JP7357558B2 - Multilayer structure, packaging material comprising the multilayer structure, vacuum packaging bag, and vacuum insulation body - Google Patents

Description

The present invention relates to a multilayer structure having an aluminum vapor-deposited layer, a packaging material, a vacuum packaging bag, and a vacuum insulation body including the multilayer structure.

Insulators made of urethane foam are used as insulation materials for refrigerators, insulation panels for homes, etc. In recent years, vacuum heat insulators have also been used as an alternative heat insulator. Vacuum insulation can provide the same insulation properties as insulation made of urethane foam, but is thinner and lighter. Vacuum heat insulators are expanding their uses and demand as heat insulators used to insulate heat transfer devices such as heat pump applied devices, heat storage devices, living spaces, vehicle interior spaces, and the like.

Examples of the vacuum insulation body include a configuration including a vacuum packaging bag and a core material placed inside the vacuum packaging bag. One of the properties required of vacuum packaging bags used for vacuum insulation is gas barrier properties. For this reason, studies have been made on vacuum packaging bags with improved gas barrier properties and gas barrier films for use therein, and, for example, films provided with an aluminum vapor-deposited layer or a silica vapor-deposited layer have been provided.

These vapor-deposited layers are usually thin layers with a thickness of several tens of nanometers to a hundred and several tens of nanometers, so in order to produce a film with stable barrier properties, it is necessary to improve the adhesion with the base film. It was necessary to secure sufficient supplies. For example, Patent Document 1 discloses a vapor-deposited film in which a vapor-deposited layer is laminated on a base film containing a vinyl alcohol polymer and a saturated ketone, the vapor-deposited film having a content of the saturated ketone of 0.01 ppm or more and 100 ppm or less. It is described that the film has excellent adhesion of the vapor deposited layer to the base film.

JP2015-071248A

However, the above conventional films may not have sufficient adhesion between the base material and the deposited layer under harsher conditions such as long-term use or high temperature and high humidity. When a vacuum heat insulator is produced, its heat insulating performance may deteriorate significantly when used under harsh conditions.

The present invention has been made based on the above circumstances, and its purpose is to improve the adhesion between the base material and the vapor deposited layer under severe conditions while maintaining the adhesion between the base material and the vapor deposited layer under normal conditions. An object of the present invention is to provide a multilayer structure having excellent properties, as well as a packaging material, a vacuum packaging bag, and a vacuum insulation body including the multilayer structure.

That is, the present invention [1] has a structure (XY) in which an aluminum vapor-deposited layer (Y) is laminated on at least one surface of a base material (X) consisting of a film mainly composed of a vinyl alcohol polymer. , the surface hardness of the surface side of the aluminum vapor deposited layer (Y) of the structure (XY) measured in accordance with ISO15477-1:2015 by the nanoindentation method at a set load of 300 μN is 0.260 GPa or more and 0.390 GPa or less. , multilayer structure;
[2] The multilayer structure of [1], wherein the vinyl alcohol polymer is an ethylene-vinyl alcohol copolymer having an ethylene unit content of 10 to 65 mol% and a saponification degree of 90 mol% or more;
[3] The multilayer structure of [1] or [2], wherein the average thickness of the aluminum vapor deposited layer (Y) is 15 nm or more and 150 nm or less;
[4] The multilayer structure according to any one of [1] to [3], in which the aluminum vapor-deposited layer (Y) is laminated on both sides of the base material (X) made of a film containing a vinyl alcohol polymer as a main component;
[5] Any of [1] to [4] whose oxygen permeability at 20°C and 85% RH is 1.5 cc/m ² ·day · atm or less, measured in accordance with JIS K7126-2:2006. That multilayer structure;
[6] Base material (X) consisting of a film mainly composed of vinyl alcohol polymer and aluminum vapor deposited layer (Y) measured in accordance with JIS K6854-3:1999 while dropping water on the peeled interface. The multilayer structure according to any one of [1] to [5], which has a T-peel strength of 250 gf/15 mm or more;
[7] The multilayer structure according to any one of [1] to [6], which has a structure in which a layer (Z) containing an organic polymer is laminated on one side of the aluminum vapor-deposited layer (Y);
[8] The method for producing a multilayer structure according to any one of [1] to [7], in which the surface temperature of the base material (X) made of a film containing a vinyl alcohol polymer as a main component is 60°C or less. A method for manufacturing a multilayer structure, comprising a step of forming an aluminum vapor deposited layer (Y) in a state;
[9] [1] to [7]: A packaging material comprising any of the multilayer structures;
[10] A vacuum packaging bag obtained by reducing the pressure inside the packaging material of [9];
[11] A vacuum insulation body, wherein the vacuum packaging bag of [10] has a core material inside;
This is achieved by

According to the present invention, a multilayer structure that maintains the adhesion between the base material and the vapor deposited layer under normal conditions and has excellent adhesion between the base material and the vapor deposited layer under severe conditions, and a package including the multilayer structure materials, vacuum packaging bags and vacuum insulation materials.

It is a schematic diagram showing an example of the melt extrusion apparatus which forms a base material (X) into a film.

Embodiments of the present invention will be described below. Note that in the following description, specific materials (compounds, etc.) may be exemplified as materials that exhibit specific functions, but the present invention is not limited to embodiments using such materials. Further, the illustrated materials may be used alone or in combination of two or more, unless otherwise specified.

The multilayer structure of the present invention has a structure (XY) in which an aluminum vapor-deposited layer (Y) is laminated on at least one surface of a base material (X) made of a film containing a vinyl alcohol polymer as a main component. , the surface hardness of the surface side of the aluminum vapor deposited layer (Y) of the structure (XY) measured in accordance with ISO15477-1:2015 by the nanoindentation method at a set load of 300 μN is 0.260 GPa or more and 0.390 GPa or less. . In particular, the surface hardness of the surface side of the aluminum vapor deposited layer (Y) of the structure (XY) measured in accordance with ISO15477-1:2015 by the nanoindentation method at a set load of 300 μN is 0.260 GPa or more and 0.390 GPa or less. This tends to improve the adhesion between the base material (X) and the layer (Y) under severe conditions. The reason is not clear, but because the surface hardness is below a certain value, the aluminum during vapor deposition migrates into the base material (X), resulting in a high anchoring effect, resulting in poor adhesion under harsh conditions. This is thought to have occurred. On the other hand, when the surface hardness is at least a specific value, the multilayer structure of the present invention tends to have good barrier properties. Hereinafter, in this specification, "adhesion between the base material (X) and the layer (Y) under severe conditions" may be abbreviated as "adhesion under severe conditions." In addition, excellent adhesion under harsh conditions tends to maintain performance over a long period of time under general-purpose conditions. There is a tendency to be able to demonstrate this.

[Base material (X)]
The multilayer structure of the present invention has a base material (X) made of a film containing a vinyl alcohol polymer as a main component. Here, "consisting as a main component" means that the proportion of the vinyl alcohol polymer in the film constituting the base material (X) is more than 50% by mass, and such proportion is 70% by mass or more. It is preferably 90% by mass or more, more preferably 95% by mass or more, and the base material (X) may be a film consisting essentially only of a vinyl alcohol polymer. When the multilayer structure of the present invention includes the base material (X), the multilayer structure of the present invention tends to have good gas barrier properties and adhesion under severe conditions.

