WO2021039646A1 - 多層構造体、真空包装袋および真空断熱体 - Google Patents

多層構造体、真空包装袋および真空断熱体 Download PDF

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Publication number
WO2021039646A1
WO2021039646A1 PCT/JP2020/031678 JP2020031678W WO2021039646A1 WO 2021039646 A1 WO2021039646 A1 WO 2021039646A1 JP 2020031678 W JP2020031678 W JP 2020031678W WO 2021039646 A1 WO2021039646 A1 WO 2021039646A1
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Prior art keywords
layer
vapor deposition
mol
overcoat layer
less
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Ceased
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PCT/JP2020/031678
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English (en)
French (fr)
Japanese (ja)
Inventor
久 石原
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.)
Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to KR1020227009549A priority Critical patent/KR20220054339A/ko
Priority to JP2021542847A priority patent/JP7610514B2/ja
Priority to CN202080059584.3A priority patent/CN114258346B/zh
Publication of WO2021039646A1 publication Critical patent/WO2021039646A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/082—Layered products comprising a layer of metal comprising metal 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 comprising vinyl resins; comprising acrylic resins
    • 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
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    • 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
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    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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    • B65D31/02—Bags or like containers made of paper and having structural provision for thickness of contents with laminated walls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
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    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/38—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0853—Ethylene vinyl acetate copolymers
    • C08L23/0861—Saponified copolymers, e.g. ethylene vinyl alcohol copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/06—Arrangements using an air layer or vacuum
    • F16L59/065—Arrangements using an air layer or vacuum using vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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Definitions

  • the present invention relates to a multilayer structure, a vacuum packaging bag and a vacuum insulation body.
  • polyurethane foam has been widely used as a heat insulating body used for refrigerators, housing heat insulating walls, storage tanks, and the like.
  • a vacuum insulator has also been used as an alternative insulator.
  • the vacuum insulation makes it possible to achieve insulation properties equivalent to those of a urethane foam insulator in a thinner and lighter form.
  • the vacuum heat insulating body is expanding its use and demand as a heat insulating body used for heat insulating heat transfer equipment such as heat pump application equipment, heat storage equipment, living space, vehicle interior space, and the like.
  • Examples of the vacuum heat insulating body include a configuration including a vacuum packaging bag and a core material arranged inside surrounded by the vacuum packaging bag, and one of the characteristics required for the vacuum packaging bag is barrier property. is there. Therefore, a vacuum packaging bag having an enhanced barrier property and a barrier film used for the vacuum packaging bag have been proposed.
  • Patent Document 1 describes a film used for a vacuum packaging bag having enhanced gas barrier properties, which contains a vapor-deposited film on one side of an ethylene-vinyl alcohol copolymer film and an inorganic substance in polyvinyl alcohol so as to be adjacent to the vapor-deposited film.
  • a gas barrier film having a coated layer is described.
  • the barrier property may be lowered when a physical stress such as stretching or bending is applied in the manufacturing process of a vacuum heat insulating body or the like.
  • An object of the present invention is to provide a multilayer structure, a vacuum packaging bag, and a vacuum heat insulating body that can maintain a high barrier property even when subjected to physical stress such as bending.
  • the present invention includes [1] a base material (X), an inorganic vapor deposition layer (Y), and an overcoat layer (Z) in this order, and the base material (X) is made of a biaxially stretched polyvinyl alcohol-based resin film and is overcoated.
  • the coat layer (Z) contains a modified polyvinyl alcohol (A) having a vinyl alcohol unit (a) and a monomer unit (b) having a polar group other than the vinyl alcohol unit (a), and the overcoat layer (Z).
  • Multi-layer structure (1) Analysis in the depth direction by TOF-SIMS is performed at five arbitrarily selected points on the surface of the overcoat layer (Z). (2) For each detected fragment, the average value (I (B)) of the maximum intensity of the fragment at each measurement point, and the measurement point between the measurement start point and the maximum intensity measurement point at each measurement point. The average value of the intensities (I (C)) is obtained, and these ratios are defined as the intensity ratio (I (B) / I (C)). (3) The maximum intensity ratio (I (B) / I (C) MAX ) of the obtained intensity ratios for each fragment is defined as the maximum intensity ratio (I (B) / I (C) MAX).
  • the multilayer structure according to any one of [1] to [4] further comprising a base material (X), an inorganic vapor deposition layer (Y), and a layer (J) other than the overcoat layer (Z); [6] At least two layers of the other layer (J) are provided, and a base material (X), an inorganic vapor deposition layer (Y), and an overcoat layer (Z) are placed between the other layers (J) of the at least two layers.
  • the biaxially stretched polyvinyl alcohol-based resin film is biaxially stretched mainly containing an ethylene-vinyl alcohol copolymer having an ethylene unit content of 10 mol% or more and 65 mol% or less and a saponification degree of 90 mol% or more.
  • the multilayer structure according to any one of [1] to [6], which is a film; [8] In the Gelbofrec test based on ASTM F392, JIS K7126 under the conditions of 40 ° C., 0% RH (carrier gas side), and 90% RH (oxygen supply side) after repeated reciprocating movements three times.
  • a vacuum insulating body comprising the vacuum packaging bag of [9] and a core material arranged inside the vacuum packaging bag, and the inside of which is depressurized; Is achieved by providing.
  • the present invention it is possible to provide a multi-layer structure, a vacuum packaging bag and a vacuum heat insulating body that can maintain a high barrier property even when subjected to physical stress such as bending.
  • gas barrier property means the ability to barrier gases other than water vapor unless otherwise specified.
  • barrier property when simply described as “barrier property”, it means both gas barrier property and water vapor barrier property.
  • the property of "maintaining a high barrier property even when subjected to physical stress such as bending” may be expressed as "flexion resistance”.
