JP5330179B2 - Vacuum insulation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vacuum heat insulator, which can maintain an excellent heat-insulating effect without deterioration of gas barrier property during a manufacturing process. <P>SOLUTION: In the vacuum heat insulator 10, a packaging material 11 is formed using a laminated product including a base material and a gas barrier layer. The gas barrier layer is formed of a composition including a hydrolytic condensate of a compound (L) and a neutralized material of a polymer (X) containing carboxyl group or carboxylic anhydride group. The compound (L) includes a specific compound (A) containing M<SP>1</SP>(Al, Ti or Zr) coupled with hydrolytic characteristic group and a specific compound (B) containing Si coupled with hydrolytic characteristic group. The -COO-group of the polymer (X) is at least partially neutralized with divalent or more metal ions. The compound (B) of 80 mol% or more is composed of a compound represented by a predetermined formula. The ratio of [the mole number of M<SP>1</SP>of the compound (A)]/[the mole number of Si atom of the compound (B)] ranges from 0.1/99.9 to 35.0/65.0. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a vacuum heat insulator, and for example, relates to a vacuum heat insulator that can be used in various applications that require heat insulation and cold insulation.

  Conventionally, a heat insulating material made of polyurethane foam has been used as a heat insulating material for a refrigerator or a heat insulating panel for a residential heat insulating wall. In recent years, vacuum insulators composed of a gas barrier laminate film and a core material have been used as a superior material instead of this. Along with this, the applications and usage conditions of vacuum insulators have also diversified, and the performance level required for vacuum insulators has increased.

  A vacuum heat insulating body composed of a gas barrier laminate film and a core material is characterized in that it can be made thinner and lighter than a conventional heat insulating body made of polyurethane foam. In recent years, natural refrigerant heat pump water heaters, which have become popular as high-efficiency hot water supply systems, are commonly used to boil hot water at low electricity prices at night and to keep warm in hot water storage tanks. Volume can be a problem, but this problem can be mitigated by using a thin vacuum insulator.

  Aluminum foil is mainly used as the gas barrier material of the vacuum heat insulator, but aluminum is a good conductor of heat. Therefore, a so-called heat bridge in which heat is conducted through the aluminum portion of the laminate film is generated, and there is a problem that the heat insulating performance is deteriorated.

  For the purpose of solving the problem of heat bridge, a vacuum heat insulator using a gas barrier film using a thin metal layer as a gas barrier layer or a gas barrier film using a gas barrier layer made of a metal oxide has been proposed. Such a gas barrier film can be obtained by depositing a metal (such as aluminum) or a metal oxide (such as silica or alumina) on the surface of a film such as a polyester film or an ethylene-vinyl alcohol copolymer film. For example, a gas barrier film obtained by vapor-depositing aluminum on a film made of an ethylene-vinyl alcohol copolymer resin is used for the vacuum heat insulator described in Patent Document 1.

  However, pinholes are easily generated in the vapor deposition layer obtained by the vapor deposition method. For example, when manufacturing a laminate film or transporting a product, pinholes may occur in the deposited layer. In addition, defects such as pinholes may occur in the vapor deposition layer, which can cope with the expansion / contraction of the base material due to changes in use temperature. As a result, when the vapor deposition layer is used as a gas barrier layer, problems such as low gas barrier properties and unstable gas barrier properties are likely to occur, and there is a problem in reliability.

  In order to cope with such a problem, a vacuum insulator using a laminate in which a gas barrier layer made of a resin and an inorganic layered compound is formed on a vapor deposition layer made of a metal compound (alumina or the like) has been proposed. (Patent Document 2). However, the gas barrier property is still insufficient, and the maintenance of a sufficient heat insulating effect over a long period of time has not been achieved.

  As a result of investigations to solve the above-mentioned problems, the present inventors have found that an excellent heat insulation effect can be maintained over a long period of time by using a specific gas barrier layer as a packaging material for a vacuum heat insulator. (Patent Document 3). The gas barrier layer is obtained by immersing a gas barrier layer composed of a composition containing a hydrolysis condensate of a metal alkoxide and a polymer containing a —COO— group in a solution containing a divalent or higher metal ion. . By this treatment, the —COO— group in the polymer is neutralized.

JP-A-10-122477 Japanese Patent Laid-Open No. 11-257574 JP 2006-308086 A

  According to the method of Patent Document 3, it is possible to dramatically improve the characteristics of the gas barrier layer. However, in order to apply to a wide range of uses, there is a need for a gas barrier laminate capable of maintaining a higher gas barrier property for a long period without causing a decrease in gas barrier property in the production process. In addition, in order to improve production efficiency, the dimensional stability at the time of processing such as laminating and the flexibility of the gas barrier laminate are increased, and the mechanical properties of the gas barrier laminate are added to the mechanical properties inherent to the base material. It is necessary to bring close physical properties. As a result of repeated studies to solve the above problems, the present inventors have found that the above problems can be solved by thinning the gas barrier layer while maintaining the gas barrier properties and strength. However, when the gas barrier layer disclosed in Patent Document 3 is thinned, the gas barrier property may decrease exponentially.

  In view of such a situation, one of the objects of the present invention is to provide a vacuum insulator that maintains an excellent heat insulating effect over a long period of time without deteriorating gas barrier properties in the production process.

  As a result of repeated studies to achieve the above object, the present inventors have found that an excellent gas barrier layer can be obtained by using a specific composition. Furthermore, it discovered that the said objective can be achieved by using the gas-barrier laminated body containing this gas barrier layer for the packaging material of a vacuum heat insulating body, and came to completion of this invention.

That is, the vacuum heat insulating body of the present invention is a vacuum heat insulating body including a core material and a packaging material for wrapping the core material, and a space portion in the packaging material is in a vacuum state, and the packaging material is a gas barrier laminate. The gas barrier laminate includes a base material and at least one layer having gas barrier properties laminated on the base material. The layer having gas barrier property includes a hydrolysis condensate of at least one compound (L) containing a hydrolyzable characteristic group, and at least one functional group selected from a carboxyl group and a carboxylic anhydride group. It consists of a composition containing the neutralized material of polymer (X) to contain. The compound (L) includes a compound (A) and a compound (B) containing Si to which a hydrolyzable characteristic group is bonded. The compound (A) is at least one compound represented by the following formula (I).
M ¹ X ¹ _m Y ¹ _nm (I)
[In Formula (I), M ¹ represents any one selected from Al, Ti, and Zr. X ¹ represents any one selected from F, Cl, Br, I, OR ¹ , R ² COO, R ³ COCHCOR ⁴ , and NO ₃ . Y ¹ represents any one selected from F, Cl, Br, I, OR ⁵ , R ⁶ COO, R ⁷ COCHCOR ⁸ , NO ₃ and R ⁹ . R ¹ , R ² , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group. n is equal to the valence of M ¹ . m represents an integer of 1 to n. ]

The compound (B) includes at least one compound represented by the following formula (II).
Si (OR ¹⁰ ) _p R ¹¹ _4-pq X ² _q (II)
[In the formula (II), R ¹⁰ represents an alkyl group. R ¹¹ represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X ² represents a halogen atom. p and q represent the integer of 0-4 each independently. 1 ≦ p + q ≦ 4. ]

At least a part of the —COO— group contained in the functional group of the polymer (X) is neutralized with a divalent or higher valent metal ion. The proportion of the compound represented by the formula (II) in the compound (B) is 80 mol% or more. In the composition, a ratio of [number of moles of the M ¹ atom derived from the compound (A)] / [number of moles of Si atom derived from the compound (B)] is 0.1 / 99.9 to 35. It is in the range of 0.0 / 65.0.

  The gas barrier laminate used in the present invention exhibits high gas barrier properties even when the gas barrier layer is thinned, and has excellent toughness. Therefore, the gas barrier laminate exhibits stable gas barrier performance without being affected by an impact during manufacture or handling of the gas barrier laminate. Therefore, the vacuum heat insulating body of the present invention manufactured using the gas barrier laminate can maintain the internal pressure of the space portion in the packaging material for wrapping the core material of the vacuum heat insulating body for a long time. Therefore, the thermal conductivity of the vacuum heat insulator can be kept low, and stable high heat insulation performance can be exhibited.

  Further, in the gas barrier laminate used in the present invention, the gas barrier layer can be made thin while maintaining high characteristics, and therefore the mechanical properties of the gas barrier laminate can be brought close to those of the base film. Therefore, the gas barrier laminate used in the present invention is excellent in mechanical properties such as flexibility and tensile strength and elongation, and dimensional stability during processing.

  In addition, when the vapor deposition layer of metal or metal oxide and the gas barrier layer used in the present invention are used in combination, the gas barrier layer protects the vapor deposition layer and suppresses the occurrence of defects such as pinholes. Even if it occurs, the influence of the pinhole is reduced by the high gas barrier property of the gas barrier layer. Therefore, by using a vapor deposition layer of metal or metal oxide in combination with the gas barrier layer used in the present invention, a vacuum insulator having particularly excellent characteristics can be obtained.

It is sectional drawing which shows an example about the vacuum heat insulating body of this invention. It is sectional drawing which shows another example about the vacuum heat insulating body of this invention.

  Embodiments of the present invention will be described below. In the following description, a specific compound may be exemplified as a substance that exhibits a specific function, but the present invention is not limited to this. In addition, the materials exemplified may be used alone or in combination unless otherwise specified.

  The vacuum heat insulating body of the present invention includes a core material and a packaging material for packaging the core material. The space in the packaging material is in a vacuum state. The packaging material includes a specific gas barrier laminate. Hereinafter, the gas barrier laminate may be referred to as “the gas barrier laminate of the present invention” or simply “gas barrier laminate”. The gas barrier laminate of the present invention includes a substrate and at least one specific gas barrier layer (a layer having gas barrier properties) laminated on the substrate. Hereinafter, the specific gas barrier layer may be referred to as “the gas barrier layer of the present invention” or simply “the gas barrier layer”.

  The configuration of the packaging material used in the vacuum insulator of the present invention is not limited as long as it includes the gas barrier laminate of the present invention, and is determined according to the purpose of use of the vacuum insulator and the manufacturing method. An example of the packaging material is a packaging material obtained by heat-sealing the gas barrier laminate of the present invention.

  In the vacuum heat insulating body of the present invention, all of the packaging material may be formed using the gas barrier laminate of the present invention, or a part of the packaging material may be formed of a material other than the gas barrier laminate. . In one example, the gas barrier laminate of the present invention is used for 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100% of the area when the packaging material is developed. Hereinafter, the gas barrier laminate of the present invention will be described in detail.

[Gas barrier laminate]
The gas barrier laminate used in the present invention includes a substrate and at least one layer having gas barrier properties laminated on the substrate. The layer (the gas barrier layer of the present invention) is made of a specific composition. The composition comprises a hydrolyzate condensate of at least one compound (L) containing a hydrolyzable characteristic group and at least one functional group selected from a carboxyl group and a carboxylic anhydride group. And a neutralized product of the combined (X). The compound (L) is at least one compound containing a hydrolyzable characteristic group, and is typically at least one compound containing a metal atom to which the hydrolyzable characteristic group is bonded. . The compound (L) includes a compound (A) and a compound (B) containing Si to which a hydrolyzable characteristic group is bonded. Hereinafter, at least one functional group selected from a carboxyl group and a carboxylic anhydride group contained in the polymer (X) may be referred to as “functional group (F)”. At least a part of the —COO— group contained in the functional group (F) is neutralized with a divalent or higher valent metal ion. From another viewpoint, the —COO— group contained in the functional group (F) constitutes a salt with a divalent or higher metal ion.

  The gas barrier layer is laminated on at least one surface of the substrate. A gas barrier layer may be laminated | stacked only on the single side | surface of a base material, and may be laminated | stacked on both surfaces of a base material. The gas barrier laminate used in the present invention may include layers other than the gas barrier layer.

  The proportion of the hydrolyzed condensate of compound (L) and the neutralized product of polymer (X) in the composition is, for example, 50% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight. % Or more, or 98% by weight or more.

[Hydrolysis condensate]
The composition which comprises a gas barrier layer contains the hydrolysis-condensation product of a compound (L). By hydrolyzing the compound (L), at least a part of the characteristic group of the compound (L) is substituted with a hydroxyl group. Furthermore, the hydrolyzate condenses to form a compound in which metal atoms are bonded through oxygen. When this condensation is repeated, it becomes a compound that can be regarded as a metal oxide substantially. Here, in order for this hydrolysis and condensation to occur, it is important that the compound (L) contains a hydrolyzable characteristic group (functional group). When those groups are not bonded, hydrolysis / condensation reaction does not occur or becomes extremely slow, and it is difficult to obtain the effects of the present invention. Si may be classified as a metalloid element, but in this specification, Si is described as a metal.

  This hydrolysis-condensation product can be manufactured from a specific raw material using the method used by the well-known sol-gel method, for example. The raw materials include compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed / condensed, A compound in which the compound (L) is completely hydrolyzed and partly condensed, or a combination thereof is used. These raw materials may be produced by a known method, or commercially available ones may be used. Although there is no particular limitation, for example, a condensate obtained by hydrolysis and condensation of about 2 to 10 molecules can be used as a raw material. Specifically, for example, a material obtained by hydrolyzing and condensing tetramethoxysilane into a dimer to 10-mer linear condensate can be used as a raw material.

Compound (A) is at least one compound represented by the following formula (I).
M ¹ X ¹ _m Y ¹ _nm (I)
[In Formula (I), M ¹ represents any one selected from Al, Ti, and Zr. X ¹ represents any one selected from F, Cl, Br, I, OR ¹ , R ² COO, R ³ COCHCOR ⁴ , and NO ₃ . Y ¹ represents any one selected from F, Cl, Br, I, OR ⁵ , R ⁶ COO, R ⁷ COCHCOR ⁸ , NO ₃ and R ⁹ . R ¹ , R ² , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group. n is equal to the valence of M ¹ . m represents an integer of 1 to n. ]

X ¹ and Y ¹ may be the same or different. M ¹ is preferably Al from the viewpoint of gas barrier properties of the resulting gas barrier laminate. X ¹ is a group having hydrolyzability. X ¹ is preferably any one selected from Cl, OR ¹ , and NO ₃ , and more preferably OR ¹ . Y ¹ is preferably any one selected from Cl, OR ⁵ , and NO ₃ , and more preferably OR ⁵ .

The carbon number of the alkyl group used for R ¹ , R ² , R ⁵ and R ⁶ is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, for example 1 or more and 4 or less. R ¹ and R ⁵ are preferably a methyl group, an ethyl group, an iso-propyl group, an n-butyl group, or a t-butyl group, and particularly preferably an iso-propyl group or an n-butyl group. The number of carbon atoms of the alkyl group used for R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less. R ³ , R ⁴ , R ⁷ and R ⁸ are preferably a methyl group or an ethyl group. R ³ COCHCOR ⁴ and R ⁷ COCHCOR ⁸ can be coordinated to atom M ¹ at the carbonyl group. R ⁹ is preferably a methyl group or an ethyl group. R ⁹ usually does not have a functional group. In the formula (I), [nm] may be 0 or 1, for example.