The vinyl alcohol polymer may be one having vinyl alcohol units obtained by saponifying vinyl ester units, such as polyvinyl alcohol (hereinafter sometimes abbreviated as "PVA"), ethylene-vinyl Examples include alcohol copolymers (hereinafter sometimes abbreviated as "EVOH"). Vinyl alcohol polymers can be used alone or in combination of two or more.

PVA is produced, for example, by homopolymerizing a vinyl ester such as vinyl acetate, and then saponifying the homopolymerization. Further, PVA may be modified PVA, for example, even if it is produced by copolymerizing vinyl acetate and an unsaturated monomer copolymerizable with vinyl acetate and then saponifying the PVA. It may be produced by modification, and the amount of modification is usually less than 10 mol%.

Examples of unsaturated monomers copolymerizable with vinyl acetate include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, and α-octadecene, 3-buten-1-ol, and 4-pentyne. -1-ol, 5-hexen-1-ol and other hydroxy group-containing α-olefins and their acylated derivatives, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, undecylenic acid unsaturated acids, their salts, monoesters, or dialkyl esters, nitriles such as acrylonitrile, methacrylonitrile, amides such as diacetone acrylamide, acrylamide, methacrylamide, ethylene sulfonic acid, allylsulfonic acid, methalylsulfonic acid Olefin sulfonic acids such as or their salts, alkyl vinyl ethers, dimethylallyl vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinyl ethylene carbonate, 2,2-dialkyl-4-vinyl-1,3-dioquinrane, glycerin monoallyl ether , 3,4-diacetoxy-1-butene, substituted vinyl acetates such as isopropenyl acetate, 1-methoxyvinyl acetate, vinylidene chloride, 1,4-diacetoxy-2-butene, vinylene carbonate, etc. Can be mentioned.

Examples of the above-mentioned post-modification methods include methods of converting PVA into acetoacetate, acetal, urethane, ether, grafting, phosphoric ester, and oxyalkylen.

The number average degree of polymerization of PVA is preferably 1,100 to 4,000, more preferably 1,200 to 2,600. When the degree of polymerization of PVA is within the above range, the resulting film tends to have good mechanical strength and processability. Further, the degree of saponification of PVA is preferably 95 to 100 mol%, more preferably 99 to 100 mol%. When the degree of saponification is within the above range, the resulting film tends to have good moisture resistance.

EVOH is usually obtained by saponifying a copolymer of 10 to 65 mol% ethylene and vinyl ester, and a typical example of such vinyl ester is vinyl acetate, but it can also be used with other fatty acid vinyls. Esters (vinyl propionate, vinyl pivalate, etc.) can also be used.

The ethylene unit content of EVOH is preferably 10 to 65 mol%, more preferably 15 to 55 mol%, even more preferably 20 to 50 mol%. When the ethylene unit content is 10 mol% or more, melt moldability tends to improve, and when the ethylene unit content is 65 mol% or less, gas barrier properties tend to improve. Note that the ethylene content of EVOH can be determined by nuclear magnetic resonance (NMR) method.

The saponification degree of EVOH is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more. When the degree of saponification is 90 mol% or more, gas barrier properties under high humidity tend to be good. On the other hand, the degree of saponification of EVOH may be 100 mol% or less. In addition, when EVOH contains a blend of two or more different types of EVOH, each ethylene unit content or saponification degree calculated from the blended weight ratio is defined as the ethylene content or saponification degree of EVOH.

EVOH may have units derived from monomers other than ethylene, vinyl ester, and saponified products thereof, as long as the object of the present invention is not impaired. When EVOH has the other monomer units, the content of the other monomer units relative to the total structural units of EVOH is preferably 30 mol% or less, more preferably 20 mol% or less, and 10 mol% or less. It is more preferable, and particularly preferably 5 mol% or less. Moreover, when EVOH has a unit derived from the above-mentioned other monomer, the lower limit may be 0.05 mol% or 0.10 mol%. Examples of the other monomers include alkenes such as propylene, butylene, pentene, and hexene; 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, 3,4- Diacyloxy-1-butene, 3-acyloxy-4-methyl-1-butene, 4-acyloxy-2-methyl-1-butene, 4-acyloxy-3-methyl-1-butene, 3,4-diacyloxy-2- Methyl-1-butene, 4-acyloxy-1-pentene, 5-acyloxy-1-pentene, 4,5-diacyloxy-1-pentene, 4-acyloxy-1-hexene, 5-acyloxy-1-hexene, 6- Alkenes having ester groups such as acyloxy-1-hexene, 5,6-diasiloxy-1-hexene, 1,3-diacetoxy-2-methylenepropane, or saponified products thereof; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, etc. unsaturated acids or their anhydrides, salts, or mono- or dialkyl esters; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefins such as vinylsulfonic acid, allylsulfonic acid, and methalylsulfonic acid. Sulfonic acid or its salt; vinyl silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxy-ethoxy)silane, γ-methacryloxypropylmethoxysilane; alkyl vinyl ethers, vinyl ketone, N-vinylpyrrolidone, vinyl chloride , vinylidene chloride, etc.

The EVOH may be an EVOH that has been post-modified by urethanization, acetalization, cyanoethylation, oxyalkylenation, or the like.

The melt flow rate (MFR) at 190° C. and a load of 2160 g measured in accordance with JIS K 7210:2014 for EVOH is preferably 0.5 g/10 min or more, more preferably 1.0 g/10 min or more. On the other hand, the MFR of EVOH is preferably 20 g/10 min or less, more preferably 10 g/10 min or less, even more preferably 5.0 g/10 min or less. When the MFR of EVOH is within the above range, melt moldability tends to be excellent.

The base material (X) may include, for example, resins other than vinyl alcohol polymers, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, and antioxidants, as long as they do not impede the effects of the present invention. , ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, desiccants, reinforcing agents such as various fibers, and other components may be contained. In particular, when EVOH is used as the vinyl alcohol polymer, it is preferable to contain metal salts, carboxylic acid compounds, phosphoric acid compounds, boron compounds, etc. from the viewpoint of thermal stability and viscosity adjustment.

Known methods can be used to form the film of the base material (X), such as a casting method in which a solution of a vinyl alcohol polymer is cast onto a metal surface such as a drum or an endless belt to form a film; Alternatively, the film may be formed by a melt molding method in which the film is melt-extruded using an extruder.

An example of melt-extruding the base material (X) will be described with reference to FIG. 1. The extrusion apparatus shown in FIG. 1 includes a die 60 that melt-extrudes the vinyl alcohol polymer 100, a first conveyance roll (casting roll) 70 that conveys the vinyl alcohol polymer 100 extruded from the die 60, and a second conveyance roll. 80 and a take-off machine 90, and an air knife 110 disposed on the opposite side of the casting roll 70 of the vinyl alcohol polymer 100. Air A can be blown from the air knife 110 with arbitrary strength. A film roll 101 of the vinyl alcohol polymer 100 is obtained by melt-extruding the vinyl alcohol polymer 100 using this extrusion device and winding it up on a take-up machine 90 while being conveyed by the casting roll 70 and the second conveyance roll 80. .

