WO1991005004A1 - Film de polyethylene a orientation biaxiale - Google Patents
Film de polyethylene a orientation biaxiale Download PDFInfo
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- WO1991005004A1 WO1991005004A1 PCT/JP1990/001307 JP9001307W WO9105004A1 WO 1991005004 A1 WO1991005004 A1 WO 1991005004A1 JP 9001307 W JP9001307 W JP 9001307W WO 9105004 A1 WO9105004 A1 WO 9105004A1
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- film
- polyethylene
- weight
- stretching
- temperature
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
- B32B37/085—Quenching
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/0625—LLDPE, i.e. linear low density polyethylene
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
- B32B2038/0028—Stretching, elongating
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- 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
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/046—LDPE, i.e. low density polyethylene
-
- 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
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
Definitions
- TECHNICAL FIELD The present invention relates to a packaging material, and more specifically, a polyethylene-based packaging film having a small thickness unevenness, which produces a specific ethylene-based copolymer, stretchability oriented under specific conditions, and shrinking.
- TECHNICAL FIELD The present invention relates to a monolayer or multilayer biaxially stretched biaxially stretched film having excellent properties and deformation recovery properties, and a method for producing the same. Background art
- plasticized polyvinyl chloride have been used as heat-shrinkable films because of their excellent properties in transparency and self-adhesion. Since plasticizers are used, the amount of water vapor permeation increases and loss or deterioration of the packaged product is likely to occur, the plasticizer easily migrates to the packaged product and becomes contaminated. Has problems of safety and health and pollution, such as the generation of harmful hydrogen chloride gas when the film is blown during the packaging work, and also when the waste is incinerated.
- films that can be used in place of plasticized polyvinyl chloride are made of ethylene-based resins such as polyethylene, ethylene-vinyl acetate copolymer, etc. Actively performed with polybutadiene resin and the like.
- the film obtained by the present invention improved the stability of the stretched tube and the uniformity of stretching, and also exhibited the effect of reducing unevenness in thickness.
- the unevenness in thickness was further reduced from the viewpoint of suitability for packaging machine and printability. Things were desired.
- films obtained from the above-mentioned polyethylene resin or polybutadiene resin have no problems of safety and health and pollution, they are not yet satisfactory as stretch films.
- stretch films For example, when stretching unstretched low-density polyethylene film as stretch packaging, only a certain part of the film is stretched, causing a so-called necking phenomenon in which extreme unevenness in thickness occurs.The elastic recovery rate is also small, resulting in a beautiful packaging finish. Absent.
- the film strength is low and the transparency is not sufficient.
- a film obtained by adding an anti-fogging agent and an adhesive to these materials is commercially available as stretch film.
- the manufacturing method is based on the one-die method or the inflation method, and does not exhibit heat shrinkage.
- the film is weak and easily breaks at corners of the tray, etc. Not reached.
- one type of packaging film can be used for stretch packaging and shrink packaging so that it is not necessary to change the packaging film even if the material to be packaged changes. Things are strongly desired.
- tray packaging using automatic stretch packaging machines, automatic shrink packaging machines, etc. has been performed at the production area, and the packaged products have been packed and packed in corrugated boxes, etc., and sent to convenience stores and supermarkets.
- Increasing cases of unpacking, display, and sale in markets, etc. are increasing, but due to the stacking load during transportation, the film on the tray surface loses its tension or becomes wrinkled, making it unattractive. In fact, they are repackaged at backyards such as convenience stores and supermarkets. Therefore, there is a demand for a packaging material that does not lose the film tension on the tray surface even when transported in a stacked state or the like. Disclosure of the invention
- the present invention overcomes the drawbacks of the stretch film described above, and is excellent in transparency, gloss, tear strength, and low heat resistance, has a suitable gas permeability, has low water vapor permeability, and has a low water vapor permeability.
- a biaxially stretched film with small thickness unevenness using a polyethylene-based resin with no loss, no plasticizer migration and no hydrogen chloride gas during combustion, and also has heat shrinkage and stretchability, and a hot plate Allows for heat sealing, The seal part does not come off even if it adheres, the shrink wrapping finish is good, and the film after shrink wrapping has a good return even if it is locally stretched, so we studied diligently to provide a film that does not need to be repackaged.
- a single-layer biaxially stretched film obtained by stretching an unstretched film mainly composed of a composition containing a specific linear low-density polyethylene as a main component under known conditions, and a layer of the same main component as an intermediate layer The inventors have found that a film obtained by stretching and orienting the unstretched multilayer film under the low tensile strength conditions can be suitable for the purpose, and have completed the present invention.
- a biaxially stretched borylene-based film comprising the following linear low-density polyethylene as the main component (A). (Hereinafter referred to as (1) biaxially stretched film
- a biaxially stretched polyethylene film comprising a composition comprising, as a main component, 0.5 to 3.0 parts by weight of the surfactant composition D). (Hereinafter referred to as “(2) Stretch shrink film”)
- the intermediate layer is composed of a composition containing the following linear low-density polyethylene as the main component, and the innermost layer and the outermost layer are the following ethylene- ⁇ -olefin copolymer of the following (II): 20 to 60% by weight.
- a biaxially stretched polyethylene film having an intermediate layer having a thickness of at least 60% of the total thickness, and an innermost layer and an outermost layer each having a thickness of at least 1 fim. (Hereafter referred to as (3) multilayer stretch shrink film.)