  • the multilayer structure of the present invention includes a base material (X), an inorganic vapor deposition layer (Y), and an overcoat layer (Z) in this order, and the base material (X) is a biaxially stretched polyvinyl alcohol-based resin film (hereinafter, "two"). (Sometimes abbreviated as "axially stretched PVA-based resin film"), and the overcoat layer (Z) is a monomer unit (b) having a vinyl alcohol unit (a) and a polar group other than the vinyl alcohol unit (a).
  • modified PVA (A) Is contained (hereinafter, may be abbreviated as "modified PVA (A)"), and the thickness of the overcoat layer (Z) is 0.003 ⁇ m or more and 5 ⁇ m or less.
  • the multilayer structure of the present invention is good because it is provided with an inorganic vapor deposition layer (Y) on a base material (X) and an overcoat layer (Z) containing a modified PVA (A) having a specific thickness. It tends to show a good bending resistance.
  • the base material (X) and the inorganic vapor deposition layer (Y) may be in direct contact with each other, or other layers may intervene.
  • the inorganic thin-film deposition layer (Y) and the overcoat layer (Z) may be in direct contact with each other, or other layers may intervene, but the inorganic thin-film deposition layer (Y) and the overcoat layer (Z) may be in direct contact with each other. ) Is preferably in direct contact with. Further, in the multilayer structure, an inorganic vapor deposition layer (Y) and an overcoat layer (Z) may be provided on both sides of the base material (X), respectively.
  • the multilayer structure of the present invention exhibits excellent gas barrier properties by having a base material (X) made of a biaxially stretched PVA-based resin film. Further, since the base material (X) is composed of a biaxially stretched PVA-based resin film, the affinity with the inorganic vapor deposition layer (Y) described later is enhanced, and the bending resistance is improved.
  • the biaxially stretched PVA-based resin film is a biaxially stretched film containing PVA-based resin as a main component.
  • the principal component is the component having the highest content on a mass basis.
  • the content of the PVA-based resin in the base material (X), that is, the biaxially stretched PVA-based resin film is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 99% by mass or more.
  • the PVA-based resin may have a vinyl alcohol unit in which the vinyl ester unit is saponified.
  • a polyvinyl alcohol hereinafter, may be abbreviated as "PVA”
  • PVA polyvinyl alcohol
  • EVOH alcohol copolymer
  • EVOH resin is preferable as the PVA-based resin from the viewpoint of obtaining a multilayer structure having excellent bending resistance. That is, the base material (X) is preferably made of a biaxially stretched EVOH resin film.
  • the PVA resin for example, vinyl esters such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate and vinyl versatic acid are polymerized alone. Then, the saponified PVC resin can be mentioned. Further, the PVA resin in the present invention may be a copolymerized modified or post-modified modified PVA resin. The homopolymerization of the vinyl ester and the saponification of the vinyl ester homopolymer can be carried out by a known method.
  • the copolymerized PVA resin is produced, for example, by copolymerizing the above-mentioned vinyl ester with an unsaturated monomer copolymerizable with the vinyl ester and then saponifying the resin, and the amount of the modification is usually the same. It is less than 10 mol%.
  • Examples of unsaturated monomers copolymerizable with vinyl esters include olefins such as ethylene, propylene, isobutylene, ⁇ -octene, ⁇ -dodecene and ⁇ -octadecene; 3-butene-1-ol and 4-pentene-1. Hydroxy group-containing ⁇ -olefins such as -ol and 5-hexene-1-ol and derivatives such as acylated products thereof; non-residuals such as acryloic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, and undecylene acid.
  • olefins such as ethylene, propylene, isobutylene, ⁇ -octene, ⁇ -dodecene and ⁇ -octadecene
  • the post-modified PVA resin is obtained by post-modifying PVA by a method such as acetoacetic esterification, acetalization, urethanization, etherification, grafting, phosphate esterification, or oxyalkyleneization.
  • the viscosity average degree of polymerization of the PVA resin is preferably 1100 or more, more preferably 1200 or more.
  • the viscosity average degree of polymerization of the PVA resin is preferably 4000 or less, more preferably 2600 or less.
  • the viscosity average degree of polymerization of the PVA resin is 1100 or more, the mechanical strength of the obtained vacuum packaging bag becomes good, which is preferable.
  • the viscosity average degree of polymerization is 4000 or less, the processability at the time of film formation and stretching becomes good, which is preferable.
  • the degree of saponification of the PVA resin is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more. Further, the degree of saponification of the PVA resin may be 100 mol% or less or 99.9 mol% or less. When the degree of saponification is within the above range, the water resistance is improved and the gas barrier property against humidity is improved, which is preferable.
  • the viscosity average degree of polymerization and the degree of saponification of the PVA resin can be measured according to the method described in JIS K 6726 (1994).
  • the EVOH resin is usually copolymerized with ethylene and a vinyl ester such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate and vinyl versatic acid. Obtained by converting coalescence into Ken.
  • the production and saponification of a copolymer of ethylene and vinyl ester can be carried out by a known method.
  • the degree of saponification of the vinyl ester component of the EVOH resin is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more. By setting the degree of saponification to 90 mol% or more, the gas barrier property can be enhanced.
  • the degree of saponification of the EVOH resin may be 100 mol% or less, or 99.99 mol% or less.
  • the degree of saponification of the EVOH resin is measured by nuclear magnetic resonance (1 H-NMR) measurement, and the peak area of hydrogen atoms contained in the vinyl ester structure and the peak area of hydrogen atoms contained in the vinyl alcohol structure are measured. Desired.
  • the ethylene unit content of the EVOH resin is preferably 10 mol% or more, more preferably 15 mol% or more, further preferably 20 mol% or more, still more preferably 25 mol% or more.
  • the ethylene unit content of the EVOH resin is preferably 65 mol% or less, more preferably 55 mol% or less, still more preferably 50 mol% or less.
  • the gas barrier property and the bending resistance under high humidity tend to be kept good.
