CN1502466A - Multilayer film for thermal-lamination, laminated body and thermal-moulding container - Google Patents
Multilayer film for thermal-lamination, laminated body and thermal-moulding container Download PDFInfo
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- CN1502466A CN1502466A CNA200310113673XA CN200310113673A CN1502466A CN 1502466 A CN1502466 A CN 1502466A CN A200310113673X A CNA200310113673X A CN A200310113673XA CN 200310113673 A CN200310113673 A CN 200310113673A CN 1502466 A CN1502466 A CN 1502466A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/22—Boxes or like containers with side walls of substantial depth for enclosing contents
- B65D1/26—Thin-walled containers, e.g. formed by deep-drawing operations
- B65D1/28—Thin-walled containers, e.g. formed by deep-drawing operations formed of laminated material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The present invention provides a multi-layer film for thermal lamination and a laminated sheet which can be easily thermally laminated on a sheet composed of a styrene-based polymer and has a sufficient bonding strength, and a thermoformed container which maintains a sufficient bonding strength, even after executing the thermal molding of the laminated sheet and boiling it. The multi-layer film for thermal lamination consists of layers (A), (B) and (C) laminated in the order of the layers (A)/(B)/(C) with the layers (A) and (C) constituting the surface layers respectively. The layer (A) is composed of a polypropylene-based polymer. The layer (B) is composed of a polypropylene-based polymer of 30 to 70 wt.% and an ethylene-based polymer of 30 to 70 wt.%. The layer (C) is composed of 30 to 70% ethylene-based polymer having a density of 0.90 to 0.97 g/cm <3>, of a petroleum resin of 10 to 50 wt.% having a softening point of 110 to 150 DEG C, and of an amorphous or poorly crystalline ethylene-alpha-olefin random copolymer of 10 to 50 wt.%.
Description
Technical field
The present invention relates to have heat lamination multilayer film excellent and heat lamination polystyrene sheet material or film, with the layered product that is pressed with polystyrene sheet material or film on this multilayer film upper strata, and the thermoformed containers that constitutes by this layered product, when being specifically related to heat lamination and during Heat forming and polystyrene sheet material or film have sufficient bond strength, the heat lamination that is suitable for processing is with multilayer film and layered product, and the container molding of practical physical properties excellent such as anti-the boiling property that constitutes by layered product, fuel resistance.
Background technology
Because the polystyrene resin hot formability is good, low price is so be widely used as containers for food use.But because polystyrene resin resistance to effect of heat and fuel resistance are poor, and there is not adhesive bonding property with polyalkenes hydrocarbon system lid material, so, re-use after need fitting with other resin.Particularly in needing the purposes of fuel resistance, need polypropylene-based film adhered on polystyrene sheet material or film more.At this moment; for with polystyrene sheet material or film and polypropylene-based film laminating; all the time; people utilize adhesives with polystyrene sheet material or film and polypropylene-based film adhered; the method of fitting by adhesives has not only increased flow chart, and uses adhesives also to be unfavorable for environmental protection and safety and sanitation.
In addition, in order to improve the designability of container, normally make the polypropylene-based film adhered of polystyrene sheet material or film and process printing, but, usually be used alone or as a mixture nitrocotton, amilan, chlorinated polypropylene, urethane resin as polypropylene-based film with the printing-ink resin, and use the printing-ink of these materials and the polystyrene resin can not be bonding, so, need press on polypropylene-based film upper strata and state printing-ink, and then the adhesives that coating can be bonding with polystyrene resin in the above, for this reason, can increase cost.
Therefore, the someone proposes the method (for example, with reference to patent documentation 1) with polystyrene and other resin coextrusion.Disclosed the material that in the copolymer resins that contains ethene and vinyl acetate, is added with adhesives in the patent documentation 1, it can be bonding with polystyrene, thereby can used as with other resin of polystyrene coextrusion, but its bond strength deficiency, and its poor heat resistance, boil after Heat forming when handling, binding power reduces, and peels off sometimes.In addition, for realizing coextrusion, need be used to form the equipment of multi-layer sheet.
So, if by heating can make polystyrene and the film that constitutes by other resin bonding, just can be with easy equipment realization lamination, so people expect to occur to add heat bonding and the higher film of binding power on the polystyrene sheet material.
As such film, have a kind of on the thermoplastic resin membrane film (for example, with reference to patent documentation 2～4) of lamination ethylene-alpha-olefine interpolymer and the adhesive resin composition that constitutes by petroleum resin.But this film is insufficient in the leak tightness of the low-temperature region below 120 ℃.In addition, according to the inventor's etc. research, these films are insufficient with the adhesive bonding property of the transparent polystyrene sheet material that is combined with buna-S (the system Asaflex of Asahi Chemical Industry etc.).In addition, the somebody proposes the ethene alpha-olefin copolymer resins, alkene hydrocarbon system neoprene of lamination specific density on the thermoplastic resin membrane, the thermoplastic resin composition's that is made of tackifier film (for example the patent documents 5).But even also have sufficient bond strength for realizing under the situation of low temperature adhesion, then the adhesive resin composition layer need have thickness sufficient.
[patent documentation 1] spy opens clear 54-10384 number
[patent documentation 2] spy opens flat 11-323040 number
[patent documentation 3] spy opens flat 11-323038 number
[patent documentation 4] spy opens flat 11-335497 number
[patent documentation 5] spy opens flat 11-269319 number
Summary of the invention
Under such background, the objective of the invention is to, providing needn't be to the sheet material or the thin film cladding adhesives that are made of styrenic, no matter have not film printed and also be easy to realize heat lamination heat lamination and that have abundant bond strength with multilayer film and layered product, even and by also keeping the thermoformed containers of abundant bond strength after the heat treatments such as boiling of making that this layered product Heat forming makes.
