TW201634262A - Multilayer structure, packaging material and product using same, and protective sheet for electronic device - Google Patents

Abstract

The present invention relates to a multilayer structure including a substrate (X) and a layer (Y) layered on the substrate (X), wherein the layer (Y) includes an organic phosphorus compound (BO) and a compound (A) including aluminum, and the exposure dose of sputter ions necessary until the ratio IBO/IA of the intensity IA of negative secondary ions having the highest intensity among secondary ions originating from the compound (A) including aluminum and the intensity IBO of negative secondary ions having the highest intensity among secondary ions originating from the organic phosphorus compound (BO) is 3.10 x 10<SP>12</SP> ions/cm2 to 7.30 x 10<SP>13</SP> ions/cm2 when composition analysis in the depth direction of the layer (Y) is performed using a time-of-flight secondary ion mass spectrometer provided with a bismuth cluster ion (Bi3 2+) source as a primary ion source and a fullerene ion (C60 2+) source as a sputter ion source.

Description

Multi-layer structure, packaging materials and articles using the same, and protective sheets for electronic devices

The present invention relates to a multilayer structure, a packaging material and article using the same, and a protective sheet for an electronic device.

A multilayer structure in which a gas barrier layer using aluminum or aluminum oxide as a constituent component is formed on a plastic film has been widely known in the past. These multilayer structures are often used as packaging materials for protecting articles (for example, foods) which are easily deteriorated by oxygen. Most of the gas barrier layers are formed on a plastic film by a dry process such as physical vapor deposition (PVD) or chemical vapor deposition (CVD). Further, these multilayer structures are also used as constituent members of protective sheets for electronic devices requiring gas barrier properties and water vapor barrier properties for the purpose of protecting electronic devices.

For example, an aluminum vapor-deposited film has a light-shielding property in addition to gas barrier properties, and is mainly used as a packaging material for dry foods.

On the other hand, an alumina-deposited film having transparency, Features such as identifiable content, and the use of metal detectors for foreign object inspection or microwave oven heating. Therefore, the film is started from the packaging of retort pouch food and is widely used as a packaging material.

A multilayer structure having a gas barrier layer containing aluminum, for example, a multilayer structure having a transparent gas barrier layer composed of a reaction product of alumina particles and a phosphorus compound has been disclosed in Patent Document 1. Patent Document 1 discloses a method of forming the transparent gas barrier layer by a reactive sputtering method.

In addition, a multilayer structure having a gas barrier layer containing alumina, for example, a multilayer structure having a transparent gas barrier layer composed of a reaction product of alumina particles and a phosphorus compound is disclosed in Patent Document 2. One of the methods for forming the gas barrier layer is to apply a coating liquid containing alumina particles and a phosphorus compound on a plastic film, and a method of drying and heat treatment is disclosed in Patent Document 2.

However, the conventional multilayer structure having a gas barrier layer has excellent gas barrier properties at the initial stage, but when physical stress is applied due to deformation or punching, defects such as cracks or sand holes are formed in the gas barrier layer. There is a situation in which the gas barrier property is lowered.

Therefore, there is a multilayer structure in which gas barrier properties can be maintained at a high efficiency even when subjected to physical stress such as deformation and squeezing, and it is also disclosed in Patent Document 3 and Patent Literature. 4.

However, the inventors will use Patent Document 3 and Patent Literature. When the multilayered structure disclosed in the fourth embodiment is used as a packaging material for a sterilized bag food, the adhesion between the layers after the sterilizing treatment is lowered, and an appearance failure such as lamination cannot be caused. In addition, when the multilayer structure disclosed in Patent Document 3 and Patent Document 4 is used as an electronic device, the interlayer adhesion force is lowered under high temperature and high humidity, and an appearance defect such as lamination cannot be caused. .

Therefore, there is an urgent need to find a multilayer structure having gas barrier properties which have good characteristics even after sterilization treatment. Further, an electronic device which is used for a multilayer structure having high barrier properties at high temperatures and high humidity and having high barrier properties.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2003-251732

[Patent Document 2] WO2011/122036

[Patent Document 3] JP-A-2013-208794

[Patent Document 4] JP-A-2013-208793

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel multilayer structure having excellent gas barrier properties and water vapor barrier properties and excellent bactericidal resistance, and a packaging material using the same.

Moreover, another object of the present invention is to provide a use device A protective sheet of an electronic device having excellent gas barrier properties and water vapor barrier properties and having a novel multilayer structure with high-level adhesion between high-temperature and high-humidity.

As a result of intensive studies, the present inventors have found that a multilayer structure having a specific layer can achieve the above object, and thus completed the present invention.

The present invention provides a multilayer structure comprising a substrate (X) and a multilayer structure laminated to the layer (Y) of the substrate (X), wherein the layer (Y) contains aluminum-containing The compound (A) and the organophosphorus compound (BO) are used as a source of fullerene ions (C ₆₀ ²⁺ ) having a source of a cerium cluster ion (Bi ₃ ²⁺ ) as a primary ion source as a sputter ion source. When the time-of-flight secondary ion mass spectrometer performs composition analysis on the depth direction of the layer (Y), the intensity I _A of the negative secondary ion having the highest intensity among the secondary ions generated from the aluminum-containing compound (A) irradiation amount of secondary ions generated from an organic phosphorus compound (BO) having an intensity in the highest negative secondary ion intensity ratio of I _BO I _BO / I _a is less than the time necessary sputter ion plating 0.05 3.10 ×10 ¹² ions/cm ² or more and 7.30 × 10 ¹³ ions/cm ² or less.

In the multilayer structure of the present invention, the aluminum-containing compound (A) may be a compound (Ab) containing a reaction product (D) of an aluminum-containing metal oxide (Aa) and an inorganic phosphorus compound (BI).

In the multilayer structure of the present invention, the ratio W _BO /W _BI of the mass W _BI of the inorganic phosphorus compound (BI) in the layer (Y) to the mass W _BO of the organic phosphorus compound (BO) satisfies 0.01/99.99 ≦W. The relationship between _BO /W _BI <1.00/99.00 is preferred.