  • the gas barrier property can be enhanced.
  • the ethylene unit content of the EVOH resin can be determined by the NMR method.
  • the EVOH resin may have a unit derived from a monomer other than ethylene, vinyl ester and a saponified product thereof as long as the object of the present invention is not impaired.
  • the content of the other monomer unit with respect to all the monomer units of the EVOH resin is preferably 30 mol% or less, more preferably 20 mol% or less, and 10 It is more preferably mol% or less, and particularly preferably 5 mol% or less.
  • the lower limit thereof may be 0.05 mol% or 0.10 mol%.
  • Examples of the other monomer include alkenes such as propylene, butylene, penten, and hexene; 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, 3,4-.
  • vinyl silane compounds such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri ( ⁇ -methoxy-ethoxy) silane, ⁇ -methacryloxypropyl methoxysilane; alkyl vinyl ethers, vinyl ketone, N-vinylpyrrolidone, vinyl chloride , Vinylidene chloride and the like.
  • the average ethylene unit content or saponification degree of the entire EVOH resin is defined as the ethylene unit content or saponification degree of the EVOH resin. ..
  • the biaxially stretched PVA-based resin film is, for example, a carboxylic acid compound, a phosphoric acid compound, a boron compound, a metal salt, a stabilizer, an antioxidant, an ultraviolet absorber, and an antistatic agent as long as the effect of the present invention is not impaired.
  • Other components such as agents, lubricants, colorants, fillers, desiccants, reinforcing agents such as various fibers may be contained.
  • a film formed by using a PVA-based resin is used as the base material (X).
  • a known method can be applied to such a film forming method.
  • examples thereof include a melt molding method in which the film is melt-extruded.
  • the PVA-based resin film is biaxially stretched according to a known method such as simultaneous biaxial stretching and sequential biaxial stretching.
  • the draw ratio is 2.5 times or more and 4.5 times or less in the vertical direction (MD direction) and 2 in the horizontal direction (TD direction) from the viewpoint of thickness uniformity, barrier property, mechanical properties and film forming property. .5 times or more and 4.5 times or less, and the surface stretching ratio is preferably in the range of 7 times or more and 15 times or less, 2.5 times or more and 3.5 times or less in the vertical direction, and 2.5 times or more and 3.5 times in the horizontal direction. It is more preferable that the surface stretching ratio is 8 times or more and 12 times or less. If the PVA-based resin film is not biaxially stretched, the bending resistance and gas barrier property may decrease.
  • the thickness of the base material (X) is not particularly limited, but from the viewpoint of industrial productivity, 5 ⁇ m or more is preferable, 8 ⁇ m or more is more preferable, and 10 ⁇ m or more is further preferable.
  • the thickness of the base material (X) is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, further preferably 40 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
  • the thickness is the average value of the values measured at any five points. Hereinafter, the same applies to other thicknesses.
  • the inorganic vapor deposition layer (Y) is usually a layer having a barrier property against oxygen and water vapor, and can be formed by vapor deposition of an inorganic substance.
  • Inorganic materials include metals (eg, aluminum), metal oxides (eg, silicon oxide, aluminum oxide), metal nitrides (eg, silicon nitride), metal nitrides (eg, silicon nitride), or metal nitrides.
  • metals eg, aluminum
  • metal oxides eg, silicon oxide, aluminum oxide
  • metal nitrides eg, silicon nitride
  • metal nitrides eg, silicon nitride
  • metal nitrides eg, silicon nitride
  • metal nitrides eg, silicon nitride
  • metal nitrides eg, silicon nitride
  • metal nitrides eg, silicon nitride
  • metal nitrides
  • the method for forming the inorganic vapor deposition layer (Y) is not particularly limited, and physical vapor deposition such as vacuum vapor deposition (for example, resistance heating vapor deposition, electron beam deposition, molecular beam epitaxy method, etc.), sputtering method, ion plating method, etc. Methods; Thermochemical Vapor Deposition (eg, Catalytic Chemical Vapor Deposition), Photochemical Vapor Deposition, Plasma Chemical Vapor Deposition (eg, Capacitive Bonded Plasma, Induced Bonded Plasma, Surface Wave Plasma, Electron Cyclotron Resonance, Dual magnetron, atomic layer deposition method, etc.), chemical vapor deposition method such as organic metal vapor deposition method, etc. can be mentioned.
  • vacuum vapor deposition for example, resistance heating vapor deposition, electron beam deposition, molecular beam epitaxy method, etc.
  • sputtering method ion plating method, etc.
  • ion plating method etc.
  • the thickness of the inorganic thin-film vapor deposition layer (Y) varies depending on the type of the components constituting the inorganic thin-film vapor deposition layer (Y), but is preferably 0.002 ⁇ m or more and 0.5 ⁇ m or less, more preferably 0.005 ⁇ m or more and 0.2 ⁇ m or less. More preferably, it is 0.01 ⁇ m or more and 0.1 ⁇ m or less.
  • the thickness of the inorganic thin-film deposition layer (Y) is 0.002 ⁇ m or more, the barrier property against oxygen and water vapor tends to be better. Further, when the thickness of the inorganic thin-film deposition layer (Y) is 0.5 ⁇ m or less, the barrier property after bending tends to be more maintained.
  • the overcoat layer (Z) contains modified PVA (A).
  • the modified PVA (A) has a vinyl alcohol unit (a) and a monomer unit (b) having a polar group.
  • the monomer unit (b) does not include the vinyl alcohol unit (a).
  • the modified PVA (A) is not particularly limited as long as it has a vinyl alcohol unit (a) and a monomer unit (b), but it is preferably not alkylene modified.
  • the vinyl alcohol unit (a) is a unit represented by ⁇ CH 2 CH (OH) ⁇ .
