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WO2015166848A1 - Film d'étanchéité multicouche - Google Patents

Film d'étanchéité multicouche Download PDF

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Publication number
WO2015166848A1
WO2015166848A1 PCT/JP2015/062162 JP2015062162W WO2015166848A1 WO 2015166848 A1 WO2015166848 A1 WO 2015166848A1 JP 2015062162 W JP2015062162 W JP 2015062162W WO 2015166848 A1 WO2015166848 A1 WO 2015166848A1
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WO
WIPO (PCT)
Prior art keywords
layer
resin
weight
density polyethylene
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/062162
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English (en)
Japanese (ja)
Inventor
直彦 倉本
知己 田島
省吾 貞廣
佐藤　豪一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sun-Tox Co Ltd
Original Assignee
Sun-Tox Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sun-Tox Co Ltd filed Critical Sun-Tox Co Ltd
Priority to KR1020167026174A priority Critical patent/KR20160147721A/ko
Priority to CN201580022967.2A priority patent/CN106255595A/zh
Priority to JP2016516330A priority patent/JP6441322B2/ja
Publication of WO2015166848A1 publication Critical patent/WO2015166848A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Definitions

  • the present invention relates to a multilayer sealant film. More specifically, the present invention relates to a multilayer sealant film that provides a hermetic package that can be opened smoothly with a light force without generation of a thread-like or film-like peeled material when the heat seal portion is opened.
  • Packaging bags that can be sealed by heat sealing are widely used for packaging various products such as food, clothing, and industrial parts.
  • a packaging bag is made of a packaging material formed by laminating a base film and a sealant film having a heat seal layer as an outermost layer for enabling heat sealing.
  • the packaging material is formed into a bag shape so that the heat seal layer is on the inside, and after the contents are stored, the heat seal layer of the opening is thermocompressed to be used as a sealed package.
  • opening the sealed package hold the vicinity of the heat seal part of each of the front and back films constituting the package with the fingertips of both left and right hands and pull the two films apart to destroy the heat seal part.
  • a method of regenerating the opening is common.
  • the sealant film may be a multilayer film including a heat seal layer that is melted or softened by heat in order to enable heat sealing of the packaging material.
  • the sealant film has been studied from the viewpoints of heat seal strength, easy openability and other aspects, and various layer configurations have been proposed. In Japanese Patent No.
  • a sealant film composed of a laminate of a linear low density polyethylene (LLDPE) and a mixture of polyethylene and a layer composed of a polypropylene resin
  • LLDPE linear low density polyethylene
  • An easy-opening polyolefin laminate comprising a laminate layer containing, an intermediate layer composed of a mixture of polypropylene (PP) and LLDPE, and a heat seal layer composed of PP has been proposed.
  • PP polypropylene
  • PP polypropylene
  • PP polypropylene
  • An object of the present invention is to provide a sealant film that provides a hermetic package that can be easily opened without relying on heat seal conditions and having high heat seal strength.
  • the present inventors have conducted not only delamination but also cohesive failure in which one of the multilayers constituting the sealant film is broken, and delamination.
  • the laminate layer (A) is 30 to 70 parts by weight of polybutene resin (A1), A resin composition comprising 20 to 60 parts by weight of a linear low density polyethylene resin (A2) and 10 to 50 parts by weight of a low density polyethylene resin (A3) having a density of 0.930 g / cm 3 or more, wherein The total of the polybutene resin (A1), the linear low density polyethylene resin (A2) and the low density polyethylene resin (A3) is 100 parts by weight, At least one of the at least one intermediate layer (B) constitutes the intermediate layer (B) from the long-chain branched linear low density polyethylene (B1) having the following characteristics (1) to (3): When the total amount of the resin is 100 parts by weight, the resin
  • the amount of the amorphous component measured by the temperature rising elution fractionation method is 1 to 4% by weight
  • the number of branches having 8 or more carbon atoms measured by 13 C-NMR is 1,000 carbon atoms. The number is 1.5 to 5.0 per piece.
  • FIG. 1 is a schematic cross-sectional view of the packaging material 2 of the present invention.
  • FIG. 2 is a schematic explanatory view of the hermetic package 5 of the present invention.
  • FIG. 3 is a schematic explanatory view for explaining a mechanism at the time of opening the heat seal portion of the hermetic package of the present invention.
  • the “packaging material” refers to a material for producing a packaging bag obtained by sticking the multilayer sealant film of the present invention to a base film.
  • “Packaging bag” refers to a bag-like product having an opening obtained by processing a packaging material.
  • the “sealed package” refers to a sealed bag obtained by storing the contents in a packaging bag and heat-sealing the opening.
  • the multilayer sealant film of the present invention is A laminate layer (A) which is the outermost layer; At least one intermediate layer (B); Heat seal layer (C) which is the other outermost layer Have
  • a laminate layer (A) which is the outermost layer
  • Heat seal layer (C) which is the other outermost layer
  • the resin density is a value measured according to ASTM D1505;
  • the melting point of the resin is the peak top temperature of the peak showing the maximum endotherm in the endothermic curve during temperature rise using a differential scanning calorimeter,
  • the melt flow rate (MFR) is a value measured at a load of 2.16 kg at the temperature specified below for each resin in accordance with JIS K 6758.