Any conditions may be used during melt molding as long as the vinyl alcohol polymer can be melted. In order to make the surface hardness of the layer (Y) surface side of the structure (XY) described below 0.390 GPa or less, the temperature of the casting roll is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and even more preferably 90 ° C. or lower. . On the other hand, in order to make the surface hardness 0.260 GPa or more, the casting roll temperature is preferably 40°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher. Further, the base material (X) may be subjected to changes in the take-up speed of the take-off machine 90, stretching, heat treatment, etc., as long as the effects of the present invention are achieved.

The base material (X) has been subjected to surface treatment such as UV ozone treatment, high concentration ozone water treatment, excimer ozone treatment, corona treatment, oxygen plasma treatment, or AP plasma treatment, within a range that does not impair the effects of the present invention. Good too.

The average thickness of the base material (X) is not particularly limited, but from the viewpoint of industrial productivity, it is preferably 5 to 100 μm, more preferably 8 to 50 μm, and preferably 10 to 20 μm. Particularly preferred.

[Layer (Y)]
The multilayer structure of the present invention tends to have excellent gas barrier properties and adhesion under severe conditions by including the aluminum vapor deposited layer (Y). The term "aluminum evaporation layer" as used herein means a evaporation layer containing aluminum as a main component, and the proportion of aluminum in the evaporation layer is more than 50% by mass, preferably 70% by mass or more, more preferably 90% by mass or more. More preferably, the vapor deposited layer is made of substantially only aluminum. In addition, if aluminum oxide is unavoidably produced during vapor deposition, some aluminum oxide may be included, but the unavoidable amount of aluminum oxide will affect the effect of the present invention. It does not give The multilayer structure of the present invention preferably includes layers (Y) on both sides of the base material (X) from the viewpoint of further improving gas barrier properties.

The lower limit of the average thickness of the layer (Y) is preferably 15 nm, more preferably 20 nm, and even more preferably 30 nm. The upper limit of the average thickness of the layer (Y) is preferably 150 nm, more preferably 130 nm, and even more preferably 100 nm. When the average thickness of the vapor deposited layer is at least the above lower limit, gas barrier properties tend to be good. On the other hand, when the average thickness of the vapor deposited layer is below the above upper limit, heat bridges are less likely to occur in the vacuum heat insulating body using the multilayer structure of the present invention, and the heat insulating performance tends to be good.

Examples of methods for forming the layer (Y) include vacuum evaporation, sputtering, ion plating, and chemical vapor deposition (CVD). Among these, the vacuum evaporation method is preferred from the viewpoint of productivity. As a heating method for vacuum deposition, any one of an electron beam heating method, a resistance heating method, and an induction heating method is preferable. Further, in order to improve the adhesion of the layer (Y) to the base material (X) on which it is formed, a plasma assist method or an ion beam assist method may be employed for vapor deposition.

The upper limit of the surface temperature of the base film during vapor deposition is preferably 60°C, more preferably 55°C, and even more preferably 50°C. Further, the lower limit of the surface temperature of the base film during vapor deposition is not particularly limited, but is preferably 0°C, more preferably 10°C, and even more preferably 20°C.

Since layer (Y) is an aluminum vapor-deposited layer, it has excellent light-shielding properties and metallic luster, and can be used in food packaging materials and decorative films to suppress deterioration of contents or base materials due to UV transmission. can. On the other hand, in applications for vacuum insulation boards, in addition to the above, by reflecting near-infrared to infrared rays, it is possible to provide a multilayer structure with excellent insulation performance.

[Structure (XY)]
The multilayer structure of the present invention has a structure (XY) in which a layer (Y) is laminated on at least one surface of a base material (X). Here, "laminated" may mean that an adhesive layer is interposed between the base material (X) and the layer (Y), but from the viewpoint of improving adhesion under severe conditions, the base material (X) Preferably, the layers (Y) are directly laminated. Since the multilayer structure of the present invention has a structure (XY) and a surface hardness of 0.260 GPa or more and 0.390 GPa or less, it tends to have high gas barrier properties and excellent adhesion under severe conditions.

The surface hardness of the surface side of the aluminum vapor deposited layer (Y) of the structure (XY) by the nanoindentation method at a set load of 300 μN, measured in accordance with ISO15477-1:2015, is 0.390 GPa or less, and 0.380 GPa or less. is preferable, and 0.370 GPa or less is more preferable. Further, the surface hardness is 0.260 GPa or more, preferably 0.280 GPa or more, more preferably 0.300 GPa or more, and even more preferably 0.320 GPa or more. The surface hardness of the surface side of the aluminum vapor deposited layer (Y) of the structure (XY) by the nanoindentation method at a set load of 300 μN, measured in accordance with ISO15477-1:2015, is related to the crystallinity of the structure (XY). When the surface hardness exceeds the above range, the adhesion under harsh conditions tends to decrease significantly, and the reason for this is that the crystallinity of the base material (X) increases significantly, and the aluminum during vapor deposition There is a possibility that the migration of the particles to the base material (X) was suppressed. On the other hand, if the surface hardness is less than the above range, the crystallinity of the base material (X) will decrease, resulting in uneven thickness and thinning during film transport, a tendency for vapor deposition to occur, and oxygen barrier properties will deteriorate. It becomes a trend.

The surface hardness of the surface side of the aluminum vapor deposited layer (Y) of the structure (XY) measured in accordance with ISO15477-1:2015 by the nanoindentation method at a set load of 300 μN is determined by the addition of a crystal nucleating agent, casting, etc. It can be adjusted by the roll temperature, take-up speed, stretching and heat treatment conditions. In particular, when the base material (X) is stretched, the crystallinity of the base material (X) tends to increase, so the surface hardness of the structure (XY) tends to increase. Therefore, the base material (X) is preferably unstretched. In addition, from the viewpoint of the strength of the film during vapor deposition, when the base material (X) is not stretched, it is preferable that it is finely oriented in the MD direction, and such fine orientation is formed by extrusion molding of the base material (X). There is a tendency to

The adhesion between the base material (X) and the layer (Y) of the structure (XY) under normal conditions can be evaluated by T-peel strength measured in accordance with JIS K6854-3:1999. The methods described in the Examples can be applied. The above T-peel strength is preferably 300 gf/15 mm or more, more preferably 400 gf/15 mm or more, and even more preferably 500 gf/15 mm or more. The T-type peel strength may be 10 kgf/15 mm or less, or 5 kgf/15 mm or less.

The adhesion under severe conditions between the base material (X) and the layer (Y) of the structure (XY) is determined by the T-peel strength measured in accordance with JIS K6854-3:1999 while dropping water on the peeling interface. The evaluation can be carried out using the methods described in Examples. The above T-peel strength is preferably 250 gf/15 mm or more, more preferably 350 gf/15 mm or more, and even more preferably 400 gf/15 mm or more. The T-type peel strength may be 10 kgf/15 mm or less, or 5 kgf/15 mm or less.

