JP6091396B2 - Vacuum insulation - Google Patents

Description

  The present invention relates to a vacuum heat insulating body including a covering material and a core material disposed inside the covering material, and the inside of which is decompressed.

  Thermal insulators made of urethane foam (polyurethane foam) are used as refrigerator thermal insulation, residential thermal insulation panels, and the like. In recent years, vacuum insulators have also been used as an alternative insulator. The vacuum insulator makes it possible to achieve a heat insulation characteristic equivalent to that of a heat insulator made of urethane foam with a thinner and lighter heat insulator. Vacuum insulators are expanding their applications and demands as insulators used to insulate heat transfer devices such as heat pump applied devices, heat storage devices, living spaces, vehicle interior spaces, and the like.

  One of the characteristics required for a coating material for a vacuum insulator is gas barrier properties. For this reason, coating materials with improved gas barrier properties have been proposed.

  As a coating material with improved gas barrier properties, for example, a coating material provided with a transparent gas barrier coating containing a reaction product of alumina particles and a phosphorus compound is known (Patent Document 1: International Publication No. 2011-122036). . This transparent gas barrier film is formed by applying a coating liquid containing alumina particles and a phosphorus compound on a substrate.

International Publication No. 2011-122036

  However, although the above conventional coating materials are excellent in initial gas barrier properties, defects such as cracks and pinholes may occur in the gas barrier coating when subjected to physical stress such as deformation and impact. In some cases, gas barrier properties could not be secured over a period of time. When the core material is packaged, the coating material of the vacuum heat insulator is subjected to physical stress by evacuation for decompressing the inside thereof. Thereafter, the coating material is subjected to various physical stresses during the transportation, installation, construction and other stages of the vacuum insulator. When the gas barrier property of the covering material is deteriorated, the internal pressure of the vacuum heat insulating material is increased and the heat insulating property is deteriorated. For this reason, there is a need for a vacuum insulator that can maintain the gas barrier property of the coating material at a high level even under physical stress.

  An object of the present invention is to provide a vacuum heat insulating body suitable for maintaining a gas barrier property of a coating material at a high level even under physical stress.

  The vacuum insulator according to the present invention is a vacuum insulator including a covering material and a core material disposed inside the covering material, wherein the inside is decompressed, and the covering material is a base material (X) includes a multilayer structure having one or more layers (Y) and (Z), wherein the layer (Y) includes an aluminum atom and the layer (Z) includes a monomer unit having a phosphorus atom. The layer (Y) and the layer (Z) are laminated adjacent to each other.

  In the vacuum insulator according to the present invention, at least one set of the base material (X), the layer (Y), and the layer (Z) is the base material (X) / the layer (Y) / the layer (Z ) May be stacked in this order.

  In the vacuum insulator according to the present invention, the polymer (E) may be a homopolymer or copolymer of (meth) acrylic acid esters having a phosphate group at the end of the side chain.

  In the vacuum insulator according to the present invention, the polymer (E) may be a homopolymer of acid phosphooxyethyl (meth) acrylate.

  In the vacuum insulator according to the present invention, the polymer (E) may have a repeating unit represented by the following general formula (I).

In the vacuum insulator according to the present invention, the layer (Y) may be a layer (YA) containing the reaction product (R). The reaction product (R) is a reaction product obtained by a reaction between a metal oxide (A) containing aluminum and a phosphorus compound (B). The infrared absorption spectrum of the layer (YA) is 800 to 1400 cm ^{−. The} wave number (n ¹ ) that maximizes infrared absorption in the range of ¹ may be in the range of 1080 to 1130 cm ⁻¹ .

  In the vacuum insulator according to the present invention, the layer (Y) may be an aluminum deposition layer (YB) or an aluminum oxide deposition layer (YC).

  In the vacuum heat insulating body according to the present invention, the base material (X) may include at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer.

  In the vacuum insulator according to the present invention, the multilayer structure is a part of the substrate (X), the layer (Y) or the layer (Z), or the substrate (X) or the layer (Y). An inorganic vapor deposition layer may be included together with the layer (Z).

The vacuum insulator according to the present invention may have an oxygen permeability of 2 ml / (m ² · day · atm) or less under the conditions of 20 ° C. and 85% RH of the covering material.

In the vacuum heat insulating body according to the present invention, the covering material is held for 5 minutes in a state where it is stretched 5% in one direction under the conditions of 23 ° C. and 50% RH, and then the covering material is subjected to the conditions of 20 ° C. and 85% RH. The oxygen permeability measured below may be 4 ml / (m ² · day · atm) or less.

  ADVANTAGE OF THE INVENTION According to this invention, even if it receives physical stress, the vacuum heat insulating body suitable for maintaining the gas barrier property which a coating | covering material has at a high level is obtained.

It is sectional drawing which shows one form of the vacuum heat insulating body by this invention. It is sectional drawing which shows another one form of the vacuum heat insulating body by this invention.

  Hereinafter, embodiments of the present invention will be described. In the following description, a specific material (such as a compound) may be exemplified as a material that exhibits a specific function. However, the present invention is not limited to an embodiment using such a material. Moreover, as long as there is no description in particular, the material illustrated may be used individually by 1 type, and may use 2 or more types together.

[Vacuum insulation]
The vacuum heat insulating body is a heat insulating body that includes a covering material and a core material disposed inside the covering material and in which the inside where the core material is disposed is decompressed.

  One form of the vacuum heat insulating body by this invention is illustrated in FIG. The vacuum heat insulating body 1 includes powder as the core material 51. The core material 51 is disposed inside the coating material 10. The covering material 10 is composed of two film materials 31 and 32, and the film materials 31 and 32 are joined to each other at the peripheral edge 11 thereof. In the central portion surrounded by the peripheral edge portion 11, the covering material 10 functions as a partition wall 20 that separates the inside and the outside in which the core material 51 is accommodated, and the core material 51 is caused by a pressure difference between the inside and the outside of the heat insulator. It is in close contact.

  Another embodiment of the vacuum insulator according to the present invention is illustrated in FIG. The vacuum heat insulating body 2 is different from the vacuum heat insulating body 1 in that it includes a molded body integrally formed as the core material 52, but has the same configuration as the vacuum heat insulating body 1 in other points. The core material 52, which is a molded body, is typically a resin foam.

  The material and shape of the core material are not particularly limited as long as they are suitable for heat insulation. Examples of the core material include pearlite powder, silica powder, precipitated silica powder, diatomaceous earth, calcium silicate, glass wool, rock wool, artificial (synthetic) wool, and resin foam (for example, styrene foam, urethane foam). Can be used. As the core material, a hollow container formed in a predetermined shape, a honeycomb structure, or the like can be used.

  In the vacuum heat insulating body 1, the coating | covering material 10 (film material 31 and 32) contains the multilayer structure demonstrated below. The vacuum heat insulating body 1 may further include members other than the covering material 10 and the core materials 51 and 52. The covering material 10 may be composed of only a multilayer structure, or may be a laminate of members other than the multilayer structure. As long as the covering material 10 is a layered laminate suitable for forming the vacuum heat insulating body 1 and includes the following multilayer structure, the thickness and material thereof are not particularly limited.

[Multilayer structure]
The multilayer structure is a multilayer structure having at least one base (X), layer (Y) and layer (Z), wherein the layer (Y) contains aluminum atoms and the layer (Z) contains phosphorus atoms. And a polymer (E) containing a monomer unit having at least one layer (Y) and a layer (Z) are laminated adjacent to each other. This multilayer structure is excellent in characteristics (hereinafter sometimes referred to as “bending resistance”) that suppress a decrease in gas barrier properties of the film material due to physical stress.

[Layer (Y)]
The layer (Y) of the multilayer structure may be a layer (YA) containing a reaction product (R) formed by a reaction of at least a metal oxide (A) containing aluminum and a phosphorus compound (B). . Alternatively, the layer (Y) is a layer that is an aluminum deposition layer (hereinafter may be referred to as “layer (YB)”) or an aluminum oxide deposition layer (hereinafter may be referred to as “layer (YC)”). Hereinafter, these will be described in order.

[Layer (YA)]
When the layer (Y) of the multilayer structure is the layer (YA), in the infrared absorption spectrum of the layer (YA), the wave number (n ¹ ) at which the infrared absorption in the range of 800 to 1400 cm ⁻¹ is maximized. May be in the range of 1080 to 1130 cm ⁻¹ .

Hereinafter, the wave number (n ¹ ) may be referred to as “maximum absorption wave number (n ¹ )”. The metal oxide (A) usually reacts with the phosphorus compound (B) in the form of particles of the metal oxide (A).

  Typically, the layer (YA) included in the multilayer structure has a structure in which the metal oxide (A) particles are bonded to each other via a phosphorus atom derived from the phosphorus compound (B). The form bonded via a phosphorus atom includes the form bonded via an atomic group containing a phosphorus atom, for example, bonded via an atomic group containing a phosphorus atom and not containing a metal atom. Are included.

  In the layer (YA) of the multilayer structure, the number of moles of metal atoms that are bonded to the metal oxide (A) particles and are not derived from the metal oxide (A) is determined by the metal oxide ( A) is preferably in the range of 0 to 1 times the number of moles of phosphorus atoms bonding the particles to each other (for example, in the range of 0 to 0.9 times), for example, 0.3 times or less, 0.05 It may be less than twice, less than 0.01 times, or 0 times.

  The layer (YA) of the multilayer structure may partially contain a metal oxide (A) and / or a phosphorus compound (B) that is not involved in the reaction.

In general, a metal atom and a phosphorus compound react to react a metal atom (M) constituting the metal compound and a phosphorus atom (P) derived from the phosphorus compound bonded via an oxygen atom (O). When a bond represented by is generated, a characteristic peak occurs in the infrared absorption spectrum. Here, the characteristic peak shows an absorption peak at a specific wave number depending on the environment or structure around the bond. As a result of the study by the present inventors, when the absorption peak based on the M—O—P bond is located in the range of 1080 to 1130 cm ⁻¹ , excellent gas barrier properties are expressed in the obtained multilayer structure. I understood. In particular, when the absorption peak appears as an absorption peak of the maximum absorption wave number in the region of 800 to 1400 cm ⁻¹ where absorption derived from bonds between various atoms and oxygen atoms is generally observed, in the obtained multilayer structure Furthermore, it turned out that the outstanding gas-barrier property is expressed.

In addition, although this invention is not limited at all, the metal oxide (A) particle | grains are via the phosphorus atom derived from a phosphorus compound (B), and the metal atom which does not originate in a metal oxide (A) And a metal atom (M) constituting the metal oxide (A) and a phosphorus atom (P) which are bonded via an oxygen atom (O). In the infrared absorption spectrum of the layer (YA), the absorption peak based on the M—O—P bond is 1080 due to the relatively fixed environment of the surface of the metal oxide (A) particles. It is considered that it appears as an absorption peak of the maximum absorption wave number in the region of 800 to 1400 cm ^{−1 in} the range of ˜1130 cm ⁻¹ .

In contrast, when a metal compound that does not form a metal oxide such as a metal alkoxide or a metal salt and a phosphorus compound (B) are mixed in advance and then hydrolytically condensed, the metal atom derived from the metal compound and A complex in which phosphorus atoms derived from the phosphorus compound (B) are mixed almost uniformly and reacted is obtained, and in the infrared absorption spectrum, the maximum absorption wave number (n ¹ ) in the range of 800 to 1400 cm ⁻¹ is 1080 to 1130 cm ^−. Beyond the range of ¹ .

The maximum absorption wave number (n ¹ ) is preferably in the range of 1085 to 1120 cm ⁻¹ , and more preferably in the range of 1090 to 1110 cm ⁻¹ , because a multilayer structure having excellent gas barrier properties is obtained.

In the infrared absorption spectrum of the layer (YA) of the multilayer structure, absorption of stretching vibrations of hydroxyl groups bonded to various atoms may be observed in the range of 2500 to 4000 cm ⁻¹ . Examples of hydroxyl groups that are absorbed in this range include hydroxyl groups that exist on the surface of the metal oxide (A) portion and have the form of M-OH, and are bonded to phosphorus atoms (P) derived from the phosphorus compound (B). And a hydroxyl group having a P—OH form, a hydroxyl group having a C—OH form derived from the polymer (C) described later, and the like. The amount of the hydroxyl group present in the layer (YA) can be related to the absorbance (α ² ) at the wave number (n ² ) of maximum absorption based on the stretching vibration of the hydroxyl group in the range of 2500 to 4000 cm ⁻¹ . Here, the wave number (n ² ) is a wave number that maximizes infrared absorption based on the stretching vibration of hydroxyl groups in the range of 2500 to 4000 cm ⁻¹ in the infrared absorption spectrum of the layer (YA). Hereinafter, the wave number (n ² ) may be referred to as “maximum absorption wave number (n ² )”.

As the amount of hydroxyl groups present in the layer (YA) increases, the density of the layer (YA) decreases, and as a result, gas barrier properties tend to decrease. In the infrared absorption spectrum of the layer (YA) of the multilayer structure, the ratio of the absorbance (α ¹ ) and the absorbance (α ² ) at the maximum absorption wavenumber (n ¹ ) [absorbance (α ² ) / absorbance ( It is considered that the smaller the [alpha] ¹ )], the more effectively the particles of the metal oxide (A) are bonded through the phosphorus atom derived from the phosphorus compound (B). Therefore, the ratio [absorbance (α ² ) / absorbance (α ¹ )] is preferably 0.2 or less, and preferably 0.1 or less, from the viewpoint of highly expressing the gas barrier properties of the resulting multilayer structure. It is more preferable. The multilayer structure in which the layer (YA) has the above ratio [absorbance (α ² ) / absorbance (α ¹ )] is the number of moles of metal atoms (N _M ) constituting the metal oxide (A) described later. And the ratio of the number of moles of phosphorus atoms derived from the phosphorus compound (B) (N _P ), heat treatment conditions, and the like. Although not particularly limited, in the infrared absorption spectrum of the precursor layer for later layers (YA), maximum absorbance in the range 800～1400Cm ^-1 and (α ¹ '), 2500~4000cm ^-1 The maximum absorbance (α ² ′) based on the stretching vibration of the hydroxyl group in the range may satisfy the relationship of absorbance (α ² ′) / absorbance (α ¹ ′)> 0.2.

In the infrared absorption spectrum of the layer (YA) of the multilayer structure, the half width of the absorption peak having a maximum at the maximum absorption wave number (n ¹ ) is 200 cm ⁻¹ or less from the viewpoint of the gas barrier property of the resulting multilayer structure. Preferably, it is 150 cm ⁻¹ or less, more preferably 130 cm ⁻¹ or less, more preferably 110 cm ⁻¹ or less, even more preferably 100 cm ⁻¹ or less, and even more preferably 50 cm. Particularly preferably, it is ⁻¹ or less. Although this invention is not limited at all, when the particles of the metal oxide (A) are bonded to each other via a phosphorus atom, the particles of the metal oxide (A) are phosphorous derived from the phosphorus compound (B). Metal atoms (M) and phosphorus atoms (P) constituting the metal oxide (A) are bonded with oxygen atoms (O) through atoms and without metal atoms not derived from the metal oxide (A). When the bond represented by M-O-P is formed through the metal oxide (A), the maximum absorption wave number (n ¹ ) is maximized due to the relatively fixed environment of the surface of the metal oxide (A) particles. It is considered that the half width of the absorption peak having a value falls within the above range. In this specification, the half width of the absorption peak of the maximum absorption wave number (n ¹ ) is the wave number of two points having an absorbance (absorbance (α ¹ ) / 2) that is half of the absorbance (α ¹ ) at the absorption peak. It can be obtained by calculating the difference.

  The infrared absorption spectrum of the layer (YA) is measured by the ATR method (total reflection measurement method), or the layer (YA) is scraped from the multilayer structure and the infrared absorption spectrum is measured by the KBr method. Can be obtained.