  • ⁇ Laminate layer (A)> The laminate layer (A) is used for adhesion to the base film located on the base film side when the multilayer sealant film of the present invention is laminated with the base film to form a packaging material. It is a layer that cohesively breaks from the multilayer seal portion.
  • This laminate layer (A) Polybutene resin (A1), Linear low density polyethylene (A2) and Density 0.930g / cm 3 It consists of the resin composition containing the low density polyethylene (A3) which is the above.
  • the laminate layer (A) contains the low-density polyethylene (A3) together with the polybutene-based resin (A1) and the linear low-density polyethylene (A2), the compatibility between the polybutene-based resin (A1) and other resins is achieved.
  • the cohesiveness of the laminate layer (A) is improved when the package is opened, which contributes to the opening.
  • the cohesive fracture property depends on the compatible state of the resin constituting the laminate layer, the cohesive fracture property can obtain a desired opening property regardless of the heat seal condition when forming the package.
  • the laminate layer (A) containing the polybutene resin (A1) has irregularities on the surface thereof, and thus the base Adhesiveness with the material film is also improved.
  • the ratio of the polybutene resin (A1), the linear low density polyethylene (A2) and the low density polyethylene (A3) within the following ranges, a high level of transparency and image clarity are obtained. be able to.
  • the polybutene-based resin (A1) is selected from a homopolymer of 1-butene and a copolymer of 1-butene and another ⁇ -olefin.
  • the ⁇ -olefin is preferably an ⁇ -olefin having 2, 3 or 5 to 10 carbon atoms, specifically, for example, ethylene, propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene. And so on.
  • a copolymer of 1-butene and another ⁇ -olefin for example, a copolymer of 1-butene and one or more ⁇ -olefins selected from the group consisting of ethylene and propylene is preferable.
  • the polybutene resin (A1) is preferably a 1-butene homopolymer, an ethylene / 1-butene copolymer, a propylene / 1-butene copolymer or an ethylene / propylene / 1-butene copolymer. .
  • a random copolymer is preferable.
  • the content of 1-butene unit in the polybutene-based resin (A1) is preferably 50 parts by weight or more and more preferably 70 parts by weight or more when the entire copolymer is 100 parts by weight.
  • Most preferred as the polybutene resin (A1) is a homopolymer of 1-butene.
  • the density of the polybutene resin (A1) is preferably 0.900 to 0.930 g / cm. 3 More preferably, 0.910 to 0.920 g / cm 3 It is. When the density of the polybutene resin is too low, blocking of the multilayer sealant film tends to occur. On the other hand, when the density is too high, the multilayer sealant film is curled and handling properties are lowered.
  • the melting point of the polybutene resin (A1) is preferably 50 to 135 ° C., more preferably 70 to 125 ° C. When this melting point is less than 50 ° C., the appearance of the peeled surface at the time of opening is inferior. When the melting point exceeds 135 ° C., the opening strength may become excessively high.
  • the MFR (190 ° C.) of the polybutene resin (A1) is preferably from 0.1 to 50.0 g / 10 minutes, and preferably from 1.0 to 20.0 g / 10 minutes in consideration of film forming properties. Is more preferable.
  • the content of the polybutene resin (A1) in the laminate layer (A) is 100 weights in total of the polybutene resin (A1), the linear low density polyethylene (A2), and the low density polyethylene (A3) in the laminate layer (A). 30 to 70 parts by weight, and preferably 35 to 60 parts by weight with respect to parts.
  • the content of the polybutene resin (A1) is less than 30 parts by weight, the cohesive failure of the laminate layer (A) is difficult to occur at the time of opening and the opening strength becomes excessively high. It becomes easy.
  • the content of the polybutene resin (A1) exceeds 70 parts by weight, the appearance of the peeled surface at the time of opening is inferior.
  • the linear low density polyethylene (A2) is a thermoplastic resin obtained by copolymerization of ethylene and a small amount of other ⁇ -olefin.
  • the ⁇ -olefin include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.
  • the content of the ⁇ -olefin unit in the linear low density polyethylene (A2) is preferably 30 mol% or less, more preferably in the range of 2 to 20 mol%.
  • the density of the linear low density polyethylene (A2) is preferably 0.900 to 0.945 g / cm. 3 More preferably, 0.910 to 0.940 g / cm 3 It is.
  • the density of the linear low density polyethylene (A2) is too low, the transparency and image clarity of the packaging material may be insufficient, and the multilayer sealant film is likely to be blocked.
  • the density of the linear low density polyethylene (A2) is too high, the multilayer sealant film may be curled and handling properties may be lowered.
  • the melting point of the linear low density polyethylene (A2) is preferably 130 ° C. or less, more preferably 100 to 130 ° C. When the melting point of the linear low density polyethylene (A2) is too low, the multilayer sealant film may be easily blocked. On the other hand, when the melting point of the linear low-density polyethylene (A2) is too high, the multilayer sealant film may curl and handling properties may decrease.
  • the MFR (190 ° C.) of the linear low density polyethylene (A2) is preferably from 0.1 to 50.0 g / 10 minutes, more preferably from 2.0 to 20.0 g / 10 minutes.
  • the MFR of the linear low density polyethylene (A2) is too low, the viscosity at the time of melting becomes excessively high, so that the resin pressure in the extruder rises during the production of the multilayer sealant film, and the productivity is remarkably deteriorated.
