JP7150715B2 - vacuum insulation - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vacuum heat insulating material having excellent long-term reliability for use and storage under high temperature and high humidity and high quality stability.

BACKGROUND ART Conventionally, heat insulating materials made of polyurethane foam have been used as heat insulating materials for refrigerators and heat insulating panels for houses. In recent years, as a superior material, a vacuum heat insulating material composed of an outer covering material having gas barrier properties and a core material has come to be used. A vacuum heat insulating material can be made thinner and lighter than a conventional heat insulating material made of polyurethane foam. In recent years, natural refrigerant heat pump water heaters, which are becoming popular as highly efficient hot water supply systems, are generally used to boil water at night when electricity rates are low and keep it warm in the hot water storage tank. can be a problem, but the use of thin vacuum insulation can alleviate this problem.

In such a vacuum heat insulating material, since the inside is maintained at a high degree of vacuum to reduce the gas heat transfer and improve the heat insulating property, in order to maintain the heat insulating property over a long period of time, it is extremely A jacket material with good gas barrier properties should be used.

From the standpoint of moldability, resins, particularly thermoplastic resins, are preferable as the material used for the outer covering material. For example, ethylene-vinyl alcohol copolymer and polyvinylidene chloride, which are typical examples of resins with excellent gas barrier properties, are used. is mentioned. However, such gas-barrier resins are insufficient for the gas-barrier properties required for outer covering materials for vacuum heat insulating materials, and it is difficult to maintain the heat insulating properties of the obtained vacuum heat insulating materials over a long period of time. rice field. Therefore, in order to improve the gas barrier properties of the outer covering material, outer covering materials in which a metal foil such as aluminum is laminated on a film made of the thermoplastic resin are widely used.

However, although the vacuum heat insulating material having the outer covering material containing the metal foil can maintain a high degree of vacuum for a long period of time, metals such as aluminum have high thermal conductivity (for example, the thermal conductivity of aluminum is high). The heat transfer rate is about 200 W/m K, while polypropylene resin is about 0.23 W/m K, and air is about 0.02 W/m K). is known to occur and the thermal insulation performance is greatly reduced.

Therefore, for the purpose of reducing heat bridges and improving gas barrier properties, a very thin inorganic deposition layer made of a metal such as aluminum and/or a metal oxide such as silica or alumina is added to the gas barrier properties. Jackets have been used that include laminates laminated to superior thermoplastic layers. For example, Patent Literature 1 describes a technique of using an aluminum vapor-deposited polyethylene terephthalate film as a gas barrier layer to reduce heat bridging.

Furthermore, in Patent Document 2, even when the vacuum heat insulating material is used under high temperature conditions (for example, 100 ° C., 0% RH), in order to provide sufficient long-term reliability and heat resistance, ethylene-vinyl alcohol copolymer A covering material including a laminate obtained by laminating an inorganic deposition layer and a composite resin layer containing an inorganic substance on polyvinyl alcohol is described.

In Patent Document 3, as a coating material having excellent gas barrier properties even under high-temperature and high-humidity conditions, a transparent gas barrier layer having a polyvinyl alcohol-based resin layer and a layer containing a reaction product of a metal oxide and a phosphorus compound is provided. A coating is described.

JP 2010-138956 A Japanese Patent Application Laid-Open No. 2008-114520 JP 2011-226644 A

However, it is difficult to achieve both long-term reliability and quality stability during use and storage under high-temperature and high-humidity conditions. Problems when using and storing under high temperature and high humidity conditions include cracking of the vapor deposition layer due to expansion due to moisture absorption of the polyvinyl alcohol resin layer under high temperature and high humidity conditions, and corrosion of the aluminum vapor deposition layer under high temperature and high humidity conditions. mentioned.

Furthermore, if a thermoplastic resin other than a polyvinyl alcohol-based resin is used as the base material to solve the above problems, the barrier property is not sufficiently maintained, resulting in a decrease in quality stability. In particular, the main cause is thought to be destruction of the barrier layer due to physical stress during the manufacture of the vacuum insulation material.

The present invention solves the above problems, and provides a vacuum insulation material that is excellent in long-term reliability even when used and stored under high-temperature and high-humidity conditions, and that has good quality stability in the production of the vacuum insulation material. intended to provide

That is, the present invention
[1] A laminate (U1) and a laminate (U2) are provided, and the laminate (U1) includes a substrate (X1) containing a thermoplastic resin and a layer on at least one surface of the substrate (X1). (Y1), and the water vapor permeability (Wf) after storage for 30 days under conditions of 70 ° C. and 90% RH is 0.9 g / (m ² day) or less, and the laminate (U2 ) has a substrate (X2) made of a polyvinyl alcohol-based resin and an aluminum deposition layer (Y2) on at least one surface of the substrate (X2), and at least one laminate (U1) is provided on at least one A vacuum heat insulating material provided outside the laminate (U2);
[2] The vacuum heat insulating material of [1], wherein the substrate (X2) is a film made of an ethylene-vinyl alcohol copolymer having an ethylene unit content of 10 to 65 mol% and a degree of saponification of 90 mol% or more;
[3] The vacuum heat insulating material of [1] or [2], wherein the substrate (X1) is made of at least one thermoplastic resin selected from the group consisting of polyolefin-based resins, polyester-based resins and polyamide-based resins;
[4] The vacuum heat insulating material of any one of [1] to [3], wherein the layer (Y1) is an aluminum deposited layer (Y1a);
[5] The layer (Y1) is a layer (Y1c) containing a reaction product (R) obtained by reacting a metal oxide (A) containing aluminum with an inorganic phosphorus compound (BI), and the layer (Y1c) The vacuum heat insulating material of any one of [1] to [3], wherein the maximum absorption wave number in the region of 800 to 1,400 cm ^-1 is in the range of 1,080 to 1,130 cm ^-1 in the infrared absorption spectrum of [1] to [3];
[6] The laminate (U1) has a layer (Z1) directly laminated to the layer (Y1), and the layer (Z1) contains a polymer (BO) containing phosphorus atoms [1] to [ 5] any vacuum insulation material;
[7] The vacuum of [6], wherein the layer (Z1) contains a polymer (C) having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic anhydride group, and a salt of a carboxyl group. thermal insulation;
[8] The vacuum insulation material of [6] or [7], wherein the polymer (BO) contains poly(vinylphosphonic acid);
[9] The vacuum heat insulating material of any one of [1] to [8], comprising the laminate (U1) as the outermost layer;
[10] The vacuum heat insulating material of any one of [1] to [9], comprising two or more laminates (U1);
[11] The vacuum heat insulating material of any one of [1] to [10], further comprising a polyamide film;
[12] The vacuum heat insulating material of [11], wherein the laminate (U1) and the laminate (U2) are laminated via a polyamide film;
[13] The vacuum heat insulating material of any one of [1] to [12], comprising the base material (X1) as the outermost layer and the base material (X2) inside the aluminum deposition layer (Y2);
This is achieved by providing

The vacuum insulation material of the present invention can maintain good insulation properties for a long period of time even when used and stored under high-temperature and high-humidity conditions. is. That is, according to the present invention, it is possible to provide a vacuum heat insulating material capable of achieving both long-term reliability and quality stability during use and storage under high-temperature and high-humidity conditions.

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

As used herein, the term "gas barrier property" means the ability to barrier gases other than water vapor, unless otherwise specified. In addition, in this specification, the term "barrier property" simply means both gas barrier property and water vapor barrier property.

In this specification, "/" indicates that the two layers sandwiching "/" are directly laminated, and "//" indicates that the two layers sandwiching "//" are indirectly laminated via an adhesive. It means that the layers are stacked vertically.

The vacuum heat insulating material of the present invention comprises a substrate (X1) containing a thermoplastic resin, a laminate (U1) having a layer (Y1) on at least one surface of the substrate (X1), and a polyvinyl alcohol resin. A substrate (X2) and a laminate (U2) having an aluminum deposition layer (Y2) on at least one surface of the substrate (X2), and the laminate (U1) was subjected to conditions of 70 ° C. and 90% RH. is 0.9 g/(m ² ·day) or less, and the laminate (U1) is provided outside the laminate (U2). By arranging the laminate (U1) outside the vacuum insulation material, the influence of moisture on the laminate (U2) is minimized, and deterioration of the laminate (U2) under high temperature and humidity conditions is suppressed over the long term. can. Furthermore, the laminated body (U2) located inside the vacuum heat insulating material has an aluminum vapor deposition layer (Y2) on at least one surface of the base material (X2), thereby reducing breakage of the barrier layer due to physical stress. Good quality stability can be maintained. In addition, the "outside" means the outside when the vacuum heat insulating material is produced. For example, two laminates (laminate (U1)//laminate (U2)//heat-seal layer) comprising the laminate (U1) and the laminate (U2) are prepared, the heat-seal layers are superimposed, After making a vacuum packaging bag by heat-sealing any three sides, filling the inside of the bag with a core material to evacuate the internal space, and then heat-sealing the last side to make a vacuum insulation material. The "outside" becomes the laminate (U1).

[Laminate (U1)]
The laminate (U1) has a substrate (X1) containing a thermoplastic resin and a layer (Y1) on at least one surface of the substrate (X1), and is heated at 70° C. and 90% RH for 30 days. The water vapor transmission rate (Wf) after storage is 0.9 g/(m ² ·day) or less. The water vapor permeability (Wf) is preferably 0.8 g/(m ² ·day) or less, more preferably 0.5 g/(m ² ·day) or less, and further preferably 0.3 g/(m ² ·day) or less. preferable. By providing at least one laminate (U1) that satisfies the water vapor permeability (Wf) value on the outside of the base material (X2), the polyvinyl alcohol resin layer expands due to moisture absorption under high temperature and high humidity conditions. It is possible to suppress the occurrence of cracks in the aluminum deposited layer (Y2). It also makes it possible to prevent corrosion of the aluminum deposition layer (Y2) under high temperature and high humidity conditions.

[Base material (X1)]
The substrate (X1) containing a thermoplastic resin is preferably made of a thermoplastic resin. Further, the substrate (X1) is preferably layered such as a film or sheet. More preferably, the substrate (X1) is a thermoplastic resin film.

Thermoplastic resins used for the substrate (X1) include, for example, polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof. Polyamide resins such as nylon-6, nylon-66, and nylon-12; hydroxyl group-containing polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; polystyrene; poly (meth) acrylic acid ester; polyacrylonitrile; polyvinyl acetate polyarylate; regenerated cellulose; polyimide; polyetherimide; polysulfone; polyethersulfone; polyetheretherketone; The material of the substrate (X1) is preferably polyethylene terephthalate from the viewpoint of moisture absorption resistance and heat resistance.

When the film made of the thermoplastic resin is used as the substrate (X1), the substrate (X1) may be a stretched film or a non-stretched film. A stretched film, particularly a biaxially stretched film, is preferred because the obtained laminate has excellent moisture absorption resistance and workability. The biaxially stretched film may be a biaxially stretched film produced by any one of a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tubular stretching method.

When the substrate (X1) is layered, its average thickness is preferably in the range of 1 to 1,000 μm, more preferably in the range of 5 to 500 μm, from the viewpoint of good mechanical strength and workability, and 9 to 9. A range of 200 μm is even more preferred. The average thickness is the average value of cross-sectional thicknesses at 10 arbitrarily selected points.

[Layer (Y1)]
Whether the layer (Y1) is an aluminum vapor deposition layer (Y1a) or a vapor deposition layer (Y1b) other than the aluminum vapor deposition layer (Y1a), the layer (Y1) is a metal oxide containing aluminum (A) and an inorganic phosphorus compound (BI ) may be a layer (Y1c) containing a reaction product (R) obtained by reacting with ). The layer (Y1) is preferably the layer (Y1c) from the viewpoint of reliability (long-term reliability) of maintaining heat insulation performance over a long period of time under high-temperature and high-humidity conditions.

[Layer (Y1a)]
Layer (Y1a) is a vapour-deposited layer containing mainly aluminum. The layer (Y1) may contain components other than aluminum as long as the effects of the present invention are not impaired. Other components include metals or semi-metals other than aluminum such as magnesium, tin and silicon, as well as non-metals such as carbon and nitrogen.