The inventor etc. have carried out in-depth study repeatedly for solving above-mentioned problem.Found that: use can solve above-mentioned problem by the laminated film that specific resin constitutes certain layer, thereby finishes the present invention.
Promptly, the present invention with by following (A) layer, (B) layer, (C) this three layers of formations of layer and with the order lamination of the layer of the layer of (A) layer/(B)/(C), (A) layer and (C) layer constitute the heat lamination multilayer film that superficial layer is a feature respectively, with the layered product that forms with (C) of multilayer film layer side lamination polystyrene sheet material or film in this heat lamination, and the thermoformed containers that constitutes by this layered product
(A) layer for constituting by acrylic polymer;
(B) layer that constitutes for ethylene-based polymer by the acrylic polymer of 30～70 weight % and 30～70 weight %;
(C) be by density 0.90～0.97g/cm of 30～70%
3The layer that constitutes of ethene-olefine random copolymers armorphous or that crystallinity is low of petroleum resin, 10～50 weight % of 110～150 ℃ of softening points of ethylene-based polymer, 10～50 weight %.
By constituting certain layer with specific resin, make heat lamination of the present invention have with respect to polystyrene sheet material or film and can satisfy practical, bond strength fully with multilayer film, in addition, the multilayer film that is printed is that sheet material or film also have and can satisfy practical, bond strength fully with respect to ethene.In addition, layered product and the thermoformed containers also performance excellence on practical rerum naturas such as resistances to effect of heat such as anti-boiling property, fuel resistance of using heat lamination of the present invention to obtain with multilayer film.
Therefore, heat lamination of the present invention with multilayer film applicable to being fitted in as the polystyrene thermoformed containers of article such as filling food inner face with polystyrene sheet material or film, in addition, also applicable to the sealing of lid material with polyalkenes hydrocarbon system aquaseal.
The specific embodiment
Be not particularly limited as the employed acrylic polymer of (A) of the present invention layer, be preferably the copolymer of single polymers, propylene and the alpha-olefin of propylene, but, consider aspect the resistance to effect of heat in the time of when carrying out heat lamination, from Heat forming, be preferably the fusing point measured by differential scanning calorimetry in 145～165 ℃ of scopes, be preferably propylene list polymers or the copolymer of propylene and alpha-olefin, more preferably propylene list polymers in 148～162 ℃ of scopes.In addition, when fusing point is more than 145 ℃ the time, the fold of the multilayer film in the time of preventing heat lamination, the demoulding after the Heat forming and cut edge functionally, institute thinks preferred; And below 165 ℃ the time, be difficult for during Heat forming ftractureing, institute thinks preferably.
As the copolymer of this propylene and alpha-olefin, be alpha-olefin 1～5 weight % of propylene 95～99 weight % and the carbon number except that propylene 2～10, the copolymer of alpha-olefin 1～3 weight % that is preferably propylene 97～99 weight % and the carbon number except that propylene 2～10 or their compound.As the alpha-olefin of the carbon number except that propylene 2～10, can enumerate ethene, 1-butylene, 3-methyl-1-butene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene etc.As the copolymer of this propylene and alpha-olefin, can enumerate the random copolymers and the periodic copolymer of propylene and alpha-olefin.In addition, in not influencing stable on heating scope, also can in (A) layer, add an amount of resin except that acrylic polymer.Particularly, for improving thermoformed containers of the present invention and covering the adhesive bonding property of material or give vessel side easy fissility, can add ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-octene copolymer equidensity 0.84～0.90g/cm
3Low-crystallinity or amorphous ethylene-alpha-olefin hydrocarbon copolymer.Consider that from stable on heating viewpoint addition is preferably the scope that is no more than 50 weight %.
In the present invention, (A) fusion index (hereinafter referred to as " MFR ") of layer used propylene series copolymer is considered from film system film aspect, should in the scope of 1.0～50g/10 branch (230 ℃ of temperature, load 2.16kg), be preferably in the scope that 2.0～40g/10 divides.
In the present invention, (B) there is no particular limitation for the used propylene series copolymer of layer, be preferably the copolymer of single polymers, propylene and the alpha-olefin of propylene, be preferably at propylene and the copolymer of alpha-olefin, the more preferably copolymer of the alpha-olefin of propylene and carbon number except that propylene 2～10 of the fusing point of measuring by differential scanning calorimetry in 120 ℃～140 ℃ scope, in preferred 123 ℃～137 ℃ scope.When fusing point is more than 120 ℃ the time, acrylic polymer itself is easy to make, and adhesive of resulting film (blocking) or slickness are good, and institute thinks preferred; And below 140 ℃ the time, the stretchability during Heat forming is good, and institute thinks preferred.
As the copolymer of this propylene and alpha-olefin, be alpha-olefin 1～20 weight % of propylene 80～99 weight % and the carbon number except that propylene 2～10, the copolymer of alpha-olefin 4～15 weight % that is preferably propylene 85～96 weight % and the carbon number except that propylene 2～10 or their compound.As the alpha-olefin of the carbon number except that propylene 2～10, can enumerate ethene, 1-butylene, 3-methyl-1-butene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene etc.As the copolymer of this propylene and alpha-olefin, can enumerate the random copolymers and the periodic copolymer of propylene and alpha-olefin.
The used ethylene-based polymer of the present invention (B) layer is suitable for using the low density polyethylene (LDPE) that made by high-pressure process, chain low density polyethylene (LDPE), high density polyethylene (HDPE) etc.