  Specific examples of the compound (A) include aluminum chloride, aluminum triethoxide, aluminum trinormal propoxide, aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tri-t-butoxide, aluminum triacetate, aluminum acetylacetonate, nitric acid Aluminum compounds such as aluminum; titanium compounds such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra (2-ethylhexoxide), titanium tetramethoxide, titanium acetylacetonate, titanium ethylacetoacetate; zirconium tetranormal Zirconium compounds such as propoxide, zirconium tetrabutoxide, zirconium tetraacetylacetonate and the like are included. Preferable examples of compound (A) include aluminum triisopropoxide and aluminum trinormal butoxide.

The compound (B) is at least one Si compound containing Si to which a hydrolyzable characteristic group is bonded. The compound (B) includes at least one compound represented by the following formula (II).
Si (OR ¹⁰ ) _p R ¹¹ _4-pq X ² _q (II)
[In the formula (II), R ¹⁰ represents an alkyl group. R ¹¹ represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X ² represents a halogen atom. p and q represent the integer of 0-4 each independently. 1 ≦ p + q ≦ 4. ]

Examples of the alkyl group represented by R ¹⁰ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, and the like, preferably a methyl group or an ethyl group. Examples of the halogen atom represented by X ² include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. Examples of the alkyl group represented by R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, and an n-octyl group. As the aralkyl group, For example, benzyl group, phenethyl group, trityl group and the like can be mentioned. In addition, examples of the aryl group represented by R ¹¹ include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. Examples of the alkenyl group include a vinyl group and an allyl group.

  Specific examples of the compound (B) represented by the formula (II) include tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltri Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, and vinyltrichlorosilane are included. Preferred examples of the compound (B) represented by the formula (II) include tetramethoxysilane and tetraethoxysilane.

Compound (B) may further contain at least one compound represented by the following formula (III) in addition to the compound represented by formula (II). By containing the compound represented by the formula (III), the reduction in gas barrier properties under the production process and use conditions is further reduced.
Si (OR ¹² ) _r X ³ _s Z ³ _4-rs (III)
[In the formula (III), R ¹² represents an alkyl group. X ³ represents a halogen atom. Z ³ represents an alkyl group substituted with a functional group having reactivity with a carboxyl group. r and s each independently represent an integer of 0 to 3. 1 ≦ r + s ≦ 3. ]

Examples of the alkyl group represented by R ¹² include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, and the like, and preferably a methyl group or an ethyl group. Examples of the halogen atom represented by X ³ include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. Examples of the functional group having reactivity with a carboxyl group that Z ³ has include an epoxy group, an amino group, a hydroxyl group, a halogen atom, a mercapto group, an isocyanate group, a ureido group, an oxazoline group, and a carbodiimide group. Among these, an epoxy group, an amino group, an isocyanate group, a ureido group, or a halogen atom is present from the viewpoint of particularly reducing changes in appearance such as gas barrier properties and transparency under high temperature and high humidity conditions of the obtained gas barrier laminate. Preferably, for example, at least one selected from an epoxy group, an amino group, and an isocyanate group may be used. Examples of the alkyl group substituted with such a functional group include those exemplified for R ¹² .

  Specific examples of the compound represented by the formula (III) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrichlorosilane, γ-aminopropyltrisilane. Methoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltrichlorosilane, γ-bromopropyltrimethoxysilane, γ -Bromopropyltriethoxysilane, γ-bromopropyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrichlorosilane, γ-isocyanatopropyltrimethoxysilane , .Gamma. isocyanatopropyltriethoxysilane, .gamma. isocyanate propyl trichlorosilane, .gamma.-ureidopropyltrimethoxysilane, .gamma.-ureidopropyltriethoxysilane include .gamma. ureidopropyltrimethoxysilane trichlorosilane. Preferred examples of the compound represented by the formula (III) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, and γ-chloropropyltriethoxysilane. , Γ-aminopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.

  The present inventors have found that by using a hydrolysis condensate of compound (L) containing compound (A) and compound (B), the resulting gas barrier laminate has excellent gas barrier properties. . Furthermore, surprisingly, in the gas barrier laminate, as described above, when the gas barrier layer is thinned, the gas barrier property is decreased exponentially and the excellent gas barrier property cannot be maintained. It was newly found that by using the hydrolysis condensate of L), a high gas barrier property can be maintained even if the gas barrier layer is thinned.

In any case where the compound (B) is composed only of the compound of the formula (II) and the compound (B) contains the compound of the formula (III), [the M ¹ atom derived from the compound (A) The ratio of [number of moles] / [number of moles of Si atoms derived from compound (B)] is 0.1 / 99.9 to 35.0 / 65.0 (for example, 0.1 / 99.9 to 30.0). /70.0, or 0.1 / 99.9 to 29.9 / 70.1). When the molar ratio is in this range, a gas barrier laminate exhibiting excellent gas barrier properties as described above can be obtained. If the ratio of M ¹ to the total of M ¹ and Si is lower than 0.1 mol%, the moisture resistance is lowered, the gas barrier property under high temperature and humidity conditions is lowered, and the appearance may be deteriorated. is there. Moreover, when the ratio is higher than 35 mol%, there is a problem that the gas barrier property is lowered. Further, from the viewpoint of better gas barrier properties, the ratio of [number of moles of M ¹ atom derived from compound (A)] / [number of moles of Si atom derived from compound (B)] is preferably 1.2. /98.8 to 30.0 / 70.0, more preferably 1.9 / 98.1 to 30.0 / 70.0, and even more preferably 2.8 / 97.2. It is in the range of ~ 30.0 / 70.0. The ratio is in the range of 0.5 / 99.5 to 30.0 / 70.0, in the range of 1.5 / 98.5 to 20.0 / 80.0, or 2.5 / 97.5 to 10 It may be in the range of 0.0 / 90.0.

  The present inventors use, in addition to the compound represented by the compound (A) and the formula (II), a hydrolysis condensate of the compound (L) further comprising a compound represented by the formula (III), It has been found that even under high temperature and high humidity conditions, the gas barrier laminate exhibits further excellent gas barrier properties.

  In the case where the compound (B) contains a compound represented by the formula (III), it is preferable that the following conditions are further satisfied. That is, the ratio of [number of moles of Si derived from the compound represented by formula (II)] / [number of moles of Si derived from the compound represented by formula (III)] was 99.5 / 0.5 to It is preferably in the range of 80.0 / 20.0. When this ratio is larger than 99.5 / 0.5, the gas barrier property of the resulting gas barrier laminate may be lowered under high temperature and high humidity conditions. Moreover, when this ratio is smaller than 80/20, the gas barrier property of the gas barrier laminate obtained may deteriorate. Further, this ratio is more preferably in the range of 98.0 / 2.0 to 89.9 / 10.1 from the viewpoint of improving the gas barrier properties of the gas barrier laminate.

  The total ratio of the compound (A) and the compound (B) in the compound (L) is, for example, 80 mol% or more and 100 mol% or less, 90 mol% or more, 95 mol% or more, 98 mol% or more, 99 It may be mol% or more, or 100 mol%.

  The proportion of the compound represented by the formula (II) in the compound (B) (Si compound as the compound (L)) is 80 mol% or more and 100 mol% or less, for example, 90 mol% or more, 95 mol% or more. 98 mol% or more, or 100 mol%. In one example, the compound (B) consists only of the compound represented by the formula (II), and in another example, the compound (B) is represented by the compound represented by the formula (II) and the formula (III). It consists only of a compound.

  The number of molecules condensed in the hydrolyzed condensate of compound (L) can be controlled by the conditions for performing hydrolysis and condensation. For example, the number of molecules to be condensed can be controlled by the amount of water, the type and concentration of the catalyst, the temperature at which hydrolysis condensation is performed, and the like.

  Since the gas barrier property of the composition constituting the gas barrier layer becomes better, [weight of inorganic component derived from compound (L)] / [weight of organic component derived from compound (L)] The ratio of the “total with the weight of the organic component derived from the polymer (X)” is preferably in the range of 20.0 / 80.0 to 80.0 / 20.0, and 30.5 / 69.5 More preferably, it is in the range of 70/30.

  The weight of the inorganic component derived from the compound (L) can be calculated from the weight of the raw material used when preparing the composition. That is, compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed, compound (L) Assuming that the product is completely hydrolyzed and partly condensed, or a combination of these, is completely hydrolyzed and condensed into a metal oxide, and the weight of the metal oxide is calculated as compound (L). It is regarded as the weight of the inorganic component derived from.

More specifically describing the calculation of the weight of the metal oxide, when the compound (A) represented by the formula (I) does not contain R ⁹ , when it is completely hydrolyzed and condensed, the composition formula is This is a compound represented by M ^{1 On} _{/ 2} . In addition, when the compound (A) represented by the formula (I) contains R ⁹ , when it is completely hydrolyzed / condensed, the compound represented by the formula M ¹ O _{m / 2} R ⁹ _nm It becomes. Of this compound, the M ¹ O _{m / 2} portion is a metal oxide. R ⁹ is an organic component derived from the compound (L). Moreover, it calculates similarly about a compound (B). At this time, R ¹¹ and Z ³ are organic components derived from the compound (L). The value obtained by dividing the weight of the metal oxide by the weight of the active ingredient added until the end of the step (i) described later and multiplying the value by 100 is the content (%) of the hydrolysis condensate in this specification. It is. Here, the weight of the active ingredient refers to a compound or solvent generated in the process in which the above-described compound (L) is converted into a metal oxide from the weight of all the ingredients added until the end of the step (i) described later. This is the weight excluding the weight of volatile components.

  When the polymer (X) is neutralized by ions not containing metal ions (for example, ammonium ions), the weight of the ions (for example, ammonium ions) is also the weight of the organic component derived from the polymer (X). Added to.

[Carboxylic acid-containing polymer (polymer (X))]
The composition constituting the gas barrier layer includes a neutralized product of a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group. Hereinafter, the polymer may be referred to as “carboxylic acid-containing polymer”. The neutralized product of the carboxylic acid-containing polymer can be obtained by neutralizing at least a part of the —COO— group contained in the functional group of the carboxylic acid-containing polymer with a divalent or higher metal ion. The carboxylic acid-containing polymer has two or more carboxyl groups or one or more carboxylic anhydride groups in one polymer molecule. Specifically, a polymer containing two or more structural units having one or more carboxyl groups such as an acrylic acid unit, a methacrylic acid unit, a maleic acid unit, and an itaconic acid unit in one molecule of the polymer is used. it can. Moreover, the polymer containing the structural unit which has the structure of carboxylic anhydrides, such as a maleic anhydride unit and a phthalic anhydride unit, can also be used. One type or two types of structural units having one or more carboxyl groups and / or structural units having a structure of carboxylic anhydride (hereinafter, these may be collectively referred to as “carboxylic acid-containing units (G)”) The above may be contained in the carboxylic acid-containing polymer.

  Moreover, the gas barrier property laminated body with favorable gas barrier property is obtained by making the content rate of the carboxylic acid content unit (G) which occupies for all the structural units of a carboxylic acid containing polymer into 10 mol% or more. The content is more preferably 20 mol% or more, further preferably 40 mol% or more, and particularly preferably 70 mol% or more. In addition, when a carboxylic acid containing polymer contains both the structural unit which contains 1 or more of carboxyl groups, and the structural unit which has a structure of a carboxylic anhydride, the sum total of both should just be said range.

  Other structural units other than the carboxylic acid-containing unit (G) that may be contained in the carboxylic acid-containing polymer are not particularly limited, but are methyl acrylate units, methyl methacrylate units, ethyl acrylate units, methacrylic acid. Structural units derived from (meth) acrylic esters such as ethyl units, butyl acrylate units and butyl methacrylate units; structural units derived from vinyl esters such as vinyl formate units and vinyl acetate units; styrene units, One or more structural units selected from p-styrene sulfonic acid units; structural units derived from olefins such as ethylene units, propylene units, and isobutylene units. When the carboxylic acid-containing polymer contains two or more structural units, the carboxylic acid-containing polymer is in the form of an alternating copolymer, a random copolymer, a block copolymer, or a taper. It may be in the form of a type copolymer.

  Specific examples of the carboxylic acid-containing polymer include polyacrylic acid, polymethacrylic acid, and poly (acrylic acid / methacrylic acid). The carboxylic acid-containing polymer may be at least one polymer selected from polyacrylic acid and polymethacrylic acid. Specific examples in the case of containing other structural units other than the above-described carboxylic acid-containing unit (G) include ethylene-maleic anhydride copolymers, styrene-maleic anhydride copolymers, and isobutylene-maleic anhydride. Examples thereof include an alternating copolymer, an ethylene-acrylic acid copolymer, and a saponified ethylene-ethyl acrylate copolymer.

  The molecular weight of the carboxylic acid-containing polymer is not particularly limited, but the number average molecular weight is 5,000 or more from the viewpoint of excellent gas barrier properties of the resulting gas barrier laminate and excellent mechanical properties such as drop impact strength. Preferably, it is preferably 10,000 or more, and more preferably 20,000 or more. The upper limit of the number average molecular weight of the carboxylic acid-containing polymer is not particularly limited, but is generally 1,500,000 or less.

  Further, although the molecular weight distribution of the carboxylic acid-containing polymer is not particularly limited, from the viewpoint of improving the surface appearance such as haze of the gas barrier laminate and the storage stability of the solution (U) described later, The molecular weight distribution represented by the weight average molecular weight / number average molecular weight ratio of the carboxylic acid-containing polymer is preferably in the range of 1-6, more preferably in the range of 1-5, and in the range of 1-4. More preferably.

[Neutralization (ionization)]
The neutralized product of the carboxylic acid-containing polymer is a divalent or higher-valent metal having at least a part of at least one functional group (functional group (F)) selected from the carboxyl group and carboxylic anhydride group of the carboxylic acid-containing polymer. Obtained by neutralization with ions. In other words, this polymer contains a carboxyl group neutralized with a divalent or higher metal ion.

  It is important that the metal ion neutralizing the functional group (F) is divalent or higher. When the functional group (F) is not neutralized or neutralized only by monovalent ions, a laminate having good gas barrier properties cannot be obtained. Specific examples of divalent or higher metal ions include calcium ions, magnesium ions, divalent iron ions, trivalent iron ions, zinc ions, divalent copper ions, lead ions, divalent mercury ions, barium ions, A nickel ion, a zirconium ion, an aluminum ion, a titanium ion, etc. can be mentioned. For example, the divalent or higher valent metal ion may be at least one ion selected from the group consisting of calcium ion, magnesium ion, barium ion, zinc ion, iron ion and aluminum ion.

  For example, 10 mol% or more (for example, 15 mol% or more) of the —COO— group contained in the functional group (F) of the carboxylic acid-containing polymer is neutralized with a divalent or more metal ion. When the carboxyl group and / or carboxylic anhydride group in the carboxylic acid-containing polymer is neutralized with a divalent or higher metal ion, the gas barrier laminate exhibits good gas barrier properties.