- the density is 0.870 to 0.930 gZ cm 3
- the melt flow index is 0.1 to 10 gZ 10 minutes
- the differential scanning calorimeter In the melting point measurement, the melting curve obtained when holding at 190 ° C for 30 minutes, decreasing the temperature to 100 ° C at a rate of 100 minutes, and then increasing the rate at a rate of 10 minutes (hereinafter the melting curve after quenching)
- the main peak temperature (Tma) of each of them is 118 ⁇ 5 C. Also, after holding for 30 minutes at 1-9, lowering speed to 20 at 10 / min.
- the temperature difference between Tmb and Tma should be 3 or more when the main beak temperature of the melting curve (hereinafter referred to as ⁇ cooling curve after cooling) obtained when the heating speed is increased at 10 / min is Tmbi: Linear low-density polyethylene (hereinafter referred to as quenched melting-point-decreased polyethylene)
- composition comprising one or more selected ones. (Hereafter referred to as a surfactant composition.)
- the DSC measurement method described above is performed in a nitrogen gas stream with 8 to 1 Omg of the sample sealed in an aluminum van. '
- the melting point-reducing polyethylene is, for example, ethylene, brovirene, butene-1, hexene-1, 4-methylpentene; I, octin-1, decene1-1, dodecene1-1, having 3 to 20 carbon atoms, preferably Carbon number ⁇ 3 ⁇ 12
- the copolymer can be selected from one or more copolymers of one or more ⁇ -olefins. More specifically, for example, at least 50% by weight or more of ethylene and two ⁇ -olefins are mainly used.
- copolymers of ethylene and réelle-1 are particularly preferred; terpolymers of ethylene and 4-methylbenthine-11; terpolymers of butene-11; ethylene and octene1-1; The terpolymer of the above is more preferable.
- Tnm ⁇ 5 with respect to the total endothermic area in the melting curve after quenching. If the ratio of the endothermic area in the CO range is 15% or more, the stability during stretching is particularly excellent.
- One or more of the above-mentioned (A) quenching-melting-point-lowering polyethylene may be used alone or in combination.
- Two or more of the above-mentioned resins may be used as a main component as long as they do not interfere with the object of the present invention.
- Polyolefin resins such as polyethylene, ethylene-vinyl acetate copolymer, ionomer and ethylene-propylene copolymer can be mixed and used.
- a polyethylene having a density of 0.890 to 0.930 gZ cm 3 is used as the quenching melting point-decreased polyethylene.
- the resin has a melt flow index of 0.990 to 0.920 g cm 3 .
- 0.1 to 10 gZ 10 min is used, but preferably 0.3 to 5% / 10 min.
- Stress Tutsi resistance when density is less than 0. 890 gcm 3 hot plate sheet Lumpur in automatic packaging machines too large-strength is small becomes heat shrinkable is good film for low-temperature heat sealability In this case, there is a drawback that shrinkage occurs and the finish at the bottom of the tray deteriorates.
- the density exceeds 0.930 gZcm 3
- the stretch property is reduced and the heat seal property is also reduced, and the film aimed at by the present invention cannot be obtained.
- the melt index is less than 0.1 gZIO
- the workability and the stretchability are unfavorably reduced
- it exceeds 10 g / 10 minutes it is not preferable because the stretching processability is deteriorated.
- the above Tmb-Tma of less than 3 ° C is a low melting point polyethylene-based copolymer and a surfactant composition.
- (A) quenched-melting-lowering polyethylenes are used as main components, but can contain other ethylene copolymers in the range of 20% by weight or less.
- Examples of such an ethylene copolymer to be added include a general-purpose linear low-density polyethylene resin, a low-melting-point ethylene- ⁇ -olefin copolymer copolymer described later, a high-pressure polyethylene, a copolymer of ethylene and polylobirylene, Examples include ionomers, ethylene-vinyl acrylate copolymers, and copolymers of ethylene and (meth) acrylic acid.
- the stretching stability at the time of stretching at low tensile strength which is a feature of the present invention, becomes insufficient, and the object of the present invention can be achieved. Absent.
- the ( ⁇ ) low-melting polyethylene copolymer is, for example, ethylene and propylene,directed-1, pentin-11, hexene1-1, 4-methylpentene-11, octin-11, decene1-1, or a mixture thereof. And particularly selected from copolymers of ethylene and butyne-11 are preferably used. Density effect of improving Tei ⁇ heat-sealing property of less than 0. 8 7 0 g / cm 3 in size Kunar, is likely to occur Bed King be added a surfactant composition film, roll film ⁇ Poor. In addition, there is a drawback that the sliding property of the automatic packaging machine is poor.
- Those having a density exceeding 0.90 g Z cm 3 are not preferred because the effect of improving the low-sealing property is reduced. Further, those having a melt flow index of less than 0.110 minutes are not preferred because of a reduction in workability and a decrease in storage properties, similarly to the case of linear low-density polyethylene. Melt flow index 2 0 g Z 1 0 minute which exceeds the Ru problem point there ⁇ stability of the stretched tube is deteriorated.
- the amount of the low-melting polyethylene copolymer added is 10 to 40% by weight, and if it is less than 10% by weight, the low heat sealability is not improved.
- the stretchability is slightly reduced, and when the content exceeds 40% by weight, the low-temperature heat sealability is excellent.
- a surfactant composition described later is added, the roll is unrolled from the film roll. ⁇ It is not possible to obtain the performance that simultaneously satisfies the releasability, the slipperiness in the automatic packaging machine, and the adhesiveness between films. It is preferably in the range of 20 to 35% by weight.