  In the layer (YA) of the multilayer structure, the shape of each particle of the metal oxide (A) is not particularly limited, and examples thereof include a spherical shape, a flat shape, a polyhedral shape, a fibrous shape, and a needle shape. In addition, a fibrous or needle-like shape is preferable because a multilayer structure excellent in gas barrier properties is obtained. The layer (YA) may have only particles having a single shape, or may have particles having two or more different shapes. In addition, the size of the metal oxide (A) particles is not particularly limited, and examples include nanometer-size to submicron-size particles. The size of the particles (A) is preferably in the range of 1 to 100 nm as an average particle size.

  Note that the fine structure as described above in the layer (YA) included in the multilayer structure can be confirmed by observing a cross section of the layer (YA) with a transmission electron microscope (TEM). The particle size of each particle of the metal oxide (A) in the layer (YA) is the maximum length of the longest axis of each particle in the cross-sectional observation image of the layer (YA) obtained by a transmission electron microscope (TEM). The average particle size can be obtained as an average value of the maximum lengths of the particles on an axis perpendicular to the average, and the average particle size of ten particles arbitrarily selected in the cross-sectional observation image is obtained. Can do.

  In one example, the layer (YA) that the multilayer structure has is a metal atom in which the particles of the metal oxide (A) pass through phosphorus atoms derived from the phosphorus compound (B) and are not derived from the metal oxide (A). It has a structure that is connected without intervening. That is, in one example, the metal oxide (A) particles may be bonded to each other via a metal atom derived from the metal oxide (A), but are not bonded to any other metal atom. Have Here, “the structure bonded through the phosphorus atom derived from the phosphorus compound (B) and not through the metal atom not derived from the metal oxide (A)” means the metal oxide (A) to be bonded. Means that the main chain of the bond between the particles has a phosphorus atom derived from the phosphorus compound (B) and does not have a metal atom not derived from the metal oxide (A). A structure having a metal atom in the side chain is also included. However, the layer (YA) of the multilayer structure has a structure (bonded) in which particles of the metal oxide (A) are bonded through both phosphorus atoms and metal atoms derived from the phosphorus compound (B). The main chain of the bond between the metal oxide (A) particles may partially include a structure having both a phosphorus atom and a metal atom derived from the phosphorus compound (B).

In the layer (YA) of the multilayer structure, as the bonding form of each particle of the metal oxide (A) and the phosphorus atom, for example, the metal atom (M) and the phosphorus atom ( P) may be exemplified by a form in which it is bonded via an oxygen atom (O). The particles of the metal oxide (A) may be bonded to each other via a phosphorus atom (P) derived from one molecule of the phosphorus compound (B), but phosphorus derived from two or more molecules of the phosphorus compound (B). It may be bonded via an atom (P). As a specific form of bonding between two bonded metal oxide (A) particles, a metal atom constituting one bonded metal oxide (A) particle is represented as (Mα), When the metal atom constituting the other metal oxide (A) particle is represented by (Mβ), for example, (Mα) -OPO- (Mβ) bond form; (Mα) -OP— [O—P] _n —O— (Mβ) bond form; (Mα) —O—P—Z—P—O— (Mβ) bond form; (Mα) —O—P—Z—P— [ O—P—Z—P] _n —O— (Mβ) and the like. In the example of the bonding form, n represents an integer of 1 or more, and Z represents a constituent atomic group existing between two phosphorus atoms when the phosphorus compound (B) has two or more phosphorus atoms in the molecule. And the description of other substituents bonded to the phosphorus atom is omitted. In the layer (YA) of the multilayer structure, one metal oxide (A) particle is bonded to a plurality of other metal oxide (A) particles. From the viewpoint of

The metal oxide (A) may be a hydrolysis condensate of the compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded. Examples of the characteristic group include X ^{1 of} the formula (I) described later.

  In addition, the hydrolysis-condensation product of the compound (L) can be substantially regarded as a metal oxide. Therefore, in this specification, the hydrolysis condensate of the compound (L) may be referred to as “metal oxide (A)”. That is, in this specification, “metal oxide (A)” can be read as “hydrolysis condensate of compound (L)”, and “hydrolysis condensate of compound (L)” can be referred to as “metal. It can be read as “oxide (A)”.

[Metal oxide (A)]
The metal atoms constituting the metal oxide (A) (sometimes collectively referred to as “metal atoms (M)”) have a valence of 2 or more (for example, 2 to 4 or 3 to 4). Specifically, for example, metals of Group 2 of the periodic table such as magnesium and calcium; metals of Group 12 of the periodic table such as zinc; metals of Group 13 of the periodic table such as aluminum Examples thereof include metals; metals of Group 14 of the periodic table such as silicon; transition metals such as titanium and zirconium. Silicon may be classified as a semimetal, but in this specification, silicon is included in the metal. The metal atom (M) constituting the metal oxide (A) may be one kind or two or more kinds, but it is necessary to contain at least aluminum. The metal atom (M) that can be used in combination with aluminum is selected from the group consisting of titanium and zirconium because of ease of handling for producing the metal oxide (A) and excellent gas barrier properties of the resulting multilayer structure. It is preferable that there is at least one.

  The total proportion of aluminum, titanium and zirconium in the metal atom (M) was 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%. May be. The proportion of aluminum in the metal atom (M) may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%.

  As the metal oxide (A), those produced by a liquid phase synthesis method, a gas phase synthesis method, a solid pulverization method or the like can be used. In view of the controllability of the thickness and production efficiency, those produced by the liquid phase synthesis method are preferred.

  In the liquid phase synthesis method, a hydrolyzable condensation product of the compound (L) is obtained by hydrolyzing and condensing the compound (L) having a hydrolyzable characteristic group bonded to the metal atom (M) as a raw material. A metal oxide (A) can be synthesized. However, the metal atom (M) included in the compound (L) needs to contain at least aluminum. Moreover, when manufacturing the hydrolysis-condensation product of a compound (L) with a liquid phase synthesis method, the compound (L) which a partly hydrolyzed compound (L) other than the method of using the compound (L) itself as a raw material ( L) partial hydrolyzate, compound (L) completely hydrolyzed product obtained by completely hydrolyzing compound (L), compound (L) partially hydrolyzed and condensed part of compound (L) Metal oxidation can also be achieved by condensing or hydrolyzing a hydrolysis condensate, a product obtained by condensing a part of a complete hydrolyzate of compound (L), or a mixture of two or more of these as raw materials. A thing (A) can be manufactured. The metal oxide (A) thus obtained is also referred to as “hydrolysis condensate of compound (L)” in the present specification. There are no particular restrictions on the type of the functional group (functional group) that can be hydrolyzed, and examples include halogen atoms (F, Cl, Br, I, etc.), alkoxy groups, acyloxy groups, diacylmethyl groups, nitro groups, and the like. However, a halogen atom or an alkoxy group is preferable, and an alkoxy group is more preferable because of excellent controllability of the reaction.

The compound (L) preferably contains at least one compound (L ¹ ) represented by the following formula (II) because the reaction is easily controlled and the resulting multilayer structure has excellent gas barrier properties.
AlX ¹ _m R ¹ _(3-m) (II)
[In Formula (II), X ¹ is selected from F, Cl, Br, I, R ² O—, R ³ C (═O) O—, (R ⁴ C (═O)) ₂ CH— and NO _3. Selected from the group of R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. In the formula (II), when there are a plurality of X ¹ , these X ¹ may be the same or different from each other. In the formula (II), when a plurality of R ¹ are present, these R ¹ may be the same or different from each other. In the formula (II), when a plurality of R ² are present, these R ² may be the same or different from each other. In the formula (II), when a plurality of R ³ are present, these R ³ may be the same or different from each other. In the formula (II), when a plurality of R ⁴ are present, these R ⁴ may be the same as or different from each other. m represents an integer of 1 to 3. ]

Examples of the alkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a s-butyl group, a t-butyl group, and 2-ethylhexyl. Group and the like. Examples of the aralkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a benzyl group, a phenethyl group and a trityl group. Examples of the aryl group represented by R ¹ , R ² , R ³ and R ⁴ include a phenyl group, a naphthyl group, a tolyl group, a xylyl group and a mesityl group. Examples of the alkenyl group represented by R ¹ , R ² , R ³ and R ⁴ include a vinyl group and an allyl group. For example, R ¹ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. X ¹ is preferably F, Cl, Br, I, or R ² O—. In a preferred example of the compound (L ¹ ), X ¹ is a halogen atom (F, Cl, Br, I) or an alkoxy group having 1 to 4 carbon atoms (R ² O—), and m is 3. In one example of the compound (L ¹ ), X ¹ is a halogen atom (F, Cl, Br, I) or an alkoxy group having 1 to 4 carbon atoms (R ² O—), and m is 3.

In addition to the compound (L ¹ ), the compound (L) may include at least one compound represented by the following formula.
M ¹ X ¹ _m R ¹ _(nm) (III)
[Wherein M ¹ represents Ti or Zr. X ¹ and R ¹ are as described in formula (II). However, in the formula (III), n is equal to the valence of M ^1, m represents an integer of 1 to n. ]

Specific examples of the compound (L ¹ ) include, for example, aluminum chloride, aluminum triethoxide, aluminum trinormal propoxide, aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tri-s-butoxide, aluminum tri-t-butoxide, Examples thereof include aluminum compounds such as aluminum triacetate, aluminum acetylacetonate, and aluminum nitrate. Among these, as the compound (L ¹ ), at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide is preferable. As the compound (L ¹ ), one type may be used alone, or two or more types may be used in combination.

The ratio of the compound (L ¹ ) in the compound (L) is not particularly limited. The proportion of the compound other than the compound (L ¹ ) in the compound (L) is, for example, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 0 mol%. In one example, the compound (L) consists only of the compound (L ¹ ).

Further, the compound (L) other than the compound (L ¹ ) is not particularly limited as long as the effects of the present invention can be obtained. For example, the above-mentioned hydrolyzate may be added to a metal atom such as titanium, zirconium, magnesium, calcium, zinc, or silicon. Examples thereof include a compound having a decomposable characteristic group bonded thereto. Silicon may be classified as a semimetal, but in this specification, silicon is included in the metal. Among these, the compound (L) other than the compound (L ¹ ) is preferably a compound having titanium or zirconium as a metal atom because the resulting multilayer structure is excellent in gas barrier properties. Specific examples of the compound (L) other than the compound (L ¹ ) include, for example, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra (2-ethylhexoxide), titanium tetramethoxide, titanium tetraethoxide. And titanium compounds such as titanium acetylacetonate; zirconium compounds such as zirconium tetranormal propoxide, zirconium tetrabutoxide and zirconium tetraacetylacetonate.

  By hydrolyzing the compound (L), at least a part of the hydrolyzable characteristic group of the compound (L) is substituted with a hydroxyl group. Furthermore, the hydrolyzate condenses to form a compound in which the metal atom (M) is bonded through the oxygen atom (O). When this condensation is repeated, a compound that can be substantially regarded as a metal oxide is formed. In addition, a hydroxyl group usually exists on the surface of the metal oxide (A) thus formed.

  In this specification, the oxygen atom (O) bonded to only the metal atom (M), such as the oxygen atom (O) in the structure represented by MOM, with respect to the number of moles of the metal atom (M). For example, the oxygen atom (O) in the structure represented by M—O—H is excluded, and the oxygen atom bonded to the metal atom (M) and the hydrogen atom (H) is excluded) ([[ A compound in which the number of moles of oxygen atoms (O) bonded only to metal atoms (M) / [number of moles of metal atoms (M)]) is 0.8 or more is included in the metal oxide (A) And The ratio of the metal oxide (A) is preferably 0.9 or more, more preferably 1.0 or more, and further preferably 1.1 or more. Although the upper limit of the said ratio is not specifically limited, When the valence of a metal atom (M) is set to n, it will normally be represented by n / 2.

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

  A hydrolysis condensate can be manufactured from a specific raw material by the method employ | adopted by the well-known sol-gel method, for example. The raw materials include compound (L), partial hydrolyzate of compound (L), complete hydrolyzate of compound (L), partial hydrolyzed condensate of compound (L), and complete hydrolysis of compound (L). It is possible to use at least one selected from the group consisting of a part of the product condensed (hereinafter sometimes referred to as “compound (L) component”). 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 hydrolytic condensation of about 2 to 10 compounds (L) can be used as a raw material. Specifically, for example, a product obtained by hydrolyzing and condensing aluminum triisopropoxide to form a 2- to 10-mer condensate can be used as a part of the raw material.

  The number of molecules condensed in the hydrolyzed condensate of compound (L) can be controlled by the conditions at the time of condensing or hydrolyzing the compound (L) component. 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 and time for condensation or hydrolysis condensation, and the like.

  As described above, the layer (YA) included in the multilayer structure includes the reaction product (R), and the reaction product (R) includes at least the metal oxide (A) including aluminum and the phosphorus compound (B). Is a reaction product obtained by reaction. Such a reaction product can be formed by mixing and reacting the metal oxide (A) and the phosphorus compound (B). The metal oxide (A) used for mixing with the phosphorus compound (B) (immediately before mixing) may be the metal oxide (A) itself or a composition containing the metal oxide (A). It may be in the form of a thing. In a preferred example, the metal oxide (A) is mixed with the phosphorus compound (B) in the form of a liquid (solution or dispersion) obtained by dissolving or dispersing the metal oxide (A) in a solvent.

  A preferred method for producing a solution or dispersion of the metal oxide (A) is described below. Here, a method for producing the dispersion liquid will be described by taking as an example the case where the metal oxide (A) does not contain a metal atom other than aluminum atoms, that is, the case where the metal oxide (A) is aluminum oxide (alumina). However, a similar production method can be adopted when producing a solution or dispersion containing other metal atoms. A preferred alumina dispersion is obtained by hydrolyzing and condensing aluminum alkoxide in an aqueous solution whose pH is adjusted with an acid catalyst as necessary to obtain an alumina slurry, which is peptized in the presence of a specific amount of acid. Can do.

  The temperature of the reaction system when the aluminum alkoxide is hydrolytically condensed is not particularly limited. The temperature of the reaction system is usually in the range of 2 to 100 ° C. When water and aluminum alkoxide come into contact, the temperature of the liquid rises, but as the hydrolysis proceeds, alcohol is by-produced, and when the boiling point of the alcohol is lower than that of water, the alcohol volatilizes and the temperature of the reaction system is reduced. It may not rise above the vicinity of the boiling point of the alcohol. In such a case, since the growth of alumina may be slow, it is effective to remove the alcohol by heating to around 95 ° C. The reaction time varies depending on the reaction conditions (presence / absence of acid catalyst, amount, type, etc.). The reaction time is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, and more preferably in the range of 0.5 to 6 hours. The reaction can be performed in an atmosphere of various gases such as air, carbon dioxide, nitrogen, and argon.

  The amount of water used in the hydrolytic condensation is preferably 1 to 200 mol times, more preferably 10 to 100 mol times with respect to the aluminum alkoxide. When the amount of water is less than 1 mole, hydrolysis does not proceed sufficiently, such being undesirable. On the other hand, when it exceeds 200 mol times, since manufacturing efficiency falls or a viscosity becomes high, it is unpreferable. When a component containing water (for example, hydrochloric acid or nitric acid) is used, it is preferable to determine the amount of water used in consideration of the amount of water introduced by the component.

  As an acid catalyst used for hydrolysis condensation, 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. Among these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are preferable, and nitric acid and acetic acid are more preferable. When an acid catalyst is used at the time of hydrolysis condensation, it is preferable to use an amount suitable for the type of acid so that the pH before hydrolysis condensation is in the range of 2.0 to 4.0.

  The alumina slurry obtained by hydrolysis and condensation can be used as an alumina dispersion as it is, but the obtained alumina slurry is heated in the presence of a specific amount of acid to peptize and become transparent. An alumina dispersion having excellent viscosity stability can be obtained.