[Layer (Z)]
The multilayer structure of the present invention has a layer (Z) containing an organic polymer on one side of the layer (Y) (hereinafter sometimes abbreviated as "layer (Z)") from the viewpoint of the protective properties of the layer (Y). ) may have a laminated structure. Here, "laminated" indicates that they may be laminated via an adhesive layer, but from the viewpoint of better protection properties of layer (Y), layer (Z) and layer (Y) are preferably directly laminated.

The organic polymer contained in the layer (Z) preferably has at least one functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, and a functional group containing a phosphorus atom. Further, the organic polymer may be a mixture of two or more types of organic polymers having different functional groups.

Examples of organic polymers having hydroxyl groups include vinyl alcohol polymers exemplified as materials for the base material (X). Examples of organic polymers having carboxylic acid groups include polyacrylic acid, polymethacrylic acid, or copolymers of acrylic acid and methacrylic acid, and some of the carboxyl groups in these polymers are salts. Examples include polymers.

Examples of the functional group containing a phosphorus atom include a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a phosphonic acid group, a phosphinic acid group, a phosphinic acid group, and a functional group derived therefrom (for example, a salt group). , (partial) ester compounds, halides (for example, chlorides), dehydrates), etc. Among them, phosphoric acid groups and phosphonic acid groups are preferable, and phosphonic acid groups are more preferable. Examples of polymers having a functional group containing a phosphorus atom include 6-[(2-phosphonoacetyl)oxy]hexyl acrylate, 2-phosphonooxyethyl methacrylate, phosphonomethyl methacrylate, and 11-phosphonoun methacrylate. Polymers of phosphono(meth)acrylic acid esters such as decyl and 1,1-diphosphonoethyl methacrylate; vinylphosphonic acid, 2-propene-1-phosphonic acid, 4-vinylbenzylphosphonic acid, 4-vinylphenylphosphonic acid, etc. polymers of phosphonic acids such as vinylphosphinic acid and 4-vinylbenzylphosphinic acid; phosphorylated starch, etc. The polymer may be a homopolymer of a monomer having a functional group containing at least one phosphorus atom, or a copolymer of two or more monomers. Further, as the polymer, two or more kinds of polymers made of a single monomer may be used as a mixture. Among these, polymers of phosphono(meth)acrylic acid esters and polymers of vinylphosphonic acids are preferred, and polymers of vinylphosphonic acids are more preferred. That is, as the polymer, poly(vinylphosphonic acid) is preferable. Moreover, the polymer can also be obtained by hydrolyzing a vinylphosphonic acid derivative such as a vinylphosphonic acid halide or a vinylphosphonic acid ester alone or after copolymerizing the polymer.

The layer (Z) may further contain a hydrolyzed condensate of at least one compound (L) containing a metal atom to which at least one group selected from a halogen atom and an alkoxy group is bonded. There were cases where the barrier properties were improved by including the hydrolyzed condensate of compound (L) in layer (Z). Although the cause is not clear, it is thought that the presence of the compound (L) has the effect of improving the adhesion between the layer (Y) and the layer (Z).

[Compound (L)]
When compound (L) is hydrolyzed, at least a portion of the hydrolyzable characteristic groups of compound (L) are substituted with hydroxyl groups. Further, by condensing the hydrolyzate, a hydrolyzed condensate, which is a compound in which metal atoms are bonded via oxygen, is formed. Here, in order for this hydrolytic condensation to occur, it is important that the compound (L) has a hydrolyzable characteristic group (functional group). If these groups are not bonded, the hydrolytic condensation reaction will not occur or will be extremely slow, making it difficult to obtain the effects of the present invention. Note that although Si may be classified as a metalloid element, in this specification, Si will be described as a metal. Examples of the hydrolyzable characteristic group possessed by compound (L) include X ¹ of formula (I) described below. The hydrolyzed condensate can be produced from specific raw materials using, for example, a technique used in a known sol-gel method. The raw materials include compound (L), partially hydrolyzed compound (L), completely hydrolyzed compound (L), partially hydrolyzed and condensed compound (L), and compound (L) partially hydrolyzed. It is possible to use a product in which L) is completely hydrolyzed and a part thereof is condensed, or a combination thereof. These raw materials may be produced by known methods, or commercially available ones may be used. Although there is no particular limitation, for example, a condensate obtained by hydrolytic condensation of about 2 to 10 molecules can be used as the raw material.

Compound (L) has the following general formula (I)
SiX ¹ _r R _(4-r) (I)
[In the above formula (I), X ₁ is any one selected from the group consisting of F, Cl, Br, I, R ₆ O-, R ₇ COO-, (R ₈ CO) ₂ CH-, and NO ₃ R ₅ , R ₆ , R ₇ , and R ₈ each independently represent any one group selected from the group consisting of an alkyl group, an aralkyl group, an aryl group, and an alkenyl group, and r represents an integer from 1 to 4. When a plurality of X ₁ 's exist, these X ₁ 's may be the same or different. When a plurality of R _5s exist, those R _5s may be the same or different. ]
It is preferable that it is at least one kind of compound represented by.

Specific examples of compound (L) include tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, Included are vinyltriethoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, and vinyltrichlorosilane. Among these, tetramethoxysilane and tetraethoxysilane are preferred as compound (L).
[Adhesive layer (H)]
In the multilayer structure of the present invention, it can be laminated with other members (for example, other layers such as a thermoplastic resin film layer, a paper layer, etc.) via an adhesive layer (H). The adhesive layer (H) made of an adhesive resin can be formed by applying a known adhesive to the surface of the base material (X), layer (Y), or layer (Z). The adhesive is preferably a two-component reactive polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted. Furthermore, adhesion may be further improved by adding a small amount of an additive such as a known silane coupling agent to the anchor coating agent or adhesive. Suitable examples of the silane coupling agent include those having reactive groups such as isocyanate groups, epoxy groups, amino groups, ureido groups, and mercapto groups. By strongly adhering the multilayer structure of the present invention and other members through the adhesive layer (H), barrier properties and Deterioration of appearance can be more effectively suppressed.

By increasing the thickness of the adhesive layer (H), the strength of the multilayer structure of the present invention can be increased. However, if the adhesive layer (H) is made too thick, the appearance tends to deteriorate. The average thickness of the adhesive layer (H) is preferably in the range of 0.03 to 0.18 μm, more preferably in the range of 0.04 to 0.14 μm, and more preferably in the range of 0.05 to 0.10 μm. It is particularly preferable that the By setting the average thickness of the adhesive layer (H) within this range, deterioration of barrier properties and appearance can be suppressed when manufacturing or processing the vacuum packaging bag used for the vacuum insulation body of the present invention. Furthermore, the impact resistance of the vacuum heat insulating body of the present invention can be improved.

The multilayer structure of the present invention can be laminated with other members other than the multilayer structure (for example, other layers such as a thermoplastic resin film layer and a paper layer). Lamination is possible by adhering or forming directly or via an adhesive layer (H). Specific configurations include those shown in the configuration examples of vacuum packaging bags described later.

According to the present invention, it is possible to obtain a multilayer structure that satisfies the following performance.
(Performance 1) Oxygen permeability at 20° C. and 85% RH measured in accordance with JIS K7126-2:2006 is 1.5 cc/m ² ·day · atm or less.