  • the MFR of the linear low density polyethylene (A2) is too high, blocking of the multilayer sealant film is likely to occur.
  • the content of the linear low density polyethylene (A2) in the laminate layer (A) is that of the polybutene resin (A1), the linear low density polyethylene (A2) and the low density polyethylene (A3) in the laminate layer (A).
  • the amount is 20 to 60 parts by weight, preferably 25 to 50 parts by weight based on 100 parts by weight in total. If the content of the linear low density polyethylene (A2) is less than 20 parts by weight or exceeds 60 parts by weight, the opening strength becomes excessively high in any case, so that the film is easily broken at the time of opening. .
  • the density of the low density polyethylene (A3) is preferably 0.930 g / cm. 3 Or more, more preferably 0.930 to 0.950 g / cm.
  • the melting point of the low density polyethylene (A3) is preferably 120 ° C. or less, more preferably 100 to 120 ° C. When the melting point of the low density polyethylene (A3) is too low, blocking of the multilayer sealant film is likely to occur. On the other hand, when the melting point of the low density polyethylene (A3) is too high, the multilayer sealant film is curled and the handling property is lowered.
  • the MFR (190 ° C.) of the low density polyethylene (A3) is preferably in the range of 0.1 to 50.0 g / 10 minutes, more preferably in the range of 2.0 to 20.0 g / 10 minutes.
  • the MFR of the low density polyethylene (A3) is too low, since the viscosity at the time of melting is high, in the production of the multilayer sealant film, the resin pressure in the extruder is increased and the productivity is remarkably deteriorated.
  • the MFR of (A3) is too high, the multilayer sealant film is likely to be blocked.
  • a high pressure method low density polyethylene (HPLD) generally produced by a high pressure method can be preferably used.
  • the content of the low density polyethylene (A3) in the laminate layer (A) is 100 weights in total of the polybutene resin (A1), the linear low density polyethylene (A2) and the low density polyethylene (A3) in the laminate layer (A).
  • the amount is 10 to 50 parts by weight, preferably 20 to 40 parts by weight. When this value is less than 10 parts by weight, the unsealing strength becomes excessively high, and the film is easily broken at the time of unsealing. When it exceeds 50 parts by weight, the image clarity is lowered.
  • the polybutene resin (A1), linear low density polyethylene (A2) and low density polyethylene (A3) can all be controlled by known means. For example, it can be controlled by the type and copolymerization amount of the comonomer, the molecular weight of the resin and the like. Moreover, you may select and use the material which has a desired physical property from various commercial items. [Other ingredients]
  • the laminate layer (A) is within a range that does not impair the adhesion between the laminate layer (A) and the base film and the cohesive failure performance of the laminate layer (A). In addition, other components may be contained.
  • the laminate layer (A) can be obtained by melt-mixing the above components (A1) to (A3) and other components used as necessary to form a film.
  • an extruder or the like can be used for the melt mixing, and a T-die or the like can be used for the film formation.
  • the thickness of the laminate layer (A) is preferably 1.5 ⁇ m or more, more preferably 2 ⁇ m or more in order to effectively cause cohesive failure.
  • the thickness of the laminate layer (A) will be 50 ⁇ m or less.
  • the thickness is preferably 1.5 to 50 ⁇ m, more preferably 30 ⁇ m or less.
  • This intermediate layer (B) contains the long-chain branched linear low-density polyethylene (B1) in an amount of 50 to 100 parts by weight when the total amount of the resin constituting the intermediate layer (B) is 100 parts by weight. Made of resin.
  • the thickness of the intermediate layer (B) is preferably 5 to 100 ⁇ m.
  • the long-chain branched linear low-density polyethylene (B1) in the intermediate layer (B) constituting the multilayer sealant film of the present invention is a low-density polyethylene having a branch, and thus LLDPE (linear low-density in the prior art). Common to polyethylene, described later) and LDPE (low density polyethylene).
  • the long chain branched linear low density polyethylene used in the present invention differs from LLDPE and LDPE in the prior art in at least Mw / Mn, the amount of non-crystalline components and the content of long chain branches. That is, the predetermined long chain branched linear low density polyethylene of the present invention satisfies all of the following conditions (1) to (3).
  • the ratio Mw / Mn of the weight average molecular weight Mw in terms of polystyrene and the number average molecular weight Mn measured by gel permeation chromatography is 7.5 to 15.0.
  • the amount of the amorphous component measured by the temperature rising elution fractionation method is 1 to 4% by weight, and (3) 13
  • the number of branches having 8 or more carbon atoms measured by C-NMR is 1.5 to 5.0 per 1,000 carbon atoms.
  • the long-chain branched linear low-density polyethylene (B1) in the present invention is a ratio Mw / Mn (molecular weight distribution) of weight-average molecular weight Mw in terms of polystyrene and number-average molecular weight Mn measured by gel permeation chromatography (GPC). Is 7.5 to 15.0. This value is preferably 8.5 to 14.5, and more preferably 9.5 to 13.5.
  • the multilayer sealant film of the present invention is excellent in optical properties (haze, image definition) and has a heat seal portion. It is possible to obtain the advantage of exhibiting easy-opening properties without causing film turning at the edges.
  • the long-chain branched linear low-density polyethylene (B1) in the present invention preferably has a polystyrene-equivalent weight average molecular weight Mw measured by GPC of 80,000 to 150,000, and 90,000 to 140,000.