  As an acid used at the time of peptization, a monovalent inorganic acid or organic acid such as nitric acid, hydrochloric acid, perchloric acid, formic acid, acetic acid, propionic acid can be used. Among these, nitric acid, hydrochloric acid, and acetic acid are preferable, and nitric acid and acetic acid are more preferable.

  When nitric acid or hydrochloric acid is used as the acid during peptization, the amount is preferably 0.001 to 0.4 mol times, preferably 0.005 to 0.3 mol times the aluminum atom. More preferred. When the amount is less than 0.001 mole times, peptization may not sufficiently proceed or a very long time may be required. On the other hand, when it exceeds 0.4 mole times, the temporal stability of the resulting alumina dispersion tends to be lowered.

  On the other hand, when acetic acid is used as the acid during peptization, the amount thereof is preferably 0.01 to 1.0 mol times, preferably 0.05 to 0.5 mol times with respect to aluminum atoms. More preferred. When the amount is less than 0.01 mole times, peptization may not proceed sufficiently, or problems such as a very long time may occur. On the other hand, when it exceeds 1.0 mole times, the temporal stability of the resulting alumina dispersion tends to be lowered.

  The acid to be present at the time of peptization may be added at the time of hydrolysis condensation, but when acid is lost when removing alcohol by-produced by hydrolysis condensation, the amount is in the above range. It is preferable to add it again.

  By performing peptization within the range of 40 to 200 ° C., it is possible to pept in a short time with an appropriate amount of acid used to produce an alumina dispersion having a predetermined particle size and excellent viscosity stability. be able to. When the temperature during peptization is less than 40 ° C, it takes a long time for peptization, and when it exceeds 200 ° C, the increase in peptization rate by increasing the temperature is slight, while the high pressure vessel It is not preferable because it is economically disadvantageous.

  After the peptization is completed, an alumina dispersion having a predetermined concentration can be obtained by performing dilution with a solvent or concentration by heating as necessary. However, in order to suppress thickening and gelation, it is preferable to carry out the heat concentration at 60 ° C. or lower under reduced pressure.

  It is preferable that the metal oxide (A) to be mixed with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) does not substantially contain a phosphorus atom. However, for example, due to the influence of impurities during preparation of the metal oxide (A), it is used for mixing with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition). A small amount of phosphorus atoms may be mixed in the metal oxide (A). Therefore, the metal oxide (A) used for mixing with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) within a range in which the effects of the present invention are not impaired. May contain a small amount of phosphorus atoms. The phosphorus atom content contained in the metal oxide (A) used for mixing with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) is more excellent in gas barrier properties. Since a multilayer structure can be obtained, it is preferably 30 mol% or less, based on the number of moles of all metal atoms (M) contained in the metal oxide (A) (100 mol%). % Or less, more preferably 5 mol% or less, further preferably 1 mol% or less, and may be 0 mol%.

  The layer (YA) of the multilayer structure has a specific structure in which the particles of the metal oxide (A) are bonded via phosphorus atoms derived from the phosphorus compound (B). ) And the metal oxide (A) provided for mixing with the shape and size of the metal oxide (A) particles and the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition). The shape and size of the particles A) may be the same or different. That is, the shape and size of the metal oxide (A) particles used as the raw material for the layer (YA) may change during the process of forming the layer (YA). In particular, when the layer (YA) is formed using the coating liquid (U) described later, in the coating liquid (U) and the liquid (S) described later that can be used to form the layer, Or in each process after apply | coating coating liquid (U) on base material (X), a shape and size may change.

[Phosphorus Compound (B)]
The phosphorus compound (B) contains a site capable of reacting with the metal oxide (A), and typically contains a plurality of such sites. In a preferred example, the phosphorus compound (B) contains 2 to 20 such sites (atomic groups or functional groups). Examples of such a part include a part capable of reacting with a functional group (for example, a hydroxyl group) present on the surface of the metal oxide (A). For example, examples of such a site include a halogen atom directly bonded to a phosphorus atom and an oxygen atom directly bonded to a phosphorus atom. Those halogen atoms and oxygen atoms can cause a condensation reaction (hydrolysis condensation reaction) with a hydroxyl group present on the surface of the metal oxide (A). The functional group (for example, hydroxyl group) present on the surface of the metal oxide (A) is usually bonded to the metal atom (M) constituting the metal oxide (A).

  As the phosphorus compound (B), for example, a compound having a structure in which a halogen atom or an oxygen atom is directly bonded to a phosphorus atom can be used. By using such a phosphorus compound (B), a metal oxide (A) can be used. It can be combined by condensation (hydrolysis) with a hydroxyl group present on the surface. The phosphorus compound (B) may have one phosphorus atom, or may have two or more phosphorus atoms.

The phosphorus compound (B) may be at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Specific examples of polyphosphoric acid include pyrophosphoric acid, triphosphoric acid, polyphosphoric acid condensed with four or more phosphoric acids, and the like. Examples of the derivatives include salts of phosphoric acid, polyphosphoric acid, phosphorous acid, and phosphonic acid, (partial) ester compounds, halides (such as chlorides), dehydrates (such as niline pentoxide), and the like. . In addition, examples of phosphonic acid derivatives include a hydrogen atom directly bonded to a phosphorus atom of phosphonic acid (HP (═O) (OH) ₂ ), which may have various functional groups. Substituted compounds (eg, nitrilotris (methylenephosphonic acid), N, N, N ′, N′-ethylenediaminetetrakis (methylenephosphonic acid), etc.), salts thereof, (partial) ester compounds, halides and dehydration Things are also included. Furthermore, organic polymers having a phosphorus atom, such as phosphorylated starch and polymer (E) described later, can also be used as the phosphorus compound (B). These phosphorus compounds (B) may be used alone or in combination of two or more. Among these phosphorus compounds (B), the stability of the coating liquid (U) in the case of forming the layer (YA) using the coating liquid (U) described later and the gas barrier property of the resulting multilayer structure are more excellent. Therefore, it is preferable to use phosphoric acid alone or to use phosphoric acid and other phosphorus compounds in combination.

  As described above, the layer (YA) included in the multilayer structure includes the reaction product (R), and the reaction product (R) includes at least a reaction between the metal oxide (A) and the phosphorus compound (B). Is a reaction product. Such a reaction product can be formed by mixing and reacting the metal oxide (A) and the phosphorus compound (B). The phosphorus compound (B) used for mixing with the metal oxide (A) (immediately before mixing) may be the phosphorus compound (B) itself or a form of a composition containing the phosphorus compound (B). The form of the composition containing the phosphorus compound (B) is preferable. In a preferred example, the phosphorus compound (B) is mixed with the metal oxide (A) in the form of a solution obtained by dissolving the phosphorus compound (B) in a solvent. Although any solvent can be used at that time, water or a mixed solvent containing water is a preferable solvent.

  The phosphorus compound (B) used for mixing with the metal oxide (A) or the composition containing the phosphorus compound (B) has a low metal atom content, so that a multilayer structure excellent in gas barrier properties can be obtained. To preferred. The phosphorus compound (B) or composition containing the phosphorus compound (B) to be mixed with the metal oxide (A) contains metal atoms in the phosphorus compound (B) or phosphorus compound (B). Is preferably 100 mol% or less, more preferably 30 mol% or less, and more preferably 5 mol% or less, based on the number of moles of all phosphorus atoms contained in the composition containing More preferably, it is particularly preferably 1 mol% or less, and may be 0 mol%.

[Reaction product (R)]
The reaction product (R) includes a reaction product produced by reacting only the metal oxide (A) and the phosphorus compound (B). The reaction product (R) also includes a reaction product produced by reacting the metal oxide (A), the phosphorus compound (B), and another compound. The reaction product (R) can be formed by the method described in the production method described later.

[Ratio of metal oxide (A) and phosphorus compound (B)]
In the layer (YA), the number of moles N _{M of} metal atoms constituting the metal oxide (A) and the number of moles N _{P of} phosphorus atoms derived from the phosphorus compound (B) are 1.0 ≦ (number of moles N _M ) / (Number of moles N _P ) ≦ 3.6, more preferably 1.1 ≦ (number of moles N _M ) / (number of moles N _P ) ≦ 3.0. When the value of (number of moles N _M ) / (number of moles N _P ) exceeds 3.6, the metal oxide (A) becomes excessive with respect to the phosphorus compound (B), and the particles of the metal oxide (A) Insufficient bonding occurs, and the amount of hydroxyl groups present on the surface of the metal oxide (A) increases, so that the gas barrier property and its stability tend to be lowered. On the other hand, when the value of (number of moles N _M ) / (number of moles N _P ) is less than 1.0, the phosphorus compound (B) becomes excessive with respect to the metal oxide (A), and the metal oxide (A) The excess phosphorus compound (B) that does not participate in the bond with the phosphorus compound increases, the amount of the hydroxyl group derived from the phosphorus compound (B) tends to increase, and the gas barrier property and its stability tend to decrease.

In addition, the said ratio can be adjusted with ratio of the quantity of a metal oxide (A) and the quantity of a phosphorus compound (B) in the coating liquid for forming a layer (YA). The ratio of the moles N _M and the number of moles N _P in the layer (YA) is generally constituted by a ratio in the coating solution moles of phosphorus compound of a metal atom constituting the metal oxide (A) and (B) It is the same as the ratio to the number of moles of phosphorus atoms to be made.

[Polymer (C)]
The layer (YA) of the multilayer structure may further contain a specific polymer (C). The polymer (C) is a polymer having at least one functional group (f) selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic anhydride group, and a carboxyl group salt. In the layer (YA) of the multilayer structure, the polymer (C) has one or both of particles of the metal oxide (A) and a phosphorus atom derived from the phosphorus compound (B) depending on the functional group (f) it has. It may be bound directly or indirectly. Further, in the layer (YA) of the multilayer structure, the reaction product (R) is a polymer (C) portion produced by the reaction of the polymer (C) with the metal oxide (A) or the phosphorus compound (B). You may have. In the present specification, a polymer that satisfies the requirements as the phosphorus compound (B) and includes the functional group (f) is not included in the polymer (C) but is treated as the phosphorus compound (B). .

  As the polymer (C), a polymer containing a structural unit having a functional group (f) can be used. Specific examples of such structural units include 1 functional group (f) such as a vinyl alcohol unit, an acrylic acid unit, a methacrylic acid unit, a maleic acid unit, an itaconic acid unit, a maleic anhydride unit, and a phthalic anhydride unit. Examples include structural units having at least one unit. The polymer (C) may contain only one type of structural unit having the functional group (f), or may contain two or more types of structural units having the functional group (f).

  In order to obtain a multilayer structure having better gas barrier properties and stability, the proportion of the structural unit having the functional group (f) in the total structural units of the polymer (C) is 10 mol% or more. It is preferably 20 mol% or more, more preferably 40 mol% or more, particularly preferably 70 mol% or more, and may be 100 mol%.

  When the polymer (C) is constituted by the structural unit having the functional group (f) and other structural units other than that, the type of the other structural unit is not particularly limited. Examples of such other structural units are derived from (meth) acrylic acid esters such as methyl acrylate units, methyl methacrylate units, ethyl acrylate units, ethyl methacrylate units, butyl acrylate units, and butyl methacrylate units. Structural units derived from vinyl esters such as vinyl formate units and vinyl acetate units; structural units derived from aromatic vinyls such as styrene units and p-styrene sulfonic acid units; ethylene units, propylene units, And structural units derived from olefins such as isobutylene units. When the polymer (C) contains two or more types of structural units, the polymer (C) is any of an alternating copolymer, a random copolymer, a block copolymer, and a tapered copolymer. Also good.

  Specific examples of the polymer (C) having a hydroxyl group include polyvinyl alcohol, polyvinyl acetate partially saponified products, polyethylene glycol, polyhydroxyethyl (meth) acrylate, starch and other polysaccharides, polysaccharides derived from polysaccharides Derivatives and the like. Specific examples of the polymer (C) having a carboxyl group, a carboxylic anhydride group or a carboxyl group salt include polyacrylic acid, polymethacrylic acid, poly (acrylic acid / methacrylic acid), and salts thereof. Can do. Specific examples of the polymer (C) containing a structural unit not containing the functional group (f) include an ethylene-vinyl alcohol copolymer, an ethylene-maleic anhydride copolymer, and a styrene-maleic anhydride copolymer. , Saponified products of isobutylene-maleic anhydride alternating copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, and the like. In order to obtain a multilayer structure having better gas barrier properties and its stability, the polymer (C) comprises polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polysaccharide, polyacrylic acid, polyacrylic acid salt, It is preferably at least one polymer selected from the group consisting of polymethacrylic acid and polymethacrylic acid salts.

  There is no restriction | limiting in particular in the molecular weight of a polymer (C). In order to obtain a multilayer structure having more excellent gas barrier properties and mechanical properties (such as drop impact strength), the number average molecular weight of the polymer (C) is preferably 5,000 or more, and 8,000. More preferably, it is more preferably 10,000 or more. The upper limit of the number average molecular weight of the polymer (C) is not particularly limited, and is, for example, 1,500,000 or less.

  In order to further improve the gas barrier properties, the content of the polymer (C) in the layer (YA) is preferably 50% by mass or less based on the mass of the layer (YA) (100% by mass). It is more preferably at most mass%, more preferably at most 30 mass%, and may be at most 20 mass%. The polymer (C) may or may not react with other components in the layer (YA). In the present specification, the case where the polymer (C) reacts with other components is also expressed as the polymer (C). For example, when the polymer (C) is bonded to a phosphorus atom derived from the metal oxide (A) and / or the phosphorus compound (B), it is also expressed as the polymer (C). In this case, the content of the polymer (C) is calculated by dividing the mass of the polymer (C) before bonding with the metal oxide (A) and / or the phosphorus atom by the mass of the layer (YA). To do.

  The layer (YA) of the multilayer structure has a reaction product (R) (provided that the polymer (C) portion is formed by the reaction of the metal oxide (A) containing at least aluminum with the phosphorus compound (B). The reaction product (R) and the non-reacted polymer (C), but may further include other components. Also good.

  Examples of other components include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, and aluminates; oxalates, acetates, Organic acid metal salts such as tartrate and stearate; metal complexes such as acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), cyano metal complexes; layered clay compounds; Agents; polymer compounds other than the polymer (C); plasticizers; antioxidants; ultraviolet absorbers; flame retardants and the like.

  The content of the other components in the layer (YA) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less. It is preferably 5% by mass or less, and may be 0% by mass (excluding other components).

[Thickness of layer (YA)]
The thickness of the layer (YA) of the multilayer structure (when the multilayer structure has two or more layers (YA), the total thickness of each layer (YA)) may be 4.0 μm or less. Preferably, it is 2.0 μm or less, more preferably 1.0 μm or less, and 0.9 μm or less. By reducing the thickness of the layer (YA), the dimensional change of the multilayer structure during processing such as printing and laminating can be kept low, and the flexibility of the multilayer structure is further increased. It can be close to the mechanical characteristics of.

In the multilayer structure, even when the total thickness of the layers (YA) is 1.0 μm or less (for example, 0.5 μm or less), the oxygen of the coating material constituting the vacuum insulator is 20 ° C. and 85% RH. The transmittance can be 2 ml / (m ² · day · atm) or less. Also, the thickness of the layer (YA) (when the multilayer structure has two or more layers (YA), the total thickness of each layer (YA)) is 0.1 μm or more (for example, 0.2 μm or more). It is preferable that The thickness per layer (YA) is preferably 0.05 μm or more (for example, 0.15 μm or more) from the viewpoint of better gas barrier properties of the multilayer structure. The thickness of the layer (YA) can be controlled by the concentration of a coating liquid (U) described later used for forming the layer (YA) and the coating method.