The aluminum content in the layer (Y1a) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. The aluminum content in layer (Y1a) may be substantially 100% by weight. When the aluminum content is 70% by mass or more, gas barrier properties, bending resistance, and long-term reliability of the vacuum heat insulating material under high-temperature and high-humidity conditions are improved, which is preferable. The fact that the aluminum content in the layer (Y1a) is substantially 100% by mass includes the case where a trace amount (for example, 0.1% by mass or less) of aluminum oxide is contained due to unavoidable oxidation.

Although it is preferable that the layer (Y1a) is a vapor-deposited layer consisting only of aluminum, it may inevitably undergo oxidation and partially contain aluminum oxide. When the layer (Y1a) partially contains aluminum oxide, the ratio (O _mol /Al _mol ) of the amount of oxygen atoms (O _mol ) to the amount of aluminum atoms (Al _mol ) constituting the layer (Y1a) is , is preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.1 or less, particularly preferably 0.08 or less, most preferably 0.05 or less.

The average thickness of the layer (Y1a) is preferably 60 nm or more, more preferably 70 nm or more, even more preferably 80 nm or more. The average thickness of the layer (Y1a) is preferably 200 nm or less, more preferably 150 nm or less, and even more preferably 130 nm or less. When the average thickness of the layer (Y1a) is 60 nm or more, the barrier properties of the deposited layer tend to be stably exhibited, and when the average thickness of the layer (Y1a) is 200 nm or less, the productivity is improved, which is preferable.

A vacuum vapor deposition method is preferable as a method for forming the layer (Y1a). 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 to the substrate on which the vapor deposition layer is formed and the denseness of the vapor deposition layer, a plasma assist method or an ion beam assist method may be employed for vapor deposition.

[Vapor deposition layer (Y1b) other than vapor deposition layer (Y1a)]
Layer (Y1b) is composed of metals other than aluminum, metal oxides, metal nitride oxides, metal carbonitrides, metal oxycarbides, silicon nitrides, carbon-containing silicon oxides (silicon carbonitrides), oxygen-containing silicon nitrides (silicon oxynitrides ) and the like. Among them, a deposited layer of a metal oxide such as aluminum oxide or silicon oxide is preferable.

A suitable average thickness and vapor deposition method of the layer (Y1b) are the same as those of the layer (Y1a) described above.

[Layer (Y1c)]
The layer (Y1c) contains a reaction product (R) obtained by reacting a metal oxide containing aluminum (A) with an inorganic phosphorus compound (BI).

[Metal oxide (A)]
The metal atoms constituting the metal oxide (A) (they may be collectively referred to as "metal atoms (M)") are at least one metal selected from metal atoms belonging to groups 2 to 14 of the periodic table. Atoms include at least aluminum atoms. The metal atom (M) may be an aluminum atom alone, or may include an aluminum atom and other metal atoms. In addition, you may mix and use 2 or more types of metal oxides (A) as a metal oxide (A).

The proportion of aluminum atoms in metal atoms (M) is preferably 50 mol % or more, and may be in the range of 60 mol % to 100 mol %, or in the range of 80 mol % to 100 mol %. Examples of the metal oxide (A) include metal oxides produced by methods such as a liquid phase synthesis method, a gas phase synthesis method, and a solid pulverization method.

The metal oxide (A) may be a hydrolytic condensate of a compound (E) containing a metal atom (M) to which a hydrolyzable characteristic group is attached. Examples of the characteristic group include R ¹ of general formula [I] described later. A hydrolytic condensate of compound (E) can be substantially regarded as a metal oxide. Therefore, in this specification, the hydrolytic condensate of compound (E) may be referred to as "metal oxide (A)". That is, in the present specification, "metal oxide (A)" can be read as "hydrolysis condensate of compound (E)", and "hydrolysis condensate of compound (E)" can be read as "metal oxidation It can also be read as "thing (A)".

[Compound (E) Containing Metal Atom (M) to which Hydrolyzable Specific Group is Bonded]
The compound (E) is a compound represented by the following general formula [I] (Ea ) is preferably included.
Al(R ¹ ) _k (R ² ) _3-k [I]
In the formula, R ¹ is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO ₃ , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, and a substituent. an aryloxy group having 5 to 9 carbon atoms which may be optionally substituted, an acyloxy group having 2 to 9 carbon atoms which may have a substituent, an alkenyloxy group having 3 to 9 carbon atoms which may have a substituent, It represents an optionally substituted C5-15 β-diketonato group, or an optionally substituted C1-9 acyl diacylmethyl group. R ² is an optionally substituted C 1-9 alkyl group, an optionally substituted C 7-10 aralkyl group, an optionally substituted carbon It represents an alkenyl group of 2 to 9 carbon atoms or an aryl group of 6 to 10 carbon atoms which may have a substituent. k represents an integer of 1 to 3; When there is more than one R ¹ , each R ¹ may be the same or different. When two or more R ² are present, each R ² may be the same or different.

The compound (E) may contain at least one compound (Eb) represented by the following general formula [II] in addition to the compound (Ea).
M ¹ (R ³ ) _m (R ⁴ ) _nm [II]
In the formula, M ¹ represents at least one metal atom other than an aluminum atom and selected from metal atoms belonging to groups 2 to 14 of the periodic table. R ³ is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO ₃ , optionally substituted alkoxy group having 1 to 9 carbon atoms, optionally substituted an aryloxy group having 5 to 9 carbon atoms, an acyloxy group having 2 to 9 carbon atoms which may have a substituent, an alkenyloxy group having 3 to 9 carbon atoms which may have a substituent, a substituent It represents an optionally substituted β-diketonato group having 5 to 15 carbon atoms, or a diacylmethyl group having an optionally substituted acyl group having 1 to 9 carbon atoms. R ⁴ is an optionally substituted C 1-9 alkyl group, an optionally substituted C 7-10 aralkyl group, an optionally substituted carbon It represents an alkenyl group of 2 to 9 carbon atoms or an aryl group of 6 to 10 carbon atoms which may have a substituent. m represents an integer from 1 to n. n is ^equal to the valence of M1. When two or more R ³ are present, each R ³ may be the same or different. When there are multiple ^R4 's, the ^R4 's may be the same or different.

Examples of alkoxy groups represented by R ¹ and R ³ include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, benzyloxy, diphenylmethoxy group, trityloxy group, 4-methoxybenzyloxy group, methoxymethoxy group, 1-ethoxyethoxy group, benzyloxymethoxy group, 2-trimethylsilylethoxy group, 2-trimethylsilylethoxymethoxy group and the like.

Examples of the aryloxy group represented by R ¹ and R ³ include a phenoxy group and a 4-methoxyphenoxy group.

Examples of acyloxy groups represented by R ¹ and R ³ include acetoxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy and sec-butylcarbonyl. oxy group, tert-butylcarbonyloxy group, n-octylcarbonyloxy group and the like.

Examples of alkenyloxy groups represented by R ¹ and R ³ include allyloxy, 2-propenyloxy, 2-butenyloxy, 1-methyl-2-propenyloxy, 3-butenyloxy, 2-methyl-2- propenyloxy group, 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 1-methyl-3-butenyloxy group, 1,2-dimethyl-2-propenyloxy group, 1,1-dimethyl-2 -propenyloxy group, 2-methyl-2-butenyloxy group, 3-methyl-2-butenyloxy group, 2-methyl-3-butenyloxy group, 3-methyl-3-butenyloxy group, 1-vinyl-2-propenyloxy group , 5-hexenyloxy group and the like.

Examples of the β-diketonato group represented by R ¹ and R ³ include 2,4-pentanedionato group, 1,1,1-trifluoro-2,4-pentanedionato group, 1,1,1,5 , 5,5-hexafluoro-2,4-pentanedionato group, 2,2,6,6-tetramethyl-3,5-heptanedionato group, 1,3-butanedionato group, 2-methyl-1,3- Examples include a butanedionato group, a 2-methyl-1,3-butanedionato group, a benzoylacetonato group, and the like.

Examples of the acyl group of the diacylmethyl group represented by R ¹ and R ³ include carbon atoms such as formyl group, acetyl group, propionyl group (propanoyl group), butyryl group (butanoyl group), valeryl group (pentanoyl group), hexanoyl group, etc. Aliphatic acyl groups of number 1 to 6; aromatic acyl groups (aroyl groups) such as benzoyl group and toluoyl group;

Examples of alkyl groups represented by R ² and R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and isopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.

Examples of the aralkyl group represented by R ² and R ⁴ include a benzyl group and a phenylethyl group (phenethyl group).

Examples of alkenyl groups represented by R ² and R ⁴ include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 3-butenyl, 2-butenyl, 1-butenyl, 1-methyl- 2-propenyl group, 1-methyl-1-propenyl group, 1-ethyl-1-ethenyl group, 2-methyl-2-propenyl group, 2-methyl-1-propenyl group, 3-methyl-2-butenyl group, A 4-pentenyl group and the like can be mentioned.

Examples of the aryl group represented by R ² and R ⁴ include phenyl group, 1-naphthyl group, 2-naphthyl group and the like.

Substituents that each group represented by R ¹ , R ² , R ³ and R ⁴ may have include, for example, an alkyl group having 1 to 6 carbon atoms; a methoxy group, an ethoxy group, an n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyl alkoxy groups having 1 to 6 carbon atoms such as oxy group and cyclohexyloxy group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxy alkoxycarbonyl groups having 1 to 6 carbon atoms such as carbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, cyclopropyloxycarbonyl group, cyclobutyloxycarbonyl group, cyclopentyloxycarbonyl group; Aromatic hydrocarbon groups such as phenyl group, tolyl group and naphthyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; acyl groups having 1 to 6 carbon atoms; aralkyl groups having 7 to 10 carbon atoms; aralkyloxy groups having 7 to 10 carbon atoms; alkylamino groups having 1 to 6 carbon atoms; and dialkylamino groups having alkyl groups having 1 to 6 carbon atoms.

R ¹ and R ³ are a halogen atom, NO ₃ , an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted acyloxy group having 2 to 6 carbon atoms, A β-diketonato group having 5 to 10 carbon atoms which may have a substituent, or a diacylmethyl group having an acyl group having 1 to 6 carbon atoms which may have a substituent is preferable, and has a substituent. An alkoxy group having 1 to 6 carbon atoms which may be substituted is more preferred.

R ² is preferably an optionally substituted alkyl group having 1 to 6 carbon atoms. k in formula [I] is preferably 3.

R ⁴ is preferably an optionally substituted alkyl group having 1 to 6 carbon atoms. M1 is preferably a metal atom belonging to Group ⁴ of the periodic table, more preferably titanium or zirconium. When M ¹ is a metal atom belonging to Group 4 of the periodic table, m in formula [II] is preferably 4.

Although boron and silicon are sometimes classified as semimetals, they are included in metals in this specification.

Examples of the compound (Ea) include aluminum chloride, aluminum nitrate, aluminum acetate, tris(2,4-pentanedionato)aluminum, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum and the like, among which triisopropoxyaluminum and tri-sec-butoxyaluminum are preferred. As the compound (E), two or more compounds (Ea) may be used in combination.

Examples of the compound (Eb) include tetrakis(2,4-pentanedionato)titanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and the like. and zirconium compounds such as tetrakis(2,4-pentanedionato)zirconium, tetra-n-propoxyzirconium, and tetra-n-butoxyzirconium. These may be used individually by 1 type, and may use 2 or more types of compounds (Eb) together.

As long as the effect of the present invention can be obtained in the compound (E), the ratio of the compound (Ea) to the compound (E) is not particularly limited. The ratio of compounds other than compound (Ea) (e.g., compound (Eb)) to compound (E) is, for example, preferably 20 mol% or less, more preferably 10 mol% or less, even more preferably 5 mol% or less, It may be 0 mol %.

By hydrolyzing the compound (E), at least part of the hydrolyzable characteristic groups of the compound (E) are converted to hydroxyl groups. Furthermore, the condensation of the hydrolyzate forms a compound in which the metal atom (M) is linked via the oxygen atom (O). When this condensation is repeated, compounds are formed which can be regarded as substantially metal oxides. Incidentally, hydroxyl groups are usually present on the surface of the metal oxide (A) thus formed.

In this specification, a compound in which the ratio of [number of moles of oxygen atoms (O) bonded only to metal atoms (M)]/[number of moles of metal atoms (M)] is 0.8 or more is defined as a metal shall be included in oxide (A). Here, the oxygen atom (O) bonded only to the metal atom (M) is the oxygen atom (O) in the structure represented by MOM, and the structure represented by MOH Oxygen atoms bonded to metal atoms (M) and hydrogen atoms (H) such as oxygen atoms (O) in are excluded. The ratio in the metal oxide (A) is preferably 0.9 or higher, more preferably 1.0 or higher, and even more preferably 1.1 or higher. Although the upper limit of this ratio is not particularly limited, it is usually represented by n/2, where n is the valence of the metal atom (M).

