WO2021200811A1 - 積層フィルム - Google Patents

積層フィルム Download PDF

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Publication number
WO2021200811A1
WO2021200811A1 PCT/JP2021/013264 JP2021013264W WO2021200811A1 WO 2021200811 A1 WO2021200811 A1 WO 2021200811A1 JP 2021013264 W JP2021013264 W JP 2021013264W WO 2021200811 A1 WO2021200811 A1 WO 2021200811A1
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WIPO (PCT)
Prior art keywords
resin layer
laminated film
resin
polyolefin
layer
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/JP2021/013264
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English (en)
French (fr)
Japanese (ja)
Inventor
善亨 大矢
隆一 村田
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite 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 Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Priority to CN202180025479.2A priority Critical patent/CN115335231B/zh
Priority to JP2021552553A priority patent/JP7348953B2/ja
Priority to EP21779412.2A priority patent/EP4129672A4/en
Publication of WO2021200811A1 publication Critical patent/WO2021200811A1/ja
Priority to JP2022062518A priority patent/JP7697394B2/ja
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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/414—Translucent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/58—Cuttability
    • B32B2307/581—Resistant to cut
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present invention relates to a laminated film.
  • This application claims priority based on Japanese Patent Application No. 2020-060062 filed in Japan on March 30, 2020 and Japanese Patent Application No. 2020-209113 filed in Japan on December 17, 2020. And the contents are used here.
  • a laminated film composed of a plurality of resin layers laminated is widely used as a material for a packaging body.
  • a typical laminated film includes at least a sealant layer provided for heat-sealing the object to be sealed and an outer layer provided on the side opposite to the sealant layer side.
  • a laminated film for example, a polyethylene laminate for a packaging material, which includes a stretched polyethylene film, an adhesive layer, and a heat-sealable polyethylene layer at least, and the adhesive layer contains a solvent-free adhesive, is disclosed. (See Patent Document 1).
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminated film having higher heat resistance and higher reusability than before.
  • the present invention adopts the following configuration.
  • the first resin layer and the second resin layer are provided, the first resin layer and the second resin layer contain the same type of polyolefin resin, and the second resin layer is subjected to dynamic viscoelasticity measurement and vibration frequency.
  • the elastic coefficient E'(100) at 100 ° C. and the elastic coefficient E'(110) at 110 ° C. are measured when is 1 Hz, the values of E'(110) / E'(100) are Laminated film with a value of 0.2 or more.
  • the laminated film according to [1] wherein the laminated film has a gel fraction of 30% or more. [3].
  • the laminated film further includes a third resin layer between the first resin layer and the second resin layer, and the first resin layer, the second resin layer, and the third resin layer are formed.
  • the laminated film according to any one of [1] to [4], which comprises the same type of polyolefin resin. [6].
  • the third resin layer is composed of a plurality of three or more layers, and at least one of them contains the polyolefin resin, an ethylene-vinyl alcohol copolymer, and an ethylene-vinyl alcohol-vinyl acetate copolymer.
  • a laminated film having higher heat resistance and higher reusability than the conventional one is provided.
  • the laminated film includes a first resin layer and a second resin layer, and the first resin layer and the second resin layer contain the same type of polyolefin resin, and the second resin layer.
  • DMA dynamic viscoelasticity measurement
  • the value of E'(110) / E'(100) is 0.2 or more.
  • modulus of elasticity means “modulus of storage” unless otherwise specified.
  • the laminated film of the present embodiment has high reusability because the first resin layer and the second resin layer contain the same type of polyolefin resin. Further, in the laminated film of the present embodiment, the E'(110) / E'(100) value of the second resin layer is 0.2 or more, and the heat resistance of the second resin layer is high. It has higher heat resistance than a laminated film containing a normal polyolefin resin. When such a laminated film having high heat resistance is heat-sealed, adhesion of the laminated film (particularly the second resin layer) to the heating plate in the heat-sealing device is suppressed.
  • the first resin layer contains a polyolefin-based resin.
  • the polyolefin-based resin contained in the first resin layer is not particularly limited as long as it has a structural unit derived from an olefin, and may be a copolymer of one type of olefin, or two or more types. It may be a copolymer of olefin.
  • Examples of the homopolymer of the olefin include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), metallocene-catalyzed linear low density polyethylene (mLLDPE), medium density polyethylene (MDPE), and high density polyethylene. (HDPE) and the like polyethylene; polypropylene (homopolypropylene) and the like can be mentioned.
  • Linear low density polyethylene (LLDPE) and metallocene-catalyzed linear low density polyethylene (mLLDPE) are both types of low density polyethylene (LDPE).
  • polyethylene is classified according to its density by this definition. That is, in the present specification, the low-density polyethylene (LDPE), density of 0.91 g / cm 3 or more, means a polyethylene is less than 0.93 g / cm 3. In addition, the medium density polyethylene (MDPE), density of 0.93 g / cm 3 or more, means a polyethylene is less than 0.942 g / cm 3.
  • the high-density polyethylene (HDPE) means polyethylene having a density of 0.942 g / cm 3 or more.
  • olefin copolymer examples include an ethylene-based copolymer having at least a structural unit derived from ethylene and a propylene-based copolymer having at least a structural unit derived from propylene.
  • the ethylene-based copolymer has a structural unit derived from ethylene and a structural unit derived from a monomer other than ethylene.
  • the number of structural units derived from propylene is the number of structural units derived from ethylene. More copolymers are classified as propylene-based copolymers for convenience.
  • ethylene-based copolymer examples include an ethylene-vinyl acetate copolymer (EVA), an ethylene-vinyl alcohol copolymer (EVOH), and an ethylene-vinyl alcohol-vinyl acetate copolymer (also known as ethylene-vinyl acetate).
  • EVA ethylene-vinyl acetate copolymer
  • EVOH ethylene-vinyl alcohol copolymer
  • ethylene-vinyl alcohol-vinyl acetate copolymer also known as ethylene-vinyl acetate
  • EVA partially saponified product Polymer partially saponified product, sometimes referred to herein as "EVA partially saponified product", ethylene-methyl acrylate copolymer (EMA), ethylene-methyl methacrylate copolymer (EMMA), ethylene- Ethyl acrylate copolymer (EEA), ethylene-acrylate copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethyl ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH) ), Ionomer (ION) and the like.
  • EMA ethylene-methyl acrylate copolymer
  • EMMA ethylene-methyl methacrylate copolymer
  • EAA ethylene- Ethyl acrylate copolymer
  • EAA ethylene-acrylate copolymer
  • EAA ethylene-methacrylic acid copolymer
  • E-EA-MAH ethyl ethylene-ethy
  • ionomer for example, a resin in which a copolymer of ethylene and a small amount of acrylic acid or methacrylic acid has an ion-crosslinked structure by salt formation of an acid portion thereof and metal ions. Can be mentioned.
  • the propylene-based copolymer has a structural unit derived from propylene and a structural unit derived from a monomer other than propylene.
  • examples of the propylene-based copolymer include a propylene-ethylene random copolymer (also known as polypropylene random copolymer (rPP)) and a propylene-ethylene block copolymer (also known as polypropylene block copolymer (bPP)).
  • the polyolefin-based resin contained in the first resin layer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary depending on the purpose. Can be selected.
  • the polyolefin-based resin contained in the first resin layer is preferably a polyethylene-based resin, and more preferably low-density polyethylene.
  • the first resin layer may contain other components in addition to the polyolefin-based resin as long as the effects of the present invention are not impaired.
  • the other components may be referred to as a resin component (in the present specification, may be referred to as “another resin component") and a non-resin component (in the present specification, may be referred to as “another non-resin component”). ) May be used.
  • the other resin component is not particularly limited as long as it is a resin other than the polyolefin-based resin.
  • Examples of the other non-resin component include additives known in the art.
  • Examples of the additive include antifogging agents, antiblocking agents, antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, thickeners, thickeners, heat stabilizers, lubricants, infrared absorbers, and the like. Examples include ultraviolet absorbers.