  • the long-chain branched linear low-density polyethylene (B1) in the present invention has an amorphous component amount of 1 to 4% by weight measured by a temperature rising elution fractionation method.
  • a temperature rising elution fractionation method a solution obtained by dissolving a polymer sample in a predetermined solvent at a high temperature is supplied to a TREF (Temperature Rising Elution Fractionation) column, and then cooled to precipitate and adsorb the polymer sample in the column. Then, the column temperature is gradually raised and the eluted fraction is analyzed.
  • the supply of the solvent is started, and the fraction eluted during the period in which the column temperature is maintained at 0 ° C. is used as an amorphous component. Is evaluated as the amount of non-crystalline component.
  • the amount of the amorphous component of the long-chain branched linear low-density polyethylene (B1) is preferably 1.5 to 3.0% by weight.
  • Such a temperature rising elution fractionation method can be performed, for example, using an appropriate temperature rising elution fractionation (TREF) apparatus such as a special TREF apparatus manufactured by Senshu Kagaku Co., Ltd.
  • the long-chain branched linear low-density polyethylene (B1) having the crystallinity as described above it has excellent optical properties (haze, image clarity), and the film is turned at the edge of the heat seal part. It is possible to obtain the advantage of developing easy opening without doing.
  • the long chain branched linear low density polyethylene (B1) in the present invention is 13
  • the number of branches having 8 or more carbon atoms measured by C-NMR is 1.5 to 5.0 per 1,000 carbon atoms. This value is preferably 2.0 to 5.0, and more preferably 2.5 to 4.5.
  • the multilayer film of the present invention can be used regardless of the surrounding environment such as temperature and humidity at the time of fusing and sealing.
  • a high fusing seal strength can be expressed stably, which is preferable.
  • LLDPE in the prior art is dominant when the number of carbon atoms in the branch is 6 or less, and even if there are branches having 8 or more carbon atoms, the amount is small, usually 1 or less per 1,000 carbon atoms. And stays at most 2 or less.
  • LDPE 13 In the C-NMR measurement, there are more components detected as branches having 8 or more carbon atoms than the above range in the present invention.
  • the long-chain branched linear low-density polyethylene (B1) in the present invention is 13 It can be distinguished from LLDPE and LDPE in the prior art by the amount of branching of 8 or more carbon atoms measured by C-NMR.
  • the method for measuring the amount of long chain branching in the present invention will be described below.
  • Each branch (1-octene structure) will be considered.
  • the chemical shift of each of the second and third methylene carbons from the branch end is C 8 Branch and C 6
  • the C-NMR measurement can be performed under the following conditions using an appropriate nuclear magnetic resonance analyzer such as a model “JNM-ECS400” manufactured by JEOL.
  • Solvent Mixed solvent of trichlorobenzene / heavy benzene (75/25% by volume) Sample concentration: 80 mg / 2.5 mL solution
  • Measurement mode 1H-complete decoupling Measurement temperature: 120 °
  • Pulse width 90 degree pulse Pulse repetition time: 9 seconds Integration count: 9,000 times
  • the long chain branching content in this specification is C 8
  • the unit is (pieces / 1,000 C).
  • the various parameters described above are compared in Table 2 below for typical polyethylenes.
  • the long-chain branched linear low-density polyethylene (B1) in the present invention may be synthesized by any method as long as it satisfies the above requirements.
  • it can be produced by a method using a known Ziegler-Natta catalyst, preferably with an appropriate donor compound; a method using a Phillips catalyst; a method using a metallocene catalyst.
  • the method using a metallocene catalyst is preferable in that a polymer having the above characteristics can be easily obtained.
  • the metallocene-based catalyst is a catalyst comprising a metallocene-type transition metal compound having at least one, preferably two, substituted or unsubstituted cyclopentadienyl ligands and a promoter.
  • a metallocene-type transition metal compound having at least one, preferably two, substituted or unsubstituted cyclopentadienyl ligands and a promoter.
  • the cocatalyst include organoaluminum compounds; complexes of organoboron compounds and cations; ion-exchange silicates and the like, and one or more selected from these can be used.
  • the metallocene catalyst may be supported on a suitable inorganic substance. Metallocene catalysts are already known in the art, and those skilled in the art can appropriately select and use an appropriate metallocene catalyst according to the purpose.
  • the resin constituting the intermediate layer (B) may be composed only of the long-chain branched linear low-density polyethylene (B1), and other resins besides the long-chain branched linear low-density polyethylene (B1). May be contained.
  • other resins used here include polyethylene resins (excluding the above long-chain branched linear low-density polyethylene (B1)), polypropylene resins, polybutene resins, and the like.
  • the polyethylene resin include LLDPE (linear low density polyethylene, except the above-mentioned long chain branched linear low density polyethylene (B1)), LDPE (low density polyethylene), and the like.
  • the LLDPE is an LLDPE other than the above-mentioned long-chain branched linear low-density polyethylene (B1), and the LLDPE in the prior art can be used.
  • This LLDPE is preferably a copolymer of ethylene and an ⁇ -olefin other than ethylene.
  • the ⁇ -olefin is preferably an ⁇ -olefin having 3 to 12 carbon atoms, specifically, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1- Examples include pentene, 1-decene, 1-dodecene and the like.