In order for the hydrolytic condensation to occur, it is important that the compound (E) has a hydrolyzable characteristic group. If these groups are not bonded, the hydrolytic condensation reaction does not occur or becomes extremely slow, making it difficult to prepare the intended metal oxide (A).

A hydrolytic condensate of compound (E) may be produced from a specific raw material by, for example, a technique employed in a known sol-gel method. The specific raw materials include compound (E), partial hydrolyzate of compound (E), complete hydrolyzate of compound (E), compound obtained by partially hydrolyzing and condensing compound (E), and compound ( At least one selected from the group consisting of compounds obtained by condensing a portion of the complete hydrolyzate of E) (hereinafter sometimes abbreviated as "compound (E)-based component") can be used.

In addition, the metal oxide (A) to be mixed with an inorganic phosphorus compound (BI)-containing material (inorganic phosphorus compound (BI) or a composition containing an inorganic phosphorus compound (BI)) described later contains phosphorus atoms It is preferable not to contain substantially.

[Inorganic phosphorus compound (BI)]
The inorganic phosphorus compound (BI) contains sites capable of reacting with the metal oxide (A), and typically contains a plurality of such sites. The inorganic phosphorus compound (BI) is preferably a compound containing 2 to 20 such moieties (atomic groups or functional groups). Examples of such sites include functional groups (e.g., hydroxyl groups) present on the surface of the metal oxide (A) and sites capable of condensation reaction, e.g., halogen atoms directly bonded to phosphorus atoms, phosphorus atoms and an oxygen atom directly bonded to. Functional groups (eg, hydroxyl groups) present on the surface of the metal oxide (A) are usually bonded to metal atoms (M) constituting the metal oxide (A).

Examples of inorganic phosphorus compounds (BI) include phosphoric acid, diphosphoric acid, triphosphoric acid, polyphosphoric acid in which four or more molecules of phosphoric acid are condensed, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid, and phosphine. Phosphorus oxoacids such as acids and derivatives thereof (eg, salts (eg, sodium phosphate), halides (eg, phosphoryl chloride), dehydrates (eg, diphosphorus pentoxide)), and the like.

One of these inorganic phosphorus compounds (BI) may be used alone, or two or more thereof may be used in combination. Among these inorganic phosphorus compounds (BI), it is preferable to use phosphoric acid alone or to use phosphoric acid and other inorganic phosphorus compounds (BI) in combination. By using phosphoric acid, the stability of the coating liquid (T) described later and the gas barrier properties of the obtained laminate (U1) are improved. When phosphoric acid and another inorganic phosphorus compound (BI) are used in combination, it is preferable that 50 mol % or more of the inorganic phosphorus compound (BI) is phosphoric acid.

[Reaction product (R)]
The reaction product (R) is obtained by reacting the metal oxide (A) with the inorganic phosphorus compound (BI). Here, the reaction product (R) also includes compounds produced by reacting the metal oxide (A), the inorganic phosphorus compound (BI), and other compounds. The layer (Y1c) may partially contain the metal oxide (A) and/or the inorganic phosphorus compound (BI) that do not participate in the reaction.

In the layer (Y1c), the molar ratio between the metal atoms constituting the metal oxide (A) and the phosphorus atoms derived from the inorganic phosphorus compound (BI) is [metal atoms constituting the metal oxide (A)]:[inorganic Phosphorus atom derived from phosphorus compound (B)] is preferably in the range of 1.0:1.0 to 3.6:1.0, and 1.1:1.0 to 3.0:1.0 is more preferably in the range of Outside this range, the gas barrier performance is lowered. The molar ratio in the layer (Y1c) can be adjusted by adjusting the mixing ratio of the metal oxide (A) and the inorganic phosphorus compound (BI) in the coating liquid for forming the layer (Y1c). The molar ratio in layer (Y1c) is usually the same as in the coating liquid.

In the infrared absorption spectrum of the layer (Y1c), the maximum absorption wavenumber in the region of 800 to 1,400 cm ^-1 is preferably in the range of 1,080 to 1,130 cm ^-1 . In the process in which the metal oxide (A) and the inorganic phosphorus compound (BI) react to form the reaction product (R), the metal atom (M) derived from the metal oxide (A) and the inorganic phosphorus compound (BI) and a phosphorus atom (P) derived from form a bond represented by M--O--P through an oxygen atom (O). As a result, a characteristic absorption band derived from the bond is generated in the infrared absorption spectrum of the reaction product (R). As a result of examination by the present inventors, when the characteristic absorption band based on MOP bonding is found in the region of 1,080 to 1,130 cm ⁻¹ , the obtained laminate (U1) is excellent. It was found that the gas barrier property was improved. In particular, when the characteristic absorption band is the strongest absorption in the region of 800 to 1,400 cm ⁻¹ where absorption derived from bonding between various atoms and oxygen atoms is generally observed, the obtained laminate ( U1) was found to exhibit even better gas barrier properties.

On the other hand, when a metal compound such as a metal alkoxide or a metal salt and the inorganic phosphorus compound (BI) are mixed in advance and then hydrolyzed and condensed, the metal atoms derived from the metal compound and the inorganic phosphorus compound (BI) A composite is obtained in which the originating phosphorus atoms are almost uniformly mixed and reacted. In that case, in the infrared absorption spectrum, the maximum absorption wave number in the region of 800 to 1,400 cm ⁻¹ is outside the range of 1,080 to 1,130 cm ⁻¹ .

In the infrared absorption spectrum of the layer (Y1c), the half width of the maximum absorption band in the region of 800 to 1,400 cm ⁻¹ is preferably 200 cm ⁻¹ or less, and 150 cm from the viewpoint of the gas barrier properties of the resulting laminate (U1). ⁻¹ or less is more preferable, 100 cm ⁻¹ or less is even more preferable, and 50 cm ⁻¹ or less is particularly preferable.

The infrared absorption spectrum of the layer (Y1c) can be measured by the method described in Examples. However, if it is not possible to measure by the method described in the Examples, reflectance measurements such as reflection absorption method, external reflection method, attenuated total reflection method, scraping layer (Y1c) from laminate (U1), Nujol method, tablet method However, it is not limited to these methods.

[Phosphorus compound (BH)]
The layer (Y1c) may contain a phosphorus compound (BH). In the phosphorus compound (BH), a phosphorus atom having at least one hydroxyl group and a polar group are bonded via an alkylene chain or polyoxyalkylene chain having 3 to 20 carbon atoms. The phosphorus compound (BH) has a lower surface free energy than the metal oxide (A), the inorganic phosphorus compound (BI), and their reaction products (R), and the surface in the precursor formation process of the layer (Y1c) Segregate to the side. The phosphorus compound (BH) is a phosphorus atom having at least one hydroxyl group capable of reacting with a component contained in the layer (Y1c) and other members (e.g., adhesive layer (H), other layers (e.g., ink layer)). Since it has a polar group that can react with , the adhesion is improved, and the interlayer adhesive strength can be maintained even after retort processing, so it is possible to suppress appearance defects such as interlayer peeling.

Phosphorus compound (BH), for example, the following general formula [III]
U ¹ -R ⁵ -U ² [III]
(In the formula, U ¹ represents a phosphorus atom-containing group having at least one hydroxyl group, R ⁵ represents a linear or branched alkylene group or polyoxyalkylene group having 3 to 20 carbon atoms, and U ² represents a polar represents a group.)
is indicated by The linear or branched alkylene group or polyoxyalkylene group for R ⁵ in the general formula [III] has a lower surface free energy than other components of the layer (Y) and is less soluble in the solvent used. From the viewpoint of good performance, the number of carbon atoms is preferably 3 or more and 20 or less, more preferably 4 or more and 18 or less, and even more preferably 6 or more and 14 or less.

Examples of the phosphorus atom-containing group having at least one hydroxyl group represented by U ¹ (U ¹ in the general formula [III]) include a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a phosphonous acid group, and a phosphinic acid group. and phosphite group, among which phosphoric acid group and phosphonic acid group are preferred, and phosphonic acid group is more preferred. ^The polar group represented by U2 can react with other adjacent members such as the ink layer and adhesive layer (H). Examples of such polar groups include a hydroxyl group, a carboxyl group, an amino group, etc. Among them, a hydroxyl group and a carboxyl group are preferred, and a hydroxyl group is particularly preferred.

Specific examples of phosphorus compounds (BH) include 3-hydroxypropylphosphonic acid, 4-hydroxybutylphosphonic acid, 5-hydroxypentylphosphonic acid, 6-hydroxyhexylphosphonic acid, 7-hydroxyheptylphosphonic acid, 8-hydroxyoctyl Phosphonic acid, 9-hydroxynonylphosphonic acid, 10-hydroxydecylphosphonic acid, 11-hydroxyundecylphosphonic acid, 12-hydroxydodecylphosphonic acid, 13-hydroxytridecylphosphonic acid, 14-hydroxytetradecylphosphonic acid, 15- Hydroxypentadecylphosphonic acid, 16-hydroxyhexadecylphosphonic acid, 17-hydroxyheptadecylphosphonic acid, 18-hydroxyoctadecylphosphonic acid, 19-hydroxynonadecylphosphonic acid, 20-hydroxyicosylphosphonic acid, 3-hydroxypropyldiphosphonic acid hydrogen phosphate, 4-hydroxybutyl dihydrogen phosphate, 5-hydroxypentyl dihydrogen phosphate, 6-hydroxyhexyl dihydrogen phosphate, 7-hydroxyheptyl dihydrogen phosphate, 8-hydroxyoctyl dihydrogen phosphate, 9 - hydroxynonyl dihydrogen phosphate, 10-hydroxydecyl dihydrogen phosphate, 11-hydroxy undecyl dihydrogen phosphate, 12-hydroxy dodecyl dihydrogen phosphate, 13-hydroxytridecyl dihydrogen phosphate, 14-hydroxy tetra Decyl dihydrogen phosphate, 15-hydroxypentadecyl dihydrogen phosphate, 16-hydroxyhexadecyl dihydrogen phosphate, 17-hydroxyheptadecyl dihydrogen phosphate, 18-hydroxyoctadecyl dihydrogen phosphate, 19-hydroxy nonadecyl dihydrogen phosphate, 20-hydroxyicosyl dihydrogen phosphate, 3-carboxypropylphosphonic acid, 4-carboxybutylphosphonic acid, 5-carboxypentylphosphonic acid, 6-carboxyhexylphosphonic acid, 7-carboxyheptylphosphonic acid, 8-carboxyoctylphosphonic acid, 9-carboxynonylphosphonic acid, 10-carboxydecylphosphonic acid, 11-carboxyundecylphosphonic acid, 12-carboxydodecylphosphonic acid sulfonic acid, 13-carboxytridecylphosphonic acid, 14-carboxytetradecylphosphonic acid, 15-carboxypentadecylphosphonic acid, 16-carboxyhexadecylphosphonic acid, 17-carboxyheptadecylphosphonic acid, 18-carboxyoctadecylphosphonic acid, 19-carboxynonadecylphosphonic acid, 20-carboxyicosylphosphonic acid and the like. These may be used individually by 1 type, and may use 2 or more types of phosphorus compounds (BH) together.

In the layer (Y1c), the ratio M _BH /M _BI between the number of moles M _BH of the phosphorus compound (BH) and the number of moles M _BI of the inorganic phosphorus compound (BI) is 1.0×10 ⁻⁴ ≦M _BH /M _BI Those satisfying the relationship of ≦2.0×10 ⁻² are preferable, and from the viewpoint of better adhesion, the relationship of 3.5×10 ⁻⁴ ≦M _BH /M _BI ≦1.0×10 ⁻² is satisfied. More preferably, it satisfies the relationship of 5.0×10 ⁻⁴ ≦M _BH /M _BI ≦6.0×10 ⁻³ from the viewpoint of better adhesion and barrier performance. The number of moles M _BI of the inorganic phosphorus compound (BI) in M _BH /M _BI means the inorganic phosphorus compound (BI) used to form the reaction product (R).