- the blending ratio of the low-melting polyethylene copolymer of (B) is 20 to 60% by weight, and is less than 20% by weight.
- the low-temperature sealability is poor, and the hot-plate sealability at the bottom of the tray in automatic packaging is poor.
- the film has particularly poor foldability.
- the amount exceeds 60 parts by weight the low-temperature heat sealability and the stretchability are good, but even when a surfactant composition described later is added, the roll releasability at the time of being unwound from the film roll, and automatic packaging. It is not possible to obtain the performance that simultaneously satisfies the slipperiness on the machine and the adhesiveness between the films.
- Examples of the general-purpose linear low-density polyethylene (C) include ethylene and propylene, butene-11, hexene1-1,4-methylpentene1-1, octene1-1, decene1-1, and dodecene1-1. And copolymers of one or more ⁇ -olefins having 3 to 20, preferably 4 to 8 carbon atoms.
- surfactant composition (D) examples include glycerin fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, polyethylene glycol fatty acid esters, alkyldiethanolamides, polyoxyethylene alkylamines, and boroxyethylene alkyl ethers.
- One or more nonionic surfactants are used in combination.
- Surfactant compositions in addition to imparting anti-fogging properties, combine It is necessary to be within the above range of the addition amount in order to cope with the peelability from the roll of the roll, the slipperiness in the automatic packaging machine, the same adhesiveness as the film, and the heat sealing property.
- polyglycerin fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, and alkyldiethanolamide are more preferable as surface active agents.
- components used in the above surfactant composition include daliserine monolaurate, glycerin monostearate, guhiserin monoolate, diglycerin monolaurate, diglycerol mosostearate, diglycerin monoolate, Sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, polyoxyethylene glycerin monolaurate, boroxixylene glycerin monostearate, boroxoxyethylene glycerin monooleate, polyethylene glycol mono Lauray h; s Polyethylene glycol monopalmitate, polyethylene glycol monotearate, polyethylene glycol monoolate, polyethylene glycol glycolate, polyethylene glycol triolate, lau Lujetanolamide ', Stearyl Jetanolamide, Oleyl Diethanolamide, Polyoxyethylene Lauryl Amine, Polyoxyethylene Stearyl Lamine, Polyoxyethylene Leyl Amine, Polyoxyethylene Lauryl Ether, Polyoxyethylene Lauryl
- the amount of the surfactant ('D) in the innermost and outermost layers of the stretch shrink film of (2) and the multi-layer stretch shrink film of (3) is less than 0.5 parts by weight, the anti-violence property is not sufficient. Sufficient, Tangdo Slippery in packing machine is poor, film wrapping in tray wrapping is good.Packing finish at the bottom of tray is poor. Slippery in machine and film foldability in tray packaging are good, but heat sealability is reduced and film seal at bottom is not good. It is not preferable because it becomes good.
- additives such as a lubricant, an anti-blocking agent, and an antistatic agent can be appropriately used for the purpose of providing their effective effects.
- the thickness of the intermediate layer relative to all the layers is less than 60%, the stability of the bubble at the time of stretching deteriorates.
- the thickness of each outer layer is less than 1 im, the low-temperature heat sealing property cannot be exhibited, and neither of them can achieve the purpose of the present invention.
- the thickness of each layer is limited, that is, the thickness of the intermediate layer is 60% or more of the total, and the thickness of the innermost and outermost layers after stretching is 1 / m or more.
- one or two or more polyethylene resin layers may be interposed between the intermediate layer and the innermost or outermost layer.
- Polyethylene resins that can form such a layer include, for example, a general-purpose linear low-density polyethylene, a low-melting-point ethylene-alpha-olefin copolymer described later, a high-pressure polyethylene, a combination of ethylene and polylobirylene.
- each layer of the biaxially stretched film of (1), the stretch shrink film of (2), and the multilayer stretch link film of (3) has lubricating material, anti-blocking agent, Additives such as an inhibitor and an anti-fogging agent can be appropriately used for the purpose of providing their effective effects.
- the resin is heated and melted in accordance with the film constitution and the layer constitution. , Kneaded, extruded into a single layer or multilayer structure, quenched and solidified to obtain an unstretched and stretched film, (1) under known conditions, and (2) and (3) stretched films.
- Time tensile strength Can be obtained by stretching the film under the condition that is 70 k / cn.
- tubular film formation and stretching will be described as an example, and will be specifically described.
- the resin corresponding to the composition of each film is heated and melted by extrusion as in the conventional method. Extruded into a tube, quenched and solidified to obtain an unstretched film.
- the resin composition in the above-mentioned specific range is heated and melted by three extruders corresponding to each layer and kneaded to form a tube from a three-layer annular die. It is rapidly cooled and solidified without being extruded and stretched to obtain an unstretched film.
- the obtained tubular unstretched film is tubular stretched as shown in FIG. Apply the gas pressure inside the tube at a temperature lower than the melting point of the resin, eg, below the melting point of the resin.
- the stretching ratio may not necessarily be the same in the vertical and horizontal directions, but in order to obtain physical properties such as excellent strength and shrinkage ratio, it is more than 2 times, preferably more than 2.5 times in both directions in the vertical and horizontal directions. It is preferable that the film is stretched three times or more.
