, phenylethylene resin series.
The content of the styrene series elastomer in the tack coat and ethene-unsaturated carboxylic acid ester copolymer is preferably respectively 10 quality %～100 quality %, more preferably 30 quality %～100 quality %.In addition, when with styrene series elastomer with ethene-when the unsaturated carboxylic acid ester copolymer share, its total content was preferably 20 quality %～100 quality %, 40 quality %～100 quality % more preferably.When with styrene series elastomer and ethene-when the unsaturated carboxylic acid ester copolymer share, (the styrene series elastomer: ethene-unsaturated carboxylic acid ester copolymer) be preferably 1: 9～9: 1 of content ratio separately, more preferably 2: 8～8: 2, more preferably 4: 6～6: 4.
Above-mentioned resin combination also can contain the additives such as lubricant, antistatic additive, antioxidant, heat stabilizer, ultra-violet absorber, antiseptic, antifoggant.
The thickness of tack coat is preferably 5～100 μ m, more preferably 10～85 μ m, further preferred 10～70 μ m.Thickness by making tack coat can be made the laminated body with suitable interlaminar strength in above-mentioned scope.
Laminated body of the present invention is according to its purposes, can have layer (for example sealer or decorative layer) more than 1 layer or 2 layers at substrate layer.Consider that from the angle of material recovery this layer that appends preferably contains thermoplastic resin.For example, in being intended to the laminated body of using with cap member as closed container, also can the configuration surface protective layer, this sealer be the film that is formed by thermoplastic resin implemented printing wait decorate layer.Sealer is preferably formed by nylon, PETG, polypropylene, ethylene-vinyl alcohol copolymer etc.
The thickness of sealer is preferably in the scope of 5～50 μ m, more preferably in the scope of 10～40 μ m, further preferably in the scope of 12～35 μ m.
The manufacturing of＜laminated body 〉
Laminated body of the present invention can be made by present known processing methods such as the blow moulding that utilizes coextrusion, T-shaped die head method, pressurizations.In addition, also can make respectively the film of each self-forming superficial layer, tack coat or substrate layer, they are carried out the bonding laminated body that obtains by lamination etc.The film of each of laminated body layer usefulness is such as making with the whole bag of tricks such as blow moulding, T-shaped die head method, pressurizations.
(cap member and closed container)
Cap member of the present invention can obtain by the shape that above-mentioned laminated body is shaped to regulation.For example can as described belowly obtain: after the laminated body stamping-out is circular, using forming machine was the shape (for example truncated cone shape, cylindrical shape) that can cover the peristome of closed container main body with its drawing and forming.This moment is with the mode moulding of surface level in the inboard.
Closed container of the present invention has cap member and the container body that is formed by laminated body of the present invention, this cap member on its superficial layer with the said vesse body seal.This closed container case as described below obtains: so that its superficial layer covers with the mode that the peristome of closed container main body contacts, make above-mentioned superficial layer and closed container main body bond to obtain by the method for stipulating above-mentioned cap member.The bonding of superficial layer is preferably undertaken by heat-sealing.
Container body is so long as can get final product with the container that superficial layer heat merges, and its material or shape are not particularly limited.The object lesson of container body can be enumerated sheet material, plate, cup, the bottle that forms such as by thermoplastic resins such as styrenic, polyester, polyamide.Container body can be individual layers, also can be the polylayer forest that each layer formed by thermoplastic resin.
Consider that from the angle of material recovery the preferred container body that contains the resin identical with the cap member superficial layer that uses more preferably uses the container body that contains with the same resin of superficial layer, tack coat, substrate layer.
Embodiment
Below, based on embodiment the present invention is described, but the invention is not restricted to these embodiment.
[embodiment 1]
As the resin material that forms superficial layer, use is with rubber modified polystyrene (Japanese polystyrene (strain) H550 processed, glass transition temperature is 100 ℃) 20 mass parts and polystyrene (Japanese polystyrene (strain) G440K processed) 80 mass parts granulations and the hybrid resin that mixes.
Below, this hybrid resin is denoted as thermoplastic resin B.
The resin material that forms tack coat can use particle as described below, and this particle uses barrel temperature and mold temperature to be set in 220 ℃ in the same way 45mm φ biaxial extruder, following 4 kinds of compositions are carried out melting mixing and obtains.