[Polymer (C)]
The layer (Y1c) may contain the polymer (C). The polymer (C) is a polymer having at least one functional group selected from the group consisting of hydroxyl groups, carboxyl groups, carboxylic acid anhydride groups, and salts of carboxyl groups. The polymer (C) may be a homopolymer of a monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic anhydride group, and a salt of a carboxyl group. It may be a copolymer having monomers.

Examples of the polymer (C) include polyvinyl alcohol polymers such as polyethylene glycol; polyvinyl alcohol; modified polyvinyl alcohol containing 1 to 50 mol% of an α-olefin unit having 4 or less carbon atoms; Polysaccharides such as cellulose and starch; (meth)acrylic acid polymers such as polyhydroxyethyl (meth)acrylate, poly(meth)acrylic acid, ethylene-acrylic acid copolymer; ethylene-maleic anhydride copolymer Maleic acid-based polymers such as a hydrolyzate of coalescence, a hydrolyzate of a styrene-maleic anhydride copolymer, a hydrolyzate of an isobutylene-maleic anhydride alternating copolymer, and the like. Among these, polyethylene glycol and polyvinyl alcohol polymers are preferred. In addition, as a polymer (C), you may mix and use 2 or more types of polymers (C).

Although the molecular weight of the polymer (C) is not particularly limited, the number average molecular weight of the polymer (C) is , is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more. The upper limit of the number average molecular weight of the polymer (C) is not particularly limited, and is, for example, 1,500,000 or less.

When the layer (Y1c) contains the polymer (C), the content thereof is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the weight of the layer (Y1c). , 20% by mass or less. The polymer (C) may or may not react with other components in the layer (Y1c).

[Other components in layer (Y1c)]
The layer (Y1c) can further contain other components. Other components contained in the layer (Y1c) include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogensulfates, and borates; oxalates, acetates; , tartrate, stearate and other organic acid metal salts; cyclopentadienyl metal complexes (e.g., titanocene), cyano metal complexes (e.g., Prussian blue) and other metal complexes; layered clay compounds; cross-linking agents; polymer compounds a plasticizer; an antioxidant; an ultraviolet absorber; and a flame retardant. The content of the other components in the layer (Y1c) is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, particularly preferably 5% by mass or less, and 0% by mass (other ) may be used.

[Physical properties of layer (Y1c)]
The C/Al ratio at the surface of the layer (Y1c) not in contact with the substrate (X1) to 5 nm measured by X-ray photoelectron spectroscopy (XPS method) is in the range of 0.1 to 15.0. It is preferably in the range of 0.3 to 10.0, particularly preferably in the range of 0.5 to 5.0. Good adhesion is exhibited when the phosphorus compound (BH) is present on the surface of the layer (Y1c). The C/Al ratio can be measured by simultaneous angle-resolved X-ray photoelectron spectroscopy.

The water contact angle of the layer (Y1c) is preferably in the range of 25° to 100°, more preferably in the range of 40° to 85°, more preferably 55° to 70° from the viewpoint of exhibiting good adhesion. ° range is particularly preferred. When the phosphorus compound (BH) is present on the surface of the layer (Y1c), the water contact angle of the layer (Y1c) falls within the above range, exhibiting good adhesion. A water contact angle can be measured using a contact angle meter. As the contact angle meter, for example, a fully automatic contact angle meter (DMo-901, etc.) manufactured by Kyowa Interface Science Co., Ltd. can be used.

[Layer (Z1)]
The laminate (U1) may have a layer (Z1). Layer (Z1) contains a polymer (BO) having a plurality of phosphorus atoms. It is preferable that the layer (Z1) is formed adjacent to the layer (Y1) from the viewpoint of enhancing the bending resistance. The layer (Z1) may be composed only of the polymer (BO), or may further contain the polymer (C) described above. When the layer (Z1) contains the polymer (BO) and the polymer (C), the mass ratio W _BO :W _C is preferably in the range of 15:85 to 99:1, 60:40 to 90 :10 is more preferable.

[Polymer having a plurality of phosphorus atoms (BO)]
A polymer (BO) containing a plurality of phosphorus atoms is at least one selected from the group consisting of a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a phosphonous acid group, a phosphinic acid group, and a phosphinic acid group. is preferably a polymer having a functional group of Below, these functional groups may be referred to as "functional groups (PF)". As the functional group possessed by the polymer (BO), a phosphoric acid group and a phosphonic acid group are preferable, and a phosphonic acid group is more preferable.

Examples of the polymer (BO) include 6-[(2-phosphonoacetyl)oxy]hexyl acrylate, 2-phosphonooxyethyl methacrylate, phosphonomethyl methacrylate, 11-phosphonoundecyl methacrylate, 1,1-di Polymers of phosphono (meth) acrylic acid esters such as phosphonoethyl methacrylate; polymers of phosphonic acids such as vinylphosphonic acid, 2-propene-1-phosphonic acid, 4-vinylbenzylphosphonic acid, and 4-vinylphenylphosphonic acid coalescence; polymers of phosphinic acids such as vinylphosphinic acid and 4-vinylbenzylphosphinic acid; and phosphorylated starch. The polymer (BO) may be a homopolymer of a monomer having at least one functional group (PF), or may be a copolymer of two or more monomers. Further, as the polymer (BO), two or more kinds of polymers composed of a single monomer may be mixed and used. Among them, phosphono(meth)acrylic acid ester polymers and phosphonic acid polymers are preferred, and phosphonic acid polymers are more preferred. A preferred example of the polymer (BO) is poly(vinylphosphonic acid). The polymer (BO) can also be obtained by homopolymerizing or copolymerizing vinylphosphonic acid derivatives such as vinylphosphonic acid halides and vinylphosphonic acid esters, followed by hydrolysis.

The polymer (BO) may also be a copolymer of a monomer having at least one functional group (PF) and another vinyl monomer. Examples of other vinyl monomers that can be copolymerized with the monomer having a functional group (PF) containing a phosphorus atom include (meth)acrylic acid, (meth)acrylic acid esters, acrylonitrile, methacrylonitrile, Styrene, nuclear-substituted styrenes, alkyl vinyl ethers, alkyl vinyl esters, perfluoroalkyl vinyl ethers, perfluoroalkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleimide, phenylmaleimide, etc. . Among these, (meth)acrylates, acrylonitrile, styrene, maleimide, and phenylmaleimide are preferred.

Although the molecular weight of the polymer (BO) is not particularly limited, the number average molecular weight is preferably in the range of 1,000 to 100,000. When the number average molecular weight is within this range, both the effect of improving the bending resistance by laminating the layer (Z1) and the viscosity stability of the coating liquid (S), which will be described later, can be achieved at a high level. Further, when the molecular weight of the polymer (BO) per phosphorus atom is in the range of 100 to 500, the effect of improving the bending resistance can be further enhanced.

The layer (Z1) may further contain other components. Other ingredients include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogensulfates, and borates; oxalates, acetates, tartrates, and stearates. metal complexes such as cyclopentadienyl metal complexes (such as titanocene) and cyano metal complexes; layered clay compounds; cross-linking agents; polymer compounds other than polymer (BO) and polymer (C): Plasticizers; antioxidants; UV absorbers; flame retardants and the like. The content of the other components in the layer (Z1) is preferably 50% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and 5% by mass. It is particularly preferably below, and may be 0% by mass (not including other components).

The average thickness per layer of the layer (Z1) is preferably 0.005 μm or more from the viewpoint of better adhesion to other members. Although the upper limit of the average thickness of the layer (Z1) is not particularly limited, it is preferably 0.3 μm or less from the viewpoint of economy. The average thickness of the layer (Z1) can be controlled by the concentration of the coating liquid (S) used for forming the layer (Z1), which will be described later, and the coating method thereof.

[Method for producing layer (Y1)]
The layer (Y1a) and layer (Y1b) can be formed by a general vapor deposition method such as the vapor deposition method described above.

When forming layer (Y1c), steps (I), (II) and (III) may be included. In step (I), a coating liquid (T) is prepared by mixing a metal oxide (A), an inorganic phosphorus compound (BI) and a solvent. In step (II), a precursor layer of the layer (Y1c) is formed on the substrate (X1) by applying the coating liquid (T) onto the substrate (X1). In step (III), the layer (Y1c) is formed on the substrate (X1) by heat-treating the precursor layer at a temperature of 210° C. or higher. Details of steps (I) to (III) will be described below.

[Step (I)]
In step (I), a metal oxide (A), an inorganic phosphorus compound (BI) and a solvent are mixed at least to prepare a coating liquid (T) containing them. In one aspect, in step (I), the metal oxide (A) and the inorganic phosphorus compound (BI) are reacted in a solvent.

When mixing the metal oxide (A), the inorganic phosphorus compound (BI) and the solvent, other compounds (for example, the polymer (C)) may coexist.

Step (I) preferably includes the following steps (I-1) to (I-3).
Step (I-1): A step of preparing a dispersion (J) containing a metal oxide (A).
Step (I-2): A step of preparing a solution (K) containing an inorganic phosphorus compound (BI).
Step (I-3): A step of mixing the dispersion (J) obtained in steps (I-1) and (I-2) with the solution (K).

Step (I-2) may be performed prior to step (I-1), may be performed simultaneously with step (I-1), or may be performed after step (I-1). good.

[Step (I-1)]
In step (I-1), a dispersion (J) containing metal oxide (A) is prepared. Dispersion (J) may be a dispersion of metal oxide (A). The dispersion liquid (J) is prepared, for example, by mixing a compound (E)-based component, water, and, if necessary, an acid catalyst or an organic solvent, according to a technique employed in a known sol-gel method, and compound (E ) can be prepared by condensation or hydrolytic condensation of the system components. The dispersion of the metal oxide (A) obtained by condensation or hydrolytic condensation of the compound (E)-based component can be used as it is as the dispersion (J) containing the metal oxide (A). Therefore, the dispersion liquid (J) may be subjected to a specific treatment (such as deflocculation as described above, addition or subtraction of solvent for concentration control, etc.). The solvent used in step (I-1) is not particularly limited, but alcohols such as methanol, ethanol and isopropanol, water and mixed solvents thereof are preferred.

Step (I-1) may include a step of condensing (eg, hydrolytically condensing) at least one compound selected from compound (E) and a hydrolyzate of compound (E). Specifically, step (I-1) may include a step of condensing or hydrolytically condensing at least one compound selected from the compound (E) components described above.

Acid catalysts used for hydrolytic condensation include, for example, hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, formic acid, acetic acid, lactic acid, butyric acid, oxalic acid, maleic acid, benzoic acid, p-toluenesulfonic acid and the like. , sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are preferred, and nitric acid and acetic acid are more preferred. When an acid catalyst is used during hydrolytic condensation, it is preferable to use an appropriate amount depending on the type of acid so that the pH before hydrolytic condensation is in the range of 2.0 to 4.0.

[Step (I-2)]
In step (I-2), a solution (K) containing an inorganic phosphorus compound (BI) is prepared. Solution (K) is prepared by dissolving inorganic phosphorus compound (BI) in a solvent. When the solubility of the inorganic phosphorus compound (BI) is low, the dissolution may be promoted by heat treatment or ultrasonic treatment.

The solvent used for preparing the solution (K) may be appropriately selected according to the type of the inorganic phosphorus compound (BI), but it preferably contains water. Solvents include methanol, ethanol, tetrahydrofuran, 1,4-dioxane, trioxane, dimethoxyethane, acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, Organic solvents such as n-butyl cellosolve, glycerin, acetonitrile, N,N-dimethylformamide, dimethylsulfoxide and sulfolane may be included.

[Step (I-3)]
In step (I-3), the dispersion (J) and the solution (K) are mixed. Mixing of the dispersion liquid (J) and the solution (K) is preferably carried out under stirring. At this time, the solution (K) may be added to the dispersion (J) being stirred, or the dispersion (J) may be added to the solution (K) being stirred. By continuing stirring for about 30 minutes after the completion of mixing, it may be possible to obtain a coating liquid (T) with excellent storage stability.

The temperature of the dispersion (J) and solution (K) when mixed in step (I-3) is preferably 50° C. or less, more preferably 30° C. or less, and 20° C. or less. is more preferred.

The coating liquid (T) may contain a phosphorus compound (BH) and/or a polymer (C). Moreover, the coating liquid (T) may contain at least one acid compound selected from acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid, if necessary.

The solution obtained in step (I-3) can be used as the coating liquid (T) as it is. In this case, the solvent contained in the dispersion liquid (J) or the solution (K) usually becomes the solvent for the coating liquid (T). Alternatively, the coating liquid (T) may be obtained by adding an organic solvent, adjusting the pH, and adding additives to the solution obtained in step (I-3).