  • the polystyrene-equivalent molecular weight distribution Mw / Mn measured by GPC is preferably 1.5 to 5.0, Preferably, the amount of non-crystalline component measured by the temperature rising elution fractionation method is 1 to 5% by weight, and 13
  • the number of branches having 8 or more carbon atoms measured by C-NMR is preferably less than 5.0 per 1,000 carbon atoms, and more preferably less than 3.0.
  • the measuring method of these parameters is the same as that of the long chain branched linear low density polyethylene (B1).
  • the MFR measured at 190 ° C. and a load of 2.16 kg in accordance with JIS K 7210 is preferably 0.5 to 20 g / 10 min.
  • Such LLDPE can be obtained by a known method. For example, it can be synthesized by a chromium catalyst alone or a catalyst system using a chromium catalyst and a Ziegler-Natta catalyst in combination.
  • -LDPE- The LDPE is not particularly limited, and a conventional LDPE can be used.
  • the MFR measured at 190 ° C. and a load of 2.16 kg in accordance with JIS K 7210 is preferably 0.1 to 50 g / 10 minutes.
  • polypropylene resin As said polypropylene resin, the homopolymer of propylene and the copolymer of a propylene and a copolymerization component can be mentioned.
  • the copolymer component for example, ethylene and ⁇ -olefin are preferable, and specifically, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene. 4-methyl-1-pentene can be used, and one or more selected from these can be used.
  • the proportion of the copolymer component in this polypropylene resin is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol% or less.
  • the MFR measured with a load of 2.16 kg at 230 ° C. in accordance with JIS K 7210 is preferably 0.5 to 50 g / 10 min.
  • -Polybutene resin- As said polybutene-type resin, the same thing as the polybutene-type resin (A1) contained in the laminate layer (A) which comprises the multilayer sealant film of this invention can be used.
  • the amount of the long-chain branched linear low-density polyethylene (B1) used in the intermediate layer (B) constituting the multilayer sealant film of the present invention is 100 parts by weight of the total resin constituting the intermediate layer (B). Furthermore, it is 50 parts by weight or more, and preferably 60 parts by weight or more.
  • the optical properties haze, image definition
  • the film is turned over at the edge of the heat seal part. It is possible to obtain an advantage of easily opening.
  • the intermediate layer (B) is a petroleum resin, a terpene resin, a rosin, an antiblocking agent, an antioxidant, a light stabilizer lubricant, and an antistatic agent as long as the function of the layer is not impaired.
  • Other components such as an antifogging agent, a coloring agent, a nucleating agent, and an antibacterial agent may be contained.
  • middle layer (B) can be obtained by melt-mixing said resin and the other component used as needed, and forming into a film form.
  • an extruder or the like can be used for the melt mixing, and a T-die or the like can be used for the film formation.
  • the thickness of the intermediate layer (B) is not particularly limited as long as it does not impair the adhesion to the laminate layer (A) and / or the heat seal layer (C) and the cohesive failure performance of the laminate layer (A).
  • the thickness is preferably about 3 to 50 ⁇ m, more preferably about 4 to 45 ⁇ m. If the intermediate layer (B) is too thin, adhesion to the laminate layer (A) and / or the heat seal layer (C) may be insufficient.
  • the sheet seal layer (C) is a layer having a function of sealing the package obtained by thermocompression of the opposed heat seal layers (C) when the packaging bag is heat sealed.
  • This heat seal layer (C) contains a propylene random copolymer (C1).
  • propylene random copolymer (C1) examples include a copolymer of propylene and an ⁇ -olefin.
  • the ⁇ -olefin is preferably an ⁇ -olefin having 2 or 4 to 10 carbon atoms. Specific examples include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1 pentene and the like. be able to. Particularly preferred is a propylene-ethylene random copolymer or a propylene-ethylene-butene random copolymer.
  • the content of propylene units in the propylene random copolymer (C1) is preferably 80 to 99% by weight, more preferably 85 to 98% by weight when the total amount of the copolymer is 100% by weight. is there.
  • the melting point of the propylene random copolymer (C1) is not particularly limited, but the melting point is preferably in the range of 115 to 155 ° C. from the viewpoint of obtaining good low temperature heat sealability, More preferably, it is within the range of 120 to 150 ° C. When the melting point of the propylene random copolymer (C1) is too low, the heat resistance of the heat seal part may be inferior. On the other hand, when the melting point is too high, the low temperature heat sealability may be insufficient.
  • the MFR (230 ° C.) of the propylene random copolymer (C1) is not particularly limited, but it is preferably 0.5 to 50.0 g / 10 minutes in view of film forming properties.
  • the resin constituting the heat seal layer (C) may be formed of the propylene random copolymer (C1) alone, and contains other resins in addition to the propylene random copolymer (C1). May be.
  • the other resins used here include other thermoplastic resins in addition to the polybutene-based resins described above, the same types of resins as LLDPE and LDPE.
  • the amount of other resin used in the resin constituting the heat seal layer (C) is preferably 10 parts by weight or less when the total amount of the resin is 100 parts by weight. That is, the amount of the propylene random copolymer (C1) used is preferably 90 parts by weight or more.
  • the heat seal layer (C) is a petroleum resin, terpene resin, rosin, anti-blocking agent, antioxidant, light stabilizer, lubricant, electrification as long as the function of the layer is not impaired. You may contain other components, such as an inhibitor, an antifogging agent, a coloring agent, a nucleus agent, and an antibacterial agent.