  • the ratio of the vinyl alcohol unit (a) to all the monomer units constituting the modified PVA (A) is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 75 mol% or more, and even more preferably 80 mol. %, 85 mol%, 90 mol% or 95 mol% or more may be even more preferable.
  • the monomer unit (b) is a monomer unit other than the vinyl alcohol unit (a) and has a polar group.
  • the polar group may be a monovalent group or a divalent or higher valent group.
  • the polar group is not particularly limited, but is preferably at least one selected from the group consisting of a carboxy group, an ester group (-COO-) and a silanol group from the viewpoint of further improving bending resistance.
  • the polar group may be a group represented by -COOR (R is a hydrocarbon group) as a group containing an ester group.
  • R is a hydrocarbon group
  • an alkyl group is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.
  • a silanol group refers to a group (Si-OH) in which a hydroxyl group (-OH) is bonded to a silicon atom.
  • the modified PVA (A) can be produced by a method such as copolymerization modification or post-modification, similar to the modified PVA that can be used for the base material (X) described above.
  • the monomer unit (b) having a carboxy group unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, and undecylene acid are used as unsaturated monomers. As a result, it can be introduced into the modified PVA (A).
  • the monomer unit (b) having an ester group can be introduced into the modified PVA (A) by using an unsaturated acid ester or the like as an unsaturated monomer or adjusting the degree of saponification. ..
  • the monomer unit (c) having a silanol group includes an unsaturated double bond and trialkoxy such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri ( ⁇ -methoxy-ethoxy) silane, and ⁇ -methacryloxypropylmethoxysilane.
  • trialkoxy such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri ( ⁇ -methoxy-ethoxy) silane, and ⁇ -methacryloxypropylmethoxysilane.
  • the proportion of the monomer unit (b) having a polar group in all the monomer units constituting the modified PVA (A) is preferably 0.05 mol% or more, more preferably 0.10 mol% or more.
  • the proportion of the monomer unit (b) having a polar group is preferably 30 mol% or less, more preferably 25 mol% or less.
  • the modified PVA (A) has a monomer unit (b) containing a carboxy group as a polar group
  • the monomer unit (b) containing a carboxy group in all the monomer units constituting the modified PVA (A).
  • the ratio of is preferably 0.05 mol% or more, and more preferably 0.50 mol% or more.
  • the proportion of the monomer unit (b) containing a carboxy group is preferably 10 mol% or less, more preferably 5 mol% or less.
  • the modified PVA (A) has a monomer unit (b) containing an ester group as a polar group
  • the ratio of the above is preferably 5 mol% or more, and more preferably 10 mol% or more.
  • the proportion of the monomer unit (b) containing an ester group is preferably 30 mol% or less, more preferably 25 mol% or less.
  • the modified PVA (A) has a monomer unit (b) containing a silanol group as a polar group
  • the ratio of is preferably 0.05 mol% or more, and more preferably 0.1 mol% or more.
  • the proportion of the monomer unit (b) containing a silanol group is preferably 5 mol% or less, more preferably 2 mol% or less.
  • the modified PVA (A) may have a monomer unit (b) containing a carboxy group or a silanol group, and may further have a monomer unit (b) containing an ester group.
  • a preferable ratio of the monomer unit (b) containing a carboxy group or a silanol group in all the monomer units constituting the modified PVA (A) is the above-mentioned monomer containing a carboxy group or a silanol group. This is similar to the preferred proportion of unit (b).
  • the ratio of the monomer unit (b) containing an ester group in all the monomer units constituting the modified PVA (A) is preferably 0.1 mol% or more and 10 mol% or less, and 0. 3 mol% or more and 5 mol% or less are more preferable, and 1 mol% or more and 3 mol% or less may be further preferable.
  • the ratio of each monomer unit is in the above range, the bending resistance tends to be more excellent.
  • the total content ratio of the vinyl alcohol unit (a) and the monomer unit having a polar group (b) in all the monomer units constituting the modified PVA (A) is preferably 95 mol% or more, preferably 99 mol. % Or more is more preferable, and 99.9 mol% or more may be further preferable.
  • the viscosity average degree of polymerization of the modified PVA (A) is preferably 1000 or more and 4000 or less, and more preferably 1200 or more and 2600 or less.
  • the viscosity average degree of polymerization of the modified PVA (A) is 1000 or more, the mechanical strength of the obtained vacuum packaging bag becomes good, which is preferable.
  • the viscosity average degree of polymerization is 4000 or less, the film-forming property and the like are improved, which is preferable.
  • the content of the modified PVA (A) in the overcoat layer (Z) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90% by mass. % Or more is particularly preferable, and 95% by mass or more may be used, and the overcoat layer (Z) may be substantially composed of only the modified PVA (A), or may be composed of only the modified PVA (A). You may be.
  • the overcoat layer (Z) may contain components other than the modified PVA (A) as long as the effects of the present invention are not impaired.
  • Other components that can be contained in the overcoat layer (Z) include, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, and oxalates.
  • Organic acid metal salts such as acetates, tartrates, stearate, metal complexes such as cyclopentadienyl metal complexes (eg titanosen), cyanometal complexes (eg Prussian blue), layered clay compounds, cross-linking agents, Examples thereof include polymer compounds other than modified PVA (A), plasticizers, antioxidants, ultraviolet absorbers, flame retardants and the like.
  • the content of the other component in the overcoat layer (Z) is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, particularly preferably less than 5% by mass, and 0% by mass. It may be (does not contain other components).
  • the thickness of the overcoat layer (Z) is 0.003 ⁇ m or more, preferably 0.02 ⁇ m or more, and more preferably 0.06 ⁇ m or more.
  • the thickness of the overcoat layer (Z) is 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, further preferably 0.2 ⁇ m or less, and particularly preferably 0.15 ⁇ m or less. If the thickness of the overcoat layer (Z) is out of the above range, the barrier property after bending tends to decrease.
  • the maximum strength ratio (I (B) / I (C) MAX ) obtained in the following procedures (1) to (3) is 1.20 or more.