An organic solvent may be added to the solution obtained in step (I-3) as long as the stability of the resulting coating liquid (T) is not impaired. Addition of the organic solvent may facilitate the application of the coating liquid (T) onto the substrate (X1) in step (II). As the organic solvent, one that is uniformly mixed in the resulting coating liquid (T) is preferred. Examples of organic solvents include methanol, ethanol, tetrahydrofuran, 1,4-dioxane, trioxane, dimethoxyethane, acetone, methyl ethyl ketone, ethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, glycerin, acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, sulfolane and the like can be used.

From the viewpoint of the storage stability of the coating liquid (T) and the coatability of the coating liquid (T) to the substrate (X1), the solid content concentration of the coating liquid (T) is in the range of 1 to 20% by mass. preferably in the range of 2 to 15% by mass, and even more preferably in the range of 3 to 10% by mass. The solid content concentration of the coating liquid (T) can be calculated, for example, by dividing the mass of the solid content remaining after the solvent of the coating liquid (T) is distilled off by the mass of the coating liquid (T) subjected to the treatment.

From the viewpoint of the storage stability of the coating liquid (T) and the barrier properties of the vacuum insulation material, the pH of the coating liquid (T) is preferably in the range of 0.1 to 6.0, more preferably 0.2 to 5.0. more preferably in the range of 0.5 to 4.0. The pH of the coating liquid (T) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound.

As a method for adjusting the viscosity of the coating liquid (T) to be within the above range, for example, methods such as adjusting the concentration of solids, adjusting the pH, and adding a viscosity modifier can be employed. It is not limited.

As long as the effects of the present invention can be obtained, the coating liquid (T) includes, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogensulfates, borates; , acetate, tartrate, stearate and other organic acid metal salts; cyclopentadienyl metal complexes (e.g., titanocene), cyano metal complexes (e.g., Prussian blue) and other metal complexes; layered clay compounds; Polymer compounds; plasticizers; antioxidants; UV absorbers; flame retardants, and other substances mentioned above.

[Step (II)]
In step (II), a precursor layer of the layer (Y1c) is formed on the substrate (X1) by applying the coating liquid (T) onto the substrate (X1). The coating liquid (T) may be applied directly onto at least one surface of the substrate (X1), or may be applied onto the substrate (X1) via another layer. In addition, before coating the coating liquid (T), the surface of the substrate (X1) is treated with a known anchor coating agent, or the surface of the substrate (X1) is coated with a known adhesive. For example, the adhesive layer (H) may be formed on the surface of the substrate (X1).

The coating liquid (T) may be degassed and/or defoamed as necessary. Methods for degassing and/or defoaming treatment include, for example, methods using reduced pressure, heating, centrifugation, ultrasonic waves, and the like, and methods involving reduced pressure are preferred.

The coating liquid (T) when applied in step (II) has a viscosity measured with a Brookfield type rotational viscometer (SB type viscometer: rotor No. 3, rotation speed 60 rpm) The temperature is preferably 3,000 mPa·s or less, more preferably 2,000 mPa·s or less. When the viscosity is 3,000 mPa·s or less, the leveling property of the coating liquid (T) is improved, and a vacuum heat insulating material having a more excellent appearance can be obtained. The viscosity of the coating liquid (T) applied in step (II) can be adjusted by adjusting the concentration, temperature, stirring time and stirring intensity after mixing in step (I-3). For example, the viscosity may be lowered by extending the stirring after mixing in step (I-3).

The method of applying the coating liquid (T) onto the substrate (X1) is not particularly limited, and examples thereof include casting, dipping, roll coating, gravure coating, screen printing, reverse coating, and spray coating. , kiss coating method, die coating method, metering bar coating method, chamber doctor combined coating method, curtain coating method, bar coating method, and other known methods can be used.

Generally, in step (II), the precursor layer of layer (Y1c) is formed by removing the solvent in coating liquid (T). There is no particular limitation on the method for removing the solvent, and a known drying method can be applied. Examples of drying methods include hot air drying, hot roll contact, infrared heating, and microwave heating. The drying temperature is preferably 0 to 15° C. or more lower than the flow initiation temperature of the substrate (X1). When the coating liquid (T) contains the polymer (C), the drying temperature is preferably 15 to 20° C. or more lower than the thermal decomposition initiation temperature of the polymer (C). The drying temperature is preferably in the range of 70 to 200°C, more preferably in the range of 80 to 180°C, even more preferably in the range of 90 to 160°C. Solvent removal may be carried out under normal pressure or under reduced pressure. Alternatively, the solvent may be removed by heat treatment in step (III) described below.

In one example of laminating the layer (Y1c) on both sides of the layered substrate (X1), first, the coating liquid (T) is applied to one surface of the substrate (X1), and then the solvent is removed. to form a first layer (precursor layer of the first layer (Y1c)). Next, after coating the coating liquid (T) on the other surface of the substrate (X1), the second layer (precursor layer of the second layer (Y1c)) is formed by removing the solvent. . The composition of the coating liquid (T) applied to each surface may be the same or different.

[Step (III)]
In step (III), the layer (Y1c) is formed by heat-treating the precursor layer (precursor layer of layer (Y1c)) formed in step (II) at a temperature of 210° C. or higher.

In step (III), a reaction proceeds in which the particles of the metal oxide (A) are bonded together via phosphorus atoms (phosphorus atoms derived from the phosphorus compound (D)). From another point of view, in step (III), the reaction that produces the reaction product (R) proceeds. The temperature of the heat treatment is preferably in the range of 210°C to 230°C, more preferably in the range of 215°C to 225°C, in order to allow the reaction to proceed sufficiently and develop the desired barrier properties. preferable. At 200° C. or less, there is a tendency that sufficient barrier performance cannot be obtained. The preferred upper limit of the heat treatment temperature varies depending on the type of the base material (X1), etc. However, when a thermoplastic resin film made of a polyester resin is used as the base material (X1), the temperature of the heat treatment is set from the viewpoint of heat resistance. It is preferably 230° C. or less. The heat treatment may be performed under an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like.

The heat treatment time is preferably in the range of 0.1 second to 1 hour, more preferably in the range of 1 second to 15 minutes, even more preferably in the range of 5 to 300 seconds.

The method of the present invention may include a step of irradiating the precursor layer of the layer (Y1c) or the layer (Y1c) with ultraviolet rays. UV irradiation may be performed at any stage after step (II) (for example, after removal of the solvent of the applied coating liquid (T) is almost completed). The method is not particularly limited, and known methods can be applied. The wavelength of the ultraviolet rays to be irradiated is preferably in the range of 170-250 nm, more preferably in the range of 170-190 nm and/or in the range of 230-250 nm. Radiation such as electron beams or γ-rays may be applied instead of ultraviolet irradiation. By irradiating with ultraviolet rays, the gas barrier performance of the laminate (U1) may be exhibited at a higher level.

In order to arrange the adhesive layer (H) between the substrate (X1) and the layer (Y1c), before applying the coating liquid (T), the surface of the substrate (X1) is coated with a known anchor coating agent. or a known adhesive may be applied to the surface of the substrate (X1). In that case, it is preferable to carry out an aging treatment. Specifically, after coating the coating liquid (T) and before the heat treatment step (III), the substrate (X1) coated with the coating liquid (T) is cooled to a relatively low temperature. It is preferable to leave it for a long time. Specifically, the temperature of the aging treatment is preferably less than 110°C, more preferably 100°C or less, and even more preferably 90°C or less. Moreover, the temperature of the aging treatment is preferably 10° C. or higher, more preferably 20° C. or higher, and even more preferably 30° C. or higher. On the other hand, the aging treatment time is preferably in the range of 0.5 to 10 days, more preferably in the range of 1 to 7 days, and even more preferably in the range of 1 to 5 days. By performing such aging treatment, the adhesive force between the substrate (X1) and the layer (Y1c) becomes stronger.

[Method for producing layer (Z1)]
Forming the layer (Z1) may include a step of applying a coating liquid (S) onto the layer (Y1).

[Coating liquid (S)]
The coating liquid (S) is usually a solution in which the polymer (BO) is dissolved in a solvent. The coating liquid (S) may be prepared by dissolving the polymer (BO) in a solvent. Also, the solution obtained when the polymer (BO) is produced may be used as it is. When the solubility of the polymer (BO) is low, the dissolution may be promoted by heat treatment or ultrasonic treatment.

The solvent used in the coating liquid (S) may be appropriately selected according to the type of the polymer (BO), but is preferably water, alcohols, or a mixed solvent thereof. Solvents include ethers such as tetrahydrofuran, dioxane, trioxane and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol; acetonitrile; amides such as dimethylformamide; dimethylsulfoxide; sulfolane;

The coating liquid (S) may contain the above-described other components that the layer (Z) may contain.

The solid content concentration of the polymer (BO) in the coating liquid (S) is preferably in the range of 0.01 to 60% by mass, and 0.1 to 50% by mass, from the viewpoint of the storage stability and coatability of the solution. It is more preferably in the range of 0.2 to 40% by mass, more preferably in the range of 0.2 to 40% by mass. The solid content concentration can be determined by a method similar to the method described for the coating liquid (T).

From the viewpoint of the storage stability of the coating liquid (S) and the gas barrier properties of the laminate (U1), the pH of the coating liquid (S) is preferably in the range of 0.1 to 6.0, preferably 0.2 to 5. It is more preferably in the range of 0.0, more preferably in the range of 0.5 to 4.0. The pH of the coating liquid (S) can be adjusted by known methods such as adding an acidic compound or a basic compound.

Moreover, the coating liquid (S) may be deaerated and/or defoamed as necessary. Methods for degassing and/or defoaming treatment include, for example, methods using reduced pressure, heating, centrifugation, ultrasonic waves, and the like, and methods involving reduced pressure are preferred.

The coating liquid (S) at the time of coating has a viscosity of 3,000 mPa at the temperature at the time of coating, measured with a Brookfield type rotational viscometer (SB type viscometer: rotor No. 3, rotation speed 60 rpm). ·s or less, and more preferably 2,000 mPa·s or less. When the viscosity is 3,000 mPa·s or less, the leveling property of the coating liquid (S) is improved, and a vacuum heat insulating material having a more excellent appearance can be obtained.

As a method for adjusting the viscosity of the coating liquid (S), for example, methods such as adjusting the concentration of solids, adjusting the pH, and adding a viscosity modifier can be employed. As long as the effects of the present invention are obtained, the coating liquid (S) may contain other substances described above.

The method of applying the coating liquid (S) is not particularly limited, and examples thereof include casting, dipping, roll coating, gravure coating, screen printing, reverse coating, spray coating, kiss coating, die coating, Known methods such as a metering bar coating method, a chamber doctor combined coating method, a curtain coating method and a bar coating method can be employed.

The layer (Z1) is usually formed by removing the solvent in the coating liquid (S). A method for removing the solvent of the coating liquid (S) is not particularly limited, and for example, a known drying method such as a hot air drying method, a hot roll contact method, an infrared heating method, or a microwave heating method can be applied. The drying temperature is preferably 0 to 15° C. or more lower than the flow initiation temperature of the substrate (X1). The drying temperature is preferably in the range of 70 to 200°C, more preferably in the range of 80 to 180°C, even more preferably in the range of 90 to 160°C. Solvent removal may be carried out under normal pressure or under reduced pressure. Further, when the coating liquid (S) is applied between step (II) and step (III), the solvent may be removed by heat treatment in step (III).

[Adhesive layer (H)]
In the laminate of the present invention, the layer (Y1) may be laminated so as to be in direct contact with the substrate (X1), but the adhesive layer disposed between the substrate (X1) and the layer (Y1) The layer (Y1) may be laminated on the substrate (X1) via the layer (H). According to this configuration, the adhesiveness between the substrate (X1) and the layer (Y1) can be enhanced in some cases. As the adhesive, a two-liquid reaction type polyurethane adhesive obtained by mixing and reacting a polyisocyanate component and a polyol component is preferable. Also, by adding a small amount of additive such as a known silane coupling agent, it may be possible to further improve the adhesiveness. Preferred examples of silane coupling agents include silane coupling agents having reactive groups such as isocyanate groups, epoxy groups, amino groups, ureido groups, and mercapto groups. By strongly bonding the substrate (X1) and the layer (Y1) via the adhesive layer (H), deterioration of the barrier properties and appearance of the vacuum heat insulating material of the present invention can be more effectively suppressed.