  • the heat seal layer (C) can be obtained by melt-mixing the above resin and other components used as necessary, and forming into a film. For example, an extruder or the like can be used for the melt mixing, and a T-die or the like can be used for the film formation.
  • the thickness of the heat seal layer (C) is not particularly limited as long as it does not impair the adhesion between the heat seal layers (C).
  • the thickness is preferably about 1.5 to 50 ⁇ m, more preferably 30 ⁇ m or less. If the heat seal layer (C) is too thin, the heat sealability may be insufficient. On the other hand, if the heat seal layer (C) is too thick, it is not preferable in that the economy is inferior and the weight of the resulting packaging bag increases.
  • the multilayer sealant film of the present invention is constituted by laminating the laminate layer (A), the intermediate layer (B), and the heat seal layer (C) in this order.
  • the intermediate layer may be a single layer, or may be composed of a multilayer having the same function or a multilayer having a different function.
  • Each layer in the multilayer sealant film is preferably laminated under non-stretched or low-stretch conditions, and particularly preferably laminated substantially unstretched.
  • Each layer in the multilayer sealant film is preferably laminated by a coextrusion method.
  • the film forming method for each layer is preferably a non-stretching method.
  • a feed block method using a T die or a co-extrusion method by a multi-manifold method is suitable. is there.
  • an extrusion method using the T-die for example, The resin or resin composition melt constituting each layer is extruded from each extruder by a T-die method, Winding after cooling with a temperature-adjustable roll; Winding after cooling with a temperature-adjustable water bath; Winding after cooling by air cooling method; Winding after cooling by water cooling method Etc.
  • the multilayer sealant film obtained by these methods is a low-stretched film or a substantially unstretched film that is slightly stretched by a tension during winding.
  • the thickness of the multilayer sealant film of the present invention can be, for example, 10 to 150 ⁇ m, and preferably 15 to 120 ⁇ m.
  • the laminate layer (A), intermediate layer (B) and heat seal layer (C) are subjected to appropriate surface treatment such as corona discharge treatment and flame treatment prior to lamination for the purpose of improving the adhesion of each layer. Also good. There is no restriction
  • the multilayer sealant film of the present invention as described above can be used as a packaging material by sticking to the base film with the laminate layer (A) as the sticking surface.
  • FIG. 1 is a schematic cross-sectional view of a packaging material 2 in which a multilayer sealant film 1 of the present invention comprising a laminate layer A, an intermediate layer B, and a heat seal layer C is attached to a base film 3 with the laminate layer A as an attachment surface. It is shown.
  • the material which comprises a base film can be suitably selected according to the intensity
  • the base film preferably has, for example, a layer made of one or more resins selected from the group consisting of polypropylene resin, polyethylene resin, polyethylene terephthalate resin and polyamide resin, or a layer made of metal.
  • the base film include a biaxially stretched polyester film, a biaxially stretched polyamide film, and a biaxially stretched polypropylene film; Deposition film obtained by depositing metal film on biaxially stretched polyester film, biaxially stretched polyamide film, biaxially stretched polypropylene film, etc .; Laminated film of biaxially stretched polyester film, biaxially stretched polyamide film, biaxially stretched polypropylene film and other thermoplastic resin films Etc.
  • the thickness of the base material can be appropriately set depending on the use of the packaging material, and can be, for example, about 10 to 300 ⁇ m.
  • the base material may be printed with the product name of the contents, the name of the manufacturer, and the like.
  • the surface of the substrate on the side where the multilayer sealant film of the present invention is laminated may be subjected to appropriate surface treatment such as corona discharge treatment or flame treatment for the purpose of improving adhesion.
  • the multilayer sealant film of the present invention is affixed to the substrate film with the laminate layer (A) as the affixing surface.
  • the thermocompression bonding temperature is preferably not less than the softening temperature of the laminate layer (A)
  • the thermocompression bonding pressure is preferably not less than about 0.1 MPa
  • the thermocompression bonding time Is preferably about 0.5 to 5.0 seconds.
  • the adhesive for example, a molten resin (for example, a melted polyethylene resin) can be used, and a commercially available adhesive may be used. Examples of the method for applying the adhesive include transfer means such as gravure, gravure reverse, and offset; scraping means such as a bar and a comma bar.
  • a packaging bag can be obtained by processing the packaging material obtained as described above into a bag shape having an opening with the heat seal layer (C) on the inside.
  • the packaging material can be formed into a bag shape by folding the packaging material into an appropriate size with the heat seal layer (C) on the inside, and heat sealing the ends.
  • the heat seal temperature is preferably set to a temperature at which the heat seal layers (C) can be thermocompression-bonded, for example, about 100 to 200 ° C.
  • the heat seal pressure can be set, for example, to about 0.1 to 1.0 MPa
  • the heat seal time can be set, for example, to about 0.5 to 5.0 seconds.
  • the packaging bag manufactured using the multilayer sealant film of the present invention is excellent in transparency and image clarity even after heat sealing the heat seal layer (C).
  • the transparency of the packaging material after heat sealing the heat seal layer (C) can be, for example, 10% or less, preferably 8% or less,
  • the image definition can be, for example, 55% or more, and preferably 65% or more.