Density to this ethylene-based polymer is not particularly limited, but considers from the system membrane stability aspect of multilayer film, should be at 0.90～0.97g/cm
3Scope in, be preferably at 0.92～0.97g/cm
3Scope in, more preferably at 0.925～0.970g/cm
3Scope in.
When considering film forming, the MFR of the ethylene-based polymer that the present invention is used is preferably in the scope of 1～50g/10 branch (190 ℃ of temperature, load 2.16kg), more preferably in the scope that 2～20g/10 divides.
The acrylic polymer that (B) of the present invention layer is used and the cooperation ratio of ethylene-based polymer are acrylic polymer 30～70 weight %, ethylene-based polymer 30～70 weight %.When the use level of ethylene-based polymer was less than 30 weight %, fold took place in the spring rate step-down of film easily during heat lamination.And when the use level of acrylic polymer surpasses 70 weight %, reduce with the interlaminar strength of (C) layer, be provided with after the Heat forming under the situation of cover material, by on the container during peel-off covers material, cause sometimes (C) layer and (B) layer between peeling off.
The used ethylene-based polymer density of the present invention (C) layer is 0.90～0.97g/cm
3, be suitable for using the low density polyethylene (LDPE) that makes by high-pressure process, chain low density polyethylene (LDPE), high density polyethylene (HDPE) etc.
When the density of this ethylene-based polymer less than 0.90g/cm
3The time, resistance to effect of heat is low, and when thermoformed containers being boiled processing, container mist might occur and maybe might cause film to be peeled off in vain.When density is 0.97g/cm
3When above, will cause reducing with the bond strength of polystyrene sheet material or film.
When considering film forming, the MFR of the ethylene-based polymer that the present invention is used is preferably in the scope of 0.5～20g/10 branch (190 ℃ of temperature, load 2.16kg), more preferably the scope of 1～10g/10 branch.
The used softening point of the present invention (C) layer is 110～150 ℃ petroleum resin so long as be selected from aliphatics through-stone oleoresin, aromatic through-stone oleoresin, copolymerization through-stone oleoresin, alicyclic through-stone oleoresin, terpenic series petroleum resin and get final product, in addition without limits, but elect the alicyclic series petroleum resin especially as.In addition, these petroleum resin can also be mixed use.When 110 ℃ of the softening point deficiencies of petroleum resin, resistance to effect of heat reduces.And when softening point surpasses 150 ℃, with the adhesive bonding property reduction of polystyrene sheet material or film.In addition, the softening point of petroleum resin is the softening points that record with ball-and-ring method according to JIS K2207.
The used low or armorphous ethylene-alpha-olefin hydrocarbon copolymer of crystallinity of the present invention (C) layer is not particularly limited, and being suitable for using density is 0.84～0.90g/cm
3Ethene and the carbon number copolymer that is 3～10 alpha-olefin or their compound.As carbon number is that 3～10 alpha-olefin can be enumerated propylene, 1-butylene, 3-methyl-1-butene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene etc.As the low or armorphous ethylene-alpha-olefin hydrocarbon copolymer of above-mentioned crystallinity, be suitable for using ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-octene copolymer.
The density of above-mentioned crystallinity ethylene-alpha-olefin hydrocarbon copolymer low or amorphous is 0.84～0.90g/cm
3, be preferably 0.850～0.895g/cm
3When density is 0.84g/cm
3When above, be easy to make the low or armorphous ethylene-alpha-olefin hydrocarbon copolymer of crystallinity, institute thinks preferred; And work as density is 0.90g/cm
3When following, can form the multilayer film good with the adhesive bonding property of polyethylene-based sheet material or film, institute thinks preferred.
The crystallinity of the above-mentioned crystallinity ethylene-alpha-olefin hydrocarbon copolymer low or amorphous of trying to achieve by the X-ray diffraction method is below 40%, to be preferably below 30%.
Alpha-olefin unit content in the above-mentioned crystallinity ethylene-alpha-olefin hydrocarbon copolymer low or amorphous is preferably 5～40 weight %, more preferably 10～30 weight %.In addition, above-mentioned crystallinity ethylene-alpha-olefin hydrocarbon copolymer low or amorphous can use the product that is obtained by modifications such as maleic acid, acrylic acid, carboxylic acid or derivatives thereofs.
Consider that from the viewpoint of film forming the MFR of above-mentioned crystallinity ethylene-alpha-olefin hydrocarbon copolymer low or amorphous is preferably in the scope of 0.5～30g/10 branch (230 ℃ of temperature, load 2.16kg), more preferably in the scope that 1～20g/10 divides.
The cooperation ratio of ethylene-based polymer, petroleum resin and the crystallinity ethylene-alpha-olefin hydrocarbon copolymer low or amorphous that (C) of the present invention layer is used is: ethylene-alpha-olefin hydrocarbon random copolymers 10～50 weight % that ethylene-based polymer 30～70 weight %, petroleum resin 10～50 weight %, amorphous or crystallinity are low.Wherein, the use level particular importance of petroleum resin.When petroleum resin use level during less than 10 weight %, the poor adhesion of polystyrene sheet material or film, and when printing on heat lamination (C) layer side surface with multilayer film, the poor adhesion of this multilayer film and printing-ink is so will not select for use.And when the petroleum resin use level surpasses 50 weight %, violent to the diffusion on petroleum resin surface, make film stick together, rough sledding such as print roller take place to pollute,, will not select for use for this reason.When the cooperation ratio less than 10 weight % of crystallinity ethylene-alpha-olefin hydrocarbon copolymer low or amorphous, with the poor adhesion of polystyrene sheet material or film; And when surpassing 70 weight %, the poor adhesion after the heat treatment such as boil, so will not select for use.As for the cooperation ratio of ethylene-based polymer, poor with the interlaminar strength of (B) layer when less than 30 weight %, therefore, be provided with after the Heat forming under the situation of cover material, when by container peel-off covers material, (C) layer might produce with (B) interlayer and peel off.And when surpassing 70 weight %, with the poor adhesion of polystyrene sheet material or film, so will not select for use.