[Layer (YB) and Layer (YC)]
The layer (Y) of the multilayer structure may be a layer (YB) that is an aluminum deposition layer or a layer (YC) that is an aluminum oxide deposition layer. These vapor deposition layers can be manufactured by the same method as the inorganic vapor deposition layer mentioned later.

[Layer (Z)]
The layer (Z) included in the multilayer structure includes a polymer (E) including a monomer unit having a phosphorus atom. By forming the layer (Z) adjacent to the layer (Y), the bending resistance of the multilayer structure can be greatly improved.

[Polymer (E)]
The polymer (E) has a plurality of phosphorus atoms in its molecule. In one example, the phosphorus atom is contained in an acidic group or derivative thereof. Examples of the acidic group containing a phosphorus atom include a phosphoric acid group, a polyphosphoric acid group, a phosphorous acid group, and a phosphonic acid group. At least 1 phosphorus atom contains the site | part which can react with a metal oxide (A) among several phosphorus atoms which a polymer (E) has. In a preferred example, the polymer (E) contains about 10 to 1000 such phosphorus atoms. The site | part of the structure described with respect to the phosphorus compound (B) can be mentioned as an example of the site | part regarding the phosphorus atom which can react with a metal oxide (A).

  The polymer (E) is not particularly limited as long as the above conditions are satisfied, but a preferable example is a homopolymer or copolymer of (meth) acrylic acid esters containing a phosphate group at the end of the side chain. Can do. These polymers can be synthesized by synthesizing monomers of (meth) acrylic acid esters having a phosphate group at the end of the side chain and homopolymerizing them or copolymerizing with other vinyl group-containing monomers. Can be obtained at

  The (meth) acrylic acid ester containing a phosphate group at the side chain terminal used in the present invention may be at least one compound represented by the following general formula (IV).

[In the formula (IV), R ⁵ and R ⁶ are a hydrogen atom or an alkyl group selected from a methyl group, an ethyl group, a normal propyl group, and an isopropyl group, and some of the hydrogen atoms contained in the alkyl group are It may be substituted with other atoms or functional groups. Moreover, n is a natural number and is typically an integer of 1-6. ]

In a typical example, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom or a methyl group.

  Among the monomers represented by the general formula (IV), examples of monomers that can be suitably used in the present invention include acid phosphooxyethyl acrylate, acid phosphooxyethyl methacrylate, and acid phosphooxypolyoxyethylene glycol acrylate. Acid phosphooxypolyoxyethylene glycol methacrylate, acid phosphooxypolyoxypropylene glycol acrylate, acid phosphooxypolyoxypropylene glycol methacrylate, 3-chloro-2-acid phosphooxypropyl acrylate and 3-chloro-2-acid phosphooxypropyl A methacrylate etc. can be mentioned. Among these, a homopolymer of acid phosphooxyethyl methacrylate is more preferable from the viewpoint of obtaining a multilayer structure excellent in bending resistance. However, monomers that can be used in the present invention are not limited to these. Some of these monomers are sold under the trade name “Phosmer” by Unichemical Co., Ltd., and can be purchased and used as appropriate.

  The polymer (E) may be a homopolymer of a monomer represented by the general formula (IV), or a copolymer using two or more monomers represented by the general formula (IV). It may be a combination, or may be a copolymer of at least one monomer represented by the general formula (IV) and another vinyl monomer.

  Other vinyl monomers that can be copolymerized with the monomer represented by the general formula (IV) are particularly limited as long as they can be copolymerized with the monomer represented by the general formula (IV). Instead, known ones can be used. Examples of such vinyl monomers include acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, acrylonitrile, methacrylonitrile, styrene, nucleus-substituted styrenes, alkyl vinyl ethers, alkyl vinyl esters, pars. Fluoro-alkyl vinyl ethers, perfluoro-alkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleimide, or phenylmaleimide. Among these vinyl monomers, those that can be particularly preferably used are methacrylic acid esters, acrylonitrile, styrenes, maleimide, and phenylmaleimide.

  In order to obtain a multilayer structure having better bending resistance, the proportion of the structural unit derived from the monomer represented by formula (IV) in the total structural units of the polymer (E) is 10 It is preferably at least mol%, more preferably at least 20 mol%, further preferably at least 40 mol%, particularly preferably at least 70 mol%, and may be 100 mol%. .

Although there will be no restriction | limiting in particular if a polymer (E) satisfy | fills the said conditions, As a preferable another example, the homopolymer or copolymer of vinylphosphonic acid containing a phosphoric acid group can be mentioned. Here, the “vinyl phosphonic acids” mean those satisfying the following requirements.
(A) A phosphonic acid having a substituent, a phosphinic acid having a substituent, or an ester thereof.
(B) The carbon chain of the substituent is bonded to the phosphorus atom in the molecule (phosphonic acid group, phosphinic acid group or phosphorus atom in their ester) via a phosphorus-carbon bond. There are carbon-carbon double bonds in the carbon chain. A part of the carbon chain may constitute a carbocyclic ring.
(C) At least one hydroxyl group is bonded to the phosphorus atom in the molecule (phosphonic acid group, phosphinic acid group or phosphorus atom in their ester).

  One example of the vinyl phosphonic acid is a phosphonic acid and / or phosphinic acid having a substituent, and satisfies the requirement (b). For example, an example phosphonic acid is a phosphonic acid having a substituent, and satisfies the requirement (b).

  The carbon number contained in the carbon chain of the substituent bonded to the phosphorus atom may be in the range of 2 to 30 (for example, in the range of 2 to 10). Examples of the substituent include a hydrocarbon chain having a carbon-carbon double bond (for example, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-methyl-1-propenyl group, 2-methyl-2). -Propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 1-hexenyl group, 1,3-hexadienyl group, 1,5-hexadienyl group and the like. The hydrocarbon chain having a carbon-carbon double bond may contain one or more oxycarbonyl groups in the molecular chain. Examples of the carbocycle include a benzene ring, naphthalene ring, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopropene ring, cyclobutene ring, cyclopentene ring and the like. In addition to the hydrocarbon chain having a carbon-carbon double bond on the carbocycle, one or more saturated hydrocarbon chains (for example, a methyl group, an ethyl group, a propyl group, etc.) may be bonded. Examples of the substituent bonded to the phosphorus atom include a hydrocarbon chain having the carbon-carbon double bond such as a vinyl group, and a carbon having the hydrocarbon chain bonded to the carbocycle such as a 4-vinylbenzyl group. Includes a ring.

  The ester group constituting the ester is a structure in which a hydrogen atom of a hydroxyl group bonded to a phosphorus atom of phosphinic acid or phosphonic acid is substituted with an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, A butyl group, a pentyl group, a hexyl group, etc. are mentioned.

  The polymer (E) can be obtained by polymerizing vinyl phosphonic acid monomers or copolymerizing with other vinyl group-containing monomers. The polymer (E) can also be obtained by hydrolyzing a vinylphosphonic acid derivative such as a phosphonic acid halide or ester, either alone or copolymerized.

  Examples of monomers of vinylphosphonic acids that can be suitably used include alkenylphosphonic acids such as vinylphosphonic acid and 2-propene-1-phosphonic acid; 4-vinylbenzylphosphonic acid, 4-vinylphenylphosphonic Alkenyl aromatic phosphonic acids such as acid; Phosphono (meta) such as 6-[(2-phosphonoacetyl) oxy] hexyl acrylate, phosphonomethyl methacrylate, 11-phosphonoundecyl methacrylate, 1,1-diphosphonoethyl methacrylate ) Acrylic acid esters; phosphinic acids such as vinyl phosphinic acid and 4-vinylbenzyl phosphinic acid. Among them, poly (vinyl phosphonic acid), which is a homopolymer of vinyl phosphonic acid, is more preferable in that a multilayer structure excellent in bending resistance can be obtained. However, the monomer which can be used is not limited to these.

  The polymer (E) may be a homopolymer of a monomer of vinylphosphonic acid, a copolymer using two or more monomers of vinylphosphonic acid, or at least 1 Copolymers of monomers of various types of vinyl phosphonic acids and other vinyl monomers may be used.

  Other vinyl monomers that can be copolymerized with vinylphosphonic acid monomers are not particularly limited as long as they are copolymerizable with vinylphosphonic acid monomers, and known ones can be used. Examples of such vinyl monomers include acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, acrylonitrile, methacrylonitrile, styrene, nucleus-substituted styrenes, alkyl vinyl ethers, alkyl vinyl esters, pars. Fluoro-alkyl vinyl ethers, perfluoro-alkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleimide, or phenylmaleimide. Among these vinyl monomers, those that can be particularly preferably used are methacrylic acid esters, acrylonitrile, styrenes, maleimide, and phenylmaleimide.

  In order to obtain a multilayer structure having better bending resistance, the proportion of structural units derived from monomers of vinylphosphonic acids in the total structural units of the polymer (E) is 10 mol% or more. It is preferably 20 mol% or more, more preferably 40 mol% or more, particularly preferably 70 mol% or more, and may be 100 mol%.

  The polymer (E) may be a polymer having a repeating unit represented by the following general formula (I), more specifically poly (vinyl phosphonic acid).

  There is no particular limitation on n. For example, n is a number that satisfies the number average molecular weight described below.

  Although there is no restriction | limiting in particular in the molecular weight of a polymer (E), Typically, the number average molecular weight of a polymer (E) exists in the range of 1,000-100,000. When the number average molecular weight is in this range, the bending resistance improving effect by laminating the layer (Z) and the viscosity stability of the coating liquid (V) containing the polymer (E) described later are at a high level. Can be compatible. Further, when the molecular weight of the polymer (E) per phosphorus atom is in the range of 150 to 500, the effect of improving the bending resistance by laminating the layer (Z) may be further enhanced. is there.

  The layer (Z) of the multilayer structure may be composed only of the polymer (E) containing a monomer unit having a phosphorus atom, but may further contain other components.

  Examples of other components include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, and aluminates; oxalates, acetates, Organic acid metal salts such as tartrate and stearate; metal complexes such as acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), cyano metal complexes; layered clay compounds; Agents; polymer compounds other than the polymer (E); plasticizers; antioxidants; ultraviolet absorbers; flame retardants and the like.

  The content of the other components in the layer (Z) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less. It is preferably 5% by mass or less, and may be 0% by mass (excluding other components).

  The polymerization reaction for forming the polymer (E) can be performed using a polymerization initiator in a solvent in which both the monomer component as a raw material and the polymer to be produced are dissolved. Examples of polymerization initiators include 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate), dimethyl Examples include azo initiators such as 2,2-azobisisobutyrate, peroxide initiators such as lauryl peroxide, benzoyl peroxide, and tert-butyl peroctoate. When copolymerizing with other vinyl monomers, a solvent is appropriately selected depending on the combination of comonomers. You may use 2 or more types of mixed solvents as needed.

  The polymerization reaction of an example is performed at a polymerization temperature of 50 to 100 ° C. while dropping a mixed solution consisting of a monomer, a polymerization initiator and a solvent into the solvent, and after the completion of the addition, the polymerization temperature is about 1 to 24 hours. The temperature is maintained and stirring is continued to complete the polymerization.

  When the monomer component is 1, the solvent is preferably used in a weight ratio of about 1.0 to 3.0, and the polymerization initiator is preferably used in a weight ratio of about 0.005 to 0.05. A more preferred weight ratio is 1.5 to 2.5 for the solvent and about 0.01 for the polymerization initiator. If the amount of the solvent and polymerization initiator used is not within the above ranges, the polymer may gel and become insoluble in various solvents, and problems such as the inability to apply using the solution may occur.

  The layer (Z) of the multilayer structure can be formed by applying a solution of the polymer (E). Although any solvent can be used at that time, water, alcohols or a mixed solvent thereof can be mentioned as a preferred solvent.

[Thickness of layer (Z)]
The thickness per layer of the layer (Z) is 0.005 μm or more, preferably 0.03 μm or more, and preferably 0.05 μm or more (for example, 0.2 μm or more, for example) from the viewpoint of better bending resistance of the multilayer structure. 15 μm or more) is more preferable. The upper limit of the thickness of the layer (Z) is not particularly limited, but the effect of improving the bending resistance reaches saturation when the thickness is 1.0 μm or more. Therefore, it is economical that the upper limit of the thickness of the layer (Z) is 1.0 μm. Is preferable. The thickness of the layer (Z) can be controlled by the concentration of a coating liquid (V) described later used for forming the layer (Z) and the coating method.

[Substrate (X)]
There is no restriction | limiting in particular in the material of the base material (X) which a multilayer structure has, The base material which consists of various materials can be used. Examples of the material of the substrate (X) include resins such as thermoplastic resins and thermosetting resins; fiber aggregates such as fabrics and papers; wood; glass; metals; metal oxides and the like. The base material may have a composite structure or a multilayer structure made of a plurality of materials.

  There is no restriction | limiting in particular in the form of base material (X), A layered base material, such as a film and a sheet, may be sufficient, The cup shape which cut off some hollow solids, such as a hollow sphere and a polyhedron, and a cylinder It may be a molded body having various three-dimensional shapes such as a pipe-like cylindrical shape having other shapes.

  Examples of the layered substrate include a thermoplastic resin film layer, a thermosetting resin film layer, a fiber polymer sheet (fabric, paper, etc.) layer, a wood sheet layer, a glass layer, an inorganic vapor deposition layer, a metal oxide layer, and Examples thereof include a single-layer or multi-layer substrate including at least one layer selected from the group consisting of metal foil layers. Among these, a substrate including at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer is preferable. In this case, the substrate may be a single layer or a plurality of layers. It may be a layer. A multilayer structure (laminated structure) using such a substrate is excellent in workability to a covering material and various properties required when used as a packaging material for a core material.

  Examples of the thermoplastic resin film that forms the thermoplastic resin film layer include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof. Resins; Polyamide resins such as nylon-6, nylon-66, nylon-12; hydroxyl group-containing polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; polystyrene; poly (meth) acrylic acid ester; polyacrylonitrile; Polyvinylate; Polyarylate; Regenerated cellulose; Polyimide; Polyetherimide; Polysulfone; Polyethersulfone; Polyetheretherketone; Ionomer resin, etc. It can be mentioned films obtained by molding a plastic resin. The base material of the laminate used for the packaging material for packaging the core material is preferably a film made of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, or nylon-66.

  The thermoplastic resin film may be a stretched film or an unstretched film. A stretched film, particularly a biaxially stretched film is preferred because the processability (printing, laminating, etc.) of the resulting multilayer structure is excellent. The biaxially stretched film may be a biaxially stretched film produced by any one of a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tubular stretching method.

  Examples of the paper used for the paper layer include kraft paper, fine paper, imitation paper, glassine paper, parchment paper, synthetic paper, white board paper, Manila ball, milk carton base paper, cup base paper, ivory paper, and the like.

  It is preferable that the inorganic vapor deposition layer has a barrier property against oxygen gas or water vapor. As the inorganic vapor deposition layer, a light shielding property such as a metal vapor deposition layer such as aluminum or a material having transparency can be appropriately used. An inorganic vapor deposition layer can be formed by vapor-depositing an inorganic substance on a vapor deposition substrate, and the entire laminate in which the inorganic vapor deposition layer is formed on the vapor deposition substrate is used as a base material (X) having a multilayer structure. Can be used. Examples of the inorganic deposited layer having transparency include a layer formed from an inorganic oxide such as aluminum oxide, silicon oxide, silicon oxynitride, magnesium oxide, tin oxide, or a mixture thereof; silicon nitride, silicon carbonitride, etc. A layer formed from an inorganic nitride of the above; a layer formed from an inorganic carbide such as silicon carbide. Among these, a layer formed from aluminum oxide, silicon oxide, magnesium oxide, and silicon nitride is preferable from the viewpoint of excellent barrier properties against oxygen gas and water vapor.