- the unstretched film obtained as described above is supplied to, for example, a tubular stretching machine as shown in FIG. Angle range at which orientation occurs
- (1) shall be the ⁇ melting point below 1 5 to 35 e C of the film surface temperature in the expansion ⁇ point main raw material resin (main raw material resin of the middle Q layer in the case of multilayer>.
- the film surface temperature falls by 30 to 50 from the surface angle at the stretching end point within a distance of 1.0 to 1.5 times the vertical distance of the stretching zone. Cool to make sure.
- the tensile strength S is less than 30 kg / cTtf, the stability of the stretched bubble is deteriorated, and the elastic recovery of the obtained film is less than 90%. . If the tensile strength S exceeds 170 kg / cm 2 , the resulting film will have excellent heat shrinkage, etc., but for example, the tensile resistance at 50% elongation will be large, the elongation will be small, and the stretchability will be poor. However, it is not suitable for the present invention, which aims to have both stretch properties and shrink properties.
- the stretching ratio does not have to be the same in the vertical and horizontal directions, it is preferable that the stretching ratio is approximately the same in the vertical and horizontal directions in order to obtain a good balance of physical properties such as strength.
- the stretching ratio is preferably 8 to 25 times in area ratio.
- the rim stretched as described above and taken out from the stretching device can be annealed as needed.
- the axially stretched film (1) is a uniform film having a small thickness unevenness, and the stretch shrink film (2) and the multilayer stretch film (3).
- the link film has a thickness unevenness of less than 8% and a uniform thickness, a tensile resistance at 50% pulling of 50 OkgZCtt or less, excellent stretchability, and a shrinkage at 90 with an area shrinkage of 20% or more. It has sufficient performance as a film. Furthermore, the elastic recovery rate after one minute after elongating 30% of the film that has been heat shrunk to an area shrinkage of 15% at 90% is 90% or more.
- FIG. 1 is a diagram showing a schematic diagram of a stretching apparatus used in an embodiment of the present invention.
- a and B indicate the length (unit: em) of the ⁇ side after quenching.
- a and B indicate the length (unit: cm) of the ⁇ after cooling.
- Tmax The maximum value (Tmax), the minimum value (Tmin) and the average value (T) were calculated for the chart measured in the circumferential direction of the tube at a full scale of 8 zm using a 6C) and calculated by the following formula.
- Thickness unevenness X 100
- T is the arithmetic mean value of the values read from the chart corresponding to 10 intervals of the measurement film.
- the film is uniformly sagged so that the area shrinkage is 15%, set in a wooden frame, heat-treated in a 9 CTC oven, and removed when the film no longer sags.
- trays with a height of 12 countries are packed without any contents, and under the same conditions as (3): f packaging.
- the film in the center of the tray was pressed with a finger until it hit the tray, released, and after fe was measured, the time required for the 7 films to return to the original state was measured, and the evaluation was performed according to the following criteria.
- each layer of the laminate was read by observing the cross section of the film with a microscope.
- the melting point Tmb of the raw resin is 124, the melting point after quenching Tma is 119, and the endothermic area ratio of the main peak part at Tma ⁇ 5 to the total absorption area in the melting curve after quenching is 22%, which is a linear low.
- the stability during stretching was good, there was no vertical movement of the stretching point or swing of the stretching tube, and no uneven stretching state such as necking was observed.
- the obtained stretched film has a thickness of 20.8; u, thickness unevenness of 5%, and 90.
- the area shrinkage in C was 33%.
- the melting point of the raw material resin was 124.
- the obtained stretched film had an average thickness of 15.3 u, a thickness unevenness of 6%, and an area shrinkage at 90 of 48%.
- a confectionery box having a size of 12 cm, a width of 18 cm and a height of 3 cra was used in the same manner as in Example 1 at a packaging speed of 20 pieces / min, a shrink tunnel temperature of 100 and a shrink tunnel passage time of 3
- a packaging speed of 20 pieces / min a packaging speed of 20 pieces / min
- a shrink tunnel temperature of 100 a shrink tunnel passage time of 3
- Consists of a terpolymer of ethylene and 4-methylpentyceene 1 and puttin-1 as comonomer and has a total degree of branching of 2.1 and 25.
- Degree 0.916 g / cm 3 , Melt index 1.2 gZ 10 min, Melting point Tmb of raw material resin is 124 ° C, Melting point Tma after sudden cooling is 119, Tma ⁇ 5 C for total absorption area in melting curve after quenching a main beak endothermic area ratio of 22% linear low density Boriechiren resin of a two component copolymer of Puchin 1 as ethylene with a comonomer, the degree of branching density 0.920 gZcm 3 in 1.0 25, melt-in deck scan 1.0 g / 10 min, the melting point of the raw resin is 126 e C, the melting point after quenching is 126, and the linear low-density polyethylene resin whose main peak after quenching is not in the range of 118
- Example 2 Was mixed, kneaded, and extruded in the same manner as in Example 1 to obtain an unstretched film. Further, when biaxial stretching was performed in the same manner as in Example 1, there was no vertical movement of the elongation point or swing of the tube, the stability was good, and no uneven stretching state was observed.
- the obtained stretched film had a thickness of 21.22 and a thickness unevenness of 7%.