In the multilayer structure of the present invention, the organophosphorus compound (BO) may have a phosphate group, a phosphonous acid group, a phosphonphonic acid group, a phosphinic acid group, a phosphine. A polymer of at least one functional group selected from the group consisting of a Phosphinic acid group and a Phosphinous acid group.

The multilayer structure of the present invention contains a polymer compound (F) which is a polymer having at least one functional group selected from the group consisting of an ether bond, a carbonyl group, a hydroxyl group, and a carboxyl group ( Fa), the mass ratio of the organophosphorus compound (BO) to the polymer (F) may be in the range of 60:40 to 99:1.

In the multilayer structure of the present invention, the substrate (X) may contain at least one layer selected from the group consisting of a thermoplastic resin film and paper.

Moreover, the present invention provides a packaging material comprising any of the foregoing multilayer structures.

The aforementioned packaging material may further have a layer formed by extrusion coating lamination.

The foregoing packaging material is a vertical bag filling sealed bag, a vacuum packaging bag, a pouch, a laminated tubular container, an infusion bag, a paper container, a long bag, a cover material for a container, or may be an in-mold Label container.

Further, the present invention is to provide an article which is at least a part of using any of the foregoing packaging materials.

The above-mentioned product may be a function containing a content, a content as a core material, a reduced pressure inside the product, and a function of a vacuum heat insulator.

Further, the present invention provides a protective sheet of an electronic device comprising any of the foregoing multilayer structures.

The protective sheet of the electronic device may be a protective sheet for protecting the surface of the photoelectric conversion device, the information display device, or the illumination device.

Further, the present invention provides an electronic device including any of the foregoing protective sheets.

According to the content of the present invention, a novel multilayer structure having excellent gas barrier properties and water vapor barrier properties and excellent bactericidal resistance can be obtained and a packaging material using the same. That is, according to the content of the present invention, it is possible to obtain not only excellent gas barrier properties and water vapor barrier properties, but also excellent gas barrier properties and water vapor barrier properties after sterilization treatment, and no sterilization treatment. A novel multilayer structure having a high-level adhesion (peeling strength) and a packaging material using the same, which causes appearance defects such as delamination. Further, according to the present invention, it is possible to obtain a protective sheet of an electronic device using a novel multilayer structure having excellent gas barrier properties and water vapor barrier properties and having high-level adhesion between high-temperature and high-humidity. That is, according to the content of the present invention, it is possible to obtain a temperature and humidity test which has not only excellent gas barrier properties and water vapor barrier properties but also excellent gas barrier properties and water vapor barrier properties after the temperature and humidity test. After that, there will be no appearance defects such as peeling, and there will be high-rise An electronic device for protecting a sheet of a novel multilayer structure with a bonding force (peel strength).

10‧‧‧Vertical bag filled sealed bag

11‧‧‧Multilayer structure

11a‧‧‧End

11b‧‧‧ Body Department

11c, 411, 412, 413, 414, 611‧‧‧ peripheral parts

20‧‧‧flat pouch

360‧‧‧ Container

361, 362, 363‧‧ ‧ multi-layer labels

361a‧‧‧through hole

370‧‧‧ container body

371‧‧‧Flange

372‧‧‧ Body Department

373‧‧‧ bottom

371a‧‧‧ convex

40‧‧‧Electronic devices

41‧‧‧Electronic device body

42‧‧‧ Sealing material

43‧‧‧Protective sheet (multilayer structure)

401‧‧‧Infusion bag (bag)

420, 620‧‧‧ next door

431‧‧‧Infusion bag body

432‧‧‧ Portion member

433‧‧‧ hanging hole

50‧‧‧Extrusion coating laminating device

51‧‧‧Extrusion machine

52‧‧‧T mode

53‧‧‧Cooling roller

54‧‧‧Rubber roller

501‧‧‧ Laminate

502‧‧‧Resin film

503‧‧‧Laminated film (multilayer structure)

601, 602‧‧‧ vacuum insulation

410a, 410b, 631, 632‧‧‧ film materials

651, 652‧‧‧ core material

Fig. 1 is a schematic view showing a vertical bag-filled sealed bag according to an embodiment of the present invention.

Fig. 2 is a schematic view showing a flat pouch according to an embodiment of the present invention.

Fig. 3 is a schematic view showing an infusion bag according to an embodiment of the present invention.

Fig. 4 is a schematic view showing an in-mold label (In Mold Labeling) container according to an embodiment of the present invention.

Fig. 5 is a perspective view showing a partial mode of an extrusion coating laminating apparatus used for the production of a multilayered structure according to an embodiment of the present invention.

Fig. 6 is a schematic view showing a vacuum heat insulator according to an embodiment of the present invention.

Fig. 7 is a schematic view showing another vacuum heat insulator according to an embodiment of the present invention.

Fig. 8 is a partial cross-sectional view showing an electronic device according to an embodiment of the present invention.

[Formation of the Invention]

The present invention will be described by way of the following examples. Further, in the following description, the present invention is not limited by the examples, the examples, the conditions, the methods, the numerical ranges, and the like. Further, the exemplified substances may be used singly or in combination of two or more kinds, unless otherwise noted.

In the present specification, in the meaning of "specifying a specific layer on a specific member (base material, layer, etc.)", in addition to the case where the specific layer is laminated in contact with the member, It is also included in the case where the specific layer is laminated over the member in which the other layer is sandwiched. The description of "a specific layer is formed on a specific member (base material, layer, etc.)" and "a specific layer is disposed on a specific member (base material, layer, etc.)" has the same meaning. In addition, when there is no special comment, the meaning of "the liquid (coating liquid, etc.) is applied to a specific member (base material, layer, etc.)" is also the case where the liquid is directly applied to the member. The case where the liquid is coated on other layers formed on the member.

In this specification, there is a case where the layer (Y) of the symbol (Y) is attached as in the case of "layer (Y)" to distinguish it from other layers. The symbol (Y) is not technical in meaning without special comments. The substrate (X), the compound (A), and other symbols are also the same. However, as in the case of a hydrogen atom (H), the case where a specific element is clearly indicated is excluded.