[Vacuum packaging bag]
A vacuum packaging bag is a packaging material that is used by reducing the pressure inside, and is equipped with a film material (hereinafter sometimes referred to as a "laminate") as a partition wall separating the inside and the outside. The vacuum packaging bag of the present invention comprises a base material (X), a layer (Y), or a multilayer structure of the present invention consisting of a base material (X), a layer (Y), and a layer (Z), and other materials other than the multilayer structure. (for example, a thermoplastic resin film layer, other layers such as a paper layer, etc.). Further, the vacuum packaging bag may include a plurality of the multilayer structures. A vacuum packaging bag having such other members (other layers, etc.) can be manufactured by adhering or forming the other members (other layers, etc.) directly or via an adhesive layer. By providing the vacuum packaging bag with such other members (such as other layers), the characteristics of the vacuum packaging bag can be improved or new characteristics can be imparted. For example, it is possible to impart heat-sealability to the vacuum packaging bag of the present invention, or to further improve barrier properties and mechanical properties.

In particular, by making the surface layer of the vacuum packaging bag a polyolefin layer (hereinafter sometimes abbreviated as PO layer), it is possible to impart heat sealability to the vacuum packaging bag and improve the mechanical properties of the vacuum packaging bag. This is preferable because it can be done. From the viewpoint of further improving heat sealability and mechanical properties, the polyolefin is preferably polypropylene or polyethylene. Furthermore, in order to improve the mechanical properties of the vacuum packaging bag, at least one film selected from the group consisting of biaxially oriented polypropylene film, polyester film, polyamide film, and polyvinyl alcohol film may be laminated as another layer. is preferred. From the viewpoint of improving mechanical properties, polyethylene terephthalate (PET) is preferred as the polyester, nylon-6 is preferred as the polyamide, and ethylene-vinyl alcohol copolymer is preferred as the polyvinyl alcohol film. Note that an adhesive layer (H) may be provided between each layer, if necessary.

The vacuum packaging bag used for the vacuum insulation body of the present invention may have the following configuration, for example, from the outer layer to the inner layer of the vacuum insulation body. In the following configuration, "/" represents that two layers sandwiching "/" are directly laminated. Moreover, "//" represents that two layers sandwiching "//" are laminated indirectly via an adhesive layer (H).
(1) Layer (Y)/base material (X)//PO layer,
(2) polyester layer//layer (Y)/base material (X)//PO layer,
(3) polyamide layer//layer (Y)/base material (X)//PO layer,
(4) PO layer // layer (Y) / base material (X) // PO layer,
(5) layer (Y)/base material (X)/layer (Y)//PO layer,
(6) Polyester layer // layer (Y) / base material (X) / layer (Y) // PO layer,
(7) Polyamide layer // layer (Y) / base material (X) / layer (Y) // PO layer,
(8) PO layer // layer (Y) / base material (X) / layer (Y) // PO layer,
(9) Polyester layer/layer (Y)//base material (X)//PO layer,
(10) polyamide layer//layer (Y)/base material (X)//PO layer,
(11) PO layer // layer (Y) / base material (X) // PO layer,
(12) polyester layer/layer (Y)//layer (Y)/base material (X)//PO layer,
(13) polyamide layer/layer (Y)//layer (Y)/base material (X)//PO layer,
(14) PO layer/layer (Y)//layer (Y)/base material (X)//PO layer,
(15) polyester layer/layer (Y)//layer (Y)/base material (X)/layer (Y)//PO layer,
(16) polyamide layer/layer (Y)//layer (Y)/base material (X)/layer (Y)//PO layer,
(17) PO layer/layer (Y)//layer (Y)/base material (X)/layer (Y)//PO layer,
(18) polyamide layer//polyester layer/layer (Y)//layer (Y)/base material (X)//PO layer,
(19) PO layer // polyester layer / layer (Y) // layer (Y) / base material (X) // PO layer,
(20) polyamide layer//polyester layer/layer (Y)//layer (Y)/base material (X)//PO layer,
(21) PO layer // polyester layer / layer (Y) // layer (Y) / base material (X) // PO layer,
(22) layer (Z)/layer (Y)/base material (X)//PO layer,
(23) polyester layer // layer (Z) / layer (Y) / base material (X) // PO layer,
(24) polyamide layer // layer (Z) / layer (Y) / base material (X) // PO layer,
(25) PO layer // layer (Z) / layer (Y) / base material (X) // PO layer,
(26) layer (Z) / layer (Y) / base material (X) / layer (Y) / layer (Z) //PO layer,
(27) polyester layer // layer (Z) / layer (Y) / base material (X) / layer (Y) / layer (Z) // PO layer,
(28) polyamide layer // layer (Z) / layer (Y) / base material (X) / layer (Y) / layer (Z) // PO layer,
(29) PO layer // layer (Z) / layer (Y) / base material (X) / layer (Y) / layer (Z) // PO layer,
(30) polyester layer/layer (Z)/layer (Y)//base material (X)//PO layer,
(31) polyamide layer/layer (Z)/layer (Y)//base material (X)//PO layer,
(32) PO layer/layer (Z)/layer (Y)//base material (X)//PO layer,
(33) polyester layer/layer (Y)//layer (Z)/layer (Y)/base material (X)//PO layer,
(34) polyamide layer/layer (Y)//layer (Z)/layer (Y)/base material (X)//PO layer,
(35) PO layer/layer (Y)//layer (Z)/layer (Y)/base material (X)//PO layer,
(36) polyester layer/layer (Y)//layer (Z)/layer (Y)/base material (X)/layer (Y)//layer (Z)/PO layer,
(37) polyamide layer/layer (Y)//layer (Z)/layer (Y)/base material (X)/layer (Y)/layer (Z)//PO layer,
(38) PO layer/layer (Y)//layer (Z)/layer (Y)/substrate (X)/layer (Y)/layer (Z)//PO layer,
(39) polyamide layer//polyester layer/layer (Y)//layer (Z)/layer (Y)/base material (X)//PO layer,
(40) PO layer // polyester layer / layer (Y) // layer (Z) / layer (Y) / base material (X) // PO layer,
(41) polyamide layer//polyester layer/layer (Y)//layer (Z)/layer (Y)/base material (X)//PO layer,
(42) PO layer // polyester layer / layer (Y) // layer (Z) / layer (Y) / base material (X) // PO layer,

Among the configurations of the vacuum packaging bags exemplified above, it is preferable that at least one or more of the following requirements be satisfied.
(1) At least one base material (X) is located closer to the core material than at least one layer (Y).
(2) At least one layer (Y) is directly laminated on at least one base material (X).

[Core material]
The core material used in the vacuum heat insulating body of the present invention is not particularly limited as long as it has heat insulating properties. For example, examples of core materials include perlite powder, silica powder, precipitated silica powder, diatomaceous earth, calcium silicate, glass wool, rock wool, and resin foams (eg, styrene foam and urethane foam). Furthermore, a hollow container made of resin or an inorganic material, a honeycomb-like structure, or the like may be used as the core material. Further, if necessary, the core material may contain an adsorbent that adsorbs water vapor, gas, and the like.