  Note that the carboxylic anhydride group is considered to contain two —COO— groups. That is, when there are a moles of carboxyl groups and b moles of carboxylic anhydride groups, the total number of —COO— groups contained is (a + 2b) moles. The proportion of the -COO- group contained in the functional group (F) that is neutralized with a divalent or higher metal ion is preferably 60 mol% or more and 100 mol% or less, more preferably 70 mol% or more. More preferably, it is 80 mol% or more. By increasing the proportion of neutralization, higher gas barrier properties can be realized.

  The degree of neutralization (ionization degree) of the functional group (F) is determined by measuring the infrared absorption spectrum of the gas barrier laminate by the ATR method (total reflection measurement method) or scraping the gas barrier layer from the gas barrier laminate, The infrared absorption spectrum can be obtained by measuring by the KBr method. It can also be obtained from the value of the fluorescent X-ray intensity of the metal element used for ionization by fluorescent X-ray measurement.

The infrared absorption spectrum peak attributed to C = O stretching vibration of the carboxyl group or carboxylic anhydride group before the neutralization (ionization front) is observed in the range of 1600cm ^-1 ~1850cm ^-1, neutralization (ionization ), The C═O stretching vibration of the carboxyl group is observed in the range of 1500 cm ^{−1 to} 1600 cm ⁻¹ , so that both can be separated and evaluated in the infrared absorption spectrum. Specifically, the ratio is obtained from the maximum absorbance in each range, and the ionization degree of the polymer constituting the gas barrier layer in the gas barrier laminate can be calculated using a calibration curve prepared in advance. A calibration curve can be created by measuring infrared absorption spectra for a plurality of standard samples having different degrees of neutralization.

  When the film thickness of the gas barrier layer is 1 μm or less and the substrate contains an ester bond, the ester bond peak of the substrate is detected in the infrared absorption spectrum by the ATR method, and the carboxylic acid-containing polymer constituting the gas barrier layer Since it overlaps with the —COO— peak of (= polymer (X)), the degree of ionization cannot be determined accurately. Therefore, the ionization degree of the polymer (X) constituting the gas barrier layer having a thickness of 1 μm or less is calculated based on the result of the fluorescent X-ray measurement.

  Specifically, the ionization degree of the polymer (X) constituting the gas barrier layer laminated on the substrate not containing an ester bond is measured by an infrared absorption spectrum. Next, the fluorescence X-ray intensity of the metal element used for ionization is determined by fluorescent X-ray measurement for the laminate in which the degree of ionization is measured. Then, the same measurement is implemented about the laminated body from which only an ionization degree differs. A correlation between the degree of ionization and the fluorescent X-ray intensity of the metal element used for ionization is obtained, and a calibration curve is created. And X-ray fluorescence measurement is performed about the gas-barrier laminated body using the base material containing an ester bond, and an ionization degree is calculated | required based on the said calibration curve from the fluorescence X-ray intensity of the metal element used for ionization.

[Compound (P)]
The composition constituting the gas barrier layer may contain a compound (P) containing two or more amino groups. Compound (P) is a compound different from compound (L) and polymer (X). When the compound (P) is further included, at least a part of the —COO— group contained in the functional group (F) of the polymer (X) is neutralized and / or reacted with the compound (P); Become. As the compound (P), alkylene diamines, polyalkylene polyamines, alicyclic polyamines, aromatic polyamines, polyvinylamines, and the like can be used, but the gas barrier property of the gas barrier laminate is improved. Therefore, alkylene diamine is preferable.

  Specific examples of the compound (P) include hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane. , Xylylenediamine, chitosan, polyallylamine, polyvinylamine and the like. From the viewpoint of improving the gas barrier properties of the gas barrier laminate, ethylenediamine, propylenediamine, and chitosan are preferable.

  The molar ratio of [amino group contained in compound (P)] / [-COO-group contained in functional group of carboxylic acid-containing polymer] has better characteristics under high temperature and high humidity conditions of the gas barrier laminate. From the viewpoint of becoming, it is preferably in the range of 0.2 / 100 to 20/100, more preferably in the range of 0.5 / 100 to 15/100, and in the range of 1/100 to 10/100. It is particularly preferred.

  When adding the compound (P) to the carboxylic acid-containing polymer, the compound (P) may be neutralized with an acid in advance. Examples of the acid used for neutralization include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and carbonic acid. From the viewpoint of better gas barrier properties of the resulting gas barrier laminate, it is preferable to use hydrochloric acid, acetic acid, and carbonic acid.

[Compound Q]
The composition constituting the gas barrier layer may contain a compound (Q) containing two or more hydroxyl groups. When the compound (Q) is further included, at least a part of the —COO— group contained in the functional group (F) of the polymer (X) reacts with the compound (Q) to form an ester bond. It becomes. According to this configuration, the gas barrier property after elongation of the gas barrier laminate is improved. More specifically, by adding the compound (Q), the gas barrier layer is hardly damaged even when the gas barrier laminate is elongated. As a result, high gas barrier properties are maintained even after being stretched. For example, the gas barrier property of the gas barrier laminate is not easily lowered even after elongation due to tension during processing such as lamination.

  Compound (Q) is a compound different from compound (L) and polymer (X). The compound (Q) includes a low molecular weight compound and a high molecular weight compound. Preferred examples of the compound (Q) include polyvinyl alcohol, partially saponified polyvinyl acetate, ethylene-vinyl alcohol copolymer, polyethylene glycol, polyhydroxyethyl (meth) acrylate, polysaccharides such as starch, and starches. Polymer compounds such as polysaccharide derivatives derived from saccharides are included.

  Further, the composition constituting the gas barrier layer may be carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, phosphate, boric acid within the range not impairing the effects of the present invention. Salts, inorganic acid metal salts such as aluminate; organic acid metal salts such as oxalate, acetate, tartrate, stearate; acetylacetonate metal complexes such as aluminum acetylacetonate, titanocene, etc. Metal complexes such as cyclopentadienyl metal complexes and cyano metal complexes; layered clay compounds, crosslinking agents, plasticizers, antioxidants, ultraviolet absorbers, flame retardants and the like may be contained. The composition constituting the gas barrier layer may contain a metal oxide fine powder, a silica fine powder, and the like.

[Base material]
As a base material used for the gas barrier laminate of the present invention, a thermoplastic resin film or a thermosetting resin film can be used. Among these, a thermoplastic resin film is useful as a base material for a gas barrier laminate used for a vacuum heat insulator. Further, from the viewpoint of further enhancing the gas barrier property, a gas barrier resin film can also be used as the substrate. In addition, the base material may have a multilayer structure composed of a plurality of materials.

  Examples of the thermoplastic resin film include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate and copolymers thereof; polyamide 6, polyamide 66, Polyamide resins such as polyamide 12; polystyrene, poly (meth) acrylate, polyacrylonitrile, polyvinyl acetate, polycarbonate, polyarylate, regenerated cellulose, polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone And a film obtained by molding an ionomer resin or the like. As the base material of the laminate used for the vacuum insulator, a film made of polyethylene, polypropylene, polyethylene terephthalate, polyamide 6 or polyamide 66 is preferable. The thermoplastic resin film may be either an unstretched film or a stretched film, but a stretched film is preferred from the viewpoint of moldability.

  Examples of the material for the gas barrier resin film include an ethylene-vinyl alcohol copolymer or polyvinylidene chloride, and a sheet obtained by forming the resin into a film can be used as the gas barrier resin film. A preferred example of the gas barrier resin film is made of a stretched ethylene-vinyl alcohol copolymer. That is, a preferred example of the substrate is made of an ethylene-vinyl alcohol copolymer. An inorganic layer (for example, an inorganic layer containing aluminum atoms) may be disposed between the base material made of an ethylene-vinyl alcohol copolymer and the gas barrier layer.

  Further, the gas barrier laminate may further include an adhesive layer (H) disposed between the base material and the gas barrier layer. According to this structure, the adhesiveness of a base material and a gas barrier layer can be improved. The adhesive layer (H) made of an adhesive resin can be formed by treating the surface of the substrate with a known anchor coating agent or applying a known adhesive to the surface of the substrate. As a result of examining various adhesive resins, it is preferable that an adhesive resin containing a urethane bond and having a nitrogen atom (a nitrogen atom of the urethane bond) occupying the entire resin is in a range of 0.5 to 12% by weight. It was found. By using such an adhesive resin, the adhesion between the substrate and the gas barrier layer can be particularly enhanced. By strongly bonding the base material and the gas barrier layer through the adhesive layer (H), it is possible to suppress deterioration of the gas barrier property and appearance when the gas barrier laminate is subjected to processing such as printing or lamination. . The content of nitrogen atoms (urethane bond nitrogen atoms) contained in the adhesive resin is more preferably in the range of 2 to 11% by weight, and still more preferably in the range of 3 to 8% by weight.

  As the adhesive resin containing a urethane bond, a two-component reactive polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable.

  By increasing the thickness of the adhesive layer (H), the strength of the gas barrier laminate can be increased. However, when the adhesive layer (H) is too thick, the appearance deteriorates. The thickness of the adhesive layer (H) is preferably in the range of 0.03 μm to 0.18 μm. According to this configuration, when processing such as lamination is performed on the gas barrier laminate, it is possible to suppress deterioration of the gas barrier property and appearance, and further, the drop strength of the vacuum insulator using the gas barrier laminate can be reduced. Can be increased. The thickness of the adhesive layer (H) is more preferably in the range of 0.04 μm to 0.14 μm, and still more preferably in the range of 0.05 μm to 0.10 μm.

  In the gas barrier laminate used in the present invention, the total thickness of the gas barrier layers contained in the laminate is preferably 1.0 μm or less, for example 0.9 μm or less. By making the gas barrier layer thin, the dimensional change of the gas barrier laminate during processing such as laminating can be kept low. Further, by making the gas barrier layer thin, the flexibility of the gas barrier laminate is increased, and the mechanical properties of the gas barrier laminate can be brought close to the mechanical properties of the film itself used for the substrate. The thickness of one gas barrier layer is preferably 0.05 μm or more (for example, 0.15 μm or more) from the viewpoint of improving the gas barrier property of the gas barrier laminate. Further, the total thickness of the gas barrier layer is more preferably 0.1 μm or more (for example, 0.2 μm or more). The thickness of the gas barrier layer can be controlled by the concentration of the solution used for forming the gas barrier layer and the coating method.

  In addition, the laminate of the present invention may include a layer made of an inorganic material (hereinafter sometimes referred to as “inorganic layer”) between the base material and the gas barrier layer. From the viewpoint of obtaining a vacuum heat insulator having high heat insulation performance, an inorganic layer is preferably disposed between the substrate and the gas barrier layer. The inorganic layer can be formed of an inorganic material such as a metal or an inorganic oxide. The inorganic layer can be formed by a vapor deposition method such as a vapor deposition method.

  The inorganic substance which comprises an inorganic layer should just have a gas barrier property with respect to oxygen, water vapor | steam, etc. For example, the inorganic layer can be formed using a metal such as aluminum, an inorganic oxide such as aluminum oxide, silicon oxide, silicon oxynitride, magnesium oxide, tin oxide, or a mixture thereof. Among these, aluminum, aluminum oxide, silicon oxide, and magnesium oxide can be preferably used from the viewpoint of excellent barrier properties against gases such as oxygen and water vapor. In a preferred example, the inorganic layer contains aluminum atoms.

  Although the preferable thickness of an inorganic layer changes with kinds of inorganic substance which comprises an inorganic layer, it is the range of 2 nm-500 nm normally. Within this range, a thickness that provides good gas barrier properties and mechanical properties of the gas barrier laminate may be selected. When the thickness of the inorganic layer is less than 2 nm, the development of the barrier property of the inorganic layer with respect to gases such as oxygen and water vapor is not reproducible, and the sufficient gas barrier property may not be exhibited. When the thickness of the inorganic layer exceeds 500 nm, the gas barrier property of the inorganic layer tends to be lowered when the gas barrier laminate is pulled or bent. The thickness of the inorganic layer is preferably in the range of 5 to 200 nm, more preferably in the range of 10 to 100 nm.

  The inorganic layer can be formed by depositing an inorganic oxide on the substrate. Examples of the forming method include a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method (CVD), and the like. Among these, the vacuum evaporation method is preferably used from the viewpoint of productivity. As a heating method in performing vacuum deposition, any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable. Moreover, in order to improve the adhesiveness of an inorganic layer and a base material, and the denseness of an inorganic layer, you may vapor-deposit using a plasma assist method or an ion beam assist method. Moreover, in order to raise the transparency of an inorganic layer, you may employ | adopt the reactive vapor deposition method which blows in oxygen gas etc. and produces a reaction in the case of vapor deposition.

The gas barrier laminate of the present invention may include layers other than the base material and the gas barrier layer of the present invention. For example, the gas barrier laminate of the present invention may include layers such as a polyolefin layer, a gas barrier resin layer, a polyamide layer, and a polyester layer. Examples of the layer configuration of the gas barrier laminate of the present invention include the following configurations. Hereinafter, the multilayer film including the base material and the gas barrier layer of the present invention may be referred to as “gas barrier multilayer film”. The gas barrier multilayer film is also a kind of the gas barrier laminate of the present invention.
(1) Gas barrier multilayer film / polyolefin layer (hereinafter sometimes referred to as “PO layer”),
(2) Gas barrier multilayer film / gas barrier resin layer / PO layer,
(3) Gas barrier multilayer film / polyamide layer / PO layer,
(4) Polyamide layer / gas barrier multilayer film / PO layer,
(5) Polyamide layer / Gas barrier multilayer film / Polyester layer / PO layer,
(6) Gas barrier multilayer film / polyamide layer / gas barrier resin layer / PO layer,
(7) Polyamide layer / Gas barrier multilayer film / Gas barrier resin layer / PO layer,
(8) Gas barrier multilayer film / polyester layer / PO layer,
(9) Polyester layer / gas barrier multilayer film / PO layer,
(10) Gas barrier multilayer film / polyester layer / gas barrier resin layer / PO layer,
(11) Polyester layer / Gas barrier multilayer film / Gas barrier resin layer / PO layer,
(12) PO layer / gas barrier multilayer film / PO layer,
(13) PO layer / gas barrier multilayer film / gas barrier resin layer / PO layer,
(14) PO layer / gas barrier multilayer film / polyamide layer / PO layer,
(15) PO layer / polyamide layer / gas barrier multilayer film / PO layer,
(16) PO layer / gas barrier multilayer film / polyamide layer / gas barrier resin layer / PO layer,
(17) PO layer / polyamide layer / gas barrier multilayer film / gas barrier resin layer / PO layer,
(18) PO layer / gas barrier multilayer film / polyester layer / PO layer,
(19) PO layer / polyester layer / gas barrier multilayer film / PO layer,
(20) PO layer / gas barrier multilayer film / polyester layer / gas barrier resin layer / PO layer,
(21) PO layer / polyester layer / gas barrier multilayer film / gas barrier resin layer / PO layer.

  An adhesive layer may be disposed between the layers. The polyolefin layer (PO layer), polyamide layer, polyester layer, and gas barrier resin layer will be described below.