[multilayer structure]

The multilayer structure of the present invention comprises a substrate (X) and an aluminum-containing layer (Y). Layer (Y) is a compound containing aluminum (A) (hereinafter, also only It is called "compound (A)") and organophosphorus compound (BO). In the following description, the phrase "multilayer structure" means a multilayer structure including the substrate (X) and the layer (Y), unless otherwise noted.

In the layer (Y), at least a portion of the compound (A) is reacted with at least a portion of the organophosphorus compound (BO). Further, in the case where the layer (Y) contains the inorganic phosphorus compound (BI), at least a part of the compound (A) and at least a part of the organophosphorus compound (BO) and/or the inorganic phosphorus compound (BI) may be used. Carry out the reaction. When the compound (A) in the layer (Y) is reacted, a part of the compound (A) constituting the reaction product is also regarded as the compound (A). In this case, the mass of the compound (A) used to form the reaction product (the mass of the compound (A) before the reaction) is the mass of the compound (A) contained in the layer (Y). Further, the inorganic phosphorus compound (BI) and/or the organophosphorus compound (BO) in the layer (Y) are reacted, and the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BO) constituting the reaction product are part of the reaction product. Also considered as inorganic phosphorus compound (BI) and / or organic phosphorus compound (BO). In this case, the mass of the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BO) used for the reaction product (the mass of the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BO) before the reaction), It is included in the mass of the inorganic phosphorus compound (BI) and/or the organic phosphorus compound (BO) contained in the layer (Y).

In the multilayer structure of the present invention, when the composition of the layer (Y) is analyzed in the depth direction, the intensity I _A of the negative secondary ion having the highest intensity among the secondary ions generated from the aluminum-containing compound (A) is The ratio of the intensity I _BO of the negative secondary ion having the highest intensity among the secondary ions generated by the organophosphorus compound (BO) I _BO /I _A is the amount of the sputter ion necessary to reach 0.05, 3.10 ×10 ¹² ions/cm ² or more, 7.30×10 ¹³ ions/cm ² or less, and more preferably 3.10×10 ¹² ions/cm ² or more and 3.10×10 ¹³ ions/cm ² or less, and 3.30×10 ¹² ions/cm. ² or more and 1.30 × 10 ¹³ ions/cm ² or less is preferable. When the irradiation amount of the sputtering ions necessary for I _BO /I _{A is} less than 0.05 is less than 3.10 × 10 ¹² ions/cm ² , the amount of the organic phosphorus compound (BO) is too small, so the adhesion between the layers is lowered. . Further, when the irradiation amount of the sputter ion necessary for I _BO /I _{A is} less than 0.05 is more than 7.30 × 10 ¹³ ions / cm ² , it is produced by the organic phosphorus compound (BO) present on the outermost surface of the layer (Y). The functional group containing a phosphorus atom is excessive, and hydrophilicity is increased, so that the adhesion is lowered.

The above "I _BO /I _{A is} less than 0.05" means that the organic phosphorus compound (BO) is hardly present in the layer (Y) when compared with the amount of the aluminum-containing compound (A). In the layer (Y), when the ions are sputtered, I _BO /I _A is successively lowered, that is, in the depth direction of the layer (Y), the closer to the surface closest to the substrate (X) (for example, the phase) When the side of the adjoining surface is on the side, the amount of the organophosphorus compound (BO) is gradually lowered, and in the vicinity of the surface closest to the substrate (X) (for example, the adjacent junction), the organophosphorus compound (BO) is almost For not exists. This is shown in the depth direction of the layer (Y), from the vicinity of the surface closest to the substrate (X) on the opposite side (the surface farthest from the substrate (X)), to the nearest substrate ( The amount of the organophosphorus compound (BO) is gradually lowered until the side of the X) side. Since the layer (Y) of the multilayered structure of the present invention has the above-described cross-sectional structure, excellent barrier properties and high-layer adhesion (peeling strength) can be obtained.

The composition analysis of the depth direction of the above layer (Y) is to use a source of fullerene ions (C ₆₀ ²⁺ ) having a source of a cerium cluster ion (Bi ₃ ²⁺ ) as a primary ion source as a source of sputtering ions. Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS) was analyzed. The analysis conditions are as described in the examples below.

As described above, when the irradiation amount of the sputter ion is within the above-mentioned specific range, even after the sterilization treatment or the high temperature and high humidity, the barrier property is excellent, the appearance defect such as peeling does not occur, and the high-level indirect Focus on (peel strength).

The contents of the substrate (X) and the layer (Y) will be described below.

[Substrate (X)]

The material of the substrate (X) is not particularly limited, and a substrate formed of various materials can be used. The material of the substrate (X) is, for example, a resin such as a thermoplastic resin or a thermosetting resin; a fiber assembly such as a cloth or a paper; wood; glass or the like. Among these, a thermoplastic resin and a fiber aggregate are preferred, and a thermoplastic resin is preferred. The form of the substrate (X) is not particularly limited, and may be a layer such as a film or a sheet. The substrate (X) is preferably one containing at least one selected from the group consisting of a thermoplastic resin film and paper, and preferably a thermoplastic resin film, and more preferably a thermoplastic resin film.

a thermoplastic resin used for the substrate (X), for example, polyethylene Polyolefin resin such as olefin or polypropylene; polyethylene terephthalate (PET), polyethylene 2,6-naphthalenedicarboxylate, polybutylene terephthalate or copolymers thereof Ester resin; polyamine resin such as nylon-6, nylon-66, nylon-12; hydroxyl group-containing polymer such as polyvinyl alcohol or ethylene-vinyl alcohol copolymer; polystyrene; poly(meth)acrylate Polyacrylonitrile; Polyvinyl acetate; Polycarbonate; Polyacrylate; Regenerated cellulose; Polyimine; Polyether quinone; Polyfluorene; Polyether oxime; Polyetheretherketone; Ionic polymer resin . In the case where the multilayer structure is used as a packaging material, the material of the substrate (X) is selected from a group consisting of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, and nylon-66. One type of thermoplastic resin is preferred.

When the film formed of the thermoplastic resin is used as the substrate (X), the substrate (X) may be an extended film or an extended film. From the viewpoint of the excellent workability (printing, lamination, etc.) of the obtained multilayered structure, it is preferred to extend the film, particularly the biaxially stretched film. The biaxially stretched film may be a biaxially stretched film obtained by any one of a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tubular stretching method.