  • FIG. 2 shows a sealed package 5 in which a package comprising the multilayer sealant film 1 and the substrate film 3 of the present invention is sealed as a heat seal 4 by heat-sealing at the opening after the contents 6 are stored.
  • a schematic illustration is shown.
  • This packaging body is easily and easily grasped by the fingertips of the left and right hands, respectively, in the vicinity of the heat seal portion, and pulled perpendicularly to the film surface and in the direction in which the two films are separated from each other. Can be opened smoothly.
  • One of the characteristics of the present invention is that the opening is performed by co-operation of cohesive failure and delamination.
  • FIG. 3 is a schematic explanatory diagram for explaining a mechanism at the time of opening the heat seal portion of the hermetic package.
  • the heat seal part is pulled in two directions indicated by arrows, and the delamination of the heat seal layer (C) and the intermediate layer (B) proceeds along with the cohesive failure of the laminate layer (A). Has been shown.
  • the said package body shows the easy and smooth opening characteristic stably irrespective of heat seal conditions.
  • the opening strength of the sealed package can be, for example, 40 N / bag or less, preferably 10 to 40 N / bag, and more preferably 15 to 35 N / bag.
  • the bursting strength representing the sealing property of the package can be, for example, 10 kPa or more, and preferably 15 kPa or more.
  • the physical properties of the resin and film were measured as follows. (1) MFR Based on JISK6758, MFR was measured at 230 ° C. for polypropylene and 190 ° C. for polybutene and polyethylene. (2) Melting point Approximately 5 mg of a resin sample was precisely weighed and sealed in an aluminum pan. This was mounted on a differential scanning calorimeter (model “SSC / 5200” manufactured by Seiko Instruments Inc.) and in a nitrogen stream at 20 mL / min. The temperature is raised to 230 ° C., held at this temperature for 10 minutes, cooled to ⁇ 10 ° C.
  • the film (packaging material) was visually checked for tears, and the following determinations were made.
  • PB1 Polybutene homopolymer (manufactured by Mitsui Chemicals, Inc., BL4000, density 0.915 g / cm 3 , melting point 112 ° C., MFR 1.8 g / 10 min)
  • PB2 1-butenepropylene random copolymer (manufactured by Mitsui Chemicals, Inc., BL2481, density 0.900 g / cm 3 melting point 75 ° C., MFR 4.0 g / 10 min, butene content 79.2 parts by weight)
  • LLDPE1 linear low density polyethylene (Ube Maruzen Polyethylene Co., Ltd.
  • LLDPE2 linear low-density polyethylene (Sumitomo Chemical Co., Ltd. CW8003, density 0.912 g / cm 3 , melting point 110 ° C., MFR 8.0 g / 10 min)
  • LDPE1 Low-density polyethylene (Ube Maruzen Polyethylene Co., Ltd. Z372, density 0.934 g / cm 3 , melting point 118 ° C., MFR 5.0 g / 10 min)
  • LDPE2 Low density polyethylene (U322 Maruzen Polyethylene Co., Ltd.
  • LLDPE3 Low density polyethylene (L705 manufactured by Sumitomo Chemical Co., Ltd., density 0.919 g / cm 3 , melting point 107 ° C., MFR 7.0 g / 10 min)
  • Long-chain branched LLDPE2 (manufactured by Sumitomo Chemical Co., Ltd.
  • LLDPE3 (manufactured by Sumitomo Chemical Co., Ltd., GH051 melting point 109 ° C., MFR 0.4 g / 10 min, Mw / Mn 13.2, amorphous component 2.2 wt%)
  • PP1 propylene-ethylene random copolymer (manufactured by Nippon Polypro Co., Ltd.
  • R-PP1 propylene-ethylene-1-butene random copolymer (manufactured by Prime Polymer Co., Ltd. F794NV, melting point 134 ° C., MFR 5.0 g / 10 min)
  • R-PP2 Propylene-ethylene random copolymer (Nippon Polypro Co., Ltd. WFX4TA, melting point 126 ° C., MFR 7.0 g / 10 min)
  • the content of the long chain branch shown in the “long chain branch” column is the number of carbon atoms per 1,000 carbon atoms, measured under the following conditions and calculated from the result of 13 C-NMR according to the following formula (1).
  • the amorphous component content is measured during the period in which the column supply after the sample supply is cooled to 0 ° C. and then the supply of the solvent is started and the column temperature is maintained at 0 ° C. This is the weight ratio of the fraction eluted in the total fraction.
  • Measuring equipment Model number "TREF equipment special type", manufactured by Senshu Kagaku Co., Ltd.
  • Extruder for layer A a mixture of 35 parts by weight of PB1, 50 parts by weight of LLDPE1 and 15 parts by weight of LDPE1
  • Extruder for layer B long-chain branched LLDPE1 C
  • layer extruder R-PP1
  • the resin temperature was 230 ° C.
  • the resin was melted at a residence time of 1 minute
  • the condition of T die temperature 230 ° C. from each T die having a die lip gap of 1.5 mm by the coextrusion method with the feed block method 3 layers were combined and passed through a cooling roll at 30 ° C. to obtain a multilayer film.
  • This multilayer film had a three-layer structure, the total thickness was 20 ⁇ m, and the three-layer thickness structure was an A layer of 4 ⁇ m, a B layer of 11 ⁇ m, and a C layer of 5 ⁇ m.