  Although the preferable thickness of an inorganic vapor deposition layer changes with kinds of component which comprises an inorganic vapor deposition layer, it is in the range of 2-500 nm normally. Within this range, a thickness that improves the barrier properties and mechanical properties of the multilayer structure may be selected. If the thickness of the inorganic vapor deposition layer is less than 2 nm, the reproducibility of the barrier property development of the inorganic vapor deposition layer with respect to oxygen gas or water vapor tends to decrease, and the inorganic vapor deposition layer may not exhibit sufficient barrier properties. is there. On the other hand, when the thickness of the inorganic vapor deposition layer exceeds 500 nm, the barrier property of the inorganic vapor deposition layer tends to be lowered when the multilayer structure is pulled or bent. The thickness of the inorganic vapor deposition layer is more preferably in the range of 5 to 200 nm, and still more preferably in the range of 10 to 100 nm.

  Examples of the method for forming the inorganic vapor deposition layer include vacuum vapor deposition, sputtering, ion plating, and chemical vapor deposition (CVD). Among these, the vacuum evaporation method is preferable from the viewpoint of productivity. As a heating method in performing vacuum vapor deposition, any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable. Further, in order to improve the adhesion to the vapor deposition substrate on which the inorganic vapor deposition layer is formed and the denseness of the inorganic vapor deposition layer, the plasma assist method or the ion beam assist method may be employed for vapor deposition. Moreover, in order to raise the transparency of an inorganic vapor deposition 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.

  When the substrate (X) is layered, the thickness thereof is preferably in the range of 1 to 1000 μm, preferably 5 to 500 μm from the viewpoint of improving the mechanical strength and workability of the resulting multilayer structure. More preferably, it is in the range of 9 to 200 μm.

[Adhesive layer (H)]
In the multilayer structure, the layer (Y) and / or the layer (Z) may be laminated so as to be in direct contact with the substrate (X), but the substrate (X) and the layer (Y) and / or The layer (Y) and / or the layer (Z) may be laminated on the substrate (X) via an adhesive layer (H) disposed between the layer (Z). According to this configuration, the adhesion between the substrate (X) and the layer (Y) and / or the layer (Z) may be improved. The adhesive layer (H) may be formed of an adhesive resin. The adhesive layer (H) made of an adhesive resin can be formed by treating the surface of the substrate (X) with a known anchor coating agent or applying a known adhesive to the surface of the substrate (X). As the adhesive, a two-component reactive polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable. Moreover, adhesiveness may be further improved by adding a small amount of additives such as a known silane coupling agent to the anchor coating agent or adhesive. Preferable examples of the silane coupling agent include silane coupling agents having a reactive group such as an isocyanate group, an epoxy group, an amino group, a ureido group, and a mercapto group. When the substrate (X) and the layer (Y) and / or the layer (Z) are strongly bonded via the adhesive layer (H), the multilayer structure is subjected to processing such as printing or lamination. Deterioration of gas barrier properties and appearance can be more effectively suppressed.

  By increasing the thickness of the adhesive layer (H), the strength of the multilayer structure can be increased. However, when the adhesive layer (H) is too thick, the appearance tends to deteriorate. The thickness of the adhesive layer (H) is preferably in the range of 0.03 to 0.18 μm. According to this configuration, when processing such as printing or laminating is performed on the multilayer structure, it is possible to more effectively suppress deterioration of gas barrier properties and appearance, and further, a packaging material using the multilayer structure. The drop strength can be increased. The thickness of the adhesive layer (H) is more preferably in the range of 0.04 to 0.14 μm, and still more preferably in the range of 0.05 to 0.10 μm.

[Configuration of multilayer structure]
The multilayer structure (laminate) may be composed of only the base material (X), the layer (Y), and the layer (Z), or the base material (X), the layer (Y), the layer (Z), and the adhesion You may be comprised only by the layer (H). The multilayer structure may include a plurality of layers (Y) and / or a plurality of layers (Z). In addition, the multilayer structure includes other members (for example, a thermoplastic resin film layer, a paper layer, an inorganic vapor deposition layer, etc.) other than the base material (X), the layer (Y), the layer (Z), and the adhesive layer (H). And the like. In the multilayer structure having such other members (other layers, etc.), for example, the layer (Y) and the layer (Z) are laminated on the substrate (X) directly or via the adhesive layer (H). Later, it can be manufactured by further bonding or forming the other member (other layer or the like) directly or via an adhesive layer. By including such other members (such as other layers) in the multilayer structure, the characteristics of the multilayer structure can be improved or new characteristics can be imparted. For example, heat sealability can be imparted to the multilayer structure, and barrier properties and mechanical properties can be further improved.

  In particular, by using a polyolefin layer as the outermost surface layer of the multilayer structure, it is possible to impart heat sealability to the multilayer structure or to improve the mechanical properties of the multilayer structure. From the viewpoint of improving heat sealability and mechanical properties, the polyolefin is preferably polypropylene or polyethylene. Further, in order to improve the mechanical properties of the multilayer structure, at least one film selected from the group consisting of a film made of polyester, a film made of polyamide, and a film made of a hydroxyl group-containing polymer is laminated as another layer. It is preferable. From the viewpoint of improving mechanical properties, the polyester is preferably polyethylene terephthalate (PET), the polyamide is preferably nylon-6, and the hydroxyl group-containing polymer is preferably an ethylene-vinyl alcohol copolymer. In addition, you may provide the layer which consists of an anchor coat layer and an adhesive agent between each layer as needed.

  The multilayer structure can be formed by laminating at least one pair of layers (Y) and (Z) and at least one other layer (including a base material). Examples of other layers include polyester layers, polyamide layers, polyolefin layers (which may be pigment-containing polyolefin layers, heat-resistant polyolefin layers, or biaxially stretched heat-resistant polyolefin layers), hydroxyl group-containing polymer layers (for example, ethylene- Vinyl alcohol copolymer layer), paper layer, inorganic vapor deposition film layer, thermoplastic elastomer layer, and adhesive layer. As long as the multilayer structure includes a base material, a layer (Y) and a layer (Z), and at least one pair of the layer (Y) and the layer (Z) is laminated adjacently, these other layers and layers (Y), the number of layers (Z) and the order of lamination are not particularly limited. As a preferred example, at least one set of the base material (X), the layer (Y), and the layer (Z) is laminated in the order of the base material (X) / layer (Y) / layer (Z). A multilayer structure having a structure may be mentioned. In addition, these other layers can also be replaced with a molded body (molded body having a three-dimensional shape) made of the material.

Specific examples of the structure of the multilayer structure are shown below. In the following specific examples, each layer may be replaced with a molded body (molded body having a three-dimensional shape) made of the material. The multilayer structure may have an adhesive layer such as an adhesive layer (H), but the description of the adhesive layer is omitted in the following specific examples. In the following specification, the layer (YZ) means a structure in which the layer (Y) and the layer (Z) are adjacently stacked, and the order is layer (Y) / layer (Z) or layer. Either (Z) / layer (Y) may be used.
(1) Layer (YZ) / Polyester layer,
(2) layer (YZ) / polyester layer / layer (YZ),
(3) layer (YZ) / polyamide layer,
(4) layer (YZ) / polyamide layer / layer (YZ),
(5) Layer (YZ) / Polyolefin layer,
(6) Layer (YZ) / Polyolefin layer / Layer (YZ),
(7) Layer (YZ) / Hydroxyl-containing polymer layer,
(8) Layer (YZ) / Hydroxyl-containing polymer layer / Layer (YZ),
(9) Layer (YZ) / paper layer,
(10) layer (YZ) / paper layer / layer (YZ),
(11) layer (YZ) / inorganic vapor deposition layer / polyester layer,
(12) Layer (YZ) / Inorganic vapor deposition layer / Polyamide layer,
(13) Layer (YZ) / Inorganic vapor deposition layer / Polyolefin layer,
(14) Layer (YZ) / Inorganic vapor deposition layer / Hydroxyl-containing polymer layer,
(15) Layer (YZ) / Polyester layer / Polyamide layer / Polyolefin layer,
(16) Layer (YZ) / Polyester layer / Layer (YZ) / Polyamide layer / Polyolefin layer,
(17) Polyester layer / layer (YZ) / polyamide layer / polyolefin layer,
(18) layer (YZ) / polyamide layer / polyester layer / polyolefin layer,
(19) layer (YZ) / polyamide layer / layer (YZ) / polyester layer / polyolefin layer,
(20) Polyamide layer / layer (YZ) / polyester layer / polyolefin layer,
(21) Layer (YZ) / Polyolefin layer / Polyamide layer / Polyolefin layer,
(22) layer (YZ) / polyolefin layer / layer (YZ) / polyamide layer / polyolefin layer,
(23) Polyolefin layer / layer (YZ) / polyamide layer / polyolefin layer,
(24) Layer (YZ) / Polyolefin layer / Polyolefin layer,
(25) layer (YZ) / polyolefin layer / layer (YZ) / polyolefin layer,
(26) Polyolefin layer / layer (YZ) / polyolefin layer,
(27) Layer (YZ) / Polyester layer / Polyolefin layer,
(28) Layer (YZ) / Polyester layer / Layer (YZ) / Polyolefin layer,
(29) Polyester layer / layer (YZ) / polyolefin layer,
(30) layer (YZ) / polyamide layer / polyolefin layer,
(31) layer (YZ) / polyamide layer / layer (YZ) / polyolefin layer,
(32) Polyamide layer / layer (YZ) / polyolefin layer,
(33) layer (YZ) / polyester layer / paper layer,
(34) layer (YZ) / polyamide layer / paper layer,
(35) layer (YZ) / polyolefin layer / paper layer,
(36) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyester layer / polyolefin layer,
(37) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyamide layer / polyolefin layer,
(38) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyolefin layer,
(39) Paper layer / Polyolefin layer / Layer (YZ) / Polyester layer / Polyolefin layer,
(40) Polyolefin layer / paper layer / layer (YZ) / polyolefin layer,
(41) Paper layer / layer (YZ) / polyester layer / polyolefin layer,
(42) Paper layer / layer (YZ) / polyolefin layer,
(43) layer (YZ) / paper layer / polyolefin layer,
(44) layer (YZ) / polyester layer / paper layer / polyolefin layer,
(45) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyolefin layer / hydroxyl group-containing polymer layer,
(46) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyolefin layer / polyamide layer,
(47) Polyolefin layer / paper layer / polyolefin layer / layer (YZ) / polyolefin layer / polyester layer.

[Characteristics and applications of vacuum insulation, particularly suitable layer structure]
According to a preferred embodiment of the present invention, it is possible to achieve one or both of the following performances for the vacuum insulator. In a preferred example, the thickness of the layer (Y) (when the multilayer structure has two or more layers (Y), the total thickness of each layer (Y)) is 1.0 μm or less (for example, 0.5 μm or more). The following performance can be realized by the multilayer structure having a thickness of 1.0 μm or less. The details of the measurement conditions for oxygen permeability will be described in Examples.
(Performance 1) The oxygen permeability of the coating material under the conditions of 20 ° C. and 85% RH is 2 ml / (m ² · day · atm) or less, preferably 1.5 ml / (m ² · day · atm) or less. .
(Performance 2) Oxygen permeability of the coating material under the conditions of 20 ° C. and 85% RH after holding the coating material for 5 minutes in a state stretched 5% in one direction under the conditions of 23 ° C. and 50% RH Is 4 ml / (m ² · day · atm) or less, preferably 2.5 ml / (m ² · day · atm) or less.

  Since the vacuum heat insulator according to the present invention includes the above-described multilayer structure, it has excellent gas barrier properties and can maintain the gas barrier properties at a high level even when subjected to physical stress such as deformation or impact. . The vacuum insulator according to the present invention can have a barrier property against water vapor in addition to the gas barrier property. In that case, even when subjected to physical stress such as deformation and impact, the water vapor barrier property can be maintained at a high level.

  Application of heat sealing is suitable for the production of the vacuum heat insulator according to the present invention. When heat sealing is performed, it is usually necessary to dispose a heat-sealable layer on the inner side of the molded product or on both the inner side and the outer side of the molded product. When the heat-sealable layer is only on the inner side of the molded product (bag), the seal of the body portion is usually a palm-sealed seal. When the heat-sealable layer is on both the inner side and the outer side of the molded product, the seal of the body part is usually an envelope sticker. As the heat-sealable layer, a polyolefin layer (hereinafter sometimes referred to as “PO layer”) is preferable. Heat sealing is a useful technique when mass-producing vacuum insulation by sealing a film material.

  Since the vacuum heat insulating body according to the present invention can maintain a heat insulating effect for a long period of time, heat insulating materials for home appliances such as heat pump application equipment such as refrigerators and hot water supply equipment and rice cookers, walls, ceilings, attics and floors It can be used for heat insulation panels for residential use, vehicle roofing materials, vending machines, etc.

  As described above, the coating layer of the vacuum heat insulating body may be formed by laminating the multilayer structure and at least one other layer. Examples of other layers include a polyester layer, a polyamide layer, a polyolefin layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.

  Particularly preferable coating materials for constituting the vacuum heat insulating material include barrier multilayer / polyamide layer / PO layer and polyamide layer / barrier multilayer / PO layer. The Here, the barrier multilayer film is a laminate including the substrate (X), the layer (Y), and the layer (Z), particularly a laminate obtained by laminating the substrate (X) and the layer (YZ). An adhesive layer may be provided between the layers. Moreover, when the layer (YZ) is laminated | stacked only on one surface of a base material, a layer (YZ) may exist in the outer side of a vacuum heat insulating body with respect to a base material, and may exist inside.

[Method for producing multilayer structure]
Hereinafter, the manufacturing method of a multilayer structure is demonstrated.

  The method for producing a multilayer structure may include a step (IV) of forming a layer (Z) by applying a coating liquid (V) containing a polymer (E) containing a monomer unit having a phosphorus atom. preferable.

  When the layer (Y) of the multilayer structure is a layer (YB) that is an aluminum deposition layer or a layer (YC) that is an aluminum oxide deposition layer, the layer (YB) and the layer (YC) Since can be formed by the general vapor deposition method described above, detailed description is omitted. Hereinafter, the layer (Y) included in the multilayer structure is a layer (YA) including a reaction product (R) obtained by reacting at least a metal oxide (A) including aluminum and a phosphorus compound (B). The case will be described in particular detail. In addition, about the formation method (process (IV) mentioned later) of a layer (Z), when the layer (Y) is any of a layer (YA), a layer (YB), and a layer (YC), the same formation method Can be adopted.

  When the layer (Y) of the multilayer structure is a layer (YA) containing a reaction product (R) formed by a reaction of at least a metal oxide (A) containing aluminum and a phosphorus compound (B), a multilayer The method for producing a structure preferably includes steps (I), (II), (III) and (IV). In the step (I), a metal oxide (A) containing at least aluminum, at least one compound containing a site capable of reacting with the metal oxide (A), and a solvent are mixed with each other to obtain a metal oxide. (A) A coating liquid (U) containing the at least one compound and the solvent is prepared. In the step (II), a precursor layer of the layer (YA) is formed on the substrate (X) by applying the coating liquid (U) on the substrate (X). In step (III), the precursor layer is heat-treated at a temperature of 140 ° C. or higher to form a layer (YA) on the substrate (X). In step (IV), the layer (Z) is formed by applying a coating liquid (V) containing a polymer (E) containing a monomer unit having a phosphorus atom. The above steps are typically performed in the order of (I), (II), (III), and (IV), but the layer (Z) is placed between the substrate (X) and the layer (YA). In the case of forming in (4), step (IV) may be carried out before step (II). Further, as will be described later, the step (III) can be performed after the step (IV).

[Step (I)]
Hereinafter, the at least one compound containing a site capable of reacting with the metal oxide (A) used in the step (I) may be referred to as “at least one compound (Z)”. In step (I), at least the metal oxide (A), at least one compound (Z), and a solvent are mixed. In one aspect, in the step (I), a raw material containing the metal oxide (A) and at least one compound (Z) is reacted in a solvent. The raw material may contain other compounds in addition to the metal oxide (A) and at least one compound (Z). Typically, the metal oxide (A) is mixed in the form of particles.