Paper used for the substrate (X), for example, drawing paper, top quality paper, mold paper, cellophane, parchment paper, synthetic paper, white paper, Manila paper, milk carton base paper, cup (use) base paper, ivory paper Wait. When paper is used as the substrate (X), a multilayer structure for a paper container can be obtained.

When the substrate (X) is in the form of a layer, the thickness thereof is obtained The structure has a good mechanical strength and workability, and is preferably 1 to 1,000 μm, preferably 5 to 500 μm, and more preferably 9 to 200 μm.

[layer (Y)]

The layer (Y) contains the compound (A) and an organic phosphorus compound (BO). The compound (A) is an aluminum-containing compound. Further, the layer (Y) preferably contains an inorganic phosphorus compound (BI). The inorganic phosphorus compound (BI) and the organic phosphorus compound (BO) have a functional group containing a phosphorus atom. The contents of the compound (A), the inorganic phosphorus compound (BI), and the organophosphorus compound (BO) will be described below.

[Aluminum-containing compound (A)]

The compound (A) may be an aluminum-containing metal oxide (Aa) or an aluminum-containing metal oxide (Aa) (hereinafter also referred to as "metal oxide (Aa)") and an inorganic phosphorus compound (BI). The compound (Ab) (hereinafter, also referred to as "compound (Ab))) of the reaction product (D) obtained by the reaction may be used.

[Aluminum-containing metal oxide (Aa)]

The aluminum-containing metal oxide (Aa) is usually reacted with an inorganic phosphorus compound (BI) in the form of particles.

a metal atom constituting an aluminum-containing metal oxide (Aa) (these are also collectively referred to as "metal atom (M)"), which is a week At least one metal atom selected from the metal atoms of Groups 2 to 14 of the period, but containing at least aluminum. The metal atom (M) may be aluminum alone or may contain aluminum or other metal atoms. Further, the metal oxide (Aa) may be used in combination of two or more kinds of metal oxides (Aa).

The proportion of aluminum in the metal atom (M) is usually 50 mol% or more, and may be 60 to 100 mol%, or 80 to 100 mol%. In the example of the metal oxide (Aa), for example, a metal oxide obtained by a method such as a liquid phase synthesis method, a gas phase synthesis method, or a solid pulverization method is included.

The metal oxide (Aa) may be a hydrolysis condensate of the compound (E) containing a metal atom (M) bonded to a hydrolyzable characteristic group. Examples of the characteristic group include, for example, R ^{1 of the above} formula [I]. The hydrolysis condensate of the compound (E) can be substantially regarded as a metal oxide. Therefore, in the present specification, the hydrolysis condensate of the compound (E) may also be referred to as "metal oxide (Aa)". In other words, in the present specification, "metal oxide (Aa)" can be interpreted as "hydrolysis condensate of compound (E)", and "hydrolysis condensate of compound (E)" can be interpreted as "metal oxide (Aa)""."

[Compound (E) containing a metal atom (M) bonded to a hydrolyzable characteristic group]

From the viewpoint of easily controlling the reaction mechanism with the inorganic phosphorus compound (BI) and making the gas barrier property of the obtained multilayer structure more excellent, the compound (E) contains at least one compound represented by the following formula [I]. (Ea) is better.

Al(R ¹ ) _k (R ² ) _3-k [I]

In the formula, R ¹ is a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), NO ₃ , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, and a carbon number which may have a substituent 2~ a decyloxy group of 9 or more, an alkenyloxy group having 3 to 9 carbon atoms which may have a substituent, a β-diketone group having 5 to 15 carbon atoms which may have a substituent, or a carbon number of 1 to 9 which may have a substituent The fluorenyl group of the fluorenyl group. R ² is an alkyl group having 1 to 9 carbon atoms which may have a substituent, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 9 carbon atoms which may have a substituent, or may have The substituent has a carbon number of 6 to 10 aryl groups. k is an integer from 1 to 3. There are many cases where R ¹ exists, and R ¹ may be the same or different from each other. R ² is present the majority of circumstances, each of R ² may be the same or, different also.

The compound (E) may contain, in addition to the compound (Ea), at least one compound (Eb) represented by the following formula [II].

M ¹ (R ³ ) _m (R ⁴ ) _nm [II]

In the formula, M ¹ is a metal atom other than an aluminum atom, and is at least one metal atom selected from the metal atoms of Groups 2 to 14 of the periodic table. R ³ is a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), NO ₃ , an alkoxy group having a carbon number of 1 to 9 which may have a substituent, and a carbon number of 2 to 9 which may have a substituent. An oxy group, an alkenyloxy group having 3 to 9 carbon atoms which may have a substituent, a β-diketone group having 5 to 15 carbon atoms which may have a substituent, or a mercapto group having 1 to 9 carbon atoms which may have a substituent Dimethyl group. R ⁴ is an alkyl group having 1 to 9 carbon atoms which may have a substituent, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 9 carbon atoms which may have a substituent, or may have The substituent has a carbon number of 6 to 10 aryl groups. m is an integer from 1 to n. n represents the valence of M ¹ . R ³ is present the majority of circumstances, each of R ³ may be the same or, different also. R ⁴ is present the majority of circumstances, each of R ⁴ may be the same or, different also.

Alkoxy groups of R ¹ and R ³ , for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert- Butoxy, benzyloxy, diphenylmethoxy, triphenylmethoxy, 4-methoxybenzyloxy, methoxymethoxy, 1-ethoxyethoxy, benzyloxy An oxy group, a 2-trimethyldecyl ethoxy group, a 2-trimethyl decyl ethoxy methoxy group, a phenoxy group, a 4-methoxyphenoxy group, or the like.

Alkoxy groups of R ¹ and R ³ , for example, ethoxycarbonyl, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyl An oxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, an n-octylcarbonyloxy group or the like.