  • the other components contained in the first resin layer may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof are arbitrary depending on the purpose. Can be selected.
  • the content of the polyolefin-based resin with respect to the total mass of the first resin layer (the polyolefin-based resin of the same type as the polyolefin-based resin contained in the second resin layer, and the polyolefin-based resin contained in the second resin layer).
  • the ratio of the total content of the polyolefin-based resin that is not the same type) is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, for example, 97 to 100% by mass, and 99. It may be any of ⁇ 100% by mass. When the ratio is at least the lower limit value, the effect of the first resin layer containing the polyolefin resin can be obtained more remarkably.
  • the ratio is usually the content of the polyolefin-based resin (polyolefin of the same type as the polyolefin-based resin contained in the second resin layer) with respect to the total content (parts by mass) of the components that do not vaporize at room temperature in the first resin composition described later. It is the same as the ratio of the total content) (parts by mass) of the based resin and the polyolefin-based resin contained in the second resin layer and not the same type as the polyolefin-based resin.
  • the first resin layer and the second resin layer contain the same type of polyolefin resin.
  • the total amount (mol) of the constituent units is taken into account.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • mLLDPE metallocene-catalyzed linear low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • EMA resin ethylene-methyl methacrylate copolymer
  • EMMA resin ethylene-vinyl alcohol copolymer
  • EVOH ethylene-vinyl alcohol copolymer
  • EVA ethylene-vinyl alcohol-vinyl acetate All copolymers (EVA partially saponified products) and the like are the same type because the ratio of the amount (mol) of the structural unit derived from ethylene to the total amount (mol) of the structural unit is 20 mol% or more. And.
  • the ratio of the amount (mol) of the constituent unit derived from ethylene to the total amount (mol) of the constituent unit is 20 mol. If it is less than%, it is not considered to be the same kind as the above-mentioned low-density polyethylene or the like.
  • the ratio of the amount (mol) of the common constituent unit to the total amount (mol) of the constituent units is preferably 30 mol% or more, more preferably 40 mol. % Or more, more preferably 50 mol% or more, and for example, 60 mol% or more, 70 mol% or more, and 80 mol% or more may be used.
  • the ratio of the content of the polyolefin-based resin of the same type as the polyolefin-based resin contained in the second resin layer to the total mass of the first resin layer is preferably 80 to 100% by mass, preferably 90 to 90 to 100% by mass. It is more preferably 100% by mass, and may be, for example, either 95 to 100% by mass and 99 to 100% by mass. When the ratio is at least the lower limit value, the reusability of the laminated film becomes higher.
  • the ratio of the content of the low-density polyethylene to the total mass of the first resin layer in the first resin layer is preferably 70 to 100% by mass, preferably 80 to 80 to 100% by mass. It is more preferably 100% by mass, and even more preferably 90 to 100% by mass. When the ratio is at least the lower limit value, the effect obtained by the first resin layer containing low-density polyethylene becomes higher.
  • room temperature means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.
  • the first resin layer may be composed of one layer (single layer) or may be composed of two or more layers.
  • the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
  • the thickness of the first resin layer can be arbitrarily set according to the use of the laminated film, and is not particularly limited.
  • the thickness of the first resin layer is usually preferably 5 to 100 ⁇ m, more preferably 10 to 80 ⁇ m, and even more preferably 20 to 60 ⁇ m.
  • the thickness of the first resin layer is at least the above lower limit value, the strength of the first resin layer is further improved, and the effect of the laminated film including the first resin layer can be obtained more remarkably. ..
  • the thickness of the first resin layer is equal to or less than the upper limit value, excessive thickness is suppressed.
  • the total thickness of the plurality of layers may be set to be the above-mentioned preferable thickness of the first resin layer.
  • the first resin layer is preferably a non-stretched layer (film). Since the first resin layer is a non-stretched layer, the moldability of the laminated film is improved.
  • the first resin layer is suitable as, for example, a sealant layer.
  • the second resin layer contains a polyolefin-based resin of the same type as the polyolefin-based resin contained in the first resin layer.
  • the same type of polyolefin resin contained in the second resin layer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are intended. It can be selected arbitrarily according to the situation.
  • the polyolefin-based resin of the same type contained in the second resin layer is preferably a polyethylene-based resin, and more preferably a high-density polyethylene. It is easier for the second resin layer containing a polyethylene-based resin, particularly high-density polyethylene, to have an E'(110) / E'(100) value of 0.2 or more. That is, both the first resin layer and the second resin layer preferably contain a polyethylene-based resin, and more preferably the second resin layer contains high-density polyethylene.
  • the second resin layer may contain other components in addition to the polyolefin-based resin of the same type as the polyolefin-based resin contained in the first resin layer, as long as the effects of the present invention are not impaired.
  • the other components in the second resin layer are a resin component (sometimes referred to as “another resin component” in the present specification) and a non-resin component (in the present specification, “another non-resin component”). It may be called any of).
  • the other resin component in the second resin layer is not particularly limited as long as it is a resin other than the polyolefin-based resin of the same type as the polyolefin-based resin contained in the first resin layer.
  • the other resin component in the second resin layer include a polyolefin-based resin that is not the same type as the polyolefin-based resin contained in the first resin layer, and a resin other than the polyolefin-based resin.
  • Examples of the polyolefin-based resin that is not the same as the polyolefin-based resin contained in the first resin layer include the same polyolefin-based resins as those mentioned above as the polyolefin-based resin contained in the first resin layer.
  • non-resin component in the second resin layer examples include the same as the non-resin component in the first resin layer.
  • the other components contained in the second resin layer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary depending on the purpose. Can be selected.
  • the content of the polyolefin-based resin with respect to the total mass of the second resin layer (the same type of polyolefin-based resin as the polyolefin-based resin contained in the first resin layer and the same type of polyolefin-based resin contained in the first resin layer).
  • the ratio of the total content of the non-polyolefin resin and the non-polyolefin resin is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, for example, 97 to 100% by mass, and 99 to 99 to 100% by mass. It may be any of 100% by mass. When the ratio is at least the lower limit value, the effect of the second resin layer containing the polyolefin resin can be obtained more remarkably.
  • the ratio is usually the content of the polyolefin-based resin (polyolefin of the same type as the polyolefin-based resin contained in the first resin layer) with respect to the total content (parts by mass) of the components that do not vaporize at room temperature in the second resin composition described later. It is the same as the ratio of the total content) (parts by mass) of the based resin and the polyolefin-based resin contained in the first resin layer and not the same type as the polyolefin-based resin.
  • the ratio of the content of the polyolefin-based resin of the same type as the polyolefin-based resin contained in the first resin layer to the total mass of the second resin layer is preferably 80 to 100% by mass, preferably 90 to 90 to 100% by mass. It is more preferably 100% by mass, and may be, for example, either 95 to 100% by mass and 99 to 100% by mass. When the ratio is at least the lower limit value, the reusability of the laminated film becomes higher.
  • the ratio of the content of the high-density polyethylene to the total mass of the second resin layer in the second resin layer is preferably 70 to 100% by mass, preferably 80 to 80 to 100% by mass. It is more preferably 100% by mass, and even more preferably 90 to 100% by mass. When the ratio is at least the lower limit value, the heat resistance of the second resin layer is remarkably improved.
  • the second resin layer may be irradiated with an electron beam. That is, the laminated film may be irradiated with an electron beam, and it is preferable that the laminated film is irradiated with an electron beam from the second resin layer side.
  • the second resin layer can be easily set to 0. It can be 2 or more. It is presumed that the reason is that the crosslink density of the resin in the second resin layer is increased by the electron beam irradiation.
  • a preferable second resin layer irradiated with an electron beam is, for example, a second resin layer not irradiated with an electron beam containing low-density polyethylene (in the present specification, the second resin layer in this case is an electron beam.
  • the electron beam-irradiated laminated film for example, the laminated film including the unirradiated second resin layer containing low-density polyethylene (in the present specification, the laminated film in this case).
  • the film is electron beam irradiated.