[Vacuum insulation]
In the vacuum insulation body of the present invention, the space inside the vacuum packaging bag is in a vacuum state. The vacuum state here does not necessarily mean an absolute vacuum state, but indicates that the pressure in the space inside the vacuum packaging bag is sufficiently lower than atmospheric pressure. The internal pressure is determined based on the required performance and ease of manufacture, but is usually 2 kPa (approximately 15 Torr) or less in order to exhibit insulation performance. In order to fully exhibit the insulation effect of the vacuum insulator of the present invention, the internal pressure of the vacuum packaging bag is preferably 200 Pa (approximately 1.5 Torr) or less, more preferably 20 Pa or less, and 2 Pa or less. It is even more preferable that there be. There is no limit to the lower limit of the pressure in the space within the vacuum packaging bag, but the pressure may be in the range of 0.001 Pa to 2 KPa.

When the vacuum insulator of the present invention is stored at 100°C immediately after production, the upper limit of the thermal conductivity one day after storage is preferably 3.0 mW/(m・K), and 2.5 mW/(m・K). ) is more preferable. On the other hand, the lower limit of the thermal conductivity one day after the storage is preferably 1.0 mW/(m·K), more preferably 1.2 mW/(m·K). If the thermal conductivity exceeds the upper limit, the heat insulation performance of the vacuum heat insulator may be insufficient. Conversely, if the thermal conductivity is less than the lower limit, the manufacturing cost of the vacuum heat insulator may increase. Here, "thermal conductivity" is a value measured in accordance with JIS-A1412-1 (1999).

The vacuum heat insulating body of the present invention can maintain heat insulating performance for a long period of time. Regarding the heat insulation performance, it is preferable that the vacuum heat insulator of the present invention is stored at 100°C immediately after production, and the thermal conductivity after 90 days from storage is 4.8 mW/(m K) or less, and 4.5 mW. /(m·K) or less is more preferable. The thermal conductivity after 90 days of storage may be 2.0 mW/(m·K) or more.

The vacuum heat insulating body of the present invention can be manufactured by a commonly used method. A vacuum heat insulator of any shape and size can be formed depending on the purpose of use. For example, the vacuum insulation body of the present invention can be manufactured by the following methods 1 to 3.
(Method 1) First, two multilayer structures each having a heat seal layer disposed on at least one surface are prepared. The two multilayer structures are stacked one on top of the other so that each heat-sealing layer is on the inside, and three arbitrary sides are heat-sealed to produce a vacuum packaging bag. Next, the inside of the vacuum packaging bag is filled with a core material. Next, the space inside the vacuum packaging bag is evacuated, and the last side is heat-sealed in that state. In this way a vacuum insulation body is obtained.
(Method 2) First, a single multilayer structure is folded so that the heat seal layer is on the inside, and two arbitrary sides are heat sealed to produce a vacuum packaging bag. Next, the inside of the vacuum packaging bag is filled with a core material. Next, the space inside the vacuum packaging bag is evacuated, and the last side is heat-sealed in that state. In this way a vacuum insulation body is obtained.
(Method 3) First, the core material is sandwiched between two multilayer structures, or the multilayer structures are bent to sandwich the core material. Next, the peripheral edge where the multilayer structure overlaps is heat-sealed, leaving a vacuum exhaust port, to produce a vacuum packaging bag in which the core material is disposed. Next, the space inside the vacuum packaging bag is evacuated, and the vacuum exhaust port is heat-sealed in that state. In this way a vacuum insulation body is obtained.

[Application]
The vacuum heat insulating body of the present invention can be used in various applications that require cold or warm insulation. In particular, even when the vacuum heat insulator of the present invention is used under high temperature and high humidity conditions, its heat insulating performance is extremely unlikely to deteriorate over time, making it possible to achieve a sufficient service life as a heat insulating material. Tanks for water heaters, tanks for hot water toilets, tanks for vending machines, tanks for fuel cells, tanks for cars, bags for keeping food warm, keeping hot plastic bottles and cans warm, keeping washing machine drums warm, coffee It is also useful for all kinds of heat retention applications that require insulation, such as tea servers, jar pots, etc.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples.

Materials used in Examples and Comparative Examples are shown.
EVOH1: Ethylene unit content 32 mol%, saponification degree 100 mol%, MFR 1.6 g/10 min (190°C, 2160 g load)
PVA: Polyvinyl alcohol; "Kuraray Poval (trademark) 60-98 (trade name)" manufactured by Kuraray Co., Ltd.
PET12: Biaxially oriented polyethylene retephthalate film; manufactured by Toray Industries, Inc., "Lumirror (trademark) P60" (trade name), average thickness 12 μm
PE50: Unstretched linear low-density polyethylene film; manufactured by Idemitsu Unitec Co., Ltd., “Unilux (registered trademark) LS-760C, average thickness 50 μm
OPA15: Biaxially stretched polyamide film; manufactured by Unitika Co., Ltd., "Emblem (registered trademark) ON-BC", average thickness 15 μm
CPP60: Unstretched polypropylene film; “CP RXC-22” manufactured by Mitsui Chemicals Tohcello Co., Ltd., average thickness 60 μm

[Manufacture example 1]
EVOH1 pellets were melted at 240°C and extruded from a die onto a casting roll at 77°C to obtain a base material (X-1) which is an unstretched EVOH film with an average thickness of 15 μm at a take-up speed of 100 m/min. .

[Manufacture example 2]
The same method as in Production Example 1 was used, except that EVOH1 pellets were melted at 240 °C and extruded from a die onto a casting roll at 77 °C, and at the same time, air was blown at a wind speed of 30 m / sec using an air knife. A film was formed to obtain a base material (X-2) which was an unstretched EVOH film with an average thickness of 15 μm.

[Manufacture example 3]
A film was formed in the same manner as in Production Example 1, except that the discharge amount was changed and the average thickness of the film obtained was 12 μm, to obtain a substrate (X-3) that was an unstretched EVOH film.

[Manufacture example 4]
EVOH1 pellets were melted at 240°C and extruded from a die onto a casting roll at 77°C to produce an unstretched EVOH film with an average thickness of 170 μm. The obtained unstretched film was brought into contact with hot water at 80°C for 10 seconds, and stretched by 3.2 times in the machine direction (MD) direction and 3.0 times in the transverse (TD) direction at 90°C using tenter-type simultaneous biaxial stretching equipment. The film was stretched and further heat treated for 5 seconds in a tenter set at 170°C to obtain a base material (X'-1) which was a biaxially stretched EVOH film with a total width of 3.6 m and an average thickness of 15 μm.

[Manufacture example 5]
Film formation, stretching, and heat treatment were performed in the same manner as in Production Example 4, except that the discharge amount was changed, to obtain a base material (X'-2) that is a biaxially stretched EVOH film with an average thickness of 12 μm.

[Manufacture example 6]
Kaolin (manufactured by Imerys, "DB-KOTE" (average particle diameter: 0.77 μm, surface area: 10 (B.E.T.m ² /g), Surface treatment: none)) A film was formed in the same manner as in Production Example 1, except that 4 parts by mass were dry blended using a tumbler and then melted, and the base material (X'-3), which is an unstretched EVOH film, was Obtained.

[Manufacture example 7]
A film was formed in the same manner as in Production Example 1, except that the temperature of the casting roll was changed to 17° C., to obtain a substrate (X'-4) which was an unstretched EVOH film.