In the present invention, (A) Ceng thickness is not particularly limited, but considers that from the rigidity and the forming characteristics aspect of multilayer film thickness is 2～30 μ m, preferably in the scope of 3～20 μ m.
In the present invention, (B) Ceng thickness is not particularly limited, but considers that from the rigidity and the forming characteristics aspect of multilayer film thickness is 5～50 μ m, preferably in the scope of 7～30 μ m.
In the present invention, (C) Ceng thickness is not particularly limited, and is 1～20 μ m, preferably in the scope of 2～10 μ m.When the thickness of (C) layer is 1 μ m when above, be of value to the bond strength with the polystyrene sheet material, institute thinks preferably; And when its thickness when 20 μ m are following, film blocking is little, institute thinks preferred.
The gross thickness of polyalkenes hydrocarbon system multilayer film of the present invention is considered from the aspects such as processability of this film, is preferably 10～100 μ m, more preferably in the scope of 15～60 μ m.
In the present invention, (A) layer that constitutes by acrylic polymer, (B) layer that is made of the ethylene-based polymer of the acrylic polymer of 30～70 weight % and 30～70 weight % is by density 0.90～0.97g/cm of 30～70 weight %
3Petroleum resin and the amorphous of 10～50 weight % or (C) layer that the low ethylene-alpha-olefin hydrocarbon random copolymers of crystallinity constitutes of 110～150 ℃ of softening points of ethylene-based polymer, 10～50 weight %, with the order lamination of layer of the layer of (A) layer/(B)/(C), by (A) layer and (C) layer constitute heat lamination of the present invention each superficial layer with multilayer film.Heat lamination of the present invention with multilayer film by heat lamination so that its (C) layer and polystyrene sheet material or film is bonding, thereby given play to the effect that can reach the object of the invention.
As required, in the scope that does not hinder effect of the present invention, also can in heat lamination of the present invention each layer, add additives such as oxidation inhibitor, lubricant, anti blocking agent, antistatic additive, antidim compound with multilayer film.
In addition, as long as without detriment to plunger bond strength, heat lamination of the present invention with multilayer film also can (A) layer and (B) between the layer or (B) layer and (C) layer between the recovery raw material etc. of the film loss that takes place during by air tight resin such as saponified, the polyvinylchloride of ethylene-vinyl acetate copolymer or forming thin film of setting constitute layer.
The method for making of polyalkenes hydrocarbon system multilayer film of the present invention can be used well-known method.For example can enumerate the co-extrusion modling method of utilizing shunting (feed block) or multi path (multi-manifold), extruding layer platen press etc., wherein preferably use the co-extrusion modling method.The fusion of each layer resin is mixed and is preferably carried out under 180～250 ℃ temperature.
Method more specifically as the co-extrusion modling method has, and for example utilizes the T modulus method to melt extrude resin, but by the roll cooling of temperature adjustment and the method for batching continuously; Or melt extrude by the blown film method, but the gas tank (air chamber) by utilizing temperature adjustment but air-cooling or the water cooling cooling of the tank of utilization temperature adjustment and the method for batching continuously etc.
In addition, heat lamination of the present invention both can not stretch with multilayer film, can implement to stretch in the scope that does not hinder forming characteristics yet.
The purposes of heat lamination of the present invention with multilayer film is not particularly limited, can carry out heat lamination to realize heat lamination bonding with (C) layer of multilayer film and polystyrene sheet material or film, use (C) the layer side lamination polystyrene sheet material or the film of multilayer film then in heat lamination, thereby form layered product; Or with warm-up mill heating, pressing, realize bonding with the intensity of abundance.In addition, as required, can be in heat lamination with the printing of (C) of multilayer film layer side surface, even there is printing ink the centre, heat lamination of the present invention also can have sufficient bond strength with multilayer film and polystyrene sheet material or film.
In heat lamination of the present invention during with (C) layer side surface printing of multilayer film, as printing ink, the preferred printing-ink that contains acrylic resin that uses is considered in the Thermoadhesive aspect from polystyrene sheet material or film laminating the time.
Being not particularly limited as the printing-ink that contains acrylic resin, can be can be the printing ink that prints on sheet material or the film in the commercial polysterol usually.In addition, also be not particularly limited, can use well-known methods such as intaghlio printing, hectographic printing, aniline printing, thick serigraphy brush, many usually use intaghlio printings for method of printing.
The layered product that heat lamination lamination of the present invention obtains with multilayer film on polystyrene sheet material or film can be made the container of practical physical properties excellent such as resistance to effect of heat, fuel resistance such as anti-boiling property by Heat forming.Even when this layered product boiled heat treatments such as processing when Heat forming or to the container of Heat forming, heat lamination was with also having sufficient bond strength between multilayer film and polystyrene sheet material or the film.Heat forming can be used any method, can enumerate vacuum forming usually, press empty moulding, press empty vacuum forming or hot plate press empty moulding etc. after the heating behind in-mold moldings such as metal die the methods such as method of cooling again.
[embodiment]
In order to be described more specifically the present invention, below enumerate embodiment and comparative example describes, but the present invention and be limited to these embodiment.In addition, the evaluation method of the film that is obtained by following examples and comparative example is carried out according to following method.