  The polyolefin layer can be used as a heat seal layer. The polyolefin layer includes low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-α olefin copolymer, ionomer, ethylene-acrylic acid. A layer made of a resin such as a copolymer, an ethylene-methyl acrylate copolymer, an ethylene-methacrylic acid copolymer, an ethylene-propylene copolymer, or a mixture of two or more thereof may be used. Moreover, you may use the sheet | seat which made those resin into a film. A preferred polyolefin layer is a layer made of low-density polyethylene, linear (linear) low-density polyethylene, high-density polyethylene, or polypropylene, or a sheet obtained by filming these resins. The polyolefin layer is more preferably made of linear (linear) low density polyethylene or polypropylene. These polyolefin layers may be either stretched or unstretched, but the polyolefin layer disposed on the inner surface when the gas barrier laminate is used as a packaging material is unstretched from the viewpoint of heat seal strength. It is preferable. Therefore, the polyolefin layer disposed on the inner surface when the gas barrier laminate is used as a packaging material is made of unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, or unstretched polypropylene. Most preferred.

  The thickness of the polyolefin layer is not particularly limited, but from the viewpoint of mechanical toughness, impact resistance, puncture resistance, etc., it is preferably in the range of 10 μm to 200 μm, and in the range of 20 μm to 150 μm. More preferred.

  As the polyamide layer, a film obtained by extruding at least one resin selected from nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, and nylon MXD6 resin can be used. These polyamide layers may be either stretched or unstretched. A preferred polyamide layer includes a film made of nylon 6 or nylon 66 (for example, a uniaxial or biaxially stretched film).

  The thickness of the polyamide layer is not particularly limited, but is preferably in the range of 5 μm to 200 μm from the viewpoint of mechanical toughness, impact resistance, puncture resistance, and the like, and may be in the range of 5 μm to 100 μm. More preferred.

  As the polyester layer, a film obtained by extruding at least one resin selected from polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, and polybutylene naphthalate can be used. These polyester layers may be stretched or unstretched. A preferred polyester layer is a sheet obtained by forming or stretching polyethylene terephthalate or polyethylene naphthalate. A vapor deposition layer made of a metal (for example, aluminum) or a metal oxide (for example, aluminum oxide or silicon oxide) may be provided on one side or both sides of the polyester layer. As a method for vapor deposition of metal or metal oxide, the same method as described later can be used.

  The thickness of the polyester layer is not particularly limited, but is preferably in the range of 5 μm to 200 μm from the viewpoint of mechanical toughness, impact resistance, puncture resistance, and the like, and may be in the range of 5 μm to 100 μm. More preferred.

  As the gas barrier resin layer, a layer made of a resin such as ethylene-vinyl alcohol copolymer or polyvinylidene chloride, or a sheet obtained by forming a film of these resins can be used. The gas barrier resin layer is preferably made of a stretched ethylene-vinyl alcohol copolymer. A vapor deposition layer made of a metal (for example, aluminum) or a metal oxide (for example, aluminum oxide or silicon oxide) may be provided on one surface or both surfaces of the gas barrier resin layer. As a method for vapor deposition of metal or metal oxide, the same method as described later can be used.

  The gas barrier multilayer film, the polyolefin layer, the polyamide layer, the polyester layer, and the gas barrier resin layer may be bonded to other layers by a known method such as a dry lamination method, a wet lamination method, or a hot melt lamination method. For example, an unstretched polyolefin film, a stretched polyolefin film, an unstretched polyamide film, a stretched polyamide film, and another layer (film) may be bonded together. Further, a polyolefin layer or a polyamide layer may be formed on another layer (film) by a known T-die extrusion method or the like. Moreover, you may arrange | position an adhesive layer between each layer as needed. The adhesive layer is formed using an anchor coat agent, an adhesive, an adhesive resin, or the like.

  Moreover, you may use oxygen absorbents, such as an unsaturated fatty acid, and moisture adsorption agents, such as a synthetic zeolite, a silica powder, an alumina powder, a lithium hydroxide powder, a barium hydroxide powder, as needed. The oxygen absorbent and the moisture absorbent may be included in each layer of the gas barrier laminate, or may be used in combination with the core material. Moreover, these can also be used as a core material.

  The core material used for the vacuum heat insulating body of the present invention is not particularly limited as long as it has heat insulating properties. Examples of the core material include pearlite powder, silica powder, precipitated silica powder, diatomaceous earth, calcium silicate, glass wool, rock wool, and resin foam (for example, styrene foam and urethane foam). Further, a hollow container made of resin or inorganic material, a honeycomb structure, or the like may be used as the core material.

  An example of a vacuum heat insulator when powder is used as a core is shown in FIG. 1 includes a packaging material 11 and a powder 12 packaged in the packaging material 11. Moreover, an example of the vacuum heat insulating body at the time of using a plate-shaped foam as a core material is shown in FIG. The vacuum heat insulating body 20 in FIG. 2 includes a packaging material 11 and a foam 22 packaged in the packaging material 11.

  In the vacuum heat insulating body of the present invention, the space in the packaging material is in a vacuum state. A vacuum state here does not necessarily mean an absolute vacuum state, but shows that the pressure of the space part in a packaging material is fully lower than atmospheric pressure. The internal pressure is determined based on required performance, ease of manufacture, and the like, but is usually 2 kPa (about 15 Torr) or less in order to exhibit heat insulation performance. In order to sufficiently exhibit the heat insulating effect of the vacuum heat insulating body of the present invention, the internal pressure of the packaging material is preferably 200 Pa (about 1.5 Torr) or less, more preferably 20 Pa or less, and 2 Pa or less. More preferably. Although there is no limitation in the minimum of the pressure of the space part in a packaging material, a pressure may exist in the range of 0.001 Pa-2 KPa.

  The vacuum heat insulating body of the present invention can be manufactured by a usual method. A vacuum heat insulator having an arbitrary shape and size can be formed according to the purpose of use. For example, the vacuum heat insulating body of the present invention can be manufactured by the following first to third methods. In the first method, first, two gas barrier laminates having a seal layer disposed on at least one surface are prepared. The two gas barrier laminates are superposed so that each heat seal layer is inside the packaging material, and any three sides are heat sealed. Next, the core material is filled into the packaging material. Next, the space inside the packaging material is evacuated, and the last side is heat-sealed as it is. In this way, a vacuum insulator is obtained. In the second method, first, one gas barrier laminate is folded so that the heat seal layer is inside the packaging material, and any two sides are heat sealed. Next, the core material is filled into the packaging material. Next, the space inside the packaging material is evacuated, and the last side is heat-sealed as it is. In this way, a vacuum insulator is obtained. In the third method, first, the core material is sandwiched between two gas barrier laminates, or the core material is sandwiched by bending one gas barrier laminate. Next, the peripheral edge where the gas barrier laminate is overlapped is heat-sealed leaving a vacuum exhaust port. Next, the space inside the packaging material is evacuated, and the vacuum exhaust port is heat-sealed as it is. In this way, a vacuum insulator is obtained.

  The fine structure of the gas barrier layer is not particularly limited. However, when the gas barrier layer has the fine structure described below, it is preferable because a decrease in gas barrier properties when the gas barrier laminate is stretched can be suppressed. A preferable fine structure is a sea-island structure composed of a sea phase (α) and an island phase (β). The island phase (β) is a region where the ratio of the hydrolysis condensate of the compound (L) is higher than that of the sea phase (α).

  Each of the sea phase (α) and the island phase (β) preferably further has a fine structure. For example, the sea phase (α) is composed of a sea phase (α1) mainly composed of a neutralized product of a carboxylic acid-containing polymer and an island phase (α2) mainly composed of a hydrolysis condensate of the compound (L). The sea island structure to be formed may be further formed. The island phase (β) is composed of a sea phase (β1) mainly composed of a neutralized product of a carboxylic acid-containing polymer and an island phase (β2) mainly composed of a hydrolysis condensate of the compound (L). The sea island structure to be formed may be further formed. The ratio (volume ratio) of [island phase (β2) / sea phase (β1)] in the island phase (β) is the ratio of [island phase (α2) / sea phase (α1)] in the sea phase (α). Is preferably larger. The diameter of the island phase (β) is preferably in the range of 30 nm to 1200 nm, more preferably in the range of 50 to 500 nm, and still more preferably in the range of 50 nm to 400 nm. The diameter of the island phase (α2) and the island phase (β2) is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 20 nm or less.

  In order to obtain the structure as described above, it is necessary that the appropriate hydrolysis condensation of the compound (L) occurs in preference to the crosslinking reaction between the compound (L) and the carboxylic acid-containing polymer. For this purpose, the specific compound (L) is used in an appropriate ratio with the carboxylic acid-containing polymer, and the compound (L) is preliminarily hydrolyzed and condensed before mixing with the carboxylic acid-containing polymer. A method such as using a condensation catalyst can be employed.

  Moreover, when specific manufacturing conditions were selected, it was found that a region where the ratio of the hydrolysis condensate of compound (L) is high is formed in a layered manner on the surface of the gas barrier layer. Hereinafter, the layer of the hydrolytic condensate of compound (L) formed on the surface of the gas barrier layer may be referred to as “skin layer”. By forming the skin layer, the water resistance and moisture resistance of the gas barrier layer surface are improved. The skin layer made of the hydrolyzed condensate of compound (L) has a characteristic that the hydrophobic property is imparted to the surface of the gas barrier layer, and the gas barrier layer does not stick even when the gas barrier layers wet with water are stacked. To grant. The presence or absence of the skin layer of the gas barrier layer or the state of the formed skin layer varies depending on the production conditions. As a result of intensive studies, the present inventors have found that there is a correlation between the contact angle between the gas barrier layer and water and the preferred skin layer, and the preferred skin layer is formed when the contact angle satisfies the following conditions. I found out. When the contact angle between the gas barrier layer and water is less than 20 °, the formation of the skin layer may be insufficient. In this case, the surface of the gas barrier layer is likely to swell with moisture, and if the laminates are stacked in a wet state, they may rarely stick together. Further, when the contact angle is 20 ° or more, the skin layer is sufficiently formed, and the surface of the gas barrier layer does not swell with moisture, so that no sticking occurs. The contact angle between the gas barrier layer and water is preferably 24 ° or more, and more preferably 26 ° or more. On the other hand, when the contact angle is larger than 65 °, the skin layer becomes too thick and the transparency of the gas barrier laminate is lowered. Therefore, the contact angle is preferably 65 ° or less, more preferably 60 ° or less, and still more preferably 58 ° or less.

[Method for producing gas barrier laminate]
Hereinafter, a method for producing the gas barrier laminate used in the present invention will be described. According to this method, a gas barrier laminate can be easily produced. Since the materials used in this manufacturing method and the configuration of the laminate are the same as those described above, description of overlapping portions may be omitted.

  The production method of the present invention includes steps (i) and (ii).

  Step (i) is a step of forming, on a substrate, a layer made of a composition containing a hydrolysis condensate of compound (L) containing a hydrolyzable characteristic group and polymer (X). . The layer is formed directly on the substrate or is formed on the substrate via another layer. Compound (L) includes compound (A) and compound (B). It should be noted that the reactivity of hydrolysis and condensation of the compound (L) can be controlled by adding the compound (D) having a carboxyl group-containing molecular weight of 100 or less to the compound (L). The gas barrier property of the body is improved. Details of the compound (D) will be described later.

  About a compound (A) and a compound (B), and the ratio of those compounds, it is the same as that of what was demonstrated about the composition which comprises a gas barrier layer.

  The next step (ii) is a step of bringing the layer formed in step (i) into contact with a solution containing divalent or higher-valent metal ions (hereinafter, this step may be referred to as an ionization step). For example, it can be performed by spraying a solution containing divalent or higher metal ions on the formed layer, or immersing both the base material and the layer on the base material in a solution containing divalent or higher metal ions. . By step (ii), at least a part of the —COO— group contained in the functional group (F) of the polymer (X) is neutralized.

Hereinafter, step (i) will be described in detail. In addition, when the compound (L) which is not hydrolytically condensed and a carboxylic acid containing polymer are mixed, both may react and it may become difficult to apply | coat a solution (U). Therefore, step (i)
(Ia) a solution comprising at least one compound selected from the compound (A) and a partial hydrolysis condensate of the compound (A), and a compound (D) containing a carboxyl group and having a molecular weight of 100 or less Preparing (S);
(Ib) preparing a solution (T) by mixing the solution (S) with at least one compound selected from the compound (B) and a partially hydrolyzed condensate of the compound (B);
(Ic) forming a hydrolysis condensate (oligomer (V)) of a plurality of compounds (L) containing the compound (A) and the compound (B) in the solution (T);
(Id) a step of preparing a solution (U) by mixing the solution (T) having undergone the step (ic) and the polymer (X);
(Ie) including a step of forming a layer by applying the solution (U) to a substrate and drying it.

  More specifically, the oligomer (V) obtained by hydrolyzing and condensing the compound (L) includes a compound (L) partially hydrolyzed, a compound (L) completely hydrolyzed, a compound (L ) Is partially hydrolyzed and condensed, and compound (L) is at least one metal element-containing compound selected from completely hydrolyzed and partially condensed. Hereinafter, such a metal element-containing compound may be referred to as “compound (L) -based component”. Hereinafter, the step (ia), the step (ib), the step (ic), the step (id), and the step (ie) will be described more specifically.

  Step (ia) is a step of hydrolyzing and condensing the compound (A) constituting the compound (L) under specific conditions. It is preferable to hydrolyze and condense the compound (A) in a reaction system containing the compound (A), an acid catalyst, water and, if necessary, an organic solvent. Specifically, a technique used in a known sol-gel method can be applied. When hydrolyzing and condensing, it is extremely important to add a compound (D) containing a carboxyl group and having a molecular weight of 100 or less (hereinafter sometimes simply referred to as compound (D)) in order to control the reaction. Preferably, by adding the compound (D), gelation can be suppressed in the step of hydrolyzing and condensing the compound (A).

  Compound (D) is compound (A), compound (A) partially hydrolyzed, compound (A) completely hydrolyzed, compound (A) partially hydrolyzed and condensed, And a metal element-containing compound containing at least one compound selected from those in which the compound (A) is completely hydrolyzed and partially condensed (hereinafter, this metal element-containing compound is referred to as “compound (A) component”). And the compound (D) acts on the compound (A) system component, the above-mentioned effect is exhibited. The method for adding the compound (D) is not particularly limited as long as the compound (A) is added before the component of the compound (A) is gelled by the hydrolysis condensation reaction. be able to. First, compound (D), water, and an organic solvent as necessary are mixed to prepare an aqueous solution of compound (D). Subsequently, an aqueous solution of compound (D) is added to the compound (A) system component, A solution (S) in which the compound (D) acts on the compound (A) component can be obtained. Although there is no restriction | limiting in the usage-amount of the water mixed with a compound (D), From the viewpoint of obtaining a uniform solution (S) with a high concentration, ratio of [number of moles of water] / [number of moles of compound (D)] Is preferably in the range of 25/1 to 300/1, more preferably in the range of 50/1 to 200/1, and even more preferably in the range of 75/1 to 150/1.

  From the viewpoint of improving the reaction control of the compound (A) and the gas barrier property of the gas barrier laminate with respect to the amount of the compound (D) used, [number of moles of the compound (D)] / [number of moles of the compound (A)] ] Is preferably in the range of 0.25 / 1 to 30/1, more preferably in the range of 0.5 / 1 to 20/1, and 0.75 / 1 to 10/1. More preferably, it is in the range.