[Manufacture example 8]
Synthetic silica (Fuji Silysia Chemical Co., Ltd. "Silysia 310P" average particle diameter 2.7 μm measured by laser method) was added to 100 parts by mass of EVOH1 pellets using a tumbler so that the amount was 0.03 parts by mass. A base material (X-4), which is an unstretched EVOH film, was produced in the same manner as in Production Example 1, except that it was dry blended and then melted at 240°C.

<Evaluation method>
(1) Average thickness of layer (Y) and layer (Z) After cutting the multilayer structures obtained in Examples and Comparative Examples with a microtome to expose the cross section, the cross section was examined using a scanning electron microscope (S. The average thicknesses of the layer (Y) and the layer (Z) were measured using a backscattered electron detector ("ZEISS ULTRA 55" manufactured by I-I Nano Technology Co., Ltd.).

(2) Surface hardness of layer (Y) surface side of structure (XY) by nanoindentation method Multilayer structures obtained in Examples and Comparative Examples were sampled (1 cm long x 1 cm wide) and ISO15477-1:2015 The hardness of the layer (Y) surface side of the multilayer structure was measured by the nanoindentation method measured in accordance with . The nanoindentation method is a method in which a diamond indenter of an atomic microscope is directly injected into the sample surface, the indentation depth is measured with nanometer precision, and a load-displacement curve is determined. The atomic force microscope was an environmentally controlled unit Eseep made by Hitachi High-Tech Science, the nanoindentation device was a TriboScope made by Hysitron, and the indenter was a Berkovich-type indenter SI-DF20 made by Hitachi High-Tech Science, with a set load of 300 μN. The displacement curve was measured. The hardness [GPa] is defined as the maximum load at that time divided by the projected contact area of the depression pressed by the indenter. Each sample was measured 10 times at random, and the average value was used as the hardness of the surface of the multilayer structure.

(3) T-peel strength between base material (X) and layer (Y) in dry and wet states Adhesive ("Takelac A-520" and "Takenate A-50" manufactured by Mitsui Chemicals, Inc. are mixed at a mass ratio of 6/1 to form an ethyl acetate solution with a solid content concentration of 23% by mass) was coated with a bar coater. After coating and drying with hot air at 50°C for 5 minutes to form an adhesive layer, about half of the adhesive layer was covered with a Teflon (registered trademark) sheet, PET12 was laminated on top of it, and heated to 80°C. Laminated with heated nip rolls and cured at 40°C for 72 hours, the interface between layer (Y) and PET12 was partially peeled off. (registered trademark) sheet) A sample for measurement of the layer structure of PET12 was prepared. The obtained measurement sample was cut into strips of 100 mm x 15 mm, and the T-peel strength was measured in a normal state (dry) and in a hydrated state (wet). In the wet measurement, 0.5 mL of water was dropped on the peeling surface (interface) of PET 12 and layer (Y), and the T-peel strength was measured according to JIS K 6854-1:1999. The measurement was performed five times, and the average value was used. The measurement conditions were as follows. The peel strength between the base material (X) and the layer (Y) was determined to have been measured by visually confirming that the layer (Y) was attached to the PET 12. In addition, if the T-type peel strength is 500 gf/15 mm or more in a dry state and 420 gf/15 mm or more in a wet state, it is impossible to confirm the adhesion of the layer (Y) to PET12, so 500 gf/15 mm and 420 gf/15 mm are The upper limit of measurement was taken as the upper limit.
Equipment: Autograph AGS-H manufactured by Shimadzu Corporation
Peeling speed: 250mm/min Temperature: 23℃
Humidity: 50%RH

(4) Measurement of oxygen permeability (OTR) The multilayer structures obtained in the Examples and Comparative Examples were attached to an oxygen permeation amount measuring device with the base material (X) facing the carrier gas side, and the JIS K7126-2 The oxygen permeability was measured by the isobaric method according to 2006. The measurement conditions were as follows.
Equipment: MOCON OX-TRAN2/21 manufactured by MOCON
Temperature: 20℃
Humidity on oxygen supply side: 85%RH
Humidity on carrier gas side: 0%RH
Carrier gas flow rate: 10 mL/min Oxygen pressure: 1.0 atm

(5) Thermal conductivity of vacuum insulator The vacuum insulator obtained in Example 8 was stored at 100°C immediately after production, and 1, 30, and 90 days after storage, it was measured using a thermal conductivity measuring device (Hideko Seiki). Thermal conductivity of the vacuum insulator was measured using a vacuum insulator (model FOX314, manufactured by Co., Ltd.) with one side of the vacuum insulator at 38°C and the other side at 12°C.

[Example 1]
The base material (X-1) obtained in Production Example 1 was cut while being rewound to obtain a roll having a width of 80 cm and a length of 4000 m centered on the center position of the entire width of the film.

One side of the substrate (X-1) was coated on the substrate (X-1) using a batch vapor deposition equipment ("EWA-105" manufactured by Japan Vacuum Technology Co., Ltd.) at a surface temperature of 38°C and a running speed of 200 m/min. Aluminum was vapor-deposited on the surface to obtain a multilayer structure (1-1) having a layer structure of base material (X-1)/layer (Y). The obtained multilayer structure (1-1) was evaluated according to the evaluation methods (1) to (3) above to determine the average thickness, surface hardness, base material (X) and layer (Y) of the layer (Y). ) was evaluated for T-peel strength. The results are shown in Table 2.

Using the obtained multilayer structure (1-1), two-component adhesive ("Takelac A-520" and "Takenate A-50" manufactured by Mitsui Chemicals, Inc.) was applied to one side of each of PET12 and PE50. 12 layers of PET/adhesive layer/layer (Y)/substrate (X-1)/adhesive layer/50 layers of PE were laminated while being pressed with nip rolls at 70°C, and then laminated at 40°C. A multilayer structure (1-2) was obtained by aging for several days. The OTR of the obtained multilayer structure (1-2) was evaluated according to the method described in evaluation method (4) above. The results are shown in Table 2.

[Example 2 to Example 5, Comparative Examples 1 to 5]
As described in Table 2, except for changing the type of base material (X), the average thickness of base material (X), the presence or absence of layer (Y), and the average thickness of layer (Y) as described in Table 1, Multilayer structure (2-1) to multilayer structure (5-1), multilayer structure (C1-1) to multilayer structure (C5-1), and multilayer structure (2- 2) - Multilayer structure (5-2) and multilayer structure (C1-2) - Multilayer structure (C5-2) were produced and evaluated. The results are shown in Table 2. Note that the multilayer structure C5-1 corresponding to Comparative Example 5 had a high oxygen permeation amount. This is considered to be because the surface hardness of the layer (Y) surface side of the structure (XY) was small, that is, the crystallinity of the structure (XY) was low. The reason for this is not clear, but it is thought that the decrease in the crystallinity of the structure (XY) caused unevenness in thickness and thickness during transportation, resulting in omission of vapor deposition.

[Example 6]
The base material (X-1) obtained in Production Example 1 was cut while being rewound to obtain a roll having a width of 80 cm and a length of 4000 m centered on the center position of the entire width of the film.