  • the average value of the intensities at the points (I (C)) is obtained, and these ratios are defined as the intensity ratio (I (B) / I (C)).
  • the maximum intensity ratio (I (B) / I (C) MAX ) of the obtained intensity ratios for each fragment is defined as the maximum intensity ratio (I (B) / I (C) MAX).
  • TOF-SIMS is an analysis method in which a sample is irradiated with an ion beam (primary ion), and the released secondary ions (fragments) are acquired by the TOF (Time Of Flight) method and mass spectrometrically analyzed.
  • TOF Time Of Flight
  • “Five points arbitrarily selected” means five points arbitrarily selected on the surface of the overcoat layer (Z) of the multilayer structure, and the range analyzed at each measurement place is a range of 250 ⁇ m ⁇ 250 ⁇ m. Is.
  • the average value is defined as I (B), which is between the measurement start point and the maximum intensity measurement point measured at each measurement location.
  • I (C) the average value of the measurement points.
  • I (B) and I (C) are calculated for each fragment, and the intensity ratio (I (B) / I (C)) is also calculated for each fragment.
  • the maximum intensity ratio (I (B) / I (C)) in each fragment is defined as the maximum intensity ratio (I (B) / I (C) MAX ).
  • the maximum intensity ratio (I (B) / I (C) MAX ) can be used as an index indicating the degree of uneven distribution of fragments, and the maximum intensity ratio (I (B) / I (C) MAX ) is around 1. It can be judged that the tendency is uniformly distributed, and it can be judged that the tendency is unevenly distributed when (I (B) / I (C) MAX ) is large.
  • the maximum intensity ratio (I (B) / I (C)) is used as an index for confirming that polar groups are unevenly distributed at the interface between the overcoat layer (Z) and the inorganic vapor deposition layer (Y).
  • the maximum strength ratio (I (B) / I (C) MAX ) of the overcoat layer (Z) is preferably 1.20 or more, more preferably 1.40 or more, further preferably 1.70 or more, and 2.00 or more. Is particularly preferable.
  • the maximum strength ratio (I (B) / I (C) MAX ) of the overcoat layer (Z) is equal to or higher than the above lower limit, the polar groups in the overcoat layer (Z) are at the interface with the inorganic vapor deposition layer (Y). As a result, the bending resistance tends to be improved.
  • the maximum intensity ratio (I (B) / I (C) MAX ) may be 5.00 or less, 4.00 or less, or 3.00 or less.
  • the fragment of the overcoat layer (Z) observed by TOF-SIMS is not particularly limited, and is, for example, a silicon-based fragment such as SiO 2 , an alcohol-based fragment such as C 2 H 3 O, C 3 H 5 O, or the like. Can be mentioned.
  • the surface analysis of the overcoat layer (Z) in the depth direction using TOF-SIMS can be specifically measured by the method described in Examples.
  • the method for producing the multilayer structure of the present invention is not particularly limited, and for example, modified PVA (modified PVA) is formed on the inorganic vapor deposition layer (Y) of the laminate having the inorganic vapor deposition layer (Y) on one surface of the base material (X).
  • modified PVA modified PVA
  • the laminate using the inorganic vapor deposition layer (Y) on one surface of the base material (X) used in the step (i) can be produced by the same method as the above-mentioned method for forming the inorganic vapor deposition layer (Y).
  • a commercially available product can also be used as the laminate having the inorganic thin-film deposition layer (Y) on one surface of the base material (X).
  • the coating liquid (S) containing the modified PVA (A) and the solvent is applied onto the inorganic vapor deposition layer (Y).
  • the solvent used for the coating liquid (S) is not particularly limited, but it is preferable that water is the main component, and water alone may be used.
  • water is the main component
  • water alone may be used.
  • alcohols such as methanol, ethanol and isopropanol are preferable.
  • the solid content concentration of the coating liquid (S) is determined from the viewpoints of storage stability of the coating liquid (S), coatability with respect to the inorganic vapor deposition layer (Y), and the degree of uneven distribution of polar groups in the obtained overcoat layer (Z). Therefore, 0.01 to 15% by mass is preferable, 0.05 to 10% by mass is more preferable, and 0.1 to 5% by mass is further preferable.
  • the solid content concentration can be calculated, for example, by dividing the mass of the solid content remaining after distilling off the solvent of the coating liquid (S) by the mass of the coating liquid (S) subjected to the treatment.
  • the coating method of the coating liquid (S) is not particularly limited, and for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, and a meta.
  • Known methods such as a ring bar coating method, a chamber doctor combined coating method, a curtain coating method, and a bar coating method can be adopted.
  • the thickness of the layer (Z) formed after the coating liquid (S) is applied to the inorganic vapor deposition layer (Y) can be controlled by the solid content concentration of the coating liquid (S) or the coating method.
  • the cell volume of the gravure roll may be changed.
  • the overcoat layer (Z) is formed on the inorganic vapor deposition layer (Y) by removing the solvent in the coating liquid (S) coated on the inorganic vapor deposition layer (Y). ..
  • the method for removing the solvent from the coating liquid (S) after coating is not particularly limited, and for example, a known drying method can be applied. Examples of the drying method include a hot air drying method, a hot roll contact method, an infrared heating method, a microwave heating method, and the like.
  • the drying temperature may be, for example, 80 ° C. or higher and 180 ° C. or lower, or 90 ° C. or higher and 150 ° C. or lower.
  • the coating liquid (S) is applied onto the inorganic thin-film deposition layer (Y), allowed to stand, and then dried.
  • the standing time from coating to drying is, for example, 1 second or longer, preferably 2 seconds or longer. Further, the standing time may be, for example, 1 minute or less.
  • the overcoat layer (Z) to be formed tends to be unevenly distributed near the interface with the inorganic vapor deposition layer (Y) of the polar group.