  The compound (D) is not particularly limited as long as it is a compound containing a carboxyl group and having a molecular weight of 100 or less. From the viewpoint of increasing the reaction rate between the compound (A) and the functional group (F) of the polymer (X) and improving the hot water resistance and gas barrier properties of the gas barrier laminate, acetic acid and propionic acid are used as the compound (D). And hexanoic acid, and acetic acid is most preferred.

  In step (ib), a solution (T) is prepared. Specifically, for example, a solution (S) and an organic solvent as necessary are added to the compound (B) which is a constituent component of the compound (L), and then an acid catalyst, water and an organic solvent as needed are added. The solution (T) can be prepared by the method of adding.

  In the step (ic), hydrolysis and condensation are performed in a reaction system containing, for example, the compound (A) -based component, the compound (B), the acid catalyst, water, and, if necessary, an organic solvent. A technique used in a known sol-gel method can be applied to this technique. Thereby, compound (A) system component, compound (B), compound (B) partially hydrolyzed, compound (B) completely hydrolyzed, compound (B) partially hydrolyzed A solution of the metal element-containing compound containing at least one selected from the condensed product and the compound (B) which is completely hydrolyzed and partially condensed can be obtained.

  By carrying out the reaction in such a step, the generation of gel during the preparation of the oligomer (V) can be prevented, and further the reactivity of the oligomer (V) can be controlled. Therefore, gelatinization at the time of mixing oligomer (V) and polymer (X) can be prevented.

As the acid catalyst used in step (ia) and step (ib), a known acid can be used. For example, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, Butyric acid, carbonic acid, oxalic acid, maleic acid and the like can be used. Of these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are particularly preferred. Preferred amount of acid catalyst may vary depending on the type of acid used, the metal atom to 1 mol of the compound (L), is preferably in the range of 1 × 10 ^-5 to 10 mol, 1 × 10 ^- It is more preferably in the range of ^{4 to} 5 mol, and further preferably in the range of 5 × 10 ⁻⁴ to 1 mol. When the amount of the acid catalyst used is within this range, a gas barrier laminate having a high gas barrier property can be obtained.

  Moreover, although the usage-amount of the water used by process (ia) and process (ib) changes with kinds of compound (L), with respect to 1 equivalent of characteristic groups which have the hydrolyzability of compound (L). The range is preferably 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, and still more preferably 0.2 to 3 equivalents. When the amount of water used is in this range, the gas barrier property of the resulting gas barrier laminate is particularly excellent. In addition, in the step (ia) and the step (ib), when a component containing water such as hydrochloric acid is used, the amount of water used is also taken into account the amount of water introduced by the component. Is preferably determined.

  Furthermore, in the step (ia) and the step (ib), an organic solvent may be used as necessary. The organic solvent used will not be specifically limited if it is a solvent in which compound (L) dissolves. For example, alcohols such as methanol, ethanol, isopropanol, and normal propanol are preferably used as the organic solvent, and alcohols having the same molecular structure (alkoxy component) as the alkoxy group contained in the compound (L) are more preferably used. It is done. Specifically, methanol is preferred for tetramethoxysilane and ethanol is preferred for tetraethoxysilane. The amount of the organic solvent to be used is not particularly limited, but it is preferable that the concentration of the compound (L) is 1 to 90% by weight, more preferably 10 to 80% by weight, and still more preferably 10 to 60% by weight. .

  In step (ia), step (ib), and step (ic), the temperature of the reaction system is necessarily limited when the compound (L) is hydrolyzed or condensed in the reaction system. However, it is usually in the range of 2 to 100 ° C, preferably in the range of 4 to 60 ° C, and more preferably in the range of 6 to 50 ° C. The reaction time varies depending on the reaction conditions such as the amount and type of the acid catalyst, but is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, more preferably 0.8. The range is 1 to 6 hours. The reaction can be performed in an atmosphere of various gases such as air, carbon dioxide, nitrogen, and argon.

  In the step (id), the solution (T) containing the oligomer (V) obtained in the step (ic) and the carboxylic acid-containing polymer (= polymer (X)) are mixed to form a solution (U ). The solution (U) can be prepared using the solution (T), the carboxylic acid-containing polymer, and, if necessary, water and an organic solvent. For example, a method of adding and mixing the solution (T) to a solution in which the carboxylic acid-containing polymer is dissolved can be employed. Moreover, the method of adding and mixing the solution which dissolved the carboxylic acid containing polymer in water or the organic solvent to the solution (T) is also employable. In any method, the solution (T) to be added or the solution in which the carboxylic acid-containing polymer is dissolved may be added at once, or may be added in divided portions.

  The solution in which the carboxylic acid-containing polymer in step (id) is dissolved can be prepared by the following method. What is necessary is just to select the solvent to be used according to the kind of carboxylic acid containing polymer. For example, in the case of a water-soluble polymer such as polyacrylic acid or polymethacrylic acid, water is suitable. In the case of a polymer such as an isobutylene-maleic anhydride copolymer or a styrene-maleic anhydride copolymer, water containing an alkaline substance such as ammonia, sodium hydroxide, or potassium hydroxide is preferred. In addition, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, dioxane and trioxane; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol, as long as the dissolution of the carboxylic acid-containing polymer is not hindered Glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; glycerin; acetonitrile, dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane and the like can be used in combination.

  In the carboxylic acid-containing polymer contained in the solution (U), a part of the —COO— group (eg, 0.1 to 10 mol%) contained in the functional group (F) is neutralized by monovalent ions. May be. The degree of neutralization of the functional group (F) by monovalent ions is more preferably in the range of 0.5 to 5 mol% from the viewpoint of improving the transparency of the resulting gas barrier laminate. More preferably, it is in the range of ˜3 mol%. Examples of monovalent ions include ammonium ions, pyridinium ions, sodium ions, potassium ions, and lithium ions, with ammonium ions being preferred.

  The solid content concentration of the solution (U) is preferably in the range of 3% by weight to 20% by weight from the viewpoint of the storage stability of the solution (U) and the coating property of the solution (U) on the base material. It is more preferably in the range of 4% to 15% by weight, and still more preferably in the range of 5% to 12% by weight.

  From the viewpoint of the storage stability of the solution (U) and the gas barrier properties of the resulting gas barrier laminate, the pH of the solution (U) is preferably in the range of 1.0 to 7.0, 1.0 to 6 More preferably, it is in the range of 0.0, and more preferably in the range of 1.5 to 4.0.

  The pH of the solution (U) can be adjusted by a known method, for example, acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, butyric acid, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, It can adjust by adding basic compounds, such as sodium carbonate and sodium acetate. At this time, if a basic compound that provides a monovalent cation is used in the solution, a part of the carboxyl group and / or carboxylic anhydride group of the carboxylic acid-containing polymer may be neutralized with a monovalent ion. The effect that it can be obtained.

The step (ie) will be described. The state of the solution (U) prepared in the step (id) changes with time, and finally becomes a gel-like composition. The time until the solution (U) becomes gelled depends on the composition of the solution (U). In order to stably apply the solution (U) to the substrate, it is preferable that the solution (U) has a stable viscosity over a long period of time and then gradually increases in viscosity. The solution (U) was measured with a Brookfield viscometer (B-type viscometer: 60 rpm) even after standing at 25 ° C. for 2 days, based on the total amount of the compound (L) component. Is preferably adjusted to be 1 N · s / m ² or less (more preferably 0.5 N · s / m ² or less, particularly preferably 0.2 N · s / m ² or less). The solution (U) has a viscosity of 1 N · s / m ² or less (more preferably 0.1 N · s / m ² or less, particularly preferably 0. It is more preferable to adjust the composition so as to be 05 N · s / m ² or less. The solution (U) has a viscosity of 1 N · s / m ² or less (more preferably 0.1 N · s / m ² or less, particularly preferably 0. More preferably, the composition is adjusted to be 05 N · s / m ² or less. When the viscosity of the solution (U) is in the above range, the storage stability is excellent and the gas barrier property of the obtained gas barrier laminate is often improved.

  In order to adjust the viscosity of the solution (U) to be within the above range, for example, adjusting the concentration of solids, adjusting pH, carboxymethylcellulose, starch, bentonite, tragacanth gum, stearate, alginate, A method of adding a viscosity modifier such as methanol, ethanol, n-propanol, or isopropanol can be used.

  In addition, in order to facilitate the application of the solution (U) to the base material, an organic solvent that can be uniformly mixed with the solution (U) is added so long as the stability of the solution (U) is not hindered. May be. Examples of organic solvents that can be added include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ethers such as tetrahydrofuran, dioxane, and trioxane; ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone, and methyl isopropyl ketone; ethylene glycol, Glycols such as propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; glycerin; acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethoxyethane and the like.

  In addition, the solution (U) may be carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, phosphate, borate, alumina as long as it does not impair the effects of the present invention. Inorganic acid metal salts such as acid salts; organic acid metal salts such as oxalate, acetate, tartrate and stearate; acetylacetonate metal complexes such as aluminum acetylacetonate; cyclopentadiene such as titanocene Metal complexes such as enyl metal complexes and cyano metal complexes; layered clay compounds, crosslinking agents, compounds containing two or more amino groups as described above (P), compounds containing two or more hydroxyl groups as described above (Q), and other It may contain a polymer compound, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant and the like. The solution (U) may contain fine metal oxide powder or fine silica powder.

  The solution (U) prepared in the step (id) is applied to at least one surface of the substrate in the step (ie). Before applying the solution (U), the surface of the substrate may be treated with a known anchor coating agent, or a known adhesive may be applied to the surface of the substrate. The method for applying the solution (U) to the substrate is not particularly limited, and a known method can be used. Preferred methods include, for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, a metering bar coating method, and a chamber doctor combined coating method. And curtain coating method.

  After the solution (U) is applied on the substrate in the step (ie), the solvent contained in the solution (U) is removed to obtain a laminate (laminate (I)) before the ionization step. It is done. The method for removing the solvent is not particularly limited, and a known method can be applied. Specifically, methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied alone or in combination. A drying temperature will not be restrict | limited especially if it is 15-20 degreeC or more lower than the flow start temperature of a base material, and 15-20 degreeC or more lower than the thermal decomposition start temperature of a carboxylic acid containing polymer. The drying temperature is preferably in the range of 70 ° C to 200 ° C, more preferably in the range of 80 to 180 ° C, and further preferably in the range of 90 to 160 ° C. The removal of the solvent may be carried out under normal pressure or reduced pressure.

  In the gas barrier laminate used in the present invention, a skin layer made of a hydrolyzable condensate of compound (L) is preferably formed on the surface of the gas barrier layer. Further, as described above, it is not preferable that the skin layer becomes too thick because the transparency of the gas barrier laminate is lowered. A method for forming a skin layer having an appropriate thickness will be described below. According to the results of intensive studies by the present inventors, the presence or absence of the skin layer and the state of the skin layer formation are determined by the reactivity of the hydrolyzable condensate of the compound (L), the composition of the compound (L), It depends on the solvent used in the solution (U), the drying speed of the solution (U) after the solution (U) is applied to the substrate, and the like. For example, when the contact angle of water with respect to the gas barrier layer surface is measured and the contact angle is smaller than the above-described predetermined range, the reaction time of the step (ia) and the step (ic) is increased. It is possible to increase the contact angle (that is, to form an appropriate skin layer). On the other hand, when the contact angle is larger than the predetermined range, it is possible to reduce the contact angle by shortening the reaction time of the step (ia) and the step (ic).

  By bringing the laminate (I) obtained by the above step into contact with a solution containing metal ions having a valence of 2 or more (hereinafter sometimes referred to as “solution (IW)”) by the step (ii) (ionization step). A gas barrier laminate (laminate (II)) is obtained. The ionization process may be performed at any stage as long as the effects of the present invention are not impaired.

  The solution (IW) can be prepared by dissolving, in a solvent, a compound that releases a divalent or higher valent metal ion (polyvalent metal compound) upon dissolution. As a solvent used in preparing the solution (IW), it is desirable to use water, but it may be a mixture of an organic solvent miscible with water and water. Examples of such organic solvents include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ethers such as tetrahydrofuran, dioxane, and trioxane; ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone, and methyl isopropyl ketone; ethylene glycol, propylene glycol Glycols such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; glycerin; organic solvents such as acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, and dimethoxyethane.

As the polyvalent metal compound, compounds capable of releasing the metal ions exemplified for the gas barrier laminate used in the present invention (that is, divalent or higher metal ions) can be used. For example, calcium acetate, calcium hydroxide, barium hydroxide, calcium chloride, calcium nitrate, calcium carbonate, magnesium acetate, magnesium hydroxide, magnesium chloride, magnesium carbonate, iron (II) acetate, iron (II) chloride, iron acetate ( III), iron chloride (III), zinc acetate, zinc chloride, copper acetate (II), copper acetate (III), lead acetate, mercury acetate (II), barium acetate, zirconium acetate, barium chloride, barium sulfate, nickel sulfate Lead sulfate, zirconium chloride, zirconium nitrate, aluminum sulfate, potassium alum (KAl (SO ₄ ) ₂ ), titanium (IV) sulfate, and the like can be used. Only one type of polyvalent metal compound may be used, or two or more types may be used in combination. Preferred polyvalent metal compounds include calcium acetate, calcium hydroxide, magnesium acetate, and zinc acetate. In addition, you may use these polyvalent metal compounds in the form of a hydrate.

The concentration of the polyvalent metal compound in the solution (IW) is not particularly limited, but is preferably in the range of 5 × 10 ⁻⁴ wt% to 50 wt%, more preferably 1 × 10 ⁻² wt% to 30 wt%. More preferably, it is in the range of 1 to 20% by weight.

  When the laminate (I) is brought into contact with the solution (IW), the temperature of the solution (IW) is not particularly limited, but the higher the temperature, the faster the ionization rate of the carboxyl group-containing polymer. The temperature is, for example, in the range of 30 to 140 ° C, preferably in the range of 40 ° C to 120 ° C, and more preferably in the range of 50 ° C to 100 ° C.

  It is desirable to remove the solvent remaining in the laminate after contacting the laminate (I) with the solution (IW). The method for removing the solvent is not particularly limited, and a known method can be applied. Specifically, drying methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied singly or in combination of two or more. The temperature at which the solvent is removed is not particularly limited as long as it is 15 to 20 ° C. or more lower than the flow start temperature of the substrate and 15 to 20 ° C. or lower than the thermal decomposition start temperature of the carboxylic acid-containing polymer. The drying temperature is preferably in the range of 40 to 200 ° C, more preferably in the range of 60 to 150 ° C, and still more preferably in the range of 80 to 130 ° C. The removal of the solvent may be carried out under normal pressure or reduced pressure.

  In order not to impair the appearance of the surface of the gas barrier laminate, it is preferable to remove excess polyvalent metal compound adhering to the surface of the laminate before or after removing the solvent. As a method for removing the polyvalent metal compound, washing using a solvent in which the polyvalent metal compound dissolves is preferable. As the solvent in which the polyvalent metal compound dissolves, a solvent that can be used for the solution (IW) can be used, and the same solvent as the solvent for the solution (IW) is preferably used.