[1] ethylene-methyl acrylate copolymer (Sumitomo Chemical (strain) system, trade name ア Network リ Off ト: CG4002, the content that comes from the construction unit of methyl acrylate is 31 mass parts, and melt flow rate (MFR) (190 ℃, 2.16kgf)=5g/10 minute) 55 mass parts;
[2] wire low density polyethylene (LDPE) (Sumitomo Chemical (strain) system, trade name ス ミ カ セ Application E:FV401, melt flow rate (MFR) (190 ℃, 2.16kgf)=4g/10 minute) 17 mass parts;
[3] styrene-isoprene block copolymer (Network ラ レ society system, trade name セ プ ト Application 2104) 3 mass parts;
[4] rubber modified polystyrene (Japanese polystyrene (strain) H550 processed, glass transition temperature is 100 ℃) 22 mass parts
The resin material that forms substrate layer uses the rubber modified polystyrene (Japanese polystyrene (strain) H550 processed, glass transition temperature is 100 ℃) that uses in above-mentioned tack coat.Below, this resin material is denoted as thermoplastic resin A.
Laminated body is out made by co-extrusion, and the 3 kinds 3 layers T-shaped die head casting of coextrusion processing machine with 3 extruders (extruder A, extruder B and extruder C) are used in described coextrusion.At first, in extruder A, add the thermoplastic resin B that superficial layer is used, in extruder B, add the resin combination that tack coat is used, in extruder C, add the thermoplastic resin A that substrate layer is used, and in each extruder, carry out melting mixing.Further by coextrusion that each material is stacked, make substrate layer, tack coat, superficial layer are stacked gradually the laminated body that forms.The details of above-mentioned 3 extruders are as follows.
Extruder A:60mm φ, extruder B:60mm φ, extruder C:90mm φ
Layer formation=extruder A (superficial layer)/extruder B (tack coat)/extruder C (substrate layer)
(substrate layer)
At above-mentioned melting mixing with extrude, processing temperature is respectively that extruder A is that 220 ℃, extruder B are that 190 ℃, extruder C are 230 ℃, and mold temperature is 250 ℃.
Secondly, for the substrate layer surface of laminated body, carry out Corona discharge Treatment, so that wetting tension reaches 45dyn/cm.In the laminated body of gained, surface layer thickness is 5 μ m, and adhesive layer thickness is 10 μ m, and substrate layer thickness is 100 μ m, and the thickness of whole laminated body is 115 μ m.
Further, use the smart machine (strain) of Kang Jing coating machine processed, at substrate layer sealer is set according to following program.At first; be that smears (cohesiveness mixture that the military field ケ ミ カ Le (strain) " タ ケ ラ Star Network A-515 " of host=Mitsui, the military field ケ ミ カ Le (strain) " タ ケ ネ-ト A-50 " of curing agent=Mitsui, ethyl acetate are cooperated and fully are mixed to get with 10: 1: 15 mass ratio respectively) is coated on polyester film (ユ ニ チ カ (strain) system that forms sealer with aliphatic ester; trade name " PTMX "; thickness 12 μ m, width 330mm) one side.Then, make this film on its cohesiveness mixture coated face with the sided corona treatment face pressing of laminated body after, utilize 40 ℃ baking oven heating 24 hours, obtain the surface protection laminated body.
[embodiment 2]
Use is used to form the resin material (that is, thermoplastic resin B) of superficial layer as the resin material that forms superficial layer in embodiment 1.
Use is used to form the resin material of tack coat as the resin material that forms tack coat in embodiment 1.
Use particle as the resin material that forms substrate layer, described particle is to use barrel temperature and mold temperature to be set in 220 ℃ in the same way 45mm φ biaxial extruder, following 4 kinds of compositions is carried out melting mixing obtain.