Alkenyloxy group for R ¹ and R ³ , for example, allyloxy, 2-propenyloxy, 2-butenyloxy, 1-methyl-2-propenyloxy, 3-butenyloxy, 2- Methyl-2-propenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-3-butenyloxy, 1,2-dimethyl- 2-propenyloxy, 1,1-dimethyl-2-propenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, 2-methyl-3 -butenyloxy, 3-methyl-3-butenyloxy, 1-vinyl-2-propenyloxy, 5-hexenyloxy and the like.

a β-diketone group of R ¹ and R ³ , for example, 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5 , 5,5-hexafluoro-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-butanedione, 2-methyl-1,3-butanedione, 2-methyl-1,3-butanedione, benzhydrazinyl and the like.

a fluorenyl group of a dimethyl group of R ¹ and R ³ , for example, a methyl group, an ethyl group, a propyl group (Propanoyl group), a butyl group (Butanoyl group), a pentamyl group (Pentanoyl group), a hexyl group, etc. An aliphatic fluorenyl group having 1 to 6 carbon atoms; an aromatic fluorenyl group (aryl fluorenyl group) such as a benzamidine group or a tolylylene group.

An alkyl group of R ² and R ⁴ , for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, Isoamyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1,2-dimethylbutyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.

An aralkyl group of R ² and R ⁴ , for example, a benzyl group, a phenylethyl group (phenethyl group) or the like.

Alkenyl groups of R ² and R ⁴ , for example, ethenyl, 1-propenyl, 2-propenyl, isopropenyl, 3-butenyl, 2-butenyl, 1-butenyl, 1-methyl -2-propenyl, 1-methyl-1-propenyl, 1-ethyl-1-vinyl, 2-methyl-2-propenyl, 2-methyl-1-propenyl, 3-methyl 2-butenyl, 4-pentenyl and the like.

The aryl group of R ² and R ⁴ is, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group or the like.

a substituent in R ¹ , R ² , R ³ and R ⁴ , for example, an alkyl group having 1 to 6 carbon atoms; a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group. , isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy Alkoxy group having 1 to 6 carbon atoms such as cyclohexyloxy; methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy Carbonic acid, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentyloxycarbonyl, etc. a carbonyl group; an aromatic hydrocarbon group such as a phenyl group, a tolyl group or a naphthyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a fluorenyl group having 1 to 6 carbon atoms; and an aralkyl group having 7 to 10 carbon atoms; An aralkoxy group having 7 to 10 carbon atoms; an alkylamino group having 1 to 6 carbon atoms; a dialkylamine group having an alkyl group having 1 to 6 carbon atoms; and the like.

R ¹ and R ³ , a halogen atom, NO ₃ , an alkoxy group having 1 to 6 carbon atoms which may have a substituent, a decyloxy group having 2 to 6 carbon atoms which may have a substituent, and a carbon number which may have a substituent a β-dione group of 5 to 10, or a dimethyl group having a fluorenyl group having 1 to 6 carbon atoms which may have a substituent, preferably an alkoxy group having 1 to 6 carbon atoms which may have a substituent good.

R ² and R ^{4 are} preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent. k of the formula [I] is preferably 3.

M ^{1 is} preferably a metal atom to which Group 4 of the periodic table belongs, and titanium or zirconium is preferred. M ¹ is a metal atom to which the group 4 of the periodic table belongs, and m of the formula [II] is preferably 4.

Further, although boron and antimony are classified as semi-metals, in the present specification, these are included in the metal.

Compound (Ea), for example, aluminum chloride, aluminum nitrate, aluminum acetate, ginseng (2,4-pentanedione) aluminum, trimethoxy aluminum, triethoxy Aluminum, tri-n-propoxy aluminum, triisopropoxy aluminum, tri-n-butoxy aluminum, tri-sec-butoxy aluminum, tri-tert-butoxy aluminum, etc. Aluminum triisopropoxide and tris-sec-butoxy aluminum are preferred. For the compound (E), two or more compounds (Ea) can be used in combination.

Compound (Eb), for example, tetrakis(2,4-pentanedione)titanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra ( A titanium compound such as 2-ethylhexyloxy)titanium; a zirconium compound such as tetrakis(2,4-pentanedione) zirconium, tetra-n-propoxy zirconium or tetra-n-butoxyzirconium. These may be used alone or in combination of two or more compounds (Eb).

In the compound (E), the proportion of the compound (Ea) in the compound (E) is not particularly limited as long as it is within the range of the effect of the invention. The ratio of the compound other than the compound (Ea) (for example, the compound (Eb)) to the compound (E) is, for example, preferably 20 mol% or less, more preferably 10 mol% or less, and preferably 5 mol%. The ear percentage is preferably less than or equal to 0% by mole.

When the compound (E) is hydrolyzed, at least a part of the hydrolyzable characteristic groups of the compound (E) can be converted into a hydroxyl group. Further, when the hydrolyzate is condensed, a compound obtained by bonding a metal atom (M) via an oxygen atom (O) can be formed. When the condensation reaction is repeated, a compound which is substantially regarded as a metal oxide can be formed. Further, a hydroxyl group is usually present on the surface of the metal oxide (Aa) formed by this method.

In the present specification, the ratio of [the number of moles of the oxygen atom (O) bonded to the metal atom (M)] / [the number of moles of the metal atom (M)] A compound of 0.8 or more is considered to be contained in the metal oxide (Aa). Among them, only the oxygen atom (O) bonded to the metal atom (M) is the oxygen atom (O) in the structure represented by MOM, the oxygen atom (O) in the structure represented by MOH, and the metal atom ( M) The oxygen atom bonded to the hydrogen atom (H) is not contained therein. The above ratio in the metal oxide (Aa) is preferably 0.9 or more, more preferably 1.0 or more, and still more preferably 1.1 or more. The upper limit of the ratio is not particularly limited, but generally, when the atomic valence of the metal atom (M) is n, it is usually represented by n/2.

In order to initiate the aforementioned hydrolysis condensation reaction, it is an important condition that the compound (E) has a hydrolyzable characteristic group. When the bases are not bonded, the hydrolysis condensation reaction is unlikely to occur or the reaction is extremely slow, and the metal oxide (Aa) of the target is extremely difficult to produce.