  The production method of the present invention further includes a step of heat-treating the layer formed in step (i) at a temperature of 120 to 240 ° C. after step (i) and before and / or after step (ii). But you can. That is, you may heat-process with respect to laminated body (I) or (II). The heat treatment may be performed at any stage as long as the removal of the solvent of the coated solution (U) is almost completed, but the layered product (that is, the layered product (I)) before the ionization step is performed. By performing the heat treatment, a gas barrier laminate having a good surface appearance can be obtained. The temperature of the heat treatment is preferably in the range of 120 ° C to 240 ° C, more preferably in the range of 140 to 240 ° C, and still more preferably in the range of 160 ° C to 220 ° C. The heat treatment can be performed in air, under a nitrogen atmosphere, under an argon atmosphere, or the like.

  In the production method of the present invention, the laminate (I) or (II) may be irradiated with ultraviolet rays. The ultraviolet irradiation may be performed any time after the removal of the solvent of the coated solution (U) is almost completed. The method is not particularly limited, and a known method can be applied. The wavelength of the ultraviolet rays to be irradiated is preferably in the range of 170 to 250 nm, more preferably in the range of 170 to 190 nm and / or in the range of 230 to 250 nm. Further, instead of ultraviolet irradiation, radiation such as an electron beam or γ-ray may be irradiated.

  Only one of heat treatment and ultraviolet irradiation may be performed, or both may be used in combination. By performing heat treatment and / or ultraviolet irradiation, the gas barrier performance of the laminate may be expressed to a higher degree.

  In order to dispose the adhesive layer (H) between the base material and the gas barrier layer, a treatment (treatment with an anchor coating agent or application of an adhesive) is performed on the surface of the base material before application of the solution (U). You may give it. In that case, after the step (i) (application of the solution (U)) and before the heat treatment and the step (ii) (ionization step), the substrate coated with the solution (U) is compared. It is preferable to perform an aging treatment that is allowed to stand at a low temperature for a long time. The temperature of the aging treatment is preferably in the range of 30 to 200 ° C, more preferably in the range of 30 to 150 ° C, and further preferably in the range of 30 to 120 ° C. The aging time is preferably in the range of 0.5 to 10 days, more preferably in the range of 1 to 7 days, and still more preferably in the range of 1 to 5 days. By performing such an aging treatment, the adhesive force between the base material and the gas barrier layer becomes stronger. After the aging treatment, it is preferable to perform the above heat treatment (heat treatment at 120 ° C. to 240 ° C.).

  The vacuum heat insulating body of the present invention maintains a high heat insulating effect over a long period of time and can be used for various applications that require heat insulation such as cold insulation and heat insulation. Specifically, the vacuum insulator of the present invention includes a refrigerator, a freezer, a rice cooker, a vehicle ceiling, a battery, a freezer ship, a refrigerated ship, a heat insulation container, a freezer showcase, a cold showcase, a portable cooler, and a dryer. , Thermostatic baths, cooking insulation cases, vending machines, hot water supply facilities, building materials (walls, ceilings, attics, floors), piping / conduit for hot water / cooling water / cold fluid, clothing, bedding, etc. It can be used as a vacuum insulator for various applications.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples, when describing the layer structure of the laminate, only the substance name may be described, and the “layer” may be omitted.

[Production and evaluation of gas barrier laminates]
The gas barrier laminate described below was prepared and evaluated. Evaluation was performed by the following methods (1) to (5).

(1) Contact angle The laminate was conditioned for 24 hours under conditions of a temperature of 20 ° C and a humidity of 65% RH. Thereafter, 2 μL of water was dropped onto the gas barrier layer using an automatic contact angle meter (manufactured by Kyowa Interface Science, DM500) under conditions of a temperature of 20 ° C. and a humidity of 65% RH. And the contact angle of a gas barrier layer and water was measured by the method based on Japanese Industrial Standard (JIS) -R3257.

(2) Tensile strength and elongation, Young's modulus The laminate was conditioned for 24 hours under conditions of a temperature of 23 ° C. and a humidity of 50% RH. Thereafter, the laminate was cut into 15 cm × 15 mm with respect to the MD direction and the TD direction. About the cut-out laminated body, tensile strength and Young's modulus were measured by the method based on JIS-K7127 on the conditions of temperature 23 degreeC and humidity 50% RH.

(3) Dry heat shrinkage The laminate was cut into 10 cm × 10 cm, and the length in MD and TD was measured with calipers. This laminate was heated in a dryer at 80 ° C. for 5 minutes, and the length in MD and TD after heating was measured. And the dry heat shrinkage rate (%) was measured from the following formula.
Dry heat shrinkage (%) = (l _b −l _a ) × 100 / l _b
[Wherein _lb represents a length before heating. l _a represents the length after heating. ]

(4) Degree of neutralization of carboxyl groups with metal ions (degree of ionization)
[Calculation of ionization degree by FT-IR]
Polyacrylic acid having a number average molecular weight of 150,000 was dissolved in distilled water, and the carboxyl group was neutralized with a predetermined amount of sodium hydroxide. The obtained aqueous solution of neutralized polyacrylic acid was coated on a substrate so as to have the same thickness as the gas barrier layer of the laminate to be measured for ionization degree, and dried. The substrate was coated on the surface with a two-component anchor coating agent (Mitsui Takeda Chemical Co., Ltd., Takelac 626 (trade name) and Takenate A50 (trade name), hereinafter abbreviated as “AC”). A stretched polyamide film (manufactured by Unitika Ltd., Emblem ON-BC (trade name), thickness 15 μm, hereinafter sometimes abbreviated as “OPA”) was used. In this way, a standard sample [laminated body (layer made of neutralized polyacrylic acid / AC / OPA)] having a carboxyl group neutralization degree of 0, 25, 50, 75, 80, and 90 mol% was prepared. Produced. About these samples, the infrared absorption spectrum was measured in the mode of ATR (total reflection measurement) using the Fourier-transform infrared spectrophotometer (The product made from Perkin Elmer, Spectrum One). The two peaks corresponding to the C = O stretching vibration in the layer consisting of neutralized product of polyacrylic acid, i.e., a peak observed in the range of 1600cm ^-1 ~1850cm ^-1 and 1500cm ^-1 ~1600cm ^- The ratio of the maximum absorbance was calculated for the peak observed in the range of ¹ . And the calibration curve 1 was created using the calculated ratio and the ionization degree of each standard sample.

A laminate using a stretched polyamide film (OPA) as a base material is included in the gas barrier layer in a mode of ATR (total reflection measurement) using a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer, Spectrum One). The peak of C = O stretching vibration was observed. Peak attributed to C = O stretching vibration of the carboxyl group of the ionization front of a carboxylic acid-containing polymer, was observed in the range of 1600cm ^-1 ~1850cm ^-1. Furthermore, C = O stretching vibration of the carboxyl group after being ionized was observed in the range of 1500cm ^-1 ~1600cm ^-1. Then, the ratio was calculated from the maximum absorbance in each range, and the degree of ionization was determined using the ratio and the calibration curve 1.

[Calculation of ionization degree by fluorescent X-ray]
About the laminated body using OPA mentioned above as a base material, the standard sample from which the degree of ionization differs was measured from the measurement of FT-IR. Specifically, eleven types of standard samples having different degrees of ionization (ions: calcium ions) of about 10 mol% between 0 to 100 mol% were prepared. For each sample, the fluorescence X-ray intensity of calcium element was measured using a wavelength dispersion type fluorescent X-ray apparatus (manufactured by Rigaku Corporation, ZSXmini II), and a calibration curve 2 was created from the degree of ionization measured in advance by FT-IR. did. Using the obtained calibration curve 2, the degree of calcium ionization of the laminate produced under various conditions was calculated.

  Also in the case of ionization with other metal ions (magnesium ion, zinc ion, etc.), the calibration curve 2 was created by the same method as described above, and the degree of ionization was calculated.

  For a laminate (such as PET) using a substrate other than OPA, the degree of ionization was calculated using the calibration curve 2 obtained by fluorescent X-ray intensity measurement.

(5) Weight of hydrolysis condensate and polymer (X) By the above-described method, the weight of the inorganic component derived from the compound (L) and the weight of the organic component derived from the compound (L) and the polymer (X ) And the total weight of the organic components derived from it were calculated.

<Laminated body (1)>
Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water to obtain a PAA aqueous solution having a solid content concentration of 13% by weight in the aqueous solution. Subsequently, 13% ammonia aqueous solution was added to this PAA aqueous solution to neutralize 1 mol% of the carboxyl group of PAA, thereby obtaining a partially neutralized aqueous solution of PAA.

  Further, 60 parts by weight of acetic acid and 1800 parts by weight of distilled water were mixed, and 204 parts by weight of aluminum isopropoxide (AIP) (AIP / acetic acid / distilled water = 1/1/100 (molar ratio)) was stirred into this acetic acid aqueous solution. And then heated at 80 ° C. for 1 hour to obtain an AIP aqueous solution (S1) having a concentration of 9.88% by weight.

  Subsequently, the molar ratio of Al / Si was 1.2 / 98.8, and the weight ratio of [inorganic component derived from tetramethoxysilane (TMOS) and AIP] / [partially neutralized product of PAA] was 40.2 / A mixed solution (U1) was prepared so as to be 59.8. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 8.5 parts by weight of the above 9.88% by weight AIP aqueous solution (S1) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS would be 1.95 molar equivalents, and hydrolysis and condensation reactions were carried out at 10 ° C. for 1 hour. And a mixed solution (T1) was obtained. Subsequently, after diluting the mixed solution (T1) with 425 parts by weight of distilled water and 222 parts by weight of methanol, 228 parts by weight of an aqueous solution of a partially neutralized product of PAA (concentration 13% by weight) was rapidly added while stirring. As a result, a mixed solution (U1) having a solid content concentration of 5% by weight was obtained.

  On the other hand, a two-component anchor coating agent dissolved in 67 parts by weight of ethyl acetate (Mitsui Takeda Chemical Co., Ltd .: Takelac A-626 (trade name) 1 part by weight and Takenate A-50 (trade name) 2 parts by weight) Is coated on a stretched polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror P60 (trade name), thickness 12 μm, hereinafter sometimes abbreviated as “PET”), and dried to form a base having an anchor coat layer. A material (AC (0.1 μm) / PET (12 μm)) was prepared. The mixed solution (U1) was coated on the anchor coat layer of the base material with a bar coater so that the thickness after drying was 0.4 μm, and dried at 120 ° C. for 5 minutes. Subsequently, coating was also performed on the opposite surface of the substrate in the same procedure. The obtained laminate was aged at 40 ° C. for 3 days. Next, the laminate was heat-treated at 180 ° C. for 5 minutes using a dryer. Next, the laminate was immersed in a 2% by weight calcium acetate aqueous solution (85 ° C.) for 12 seconds, and then dried at 110 ° C. for 1 minute. In this way, a laminate (1) having a structure of gas barrier layer (0.4 μm) / AC (0.1 μm) / PET (12 μm) / AC (0.1 μm) / gas barrier layer (0.4 μm) is obtained. It was.

<Laminated body (2)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 30.1 / 69.9, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 25.5 / 74.5. A mixed solution (U2) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 293 parts by weight of a 9.88% by weight AIP aqueous solution (S2) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 1 hour. And a liquid mixture (T2) was obtained. Subsequently, after diluting the obtained mixed liquid (T2) with 850 parts by weight of distilled water and 405 parts by weight of methanol, 607 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. As a result, a mixed solution (U2) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U2), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (2).

<Laminated body (3)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). And only the reaction time was changed and the liquid mixture (U3) was prepared.

  Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 8.5 parts by weight of a 9.88% by weight AIP aqueous solution (S3) was added thereto. Subsequently, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalents, and hydrolysis and condensation reactions were carried out at 10 ° C. for 5 hours. And a liquid mixture (T3) was obtained. Subsequently, after the mixture (T3) was diluted with 425 parts by weight of distilled water and 222 parts by weight of methanol, 228 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U3) having a solid content concentration of 5% by weight was obtained. Using the mixed solution (U3), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (3).

<Laminated body (4)>
AIP was changed to titanium tetraisopropoxide (TIP) to prepare a mixed solution (U4). Specifically, 1200 parts by weight of acetic acid and 1800 parts by weight of distilled water were mixed, and 284 parts by weight of TIP (TIP / acetic acid / distilled water = 1/20/100 (molar ratio)) was added to this aqueous acetic acid solution with stirring. Then, a TIP aqueous solution (S4) having a concentration of 8.6% by weight was obtained by heating at 80 ° C. for 1 hour. Subsequently, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 13.5 parts by weight of TIP aqueous solution (S4) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T4) was obtained. Then, the liquid mixture (U4) with a solid content concentration of 5 weight% was obtained with the composition and method similar to the laminated body (1).

  Using the mixed solution (U4), coating, heat treatment, ionization, and drying were performed in the same manner as in the laminate (1) to obtain a laminate (4).

<Laminated body (5)>
AIP was changed to zirconium tetraisopropoxide (ZIP) to prepare a mixed solution (U5). Specifically, 1200 parts by weight of acetic acid and 1800 parts by weight of distilled water were mixed, and 327 parts by weight of ZIP (ZIP / acetic acid / distilled water = 1/20/100 (molar ratio)) was added to this aqueous acetic acid solution with stirring. Thereafter, the mixture was heated at 80 ° C. for 1 hour to obtain a 9.8 wt% aqueous ZIP solution (S5). Next, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 13.6 parts by weight of the 9.8% by weight ZIP aqueous solution (S5) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T5) was obtained. Subsequently, a mixed liquid (U5) having a solid content concentration of 5% by weight was obtained by the same composition and method as those of the laminate (1).

  Using the mixed solution (U5), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (5).

<Laminated body (6)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). And with the same charging ratio as the laminate (3) except that the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 30.2 / 69.8, A mixed solution (U6) was prepared. Specifically, first, a mixed solution (T6) was prepared by the same composition and method as the mixed solution (T3) obtained from the laminate (3). After diluting this mixed solution (T6) with 567 parts by weight of distilled water and 283 parts by weight of methanol, 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration: 13% by weight) was rapidly added while stirring. A liquid mixture (U6) having a concentration of 5% by weight was obtained.

  Using the mixed solution (U6), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (6).

<Laminated body (7)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). And the liquid mixture (U7) was prepared by the preparation ratio similar to a laminated body (6) except having made it the molar ratio of Al / Si becoming 1.9 / 98.1. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 13.2 parts by weight of the 9.88 wt% AIP aqueous solution (S7) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T7) was obtained. Then, the liquid mixture (U7) whose solid content concentration is 5 weight% with the composition and method similar to a laminated body (6) was obtained.

  Using the mixed solution (U7), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (7).

<Laminated body (8)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). And the liquid mixture (U8) was prepared by the preparation ratio similar to a laminated body (6) except having made it the molar ratio of Al / Si becoming 2.8 / 97.2. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 19.8 parts by weight of the 9.88 wt% AIP aqueous solution (S8) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T8) was obtained. Then, the liquid mixture (U8) whose solid content concentration is 5 weight% with the composition and method similar to a laminated body (6) was obtained.