When the adhesive layer (H) is arranged between the substrate (X1) and the layer (Y1), its thickness is preferably in the range of 0.03-0.18 μm. The thickness of the adhesive layer (H) is more preferably in the range of 0.04-0.14 μm, more preferably in the range of 0.05-0.10 μm.

[Laminate (U2)]
The laminate (U2) is a laminate having a substrate (X2) made of a polyvinyl alcohol-based resin and an aluminum deposition layer (Y2) on at least one surface of the substrate (X2). Since the base material (X2) is a material with high gas barrier properties, it can maintain quality stability even if it receives physical stress during the manufacturing process of the vacuum heat insulating material, for example. Moreover, since the layer (Y2) has a good affinity with the base material (X2), it is possible to reduce the destruction of the layer (Y2) due to physical stress.

[Base material (X2)]
The laminate (U2) exhibits excellent gas barrier properties by having the substrate (X2) made of a polyvinyl alcohol-based resin. In addition, since the base material (X2) is composed of a polyvinyl alcohol resin, the compatibility with the vapor deposition layer (Y2) described later is increased, and the flex resistance is improved. The polyvinyl alcohol-based resin may be one having a vinyl alcohol unit obtained by saponifying a vinyl ester unit. Examples include polymer (hereinafter sometimes abbreviated as EVOH) resin.

The PVA resin in the present invention can usually be obtained by saponifying a vinyl ester homopolymer. Homopolymerization of vinyl esters and saponification of vinyl ester homopolymers can be carried out by known methods. Vinyl esters are typically vinyl acetate, but also other fatty acids such as vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate and vinyl versatate. It may be a vinyl ester.

The PVA resin in the present invention may be a copolymerized PVA resin (hereinafter referred to as a copolymerized modified PVA resin) or a post-modified modified PVA resin (hereinafter referred to as a post-modified PVA resin).

The copolymerized modified PVA resin in the present invention is produced by copolymerizing a vinyl ester and an unsaturated monomer copolymerizable with the vinyl ester, followed by saponification, and the amount of modification is less than 10 mol%. is.

Examples of unsaturated monomers copolymerizable with the vinyl ester include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene; 3-buten-1-ol, 4-pentyne; -Hydroxy group-containing α-olefins such as 1-ol and 5-hexen-1-ol and derivatives such as acylated products thereof; acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, undecylene unsaturated acids such as acids, their salts, monoesters, or dialkyl esters; nitriles such as acrylonitrile and methacrylonitrile; amides such as diacetone acrylamide, acrylamide, and methacrylamide; ethylenesulfonic acid, allylsulfonic acid, methallyl Olefin sulfonic acids such as sulfonic acid or salts thereof; vinyl compounds such as monoallyl ether and 3,4-diacetoxy-1-butene; substituted vinyl acetates such as isopropenyl acetate and 1-methoxyvinyl acetate; vinylidene chloride, 1,4-diacetoxy-2-butene, vinylene carbonate and the like is mentioned.

The post-modified PVA resin can be obtained by methods such as acetoacetic esterification, acetalization, urethanization, etherification, grafting, phosphate esterification, and oxyalkylenation of PVA.

The degree of polymerization of the PVA resin is preferably 1100 or more, more preferably 1200 or more. The degree of polymerization of the PVA resin is preferably 4000 or less, more preferably 2600 or less. It is preferable that the degree of polymerization of the PVA resin is 1100 or more, because the mechanical strength of the obtained vacuum heat insulating material is improved. On the other hand, when the degree of polymerization is 4000 or less, the processability during film formation and stretching is improved, which is preferable. The degree of polymerization of PVA resin can be measured according to the method described in JIS K 6726 (1994). Moreover, the degree of saponification of the PVA resin is preferably 90 mol % or more, more preferably 95 mol % or more, and even more preferably 99 mol % or more. Moreover, 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, water resistance is improved and gas barrier properties against humidity are improved, which is preferable. The degree of saponification of PVA resin can be measured according to the method described in JIS K 6726 (1994).

EVOH resins can usually be obtained by saponifying ethylene-vinyl ester copolymers. Production and saponification of the ethylene-vinyl ester copolymer can be carried out by known methods. Vinyl esters are typically vinyl acetate, but other vinyl fatty acids such as vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate and vinyl versatate. It may be an ester. The ethylene unit content of the EVOH resin is 10 mol % or more.

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, even more preferably 99 mol% or more. By setting the degree of saponification to 90 mol % or more, it is possible to improve the gas barrier properties of the vacuum heat insulating material. Moreover, the degree of saponification of the EVOH resin may be 100 mol % or less or 99.99 mol % or less. The saponification degree of the EVOH resin can be obtained by performing ¹ H-NMR measurement and measuring the peak area of the hydrogen atoms contained in the vinyl ester structure and the peak area of the hydrogen atoms contained in the vinyl alcohol structure. .

The ethylene unit content of the EVOH resin is 10 mol % or more, preferably 15 mol % or more, even more preferably 20 mol % or more, and particularly 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, and even more preferably 50 mol% or less. When the ethylene unit content is 10 mol % or more, the film or the like can maintain good gas barrier properties or dimensional stability under high humidity. On the other hand, when the ethylene unit content is 65 mol % or less, the film or the like can have improved gas barrier properties. The ethylene unit content of the EVOH resin can be determined by a nuclear magnetic resonance (NMR) method.

The EVOH resin may contain 0.0002 to 0.2 mol % of a vinylsilane compound as a copolymerization component in order to improve stability during heating and melting. Vinylsilane compounds include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxy-ethoxy)silane, and γ-methacryloxypropylmethoxysilane. Among them, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

The EVOH resin can also be copolymerized with other unsaturated monomers as long as the object of the present invention is not hindered. As other unsaturated monomers, the vinyl ester-copolymerizable unsaturated monomers mentioned above for the PVA resin can be used.

When the EVOH resin contains a mixture of two or more different types of EVOH, the ethylene unit content or saponification degree of each calculated from the blending mass ratio is the ethylene unit content or saponification degree of the EVOH resin. and

From the viewpoint of thermal stability or viscosity adjustment, EVOH resins can be mixed with acids such as carboxylic acids and phosphoric acids; metal salts such as alkali metal salts and alkaline earth metal salts; boron compounds such as boronic acids and their salts and boronic esters. It is preferable to contain the additive of

The shape of the substrate (X2) is preferably film-like. A known method for producing such a film can be used, for example, a casting type molding method in which a film is formed by casting a solution of a polyvinyl alcohol-based resin on a metal surface such as a drum or an endless belt, or an extruder. A melt molding method in which melt extrusion is performed by

As the substrate (X2), a biaxially stretched film is preferable from the viewpoint of dimensional stability and gas barrier properties. The draw ratio is 2.5 times or more and 4.5 times or less in the longitudinal direction (MD direction) and 2 times in the transverse direction (TD direction) from the viewpoint of thickness uniformity, barrier properties, mechanical properties and film-forming properties. 5 times or more and 4.5 times or less, and the areal draw ratio is preferably 7 times or more and 15 times or less. times or less, and the areal draw ratio is more preferably 8 times or more and 12 times or less. Such a stretching treatment method can be carried out according to known methods such as simultaneous biaxial stretching and sequential biaxial stretching which are usually carried out.

As the substrate (X2), a biaxially stretched PVA resin film, a biaxially stretched EVOH resin film, and the like can be suitably used, and a biaxially stretched EVOH resin film is more preferable.

Although the thickness of the substrate (X2) is not particularly limited, it is preferably 5 µm or more, more preferably 8 µm or more, and still more preferably 10 µm or more from the viewpoint of industrial productivity. Also, the thickness of the substrate (X2) is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 40 μm or less, and particularly preferably 30 μm or less.

[Layer (Y2)]
Layer (Y2) is a vapor-deposited layer of aluminum. The aspect of layer (Y2) is the same as layer (Y1a) except for the preferred average thickness. The average thickness of the layer (Y2) is preferably 20 nm or more, more preferably 40 nm or more, even more preferably 60 nm or more. Also, the average thickness of the layer (Y2) is preferably 150 nm or less, more preferably 120 nm or less, even more preferably 100 nm or less. When the average thickness of the layer (Y2) is 20 nm or more, the barrier property tends to be stably exhibited.

[Vacuum insulation]
The vacuum heat insulating material of the present invention includes a vacuum packaging bag and a core material disposed inside the vacuum packaging bag, the interior of which is decompressed. In the vacuum heat insulating material 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 within the vacuum packaging bag is sufficiently lower than the atmospheric pressure. The internal pressure is determined according to the required performance, ease of manufacture, etc., but is usually 2 kPa (approximately 15 Torr) or less in order to exhibit the heat insulation performance. The internal pressure of the vacuum packaging bag is preferably 200 Pa or less, more preferably 20 Pa or less, and even more preferably 2 Pa or less, in order to sufficiently exhibit the heat insulating effect of the vacuum heat insulating material of the present invention. The pressure in the space within the vacuum packaging bag may be 0.001 Pa or higher.

The thermal conductivity of the vacuum heat insulating material immediately after production is preferably 3.0 mW/(m·K) or less, more preferably 2.5 mW/(m·K) or less. On the other hand, the thermal conductivity immediately after production is preferably 1.0 mW/(m·K) or more, more preferably 1.2 mW/(m·K) or more. If the thermal conductivity exceeds 3.0 mW/(m·K), the heat insulation performance of the vacuum heat insulating material may be insufficient. When the thermal conductivity is 1.0 mW/(m·K) or more, a vacuum heat insulating material having good heat insulating performance can be obtained at a relatively low cost. The thermal conductivity of the vacuum insulation material measured after storage in a constant temperature and humidity chamber at 70 ° C. and 90% RH for 30 days is preferably 6.5 mW / (m K) or less, and 6.0 mW / (m K). ) below is more preferred. On the other hand, the thermal conductivity measured after storage in a constant temperature and humidity chamber at 70°C and 90% RH for 30 days is preferably 1.0 mW/(mK) or more, more preferably 1.2 mW/(mK). The above is more preferable. Here, "thermal conductivity" is a value measured according to JIS A 1412-1 (1999).

The vacuum insulation material of the present invention can be manufactured by a commonly used method. The vacuum insulation material can be formed in any shape and size depending on the purpose of use. For example, the vacuum insulation material of the present invention can be produced by the following methods 1 to 3.
(Method 1) First, prepare two laminates comprising quadrilateral laminates (U1) and (U2) having a heat-sealable layer (for example, a polyolefin layer) on at least one surface. The two laminates are superimposed so that each heat-sealable layer is on the inside, and arbitrary three 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 this state. A vacuum insulation material is thus obtained.
(Method 2) First, one laminate is folded so that the heat-sealable layer is on the inside, and arbitrary two 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 this state. A vacuum insulation material is thus obtained.
(Method 3) First, the core material is sandwiched between two laminates, or the core material is sandwiched by bending the laminate. Next, a vacuum packaging bag in which a core material is arranged is produced by heat-sealing the peripheral portion where the laminated bodies are overlapped, leaving a vacuum exhaust port. Next, the space inside the vacuum packaging bag is evacuated, and the vacuum exhaust port is heat-sealed in this state. A vacuum insulation material is thus obtained.

[Vacuum packaging bag]
A vacuum packaging bag is a packaging material that is used by depressurizing the inside, and has a film material as a partition separating the inside and the outside. The vacuum packaging bag of the present invention is a laminate composed of the laminates (U1) and (U2) and other members other than the laminate (for example, other layers such as a thermoplastic resin film layer and a paper layer). I have. Also, the vacuum packaging bag may contain one laminate or may contain a plurality of such laminates. For a vacuum packaging bag having other members (other layers, etc.), the other members (other layers, etc.) are bonded to the laminate (U1) or laminate (U2) via the adhesive layer (H). can be manufactured by By including such other members (such as other layers) in the vacuum packaging bag, the characteristics of the vacuum packaging bag can be improved or new characteristics can be imparted. For example, the vacuum packaging bag of the present invention can be imparted with heat-sealing properties, and its barrier properties and mechanical properties can be further improved.