The hydrolysis condensate of the compound (E) can be produced, for example, from a specific raw material by a known method of a sol-gel method. As the raw material, a compound obtained by partially hydrolyzing and condensing a compound (E), a partial hydrolyzate of the compound (E), a complete hydrolyzate of the compound (E), and a compound (E), and a compound (E) can be used. At least one selected from the group consisting of a compound formed by condensation of one of the complete hydrolyzates.

A metal oxide (Aa) which is mixed with an inorganic phosphorus compound (BI) (inorganic phosphorus compound (BI) or a composition containing an inorganic phosphorus compound (BI)) may be provided to substantially contain no phosphorus The atom is better.

[Compound (Ab)]

The reaction product (D) contained in the compound (Ab) is obtained by reacting a metal oxide (Aa) with an inorganic phosphorus compound (BI). Among them, a compound formed by reacting a metal oxide (Aa) with an inorganic phosphorus compound (BI) with another compound is also contained in the reaction product (D). Further, the compound (Ab) may contain a part of the metal oxide (Aa) and/or the inorganic phosphorus compound (BI) which are not related to the reaction.

In the compound (Ab), the molar ratio of the metal atom constituting the metal oxide (Aa) to the phosphorus atom produced by the inorganic phosphorus compound (BI), [the metal atom constituting the metal oxide (Aa)]: [by inorganic The phosphorus atom produced by the phosphorus compound (BI) is preferably in the range of 1.0: 1.0 to 3.6: 1.0, preferably in the range of 1.1: 1.0 to 3.0: 1.0. Outside this range, the gas barrier properties will be reduced. The molar ratio in the compound (Ab) can be adjusted by the mixing ratio of the metal oxide (Aa) to the inorganic phosphorus compound (BI) in the coating liquid for forming the compound (Ab). The molar ratio in the compound (Ab) is usually the same as the ratio in the coating liquid.

Infrared layer (Y) of the absorption spectrum, the maximum absorption wave number region of 800 ~ 1,400cm ^-1 is preferably in the range of 1,080 ~ 1,130cm ^-1. During the reaction of the metal oxide (Aa) with the inorganic phosphorus compound (BI) to form the reaction product (D), the metal atom (M) produced by the metal oxide (Aa) and the inorganic phosphorus compound (BI) are produced. The phosphorus atom (P) forms a bond represented by MOP via an oxygen atom (O). As a result, in the infrared absorption spectrum of the reaction product (D), a characteristic absorption band generated by the bonding is generated. As a result of the research, the inventors have found that when the characteristic absorption band based on the bond of MOP is present in the region of 1,080 to 1,130 cm ^-1 , the obtained multilayer structure can exhibit excellent gas barrier properties. In particular, when the characteristic absorption band is present in the region of 800 to 1,400 cm ^-1 which is generally caused by absorption of various atoms and oxygen atoms, the obtained multilayer structure is known. Shows better gas barrier properties.

On the other hand, when a metal compound such as an alkoxide metal or a metal salt is mixed with an inorganic phosphorus compound (BI) in advance and then hydrolyzed and condensed, a metal atom derived from a metal compound and an inorganic phosphorus compound (BI) can be obtained. The resulting phosphorus atom is obtained by reacting in a nearly uniform mixture. When that case, the infrared absorption spectrum, the maximum absorption wave number region of 800 ~ 1,400cm ^-1 is in the range away from the 1,080 ~ 1,130cm ^-1.

In the infrared absorption spectrum of the layer (Y), the half-height width value (FWHM) of the maximum absorption band in the region of 800 to 1,400 cm ^-1 is obtained by the viewpoint of the gas barrier property of the multilayered structure, which is 200 cm ^-1 or less. Preferably, it is preferably 150 cm ^-1 or less, more preferably 100 cm ^-1 or less, and particularly preferably 50 cm ^-1 or less.

The infrared absorption spectrum of the layer (Y) can be measured by the method described in the examples. However, when the method described in the examples cannot be measured, reflection measurement such as reflection absorption method, external reflection method, or total reflection method may be used, and a layer (Y) or a nujol mull method may be used for the multilayer structure. The tablet method may be measured by a method such as measurement, but is not limited to the methods.

a compound (Ab), a metal oxide (Aa) particle It is also possible to have a structure in which a phosphorus atom generated by an inorganic phosphorus compound (BI) is bonded to each other. The particles of the metal oxide (Aa) used as a raw material of the compound (Ab) can be changed in shape or size during the formation of the compound (Ab).

[Inorganic Phosphorus Compound (BI)]

The inorganic phosphorus compound (BI) contains a site which can react with the metal oxide (Aa), and typically contains a plurality of such sites. The inorganic phosphorus compound (BI) is preferably a compound containing 2 to 20 such sites (atoms or functional groups). An example of such a site is a site containing a condensation reaction with a functional group (for example, a hydroxyl group) present on the surface of the metal oxide (Aa). Such a moiety is, for example, a halogen atom directly bonded to a phosphorus atom, an oxygen atom directly bonded to a phosphorus atom, or the like. A functional group (for example, a hydroxyl group) present on the surface of the metal oxide (Aa) is usually bonded to a metal atom (M) constituting the metal oxide (Aa).

Inorganic phosphorus compound (BI), for example, phosphoric acid, diphosphoric acid, triphosphoric acid, and phosphoric acid of four or more molecules are condensed to obtain phosphorus such as polyphosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphinic acid, and phosphinic acid. Oxyacids, and salts thereof (e.g., sodium phosphate), and derivatives thereof (e.g., halides (e.g., phosphonium chloride), anhydrates (e.g., phosphorus pentoxide), and the like.

These inorganic phosphorus compounds (BI) may be used alone or in combination of two or more. Among the inorganic phosphorus compounds (BI), phosphoric acid is used alone, or phosphoric acid is not used. Machine phosphorus compounds (BI) are preferred for users. When phosphoric acid is used, the stability of the coating liquid (S) described later and the gas barrier properties of the obtained multilayered structure can be improved. In the case where phosphoric acid and other inorganic phosphorus compounds (BI) are used in combination, it is preferred that 50 mol% or more of the inorganic phosphorus compound (BI) is phosphoric acid.