  • the multilayer structure of the present invention has a base material (X), an inorganic vapor deposition layer (Y), and an overcoat layer (Z) in order to improve various properties (for example, heat sealability, barrier property, mechanical properties, etc.).
  • Other layers (J) other than the above may be included.
  • another layer (J) is directly or adhered to a laminate provided with a base material (X), an inorganic vapor deposition layer (Y) and an overcoat layer (Z). It can be manufactured by adhering or forming through.
  • the other layer (J) examples include, but are not limited to, an ink layer, a polyolefin layer, a polyester layer, a polyamide layer, a thermoplastic resin layer such as an ethylene-vinyl alcohol copolymer resin layer, and the like.
  • the adhesive layer is also an example of the other layer (J).
  • the multilayer structure of the present invention preferably includes at least two other layers (J), and between the other layers (J) of the at least two layers, a base material (X), an inorganic vapor deposition layer (Y), and an inorganic vapor deposition layer (Y). It is more preferable to include an overcoat layer (Z).
  • the multilayer structure of the present invention may include an ink layer for printing a product name, a pattern, or the like.
  • the ink layer include a film obtained by drying a liquid in which a polyurethane resin containing a pigment (for example, titanium dioxide) is dispersed in a solvent, but a polyurethane resin containing no pigment or an ink containing another resin as a main component is used. A dry film of the resin for forming the electronic circuit wiring may be used.
  • the ink layer coating method include a gravure printing method and various coating methods such as a wire bar, a spin coater, and a die coater.
  • the thickness of the ink layer is preferably 0.5 ⁇ m or more and 10.0 ⁇ m or less, and more preferably 1.0 ⁇ m or more and 4.0 ⁇ m or less.
  • the polyolefin layer of the present invention By using the outermost surface layer of the multilayer structure of the present invention as a polyolefin layer, it is possible to impart heat-sealing properties to the multilayer structure and improve the mechanical properties of the multilayer structure.
  • the polyolefin is preferably polypropylene or polyethylene.
  • PET polyethylene terephthalate
  • nylon-6 is preferable as the polyamide
  • ethylene-vinyl alcohol copolymer is preferable as the hydroxyl group-containing polymer.
  • the other layer (J) may be a layer formed by an extruded coat laminate.
  • the extruded coat laminating method that can be used in the present invention is not particularly limited, and a known method may be used.
  • a typical extrusion coat laminating method a laminated film is produced by sending a molten thermoplastic resin to a T-die and cooling the thermoplastic resin taken out from a flat slit of the T-die.
  • Examples of the extrusion coat laminating method other than the single laminating method include a sandwich laminating method and a tandem laminating method.
  • the sandwich laminating method is a method in which a molten thermoplastic resin is extruded onto a first base material, and a second base material is supplied from another unwinder (unwinder) and bonded to each other to prepare a laminate.
  • the tandem laminating method is a method of connecting two single laminating machines to produce a laminated body having a five-layer structure at a time.
  • the inorganic vapor deposition layer (Y) may be laminated so as to be in direct contact with the base material (X), and is between the base material (X) and the inorganic vapor deposition layer (Y).
  • the inorganic vapor deposition layer (Y) may be laminated on the base material (X) via the arranged adhesive layer (H).
  • the adhesive layer (H) By passing through the adhesive layer (H), the adhesiveness between the base material (X) and the inorganic thin-film deposition layer (Y) may be enhanced.
  • the adhesive force between the layers may be enhanced by laminating via the adhesive layer (H).
  • the adhesive constituting the adhesive layer (H) a two-component reaction type polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable. Further, the adhesiveness may be further improved by adding a small amount of an additive such as a known silane coupling agent.
  • the silane coupling agent include a silane coupling agent having a reactive group such as an isocyanate group, an epoxy group, an amino group, a ureido group and a mercapto group.
  • the thickness of the adhesive layer (H) is preferably in the range of 0.03 ⁇ m or more and 0.18 ⁇ m or less.
  • the thickness of the adhesive layer (H) is more preferably 0.04 ⁇ m or more and 0.14 ⁇ m or less, and further preferably 0.05 ⁇ m or more and 0.10 ⁇ m or less.
  • the multilayer structure of the present invention was subjected to repeated reciprocating movements three times in a Gerbofrec test based on ASTM F392, and then at 40 ° C., 0% RH (carrier gas side), and 90% RH (oxygen supply side).
  • the oxygen permeability measured according to JIS K7126 under the conditions is preferably 2.0 ml / (m 2 ⁇ day ⁇ atm) or less, more preferably 1.0 ml / (m 2 ⁇ day ⁇ atm) or less, and 0. 5 ml / (m 2 ⁇ day ⁇ atm) or less is more preferable, and 0.40 ml / (m 2 ⁇ day ⁇ atm) or less is particularly preferable.
  • the vacuum packaging bag of the present invention includes the multilayer structure of the present invention.
  • the vacuum packaging bag is a packaging bag that is usually used by reducing the pressure inside, and includes a film material containing the above-mentioned multilayer structure as a partition wall that separates the inside from the outside.
  • the vacuum packaging bag may include a plurality of the multilayer structures.
  • the surface layer of the vacuum packaging bag of the present invention is a polyolefin layer (hereinafter, may be abbreviated as PO layer) from the viewpoint of imparting heat sealability or improving mechanical properties.
  • a polyolefin layer polypropylene or polyethylene is preferable.
  • PET polyethylene terephthalate
  • nylon-6 is preferable as the polyamide
  • ethylene-vinyl alcohol copolymer resin is preferable as the PVA-based resin.
  • the vacuum packaging bag of the present invention may have the following configuration from the outer layer to the inner layer of the vacuum insulation body.
  • “/” means that they are laminated via an adhesive layer or directly, and “//” means that they are laminated through an adhesive layer.