  • the ratio of the content of the low-density polyethylene to the total mass of the unirradiated second resin layer is preferably 70 to 100% by mass, and preferably 80 to 100% by mass. More preferably, it is 90 to 100% by mass. When the ratio is at least the lower limit value, the effect of electron beam irradiation can be obtained more remarkably.
  • the electron beam irradiation of the unirradiated second resin layer or the unirradiated laminated film is preferably performed under the condition of an absorbed dose of 20 to 300 kGy.
  • the absorbed dose is at least the above lower limit value, the effect of electron beam irradiation can be obtained more remarkably.
  • the resin in the second resin layer is suppressed from being excessively crosslinked. That is, as a laminated film irradiated with an electron beam, a laminated film irradiated with an electron beam under a condition of an absorbed dose of 20 to 300 kGy can be mentioned.
  • the acceleration voltage of the unirradiated second resin layer or the unirradiated laminated film at the time of electron beam irradiation is preferably 100 to 300 kV, more preferably 120 to 280 kV, and further preferably 140 to 260 kV.
  • the acceleration voltage is at least the lower limit value, the effect of electron beam irradiation can be obtained more remarkably.
  • the acceleration voltage is not more than the upper limit value, excessive cross-linking of the resin in the second resin layer is suppressed.
  • the gel fraction of the laminated film is increased by electron beam irradiation, for example. That is, the gel fraction of the laminated film is larger than the gel fraction of the unirradiated laminated film.
  • the gel fraction of the laminated film is preferably 30% or more, and may be any of, for example, 30 to 90%, 32 to 78%, and 34 to 76%.
  • Such a laminated film has more preferable heat resistance as a laminated film provided with the second resin layer having the above-mentioned E'(110) / E'(100) values.
  • the gel fraction of the laminated film can be measured according to JIS K 6769. That is, the laminated film is immersed in an organic solvent such as xylene, the insoluble matter remaining undissolved is dried, and the mass thereof is determined to determine the mass of the laminated film before dissolution and the insoluble material derived from the laminated film after drying.
  • the gel fraction can be calculated from the mass of the object. More specifically, for example, an Xg laminated film is wrapped in a Yg stainless steel wire mesh, immersed in a heated organic solvent, and an insoluble matter derived from the laminated film is taken out from the organic solvent together with the stainless steel wire mesh. ..
  • thermomechanical analysis is performed on a laminated film
  • the temperature showing a displacement of 2000 ⁇ m is preferably 120 ° C. or higher, for example. , 125-200 ° C, and 130-195 ° C.
  • Such a laminated film has more preferable heat resistance as a laminated film provided with the second resin layer having the above-mentioned E'(110) / E'(100) values.
  • the displacement at a temperature of 100 ° C. is preferably 500 ⁇ m or less, and for example, it may be either 50 to 490 ⁇ m or 100 to 480 ⁇ m or less.
  • Such a laminated film has more preferable heat resistance as a laminated film provided with the second resin layer having the above-mentioned E'(110) / E'(100) values.
  • thermomechanical analysis of the laminated film is based on, for example, JIS K7196, and the thermal expansion amount of the sample is determined from the difference in the thermal expansion amount when the temperature of the standard sample and the target sample is raised at a constant rate. It can be done by the method of measurement.
  • the second resin layer may be composed of one layer (single layer) or may be composed of two or more layers.
  • the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
  • the thickness of the second resin layer can be arbitrarily set according to the use of the laminated film, and is not particularly limited.
  • the thickness of the second resin layer is usually preferably 5 to 100 ⁇ m, more preferably 10 to 80 ⁇ m, and even more preferably 20 to 60 ⁇ m.
  • the thickness of the second resin layer is at least the above lower limit value, the strength of the second resin layer is further improved, and the effect of the laminated film including the second resin layer can be obtained more remarkably. ..
  • the thickness of the second resin layer is equal to or less than the upper limit value, excessive thickness is suppressed.
  • the total thickness of the plurality of layers may be set to be the above-mentioned preferable thickness of the second resin layer.
  • the ratio (thickness ratio) of [thickness of the first resin layer] / [thickness of the second resin layer] is not particularly limited, but is not particularly limited, regardless of the presence or absence of the third resin layer described later. It is preferably 0.7 to 1.3. When the thickness ratio is in such a range, the effect obtained by providing the laminated film with the first resin layer and the effect obtained by providing the second resin layer are more balanced. Well obtained.
  • the second resin layer is subjected to dynamic viscoelasticity measurement (DMA: Dynamic Mechanical. Analysis), and has an elastic modulus E'(100) at 100 ° C. and a vibration frequency of 1 Hz when the vibration frequency is 1 Hz.
  • DMA Dynamic Mechanical. Analysis
  • the elastic modulus E'(110) at 110 ° C. is measured, the E'(110) / E'(100) value is 0.2 or more.
  • examples of the second resin layer for performing dynamic viscoelasticity measurement that is, the test piece of the second resin layer, have a width of 1 cm and a length of 5 cm or more.
  • the test piece is installed so that the length of the measurement target portion for which the dynamic viscoelasticity is measured is 2 cm, and the test piece is heated at a temperature rising rate of 5 ° C./min. It is preferable to perform dynamic viscoelasticity measurement. Under such conditions, the elastic modulus E'(100) and the elastic modulus E'(110) can be measured with higher accuracy.
  • the E'(110) / E'(100) value of the second resin layer is preferably 0.24 or more, for example, 0. It may be any of 3 or more, 0.4 or more, 0.5 or more and 0.6 or more.
  • the upper limit of the E'(110) / E'(100) value of the second resin layer is not particularly limited.
  • the second resin layer having an E'(110) / E'(100) value of 0.9 or less can be realized more easily.
  • the E'(110) / E'(100) value of the second resin layer can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and upper limit values.
  • the E'(110) / E'(100) value of the second resin layer is preferably 0.2 to 0.9, preferably 0.24 to 0.9. More preferably, for example, it may be any one of 0.3 to 0.9, 0.4 to 0.9, 0.5 to 0.9, and 0.6 to 0.9.
  • the E'(110) / E'(100) value of the second resin layer containing the high-density polyethylene tends to be larger.
  • the second resin layer in which the value of E'(110) / E'(100) is 0.5 or more can be more easily realized by the second resin layer containing high-density polyethylene.
  • the E'(100) of the second resin layer is not particularly limited as long as the above-mentioned conditions of the E'(110) / E'(100) values are satisfied.
  • E'(100) of the second resin layer may be 1.6 ⁇ 10 7 to 2 ⁇ 10 8 Pa.
  • the E'(110) of the second resin layer is not particularly limited as long as the above-mentioned conditions of the E'(110) / E'(100) values are satisfied.
  • the E'(110) of the second resin layer may be 1.5 ⁇ 10 7 to 2.2 ⁇ 10 8 Pa.
  • the second resin layer is preferably a non-stretched layer (film). Since the second resin layer is a non-stretched layer, the moldability of the laminated film is improved.
  • the second resin layer has heat resistance, it is suitable as, for example, an outer layer (the outermost layer on the side opposite to the sealant layer side).
  • the laminated film may further include a third resin layer other than these between the first resin layer and the second resin layer.
  • the third resin layer contains a polyolefin-based resin contained in the first resin layer and the second resin layer, and a polyolefin-based resin of the same type. That is, in the laminated film provided with the third resin layer, the first resin layer, the front second resin layer, and the third resin layer contain the same type of polyolefin resin.
  • the total amount (mol) of the constituent units is taken into account.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • mLLDPE metallocene-catalyzed linear low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • EMA resin ethylene-methyl methacrylate copolymer
  • EMMA resin ethylene-vinyl alcohol copolymer
  • EVOH ethylene-vinyl alcohol copolymer
  • EVA ethylene-vinyl alcohol-vinyl acetate All copolymers (EVA partially saponified products) and the like are the same type because the ratio of the amount (mol) of the structural unit derived from ethylene to the total amount (mol) of the structural unit is 20 mol% or more. And.