  Using the mixed solution (U8), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (8).

<Laminated body (9)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The same charging ratio as that of the laminate (2), that is, the molar ratio of Al / Si was 30/70, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 25.5. A mixed solution (U9) was prepared so as to be /74.5. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 293 parts by weight of a 9.88 wt% AIP aqueous solution (S9) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T9) was obtained. Subsequently, after diluting the obtained mixed liquid (T9) with 850 parts by weight of distilled water and 405 parts by weight of methanol, 607 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. As a result, a mixed solution (U9) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U9), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (9).

<Laminated body (10)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 0.1 / 99.9, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 80.0 / 20.0. A mixed solution (U10) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.7 part by weight of a 9.88 wt% AIP aqueous solution (S10) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T10) was obtained. Subsequently, after the mixed liquid (T10) was diluted with 212 parts by weight of distilled water and 131 parts by weight of methanol, 38 parts by weight of an aqueous solution of PAA partially neutralized (concentration 13% by weight) was rapidly added while stirring. A mixed solution (U10) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U10), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (10).

<Laminated body (11)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 29.9 / 70.1, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 36.9 / 63.1. A mixed solution (U11) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 290 parts by weight of a 9.88 wt% AIP aqueous solution (S11) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T11) was obtained. Subsequently, after the mixture (T11) was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U11) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U11), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (11).

<Laminated body (12)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 0.1 / 99.9, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 70.0 / 30.0. A mixed solution (U12) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.7 part by weight of a 9.88 wt% AIP aqueous solution (S12) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T12) was obtained. Subsequently, after the mixture (T12) was diluted with 243 parts by weight of distilled water and 144 parts by weight of methanol, 65 parts by weight of an aqueous solution (partial concentration 13% by weight) of a partially neutralized product of PAA was rapidly added while stirring. A mixed solution (U12) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U12), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (12).

<Laminated body (13)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 3.0 / 97.0, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 20.0 / 80.0. A mixed solution (U13) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 20.8 parts by weight of a 9.88 wt% AIP aqueous solution (S13) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T13) was obtained. Subsequently, after the mixture (T13) was diluted with 868 parts by weight of distilled water and 412 parts by weight of methanol, 623 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U13) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U13), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (13).

<Laminated body (14)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 3.0 / 97.0 and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 80.0 / 20.0. A mixed solution (U14) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 21.0 parts by weight of a 9.88 wt% AIP aqueous solution (S14) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T14) was obtained. Subsequently, after the mixture (T14) was diluted with 214 parts by weight of distilled water and 132 parts by weight of methanol, 39 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U14) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U14), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (14).

<Laminated body (15)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 3.0 / 97.0, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 70.0 / 30.0. A mixed solution (U15) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 21.1 parts by weight of a 9.88 wt% AIP aqueous solution (S15) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T15) was obtained. Subsequently, after diluting the mixed solution (T15) with 245 parts by weight of distilled water and 145 parts by weight of methanol, 67 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U15) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U15), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (15).

<Laminated body (16)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 2.9 / 97.1, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 10.2 / 89.8. A mixed solution (U16) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 20.3 parts by weight of a 9.88 wt% AIP aqueous solution (S16) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T16) was obtained. Subsequently, after the mixture (T16) was diluted with 1700 parts by weight of distilled water and 769 parts by weight of methanol, 1366 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U13) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U16), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (16).

<Laminated body (17)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 3.0 / 97.0, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 90.2 / 9.8. A mixed solution (U17) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 21.3 parts by weight of a 9.88 wt% AIP aqueous solution (S17) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T17) was obtained. Subsequently, after the mixed solution (T17) was diluted with 189 parts by weight of distilled water and 121 parts by weight of methanol, 17 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U17) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U17), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (17).

<Laminated body (18)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). Subsequently, the molar ratio of TMOS / γ-glycidoxydoxypropyltrimethoxysilane (GPTMOS) was 99.5 / 0.5, the molar ratio of Al / Si was 2.8 / 97.2, [TMOS, AIP and A mixed solution (U18) was prepared so that the weight ratio of [inorganic component derived from GPTMOS] / [partially neutralized product of organic component of GPTMOS and PAA] was 30.5 / 69.5. Specifically, first, 49.6 parts by weight of TMOS and 0.4 part by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and a 9.88% by weight AIP aqueous solution (S18) prepared by the same method as that for the laminate (1). 19.6 parts by weight) was added. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and the mixture was hydrolyzed at 10 ° C. for 5 hours. Decomposition | disassembly and condensation reaction were performed and the liquid mixture (T18) was obtained. Subsequently, after the mixed liquid (T18) was diluted with 566 parts by weight of distilled water and 283 parts by weight of methanol, 352 parts by weight of an aqueous solution of a partially neutralized product of PAA (concentration 13% by weight) was rapidly added while stirring. As a result, a mixed solution (U18) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U18), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (18).

<Laminated body (19)>
A mixed liquid (U19) was obtained with the same charging ratio as that of the laminate (18) except that the molar ratio of TMOS / GPTMOS was 80.0 / 20.0. Specifically, first, 36.0 parts by weight of TMOS and 14.0 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 19.8 parts by weight of a 9.88% by weight AIP aqueous solution (S19) was added thereto. Further, 3.0 parts by weight of distilled water and 7.4 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalents, and water was added at 10 ° C. for 5 hours. Decomposition and condensation reaction were performed to obtain a mixed solution (T19). Subsequently, after the mixed liquid (T19) was diluted with 520 parts by weight of distilled water and 302 parts by weight of methanol, 267 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U19) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U19), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (19).

<Laminated body (20)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). Subsequently, the molar ratio of TMOS / GPTMOS is 89.9 / 10.1, the molar ratio of Al / Si is 3.1 / 96.9, [inorganic components derived from TMOS, AIP and GPTMOS] / [organic of GPTMOS] The mixed solution (U20) was prepared so that the weight ratio of the component and the partially neutralized product of PAA was 31.5 / 68.5. Specifically, first, 42.6 parts by weight of TMOS and 7.4 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 20.6 parts by weight of a 9.88% by weight AIP aqueous solution (S20) was added thereto. Further, 3.2 parts by weight of distilled water and 7.8 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalents, and water was added at 10 ° C. for 5 hours. Decomposition | disassembly and condensation reaction were performed and the liquid mixture (T20) was obtained. Subsequently, after diluting the mixed liquid (T20) with 542 parts by weight of distilled water and 302 parts by weight of methanol, 293 parts by weight of an aqueous solution of a partially neutralized product of PAA (concentration 13% by weight) was rapidly added while stirring. A mixed liquid (U20) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U20), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (20).

<Laminated body (21)>
A mixed liquid (U21) was obtained with the same charging ratio as that of the laminate (18) except that the molar ratio of TMOS to GPTMOS was 98.0 / 2.0. Specifically, first, 48.5 parts by weight of TMOS and 1.5 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 19.2 parts by weight of a 9.88% by weight AIP aqueous solution (S21) was added thereto. Further, 3.3 parts by weight of distilled water and 8.1 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and the mixture was hydrolyzed at 10 ° C. for 5 hours. Decomposition and condensation reaction were performed to obtain a mixed solution (T21). Subsequently, after the mixed liquid (T21) was diluted with 562 parts by weight of distilled water and 285 parts by weight of methanol, 345 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U21) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U21), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (21).

<Laminated body (22)>
A mixed liquid (U22) was obtained with the same charging ratio as that of the laminate (18) except that the molar ratio of TMOS / GPTMOS was 99.9 / 0.1. Specifically, first, 49.9 parts by weight of TMOS and 0.1 part by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 21.0 parts by weight of a 9.88 wt% AIP aqueous solution (S22) was added thereto. Further, 3.3 parts by weight of distilled water and 8.1 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and the mixture was hydrolyzed at 10 ° C. for 5 hours. Decomposition | disassembly and condensation reaction were performed and the liquid mixture (T22) was obtained. Subsequently, after diluting the mixed solution (T22) with 567 parts by weight of distilled water and 283 parts by weight of methanol, 354 parts by weight of an aqueous solution (concentration 13% by weight) of a partially neutralized product of PAA was rapidly added. A mixed solution (U22) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U22), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (22).

<Laminated body (23)>
A mixed liquid (U23) was obtained at the same charging ratio as that of the laminate (18) except that the molar ratio of TMOS / GPTMOS was 70.0 / 30.0. Specifically, first, 30.0 parts by weight of TMOS and 20.0 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 17.9 parts by weight of a 9.88% by weight AIP aqueous solution (S23) was added thereto. Further, 2.9 parts by weight of distilled water and 7.0 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and hydrolysis was carried out at 10 ° C. for 5 hours. Then, a condensation reaction was performed to obtain a mixed solution (T23). Subsequently, after the mixed solution (T23) was diluted with 500 parts by weight of distilled water and 310 parts by weight of methanol, 229 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U23) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U23), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (23).

<Laminated body (24)>
For the production of the laminate (24), a mixture (U24) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. Moreover, the laminated body was produced by performing the coating and the heat treatment in the same manner as the laminated body (1). This laminate was ionized by immersing it in a 0.1% by weight aqueous calcium acetate solution (85 ° C.) for 12 seconds, and then dried in the same manner as the laminate (1) to obtain a laminate (24).

<Laminated body (25)>
For the production of the laminate (25), a mixture (U25) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. Moreover, the laminated body was produced by performing the coating and the heat treatment in the same manner as the laminated body (1). This laminate was ionized by immersion in a 0.2 wt% calcium acetate aqueous solution (85 ° C.) for 6 seconds, and then dried in the same manner as the laminate (1) to obtain a laminate (25).

<Laminated body (26)>
For the production of the laminate (26), a mixture (U26) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. Moreover, the laminated body was produced by performing the coating and the heat treatment in the same manner as the laminated body (1). This laminate was ionized by immersion in a 0.2 wt% calcium acetate aqueous solution (85 ° C.) for 12 seconds, and then dried in the same manner as the laminate (1) to obtain a laminate (26).

<Laminated body (27)>
For the production of the laminate (27), a mixed solution (U27) obtained by the same composition and method as the mixed solution (U21) obtained from the laminate (21) was used. Moreover, the laminated body was produced by performing the coating and the heat treatment in the same manner as the laminated body (1). This laminate was ionized by immersing it in a 2% by weight aqueous magnesium acetate solution (85 ° C.) for 12 seconds, and then dried in the same manner as the laminate (1) to obtain a laminate (27).

<Laminated body (28)>
For the production of the laminate (28), a mixture (U28) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. In addition, a laminate was obtained by performing coating and heat treatment in the same manner as the laminate (1). This laminate was ionized by immersing in a 2% by weight zinc acetate aqueous solution (85 ° C.) for 12 seconds, and then dried in the same manner as the laminate (1) to obtain a laminate (28).

<Laminated body (29)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). On the other hand, EDA was dissolved in 1N hydrochloric acid so that the molar ratio of ethylenediamine (EDA) / HCl was 1/2 to obtain an aqueous EDA hydrochloride solution. The mixed solution was prepared in the same ratio as in the laminate (7) except that the EDA hydrochloride aqueous solution was added so that the equivalent ratio of [amino group of EDA] / [carboxyl group of PAA] was 1.9 / 100. (U29) was prepared. Specifically, first, the mixture (T29) prepared by the same composition and method as the mixture (T7) of the laminate (7) was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred. While adding 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight), 12.7 parts by weight of an EDA hydrochloride aqueous solution was further added, and a mixed solution (U29) having a solid content concentration of 5% by weight was added. Obtained.

  Using the mixed solution (U29), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (29).

<Laminated body (30)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). On the other hand, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117, hereinafter sometimes abbreviated as “PVA”) is added to distilled water so that the concentration becomes 10% by weight, and the PVA aqueous solution is heated at 85 ° C. for 3 hours. Obtained.

  The mixed solution (U27) was prepared by adding the PVA aqueous solution at the same charging ratio as that of the laminate (7) except that the equivalent ratio of [hydroxyl group of PVA] / [carboxyl group of PAA] was 18.2 / 100. ) Specifically, first, a mixed solution (T30) prepared by the same composition and method as the mixed solution (T7) of the laminate (7) was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred. While rapidly adding 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight), and further adding 51 parts by weight of the 10% by weight PVA aqueous solution, a mixed solution (U30) having a solid content concentration of 5% by weight was added. Obtained.

  Using the mixed solution (U30), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (30).

<Laminated body (31)>
A mixed solution (U31) was prepared at the same charging ratio as that of the laminate (21) except that the acid at the time of preparing the AIP aqueous solution was propionic acid. Specifically, after mixing 74 parts by weight of propionic acid and 1800 parts by weight of distilled water, 204 parts by weight of AIP (AIP / propionic acid / distilled water = 1/1/100 (molar ratio)) is stirred in this aqueous propionic acid solution. And then heated at 80 ° C. for 1 hour to obtain an AIP aqueous solution (S31) having a concentration of 9.82% by weight. A mixed liquid (U31) was obtained by the same composition and method as the mixed liquid (U21) of the laminate (18) except that this AIP aqueous solution (S31) was used.

  Using the mixed solution (U31), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (31).

<Laminated body (32)>
A mixed solution (U32) was prepared at the same charging ratio as that of the laminate (21) except that the acid at the time of preparing the AIP aqueous solution was hexanoic acid. Specifically, after 116 parts by weight of hexanoic acid and 1800 parts by weight of distilled water were mixed, 204 parts by weight of AIP (AIP / hexanoic acid / distilled water = 1/1/100 (molar ratio)) was stirred into this aqueous hexanoic acid solution. And then heated at 80 ° C. for 1 hour to obtain an AIP aqueous solution (S32) having a concentration of 9.62% by weight. A mixed liquid (U32) was obtained by the same composition and method as the mixed liquid (U21) of the laminate (21) except that this AIP aqueous solution (S32) was used.

  Using the mixed solution (U32), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (32).

<Laminated body (33)>
For the production of the laminate (33), a mixture (U33) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. Except that the gas barrier layer was formed only on one side of the substrate, coating, heat treatment, ionization and drying were carried out in the same manner as in the laminate (1) to obtain a laminate (33).

<Laminated body (34)>
For the production of the laminate (34), a mixed solution (U34) obtained by the same composition and method as the mixed solution (U8) obtained from the laminate (8) was used. Further, except that the base material was a stretched polyamide film (OPA), coating, heat treatment, ionization and drying were carried out in the same manner as in the laminate (1) to obtain a laminate (34).

<Laminated body (35)>
In the laminated body (35), a mixed liquid (U35) obtained by the same composition and method as the mixed liquid (U21) obtained in the laminated body (21) was used. In addition, coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (34) to obtain a laminate (35).

<Laminated body (36)>
In the laminated body (36), a mixed liquid (U36) obtained by the same composition and method as the mixed liquid (U8) obtained in the laminated body (8) was used. In addition, coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (34) to obtain a laminate (36).

<Laminated body (37)>
The laminate (37) was produced under the same conditions as the laminate (35) except that the substrate was changed. In preparation of a laminated body (37), the base material with which the inorganic layer (aluminum vapor deposition layer) was laminated | stacked was used instead of the base material of a laminated body (35). Specifically, a stretched polyethylene terephthalate film (manufactured by Toray Film Processing Co., Ltd., VM-PET (trade name), thickness 12 μm, hereinafter may be abbreviated as “deposition PET”) is used. It was.