One side of the substrate (X-1) was coated on the substrate (X-1) using a batch vapor deposition equipment ("EWA-105" manufactured by Japan Vacuum Technology Co., Ltd.) at a surface temperature of 38°C and a running speed of 200 m/min. Aluminum was vapor-deposited on the surface to obtain a multilayer structure having a layer structure of base material (X-1)/layer (Y). A layer (Y') is formed on the opposite side of the obtained multilayer structure from the layer (Y) in the same manner as the layer (Y), and the layer (Y)/base material (X-1)/layer ( A multilayer structure (6-1) of Y') was obtained. Regarding the multilayer structure (6-1), the average thickness of the layer (Y), the surface hardness, and the relationship between the base material (X) and the layer (Y) were evaluated according to the evaluation methods (1) to (3) above. T-peel strength was evaluated. The results are shown in Table 2.

Using the obtained multilayer structure (1-1), two-component adhesive ("Takelac A-520" and "Takenate A-50" manufactured by Mitsui Chemicals, Inc.) was applied to one side of each of PET12 and PE50. was applied, and the composition was 12 layers of PET/adhesive layer/layer (Y)/base material (X-1)/layer (Y')/adhesive layer/50 layers of PE while being crimped with nip rolls at 70°C. A multilayer structure (6-2) was obtained by laminating and aging at 40° C. for 4 days. The OTR of the obtained multilayer structure (6-2) was evaluated according to the method described in evaluation method (4) above. The results are shown in Table 2.

One side of the substrate (X-1) was coated on the substrate (X-1) using a batch vapor deposition equipment ("EWA-105" manufactured by Japan Vacuum Technology Co., Ltd.) at a surface temperature of 38°C and a running speed of 200 m/min. Aluminum was vapor-deposited on the surface to obtain a multilayer structure having a layer structure of base material (X-1)/layer (Y). Regarding the obtained multilayer structure, the surface hardness of the structure (XY) was measured according to the method described in the evaluation method (2) above. The evaluation results are shown in Table 2. On the layer (Y) of the obtained multilayer structure, Kuraray Poval (trademark) 60 was added to a mixed solvent of water and methanol (mass ratio: water: methanol = 7:3) so that the solid content concentration was 5% by mass. A coating liquid in which -98 was dissolved was applied at a running speed of 200 m/min to obtain a multilayer structure (7-1) of base material (X-1)/layer (Y)/layer (Z). Regarding the obtained multilayer structure (7-1), the average thickness of the layer (Y) and the relationship between the base material (X) and the layer (Y) were evaluated according to the methods described in the above evaluation methods (1) and (3). T-peel strength was evaluated. The results are shown in Table 2.

Using the obtained multilayer structure (7-1), two-component adhesive ("Takelac A-520" and "Takenate A-50" manufactured by Mitsui Chemicals, Inc.) was applied to one side of each of PET12 and PE50. was applied and laminated with nip roll pressure at 70°C so that the composition was 12 layers of PET/adhesive layer/layer (Z)/layer (Y)/base material (X-1)/adhesive layer/50 layers of PE. A multilayer structure (7-2) was obtained by aging at 40° C. for 4 days. The OTR of the obtained multilayer structure (7-2) was evaluated according to the method described in evaluation method (4) above. The results are shown in Table 2.

[Example 8]
Using the multilayer structure (1-1) obtained in Example 1, two-component adhesives ("Takelac A-520" and "Takenate A" manufactured by Mitsui Chemicals, Inc., manufactured by Mitsui Chemicals, Inc.) were applied to each of one side of OPA15 and CPP60. -50'') and press-bonded with nip rolls at 70°C so that the composition was OPA 15 layer/adhesive layer/layer (Y)/base material (X-1)/adhesive layer/CPP 60 layer. A multilayer structure (8-2) was obtained by laminating and aging at 40° C. for 4 days.

The obtained multilayer structure (8-2) was cut to make two pieces of covering material with a size of 20 cm x 25 cm, stacked so that the CPP layers were on the inner surface, and heat-sealed on three sides with a width of 10 mm. A vacuum packaging bag having three sides was prepared.

A sachet containing calcium oxide as an insulating core material and an adsorbent is filled into the opening of the obtained vacuum packaging bag, and the temperature is adjusted using a vacuum insulation panel manufacturing device (model KT-500RD manufactured by NPC Corporation). A vacuum insulation body was produced by sealing a vacuum packaging bag at 20° C. and an internal pressure of 0.5 Pa. Glass fiber dried in an atmosphere of 120° C. for 4 hours was used as the heat-insulating core material. The thermal conductivity of the obtained vacuum heat insulating body was evaluated according to the method described in the evaluation method (5) above. The results were 1.9 mW/(m·K) after 1 day, 2.0 mW/(m·K) after 30 days, and 2.3 mW/(m·K) after 90 days.

60 Extruder 70 First conveyance roll (casting roll)
80 Second conveyor roll 90 Taking machine 100 Vinyl alcohol polymer 101 Vinyl alcohol polymer film roll 110 Air knife

Claims (11)

It has a structure (XY) in which an aluminum vapor-deposited layer (Y) is laminated on at least one surface of a base material (X) consisting of a film mainly composed of a vinyl alcohol polymer, and the aluminum vapor-deposited layer (XY) has a structure (XY). A multilayer structure having a surface hardness of 0.260 GPa or more and 0.380 GPa or less by a nanoindentation method at a set load of 300 μN, measured in accordance with ISO15477-1:2015 on the layer (Y) surface side. The multilayer structure according to claim 1, wherein the vinyl alcohol polymer is an ethylene-vinyl alcohol copolymer having an ethylene unit content of 10 to 65 mol% and a saponification degree of 90 mol% or more. The multilayer structure according to claim 1 or 2, wherein the average thickness of the aluminum vapor deposited layer (Y) is 15 nm or more and 150 nm or less. The multilayer structure according to any one of claims 1 to 3, wherein the aluminum vapor-deposited layer (Y) is laminated on both sides of a base material (X) made of a film containing a vinyl alcohol polymer as a main component. According to any one of claims 1 to 4, the oxygen permeability at 20° C. and 85% RH is 1.5 cc/m ² ·day · atm or less, measured in accordance with JIS K7126-2:2006. multilayer structure. The T between the base material (X) consisting of a film mainly composed of vinyl alcohol polymer and the aluminum vapor deposited layer (Y) was measured in accordance with JIS K6854-3:1999 while dropping water on the peeled interface. The multilayer structure according to any one of claims 1 to 5, having a mold peel strength of 250 gf/15 mm or more. The multilayer structure according to any one of claims 1 to 6, having a structure in which a layer (Z) containing an organic polymer is laminated on one side of an aluminum vapor-deposited layer (Y). The method for producing a multilayer structure according to any one of claims 1 to 7, wherein the surface temperature of the base material (X) made of a film containing a vinyl alcohol polymer as a main component is 60°C or less. A method for manufacturing a multilayer structure, comprising the step of forming an aluminum vapor deposited layer (Y). A packaging material comprising the multilayer structure according to any one of claims 1 to 7. A vacuum packaging bag obtained by reducing the pressure inside the packaging material according to claim 9. A vacuum insulation body, wherein the vacuum packaging bag according to claim 10 includes a core material inside.