  • the ratio of the amount (mol) of the constituent unit derived from ethylene to the total amount (mol) of the constituent unit is 20 mol. If it is less than%, it is not considered to be the same kind as the above-mentioned low-density polyethylene or the like.
  • the ratio of the amount (mol) of the common constituent unit to the total amount (mol) of the constituent units is preferably 30 mol% or more, more preferably 40 mol.
  • the laminated film provided with the third resin layer has an effect due to the provision of the third resin layer, and has high reusability.
  • the same type of polyolefin resin contained in the third resin layer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are intended. It can be selected arbitrarily according to the situation.
  • the polyolefin-based resin of the same type contained in the third resin layer is preferably a polyethylene-based resin. That is, it is preferable that the first resin layer, the second resin layer, and the third resin layer all contain a polyethylene-based resin.
  • the third resin layer may contain other components in addition to the polyolefin-based resin of the same type as the polyolefin-based resin contained in the first resin layer and the second resin layer, as long as the effects of the present invention are not impaired.
  • the other components in the third resin layer are a resin component (sometimes referred to as “another resin component” in the present specification) and a non-resin component (in the present specification, “another non-resin component”). It may be called any of).
  • the other resin component in the third resin layer is not particularly limited as long as it is a resin other than the polyolefin-based resin of the same type as the polyolefin-based resin contained in the first resin layer and the second resin layer.
  • the other resin component in the third resin layer include a polyolefin-based resin that is not the same type as the polyolefin-based resin contained in the first resin layer and the second resin layer, and a resin other than the polyolefin-based resin.
  • Examples of the polyolefin resin (including the third resin layer) used for the third resin layer include elastomer components such as ⁇ -olefin copolymer; ethylene-vinyl alcohol copolymer (EVOH); ethylene-vinyl alcohol-vinyl acetate copolymer. (EVA partially saponified product) is also mentioned.
  • the laminated film provided with the third resin layer containing an elastomer has high pinhole resistance and high strength even if it does not contain a polyamide such as nylon.
  • the laminated film provided with the third resin layer containing EVOH has an oxygen barrier property.
  • the polyolefin-based resin that is not the same type as the polyolefin-based resin contained in the first resin layer and the second resin layer is the same as that mentioned above as the polyolefin-based resin contained in the first resin layer; an elastomer such as an ⁇ -olefin copolymer. And so on.
  • the laminated film provided with the third resin layer containing the elastomer has high pinhole resistance and high strength even if it does not contain a polyamide such as nylon.
  • Examples of the resin other than the polyolefin-based resin in the third resin layer include elastomers such as styrene-ethylene / butylene-ethylene block copolymer.
  • the laminated film provided with the third resin layer containing the elastomer has high pinhole resistance and high strength even if it does not contain a polyamide such as nylon.
  • non-resin component in the third resin layer examples include the same as the non-resin component in the first resin layer.
  • the other components contained in the third resin layer may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof are arbitrary depending on the purpose. Can be selected.
  • the content of the polyolefin-based resin with respect to the total mass of the third resin layer (the polyolefin-based resin of the same type as the polyolefin-based resin contained in the first resin layer and the second resin layer, and the first resin layer and the first resin layer.
  • the ratio of the total content) of the polyolefin-based resin contained in the two resin layers and the polyolefin-based resin which is not the same type) is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, for example. , 97 to 100% by mass, and 99 to 100% by mass. When the ratio is at least the lower limit value, the effect of the third resin layer containing the polyolefin resin can be obtained more remarkably.
  • the ratio is usually the content of the polyolefin-based resin (the polyolefin-based content of the first resin layer and the second resin layer) with respect to the total content (parts by mass) of the components that do not vaporize at room temperature in the third resin composition described later.
  • the total content (part by mass) of the polyolefin-based resin of the same type as the resin and the polyolefin-based resin contained in the first resin layer and the second resin layer and not of the same type as the polyolefin-based resin is the same.
  • the ratio of the content of the polyolefin-based resin of the same type as the polyolefin-based resin contained in the first resin layer and the second resin layer to the total mass of the third resin layer is 80 to 100% by mass. Is preferable, and 90 to 100% by mass is more preferable, and for example, it may be any of 95 to 100% by mass and 99 to 100% by mass. When the ratio is at least the lower limit value, the reusability of the laminated film becomes higher.
  • the third resin layer may be composed of one layer (single layer) or may be composed of a plurality of layers of two or more layers.
  • the third resin layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
  • all the layers include the polyolefin-based resin contained in the first resin layer and the second resin layer, and the same type of polyolefin-based resin.
  • the thickness of the third resin layer can be arbitrarily set according to the use of the laminated film, and is not particularly limited.
  • the thickness of the third resin layer is usually preferably 15 to 200 ⁇ m, more preferably 30 to 160 ⁇ m, and even more preferably 50 to 120 ⁇ m.
  • the thickness of the third resin layer is at least the above lower limit value, the strength of the third resin layer is further improved, and the effect of the laminated film including the third resin layer can be obtained more remarkably. ..
  • the thickness of the third resin layer is equal to or less than the upper limit value, excessive thickness is suppressed.
  • the third resin layer is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the above-mentioned preferable thickness of the third resin layer.
  • the ratio of the thickness of the third resin layer to the thickness of the laminated film is not particularly limited, but is preferably 50 to 70%.
  • the ratio is at least the lower limit value, the effect obtained by the laminated film including the third resin layer becomes higher.
  • the ratio is not more than the upper limit value, the effect obtained by the laminated film including the first resin layer and the second resin layer becomes higher.
  • the ratio of the total thickness of the first resin layer and the second resin layer to the thickness of the laminated film is not particularly limited, but is 30 to 50%. It is preferable to have. When the ratio is at least the lower limit value, the effect obtained by the laminated film including the first resin layer and the second resin layer becomes higher. When the ratio is not more than the upper limit value, the effect obtained by the laminated film including the third resin layer becomes higher.
  • the third resin layer is preferably a non-stretched layer (film). Since the third resin layer is a non-stretched layer, the moldability of the laminated film is improved.
  • the third resin layer is suitable as an intermediate layer such as a pinhole resistant layer and an oxygen barrier layer, for example.
  • the laminated film has high pinhole resistance and high strength even if it does not contain a polyamide such as nylon.
  • a polyamide such as nylon.
  • the tip of a needle having a radius of curvature of the tip of 0.5 mm is pushed perpendicularly to the laminated film at a speed of 500 mm / min, the moment the needle penetrates the laminated film.
  • the load applied to the needle is defined as the piercing strength (N)
  • the piercing strength include those made of stainless steel.
  • the piercing strength of the laminated film is preferably 7N or more, and may be, for example, either 8N or more and 10N or more.
  • the upper limit of the piercing strength is not particularly limited, but for example, a laminated film having the piercing strength of 12 N or less can be more easily realized.
  • the laminated film having high piercing strength as described above is provided with, for example, a third resin layer, and can be realized more easily.
  • the piercing strength of the laminated film can be adjusted by adjusting the type and content of the resin contained in the first resin layer, the second resin layer, and in some cases, the third resin layer.
  • the resin layer containing an ethylene-vinyl alcohol copolymer has a high oxygen barrier property. Therefore, for example, the laminated film provided with the third resin layer containing an ethylene-vinyl alcohol copolymer has an oxygen barrier property.
  • the ethylene-vinyl alcohol copolymer is usually an ethylene-vinyl acetate copolymer and an ethylene-vinyl alcohol-vinyl acetate copolymer (in other words, an ethylene-vinyl acetate copolymer and a partially saponified product thereof).
  • Ethylene-vinyl alcohol-vinyl acetate copolymer (ethylene-vinyl acetate copolymer partially saponified product) usually has compatibility with ethylene-vinyl alcohol copolymer, and further, ethylene-vinyl alcohol copolymer.
  • non-vinyl-based polyolefin-based resins Ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer, and polyolefin-based resins (referred to as "non-vinyl-based polyolefin-based resins" in the present specification. Has compatibility with). Therefore, when the third resin layer contains the non-vinyl-based polyolefin resin and the ethylene-vinyl alcohol copolymer, the third resin layer further contains ethylene-vinyl alcohol-in addition to these resins. It is preferably a resin layer containing a vinyl acetate copolymer (in this specification, it may be referred to as "resin layer (I)").