In the coating liquid (U), the number of moles N _M of metal atoms (M) constituting the metal oxide (A) and the number of moles N _{P of} phosphorus atoms contained in the phosphorus compound (B) are 1.0 ≦ The relationship of (number of moles N _M ) / (number of moles N _P ) ≦ 3.6 is satisfied. Since the preferable range of the value of (number of moles N _M ) / (number of moles N _P ) has been described above, redundant description is omitted.

  At least one compound (Z) includes a phosphorus compound (B). The number of moles of metal atoms contained in at least one compound (Z) is preferably in the range of 0 to 1 times the number of moles of phosphorus atoms contained in the phosphorus compound (B). Typically, the at least one compound (Z) is a compound containing a plurality of sites capable of reacting with the metal oxide (A), and the number of moles of metal atoms contained in the at least one compound (Z). Is in the range of 0 to 1 times the number of moles of phosphorus atoms contained in the phosphorus compound (B).

  The ratio of (number of moles of metal atoms contained in at least one compound (Z)) / (number of moles of phosphorus atoms contained in phosphorus compound (B)) ranges from 0 to 1 (for example, from 0 to 0.9). By setting the range, a multilayer structure having more excellent gas barrier properties can be obtained. This ratio is preferably 0.3 or less, more preferably 0.05 or less, further preferably 0.01 or less, in order to further improve the gas barrier properties of the multilayer structure. It may be. Typically, at least one compound (Z) consists only of the phosphorus compound (B). In step (I), the ratio can be easily reduced.

Step (I) preferably includes the following steps (a) to (c).
Step (a): A step of preparing a liquid (S) containing the metal oxide (A).
Step (b): A step of preparing a solution (T) containing the phosphorus compound (B).
Step (c): A step of mixing the liquid (S) obtained in the steps (a) and (b) and the solution (T).

  Step (b) may be performed prior to step (a), may be performed simultaneously with step (a), or may be performed after step (a). Hereinafter, each step will be described more specifically.

  In the step (a), a liquid (S) containing the metal oxide (A) is prepared. The liquid (S) is a solution or a dispersion. The liquid (S) can be prepared, for example, by a technique adopted in a known sol-gel method. For example, the above-mentioned compound (L) component, water, and an acid catalyst or an organic solvent as necessary are mixed, and the compound (L) component is condensed or hydrolyzed by a method employed in a known sol-gel method. Can be prepared. The dispersion of the metal oxide (A) obtained by condensing or hydrolyzing the compound (L) component can be used as it is as the liquid (S) containing the metal oxide (A). However, if necessary, a specific treatment (such as peptization as described above, addition or subtraction of a solvent for concentration control) may be performed on the dispersion.

  Step (a) may include a step of condensing (for example, hydrolytic condensation) at least one selected from the group consisting of compound (L) and a hydrolyzate of compound (L). Specifically, the step (a) includes compound (L), partial hydrolyzate of compound (L), complete hydrolyzate of compound (L), partial hydrolyzed condensate of compound (L), and compound (L A step of condensing or hydrolyzing at least one selected from the group consisting of a part of the complete hydrolyzate of L) condensed may be included.

  Another example of the method for preparing the liquid (S) includes a method including the following steps. First, metal is vaporized as a metal atom by thermal energy, and the metal atom is brought into contact with a reactive gas (oxygen) to generate metal oxide molecules and clusters. Then, the metal oxide (A) particle | grains with a small particle size are manufactured by cooling them instantaneously. Next, the liquid (S) (dispersion containing a metal oxide (A)) is obtained by dispersing the particles in water or an organic solvent. In order to improve the dispersibility in water or an organic solvent, the metal oxide (A) particles may be subjected to a surface treatment or a stabilizer such as a surfactant may be added. Moreover, you may improve the dispersibility of a metal oxide (A) by controlling pH.

  As another example of the method for preparing the liquid (S), the bulk metal oxide (A) is pulverized using a pulverizer such as a ball mill or a jet mill, and dispersed in water or an organic solvent. By making it, the method of setting it as liquid (S) (dispersion containing a metal oxide (A)) can be mentioned. However, in this case, it may be difficult to control the shape and size distribution of the metal oxide (A) particles.

  There is no restriction | limiting in particular in the kind of organic solvent which can be used in a process (a), For example, alcohol, such as methanol, ethanol, isopropanol, normal propanol, is used suitably.

  The content of the metal oxide (A) in the liquid (S) is preferably in the range of 0.1 to 40% by mass, more preferably in the range of 1 to 30% by mass, More preferably, it is within the range of 20% by mass.

  In step (b), a solution (T) containing the phosphorus compound (B) is prepared. The solution (T) can be prepared by dissolving the phosphorus compound (B) in a solvent. When the solubility of the phosphorus compound (B) is low, dissolution may be promoted by heat treatment or ultrasonic treatment.

  The solvent used for preparing the solution (T) may be appropriately selected depending on the type of the phosphorus compound (B), but preferably contains water. The solvent is alcohol such as methanol and ethanol; ether such as tetrahydrofuran, dioxane, trioxane and dimethoxyethane; ketone such as acetone and methyl ethyl ketone; glycol such as ethylene glycol and propylene glycol, as long as the dissolution of the phosphorus compound (B) is not hindered. Glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide; dimethyl sulfoxide; sulfolane and the like.

  The content of the phosphorus compound (B) in the solution (T) is preferably in the range of 0.1 to 99% by mass, more preferably in the range of 0.1 to 95% by mass, More preferably, it is in the range of 1 to 90% by mass. The content of the phosphorus compound (B) in the solution (T) may be in the range of 0.1 to 50% by mass, in the range of 1 to 40% by mass, It may be in the range of 30% by mass.

  In the step (c), the liquid (S) and the solution (T) are mixed. At the time of mixing the liquid (S) and the solution (T), in order to suppress a local reaction, it is preferable to mix while suppressing the addition rate and vigorously stirring. At this time, the solution (T) may be added to the stirring liquid (S), or the liquid (S) may be added to the stirring solution (T). When mixed in the step (c), the temperature of the liquid (S) and the temperature of the solution (T) are both preferably 50 ° C. or less, more preferably 30 ° C. or less, and both 20 ° C. More preferably, it is as follows. By setting the temperature at the time of mixing to 50 ° C. or less, the metal oxide (A) and the phosphorus compound (B) are uniformly mixed, and the gas barrier properties of the resulting multilayer structure can be improved. Furthermore, the coating liquid (U) excellent in storage stability may be obtained by continuing stirring for about 30 minutes after the completion of mixing.

  Moreover, the coating liquid (U) may contain a polymer (C). The method for including the polymer (C) in the coating liquid (U) is not particularly limited. For example, the polymer (C) may be dissolved in the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T) after being added in the form of powder or pellets. Further, the polymer (C) solution may be added to and mixed with the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T). Moreover, you may add and mix the liquid (S), the solution (T), or the liquid mixture of a liquid (S) and a solution (T) to the solution of a polymer (C). Before the step (c), the liquid (S) and the solution (T) are mixed in the step (c) by containing the polymer (C) in either the liquid (S) or the solution (T). In this case, the reaction rate between the metal oxide (A) and the phosphorus compound (B) is relaxed, and as a result, a coating liquid (U) having excellent temporal stability may be obtained.

  When the coating liquid (U) contains the polymer (C), a multilayer structure including the layer (YA) containing the polymer (C) can be easily produced.

  The coating liquid (U) may contain at least one acid compound (D) selected from acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid, if necessary. Hereinafter, the at least one acid compound (D) may be simply referred to as “acid compound (D)”. The method for including the acid compound (D) in the coating liquid (U) is not particularly limited. For example, the acid compound (D) may be added as it is to the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T) and mixed. Alternatively, the acid compound (D) solution may be added to and mixed with the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T). Moreover, you may add and mix the liquid (S), the solution (T), or the liquid mixture of a liquid (S) and a solution (T) to the solution of an acid compound (D). Prior to the step (c), either the liquid (S) or the solution (T) contains the acid compound (D), whereby the liquid (S) and the solution (T) are mixed in the step (c). In some cases, the reaction rate between the metal oxide (A) and the phosphorus compound (B) is relaxed, and as a result, a coating liquid (U) having excellent temporal stability may be obtained.

  In the coating liquid (U) containing the acid compound (D), the reaction between the metal oxide (A) and the phosphorus compound (B) is suppressed, and the precipitation and aggregation of the reaction product in the coating liquid (U) are suppressed. can do. Therefore, the appearance of the obtained multilayer structure may be improved by using the coating liquid (U) containing the acid compound (D). Moreover, since the boiling point of the acid compound (D) is 200 ° C. or less, the acid compound (D) can be easily removed from the layer (YA) by volatilizing the acid compound (D) in the production process of the multilayer structure. Can be removed.

  The content of the acid compound (D) in the coating liquid (U) is preferably in the range of 0.1 to 5.0% by mass, and is preferably in the range of 0.5 to 2.0% by mass. More preferred. Within these ranges, the effect of adding the acid compound (D) can be obtained, and the acid compound (D) can be easily removed. When the acid component remains in the liquid (S), the addition amount of the acid compound (D) may be determined in consideration of the residual amount.

  The liquid obtained by mixing in the step (c) can be used as it is as the coating liquid (U). In this case, the solvent contained in the liquid (S) or solution (T) is usually the solvent for the coating liquid (U). Further, the coating liquid (U) may be prepared by treating the liquid obtained by mixing in the step (c). For example, treatments such as addition of an organic solvent, pH adjustment, viscosity adjustment, and additive addition may be performed.

  You may add an organic solvent to the liquid obtained by mixing of a process (c) in the range which does not inhibit stability of the coating liquid (U) obtained. The addition of the organic solvent may facilitate the application of the coating liquid (U) to the substrate (X) in the step (II). As an organic solvent, what is mixed uniformly in the coating liquid (U) obtained is preferable. Examples of preferred organic solvents include, for example, alcohols such as methanol, ethanol, n-propanol and isopropanol; ethers such as tetrahydrofuran, dioxane, trioxane and dimethoxyethane; ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone and methyl isopropyl ketone; Examples include glycols such as ethylene glycol and propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide and dimethylacetamide; dimethyl sulfoxide;

  From the viewpoint of the storage stability of the coating liquid (U) and the coating property of the coating liquid (U) on the substrate, the solid content concentration of the coating liquid (U) is preferably in the range of 1 to 20% by mass. More preferably, it is in the range of 2 to 15% by mass, and further preferably in the range of 3 to 10% by mass. The solid content concentration of the coating liquid (U) is determined by, for example, adding a predetermined amount of the coating liquid (U) to the petri dish, removing volatiles such as a solvent at 100 ° C. together with the petri dish, and calculating the mass of the remaining solid content. It can be calculated by dividing by the mass of the coating liquid (U) added first. At that time, measure the mass of the remaining solid every time it dries for a certain period of time, and the solid content concentration is defined as the mass of the remaining solids when the mass difference between the two consecutive masses reaches a negligible level. It is preferable to calculate.

  From the viewpoint of the storage stability of the coating liquid (U) and the gas barrier property of the multilayer structure, the pH of the coating liquid (U) is preferably in the range of 0.1 to 6.0, and is preferably 0.2 to 5.0. More preferably, it is in the range of 0.5 to 4.0.

  The pH of the coating liquid (U) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound. Examples of acidic compounds include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, and ammonium sulfate. Examples of basic compounds include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, and sodium acetate.

  The state of the coating liquid (U) changes with the passage of time, and eventually tends to become a gel-like composition or precipitate. The time until the state changes as such depends on the composition of the coating liquid (U). In order to stably apply the coating liquid (U) on the substrate (X), it is preferable that the viscosity of the coating liquid (U) is stable over a long period of time. The solution (U) had a viscosity measured with a Brookfield viscometer (B-type viscometer: 60 rpm) even after standing at 25 ° C. for 2 days, with the viscosity at the completion of step (I) as the reference viscosity. It is preferable to prepare so that it may become within 5 times the viscosity. When the viscosity of the coating liquid (U) is within the above range, a multilayer structure having excellent storage stability and more excellent gas barrier properties is often obtained.

  As a method of adjusting the viscosity of the coating liquid (U) to be within the above range, for example, a method of adjusting the concentration of solid content, adjusting pH, or adding a viscosity modifier can be employed. . Examples of viscosity modifiers include carboxymethylcellulose, starch, bentonite, tragacanth gum, stearate, alginate, methanol, ethanol, n-propanol, and isopropanol.

  As long as the effects of the present invention can be obtained, the coating liquid (U) may contain other substances than the substances described above. For example, the coating liquid (U) is an inorganic metal salt such as carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, borate, aluminate; oxalate, acetate, tartrate Organic acid metal salts such as stearates; metal complexes such as acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), cyano metal complexes; layered clay compounds; It may contain a polymer compound other than the polymer (C); a plasticizer; an antioxidant; an ultraviolet absorber;

[Step (II)]
In the step (II), a precursor layer of the layer (YA) is formed on the substrate (X) by applying the coating liquid (U) on the substrate (X). The coating liquid (U) may be applied directly on at least one surface of the substrate (X). Also, before applying the coating liquid (U), the surface of the substrate (X) is treated with a known anchor coating agent, or a known adhesive is applied to the surface of the substrate (X). Then, the adhesive layer (H) may be formed on the surface of the substrate (X). Moreover, the precursor of the layer (YA) is formed on the layer (Z) by applying the coating liquid (U) on the layer (Z) previously formed on the substrate (X) by the step (IV) described later. A body layer can also be formed.

  In addition, the coating liquid (U) may be degassed and / or defoamed as necessary. As a method of deaeration and / or defoaming treatment, for example, there are methods by evacuation, heating, centrifugation, ultrasonic waves, etc., but a method including evacuation can be preferably used.

  The viscosity of the coating liquid (U) applied in the step (II) and measured with a Brookfield rotational viscometer (SB type viscometer: rotor No. 3, rotational speed 60 rpm) The temperature is preferably 3000 mPa · s or less, and more preferably 2000 mPa · s or less. When the viscosity is 3000 mPa · s or less, the leveling property of the coating liquid (U) is improved, and a multilayer structure having a better appearance can be obtained. The viscosity of the coating liquid (U) when applied in the step (II) can be adjusted by the concentration, temperature, stirring time after mixing in the step (c) and stirring strength. For example, in some cases, the viscosity can be lowered by lengthening the stirring after mixing in the step (c).

  The method for applying the coating liquid (U) on the substrate (X) is not particularly limited, and a known method can be employed. 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 metalling bar coating method, and a chamber doctor combined coating method. And curtain coating method.

  Usually, in the step (II), the precursor layer of the layer (YA) is formed by removing the solvent in the coating liquid (U). There is no restriction | limiting in particular in the removal method of a solvent, A well-known drying method is applicable. 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 alone or in combination. The drying temperature is preferably 0 to 15 ° C. or lower than the flow start temperature of the substrate (X). When the coating liquid (U) contains the polymer (C), the drying temperature is preferably 15 to 20 ° C. lower than the thermal decomposition start temperature of the polymer (C). The drying temperature is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 180 ° C, 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. Further, the solvent may be removed by a heat treatment in step (III) described later.

  When laminating the layer (YA) on both surfaces of the layered substrate (X), the coating liquid (U) is applied to one surface of the substrate (X), and then the first layer ( First layer (YA) precursor layer) and then applying the coating liquid (U) to the other surface of the substrate (X), and then removing the solvent to remove the second layer (first layer). 2 layers (YA) precursor layers) may be formed. The composition of the coating liquid (U) applied to each surface may be the same or different.

  When a layer (YA) is laminated on a plurality of surfaces of the substrate (X) having a three-dimensional shape, a layer (a precursor layer of the layer (YA)) may be formed for each surface by the above method. Or you may form a several layer (precursor layer of a layer (YA)) simultaneously by apply | coating a coating liquid (U) to several surfaces of a base material (X), and drying it simultaneously.