1. condition determination
(1)MFR
Measure according to JIS K7210.
(2) crystallinity
Utilize X-ray diffraction method to try to achieve crystallization ratio in the low ethene-α olefine random copolymers of amorphous or crystallinity.
Use the X-ray diffraction device JDX-3500 of society of NEC system, X ray horsepower output 16kw (tube voltage: 40kV, tube current: 400mA), be Cu to electrode, measure under the condition that angle is 2 θ=9～31 degree and measure.Go out peak crystallization by the X-ray diffraction wavy separation that obtains, try to achieve crystallinity by its areal intensity ratio.
Sample adopt in advance 230 ℃ down the fusion back, to be cooled to 20 ℃ thickness with the speed of 10 ℃/minute of cooling rates be the sheet material of 1mm.
(3) measure fusing point with differential scanning calorimetry
Behind the sample of the about 5～6mg of weighing, in the inclosure aluminum pot, use differential scanning calorimetry (Seiko electronics system SSC/5200), in the nitrogen stream of supplying with the 20ml/ component velocity, be warmed up to 230 ℃, under this temperature, kept 10 minutes, then, the speed with 10 ℃/minute of cooling rates is cooled to subzero 10 ℃.Then, the peak temperature of the maximum heat absorption of expression is as fusing point in the endothermic curve that will obtain in the time of will being warmed up to 210 ℃ with the speed of 10 ℃/minute of programming rates.
(4) bond strength
Bond strength is that film has or not and fold takes place, estimates with the lamination strength after film and the polystyrene sheet material heat lamination with the appearance change that the dish material (tray) that obtains after the laminate Heat forming boils when handling during according to heat lamination.
(i) lamination strength
Use roller heated type heat lamination device, in heat lamination at each temperature with 100 ℃, 110 ℃, 120 ℃ of the roll temperatures of 70 ℃ of the roll temperatures of multilayer film side, polystyrene sheet material side, under the condition of heat lamination speed 20m/min, carrying out hot pressing between roll and carries out heat lamination again and make laminate, this laminate is cut to the short volume shape (n=10) of wide 15mm, long 200mm, use the stretching experiment machine, peel off the heat lamination part with speed 300mm/min, peel angle 180 degree, with the aviation value of the peel strength of this moment as the lamination strength under this temperature.
The (ii) generation of the fold during heat lamination
Under the condition of above-mentioned (i), observe the appearance of films made from impact resistance polystyrene (HIPS) heat lamination.
Zero: good
△: fold takes place
*: obvious fold takes place
(iii) boil the appearance change after the processing
Use vacuum to press empty make-up machine (degree of vacuum 70mmHg, pressure reciprocal of duty cycle 3kg/cm
2, 130 ℃ of temperature), the laminate that will make with High Impact Polystyrene (HIPS) (HIPS) heat lamination is shaped to dish material (long 200mm, wide 250mm, high 30mm).
Dish material after the Heat forming was flooded 30 minutes in 80 ℃ hot water, use hot water treatment.Observe the state of peeling off of appearance change, film.
Zero: good
△: have mist to a certain degree white
*: there is the white and film of mist to peel off
2. use raw material
Raw material 1: propylene list polymers
MFR (230 ℃, 2.16kg)=8.0g/10 branch
Fusing point with the differential calorimeter measurement: 162 ℃
Raw material 2: propylene-ethylene random copolymers
MFR (230 ℃, 2.16kg)=7.5g/10 branch
Ethylene contents: 0.4 weight %
Fusing point with the differential calorimeter measurement: 156 ℃
Raw material 3: propylene-ethylene-1-butene random copolymer
MFR (230 ℃, 2.16kg)=6.5g/10 branch
Ethylene contents: 3.8 weight %, 1-butene content: 3.0 weight %
Fusing point with the differential calorimeter measurement: 128 ℃
Raw material 4: propylene-ethylene-1-butene random copolymer
MFR (230 ℃, 2.16kg)=7.0g/10 branch
Ethylene contents: 2.3 weight %, 1-butene content: 1.3 weight %
Fusing point with the differential calorimeter measurement: 138 ℃
Raw material 5: straight-chain low density polyethylene (ethene-butene-1 copolymer)
1-butene content: 11.3 weight %
MFR (190 ℃, 2.16kg)=2.0g/10 branch
Density: 0.919g/cm
3
Fusing point with the differential calorimeter measurement: 106 ℃
Raw material 6: straight-chain low density polyethylene (ethene-1-hexene copolymer)
1-hexene amount: 12.4 weight %
MFR (190 ℃, 2.16kg)=2.0g/10 branch
Density: 0.912g/cm
3
Fusing point with the differential calorimeter measurement: 106 ℃
Raw material 7: low density polyethylene (LDPE) (ethylene single-polymer of making by high-pressure process)
MFR (190 ℃, 2.16kg)=5.0g/10 branch
Density: 0.924g/cm
3
Raw material 8: alicyclic ring family hydrogenated petroleum resin
140 ℃ of the waste river chemistry of trade name Alcon P140 (strain) system softening points
Raw material 9: alicyclic ring family hydrogenated petroleum resin
125 ℃ of the waste river chemistry of trade name Alcon P125 (strain) system softening points
Raw material 10: alicyclic ring family hydrogenated petroleum resin