  • the third resin layer which is the resin layer (I), has a high oxygen barrier property.
  • the non-vinyl-based polyolefin resin is a polyolefin-based resin of the same type as the polyolefin-based resin contained in the first resin layer and the second resin layer, and is preferably a polyethylene-based resin.
  • the ethylene-vinyl alcohol copolymer and the ethylene-vinyl alcohol-vinyl acetate copolymer are both polyolefins of the same type as the polyolefin-based resin contained in the first resin layer and the second resin layer. It is preferably a based resin.
  • the ratio of the amount (mol) of the structural unit derived from ethylene to the total amount (mol) of the structural unit is preferably 20 mol% or more, more preferably 20 to 80 mol%.
  • it may be any of 20 to 70 mol%, 20 to 60 mol%, and 20 to 50 mol%, 30 to 80 mol%, 40 to 80 mol%, and 50 to 80 mol%. It may be any of 30 to 70 mol%, and 40 to 60 mol%.
  • the ratio of the content of the ethylene-vinyl alcohol copolymer to the total mass of the resin layer (I) may be, for example, 25 to 70% by mass. However, in terms of increasing the uniformity and oxygen barrier property of the resin layer (I), the ratio is preferably 40 to 70% by mass, more preferably 50 to 70% by mass, for example. It may be 55 to 65% by mass.
  • the ratio is usually a copolymer of ethylene-vinyl alcohol with respect to the total content (parts by mass) of the components that do not vaporize at room temperature in the resin composition for forming the resin layer (I) (the third resin composition described later). It is the same as the ratio of the content (parts by mass) of the polymer.
  • the ratio of the content of the non-vinyl-based polyolefin resin to the total mass of the resin layer (I) may be, for example, 5 to 50% by mass. However, in terms of increasing the uniformity and oxygen barrier property of the resin layer (I), the ratio is preferably 5 to 35% by mass, more preferably 5 to 20% by mass, for example. It may be 5 to 15% by mass.
  • the ratio is usually the non-vinyl polyolefin based on the total content (parts by mass) of the components that do not vaporize at room temperature in the resin composition for forming the resin layer (I) (the third resin composition described later). It is the same as the ratio of the content (parts by mass) of the based resin.
  • the ratio of the content of the ethylene-vinyl alcohol-vinyl acetate copolymer to the total mass of the resin layer (I) is preferably 20 to 40% by mass, for example, 25 to 35. It may be% by mass. When the ratio is in such a range, the effect of using the ethylene-vinyl alcohol-vinyl acetate copolymer can be obtained more remarkably.
  • the ratio is usually ethylene-vinyl alcohol-with respect to the total content (parts by mass) of the components that do not vaporize at room temperature in the resin composition for forming the resin layer (I) (the third resin composition described later). It is the same as the ratio of the content (parts by mass) of the vinyl acetate copolymer.
  • the proportion of the amount is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and may be any of, for example, 97 to 100% by mass and 99 to 100% by mass. ..
  • the ratio is equal to or higher than the lower limit value, the oxygen barrier property of the resin layer (I) becomes higher.
  • the ratio of ethylene-vinyl alcohol to the total content (parts by mass) of components that do not vaporize at room temperature in the resin composition for forming the resin layer (I) (the third resin composition described later) is usually the same.
  • the ratio of the total content (parts by mass) of the polymer, the non-vinyl polyolefin resin, and the ethylene-vinyl alcohol-vinyl acetate copolymer is the same.
  • the laminated film When the laminated film is provided with the resin layer (I) as the third resin layer, the laminated film may be provided with only one resin layer (I) or may be provided with two or more layers.
  • the laminated film includes two or more resin layers (I), the two or more resin layers (I) may be the same or different from each other, and the combination of these resin layers (I) is the present invention. It is not particularly limited as long as the effect of the invention is not impaired.
  • the laminated film provided with the resin layer (I) as the third resin layer includes, for example, one resin layer (I) and the first resin layer side and the second resin layer side of the resin layer (I). Examples thereof include one or both provided with a third resin layer other than the one-layer or two-layer resin layer (I). More specifically, as such a laminated film, for example, other than the first resin layer, the one-layer resin layer (I) (third resin layer), and the one-layer or two-layer resin layer (I).
  • the third resin layer and the second resin layer are laminated in this order in the thickness direction of the third resin layer, and the third resin layer is a laminated film having a total of two or three layers; the first resin layer.
  • the third resin layer other than the one-layer or two-layer resin layer (I), the one-layer resin layer (I) (third resin layer), and the second resin layer in this order.
  • the thicknesses of the one-layer resin layer (I) (third resin layer), the third resin layer other than the one-layer or two-layer resin layer (I), and the second resin layer are in this order. Examples thereof include a laminated film having a total of 3 to 5 third resin layers, which are formed by being laminated in the direction.
  • the first resin layer, the resin layer (I), the third resin layer other than the resin layer (I), and the second resin layer all contain the same type of polyolefin resin.
  • the first resin layer and the second resin layer may be only one layer or may be two or more layers.
  • the laminated film is, for example, that the third resin layer is composed of a plurality of three or more layers in that it has an oxygen barrier property, and at least one of them is the non-vinyl polyolefin resin. , Ethylene-vinyl alcohol copolymer and ethylene-vinyl alcohol-vinyl acetate copolymer (that is, the resin layer (I)).
  • the third resin layer which is the resin layer (I), comprises the non-vinyl polyolefin resin, an ethylene-vinyl alcohol copolymer, and an ethylene-vinyl alcohol-vinyl acetate copolymer.
  • One kind or two or more kinds selected from the group may be a polyolefin-based resin of the same kind as the polyolefin-based resin contained in the first resin layer and the second resin layer.
  • the non-vinyl-based polyolefin-based resin is the same type of polyolefin-based resin
  • either one or both of an ethylene-vinyl alcohol copolymer and an ethylene-vinyl alcohol-vinyl acetate copolymer may be used.
  • the same type of polyolefin resin may be used, and both the ethylene-vinyl alcohol copolymer and the ethylene-vinyl alcohol-vinyl acetate copolymer may not be the same type of polyolefin resin. ..
  • the ratio of the thickness of the resin layer (I) to the thickness of the laminated film is not particularly limited, but may be 4 to 15%. preferable.
  • the resin layer (I) having the ratio of the lower limit value or more has a higher uniformity of thickness. When the ratio is not more than the upper limit value, the reusability of the laminated film becomes higher.
  • an oxygen permeation amount of the multilayer film 500ml / (m 2 ⁇ 24h ⁇ atm) but may be less, preferably 100ml / (m 2 ⁇ 24h ⁇ atm) or less, 50 ml / (m preferably from it at 2 ⁇ 24h ⁇ atm) or less, still more preferably 25ml / (m 2 ⁇ 24h ⁇ atm) or less, for example, may be 10ml / (m 2 ⁇ 24h ⁇ atm) or less .
  • the oxygen permeability of the laminated film is 0ml / (m 2 ⁇ 24h ⁇ atm) or more.
  • the haze of the laminated film measured from the outside on the second resin layer side is either 35% or less or 30% or less. However, it is preferably 20% or less.
  • the oxygen barrier property of the laminated film in which the haze is equal to or less than the upper limit value is higher. This is because the resin layer (I) has a high uniformity and the resin layer (I) has a high oxygen barrier property.
  • the term "haze" means measured in accordance with JIS K 7136: 2000.
  • each layer (the first resin layer, the second resin layer, and the third resin layer in some cases) constituting the laminated film contains the same type of polyolefin resin, the reusability is only high. Instead, each layer can be brought into close contact with each other without going through an adhesive layer. That is, the laminated film has high adhesion of each layer even if it does not have an adhesive layer. Further, the laminated film without the adhesive layer can be manufactured at low cost.