  • the vacuum insulation body of the present invention includes the vacuum packaging bag of the present invention and a core material arranged inside the vacuum packaging bag, and the inside thereof is depressurized.
  • the space inside the vacuum packaging bag is in a vacuum state.
  • the vacuum state here does not necessarily mean an absolute vacuum state, and indicates that the pressure in the space inside the vacuum packaging bag is sufficiently lower than the atmospheric pressure.
  • the pressure of the space inside the vacuum packaging bag is determined from the required performance, ease of manufacture, etc., and is usually 2 kPa (about 15 Torr) or less, preferably 200 Pa or less, and 20 Pa or less from the viewpoint of exhibiting low thermal conductivity performance. The following is more preferable, and 2 Pa or less is further preferable.
  • the pressure in the space inside the vacuum packaging bag may be 0.001 Pa or more.
  • the core material used in the vacuum heat insulating body of the present invention is not particularly limited as long as it has low thermal conductivity.
  • examples of the core material include pearlite powder, silica powder, precipitated silica powder, diatomaceous earth, calcium silicate, glass wool, rock wool, and resin foams (for example, styrene foam and urethane foam).
  • a hollow container made of resin or an inorganic material; a honeycomb-shaped structure or the like may be used.
  • the core material may contain an adsorbent that adsorbs water vapor, gas, or the like.
  • the thermal conductivity of the vacuum insulation body of the present invention immediately after production is preferably 7.0 mW / (m ⁇ K) or less, and more preferably 6.5 mW / (m ⁇ K) or less.
  • the thermal conductivity immediately after the production may be 1.0 mW / (m ⁇ K) or more.
  • the thermal conductivity is 7.0 mW / (m ⁇ K) or less, the low thermal conductivity performance of the vacuum heat insulating body tends to be good.
  • the thermal conductivity is 1.0 mW / (m ⁇ K) or more, a vacuum heat insulating body having good low thermal conductivity can be obtained at a relatively low cost.
  • the "thermal conductivity" is a value measured in accordance with JIS A 1412-1 (1999).
  • the thermal conductivity after bending by 90 ° tends to be a good value.
  • the thermal conductivity after bending at 90 ° is preferably 7.5 mW / (m ⁇ K) or less, more preferably 7.0 mW / (m ⁇ K) or less, and even more preferably 6.5 mW / (m ⁇ K) or less. ..
  • the method for producing the vacuum heat insulating body of the present invention is not particularly limited, and a commonly used method can be adopted.
  • a vacuum insulation body having an arbitrary shape and size can be manufactured by the following methods 1 to 3 according to the purpose of use and the like.
  • Method 1 First, two planar view quadrangular multilayer structures in which a layer having a heat-sealing property (for example, a polyolefin layer) is arranged on at least one surface are prepared. The two multilayer structures are superposed so that the layers having heat-sealing properties are on the inside, and arbitrary three sides are heat-sealed to prepare a packaging bag. Next, the inside of the packaging bag is filled with a core material.
  • a layer having a heat-sealing property for example, a polyolefin layer
  • Method 2 First, one planar view quadrangular multilayer structure is bent so that the layer having heat sealability is on the inside, and arbitrary two sides are heat-sealed to prepare a packaging bag. Next, the inside of the packaging bag is filled with a core material. Next, the space inside the packaging bag is evacuated, and the last side is heat-sealed in that state to obtain a vacuum insulation body.
  • Method 3 First, the core material is sandwiched between two multilayer structures, or the core material is sandwiched by bending the multilayer structure.
  • the peripheral edge portion where the multilayer structures overlap is heat-sealed leaving the vacuum exhaust port, and a packaging bag in which the core material is arranged is produced.
  • the space inside the packaging bag is evacuated, and the vacuum exhaust port is heat-sealed in that state to obtain a vacuum heat insulating body.
  • the vacuum heat insulating body of the present invention is preferably obtained by heat-sealing the multilayer structures of the present invention. Since the multilayer structure of the present invention includes the inorganic vapor deposition layer (Y), the heat bridge (aluminum foil transfers heat and heat insulation performance) found in a vacuum heat insulating body obtained from a film provided with a metal foil such as an aluminum foil. The phenomenon of dropping) is unlikely to occur, and it tends to show excellent heat insulation performance. From the viewpoint of suppressing the heat bridge, the vacuum heat insulating body of the present invention may be a vacuum heat insulating body obtained by heat-sealing the multilayer structure of the present invention and a film provided with a metal foil. Examples of the film provided with the metal foil include a layer structure such as a polyamide layer // polyester layer // metal foil // PO layer, a polyamide layer // metal foil // PO layer and a polyester layer // metal foil // PO layer. Examples include films with.
  • the vacuum insulation body of the present invention can be used for various purposes requiring cold insulation or heat insulation.
  • the vacuum heat insulating body is extremely unlikely to deteriorate over time in low thermal conductivity performance even when used at high temperature or high humidity, and has a sufficient service life as a heat insulating material.
  • -VM-XL "EVAL (registered trademark) VM-XL” manufactured by Kuraray Co., Ltd., aluminum-deposited biaxially stretched EVOH film (ethylene unit content of EVOH 32 mol%, EVOH saponification degree 99.9 mol%, thickness 12 ⁇ m)
  • -VM-PET "VM-PET1510" manufactured by Toray Industries, Inc.
  • aluminum-deposited PET film (thickness 12 ⁇ m) -PET12 “Lumirror (registered trademark) P60” manufactured by Toray Industries, Inc.
  • Thickness of Overcoat Layer (Z) The multilayer structure obtained in Examples and Comparative Examples was cut with a microtome to prepare a section (thickness 0.3 ⁇ m) for cross-sectional observation. The prepared section was fixed to a sample pedestal with carbon tape, and platinum ion sputtering was performed at an acceleration voltage of 30 kV for 30 seconds. The cross section of the multilayer structure was observed with a field emission transmission electron microscope [device: SU8000 manufactured by Hitachi High-Technologies Corporation], and the thickness of the overcoat layer (Z) was calculated. The measurement conditions were an acceleration voltage of 1 kV and a magnification of 20,000 times.