[1] ethylene-methyl acrylate copolymer (Sumitomo Chemical (strain) system, trade name ア Network リ Off ト: CG4002, the content that comes from the construction unit of methyl acrylate is 31 mass parts, and melt flow rate (MFR) (190 ℃, 2.16kgf)=5g/10 minute) 5 mass parts
[2] wire low density polyethylene (LDPE) (Sumitomo Chemical (strain) system, trade name ス ミ カ セ Application E:FV202, melt flow rate (MFR) (190 ℃, 2.16kgf)=2g/10 minute) 3 mass parts;
[3] styrene-isoprene block copolymer (Network ラ レ society system, trade name セ プ ト Application 2104) 2 mass parts;
[4] rubber modified polystyrene (Japanese polystyrene (strain) H550 processed, glass transition temperature is 100 ℃) 90 mass parts
Laminated body is made by the inflation film moulding, and 3 kinds 3 layers coextrusion blowing processing machine with 3 extruders (extruder A, extruder B and extruder C) are used in described inflation film moulding.At first, in extruder A, add the thermoplastic resin B that superficial layer is used, in extruder B, add the resin material that tack coat is used, in extruder C, add the resin material that substrate layer is used, and in each extruder, carry out melting mixing.Further by coextrusion that each material is stacked, then carry out blowing processing, make substrate layer, tack coat, superficial layer are stacked gradually the laminated body that forms.The details of above-mentioned blowing processing machine are as follows.
Mould diameter: 150mm φ
Die gap: 2mm
Extruder A:50mm φ, extruder B:50mm φ, extruder C:50mm φ
Layer formation=extruder A (blowing inner tube layer)/extruder B (blowing pipe intermediate layer)/extruder C (blowing outer tube layer)
At above-mentioned melting mixing with extrude, processing temperature is respectively that extruder A is that 200 ℃, extruder B are that 190 ℃, extruder C are 220 ℃, and mold temperature is 210 ℃.
Secondly, for the substrate layer surface of laminated body, carry out Corona discharge Treatment, so that wetting tension reaches 45dyn/cm.In the laminated body of gained, surface layer thickness is 5 μ m, and adhesive layer thickness is 28 μ m, and substrate layer thickness is 37 μ m, and the thickness of whole laminated body is 70 μ m.Further, obtain the surface protection laminated body according to similarly to Example 1 program.
[comparative example 1]
Use is used to form the resin material (that is, thermoplastic resin B) of superficial layer as the resin material that forms superficial layer in embodiment 1.
Use is used to form the resin material of tack coat as the resin material that forms tack coat in embodiment 1.
Use particle as the resin material that forms substrate layer, described particle uses barrel temperature and mold temperature to be set in 220 ℃ in the same way 45mm φ biaxial extruder, following 3 kinds of compositions are carried out melting mixing and gets.
[1] wire low density polyethylene (LDPE) (Sumitomo Chemical (strain) system, trade name ス ミ カ セ Application E:FV202, melt flow rate (MFR) (190 ℃, 2.16kgf)=2g/10 minute) 70 mass parts;
[2] styrene-isoprene block copolymer (Network ラ レ society system, trade name セ プ ト Application 2104) 10 mass parts;
[3] rubber modified polystyrene (Japanese polystyrene (strain) H550 processed) 20 mass parts
Use 3 kinds 3 layers coextrusion blowing processing machine similarly to Example 2, make the successively laminated body that forms of lamination of substrate layer, tack coat, superficial layer
In the laminated body of gained, surface layer thickness is 5 μ m, and adhesive layer thickness is 30 μ m, and substrate layer thickness is 40 μ m, and the thickness of whole laminated body is 75 μ m.Further, obtain the surface protection laminated body according to similarly to Example 1 program.
Utilize following method come Evaluation operation example 1,2 and comparative example 1 in the stack membrane that obtains.The results are shown in table 1.
＜easy fissility 〉
As adherend, using from thickness is rubber modified polystyrene sheet (Japanese polystyrene society system, the trade name: the sheet material that H640) cuts out with the size of 70mm * 90mm of 400 μ m.The superficial layer of the cap member that make this adherend, gets with being cut by the laminated body that obtains in embodiment or the comparative example carries out driving fit, is 3kg/cm at pressure 2, the time is to be under the condition of 160 ℃ or 180 ℃, to seal take the band shape (direction parallel with the 90mm length direction of adherend) of width as 20 millimeters with seal temperature in 1 second.With vertical with this banded hermetic unit and contain the mode of hermetic unit, and the interval take width as 15mm cuts, and makes the test film of 15mm * 70mm.