  • the ratio of the content of the same type polyolefin resin to the total mass of the laminated film is preferably 90% or more, more preferably 92% or more, and more preferably 95% or more. Is even more preferable.
  • the laminated film can be made into a monomaterial, and the entire laminated film can be easily reused.
  • FIG. 1 is a cross-sectional view schematically showing an example of the laminated film of the present embodiment.
  • the laminated film 1 shown here includes a first resin layer 11 and a second resin layer 12, and further includes a third resin layer 13 between the first resin layer 11 and the second resin layer 12.
  • the laminated film 1 is configured by laminating the first resin layer 11, the third resin layer 13, and the second resin layer 12 in this order in the thickness direction.
  • the first resin layer 11, the second resin layer 12, and the third resin layer 13 are all described above.
  • the third resin layer 13 has an arbitrary structure, and the laminated film 1 does not have to include the third resin layer 13.
  • One surface of the first resin layer 11 (the surface opposite to the side of the second resin layer 12, sometimes referred to as the "second surface” in the present specification) 11b is an exposed surface.
  • One surface (the surface opposite to the side of the first resin layer 11; which may be referred to as the “first surface” in the present specification) 12a of the second resin layer 12 is an exposed surface.
  • the ratio of the thickness of the third resin layer 13 to the thickness of the laminated film 1 is not particularly limited as described above, but is preferably 50 to 70%.
  • the ratio of the total thickness of the first resin layer 11 and the second resin layer 12 to the thickness of the laminated film 1 is not particularly limited as described above, but is preferably 30 to 50%.
  • the ratio (thickness ratio) of [thickness of the first resin layer 11] / [thickness of the second resin layer 12] is not particularly limited as described above, but is 0.7 to It is preferably 1.3.
  • FIG. 2 is a cross-sectional view schematically showing another example of the laminated film of the present embodiment.
  • the laminated film 2 shown here has the third resin layer 23 as the 3-1 resin layer 231 and the 3-2 resin layer 232 from the first resin layer 11 side to the second resin layer 12 side.
  • the resin layer 233, the 3rd-4th resin layer 234, and the 3rd-5th resin layer 235 are laminated in this order in this order to provide a laminated resin layer having a five-layer structure. .. That is, the laminated film 2 includes the first resin layer 11, the 3-1 resin layer 231 and the 3-2 resin layer 232, the 3rd 3rd resin layer 233, and the 3-4th resin layer 234.
  • the 3rd-5th resin layer 235 and the 2nd resin layer 12 are laminated in this order in the thickness direction thereof.
  • the laminated film 2 is the same as the laminated film 1 except that the third resin layer 23 is provided instead of the third resin layer 13.
  • both the 3-1 resin layer 231 and the 3-5 resin layer 235 are resin layers other than the resin layer (I).
  • Any one or more of the 3-2 resin layer 232, the 3-3 resin layer 233, and the 3-4 resin layer 234 is the resin layer (I), that is, a resin having an oxygen barrier property. It is preferably a layer.
  • More preferable third resin layer 23 is, for example, 3-1 resin layer 231 and 3-2 resin layer 232, 3-4 resin layer 234, and 3-5 resin layer 235. , All of which are resin layers other than the resin layer (I), and the third resin layer 233 is the resin layer (I), and examples thereof include a third resin layer having an oxygen barrier property.
  • the ratio of the thickness of the resin layer (I) to the thickness of the laminated film 2 is not particularly limited as described above, but 4 It is preferably ⁇ 15%.
  • the thickness of the 3rd-3rd resin layer 233 of the 3rd resin layer 23 is the resin layer (I)
  • the thickness of the 3rd-3rd resin layer 233 is relative to the thickness of the laminated film 2.
  • the thickness ratio is preferably 4 to 15%.
  • the ratio of the thickness of the third resin layer 23 to the thickness of the laminated film 2 is not particularly limited as described above, but is preferably 50 to 70%.
  • the ratio of the total thickness of the first resin layer 11 and the second resin layer 12 to the thickness of the laminated film 2 is not particularly limited as described above, but is preferably 30 to 50%.
  • the ratio (thickness ratio) of [thickness of the first resin layer 11] / [thickness of the second resin layer 12] is not particularly limited as described above, but is 0.7 to It is preferably 1.3.
  • the third resin layer 23 may be a laminated resin layer other than the five-layer structure.
  • the third resin layer 23 has a three-layer structure that does not include the 3-1 resin layer 231 and the 3-2 resin layer 232, and the 3rd-3rd resin layer 233 is the resin layer (I).
  • the third resin layer 23 has a two-layer structure that does not include the 3-1 resin layer 231 and the 3-2 resin layer 232 and the 3-4 resin layer 234, and the third resin layer 233 has a two-layer structure. May be the resin layer (I).
  • the third resin layer 23 has a three-layer structure that does not include the 3rd-4th resin layer 234 and the 3rd-5th resin layer 235, and the 3rd-3rd resin layer 233 is the resin layer (I).
  • the third resin layer 23 has a two-layer structure not including the 3-2 resin layer 232, the 3-4 resin layer 234, and the 3-5 resin layer 235, and the third resin layer 233 has a two-layer structure. May be the resin layer (I).
  • the third resin layer 23 may have a four-layer structure that does not include the third-2 resin layer 232, and the third third resin layer 233 may be the resin layer (I).
  • the third resin layer 23 may have a four-layer structure that does not include the 3rd-4th resin layer 234, and the 3rd-3rd resin layer 233 may be the resin layer (I).
  • the third resin layer 23 has a three-layer structure that does not include the 3-2 resin layer 232 and the 3-4 resin layer 234, and the 3rd 3rd resin layer 233 is the resin layer (I). There may be.
  • the laminated film may include other layers that do not fall under any of the first resin layer, the second resin layer, and the third resin layer as long as the effects of the present invention are not impaired. , It is preferable that the other layer is not provided.
  • the other layer is a layer that does not contain a polyolefin-based resin, and by not providing such another layer, the reusability of the laminated film becomes higher.
  • the overall thickness of the laminated film is not particularly limited, but is preferably 100 to 200 ⁇ m, for example.
  • the laminated film it is preferable that all the layers (for example, the first resin layer to the third resin layer) constituting the laminated film are non-stretched layers (films).
  • a non-stretched laminated film is particularly excellent in moldability and is suitable for forming, for example, a deep-drawn package.
  • the laminated film is produced by, for example, a feed block method in which a resin or a resin composition used as a material for forming each layer is melt-extruded using several extruders, a co-extrusion T-die method such as a multi-manifold method, or an air-cooled method. Alternatively, it can be manufactured by a water-cooled coextrusion inflation method or the like.
  • the laminated film two or more films for forming any two or more layers are separately prepared in advance, and the laminated films are laminated by a thermal (heat) laminating method or the like without using an adhesive. It can also be manufactured by laminating and, if necessary, further laminating layers other than these so as to have a desired arrangement form.
  • the resin composition which is a material for forming any of the layers in the laminated film, adjusts the type and content of the contained components so that the formed layer contains the target component at the target content. And manufacture it.
  • the ratio of the contents of the components that do not vaporize at room temperature in the resin composition is usually the same as the ratio of the contents of the components in the layer formed from the resin composition.
  • a resin composition for forming a first resin layer (the first resin layer 11 in the laminated film 1 shown in FIG. 1 and the first resin layer 11 in the laminated film 2 shown in FIG. 2) (in the present specification, the "first resin composition”. (May be referred to as), for example, those containing the polyolefin-based resin and, if necessary, other components.
  • the other component is the component described above.
  • a resin composition for forming a second resin layer (the second resin layer 12 in the laminated film 1 shown in FIG. 1 and the second resin layer 12 in the laminated film 2 shown in FIG. 2) (in the present specification, the "second resin composition”. (May be referred to as), for example, those containing the polyolefin-based resin and, if necessary, other components.
  • the other component is the component described above.