[Inorganic vapor deposited layer, compound (Ac), compound (Ad)]

The multilayer structure may further contain an inorganic vapor deposition layer. The inorganic deposited layer can be formed by vapor deposition of an inorganic substance. An inorganic substance such as a metal (for example, aluminum), a metal oxide (for example, yttrium oxide, aluminum oxide), a metal nitride (for example, tantalum nitride), a metal nitride oxide (for example, lanthanum acid oxynitride), or Metal carbide nitride (for example, niobium carbonitride) or the like. Among these, the inorganic deposited layer formed of alumina, cerium oxide, magnesium oxide, or tantalum nitride is preferred from the viewpoint of excellent barrier properties against oxygen or water vapor. The layer (Y) in the multilayer structure of the present invention may contain an inorganic vapor-deposited layer containing aluminum. For example, the layer (Y) may also contain an evaporated layer of aluminum (Ac) and/or an evaporated layer of aluminum (Ad).

The method for forming the inorganic deposited layer is not particularly limited, and a vacuum deposition method (for example, resistance heating vapor deposition, electron beam evaporation, molecular line epitaxy, etc.), sputtering, or ion plating may be used. Physical vapor phase growth method, thermal chemical vapor phase growth method (for example, catalytic chemical vapor phase growth method), photochemical vapor phase growth method, plasma chemical vapor phase growth method (for example, capacity bonding plasma, inductive coupling) Plasma, surface wave plasma, electron cyclotron resonance, dual-magnetron, atomic layer stacking Chemical vapor phase growth methods such as the method of organic metal vapor phase growth.

The thickness of the inorganic vapor-deposited layer varies depending on the type of the components constituting the inorganic vapor-deposited layer, and is preferably 0.002 to 0.5 μm, more preferably 0.005 to 0.2 μm, and more preferably 0.01 to 0.1 μm. Within this range, a thickness having a good barrier property or a mechanical property of a multilayered structure may be selected. When the thickness of the inorganic deposited layer is less than 0.002 μm, there is a tendency to reduce the reproducibility of the barrier property to the inorganic deposited layer of oxygen or water vapor, and the inorganic deposited layer may also have insufficient barrier properties. . When the thickness of the inorganic deposited layer exceeds 0.5 μm, the barrier property of the inorganic deposited layer tends to decrease when the multilayered structure is stretched or bent.

[Organic Phosphorus Compound (BO)]

A functional group containing a phosphorus atom possessed by an organophosphorus compound (BO), for example, a phosphoric acid group, a phosphonous acid group, a phosphonphonic acid group, a phosphinic acid group, a phosphinic acid ( Phosphinic acid), a Phosphinous acid group, and functional groups derived therefrom (for example, salts, (partial) ester compounds, halides (eg, chlorides), dehydrates, etc.) The phosphoric acid group and the phosphonic acid group are preferred, and the phosphonic acid group is preferred.

The organophosphorus compound (BO) is preferably a polymer (BOa) having a functional group containing the aforementioned phosphorus atom. The polymer (BOa), for example, 6-[(2-phosphoniopurinyl)oxy]hexyl acrylate, 2-phosphonium oxyethyl methacrylate, phosphinylmethyl methacrylate, methacrylic acid Phosphine such as 11-phosphinodecyl undecyl or 1,1-diphosphinodecylethyl methacrylate a polymer of mercapto (meth) acrylate; a polymer of vinylphosphonic acid such as vinylphosphonic acid, 2-propene-1-phosphonic acid, 4-vinylbenzylphosphonic acid, 4-vinylphenylphosphonic acid; A polymer of a vinylphosphonic acid such as a phosphonic acid or a 4-vinylbenzylphosphonic acid; a phosphorylated starch or the like. The polymer (BOa) may be a homopolymer of a monomer having a functional group containing at least one phosphorus atom, or a copolymer of two or more kinds of monomers. Further, the polymer (BOa) may be used in combination of two or more kinds of polymers composed of a single monomer. Among them, a polymer of a phosphinyl (meth) acrylate type and a polymer of a vinyl phosphonic acid type are preferable, and a polymer of a vinyl phosphonic acid type is preferable. That is, the polymer (BOa) is preferably poly(vinylphosphonic acid). Further, the polymer (BOa) may be obtained by separately or copolymerizing a vinylphosphonic acid derivative such as a vinylphosphonic acid halide or an ethylene phosphonate after hydrolysis.

Further, the polymer (BOa) may be a copolymer of at least one monomer having a functional group containing a phosphorus atom and another ethylene monomer. Other ethylene monomers copolymerizable with a monomer having a functional group containing a phosphorus atom, for example, (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylonitrile, styrene, nuclear-substituted styrene Classes, alkyl vinyl ethers, alkyl vinyl esters, perfluoroalkyl vinyl ethers, perfluoroalkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, isaconic acid, malayan Amine, phenylmaleimide or the like, among which (meth) acrylate, acrylonitrile, styrene, maleimide, and phenylmaleimide are preferred.

From the viewpoint of producing a multilayer structure having more excellent bending resistance, a structural unit having a monomer having a functional group containing a phosphorus atom, and a proportion of a total structural unit of the polymer (BOa), 10 More preferably, the molar percentage is more than 20% by mole, more preferably 40% by mole or more, more preferably 70% by mole or more, and may be 100% by mole.

The molecular weight of the aforementioned polymer (BOa) is not particularly limited, and it is generally preferred that the number average molecular weight is in the range of 1,000 to 100,000. When the number average molecular weight is in this range, the effect of improving the bending resistance obtained by the laminated layer (Y) having a high standard can be obtained, and the viscosity stability of the coating liquid (T) to be described later can be obtained.

In the layer (Y) of the multilayer structure, when the inorganic phosphorus compound (BI) is contained, the ratio of the mass W _BI of the inorganic phosphorus compound (BI) in the layer (Y) to the mass W _BO of the organic phosphorus compound (BO) W _BO /W _BI to satisfy the relationship of 0.01/99.99 ≦W _BO /W _BI <1.00/99.00 is preferable, and the viewpoint of improving the peel strength of the obtained layer is satisfied to satisfy 0.10/99.90 ≦W _BO /W _BI <0.99/99.01 The relationship is better, to satisfy the relationship of 0.15/99.85 ≦W _BO /W _BI <0.95/99.05 is better, to meet the relationship of 0.20/99.80 ≦W _BO /W _BI <0.93/99.07 is particularly good. . That is, with respect to W _BO is 0.01 to less than 1.00 micro, W _BI to the use of a large amount of greater than 99.00,99.99 preferred.