- the area shrinkage at 90 ° C was 28%. ⁇
- the unstretched film was stretched at a stretching temperature of 100 105 ° C., annealed in the same manner as in Example 1, folded and wound. During stretching, the tube rocked, and necking was observed in the stretched part. The draw temperature is set to 95 1 to improve such unstable situation. 0 0. When it was lowered to C, the necking of the stretched portion became intense, and the unevenness of the stretched film became worse. This time, if the stretching temperature was raised to 105 to 110 in order to suppress necking in ⁇ , the up and down movement and swinging of the stretching tube became severe, and the stability became poor.
- the first condition that is, the stretched film obtained by stretching at a stretching temperature of 100 to 10 had a thickness of 21.3, a thickness unevenness of 16%, 90, and a window shrinkage of 22%. there were.
- This film was inferior in flatness, and was packaged by an automatic shrink wrapping machine under the same conditions as in Example 1; however, the packager S did not proceed smoothly and was not suitable for automatic packaging.
- the tube oscillates greatly, and the necking phenomenon in the stretched portion is remarkable. If the stretching temperature is increased to 108 to 113 to suppress necking, the swing of the stretched tube becomes even worse, 3 ⁇ 4 state, could not be obtained.
- the first condition that is, the stretched film obtained by stretching at a stretching temperature of 103 to 108 mm has a thickness of 15.8 mm, the thickness unevenness is 13%, and the area shrinkage at 90 mm is 24%.
- This film was inferior in flatness, and was wrapped with an automatic shrink wrapping machine under the same conditions as in Example 1.
- the resulting package had shrinkage spots and was not a package having a tight feeling. .
- Example 4 70% by weight of linear low-density polyethylene consisting of a terpolymer of ethylene and comonomer with the properties shown in Table 1 and 4-methylpentene 1-1 and putene 1-1, also having the properties shown in Table 1.
- a composition comprising 30% by weight of a low-melting point polyethylene copolymer having a melting point of 74.1, and a surfactant set comprising poly (ethylene glycol oleate), oleyl jetanolamine and sorbitan trioleate.
- the composition containing 1.0 part by weight of the product was melt-kneaded at 170 to 240 mm and extruded downward from the slit of an annular die held at 240 mm.
- the slit diameter of the annular die was 75, and the slit gap was 0.8 mm.
- the extruded molten tuple-like film is mounted directly under the die.
- the outer diameter of the cylindrical mandrel that circulates 20 cooling water with an outer diameter of 66 strokes is passed through the water tank while sliding on the outer surface. And then cooled in a room to obtain a tubular unstretched film having a diameter of about 65 and a thickness of 240 / ⁇ .
- the unstretched tubular film was used as a raw material and led to a tubular uniaxial stretching apparatus A shown in FIG. 1 for expansion and stretching.
- the voltage and current of the annular infrared heater of preheater 4 were adjusted, and the film temperature at the preheater outlet was adjusted.
- the eight annular infrared heaters of the main heater 5 are divided by! To adjust the respective voltage and current to heat the film, and to supply air that flows along the tube from below the main heater and has a low speed.
- Pressurized air is sent to the tubular film between the nibble roll 2 and the high-speed nip roll 3, and depending on the air pressure and the peripheral speed ratio of the low-speed and high-speed nip rolls, the height is 5.0 times and the model is 4.0 times (area stretching ratio is 20 times).
- the air pressure (tube inner pressure) of the extending Shinji preheater and the voltage of the annular infrared heater main heat sink as tensile strength is 7 O kg / cn 2, the current, and further the amount of cooling Eyaringu 6, the temperature of the air Adjusted by
- the stability during stretching was good, there was no vertical movement of the stretching point or swing of the stretching tube, and no uneven stretching state such as necking was observed.
- Table 1 the obtained stretched film was excellent in transparency, stretchability and heat shrinkability.
- Table 1 summarizes the raw material formulation, stretching conditions, properties of the film after stretching, and the results of each test.
- Example 4 As shown in Table 1, in place of the linear low-density polyethylene used in Example 4, a linear low-density polyethylene consisting of a copolymer of ethylene and comonomer was used as a comonomer. Stretched films were prepared by almost the same ⁇ method.
- linear low-density polyethylene was used.
- the main beak temperature Tma of the melting curve after quenching was 12.6, and there was no melting point in the range of 11.8 ⁇ 5 50, and
- a linear low-density polyethylene having a temperature difference T mb -T ma of 0 between the melting curve after cooling and the main beak temperature T inb was used: /
- the stability during stretching was low, and the stretched purple rocked greatly, and repeatedly contacted the infrared heater and banked, making it impossible to obtain a stretched film.
- Example 6 the stretching behavior and the properties of the resulting stretched film Also, as in Examples 4 and 5, good packaging finish and heat sealability were exhibited without any problem, and reversion after packaging was also excellent.
- the stretched film obtained in Comparative Example 3 had good low-temperature heat sealability and good stretchability, but had problems such as poor slipperiness in an automatic packaging machine and poor finish at the bottom of the tray.
- Example 7 A stretched film was produced in the same manner as in Example 4 except that 3.5 parts by weight (Comparative Example 6) was added.
- the stretched film obtained in Example 7 had good stretchability, heat shrinkage, packaging finish, and heat sealability as in Example 4, but the stretched film obtained in Comparative Example 6 had anti-fog properties and automatic
- One of the drawbacks is that the slipperiness of the packaging machine and the film foldability of the tray packaging are good, but the heat sealability of the hot plate is poor, and the film seal at the bottom of the tray is likely to be defective1.
- Example 4 As shown in Table 1, in Example 4, the tensile strength during stretching was changed to 15 O kg / cir (Example 8) and 20 O kg / cm 2 (Comparative Example 7). Under the same conditions as above, a stretched film was produced.