In particular, it is preferable to use a polyolefin layer (hereinafter sometimes abbreviated as a PO layer) as the surface layer of the vacuum packaging bag, because the vacuum packaging bag can be given heat-sealing properties and the mechanical properties of the vacuum packaging bag can be improved. Polyolefin is preferably polypropylene or polyethylene from the viewpoint of further improving heat-sealability and mechanical properties. In order to improve the mechanical properties of the vacuum packaging bag, as another layer, at least one film selected from the group consisting of biaxially oriented polypropylene film, polyester film, polyamide film and polyvinyl alcohol film is laminated ( Lamination to U1) and/or (U2) is preferred. From the viewpoint of improving mechanical properties, polyethylene terephthalate (PET) is preferred as polyester, nylon-6 is preferred as polyamide, and ethylene-vinyl alcohol copolymer is preferred as polyvinyl alcohol. In particular, from the viewpoint of increasing pinhole resistance, it is preferable to have a polyamide film. In particular, from the viewpoint of further increasing pinhole resistance, it is more preferable that the laminate (U1) and the laminate (U2) are laminated via a polyamide film. Specifically, the layer of the laminate (U1) opposite to the substrate (X1) and the layer (Y2) of the laminate (U2) are laminated via a layer made of a polyamide resin. preferable. By interposing a polyamide film with high moisture permeability, the water retention capacity of the adhesive layer (H) between the laminate (U1) and the polyamide film is reduced, and under high temperature and high humidity conditions, the laminate (U1) and the adhesive layer (H ) can be suppressed. Further, by interposing another layer between the laminate (U1) and the laminate (U2), air bubbles generated in the adhesive layer (H) after lamination can be suppressed. Air bubbles in the adhesive layer can lead to delamination and damage to the deposited layer.

When the adhesive layer (H) is arranged between the laminate (U1) and the laminate (U2) or between another member, the thickness thereof may be in the range of 1.0 to 10.0 μm. preferable. The thickness of the adhesive layer (H) is more preferably in the range of 2.0-7.0 μm, more preferably in the range of 3.0-5.0 μm.

The vacuum packaging bag used for the vacuum insulation material of the present invention may have the following configuration, for example, from the outer layer to the inner layer of the vacuum insulation material. For example, in (1) below, the laminate (U1) is the outermost layer. The directions of the laminate (U1) and the laminate (U2) are not limited, but when the laminate (U1) is used as the outermost layer, the layer (Y1) should be laminated toward the inside so as to form a barrier from the outside. This is preferable from the viewpoint of preventing layer damage. In addition, it is preferable that the laminate (U2) has the substrate (X2) inside the vapor deposited aluminum layer (Y2) from the viewpoint of preventing cracks in the vapor deposited layer due to expansion due to moisture absorption of the polyvinyl alcohol-based resin layer. Therefore, when laminating the laminate (U1) and the laminate (U2), it is more preferable to have a configuration of base material (X1)/layer (Y1)//aluminum deposition layer (Y2)/base material (X2) from the outside. .
(1) laminate (U1) // laminate (U2) // PO layer,
(2) polyester layer // laminate (U1) // laminate (U2) // PO layer,
(3) polyamide layer // laminate (U1) // laminate (U2) // PO layer,
(4) PO layer //Laminate (U1) //Laminate (U2) //PO layer,
(5) laminate (U1) // PO layer // laminate (U2) // PO layer,
(6) laminate (U1) // polyamide layer // laminate (U2) // PO layer,
(7) laminate (U1) // laminate (U2) // laminate (U2) // PO layer,
(8) laminate (U1) // laminate (U1) // laminate (U2) // PO layer,
(9) laminate (U1) // laminate (U2) // laminate (U1) // PO layer,
(10) Laminate (U1) // Laminate (U1) // Polyamide layer // Laminate (U2) // PO layer.

When used under high-temperature and high-humidity conditions, the laminate (U1) is preferably the outermost layer. By providing it in the outermost layer, it is possible not only to prevent deterioration of the barrier properties of the laminate (U2) but also to suppress deterioration of physical properties due to hydrolysis of the inner film. For example, a polyamide layer is preferable for enhancing mechanical properties, but may cause appearance defects such as delamination due to moisture absorption under high temperature and high humidity conditions. Defects such as delamination can be suppressed by providing the laminate (U1) having a high water vapor barrier property outside the polyamide layer. Furthermore, it is preferable to provide two or more laminates (U1) from the viewpoint of providing a vacuum heat insulating material with excellent long-term reliability during use and storage under high temperature and high humidity conditions.

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

[Use]
The vacuum heat insulating material of the present invention can be used for various applications requiring cold insulation or heat insulation. In particular, even when the vacuum insulation material is used under high temperature or high humidity conditions, deterioration of the insulation performance over time is extremely difficult to occur, and it has a sufficient service life as an insulation material. Tanks for toilets, tanks for vending machines, tanks for fuel cells, tanks for automobiles, heat-retaining bags for food, heat-retaining hot PET bottles or cans, heat-retaining drums for washing machines, servers for coffee, tea, etc. It is also useful for any thermal application requiring thermal insulation such as jar pots.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited by the following examples. In addition, when a laminate including the laminate (U1) was produced in the examples, the orientation of the laminate (U1) was laminated in the order described in Table 1, "Construction". In addition, the laminated body (U2) and the laminated body (U2') are laminated in the order described in the notes in Table 1.

<Materials used in Examples>
・ “CPP RXC-18 (trade name)”: Mitsui Chemicals Tohcello Co., Ltd., unstretched polypropylene film, thickness 50 μm, sometimes abbreviated as “CPP” ・ “Kuraray Poval (registered trademark) PVA124 (trade name) ": Kuraray Co., Ltd., polyvinyl alcohol resin "PEG-20000 (trade name)": Sanyo Chemical Industries, Ltd., polyethylene glycol "Lumirror (registered trademark) P60 (trade name)": Toray Industries, Inc., two Axially stretched polyester film, thickness 12 μm, sometimes abbreviated as “OPET” ・ “VM-XL (trade name)”: manufactured by Kuraray Co., Ltd., aluminum deposited biaxially stretched ethylene-vinyl alcohol copolymer film, thickness 12 μm, sometimes abbreviated as “laminate (U2)” ・ “Unilux (registered trademark) LS-760C (trade name)”: manufactured by Idemitsu Unitech Co., Ltd., linear low-density polyethylene, abbreviated as “LLDPE”・"Takelac A520 (trade name)", "Takenate A50 (trade name)": Urethane-based two-component adhesive manufactured by Mitsui Chemicals, Inc. ・"Emblem (registered trademark) ON-BC (trade name)" : Unitika Ltd., stretched polyamide film, thickness 15 μm, sometimes abbreviated as "ONY"・"EF-XL (trade name)": Kuraray Co., Ltd., biaxially stretched ethylene-vinyl alcohol copolymer film , thickness 12 μm
・ “OP U-2 (trade name)”: manufactured by Mitsui Chemicals Tohcello Co., Ltd., biaxially oriented polypropylene film, thickness 20 μm, sometimes abbreviated as “OPP”

<Measurement method>
Measurement of Average Thickness of Layer (Y1) and Layer (Z1) The laminate (U1) obtained in Production Example was cut using a focused ion beam (FIB) to prepare a slice for cross-sectional observation. The prepared section was fixed to the sample base with a carbon tape, and platinum ion sputtering was performed at an acceleration voltage of 30 kV for 30 seconds. A cross section of the laminate (U1) was observed using a field emission transmission electron microscope, and the average thickness of each layer was calculated. The measurement conditions were as follows.
Device: JEM-2100F manufactured by JEOL Ltd.
Accelerating voltage: 200 kV
Magnification: 250,000 times

(2) Infrared absorption spectrum of layer (Y1) The infrared absorption spectrum of the layer (Y1) formed in Examples was measured by the following method.
First, the infrared absorption spectrum of the layer (Y1) laminated on the substrate (X1) was measured using a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer, "Spectrum One"). Infrared absorption spectra were measured in the ATR (total reflection measurement) mode in the range of 700 to 4000 cm ⁻¹ . When the thickness of the layer (Y1c) is 1 μm or less, an absorption peak derived from the substrate (X1) is detected in the infrared absorption spectrum by the ATR method, and the absorption intensity derived from the layer (Y1) alone can be accurately determined. may not be possible. In such a case, the infrared absorption spectrum of only the base material (X1) was separately measured, and by subtracting it, only the peak derived from the layer (Y1) was extracted.

(3) Water vapor permeability of the laminate (U1) Unstretched polypropylene film (“CPP RXC-18 (trade name)” manufactured by Mitsui Chemicals Tohcello Co., Ltd., thickness 50 μm, hereinafter sometimes abbreviated as “CPP”) , Two-liquid type adhesive (Takelac A520 manufactured by Mitsui Chemicals, Takenate A50 manufactured by Mitsui Chemicals and ethyl acetate mixed in a mass ratio of 6: 1: 9.3) is applied so that the dry film thickness is 4 μm. Then, a laminate "Laminate (U1)//CPP" with the laminate (U1) obtained in Production Example was produced. Specifically, the substrate (X1) was laminated as the outermost layer. The laminate was cut to obtain two laminates each having a size of 12 cm×12 cm. The two laminates are superimposed so that the CPP layers are on the inside, and the three sides are heat-sealed with a width of 10 mm, and then the bag is filled with calcium chloride and the remaining side is sealed to produce a laminated bag. did. The laminated bag thus obtained was placed in a thermo-hygrostat at 70° C. and 90% RH, and the operation of taking out the laminated bag and weighing it was repeated at intervals of one day to measure the amount of increase in mass. Since the water vapor permeability calculated based on the mass increase on the 5th day stabilized, the water vapor permeability at that time was taken as the water vapor permeability (Ws).
Water vapor permeability (g/(m ² ·day)) = mass increase (g)/(film surface area (m ² ) · storage time (day))
In addition, after the laminated bag was stored in a thermo-hygrostat at 70° C. and 90% RH for 30 days, the water vapor transmission rate (Wf) was measured in the same manner.

(4) Oxygen Permeability of Laminate after Gelboflex Test Regarding the gas barrier properties when the laminates obtained in Examples and Comparative Examples were subjected to physical stress, Permeability was measured and evaluated. Specifically, the produced laminate was cut into a size of 210 mm×297 mm and conditioned at 23° C. and 50% RH. Using the humidity-conditioned film, in the same atmosphere, it was formed into a cylinder with a diameter of 3.5 inches, and both ends were fixed to a gelboflex tester (manufactured by Rigaku Kogyo Co., Ltd.), with an initial interval of 7 inches and maximum bending. A 440 degree angle twist was applied for the first 3.5 inches of the stroke, followed by 2.5 inches of straight horizontal motion. The oxygen permeability was measured using an oxygen permeability measuring device ("OX-TRAN2/20" manufactured by MOCON). Specifically, the laminate was set so that the sealant (LLDPE) faced the carrier gas side, the temperature was 40° C., the humidity on the oxygen supply side was 90% RH, the humidity on the carrier gas side was 0% RH, and the oxygen pressure was was ¹ atm and the carrier gas pressure was 1 atm. Nitrogen gas containing 2% by volume of hydrogen gas was used as the carrier gas.

(5) Appearance of Laminate The appearance of the laminate was visually evaluated as follows.
A: Air bubbles etc. are not confirmed.
B: Bubbles are observed in the adhesive layer.

(6) Pinhole occurrence rate of vacuum insulation material 100 vacuum insulation materials obtained in Examples and Comparative Examples were produced, and the vacuum insulation material whose thermal conductivity immediately after production was 10 mW / (m K) or more. The pinhole occurrence rate was calculated from the number of

(7) Thermal conductivity of vacuum insulation material After storing the vacuum insulation materials obtained in Examples and Comparative Examples at 70 ° C. and 90% RH for a certain period of time, a thermal conductivity measuring device (HC- 074/600), the heat conductivity of the vacuum heat insulating material was measured by setting one side of the vacuum heat insulating material to 35°C and setting the other side to 10°C. Measurements were taken immediately after the vacuum heat insulating material was produced, and after storage in a thermo-hygrostat at 70° C. and 90% RH for 15 days and 30 days, respectively.

(8) Appearance of Vacuum Insulating Material The appearance of the vacuum insulating material after being stored in a thermo-hygrostat at 70° C. and 90% RH for 15 days, 21 days, and 30 days was visually evaluated as follows.
A: Almost no change from before storage B: Changes such as air bubbles, delamination, color unevenness, etc. were observed

<Production example of laminate (U1)>
[Production Example 1-1]
Using "Lumirror (registered trademark) P60 (trade name)" (OPET) (hereinafter sometimes abbreviated as "substrate (X1-1)") as the substrate (X1), a batch type vapor deposition apparatus (ULVAC, Inc. "EWA-105" of No. 1), and by melting and evaporating aluminum, a laminate (U1-1) having a 100 nm aluminum deposited layer (Y1-1) on one side of the substrate (X1) was obtained. .