  • the multilayer structure is set so that the vapor deposition layer side faces the oxygen supply side and the base material side faces the carrier gas side, the oxygen supply side is 40 ° C., 90% RH, 1 atm, the carrier gas side is 40 ° C., 0. It was carried out under the conditions of% RH and 1 atm.
  • As the carrier gas nitrogen gas containing 2% by volume of hydrogen gas was used.
  • the oxygen permeability after bending was evaluated based on the following evaluation criteria.
  • a core material having low thermal conductivity and a small bag containing calcium oxide as an adsorbent are filled from the opening of the obtained packaging bag, and a vacuum insulation panel manufacturing device (manufactured by NPC Co., Ltd., KT-500RD type) is used.
  • the packaging bag was sealed at a temperature of 20 ° C. and an internal pressure of 1.0 Pa to prepare a vacuum heat insulating body.
  • As the core material having low thermal conductivity glass fiber dried in an atmosphere of 160 ° C. for 4 hours was used.
  • the obtained vacuum insulation was stored at 23 ° C. and 50% RH for a certain period of time, and then one side of the vacuum insulation body was set to 38 ° C.
  • the thermal conductivity (mW / (m ⁇ k)) of the vacuum insulator was measured with the other surface side at 12 ° C. The measurement was performed on the vacuum insulation body before bending and the vacuum insulation body after bending once vertically (90 °).
  • TMS tetramethoxysilane
  • Example 1 The aluminum-deposited surface of "VM-XL” was coated with a coating liquid (S-1) by a bar coater so that the thickness after drying was 30 nm, and then allowed to stand for 3 seconds. Then, it was dried at 100 ° C. for 3 minutes to prepare a multilayer structure (1-1) in which an overcoat layer (Z) / an aluminum vapor deposition layer / a biaxially stretched EVOH layer were laminated in this order. Regarding the overcoat layer (Z) of the obtained multi-layer structure (1-1) having a three-layer structure, the maximum strength ratio (I (B) / I (C) MAX) was obtained according to the method described in the above evaluation method (4). ) was measured. The results are shown in Table 1.
  • a two-component adhesive (“Takelac A-520" and “Takenate A-50") is applied to each of one side of "PET12" and “PE50", and PET12 / adhesive layer / overcoat layer (Z) /
  • a multilayer structure (1-2) was produced by laminating so as to have an aluminum vapor deposition layer / biaxially stretched EVOH layer / adhesive layer / PE50.
  • the thickness of the overcoat layer (Z) and the oxygen permeability after bending were measured according to the methods (1) and (2) above. The results are shown in Table 1.
  • Examples 2 to 11, Comparative Examples 1 to 8 The same method as in Example 1 was used except that the layer structure (deposited film), the type of coating liquid, the standing time after coating, and the thickness of the overcoat layer (Z) were changed as shown in Table 1.
  • Three-layered multi-layered structures (2-1) to (11-1) and seven-layered multi-layered structures (2-2) to (11-2) of Examples 2 to 11, and Comparative Examples 1 to 8 The three-layered multi-layered structures (C1-1) to (C8-1) and the seven-layered multi-layered structures (C1-2) to (C8-2) were prepared and evaluated. The results are shown in Table 1.
  • Example 12 to 15 Examples 12 to 15-3 in the same manner as in Example 1 except that the type of coating liquid, the standing time after coating, and the thickness of the overcoat layer (Z) were changed as shown in Table 3.
  • Layered multilayer structures (12-1) to (15-1) and seven-layered multilayer structures (12-2) to (15-2) were produced.
  • the thickness of the overcoat layer (Z) and the oxygen permeability after bending were measured according to the methods (1) and (2) above. .. The results are shown in Table 3.
  • Example 3 in which the thickness of the overcoat layer is 0.09 ⁇ m has remarkably improved bending resistance. It turns out to be excellent. Further, from Examples 4 to 6, 12 to 15, and the like, it can be seen that good bending resistance is exhibited when a modified PVA having a silanol group, an ester group, or a carboxy group is used. When the overcoat layer (Z) is not provided as in Comparative Example 1, the bending resistance is inferior, and when non-modified PVA is used as in Comparative Examples 2 to 4, the bending resistance is inferior. It was.
  • the maximum strength ratio (I (B) / I (C) MAX ) and the bending resistance also differ depending on the difference in the standing time after coating the coating liquid. I understand. As in Example 4, after coating the coating liquid (S-1) with a bar coater, waiting for 3 seconds and then drying resulted in good bending resistance.
  • FIG. 1 shows the maximum intensity ratio (I (B) / I (C) MAX ) among the measurement results of the depth direction analysis using TOF-SIMS of Example 4, and the measurement in which the fragment is SiO 2. It is a graph which showed one of the results.
  • the X-axis (horizontal axis) is Dose intensity (a parameter in the depth direction, and the larger the value is, the deeper the measurement point is), and the Y-axis (vertical axis) is Intensity (SiO 2). It is the intensity of the fragment of, and the larger the value, the larger the abundance).

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WO2024262628A1 (ja) 2023-06-23 2024-12-26 株式会社クラレ 真空断熱材用多層フィルム、真空断熱材用蒸着多層フィルム、真空断熱材用多層構造体、真空包装袋及び真空断熱材

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JP2019002442A (ja) * 2017-06-13 2019-01-10 大日本印刷株式会社 真空断熱材用外包材、真空断熱材、および真空断熱材付き物品
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WO2024262628A1 (ja) 2023-06-23 2024-12-26 株式会社クラレ 真空断熱材用多層フィルム、真空断熱材用蒸着多層フィルム、真空断熱材用多層構造体、真空包装袋及び真空断熱材

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