[Step (III)]
In step (III), the layer (YA) is formed by heat-treating the precursor layer (precursor layer of layer (YA)) formed in step (II) at a temperature of 140 ° C. or higher.

  In step (III), a reaction in which the metal oxide (A) particles are bonded via phosphorus atoms (phosphorus atoms derived from the phosphorus compound (B)) proceeds. In another aspect, in the step (III), a reaction for generating the reaction product (R) proceeds. In order to allow the reaction to proceed sufficiently, the temperature of the heat treatment is 140 ° C. or higher, more preferably 170 ° C. or higher, and even more preferably 190 ° C. or higher. If the heat treatment temperature is low, it takes a long time to obtain a sufficient degree of reactivity, which causes a decrease in productivity. The preferable upper limit of the temperature of heat processing changes with kinds etc. of base material (X). For example, when a thermoplastic resin film made of polyamide resin is used as the base material (X), the heat treatment temperature is preferably 190 ° C. or lower. Moreover, when using the thermoplastic resin film which consists of polyester resins as a base material (X), it is preferable that the temperature of heat processing is 220 degrees C or less. The heat treatment can be performed in air, a nitrogen atmosphere, an argon atmosphere, or the like.

  The heat treatment time is preferably in the range of 0.1 second to 1 hour, more preferably in the range of 1 second to 15 minutes, and still more preferably in the range of 5 to 300 seconds. An example of the heat treatment is performed in the range of 140 to 220 ° C. for 0.1 second to 1 hour. In another example of the heat treatment, the heat treatment is performed in the range of 170 to 200 ° C. for 5 to 300 seconds (for example, 10 to 300 seconds).

  The method of the present invention for producing a multilayer structure may include irradiating the precursor layer of layer (YA) or layer (YA) with ultraviolet light. The ultraviolet irradiation may be performed at any stage after the step (II) (for example, after the removal of the solvent of the applied coating liquid (U) is almost completed). The method is not particularly limited, and a known method can be applied. The wavelength of the irradiated ultraviolet light 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. By performing ultraviolet irradiation, the gas barrier performance of the multilayer structure may be expressed more highly.

  In order to dispose the adhesive layer (H) between the substrate (X) and the layer (YA), the surface of the substrate (X) is coated with a known anchor coating agent before applying the coating liquid (U). When the treatment is performed or a known adhesive is applied to the surface of the substrate (X), an aging treatment is preferably performed. Specifically, after the coating liquid (U) is applied and before the heat treatment step of step (III), the base material (X) to which the coating liquid (U) is applied is kept at a relatively low temperature for a long time. It is preferable to leave. The temperature of the aging treatment is preferably less than 110 ° C, more preferably 100 ° C or less, and further preferably 90 ° C or less. The temperature of the aging treatment is preferably 10 ° C or higher, more preferably 20 ° C or higher, and further preferably 30 ° C or higher. 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 substrate (X) and the layer (YA) becomes stronger.

[Step (IV)]
In step (IV), a layer is formed on the substrate (X) (or on the layer (Y)) by applying a coating liquid (V) containing a polymer (E) containing a monomer unit having a phosphorus atom. (Z) is formed. Usually, the coating liquid (V) is a solution in which the polymer (E) is dissolved in a solvent.

  The coating liquid (V) may be prepared by dissolving the polymer (E) in a solvent, or the solution obtained when the polymer (E) is produced may be used as it is. When the solubility of the polymer (E) is low, dissolution may be promoted by heat treatment or ultrasonic treatment.

  The solvent used in the coating liquid (V) may be appropriately selected according to the type of the polymer (E), but is preferably water, alcohols or a mixed solvent thereof. As long as the dissolution of the polymer (E) is not hindered, the solvent is an ether such as tetrahydrofuran, dioxane, trioxane or dimethoxyethane; a ketone such as acetone or methyl ethyl ketone; a glycol such as ethylene glycol or propylene glycol; a methyl cellosolve, an ethyl cellosolve, A glycol derivative such as n-butyl cellosolve; glycerin; acetonitrile; an amide such as dimethylformamide; dimethyl sulfoxide;

  The solid content concentration of the polymer (E) in the coating liquid (V) is preferably in the range of 0.1 to 60% by mass from the viewpoint of storage stability and coating property of the solution, More preferably within the range of 50% by weight, even more preferably within the range of 1.0 to 40% by weight. The solid content concentration can be determined by the same method as described for the coating liquid (U).

  From the viewpoint of the storage stability of the coating liquid (V) and the gas barrier properties of the multilayer structure, the pH of the solution of the polymer (E) is preferably in the range of 0.1 to 6.0, 0.2 to 5 More preferably, it is in the range of 0.0, and more preferably in the range of 0.5 to 4.0.

  The pH of the coating liquid (V) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound. Examples of acidic compounds include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, and ammonium sulfate. Examples of basic compounds include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, and sodium acetate.

  Moreover, when it is necessary to control the viscosity of the coating liquid (V), for example, methods such as adjusting the solid content concentration, adjusting the pH, and adding a viscosity modifier can be employed. Examples of viscosity modifiers include carboxymethylcellulose, starch, bentonite, tragacanth gum, stearate, alginate, methanol, ethanol, n-propanol, and isopropanol.

  The coating liquid (V) may contain a substance other than the substances described above. For example, the solution of the polymer (E) includes carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, aluminates, etc .; oxalates, acetates, Organic acid metal salts such as tartrate and stearate; metal complexes such as acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), cyano metal complexes; layered clay compounds; An agent; a polymer compound other than the polymer (E); a plasticizer; an antioxidant; an ultraviolet absorber;

  In addition, the coating liquid (V) may be degassed and / or defoamed as necessary. As a method of deaeration and / or defoaming treatment, for example, there are methods by evacuation, heating, centrifugation, ultrasonic waves, etc., but a method including evacuation can be preferably used.

  The viscosity of the coating liquid (V) applied in step (IV) and measured with a Brookfield type rotational viscometer (SB type viscometer: rotor No. 3, rotation speed 60 rpm) The temperature is preferably 1000 mPa · s or less, more preferably 500 mPa · s or less. When the viscosity is 1000 mPa · s or less, the leveling property of the coating liquid (V) is improved, and a multilayer structure having a better appearance can be obtained. The viscosity of the coating liquid (V) when applied in the step (IV) can be adjusted by the concentration, temperature and the like.

  The method for applying the solution of the coating liquid (V) on the substrate (X) or the layer (Y) is not particularly limited, and a known method can be adopted. 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 metalling bar coating method, and a chamber doctor combined coating method. And curtain coating method.

  Usually, in the step (IV), the layer (Z) is formed by removing the solvent in the coating liquid (V). There is no restriction | limiting in particular in the removal method of a solvent, A well-known drying method is applicable. 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 alone or in combination. The drying temperature is preferably 0 to 15 ° C. or lower than the flow start temperature of the substrate (X). The drying temperature is preferably in the range of 70 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. When step (IV) is performed after step (II), the solvent may be removed by the heat treatment in step (III) described above.

  When laminating the layer (Z) on both sides of the layered substrate (X) with or without the layer (Y), the solvent is removed after applying the coating liquid (V) on one side. The first layer (Z) may be formed by applying the coating liquid (V) to the other surface, and then the solvent may be removed to form the second layer (Z). The composition of the coating liquid (V) applied to each surface may be the same or different.

  When a layer (Z) is laminated on a plurality of surfaces of a substrate (X) having a three-dimensional shape with or without a layer (Y), the layer (Z) is formed for each surface by the above method. May be. Or you may form a some layer (Z) simultaneously by apply | coating a coating liquid (V) to a some surface simultaneously, and making it dry.

  As described above, the steps are typically carried out in the order of (I), (II), (III), and (IV), but the layer (Z) is divided into the substrate (X) and the layer (Y). In the case where it is formed between the step (IV), the step (IV) may be carried out before the step (II), and further, the step (III) may be carried out after the step (IV). From the viewpoint of obtaining a multilayer structure having an excellent appearance, it is preferable to carry out step (IV) after step (III).

  The multilayer structure thus obtained can be used as it is as a multilayer structure for constituting a coating material for a vacuum heat insulator. However, another member (other layer or the like) may be further bonded or formed on the multilayer structure as described above to form a multilayer structure. The member can be bonded by a known method.

  In one aspect, a method for producing a multilayer structure includes a step (W) of forming a layer (Y) containing aluminum atoms, and a coating liquid (E) containing a polymer (E) containing monomer units having phosphorus atoms. Step (IV) of forming the layer (Z) by applying V) may be included. As described above, when the layer (Y) is the layer (YA), the step (W) may include steps (I), (II), and (III). Further, when the layer (Y) is the layer (YB) or the layer (YC), the step (W) may include a step of forming those layers by a vapor deposition method.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples. In addition, each measurement and evaluation in an Example and a comparative example were implemented with the method of the following (1)-(6).

(1) Infrared absorption spectrum of layer (Y) The infrared absorption spectrum of layer (YA) was measured by the following method.

First, an infrared absorption spectrum of the layer (YA) laminated on the base material (X) was measured using a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer, “Spectrum One”). The infrared absorption spectrum was measured in the ATR (total reflection measurement) mode in the range of 700 to 4000 cm ⁻¹ . When the thickness of the layer (YA) is 1 μm or less, an absorption peak derived from the base material (X) is detected in the infrared absorption spectrum by the ATR method, and the absorption intensity derived only from the layer (YA) is accurately obtained. It may not be possible. In such a case, the infrared absorption spectrum of only the substrate (X) was separately measured, and only the peak derived from the layer (X) was extracted by subtracting it. A similar method can also be adopted when the layer (YA) is laminated on the layer (Z). In addition, when the layer (YA) is formed inside the multilayer structure (for example, in the case of having a stacking order of base material (X) / layer (YA) / layer (Z)), the layer (YA) The infrared absorption spectrum is measured before forming the layer (Z), or after the layer (Z) is formed, it is peeled off at the interface of the layer (YA), and the infrared absorption spectrum of the exposed layer (YA) is measured. Can be obtained.

Based on the infrared absorption spectrum of the thus obtained layer (YA), the maximum absorption wave numbers (n ¹⁾ in the range of 800～1400Cm ^-1, and the absorbance at the maximum absorption wave (n ¹⁾ (α ¹⁾ Asked. The maximum absorption wave numbers (n ²⁾ based on the stretching vibration of the hydroxyl group in the range of 2500～4000Cm ^-1, and were determined absorbance at the maximum absorption wave (n ²⁾ a (alpha ^2). Further, the half width of the absorption peak of the maximum absorption wave number (n ¹ ) is obtained by calculating the wave number of two points having an absorbance (absorbance (α ¹ ) / 2) half of the absorbance (α ¹ ) at the absorption peak. Obtained by calculating the difference in wave numbers. When the absorption peak with the maximum absorption wave number (n ¹ ) overlaps with the absorption peak derived from other components, it is separated into absorption peaks derived from the respective components by the least square method using a Gaussian function. After that, the half width of the absorption peak of the maximum absorption wave number (n ¹ ) was obtained in the same manner as described above.

(2) Appearance of multilayer structure The appearance of the obtained multilayer structure was evaluated visually as follows.
A: It was colorless and transparent and uniform and had a very good appearance.
B: Slight cloudiness or unevenness was observed, but the appearance was good.

(3) Manufacturing method of vacuum heat insulating body The laminated body which has the following structures was produced from the obtained multilayered structure, and the vacuum heat insulating body was produced using the laminated body as a coating | covering material.

a. Laminate made of “OPA / multilayer structure / CPP” One side of a 60 μm-thick unstretched polypropylene film (Tosello CPRXC-18, (CPP), manufactured by Mitsui Chemicals, Inc.), and a stretched polyamide film (Unitika, 15 μm) Apply two-component adhesive (Mitsui Chemicals, A-520 (trade name) and A-50 (trade name)) to one side of the emblem ON-BC, (OPA). The laminate was obtained by laminating the CPP film, the OPA film, and the multilayer structure so as to have a constitution of OPA layer / adhesive layer / multilayer structure / adhesive layer / CPP layer. The multilayer structure was laminated with the side having the layer (Y) (for the multilayer structure having no layer (Y), the side having the layer (Z) or layer (Y ′)) as the OPA side.

b. Laminated body made of “OPA / multilayer structure / VM-EVOH / CPP” CPP, OPA, and biaxially stretched ethylene-vinyl alcohol copolymer film formed with an aluminum vapor deposition layer (manufactured by Kuraray Co., Ltd., VM-XL, The two-component adhesive is applied to each of one side of 12 μm thickness (VM-EVOH), and OPA layer / adhesive layer / multilayer structure / adhesive layer / VM-EVOH layer / adhesive layer / CPP A laminate was obtained by laminating a CPP film, an OPA film, a VM-EVOH film, and a multilayer structure so as to form a layer. The multilayer structure was laminated with the side having the layer (Y) (for the multilayer structure having no layer (Y), the side having the layer (Z) or the layer (Y ′)) as the VM-EVOH side. . Further, VM-EVOH was laminated with the side having the aluminum vapor deposition layer as the multilayer structure side.

  The obtained laminate was cut to obtain two coating materials 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 sealed 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). A vacuum insulator was obtained. Silica fine powder dried for 4 hours in an atmosphere at 120 ° C. was used as the heat insulating core material.

(4) Internal pressure of vacuum insulator after standing After the obtained vacuum insulator was left at 40 ° C. and 15% RH for 360 days, the pressure inside the vacuum insulator was measured using a Pirani vacuum gauge.

(5) Oxygen permeability (Os) of coating material for vacuum insulation
The oxygen transmission rate was measured using an oxygen transmission amount measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control). Specifically, a covering material having a size of 21 cm × 30 cm was cut out from the produced vacuum insulator. Set the coating material so that the layer (YZ) faces the oxygen supply side and the substrate (X) faces the carrier gas side, the temperature is 20 ° C., the humidity on the oxygen supply side is 85% RH, and the humidity on the carrier gas side Was 85% RH, the oxygen pressure was 1 atm, and the carrier gas pressure was 1 atm. The oxygen permeability (unit: ml / (m ² · day · atm)) was measured. Nitrogen gas containing 2% by volume of hydrogen gas was used as the carrier gas.

(6) Oxygen permeability (Of) of the coating material of the vacuum heat insulator after 5% stretching and holding
A covering material having a size of 21 cm × 30 cm was cut out from the produced vacuum insulator. And after leaving the covering material for 24 hours or more under the conditions of 23 ° C. and 50% RH, it is stretched 5% in one direction corresponding to the major axis direction under the same conditions, and the stretched state is maintained for 5 minutes. Thus, a multilayer structure after stretching was obtained. The oxygen transmission rate was measured using an oxygen transmission amount measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control). Specifically, the multilayer structure is set so that the layer (YZ) faces the oxygen supply side and the base material (X) faces the carrier gas side, the temperature is 20 ° C., and the humidity on the oxygen supply side is 85% RH. The oxygen permeability (unit: ml / (m ² · day · atm)) was measured under conditions where the humidity on the carrier gas side was 85% RH, the oxygen pressure was 1 atm, and the carrier gas pressure was 1 atm. Nitrogen gas containing 2% by volume of hydrogen gas was used as the carrier gas.