Use smart machine (strain) オ of Japan one ト グ ラ Off AGS500D type tension stress testing machine, under 23 ℃, make cap member carry out 180 degree from adherend with 300mm/ minute draw speed and peel off, measure the peel strength of this moment.For easy fissility, if peel strength is in the scope of 5N/15mm～30N/15mm, the balance of then judging the peel strength the when sealing intensity of adherend and cap member and cap member are peeled off is excellent, represent with mark " zero ", if peel strength is outside above-mentioned scope, the balance of then judging the peel strength the when sealing intensity of adherend and cap member and cap member are peeled off is poor, with mark " * " expression.
＜conformality test 〉
Prepare cap member and with width be the flange part of 3mm fence up have a polystyrene container made main body that internal diameter is the circular open of 62mm, it is that the circle of 70mm gets that described cap member is cut into diameter by the laminated body that will obtain in embodiment or the comparative example.The heat-sealing that cap member was carried out for 1 second at the flange part of container body with the loading of 180 ℃ temperature, 100kgf comes airtight, obtains closed container.
Then, catching an end of cap member with the state that container body is fixing, is that 45 ° direction is pullled towards the unstripped part with respect to cap member, and cap member is peeled off from container body, thereby with airtight container Kaifeng, until the peristome ratio of container body reaches 50%～75%.Behind the Kaifeng, measure the knuckle of the cap member of being pulled open by external force.If knuckle is more than 45 °, then judge the excellent shape retention property of this cap member, with mark " zero " expression, if knuckle, judges then that the conformality of this cap member is poor less than 45 °, with mark " * " expression.
Table 1
Figure BPA00001219354200121
Industrial applicibility
Therefore the conformality of laminated body of the present invention (the particularly retentivity of buckling deformation and bending distortion) excellence when using this laminated body, can provide the cap member of the excellent shape retention property that is applicable to the closed container purposes.In addition, can provide the stability of sealing intensity or easy also excellent cap member of fissility.And laminated body of the present invention mainly designs in the such mode of the cap member that is applicable to closed container, but the purposes of laminated body of the present invention is not limited to the cap member of closed container.

Claims (6)

1. laminated body, it has superficial layer, substrate layer and tack coat, described tack coat is configured between this superficial layer and the substrate layer, on the one surface with above-mentioned superficial layer bonding, on another side with above-mentioned substrate layer bonding, wherein,
Above-mentioned superficial layer is formed by the resin material that contains thermoplastic resin, and consists of a surface of this laminated body,
Above-mentioned substrate layer is formed by resin material, and this resin material contains the above amorphism thermoplastic resin of glass transition temperature in 50～150 ℃ of scopes of 40 quality %,
The thickness of above-mentioned substrate layer is 30 μ m～200 μ m, and the thickness of above-mentioned laminated body is 60 μ m～250 μ m,
Above-mentioned thermoplastic resin in the above-mentioned superficial layer is the amorphism thermoplastic resin of glass transition temperature in 50～150 ℃ scope,
Above-mentioned amorphism thermoplastic resin in the above-mentioned substrate layer and the above-mentioned amorphism thermoplastic resin in the above-mentioned superficial layer are respectively that to be selected from phenylethylene resin series and ester be at least a kind of resin in the resin independently,
Above-mentioned ester is that resin is binary acid and polyalcohol to be carried out polycondensation and the product for preparing.
2. laminated body according to claim 1, wherein, the thickness of above-mentioned superficial layer with respect to the ratio of the thickness of above-mentioned substrate layer in 1/6～1/50 scope.
3. laminated body according to claim 1, wherein, above-mentioned tack coat contains at least a kind of polymer that is selected from styrene series elastomer and the ethene-unsaturated carboxylic acid ester copolymer.
4. closed container cap member, it is formed by each described laminated body in the claim 1～3.
5. closed container, it has cap member as claimed in claim 4 and container body, this cap member on its superficial layer with the said vesse body seal.
6. closed container according to claim 5, wherein, it is resin of the same race that the said vesse main body contains with the above-mentioned amorphism thermoplastic resin that consists of above-mentioned superficial layer, described superficial layer is the superficial layer that consists of the above-mentioned laminated body of above-mentioned cap member.
CN2009801084514A 2008-03-13 2009-03-12 Laminate, cover member for hermetically sealed container using same, and hermetically sealed container Expired - Fee Related CN101970225B (en)

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