90 ℃ of the waste river chemistry of trade name Alcon P90 (strain) system softening points
Raw material 11: ethylene-propylene copolymer
Ethylene contents: 24 weight %
MFR (230 ℃, 2.16kg)=7.2g/10 branch
Density: 0.880g/cm
3
Crystallinity: 10%
Raw material 12: ethylene-propylene copolymer
MFR (230 ℃, 2.16kg)=2.0g/10 branch
Ethylene contents: 25 weight %
Density: 0.860kg/cm
3
Crystallinity: 3%
Raw material 13: ethene-butene-1 copolymer
MFR (230 ℃, 2.16kg)=7.0g/10 branch
1-butene content: 15 weight %
Density: 0.880g/cm
3
Crystallinity: 12%
Raw material 14: ethylene-vinyl acetate copolymer
MFR (190 ℃, 2.16kg)=5.0g/10 branch
Vinyl acetate content: 16 weight %
Fusing point with the differential calorimeter measurement: 87 ℃
Embodiment 1
As shown in table 1, use raw material 1 as (A) layer, will be in puddle mixer as (B) layer be the mixed material that the raw material 5 of the raw material 3 of 55 weight % and 45 weight % mixes by ratio, and in puddle mixer, will be the raw material 6 of 45 weight % as the ratio of (C) layer, the mixed material that the raw material 9 of 35 weight % and the raw material 12 of 20 weight % mix, with (A) layer raw material and (C) layer mixed material directly be in the extruder of 50mm Φ at screw rod, (B) Ceng mixed material directly is in the extruder of 75mm Φ at screw rod, carrying out fusion respectively under 220 ℃ mixes, utilize shunting (feed block) to carry out coextrusion with the formation of (A)/(B)/(C) by the T mould, cool off being adjusted on 25 ℃ the metallic roll, obtaining (A) layer thickness is 5 μ m, (B) layer thickness is 15 μ m, (C) layer thickness is three kind of three heat lamination multilayer film of 5 μ m.
Each polystyrene sheet material heat lamination with (C) aspect of the multilayer film that obtains and polystyrene foamed (PSP, thickness 2.6mm), impact resistance polystyrene (HIPS, thickness 0.3mm), transparent HIPS (Asaflex, 0.6mm) obtains laminate.And the laminate that obtains is thermoformed into the dish material.
The evaluation result of table 2 resulting laminate of expression and container.
Embodiment 2～8, comparative example 1～6
The kind of the raw material that uses except that represented (A) of table 1 layer, (B) layer, (C) layer and cooperating the thickness difference of ratio, each layer is carried out operation similarly to Example 1.The evaluation result of table 2 resulting laminate of expression and container.
Embodiment 9
On (C) layer side surface of the heat lamination that obtains by embodiment 1 with multilayer film, carry out intaghlio printing with the printing ink that contains acrylic resin (trade name Steprint T is red, Osaka printing ink make (strain) system), its printing surface and polystyrene foamed (PSP, thickness 2.6mm), impact resistance polystyrene (HIPS, thickness 0.3mm) wait each polystyrene sheet material to carry out heat lamination, obtain layered product.And the layered product that obtains is thermoformed into the dish material.
The evaluation result of table 3 resulting layered product of expression and container.
Embodiment 10
Except that using the heat lamination that is obtained by embodiment 2 with the multilayer film, other is the same with embodiment 9, obtains layered product and container.
The evaluation result of table 3 resulting layered product of expression and container.
Embodiment 11
Except that using the heat lamination that is obtained by embodiment 4 with the multilayer film, other is the same with embodiment 9, obtains layered product and container.
The evaluation result of table 3 resulting layered product of expression and container.
Embodiment 12
Except that using the heat lamination that is obtained by embodiment 8 with the multilayer film, other is the same with embodiment 9, obtains layered product and container.
The evaluation result of table 3 resulting layered product of expression and container.
Comparative example 7
Except that using the heat lamination that is obtained by comparative example 1 with the multilayer film, other is the same with embodiment 9, obtains layered product and container.
The evaluation result of table 3 resulting layered product of expression and container.
Comparative example 8
Except that using the heat lamination that is obtained by comparative example 2 with the multilayer film, other is the same with embodiment 9, obtains layered product and container.
The evaluation result of table 3 resulting layered product of expression and container.
Comparative example 9
Except that using the heat lamination that is obtained by comparative example 5 with the multilayer film, other is the same with embodiment 9, obtains layered product and container.
The evaluation result of table 3 resulting layered product of expression and container.
Comparative example 10
Except that using raw material 1 as (A) layer, (B) layer with (C) the layer, other and the embodiment 1 the same heat lamination multilayer film that obtains.And except that using the heat lamination that obtains with the multilayer film, other is the same with embodiment 9, obtains layered product and container.
The evaluation result of table 3 resulting layered product of expression and container.