- the stretched film obtained in Example 8 has a slightly higher tensile resistance at 50% elongation than the stretched film obtained in Example 4, but as a result of the packaging nest, the film does not come off from the film crib, and the tray is removed. Automatic packaging without deformation-good suitability, good packaging finish there were. However, stretched film tensile strength during stretching processing is obtained in 1 7 O kg / ctn 2 ratio greater than Comparative Examples 7 also small tensile resistance greatly elongation of the stretching Tao film. When this film was put on an automatic wrapping machine and wrapped, the film came off the film crib, and if it was forcibly wrapped, the tray would be deformed, causing a trap. In addition, heat sealability was poor, resulting in poor packaging.
- a composition of 90% by weight of quenched low-melting polyethylene having the characteristics shown in Table 2 and 10% by weight of a low-melting-point polyethylene copolymer was employed as a medium-sized employment.
- the low-melting-point polyethylene copolymer 5 has the characteristics shown in Table 2.
- composition with 0% by weight 100 Ingredients: 0.25 parts by weight of bolylene glycol oleate, 0.40 parts by weight of oleyldiethanol noramine, 0.35 parts by weight of sorbitan etholeyl oleate
- the extruded composition was melted and kneaded with three extruders (for inner layer, middle layer, and outer layer) so that it would become the innermost layer and the outermost layer. Assuming that the amount of extrusion from each pressing machine was adjusted and kept at 2 4 0 3 Than slit door of the ring ⁇ die extrusion under direction.
- the diameter of the slit of the annular die was 75 mm and the gear of the slit was .8 mm.
- the extruded three-layered fused tube-shaped film is attached directly under the die.
- the outer diameter of the cylindrical mandrel is 7.6 mm and circulates 20 cooling water inside. The water was cooled by passing through a water tank, cooled in the chamber, and taken out to obtain an unstretched film with a diameter of about 75 jets and a thickness of 240 jum.
- This tuple-shaped unstretched film was guided to a tubular biaxial stretching machine as shown in Fig. I and expanded and stretched. At this time, the voltage and current of the annular infrared heater for preheating 4 were adjusted, and the film temperature at the outlet of the preheating unit was adjusted. 8 annular infrared heaters of main heater 5 in 4 sections The film is heated by adjusting each voltage and current, and the air flowing along the tube from below the main heater is supplied to the tubular film between the low-speed nibroll 2 and the high-speed nibroll 3 to pressurize the air.
- the air pressure (tube pressure) during stretching is such that the tensile strength is 70 kg / CTrf, the voltage and current of the pre-heater and the annular infrared heater of the main heater, and the air volume and air flow of the cooling ring 6. Adjusted by temperature.
- the resulting film was excellent in transparency, stretchability, heat shrinkage, elastic recovery, and heat sealability.
- a packaging finish test was performed with an automatic packaging machine. The film was smoothly unwound from the roll, did not come off the film crib, and the film was folded well in the tray. However, the packaging was stable. In addition, heat sealing with a hot plate at 90 mm was also performed smoothly and was sufficiently welded.
- the shrinkage in the tunnel is good, the film is not wrinkled or sagged, the finish of the package is beautiful, and the return to the original state in 2 to 3 seconds with no trace of finger pressing after packaging. I returned.
- Table 2 summarizes the raw material formulation, stretching conditions, properties of the film after stretching, and the results of each test.
- the laminated stretch shrink film was produced in the same manner as in Example 9 except that the constituent resin of the intermediate layer and the innermost and outermost layers, the compounding ratio of the additive composition, the thickness ratio of each layer, and the tensile strength during stretching were changed. Was manufactured.
- I Npiku ⁇ T ma solution ⁇ after quenching as an intermediate layer resin, as shown in Table 2 is 1 2 6 e C, 1 1 S ⁇ 5 X: no melting point in the range garden, and
- the temperature difference between the main peak temperature T mb and the ⁇ temperature difference T mb—T ma of the melting curve after slow cooling is 90% by weight of linear low-density polyethylene with 0 ° C and 10% by weight of the low-melting-point polyethylene copolymer.
- composition K inner and outer layers. The same composition as used for the inner and outer layers in Example 9 was used. Extruded under the same conditions as in Example 1, quenched and taken off, diameter approx. A laminated unstretched film of 40 yum was obtained.
- this tubular unstretched film was guided to tubular biaxial stretching, and adjusted so as to have a low tensile strength of 7 O kgZ cTif. The area was stretched and stretched to a factor of 20).
- Example 10 As shown in Table 2, the same resin composition as in Example 9 was used for both the intermediate layer and the inner and outer layers, and the thickness of the intermediate layer was adjusted to 50% of the total thickness, with the exception that tf was set to 50% of the total thickness. Under exactly the same conditions, extrusion film formation and tuple-like biaxial stretching were performed. However, the stability during stretching was poor, the rocking of the purple was large, and it was possible to obtain a continuous and uniform stretched film. Comparative Example 10 0, 1 1
- Example 10 As shown in Table 2, for the intermediate layer, the same composition as in Example 9 was used, and for the inner and outer layers, in the case of Comparative Example 10, the mixing ratio of the low-temperature polyethylene cold M coalescence was 10% by weight. 6, In Comparative Example 4, a laminated stretch shrink film was produced in the same manner as in Example 9 except that the blending ratio of the low-polyester copolymer was set to 70% by weight.