  • the laminate layer (A) was wound by a winder
  • a multilayer sealant film consisting of: / intermediate layer (B) / heat seal layer (C) was obtained.
  • a corona discharge treatment was performed on one side of a biaxially stretched polyester film (product name “E2001”, thickness 12 ⁇ m) manufactured by Phutamura Chemical Co., Ltd. so that the wetting index was 40 mN / m.
  • the corona discharge-treated surface of this base film and the corona discharge-treated surface (laminate layer (A) surface) of the multilayer sealant film obtained above were bonded together with a urethane adhesive to obtain a packaging material.
  • a vertical pillow packaging machine manufactured by TOKYO AUTOMATIC MACHINE MFG.
  • Example 2 to 14 and Comparative Examples 1 to 15 In Example 1 above, the multilayer film and the packaging bag were the same as Example 1 except that the type and amount of resin supplied to the extruder for each layer and the thickness of each layer were as shown in Table 3. Were manufactured and evaluated respectively.
  • the bag-making conditions B of Example 5 are a heat seal width of 15 mm, a heat seal temperature of 200 ° C., a time of 1.0 second, and a pressure of 1.0 MPa.
  • the evaluation results are shown in Table 3. Effects of the Invention
  • the packaging material produced using the multilayer sealant film of the present invention provides a sealed package that can be easily opened without depending on heat sealing conditions.
  • the packaging material by appropriately setting the conditions for heat-sealing the packaging material, it is possible to obtain a hermetic package in which high heat-sealing strength and easy-openability are compatible.
  • the interface between the heat seal layer and the intermediate layer depends on the temperature and pressure at the time of sealing. Delamination does not function because it is broken by melting and compression, the heat seal layer and the intermediate layer are broken, and a reliable easy peel property is exhibited by the cohesive failure mode of the laminate layer.
  • the multilayer sealant film of the present invention is extremely suitable as a raw material for packaging materials for sealing and storing and trading food, clothing, miscellaneous goods, papers such as books and cards, and industrial parts.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Bag Frames (AREA)
  • Packages (AREA)

Abstract

L'invention fournit un film d'étanchéité qui possède une solidité élevée de thermo-soudage indépendamment des conditions de thermo-soudage, et qui permet d'obtenir un emballage scellé à ouverture facile. Plus précisément, l'invention concerne un film d'étanchéité multicouche qui possède : une couche stratifiée qui est la couche la plus externe; au moins une couche intermédiaire; et une couche de thermo-soudage qui est une autre des couches les plus externes. En outre, ce film d'étanchéité multicouche est mis en œuvre par collage sur un film de matériau de base du côté de ladite couche stratifiée en tant que face de collage. Ladite couche stratifiée est constituée d'une résine qui comprend 30 à 70 parties en masse de résine de polybutène, 20 à 60 parties en masse de résine de polyéthylène de faible densité à chaîne droite, et 10 à 50 parties en masse de résine de polyéthylène de faible densité dont la densité est supérieure ou égale à 0,930g/cm3. Ladite couche intermédiaire est constituée d'une résine comprenant 50 à 100 parties en masse de polyéthylène de faible densité à chaîne droite à ramification en chaîne longue. Enfin, ladite couche de thermo-soudage est constituée d'une résine comprenant un copolymère aléatoire de propylène.
PCT/JP2015/062162 2014-04-28 2015-04-15 Film d'étanchéité multicouche Ceased WO2015166848A1 (fr)

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JP2017137098A (ja) * 2016-02-04 2017-08-10 凸版印刷株式会社 易開封性包装袋
WO2017171036A1 (fr) * 2016-03-31 2017-10-05 Ｊｘエネルギー株式会社 Matériau en feuille et matériau de conditionnement d'agent de transpiration d'alcool utilisant le matériau en feuille
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CN109563282B (zh) * 2016-07-22 2022-04-15 三井化学株式会社 医疗用膜及其制造方法、医疗用涂覆组合物、医疗用具及其制造方法
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WO2020105710A1 (fr) * 2018-11-22 2020-05-28 キョーラク株式会社 Film de formage-remplissage-scellage et procédé de formage-remplissage-scellage
JP2020090326A (ja) * 2018-11-22 2020-06-11 キョーラク株式会社 製袋充填用フィルム、製袋充填方法
JP7440737B2 (ja) 2018-11-22 2024-02-29 キョーラク株式会社 製袋充填用フィルム、製袋充填方法
CN111792183A (zh) * 2020-07-09 2020-10-20 佛山市南海飞亚手袋制品有限公司 夹链防护密实包装袋及其制作方法
WO2022113600A1 (fr) * 2020-11-26 2022-06-02 三井化学株式会社 Stratifié
WO2025154815A1 (fr) * 2024-01-17 2025-07-24 三井・ダウ ポリケミカル株式会社 Stratifié pour matériau de couvercle, matériau de couvercle et récipient d'emballage
WO2025191505A1 (fr) * 2024-03-15 2025-09-18 Ｚａｃｒｏｓ株式会社 Film d'étanchéité et film stratifié

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KR20160147721A (ko) 2016-12-23
CN106255595A (zh) 2016-12-21
JP6441322B2 (ja) 2018-12-19
TW201607751A (zh) 2016-03-01
JPWO2015166848A1 (ja) 2017-04-20

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