Table 1
| Be that each layer cooperates weight % in the used resin of each layer () | Bed thickness (μ m) | ||||||||
| ???(A) | ???????????????(B) | ?????????????????????????(C) | ???(A) | ???(B) | ???(C) | ||||
| Polyethylene-based resin | Polypropylene-based resin | Polyethylene-based resin | Polyethylene-based resin | Petroleum resin | Ethene-α olefine copolymer | ||||
| Embodiment 1 | ????1 | ????3????(55) | ????5????(45) | ????6????(45) | ????8????(35) | ????11????(20) | ????5 | ????15 | ????5 |
| Embodiment 2 | ????1 | ????3????(55) | ????5????(45) | ????6????(40) | ????8????(30) | ????11????(30) | ????5 | ????15 | ????5 |
| Embodiment 3 | ????1 | ????3????(40) | ????5????(60) | ????6????(45) | ????8????(35) | ????11????(20) | ????5 | ????15 | ????5 |
| Embodiment 4 | ????2 | ????3????(55) | ????5????(45) | ????6????(35) | ????8????(25) | ????12????(40) | ????5 | ????15 | ????5 |
| Embodiment 5 | ????1 | ????4????(60) | ????6????(40) | ????6????(45) | ????8????(25) | ????12????(30) | ????5 | ????15 | ????5 |
| Embodiment 6 | ????1 | ????4????(60) | ????6????(40) | ????7????(45) | ????9????(35) | ????12????(20) | ????5 | ????15 | ????5 |
| Embodiment 7 | ????1 | ????3????(55) | ????5????(45) | ????6????(45) | ????8????(35) | ????13????(20) | ????5 | ????17 | ????3 |
| Embodiment 8 | ????1 | ????3????(55) | ????5????(45) | ????6????(55) | ????8????(25) | ????11????(20) | ????8 | ????24 | ????8 |
| Comparative example 1 | ????1 | ????3????(85) | ????5????(15) | ????6????(45) | ????8????(35) | ????11????(20) | ????5 | ????15 | ????5 |
| Comparative example 2 | ????1 | ????3????(15) | ????5????(85) | ????6????(45) | ????8????(35) | ????11????(20) | ????5 | ????15 | ????5 |
| Comparative example 3 | ????1 | ????3????(55) | ????5????(45) | ????6????(75) | ????8????(25) | ????-?????(0) | ????5 | ????15 | ????5 |
| Comparative example 4 | ????3 | ????3????(50) | ????5????(50) | ????5????(40) | ????10???(30) | ????11????(30) | ????5 | ????15 | ????5 |
| Comparative example 5 | ????1 | ????3????(45) | ????5????(55) | ????6????(55) | ????8????(5) | ????11????(40) | ????5 | ????15 | ????5 |
| Comparative example 6 | ????1 | ????3????(55) | ????5????(45) | ????14???(80) | ????9????(20) | ????-?????(0) | ????5 | ????15 | ????5 |
Table 2
| Lamination strength (N/15mm) | The generation of film fold | Anti-boiling property | |||||||||
| ????????????????PSP | ????????????????HIPS | Transparent HIPS | |||||||||
| ????110 | ????120 | ????130 | ????110 | ????120 | ????130 | ????110 | ????120 | ????130 | |||
| Embodiment 1 | ????5.4 | ????5.5 | ????6.1 | ????10.3 | ????10.5 | ????11.5 | ????5.2 | ????7.4 | ????7.4 | ????○ | ????○ |
| Embodiment 2 | ????5.1 | ????5.3 | ????5.8 | ????8.8 | ????9.5 | ????9.8 | ????5.1 | ????7.4 | ????7.2 | ????○ | ????○ |
| Embodiment 3 | ????5.5 | ????5.5 | ????6.2 | ????9.8 | ????10.4 | ????11.1 | ????5.5 | ????7.8 | ????7.9 | ????○ | ????○ |
| Embodiment 4 | ????5.6 | ????5.3 | ????5.8 | ????7.8 | ????9.7 | ????9.6 | ????6.5 | ????8.3 | ????8.7 | ????○ | ????○ |
| Embodiment 5 | ????5.1 | ????5.3 | ????5.5 | ????8.5 | ????8.9 | ????9.3 | ????5.1 | ????7.1 | ????7.3 | ????○ | ????○ |
| Embodiment 6 | ????5.0 | ????5.1 | ????5.6 | ????7.1 | ????7.3 | ????7.8 | ????5.0 | ????6.5 | ????6.8 | ????○ | ????○ |
| Embodiment 7 | ????5.1 | ????5.5 | ????6.2 | ????10.5 | ????10.3 | ????10.8 | ????5.3 | ????7.7 | ????7.5 | ????○ | ????○ |
| Embodiment 8 | ????5.7 | ????6.1 | ????7.3 | ????11.5 | ????12.3 | ????13.8 | ????6.5 | ????8.4 | ????8.8 | ????○ | ????○ |
| Comparative example 1 | ????4.5 | ????5.4 | ????5.8 | ????6.1 | ????6.4 | ????6.5 | ????4.2 | ????5.9 | ????5.5 | ????○ | ????△ |
| Comparative example 2 | ????5.1 | ????5.3 | ????6.3 | ????9.9 | ????10.8 | ????11.1 | ????5.0 | ????7.3 | ????7.6 | ????△ | ????○ |
| Comparative example 3 | ????2.3 | ????3.3 | ????3.4 | ????4.0 | ????4.8 | ????5.8 | ????0.8 | ????1.4 | ????3.2 | ????○ | ????× |
| Comparative example 4 | ????5.3 | ????6.4 | ????7.1 | ????10.5 | ????10.8 | ????11.9 | ????5.3 | ????8.1 | ????8.8 | ????× | ????× |
| Comparative example 5 | ????1.5 | ????1.9 | ????2.2 | ????2.8 | ????3.4 | ????4.4 | ????0.3 | ????1.1 | ????1.8 | ????○ | ????× |
| Comparative example 6 | ????4.1 | ????4.8 | ????5.4 | ????4.5 | ????5.3 | ????6.3 | ????2.5 | ????3.5 | ????3.8 | ????○ | ????× |
Table 3
| Lamination strength (N/15mm) | The generation of film fold | Anti-boiling property | ||||||
| ????????????????PSP | ????????????????HIPS | |||||||
| ????110 | ????120 | ????130 | ????110 | ????120 | ????130 | |||
| Embodiment 9 | ????5.0 | ????5.2 | ????5.7 | ????6.2 | ????6.4 | ????6.6 | ????○ | ????○ |
| Embodiment 10 | ????4.8 | ????5.1 | ????5.5 | ????5.9 | ????6.2 | ????6.4 | ????○ | ????○ |
| Embodiment 11 | ????5.0 | ????5.2 | ????5.6 | ????6.2 | ????6.4 | ????6.5 | ????○ | ????○ |
| Embodiment 12 | ????5.6 | ????6.0 | ????7.2 | ????6.8 | ????7.0 | ????7.3 | ????○ | ????○ |