[Example of production of coating liquid (U)]
The manufacture example of the coating liquid (U) used in order to manufacture a layer (YA) is shown.
The temperature was raised to 70 ° C. while stirring 230 parts by mass of distilled water. In the distilled water, 88 parts by mass of aluminum isopropoxide was added dropwise over 1 hour, the liquid temperature was gradually raised to 95 ° C., and the generated isopropanol was distilled off to carry out hydrolysis and condensation. After adding 4.0 parts by mass of a 60% by mass nitric acid aqueous solution to the obtained liquid and stirring the mixture at 95 ° C. for 3 hours, the aggregates of the hydrolyzed condensate particles were peptized, and then the solid content concentration was It concentrated so that it might become 10 mass% in conversion of an alumina. To 18.66 parts by mass of the dispersion thus obtained, 58.19 parts by mass of distilled water, 19.00 parts by mass of methanol, and 0.50 parts by mass of a 5% by mass aqueous polyvinyl alcohol solution are added so as to be uniform. To obtain a dispersion liquid (S1). Moreover, 3.66 mass parts of 85 mass% phosphoric acid aqueous solution was used as a solution (T1). Subsequently, both the dispersion (S1) and the solution (T1) were adjusted to 15 ° C. Next, while maintaining the liquid temperature of 15 ° C., the solution (T1) was dropped while stirring the dispersion (S1) to obtain a coating liquid (U1). While maintaining the obtained coating liquid (U1) at 15 ° C., stirring was continued until the viscosity reached 1500 mPa · s. In the coating liquid (U1), the number of moles of metal atoms (N _M ) constituting the metal oxide (A) (alumina) and the number of moles of phosphorus atoms constituting the phosphorus compound (B) (phosphoric acid) ( N _p ) (number of moles (N _M ) / number of moles (N _p )) was 1.15.

The coating solution (U2), the coating solution (U3) and the coating solution (U4) were respectively changed in the same manner except that the ratio of N _M / N _P was changed to 4.48, 1.92 and 0.82, respectively. Obtained.

[Production Example of Coating Liquid (V1-4)]
First, a round bottom flask (internal volume: 50 ml) equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was purged with nitrogen, and 12 g of methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”) was charged as a solvent. It was immersed in an oil bath and heated to 80 ° C. to start refluxing. From this time, a small amount of nitrogen gas was allowed to flow throughout the entire polymerization process. Next, a mixed solution of 8.5 g of acid phosphooxyethyl methacrylate (hereinafter sometimes abbreviated as “PHM”), 5 g of MEK, and 100 mg of azobisisobutyronitrile was prepared, and the mixture was stirred at a constant speed over 10 minutes from the dropping funnel. It was dripped at. After completion of the dropping, the temperature was maintained at 80 ° C., and stirring was continued for about 12 hours to obtain a yellowish viscous liquid polymer solution.

  The polymer solution was poured into about 10 times the amount of 1,2-dichloroethane, the supernatant was removed by decantation, the precipitate was recovered, and the polymer was isolated. The recovered polymer is dissolved in tetrahydrofuran (hereinafter sometimes abbreviated as “THF”), which is a good solvent for the polymer, and reprecipitated in about 10 times the amount of 1,2-dichloroethane by repeating the operation three times. And purified. When the molecular weight of the purified polymer was measured by gel permeation chromatography using THF as a solvent at a polymer concentration of 1 wt%, the molecular weight was about 10,000 in terms of polystyrene.

  The purified polymer was dissolved in a mixed solvent of water and isopropanol at a concentration of 10 wt% to obtain a coating liquid (V1).

  By a method similar to the preparation of the coating liquid (V1), a coating liquid (V2) comprising a homopolymer of acid phosphooxypolyoxypropylene glycol methacrylate (hereinafter sometimes abbreviated as “PHP”) was obtained. Further, similarly, a coating liquid (V3) and a coating liquid obtained by copolymerizing PHM and acrylonitrile (hereinafter sometimes abbreviated as “AN”) at a molar ratio of 2/1 and 1/1, respectively. (V4) was obtained respectively.

[Production Example of Coating Liquid (V5-8)]
A round bottom flask (internal volume: 50 ml) equipped with a stirrer and a thermometer was purged with nitrogen, charged with 2.5 g of water as a solvent, and vinylphosphonic acid (hereinafter sometimes abbreviated as “VPA”) while stirring. A mixed solution of 10 g, 2.5 g of water and 25 mg of 2,2′-azobis (2-amidinopropane) dihydrochloride (hereinafter sometimes abbreviated as “AIBA”) was added dropwise to the round bottom flask. From this time, a small amount of nitrogen gas was allowed to flow throughout the entire polymerization process. After soaking the round bottom flask in an oil bath and reacting at 80 ° C. for 3 hours, the reaction mixture is diluted with 15 g of water and filtered through a cellulose membrane (Spectra / Por (trade name) manufactured by Spectrum Laboratories). did. Next, the solvent of the filtrate was distilled off with an evaporator, and a white polymer was obtained by vacuum drying at 50 ° C. for 24 hours. When this polymer was measured by gel permeation chromatography using a 1.2 wt% NaCl aqueous solution as a solvent at a polymer concentration of 0.1 wt%, the molecular weight was about 10,000 in terms of polyethylene glycol. It was.

  The purified polymer was dissolved in a mixed solvent of water and methanol at a concentration of 10 wt% to obtain a coating liquid (V5).

  By a method similar to the preparation of the coating liquid (V5), a coating liquid (V6) composed of a homopolymer of 4-vinylbenzylphosphonic acid (hereinafter sometimes abbreviated as “VBPA”) was obtained. Further, similarly, a coating solution (V7) and a coating of a copolymer obtained by copolymerizing VPA and methacrylic acid (hereinafter sometimes abbreviated as “MA”) at a molar ratio of 2/1 and 1/1, respectively. A liquid (V8) was obtained.

[Example 1]
As a base material, a stretched polyethylene terephthalate film (manufactured by Toray Industries, Inc., “Lumirror P60” (trade name), thickness 12 μm, hereinafter sometimes abbreviated as “PET”) was prepared. On the substrate (PET), the coating liquid (U1) was applied by a bar coater so that the thickness after drying was 0.5 μm, and dried at 110 ° C. for 5 minutes. Next, heat treatment was performed at 180 ° C. for 1 minute to obtain a structure (A1) having a structure of layer (Y1) (0.5 μm) / PET (12 μm). Next, the coating liquid (V1) is applied on the layer (Y1) of the structure (A1) by a bar coater so that the thickness after drying is 0.3 μm, and dried at 110 ° C. for 5 minutes, A multilayer structure (B1) having a structure of (Z1) (0.3 μm) / layer (Y1) (0.5 μm) / PET (12 μm) was obtained.

The moisture permeability (water vapor transmission rate: WVTR) of the obtained multilayer structure (B1) was measured using a water vapor transmission amount measuring device ("MOCON PERMATRAN 3/33" manufactured by Modern Control). Specifically, the composite structure is set so that the layer (Z1) faces the water vapor supply side and the PET layer faces the carrier gas side, the temperature is 40 ° C., the water vapor supply side humidity is 90% RH, the carrier gas side The moisture permeability (unit: g / (m ² · day)) was measured under the condition of 0% RH. The moisture permeability of the multilayer structure (B1) was 0.2 g / (m ² · day).

  About the obtained multilayer structure (B1), the vacuum heat insulating body was produced by said method, and evaluation was performed.

[Example 2]
A multilayer structure and a vacuum heat insulator were obtained by the same method as in Example 1 except that the coating liquid (V) was changed to V5.

[Examples 3 to 6, 41, 42]
A multilayer structure and a vacuum heat insulating body were obtained by the same method as in Example 1 except that the thickness of the layer (Z) and the coating liquid (V) were changed according to Table 1.

[Examples 7 to 12]
A multilayer structure and a vacuum heat insulator were obtained by the same method as in Example 1 except that the coating liquid (V) used was changed according to Table 1.

[Examples 13 to 18]
A multilayer structure and a vacuum heat insulator were obtained by the same method as in Example 1 except that the heat treatment conditions and the coating liquid (V) were changed according to Table 1.

[Examples 19 to 24]
A multilayer structure and a vacuum heat insulator were obtained by the same method as in Example 1 except that the coating liquid (U) and the coating liquid (V) to be used were changed according to Table 1.

[Examples 25 and 26]
A multilayer structure and a vacuum heat insulator were obtained by the same method as in Example 1 except that the heat treatment step was performed after the formation of the layer (Z).

[Examples 27 and 28]
A multilayer structure and a vacuum insulator were obtained by the same method as in Example 1 except that the layers (Y) and (Z) were laminated on both surfaces of the substrate and the coating liquid (V) was changed according to Table 1. . The moisture permeability of the obtained multilayer structure (A1) was measured in the same manner as in Example 1, and was 0.1 g / (m ² · day) or less.

[Examples 29 and 30]
The base material was a stretched nylon film (“Emblem ONBC” (trade name), unit: 15 μm, sometimes abbreviated as “ONY”) manufactured by Unitika Ltd. and the coating solution (V) was changed according to Table 1. A multilayer structure and a vacuum heat insulator were obtained by the same method as in Example 1 except for the above.

[Examples 31 and 32]
A multilayer structure and a vacuum insulator were obtained by the same method as in Example 1 except that the base material was an aluminum oxide vapor deposition layer deposited on the PET surface and the coating liquid (V) was changed according to Table 1. .

[Examples 33 and 34]
A multilayer structure and a vacuum insulator were obtained by the same method as in Example 1 except that the substrate was a silicon oxide vapor-deposited layer deposited on the PET surface and the coating liquid (V) was changed according to Table 1. .

[Examples 35 and 36]
A multilayer structure and a vacuum insulator were obtained by the same method as in Example 1 except that the base material was an aluminum deposition layer deposited on the PET surface and the coating liquid (V) was changed according to Table 1. .

[Examples 37 and 38]
A multilayer structure and a vacuum heat insulating body are obtained by the same method as in Example 1 except that the layer (Y) is an aluminum deposited layer having a thickness of 0.03 μm and the coating liquid (V) is changed according to Table 1. It was. The aluminum layer was formed by a vacuum evaporation method.

[Examples 39 and 40]
A multilayer structure and a vacuum heat insulating body were formed in the same manner as in Example 1 except that the layer (Y) was a vapor-deposited layer of aluminum oxide having a thickness of 0.03 μm and the coating liquid (V) was changed according to Table 1. Obtained. The aluminum oxide layer was formed by a vacuum evaporation method.

[Examples 43 and 44]
A multilayer structure and a vacuum insulator were obtained by the same method as in Example 1 except that the layer (Y) was formed after the formation of the layer (Z) and the coating liquid (V) was changed according to Table 1.

[Comparative Example 1]
In Example 1, the layer (Z) was not formed as Comparative Example 1.

[Comparative Example 2]
In Example 13, the layer (Z) was not formed as Comparative Example 2.

[Comparative Example 3]
In Example 15, the layer (Z) was not formed as Comparative Example 3.

[Comparative Example 4]
In Example 17, the layer (Z) was not formed as Comparative Example 4.

[Comparative Example 5]
In Example 19, the layer (Z) was not formed as Comparative Example 5.

[Comparative Example 6]
In Example 21, the layer (Z) was not formed as Comparative Example 6.

[Comparative Example 7]
In Example 23, the layer (Z) was not formed as Comparative Example 7.

[Comparative Example 8]
In Example 27, the layer (Z) was not formed as Comparative Example 8.

[Comparative Example 9]
In Example 29, the layer (Z) was not formed as Comparative Example 9.

[Comparative Example 10]
In Example 31, the layer (Z) was not formed as Comparative Example 10.

[Comparative Example 11]
In Example 33, the layer (Z) was not formed as Comparative Example 11.

[Comparative Example 12]
In Example 35, the layer (Z) was not formed as Comparative Example 12.

[Comparative Example 13]
In Example 37, the layer (Z) was not formed as Comparative Example 13.

[Comparative Examples 14 and 15]
A multilayer was formed in the same manner as in Example 1 except that the layer (Y) was a layer (Y ′) which is a deposited layer of silicon oxide having a thickness of 0.03 μm and the coating liquid (V) was changed according to Table 1. A structure and a vacuum insulator were obtained. The silicon oxide layer was formed by a vacuum evaporation method.

[Comparative Examples 16 and 17]
A multilayer structure and a vacuum heat insulator were obtained by the same method as in Example 1 except that the layer (Y) was not formed and the coating liquid (V) was changed according to Table 1.

[Comparative Examples 18 and 19]
A multilayer structure and a vacuum insulator were obtained by the same method as in Example 1 except that the layer (Z) was formed on PET and the coating liquid (V) was changed according to Table 1. That is, in Comparative Example 18, a multilayer structure and a vacuum heat insulating body of Comparative Example 18 having a structure of layer (Y1) (0.5 μm) / PET (12 μm) / layer (Z1) (0.3 μm) were produced. .

[Comparative Example 20]
In Comparative Example 14, the layer (Z) was not formed as Comparative Example 20.

[Comparative Example 21]
In Comparative Example 16, the layer (Z) was not formed, that is, only the base material (PET) was used as Comparative Example 21.

  The production conditions and evaluation results of the above Examples and Comparative Examples are shown in Tables 1 to 3 below. In the table, “-” means “not used”, “cannot be calculated”, “not implemented”, “cannot be measured”, and the like.

  As is clear from the table, the vacuum heat insulators of each example maintained good gas barrier properties even after being subjected to a stronger physical stress (5% stretching) after production. On the other hand, after the vacuum heat insulating material of the comparative example was subjected to strong physical stress (5% stretching), the gas barrier properties of all of them were significantly reduced. In the vacuum heat insulating body of each example, a significant increase in internal pressure was suppressed even when left for a long time.

DESCRIPTION OF SYMBOLS 1, 2 Vacuum insulation body 10 Coating | covering material 11 Peripheral part 20 Partition 31, 32 Film material 51, 52 Core

Claims (10)

A vacuum insulating body comprising a coating material and a core material disposed inside the coating material, wherein the interior is depressurized;
The covering material includes a multilayer structure having one or more layers of a base material (X), a layer (Y), and a layer (Z),
The layer (Y) contains an aluminum atom, the layer (Z) contains a polymer (E) containing a monomer unit having a phosphorus atom, and at least one set of the layer (Y) and the layer (Z) Are stacked adjacent to each other,
The layer (Y) is a layer (YA) containing the reaction product (R),
The said reaction product (R) is a vacuum heat insulating body which is a reaction product formed by the reaction of the metal oxide (A) containing aluminum and the phosphorus compound (B) .   At least one set of the base material (X), the layer (Y), and the layer (Z) are laminated in the order of the base material (X) / the layer (Y) / the layer (Z). The vacuum heat insulating body of Claim 1 which has.   The said polymer (E) is a vacuum heat insulating body of Claim 1 or 2 which is a homopolymer or copolymer of (meth) acrylic acid ester which has a phosphate group at the terminal of a side chain.   The vacuum insulator according to claim 3, wherein the polymer (E) is a homopolymer of acid phosphooxyethyl (meth) acrylate. The vacuum heat insulating body according to claim 1 or 2, wherein the polymer (E) has a repeating unit represented by the following general formula (I).

[In Formula I, n is a natural number. ] Wave number infrared absorption is maximized in the region of 800～1400Cm ^-1 in the infrared absorption spectrum before SL layer (YA) (n ¹⁾ is in the range of 1080~1130cm ^-1, one of claims 1 to 5 1 The vacuum insulator according to Item. The vacuum heat insulating body according to any one of claims 1 to 6 , wherein the base material (X) includes at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer. . The multilayer structure is a part of the substrate (X), the layer (Y) or the layer (Z), or together with the substrate (X), the layer (Y) and the layer (Z), including inorganic vapor-deposited layer, a vacuum heat insulation body according to any one of claims 1-7. The vacuum heat insulating body according to any one of claims 1 to 8 , wherein the covering material has an oxygen permeability of 2 ml / (m ² · day · atm) or less under conditions of 20 ° C and 85% RH. After the coating material was held for 5 minutes in a state stretched 5% in one direction under the conditions of 23 ° C. and 50% RH, the oxygen permeability measured under the conditions of 20 ° C. and 85% RH was measured for the coating material. The vacuum insulator according to any one of claims 1 to 9 , which is 4 ml / (m ² · day · atm) or less.

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