  • the third resin layer (in the laminated film 1 shown in FIG. 1, the third resin layer 13; in the laminated film 2 shown in FIG. 2, the 3-1 resin layer 231 and the 3-2 resin layer 232, the third resin layer 3- Resin composition for forming 3 resin layer 233, 3-4 resin layer 234, and 3-5 resin layer 235) (in this specification, it may be referred to as "third resin composition").
  • the third resin composition for forming the resin layer (I) is an ethylene-vinyl alcohol copolymer.
  • the laminated film is suitable as a material for a packaging body. That is, a preferable package includes a package provided with the laminated film.
  • the package of the present embodiment can be manufactured by packaging the object to be packaged using the laminated film. At the time of manufacturing the package, the first resin layer in the laminated film may be arranged on the side of the packaged object, and the second resin layer may be arranged on the side opposite to the packaged object side to wrap the packaged object. preferable.
  • the laminated film is suitable for forming either a lid material or a bottom material of a deep-drawn package.
  • the laminated film having good moldability is particularly suitable for forming a bottom material having a recess for forming a storage portion.
  • FIG. 3 is a cross-sectional view schematically showing an example of a package including the laminated film of the present embodiment.
  • the package 101 shown here includes a lid material 8 and a bottom material 10, and is a deep-drawn package obtained by deep-drawing a resin film.
  • Either one or both of the lid material 8 and the bottom material 10 is configured by using the laminated film 1 or the laminated film 2 shown in FIG.
  • the distinction between the layers in the laminated film 1 or the laminated film 2 constituting the lid material 8 or the bottom material 10 is omitted.
  • a recess 100 is formed in the bottom material 10.
  • the package 101 is composed of a seal of a lid material 8 and a bottom material 10. More specifically, the second surface 10b of the region excluding the recess 100 of the bottom material 10 and the second surface 8b of the lid material 8 are overlapped and sealed with each other in a region near their peripheral edges. As a result, in the region of the recess 100 of the bottom material 10, the storage portion 101a is formed between the second surface 10b of the bottom material 10 and the second surface 8b of the lid material 8. The stored object 9 is stored in the storage portion 101a.
  • one surface (second surface) 10b of the bottom material 10 is the first resin layer 11 in the laminated film 1 or the laminated film 2. It is preferably the same as the second surface 11b.
  • the other surface (sometimes referred to as "first surface” in the present specification) 10a of the bottom material 10 is the same as the first surface 12a of the second resin layer 12 in the laminated film 1 or the laminated film 2. It is preferable to have.
  • one surface (second surface) 8b of the lid material 8 is the second surface 11b of the first resin layer 11 in the laminated film 1 or the laminated film 2. It is preferable that it is the same as.
  • the other surface (sometimes referred to as the "first surface” in the present specification) 8a of the lid material 8 is the same as the first surface 12a of the second resin layer 12 in the laminated film 1 or the laminated film 2. It is preferable to have.
  • the thickness of the bottom material 10 in the flat portion and the thickness of the lid material 8 may be the same as the thickness of the laminated film 1 or the laminated film 2 described above.
  • a deeply squeezed package has been described as an example of the package provided with the laminated film, but the package provided with the laminated film is not limited to the deeply squeezed package and is not limited to other packages. It may be.
  • the package body forms a storage portion for storing an object to be packaged (in other words, a stored object) by, for example, the laminated films, or the laminated film and a resin film other than the laminated film. At the same time, it can be manufactured by storing the objects to be packaged and heat-sealing the areas other than the storage portion of these films. At this time, the adhesion of the laminated film (particularly the second resin layer) to the heating plate in the heating sealing device is suppressed.
  • a laminated film having the configuration shown in FIG. 1 was produced by the procedure shown below. That is, as a resin constituting the first resin layer, low density polyethylene (LDPE) (“UBE polyethylene (registered trademark) F222NH” manufactured by Ube Maruzen Polyethylene Co., Ltd., density 0.922 g / cm 3 ) was prepared. As the resin constituting the second resin layer, high-density polyethylene (HDPE) (“Nipolon Hard (registered trademark) 4010” manufactured by Tosoh Corporation, density 0.964 g / cm 3 , melt mass flow rate 5.4 g / 10 min) was prepared. In the present specification, this HDPE may be referred to as "HDPE (1)".
  • LDPE low density polyethylene
  • HDPE high-density polyethylene
  • mLLDPE metallocene-catalyzed linear low-density polyethylene
  • the first resin layer (thickness 30 ⁇ m), the third resin layer (thickness 90 ⁇ m), and the second resin A laminated film (thickness 150 ⁇ m) composed of layers (thickness 30 ⁇ m) laminated in this order in these thickness directions was obtained.
  • HDPE (1) Tosoh's "Nipolon Hard (registered trademark) 4010", density 0.964 g / cm 3 , melt mass flow rate 5.4 g / 10 min
  • HDPE used in this example may be referred to as "HDPE (2)".
  • Example 3 When the third resin layer was formed, the same method as in Example 1 was used except that the third resin composition was used instead of mLLDPE (“Ube-Maruzen Polyethylene Co., Ltd.“ Umerit (registered trademark) 1520F ”). A laminated film was manufactured.
  • This third resin composition consists of mLLDPE (“Ube-Maruzen Polyethylene“ Umerit (registered trademark) 1520F ”) (90 parts by mass)) and an elastomer (“Toughmer (registered trademark) BL3450M” manufactured by Mitsui Chemicals, Inc.) (10% by mass). Part)) and was obtained by kneading at 200 ° C. for 10 minutes.
  • Example 4 When forming the second resin layer, it was carried out except that the second resin composition was used instead of HDPE (1) (“Nipolon Hard (registered trademark) 4010” manufactured by Tosoh Corporation, density 0.964 g / cm 3). A laminated film was produced in the same manner as in Example 1.
  • the second resin composition is HDPE (1) (Tosoh's "Niporon Hard (registered trademark) 4010") (60 parts by mass) and LDPE (Ube Maruzen Polyethylene "UBE Polyethylene (registered trademark) F222NH”) ( 40 parts by mass) was kneaded at 200 ° C. for 10 minutes.
  • the gel fraction of the laminated film obtained above was measured according to JIS K 6769. That is, a test piece (2) having a size of 3 cm ⁇ 3 cm was cut out from the laminated film, and the test piece (2) was wrapped with a 400 mesh stainless steel wire mesh (100 g). The test piece (2) wrapped in this stainless steel wire mesh was immersed in xylene (18 mL) at 110 ° C. for 24 hours. Next, the test piece (2) after immersion was taken out from the xylene together with the stainless steel wire mesh, and further vacuum-dried at 110 ° C. for 24 hours under a pressure of 1.7 kPa. The mass of the obtained dried product was determined, and the gel fraction was calculated. The results are shown in Table 2.
  • thermomechanical analyzer (“EXSTAR6000” manufactured by SII)
  • JIS K 7196 the laminated film obtained above was subjected to thermomechanical analysis in accordance with JIS K 7196, and the displacement temperature of 2000 ⁇ m was determined from the obtained thermomechanical analysis curve. I asked. The results are shown in Table 2.
  • the LDPE, the mLLDPE, the modified polyolefin resin, the Ny, the modified polyolefin resin, and the Ny are co-extruded in this order to form a sealant layer (thickness 20 ⁇ m) and an intermediate layer (thickness 20 ⁇ m).
  • the thickness of the adhesive layer (thickness 15 ⁇ m), the strength holding layer (thickness 30 ⁇ m), the adhesive layer (thickness 15 ⁇ m), and the outer layer (thickness 10 ⁇ m) are in this order.
  • a laminated film (thickness 150 ⁇ m) constructed by being laminated in the direction was obtained.
  • the E'(110) / E'(100) values of the second resin layer are 0.25 or more (0.25 to 0.7).
  • the heat resistance of the second resin layer was sufficiently large to be recognized as being sufficiently high.
  • the E'(110) / E'(100) value of the second resin layer is particularly large as 0.66 to 0.7, and the second resin layer contains HDPE. The effect of that was high.
  • all of the first resin layer to the third resin layer contained PE, and the main contained component was a polyolefin resin of the same type, and the reusability was high.