<Laminated body (38)>
The laminate (38) was produced under the same conditions as the laminate (35) except that the substrate was changed. In the production of the laminate (38), a substrate on which an inorganic layer (aluminum vapor deposition layer) was laminated was used instead of the substrate of the laminate (35). Specifically, a biaxially stretched ethylene-vinyl alcohol copolymer film (a product of Kuraray Co., Ltd., VM-XL (trade name), thickness 12 μm, hereinafter abbreviated as “deposition EVOH”) on which an aluminum deposition layer is formed. Used).

<Laminated body (39)>
In the production of the laminate (39), the molar ratio of TMOS / GPTMOS was 89.9 / 10.1, [inorganic component derived from TMOS and GPTMOS] / [partial neutralized product of organic component of GPTMOS and PAA]. A mixed solution (T39) was prepared so that the ratio was 31.5 / 68.5. Specifically, first, 46 parts by weight of TMOS and 8 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol. To this was added 3.2 parts by weight of distilled water and 7.8 parts by weight of 0.1N hydrochloric acid so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent and the pH was 2 or less. The mixture was subjected to hydrolysis and condensation reaction for 5 hours to obtain a mixed solution (T39).

  Subsequently, a partially neutralized aqueous solution of PAA was prepared in the same manner as in the laminate (1). Next, after diluting the mixed liquid (T36) with 61 parts by weight of distilled water, 308 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring to obtain a solid content concentration of 13% by weight. A liquid mixture (U39) was obtained.

  On the other hand, a two-component anchor coating agent dissolved in 67 parts by weight of ethyl acetate (Mitsui Takeda Chemical Co., Ltd .: Takelac A-626 (trade name) 1 part by weight and Takenate A-50 (trade name) 2 parts by weight) Was coated on a stretched polyethylene terephthalate film (“PET” described above) and dried to prepare a substrate (AC (0.1 μm) / PET (12 μm)) having an anchor coat layer. On the anchor coat layer of this substrate, the mixed solution (U39) was coated with a bar coater so that the thickness after drying was 1.0 μm, and dried at 120 ° C. for 5 minutes. In the same procedure, both sides of the substrate were coated to obtain a laminate. This laminate was aged at 40 ° C. for 3 days. Subsequently, the laminate was heat-treated at 180 ° C. for 5 minutes using a dryer. Next, the laminate was immersed in a 2% by weight calcium acetate aqueous solution (85 ° C.) for 12 seconds and then dried at 50 ° C. for 5 minutes. In this way, a laminate (39) having a structure of gas barrier layer (1.0 μm) / AC (0.1 μm) / PET (12 μm) / AC (0.1 μm) / gas barrier layer (1.0 μm) is obtained. It was.

<Laminated body (40)>
For the production of the laminate (40), a mixed solution (U40) obtained by the same composition and method as the mixed solution (U39) obtained from the laminate (39) was used. Also, except that the base material was OPA, coating, heat treatment and ionization drying were performed in the same manner as in the laminate (1) to obtain a laminate (40).

<Laminated body (41)>
A mixed solution (U41) was obtained in the same manner as in the laminate (39) except that the solid content concentration was changed to 5% by weight. First, after the liquid mixture (T41) prepared by the same composition and method as the liquid mixture (T39) of the laminate (39) was diluted with 542 parts by weight of distilled water and 293 parts by weight of methanol, 308 parts by weight of an aqueous solution of a Japanese product (concentration 13% by weight) was quickly added to obtain a mixed solution (U41) having a solid content concentration of 5% by weight.

  Using the mixed solution (U41), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (41).

<Laminated body (42)>
For the production of the laminate (42), a mixed solution (U42) obtained by the same composition and method as the mixed solution (U41) obtained from the laminate (41) was used. In addition, coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (34) to obtain a laminate (42).

<Laminated body (43)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). A liquid mixture (U43) was prepared so that the weight ratio of [inorganic component derived from AIP] / [partially neutralized product of PAA] was 1.0 / 99.0 without adding TMOS and GPTMOS. Specifically, 100 parts by weight of a partially neutralized aqueous solution of PAA (concentration 5% by weight) is quickly added to 2.1 parts by weight of the 9.88% by weight AIP aqueous solution (S43), and the mixed solution (U43) is added. Obtained.

  Using the mixed solution (U43), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (43).

<Laminated body (44)>
A partially neutralized aqueous solution of PAA was prepared in the same manner as in the laminate (1). A mixed solution (U44) was prepared so that the weight ratio of [inorganic component derived from titanium lactate] / [partially neutralized product of PAA] was 0.9 / 99.1. Specifically, 1.6 parts by weight of an isopropyl alcohol solution of titanium lactate (concentration 10% by weight) is added to 100 parts by weight of an aqueous solution of partially neutralized PAA (concentration 5% by weight), and a mixed solution (U44) Got.

  Using the mixed solution (U44), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (44).

<Laminated body (45)>
The molar ratio of Al / Si was 40.4 / 59.6, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 40.3 / 59.7. A mixed solution (U45) was prepared with the same charging ratio as in the laminate (3) except for the above. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 461 parts by weight of a 9.88 wt% AIP aqueous solution (S45) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. To obtain a mixed solution (T45). Subsequently, after the mixed solution (T45) was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U45) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U45), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (45).

<Laminated body (46)>
The molar ratio of Al / Si was 0.06 / 99.94, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 70.0 / 30.0. Except for the above, a mixed solution (U46) was prepared at the same charging ratio as in the laminate (3). Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.4 part by weight of a 9.88 wt% AIP aqueous solution (S46) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T46) was obtained. Subsequently, the mixed liquid (T46) was diluted with 243 parts by weight of distilled water and 144 parts by weight of methanol, and then 65 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A mixed solution (U46) having a partial concentration of 5% by weight was obtained.

  Using the mixed solution (U46), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (46).

<Laminated body (47)>
A mixed solution (U47) was prepared by changing the reaction time only at the same charging ratio as in the laminate (46).

  Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.4 part by weight of a 9.88 wt% AIP aqueous solution (S47) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 1 hour. And a mixed solution (T47) was obtained. Subsequently, after the mixed liquid (T47) was diluted with 243 parts by weight of distilled water and 144 parts by weight of methanol, 65 parts by weight of an aqueous solution (partial concentration 13% by weight) of a partially neutralized PAA was rapidly added while stirring. A liquid mixture (U47) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U47), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (47).

<Laminated body (48)>
For the production of the laminate (48), a mixture (U48) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. In addition, coating and heat treatment were performed in the same manner as in the laminate (1) to produce a laminate (48).

[Evaluation results of laminate]
The produced laminate was evaluated by the method described above. The laminates (37) and (38) were not evaluated. The stretched polyethylene terephthalate film (PET) and stretched polyamide film (OPA) used as the substrate of the laminate were evaluated in the same manner as the laminate. The production conditions for the laminate are shown in Table 1.

  Table 2 shows the evaluation results of the laminate and the substrate.

  The total thickness of the gas barrier layers of the laminate (39) is 2.0 μm. Thus, when the total thickness of the gas barrier layer is large (for example, larger than 1.0 μm), the physical properties of the laminate are greatly different from the physical properties of the base material (PET), and the workability is reduced. End up. Therefore, when the gas barrier layer is made thick, there arises a problem that productivity is lowered. On the other hand, a laminate having a thin total gas barrier layer, such as laminates (1) to (33), exhibits physical properties close to that of the base material (PET) and has good workability. Therefore, in order to produce a vacuum heat insulator with high productivity, it is important to reduce the total thickness of the gas barrier layer (for example, 1.0 μm or less).

  [Production and evaluation of vacuum insulation]

<Example 1>
One side of a 60 μm-thick unstretched polypropylene film (Tosero CP RXC-18 manufactured by Tosero Co., Ltd .; hereinafter sometimes abbreviated as “CPP”), and a 15 μm-thick stretched polyamide film (Unita Co., Ltd. emblem (OPA An adhesive was applied to each of one side of)). Then, by laminating the CPP film, the OPA film, and the laminate (9) so as to have a configuration of OPA layer / adhesive layer / laminate (9) / adhesive layer / CPP layer, the laminate is obtained. Obtained.

  The laminate was cut to obtain two laminates having a size of 70 cm × 30 cm. The two laminates were overlapped so that the CPP layers were the inner surfaces, and the three sides were heat-sealed with a width of 10 mm to produce a three-sided bag. Next, a heat insulating core material is filled from the opening of the three-sided bag, and the three-sided bag is placed at a temperature of 20 ° C. and an internal pressure of 10 Pa using a vacuum packaging machine (VAC-STAR 2500 type manufactured by Frimark GmbH). The vacuum insulator of Example 1 was obtained by sealing. Silica fine powder dried for 4 hours in an atmosphere at 120 ° C. was used as the heat insulating core material. The obtained vacuum insulator was allowed to stand at 40 ° C. and 15% RH for 360 days, and then the pressure inside the vacuum insulator was measured using a Pirani vacuum gauge.

<Examples 2 to 12>
The same as in Example 1 except that the laminate (8), (12) to (18), (21), (37), or (38) was used instead of the laminate (9). The vacuum insulators of Examples 2-12 were prepared. The vacuum insulator was allowed to stand at 40 ° C. and 15% RH for 360 days, and then the pressure inside the vacuum insulator was measured using a Pirani vacuum gauge.

<Reference Example 1>
A vacuum heat insulator of Reference Example 1 was produced in the same manner as in Example 1 except that the laminate (39) was used instead of the laminate (9). The vacuum insulator was allowed to stand at 40 ° C. and 15% RH for 360 days, and then the pressure inside the vacuum insulator was measured using a Pirani vacuum gauge.

<Comparative Examples 1-3>
Vacuum heat insulators of Comparative Examples 1 to 3 were produced in the same manner as in Example 1 except that the laminates (45) to (47) were used instead of the laminate (9). The vacuum insulator was allowed to stand at 40 ° C. and 15% RH for 360 days, and then the pressure inside the vacuum insulator was measured using a Pirani vacuum gauge.

  Table 3 shows the evaluation results of the vacuum insulators of the examples and comparative examples.

  The vacuum insulators of the examples were able to maintain a high degree of vacuum even after a storage test for 360 days at 40 ° C. and 15% RH.

  Moreover, Examples 10-12 showed that a higher vacuum degree can be maintained by laminating an inorganic vapor deposition layer on a base material and using a gas barrier resin film on the base material.

  As described above, the vacuum insulator using the gas barrier layer of the present invention exhibited excellent characteristics over a long period of time.

  INDUSTRIAL APPLICATION This invention can be utilized for the vacuum heat insulating body which can be used for the various uses which need cold preservation and heat insulation. The vacuum heat insulating body of the present invention can maintain a heat insulating effect over a long period of time. Therefore, the vacuum heat insulating body of the present invention is a heat insulating material for household appliances such as a refrigerator, a hot water supply facility and a rice cooker, a heat insulating material for a house used for a wall portion, a ceiling portion, an attic portion and a floor portion, a vehicle roof material, It can be used for insulation panels such as vending machines.

10, 20 Vacuum insulator 11 Packaging material 12 Powder 13 Foam

Claims (9)

A vacuum insulator including a core material and a packaging material for packaging the core material, wherein the space in the packaging material is in a vacuum state,
The packaging material includes a gas barrier laminate,
The gas barrier laminate includes a substrate and at least one gas barrier layer laminated on the substrate,
The layer having gas barrier property includes a hydrolysis condensate of at least one compound (L) containing a hydrolyzable characteristic group, and at least one functional group selected from a carboxyl group and a carboxylic anhydride group. Comprising a neutralized product of the polymer (X) contained,
The compound (L) includes a compound (A) and a compound (B) containing Si to which a hydrolyzable characteristic group is bonded,
The compound (A) is at least one compound represented by the following formula (I):
M ¹ X ¹ _m Y ¹ _nm (I)
[In Formula (I), M ¹ represents any one selected from Al, Ti, and Zr. X ¹ represents any one selected from F, Cl, Br, I, OR ¹ , R ² COO, R ³ COCHCOR ⁴ , and NO ₃ . Y ¹ represents any one selected from F, Cl, Br, I, OR ⁵ , R ⁶ COO, R ⁷ COCHCOR ⁸ , NO ₃ and R ⁹ . R ¹ , R ² , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group. n is equal to the valence of M ¹ . m represents an integer of 1 to n. ]
The compound (B) includes at least one compound represented by the following formula (II):
Si (OR ¹⁰ ) _p R ¹¹ _4-pq X ² _q (II)
[In the formula (II), R ¹⁰ represents an alkyl group. R ¹¹ represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X ² represents a halogen atom. p and q represent the integer of 0-4 each independently. 1 ≦ p + q ≦ 4. ]
At least a part of —COO— group contained in the functional group of the polymer (X) is neutralized with a divalent or higher metal ion,
The proportion of the compound represented by the formula (II) in the compound (B) is 80 mol% or more,
In the composition, a ratio of [number of moles of the M ¹ atom derived from the compound (A)] / [number of moles of Si atom derived from the compound (B)] is 0.1 / 99.9 to 35. Vacuum insulator in the range of 0.0 / 65.0. The compound (B) further includes at least one compound represented by the following formula (III):
Si (OR ¹² ) _r X ³ _s Z ³ _4-rs (III)
[In the formula (III), R ¹² represents an alkyl group. X ³ represents a halogen atom. Z ³ represents an alkyl group substituted with a functional group having reactivity with a carboxyl group. r and s each independently represent an integer of 0 to 3. 1 ≦ r + s ≦ 3. ]
The ratio [number of moles of Si atoms derived from the compound represented by the formula (II)] / [number of moles of Si atoms derived from the compound represented by the formula (III)] was 99.5 / 0. The vacuum insulator according to claim 1, which is in a range of 5 to 80.0 / 20.0. The vacuum heat insulating body according to claim 1 or 2, wherein the M ¹ is Al.   The ratio of [weight of inorganic component derived from the compound (L)] / [total weight of organic component derived from the compound (L) and weight of organic component derived from the polymer (X)] is: The vacuum heat insulating body of any one of Claims 1-3 which exists in the range of 20.0 / 80.0-80.0 / 20.0.   The ratio of [weight of inorganic component derived from the compound (L)] / [total weight of organic component derived from the compound (L) and weight of organic component derived from the polymer (X)] is: The vacuum heat insulating body of any one of Claims 1-3 which exists in the range of 30.5 / 69.5-70.0 / 30.0.   The vacuum heat insulating body of any one of Claims 1-5 by which the inorganic layer formed by the vapor deposition method is arrange | positioned between the said base material and the said layer which has the said gas barrier property.   The vacuum insulator according to claim 6, wherein the inorganic layer contains aluminum atoms.   The vacuum insulator according to claim 6 or 7, wherein the substrate is made of an ethylene-vinyl alcohol copolymer.   The vacuum heat insulating body of any one of Claims 1-8 whose sum total of the thickness of the layer which has the said at least 1 gas-barrier property is 1 micrometer or less.

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