- Comparative Examples 10 and 11 were particularly questionable. Although the film could be stretched without any problem, the film obtained in Comparative Example 10 was poor in heat-sealing performance. Was insufficient, and there was a part where the seal part easily separated. Although the low-temperature heat-sealing property of Comparative Example 4 was good, the releasability when unwinding the film from the film roll during the packaging test with an automatic wrapping machine was poor, and the film in the film supply section was poor. The film could not be unwound well, and the slipperiness with the automatic packaging machine was poor, and a smooth packaging test could not be performed.
- Example 9 As shown in Table 2, the same resin composition as in Example 9 was used for both the intermediate layer and the inner and outer layers, except that the surfactant in the inner and outer layers was changed to the composition shown in Table 2. Stretching was carried out in the same manner as in Example 9 except that S was set to 20 O kg Zcit to produce a laminated stretch shrink film.
- the stretched film obtained had good anti-violence properties, good slipperiness in automatic packaging machines, and good film foldability in tray wrapping, but poor heat sealability on a hot plate and poor sealing of the film at the bottom of the tray. There was a defect that easily occurred.
- Polyethylene-based biaxially stretched film of the present invention ⁇ Since linear low-density polyethylene having a specific thermal behavior is used, even when stretched under known stretching conditions, unevenness in thickness is small, suitability for packaging machine, printing Excellent suitability of ⁇ is obtained.
- low melting point polyethylene is mixed with linear low-density polyethylene: E-Tylene copolymer and surfactant.
- An unstretched film made of a polyethylene resin and a specific low-melting-point ethylene-alpha-olefin copolymer and a specific surfactant was used as the innermost and outermost layers in the innermost and outermost layers.
- the film obtained by stretching and orientation under specific conditions of S ⁇ 17 O kg cm 2 has excellent transparency, stretchability, heat shrinkage, heat sealability, and reversion after packaging. Good packaging This is a polyethylene strain shrink film.
- Thickness ratio Measurement (in) (%) 10 20 15 15 10 25 10) 0 10 10 Thickness ratio (outside) () 10 20 15 16 10 25 10 10 10 10 ⁇ is the extension ratio (culture) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 kg / cm 2) 70 70 70 150 70 70 70 70 200 70
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
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Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002039158A CA2039158C (en) | 1989-10-09 | 1990-10-09 | Biaxially stretched polyethylene film |
KR1019910700361A KR100186871B1 (ko) | 1989-10-09 | 1990-10-09 | 폴리에틸렌계 이축연신 필름 |
DE69026929T DE69026929T2 (de) | 1989-10-09 | 1990-10-09 | Biaxial orientierte polyethylenfolie |
US07/667,392 US5306549A (en) | 1989-04-10 | 1990-10-09 | Biaxially stretched polyethylene film |
EP90914781A EP0450088B1 (en) | 1989-10-09 | 1990-10-09 | Biaxially oriented polyethylene film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26197389 | 1989-10-09 | ||
JP1/261973 | 1989-10-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991005004A1 true WO1991005004A1 (fr) | 1991-04-18 |
Family
ID=17369235
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1990/001307 WO1991005004A1 (fr) | 1989-04-10 | 1990-10-09 | Film de polyethylene a orientation biaxiale |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0450088B1 (ja) |
JP (3) | JP2904903B2 (ja) |
KR (1) | KR100186871B1 (ja) |
AU (1) | AU640419B2 (ja) |
CA (1) | CA2039158C (ja) |
DE (1) | DE69026929T2 (ja) |
DK (1) | DK0450088T3 (ja) |
WO (1) | WO1991005004A1 (ja) |
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CN111662498A (zh) * | 2019-03-08 | 2020-09-15 | 中国石油化工股份有限公司 | 一种聚烯烃组合物及其制备方法和应用 |
CN113002003A (zh) * | 2021-03-18 | 2021-06-22 | 成都希瑞方晓科技有限公司 | 一种均匀膨化聚四氟乙烯带材的制备方法 |
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US5279872A (en) * | 1992-03-23 | 1994-01-18 | Viskase Corporation | Multilayer stretch/shrink film |
NZ247178A (en) * | 1992-03-23 | 1995-07-26 | Viskase Corp | Biaxially oriented heat-shrinkable multilayer film having at least two outer layers each comprising an ethylene alpha-olefin plastomer/vldpe blend and a core layer of ethylene alpha-olefin copolymer |