| Comparative example 7 | ????3.5 | ????3.8 | ????4.0 | ????3.6 | ????3.9 | ????4.2 | ????○ | ????△ |
| Comparative example 8 | ????4.0 | ????4.3 | ????4.5 | ????4.5 | ????4.7 | ????4.9 | ????△ | ????○ |
| Comparative example 9 | ????0.7 | ????1.2 | ????1.6 | ????0.9 | ????1.4 | ????1.7 | ????○ | ????× |
| Comparative example 10 | ????＜0.1 | ????＜0.1 | ????＜0.1 | ????＜0.1 | ????＜0.1 | ????＜0.1 | ????○ | ????- |
Claims (4)
1. a heat lamination multilayer film is characterized in that, by following (A) layer, (B) layer, this three layers of formations of (C) layer, and with the order lamination of layer of the layer of (A) layer/(B)/(C), (A) layer and (C) layer constitute superficial layer respectively,
(A) layer for constituting by acrylic polymer;
(B) layer that constitutes for ethylene-based polymer by the acrylic polymer of 30～70 weight % and 30～70 weight %;
(C) by density 0.90～0.97g/cm of 30～70%
3The layer that constitutes of ethene-α olefine random copolymers armorphous or that crystallinity is low of petroleum resin, 10～50 weight % of 110～150 ℃ of softening points of ethylene-based polymer, 10～50 weight %.
2. heat lamination multilayer film as claimed in claim 1 is characterized in that, at (C) layer side surface of this heat lamination with multilayer film, lamination has the printing-ink that contains acrylic resin.
Claim 1 or 2 described heat lamination with (C) layer side of multilayer film on lamination polystyrene sheet material or film and the layered product that forms.
4. the thermoformed containers that constitutes by the described layered product of claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002335959 | 2002-11-20 | ||
| JP2002335959A JP3999108B2 (en) | 2002-11-20 | 2002-11-20 | Multi-layer film for thermal lamination, laminated sheet and thermoformed container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1502466A true CN1502466A (en) | 2004-06-09 |
| CN100408324C CN100408324C (en) | 2008-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200310113673XA Expired - Fee Related CN100408324C (en) | 2002-11-20 | 2003-11-19 | Multilayer film for thermal-lamination, laminated body and thermal-moulding container |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3999108B2 (en) |
| KR (1) | KR100634739B1 (en) |
| CN (1) | CN100408324C (en) |
| TW (1) | TWI255228B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106255595A (en) * | 2014-04-28 | 2016-12-21 | 三得为株式会社 | Multi-layer sealed film |
| CN109415159A (en) * | 2016-07-04 | 2019-03-01 | 雀巢产品技术援助有限公司 | It is used to prepare the container and its capsule of drink capsule |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8765872B2 (en) | 2008-07-10 | 2014-07-01 | Mitsui Chemicals, Inc. | 4-methyl-1-pentene polymer, resin composition containing 4-methyl-1-pentene polymer, masterbatch thereof, and formed product thereof |
| TWI472537B (en) * | 2008-07-10 | 2015-02-11 | Mitsui Chemicals Inc | 4-methyl-1-pentene-based polymer and a resin composition containing 4-methyl-1-pentene-based polymer and its masterbatch and the molded product |
| KR102311420B1 (en) | 2013-12-31 | 2021-10-13 | 다우 글로벌 테크놀로지스 엘엘씨 | Multilayered films, methods of manufacture thereof and articles comprising the same |
| US20150231862A1 (en) | 2014-02-19 | 2015-08-20 | Dow Global Technologies Llc | Multilayered polyolefin films, methods of manufacture thereof and articles comprising the same |
| WO2015123827A1 (en) * | 2014-02-19 | 2015-08-27 | Dow Global Technologies Llc | High performance sealable co-extruded oriented film, methods of manufacture thereof and articles comprising the same |
| TW202222587A (en) * | 2020-11-19 | 2022-06-16 | 日商東洋紡股份有限公司 | Polyolefin resin film and mulilayer body using same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01113241A (en) * | 1987-10-27 | 1989-05-01 | Dainippon Ink & Chem Inc | Multilayer sheet for light-weight container |
| KR100312673B1 (en) * | 1998-09-28 | 2001-11-03 | 나카무라 하사오 | Multilayered film |
-
2002
- 2002-11-20 JP JP2002335959A patent/JP3999108B2/en not_active Expired - Fee Related
-
2003
- 2003-11-18 TW TW092132320A patent/TWI255228B/en not_active IP Right Cessation
- 2003-11-19 CN CNB200310113673XA patent/CN100408324C/en not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106255595A (en) * | 2014-04-28 | 2016-12-21 | 三得为株式会社 | Multi-layer sealed film |
| CN109415159A (en) * | 2016-07-04 | 2019-03-01 | 雀巢产品技术援助有限公司 | It is used to prepare the container and its capsule of drink capsule |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200422186A (en) | 2004-11-01 |
| JP2004167823A (en) | 2004-06-17 |
| KR20040044173A (en) | 2004-05-27 |
| KR100634739B1 (en) | 2006-10-16 |
| TWI255228B (en) | 2006-05-21 |
| JP3999108B2 (en) | 2007-10-31 |
| CN100408324C (en) | 2008-08-06 |
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