  • a resin layer (resin film) which is the same as the second resin layer in Example 5 except that EB irradiation is not performed is separately prepared, and E'(100) and E'(110) thereof are measured.
  • E'(110) / E'(100) value was calculated, it was 0.11.
  • the E'(110) / E'(100) value of the second resin layer was increased by the effect of EB irradiation.
  • the gel fraction of the laminated film was 42%, the displacement temperature of the laminated film was 2000 ⁇ m, and the displacement temperature was 125 ° C., and the effect of EB irradiation of the second resin layer was also recognized here.
  • the piercing strength of the laminated film was 7.4 N or more (7.4 to 10.8 N), which was sufficiently large.
  • the laminated films of Examples 1 to 5 had sufficiently high pinhole resistance and high strength even when a polyamide such as Ny was not used.
  • the laminated film of Comparative Example 1 had sufficient heat resistance because the outer layer contained Ny, and had sufficiently high strength because the strength-retaining layer contained Ny. However, the sealant layer and the intermediate layer contained PE, and the adhesive layer contained a modified polyolefin resin. As described above, the laminated film of Comparative Example 1 had layers in which the main components were resins different from each other, and the reusability was low.
  • a laminated film having the configuration shown in FIG. 2 was produced by the procedure shown below. That is, as a resin constituting the first resin layer, low density polyethylene (LDPE) (“UBE polyethylene (registered trademark) F222NH” manufactured by Ube Maruzen Polyethylene Co., Ltd., density 0.922 g / cm 3 ) was prepared. As the resin constituting the second resin layer, high-density polyethylene (HDPE) (Tosoh's "Nipolon Hard (registered trademark) 4010", density 0.964 g / cm 3 , melt mass flow rate 5.4 g / 10 min, HDPE (1)) ) was prepared.
  • LDPE low density polyethylene
  • HDPE high-density polyethylene
  • a metallocene-catalyzed linear low-density polyethylene (mLLDPE) (Ube-Maruzen Polyethylene "Umerit (registered trademark) 1520F", density 0.913 g / cm 3 ) was prepared.
  • Ethylene-vinyl alcohol-vinyl acetate copolymer (EVA partially saponified product) ("Melsen (registered trademark) -H3051R” manufactured by Tosoh Corporation) and ethylene-vinyl alcohol co-weight as the resin constituting the 3rd resin layer.
  • a coalescence (EVOH) (“Eval (registered trademark) E105B” manufactured by Kuraray Co., Ltd.) was prepared.
  • the third resin composition was produced by kneading the mLLDPE (40 parts by mass), the partially saponified EVA (30 parts by mass), and the EVOH (30 parts by mass) at 200 ° C. for 10 minutes.
  • the first resin layer Thickness 30 ⁇ m
  • 3-1 resin layer Thickness 15 ⁇ m
  • 3-2 resin layer thickness 30 ⁇ m
  • 3rd 3rd resin layer thickness 15 ⁇ m
  • 3-4 resin A laminated film composed of a layer (thickness 15 ⁇ m), a third resin layer (thickness 15 ⁇ m), and a second resin layer (thickness 30 ⁇ m) laminated in this order in these thickness directions. (Thickness 150 ⁇ m) was obtained.
  • Example 7 ⁇ Manufacturing of laminated film >> Instead of kneading the mLLDPE (40 parts by mass), the partially saponified EVA (30 parts by mass), and the EVOH (30 parts by mass) at 200 ° C. for 10 minutes during the production of the third resin composition.
  • This laminated film has a first resin layer (thickness 30 ⁇ m), a third resin layer (thickness 15 ⁇ m), a third resin layer (thickness 30 ⁇ m), and a third resin layer (thickness). 15 ⁇ m), the 3rd-4th resin layer (15 ⁇ m thick), the 3-5th resin layer (15 ⁇ m thick), and the second resin layer (30 ⁇ m thick) in this order. It was a laminated film (thickness 150 ⁇ m) constructed by being laminated in the direction.
  • Example 8 ⁇ Manufacturing of laminated film >> Instead of kneading the mLLDPE (40 parts by mass), the partially saponified EVA (30 parts by mass), and the EVOH (30 parts by mass) at 200 ° C. for 10 minutes during the production of the third resin composition.
  • This laminated film has a first resin layer (thickness 30 ⁇ m), a third resin layer (thickness 15 ⁇ m), a third resin layer (thickness 30 ⁇ m), and a third resin layer (thickness). 15 ⁇ m), the 3rd-4th resin layer (15 ⁇ m thick), the 3-5th resin layer (15 ⁇ m thick), and the second resin layer (30 ⁇ m thick) in this order. It was a laminated film (thickness 150 ⁇ m) constructed by being laminated in the direction.
  • Example 9 ⁇ Manufacturing of laminated film >> Instead of kneading the mLLDPE (40 parts by mass), the partially saponified EVA (30 parts by mass), and the EVOH (30 parts by mass) at 200 ° C. for 10 minutes during the production of the third resin composition.
  • the LDPE (10 parts by mass), the partially saponified EVA (30 parts by mass), and the EVOH (60 parts by mass) were kneaded at 200 ° C. for 10 minutes, except for the case of Example 6.
  • Laminated films were produced in the same way.
  • This laminated film has a first resin layer (thickness 30 ⁇ m), a third resin layer (thickness 15 ⁇ m), a third resin layer (thickness 30 ⁇ m), and a third resin layer (thickness). 15 ⁇ m), the 3rd-4th resin layer (15 ⁇ m thick), the 3-5th resin layer (15 ⁇ m thick), and the second resin layer (30 ⁇ m thick) in this order. It was a laminated film (thickness 150 ⁇ m) constructed by being laminated in the direction.
  • Example 10 ⁇ Manufacturing of laminated film >> A laminated film was produced by the same method as in Example 9 except that the extrusion amount of the mLLDPE was increased and the extrusion amount of the third resin composition was reduced.
  • This laminated film has a first resin layer (thickness 37.5 ⁇ m), a third resin layer (thickness 15 ⁇ m), a third-2 resin layer (thickness 30 ⁇ m), and a third resin layer. (Thickness 7.5 ⁇ m), the 3rd-4th resin layer (thickness 15 ⁇ m), the 3rd-5th resin layer (thickness 15 ⁇ m), and the second resin layer (thickness 30 ⁇ m) are arranged in this order. It was a laminated film (thickness 150 ⁇ m) constructed by being laminated in these thickness directions.
  • Example 11 ⁇ Manufacturing of laminated film >> A laminated film was produced by the same method as in Example 6 except that the mLLDPE was used instead of the third resin composition.
  • This laminated film has a first resin layer (thickness 30 ⁇ m), a third resin layer (thickness 15 ⁇ m), a third resin layer (thickness 30 ⁇ m), and a third resin layer (thickness). 15 ⁇ m), the 3rd-4th resin layer (15 ⁇ m thick), the 3-5th resin layer (15 ⁇ m thick), and the second resin layer (30 ⁇ m thick) in this order. It was a laminated film (thickness 150 ⁇ m) constructed by being laminated in the direction.
  • the piercing strength of the laminated film was 7.5 N or more (7.5 to 8.5 N), which was sufficiently large.
  • the laminated films of Examples 6 to 11 had sufficiently high pinhole resistance and high strength even when a polyamide such as Ny was not used.
  • the haze of the laminated film was 25.7% or less (16.5 to 25.7%).
  • the haze of the laminated film was 18.9% or less (16.5 to 18.9%), which was a low level, but this was the first among these laminated films. This is because the uniformity of the 3-3 resin layer is high, which is consistent with the high oxygen barrier property of these laminated films.
  • the present invention can be used for manufacturing various packaging bodies that can be reused after use.

Landscapes

  • Laminated Bodies (AREA)
  • Wrappers (AREA)
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JP7180736B1 (ja) 2021-09-21 2022-11-30 住友ベークライト株式会社 積層フィルム及び包装体
JP2024018377A (ja) * 2022-07-29 2024-02-08 住友ベークライト株式会社 積層フィルム及び包装体

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