[Production Example 1-2]
230 parts by mass of distilled water was heated to 70° C. while stirring. 88 parts by mass of aluminum isopropoxide was added dropwise to the distilled water over 1 hour, the liquid temperature was gradually raised to 95°C, and hydrolytic condensation was carried out by distilling off the generated isopropanol. 4.0 parts by mass of a 60% by mass nitric acid aqueous solution was added to the obtained liquid, and the mixture was stirred at 95° C. for 3 hours to deflocculate aggregates of particles of the hydrolytic condensate. After that, the liquid was concentrated so that the solid content concentration was 10% by mass in terms of aluminum oxide. 58.19 parts by weight of distilled water, 19.00 parts by weight of methanol, and 0.50 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol were added to 18.66 parts by weight of the dispersion liquid thus obtained, and the mixture was mixed uniformly. A dispersion was obtained by stirring to . Subsequently, 3.66 parts by mass of an 85% by mass phosphoric acid aqueous solution was added dropwise while the dispersion was stirred while the liquid temperature was maintained at 15°C, and the mixture was heated at 15°C until the viscosity reached 1,500 mPa s. Stirring was continued to obtain the desired coating liquid (T-1). The molar ratio of aluminum atoms to phosphorus atoms in the coating liquid (T-1) was aluminum atom:phosphorus atom=1.15:1.00. The solution (T-1) was coated on the base material (X1-1) with a bar coater so that the thickness after drying was 0.5 μm, dried at 110° C. for 5 minutes, and then dried at 210° C. for 1 A layer (Y1-2) was formed by heat treatment for 1 minute to obtain a laminate (U1-2). When the infrared absorption spectrum of layer (Y1-2) was measured according to (2) above, the maximum absorption wave number was 1108 cm ^-1 .

[Production Example 1-3]
A layer (Y1-3) was formed in the same manner as in Production Example 1-2 except that the heat treatment temperature was changed to 220° C. to obtain a laminate (U1-3).

[Production Example 1-4]
In a nitrogen atmosphere, 10 g of vinylphosphonic acid and 0.025 g of 2,2'-azobis(2-amidinopropane) dihydrochloride were dissolved in 5 g of water and stirred at 80°C for 3 hours. After cooling, the polymerization solution was diluted by adding 15 g of water, and filtered using a cellulose membrane, "Spectra/Por" (registered trademark) manufactured by Spectrum Laboratories. After distilling off the water in the filtrate, the filtrate was vacuum-dried at 50° C. for 24 hours to obtain poly(vinylphosphonic acid) (BO1). As a result of GPC analysis, the number average molecular weight of the polymer was 10,000 in terms of polyethylene glycol. The polymer was dissolved in a mixed solvent of water and methanol (water:methanol=7:3 by weight) to obtain a coating liquid (S-1) having a solid concentration of 1% by weight. After coating the coating liquid (S-1) on the layer (Y1-3) of the laminate (U1-3) with a bar coater, it is dried at 110 ° C. for 3 minutes to form a layer (Z1 -1) to obtain a laminate (U1-4) consisting of the substrate (X)/layer (Y1-3)/layer (Z1-1).

[Production Example 1-5]
A mixture containing 70% by mass of the polyvinyl phosphonic acid (BO1) synthesized in Preparation Example 1-4 and 30% by mass of polyvinyl alcohol (“Kuraray Poval (registered trademark) PVA124 (trade name)” manufactured by Kuraray Co., Ltd.) was prepared. . This mixture was dissolved in a mixed solvent of water and methanol (water:methanol=7:3 in mass ratio) to obtain a coating liquid (S-2) having a solid concentration of 1% by mass. After coating the coating liquid (S-2) on the layer (Y1-1) of the laminate (U1-1) with a bar coater, it is dried at 110 ° C. for 3 minutes to give an average thickness of 0.03 μm after drying. A layer (Z1-2) was formed to obtain a laminate (U1-5) consisting of base material (X)/layer (Y1-1)/layer (Z1-2).

[Production Example 1-6]
70% by mass of polyvinyl phosphonic acid (BO1) synthesized in Preparation Example 1-4, and 30% by mass of polyethylene glycol (“PEG-20000 (trade name)” manufactured by Sanyo Chemical Industries, Ltd.) having a weight average molecular weight of 20,000 A mixture was prepared. This mixture was dissolved in a mixed solvent of water and methanol (water:methanol=7:3 in mass ratio) to obtain a coating liquid (S-3) having a solid concentration of 1% by mass. After coating the coating liquid (S-3) on the layer (Y1-3) of the laminate (U1-3) with a bar coater, it is dried at 110 ° C. for 3 minutes to form a layer (Z1- 3) was formed to obtain a laminate (U1-6).

[Production Example 1-7]
A layer (Y1-4) was formed in the same manner as in Production Example 1-1, except that the average thickness of aluminum was 40 nm, to obtain a laminate (U1-7). Note that the laminate (U1-7) has a Wf of 2.5 g/(m ² /day) and does not correspond to the laminate (U1) of the present invention.

[Production Example 1-8]
A layer (Y1-5) was formed in the same manner as in Production Example 1-1 except that an aluminum oxide deposition layer was formed on one surface of the substrate (X1-1) by melting and evaporating aluminum while introducing oxygen. ) was formed to obtain a laminate (U1-8). Note that the laminate (U1-8) has a Wf of 1.7 g/(m ² /day) and does not correspond to the laminate (U1) of the present invention.

[Production Example 1-9]
A layer (Y1-6) was formed in the same manner as in Production Example 1-2 except that the heat treatment temperature was changed to 200° C. to obtain a laminate (U1-9). Note that the laminate (U1-9) has a Wf of 1.2 g/(m ² /day) and does not correspond to the laminate (U1) of the present invention.

The laminates (U1-1) to (U1-9) obtained in Production Examples 1-1 to 1-9 were measured for water vapor permeability according to the method described in (3) above.

<Production example of laminate (U2)>
A layer ( Y2-2) was formed to obtain a laminate (U2-2).

<Examples and Comparative Examples>
[Example 1]
As the laminate (U2), an aluminum vapor-deposited biaxially stretched ethylene-vinyl alcohol copolymer film (“VM-XL (trade name)” manufactured by Kuraray Co., Ltd.) was prepared. Two-liquid adhesion of unstretched LLDPE (“Unilux (registered trademark) LS-760C (trade name)” manufactured by Idemitsu Unitech Co., Ltd.) with a thickness of 50 μm, the laminate (U1-1), and the laminate (U2) An agent (mixture of Takelac A520 manufactured by Mitsui Chemicals, Takenate A50 manufactured by Mitsui Chemicals, and ethyl acetate in a mass ratio of 6:1:9.3) was applied so that the dry film thickness of the adhesive layer was 4 μm, and the layer A laminate consisting of (U1-1)/adhesive layer/laminate (U2)/adhesive layer/LLDPE layer was produced. The obtained laminate was evaluated according to the method (4) above.

The obtained laminate was cut to obtain two covering materials each having a size of 50 cm×50 cm. The two laminates were superimposed so that the LLDPE layers faced each other inside, and the three sides were heat-sealed with a width of 10 mm to prepare a three-sided vacuum packaging bag.

From the opening of the obtained vacuum packaging bag, a small bag containing calcium oxide as a heat insulating core material and an adsorbent is filled, and a vacuum heat insulating panel manufacturing apparatus (Model KT-500RD manufactured by NPC Co., Ltd.) is used. A vacuum heat insulating material was produced by sealing the vacuum packaging bag in a state of an internal pressure of 2.0 Pa at °C. A glass fiber dried in an atmosphere of 160° C. for 1 hour was used as a heat-insulating core material. The obtained vacuum heat insulating material was evaluated according to the methods (7) and (8) above.

[Examples 2 to 13, Comparative Examples 1 to 9]
A laminate and a vacuum heat insulating material were produced and evaluated in the same manner as in Example 1, except that the laminate as shown in Table 1 was produced. In addition, the laminates obtained in Examples 3 to 8, 10 and 13 were evaluated for bubble generation according to the method (5) above. Further, the vacuum heat insulating materials obtained in Examples 5 to 7, 10 and 13 and Comparative Example 8 were evaluated for pinhole generation rate according to the method (6) above.

The vacuum insulation materials obtained in Examples 1 to 13 have a smaller change in thermal conductivity over time than the vacuum insulation materials obtained in Comparative Examples 1 to 9, and the barrier properties inherent in the vacuum insulation materials are at a high level. It is suggested that the When the laminate (U2) is not used, the laminate (U1) is damaged in a vacuum, resulting in a decrease in gas barrier properties and an increase in thermal conductivity. Further, when the laminate (U1) is not used, even if the laminate (U2) is used, it is confirmed that the gas barrier property is lowered due to moisture absorption of the laminate (U2), resulting in an increase in thermal conductivity. When the heat treatment temperature of the layer (Y1c) is low, the reaction between the aluminum-containing metal oxide (A) and the inorganic phosphorus compound (BI) is insufficient, and a polar group having a high affinity for water is present, resulting in a laminate A decrease in the water vapor barrier property of (U1) is confirmed. By using the layered body (U1) and the layered body (U2) and providing the layered body (U1) with high water vapor barrier property on the outside of the layered body (U2), it is possible to maintain high gas barrier property even under high temperature and high humidity. Insulation can maintain excellent thermal conductivity.

As described above, the vacuum heat insulating material using the laminate of the present invention can maintain excellent heat insulating performance over a long period of time, especially when used under high temperature and high humidity conditions.

Claims (11)

A laminate (U1) and a laminate (U2) are provided, and the laminate (U1) includes a substrate (X1) containing a thermoplastic resin and a layer (Y1) on at least one surface of the substrate (X1). and has a water vapor transmission rate (Wf) of 0.9 g/( ^m day) or less after storage for 30 days under conditions of 70°C and 90% RH, and the laminate (U2) is A base material (X2) made of a polyvinyl alcohol-based resin and an aluminum deposition layer (Y2) on at least one surface of the base material (X2), and at least one laminate (U1) comprising at least one laminate A vacuum heat insulating material provided on the outside of (U2) , wherein the laminate (U1) and the laminate (U2) are laminated via a polyamide film . 2. The vacuum heat insulating material according to claim 1, wherein the substrate (X2) is a film comprising an ethylene-vinyl alcohol copolymer having an ethylene unit content of 10 to 65 mol % and a degree of saponification of 90 mol % or more. 3. The vacuum heat insulating material according to claim 1, wherein the substrate (X1) is made of at least one thermoplastic resin selected from the group consisting of polyolefin resins, polyester resins and polyamide resins. The vacuum heat insulating material according to any one of claims 1 to 3, wherein the layer (Y1) is an aluminum deposition layer (Y1a). The layer (Y1) is a layer (Y1c) containing a reaction product (R) of a metal oxide (A) containing aluminum and an inorganic phosphorus compound (BI), and the infrared absorption spectrum of the layer (Y1c) is 800 to The vacuum heat insulating material according to any one of claims 1 to 3, wherein the maximum absorption wave number in the region of 1,400 cm ^-1 is in the range of 1,080 to 1,130 cm ^-1 . Any one of claims 1 to 5, wherein the laminate (U1) has a layer (Z1) directly laminated to the layer (Y1), and the layer (Z1) contains a polymer (BO) containing phosphorus atoms. The vacuum insulation material described in . The vacuum according to claim 6, wherein the layer (Z1) contains a polymer (C) having at least one functional group selected from the group consisting of hydroxyl groups, carboxyl groups, carboxylic acid anhydride groups, and salts of carboxyl groups. Insulation. Vacuum insulation according to claim 6 or 7, wherein the polymer (BO) comprises poly(vinylphosphonic acid). The vacuum heat insulating material according to any one of claims 1 to 8, comprising the laminate (U1) as the outermost layer. The vacuum heat insulating material according to any one of claims 1 to 9, comprising two or more laminates (U1). The vacuum heat insulating material according to any one of claims 1 to 10 , comprising the base material (X1) as the outermost layer and the base material (X2) inside the aluminum deposition layer (Y2).