CA2118002C (en) * | 1993-11-02 | 2004-01-20 | Syuuichi Morita | Heat shrinkable polyethylene laminate film |
IT1266781B1 (it) * | 1993-11-08 | 1997-01-21 | Grace W R & Co | Pellicole multistrato orientate biassialmente e termoretraibili, procedimento per produrle e loro uso per confezionare prodotti |
US5962092A (en) * | 1994-03-28 | 1999-10-05 | Cryovac, Inc. | Oxygen-permeable multilayer film containing antifog agent and package made therefrom |
US6060136A (en) | 1995-10-13 | 2000-05-09 | Cryovac, Inc. | High modulus oxygen-permeable multilayer film |
US5491019A (en) | 1994-03-28 | 1996-02-13 | W. R. Grace & Co.-Conn. | Oxygen-permeable multilayer film |
KR100317007B1 (ko) * | 1994-09-20 | 2002-08-01 | 가부시끼가이샤 고진 | 다층폴리에틸렌계연신수축성필름및그의제조방법 |
US5736260A (en) * | 1994-10-06 | 1998-04-07 | Sumitomo Chemical Company, Limited | Multilayer packaging film |
US5770318A (en) * | 1995-01-13 | 1998-06-23 | Norton Performance Plastics Corporation | Thermoplastic seal and wrapping film |
JP3528343B2 (ja) * | 1995-07-12 | 2004-05-17 | 住友化学工業株式会社 | 多層フィルム |
US6129876A (en) * | 1996-05-03 | 2000-10-10 | Baxter International Inc. | Heat setting of medical tubings |
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US6036676A (en) * | 1996-05-03 | 2000-03-14 | Baxter International Inc. | Surface modified polymeric material formulation |
US6187400B1 (en) | 1996-05-03 | 2001-02-13 | Baxter International Inc. | Medical tubing and pump performance enhancement by ionizing radiation during sterilization |
US5741452A (en) * | 1996-05-03 | 1998-04-21 | Baxter International Inc. | Orienting extrusion processes for medical tubing applications |
US5954702A (en) * | 1996-05-03 | 1999-09-21 | Baxter International Inc. | Interface geometry for adhesive bonds |
US6328716B1 (en) | 1996-05-03 | 2001-12-11 | Baxter International Inc. | Method of using medical tubings in fluid administration sets |
US5932307A (en) * | 1996-05-03 | 1999-08-03 | Baxter International Inc. | Oriented medical tubing |
DE29609414U1 (de) * | 1996-05-25 | 1996-10-31 | Rein-Plastik KG, 21465 Reinbek | Folie für die Herstellung von Innenverpackungen |
CN1213391A (zh) * | 1996-11-22 | 1999-04-07 | 三井化学株式会社 | 热塑性树脂组合物和含该组合物的薄膜 |
KR100527652B1 (ko) * | 1996-12-10 | 2006-01-27 | 아르끄마 | 열가소성수지조성물및성형품 |
JPH10168298A (ja) * | 1996-12-10 | 1998-06-23 | Elf Atochem Japan Kk | 熱可塑性樹脂組成物及び成形品 |
JP3614810B2 (ja) * | 2001-11-01 | 2005-01-26 | 株式会社興人 | ポリエチレン系架橋シュリンクフイルム |
GB0217522D0 (en) * | 2002-07-29 | 2002-09-04 | Borealis Tech Oy | Product |
CN102941671B (zh) * | 2012-12-06 | 2016-03-30 | 上海通冷包装材料有限公司 | 吹膜机膜泡吹胀装置 |
JP6572520B2 (ja) * | 2013-07-10 | 2019-09-11 | 東ソー株式会社 | 超高分子量ポリエチレン粒子およびそれよりなる成形体 |
CN106279937B (zh) * | 2015-06-12 | 2019-04-19 | 中国石油化工股份有限公司 | 一种电磁屏蔽聚乙烯薄膜及其制备方法 |
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- 1990-10-09 DE DE69026929T patent/DE69026929T2/de not_active Expired - Fee Related
- 1990-10-09 KR KR1019910700361A patent/KR100186871B1/ko not_active IP Right Cessation
- 1990-10-09 JP JP2269556A patent/JP2927928B2/ja not_active Expired - Fee Related
- 1990-10-09 AU AU65143/90A patent/AU640419B2/en not_active Withdrawn - After Issue
- 1990-10-09 CA CA002039158A patent/CA2039158C/en not_active Expired - Fee Related
- 1990-10-09 DK DK90914781.1T patent/DK0450088T3/da active
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CN111662402A (zh) * | 2019-03-08 | 2020-09-15 | 浙江大学 | 一种聚烯烃组合物及其制备方法和应用 |
CN111662498A (zh) * | 2019-03-08 | 2020-09-15 | 中国石油化工股份有限公司 | 一种聚烯烃组合物及其制备方法和应用 |
CN111662498B (zh) * | 2019-03-08 | 2023-01-24 | 中国石油化工股份有限公司 | 一种聚烯烃组合物及其制备方法和应用 |
CN111662402B (zh) * | 2019-03-08 | 2023-02-28 | 浙江大学 | 一种聚烯烃组合物及其制备方法和应用 |
CN113002003A (zh) * | 2021-03-18 | 2021-06-22 | 成都希瑞方晓科技有限公司 | 一种均匀膨化聚四氟乙烯带材的制备方法 |
Also Published As
Publication number | Publication date |
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DE69026929D1 (de) | 1996-06-13 |
KR920701339A (ko) | 1992-08-11 |
DK0450088T3 (da) | 1996-05-28 |
JP2904904B2 (ja) | 1999-06-14 |
JPH03220250A (ja) | 1991-09-27 |
CA2039158A1 (en) | 1991-04-10 |
AU640419B2 (en) | 1993-08-26 |
JP2904903B2 (ja) | 1999-06-14 |
EP0450088B1 (en) | 1996-05-08 |
AU6514390A (en) | 1991-04-28 |
KR100186871B1 (ko) | 1999-05-15 |
JP2927928B2 (ja) | 1999-07-28 |
CA2039158C (en) | 2000-02-22 |
EP0450088A4 (en) | 1992-05-06 |
DE69026929T2 (de) | 1996-09-26 |
JPH03205430A (ja) | 1991-09-06 |
EP0450088A1 (en) | 1991-10-09 |
JPH03215034A (ja) | 1991-09-20 |
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