The layer (Y) contained in the multilayered structure of the present invention may be composed only of the aluminum-containing compound (A) and the organophosphorus compound (BO); only the aluminum-containing compound (A) and the inorganic phosphorus compound (BI), and organic phosphorus compound (BO) may be composed of only aluminum-containing metal oxides (Aa), inorganic phosphorus compounds (BI), and organophosphorus compounds (BO); Containing aluminum-containing metal oxides (Aa) a compound (Ab), an inorganic phosphorus compound (BI), and an organic phosphorus compound (BO) which are a reaction product (D) of an inorganic phosphorus compound (BI); or an aluminum-containing metal oxide (Aa), a compound (Ab), an inorganic phosphorus compound (BI), and an organic phosphorus compound (BO) comprising a reaction product (D) of an aluminum-containing metal oxide (Aa) and an inorganic phosphorus compound (BI) Also. Further, in any of the above embodiments, the layer (Y) may further contain other components. Other components, for example, mineral acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogen sulfates, and borates; oxalates, acetates, tartrates, stearates, etc. Organic acid metal salt; metal complex of a cyclopentadienyl metal complex (for example, titanocene), a cyano metal complex (for example, Prussian blue); a layered clay compound; a crosslinking agent; A polymer compound (F) other than the phosphorus compound (BO); a plasticizer; an antioxidant; a UV absorber; a flame retardant. The content of the other components in the layer (Y) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and 5% by mass or less. It is especially good, and it can also be 0% by mass (excluding other ingredients).

[polymer compound (F)]

The polymer compound (F) may, for example, be a polymer (Fa) having at least one functional group selected from the group consisting of an ether bond, a carbonyl group, a hydroxyl group, a carboxyl group, a carboxylic anhydride group, and a salt of a carboxyl group.

Polymer (Fa), for example, polyethylene glycol; polyketone; polyvinyl alcohol, a change of α-olefin unit containing 1 to 50 mol% of carbon number 4 or less Polyvinyl alcohol-based polymers such as polyvinyl alcohol and polyvinyl acetal (for example, polyvinyl butyral); polysaccharides such as cellulose, starch, and cyclodextrin; hydroxyethyl poly(meth)acrylate, poly( (meth)acrylic polymer such as methyl)acrylic acid or ethylene-acrylic acid copolymer; hydrolyzate of ethylene-maleic anhydride copolymer, hydrolyzate of styrene-maleic anhydride copolymer, and isobutylene-maleic anhydride interpolymerization A maleic acid polymer or the like such as a hydrolyzate of the substance. Among these, a polyvinyl alcohol-based polymer is more preferable, and specifically, polyvinyl alcohol and a modified polyvinyl alcohol having 1 to 15 mol% of an α-olefin unit having 4 or less carbon atoms are preferable.

The polymer (Fa) may be a homopolymer of a monomer having a polymerizable group (for example, vinyl acetate or acrylic acid), or a copolymer of two or more kinds of monomers, or may be a hydroxyl group and/or A copolymer obtained from a monomer having a carboxyl group and a monomer having no such group. Further, as the polymer (Fa), two or more kinds of polymers (Fa) may be used in combination.

The molecular weight of the polymer (Fa) is not particularly limited, and a multilayer structure having more excellent gas barrier properties and mechanical strength can be obtained. The number average molecular weight of the polymer (Fa) is preferably 5,000 or more. Preferably, it is 8,000 or more, and more preferably 10,000 or more. The upper limit of the number average molecular weight of the polymer (Fa) is not particularly limited, and is, for example, 1,500,000 or less.

From the viewpoint of maintaining a good appearance of the multilayered structure, the content of the polymer (Fa) in the layer (Y) is preferably 85% by mass or less based on the mass of the layer (Y) (100% by mass). It is preferably 50% by mass or less, more preferably 20% by mass or less, and 10% by mass. % below is especially good. The polymer (Fa) may react with the components of the layer (Y) or may not react.

In the multilayer structure of the present invention, the mass ratio of the organophosphorus compound (BO) to the polymer compound (F) is preferably in the range of 60:40 to 99:1, and is in the range of 65:35 to 91:9. It is better. Further, in the multilayer structure of the present invention, the mass ratio of the organophosphorus compound (BO) to the polymer (Fa) is preferably in the range of 60:40 to 99:1, and in the range of 65:35 to 91:9. The inside is better. This mass ratio is also the same in the coating liquid (T).

The thickness of the layer (Y) (when the multilayer structure has two or more layers (Y), the total thickness of each layer (Y)) is preferably in the range of 0.05 to 4.0 μm, preferably in the range of 0.1 to 2.0 μm. . When the layer (Y) is thinned, the dimensional change of the multilayer structure can be suppressed to a lower level during processing such as printing or lamination. Moreover, since the flexibility of the multilayer structure can be increased, the mechanical properties thereof can approach the mechanical properties of the substrate itself. When the multilayer structure of the present invention has two or more layers (Y), the thickness of each layer (Y) is preferably 0.05 μm or more from the viewpoint of gas barrier properties. The thickness of the layer (Y) can be controlled by using the concentration of the coating liquid (S) described later when the layer (Y) is formed or a coating method thereof.

The thickness of the layer (Y) can be measured by observing the cross-section of the multilayer structure using a scanning electron microscope or a transmission electron microscope.

[Manufacturing method of multilayer structure]

The description of the multilayer structure of the present invention can be applied to the present invention. In the manufacturing method, the following description will be omitted. Further, the description of the production method of the present invention is also applicable to the multilayer structure of the present invention.

The method for producing a multilayered structure of the present invention includes, for example, a precursor layer forming step (i), a coating step (ii) of a coating liquid (T) containing an organophosphorus compound (BO), and a gas barrier layer (Y). The manufacturing method of the step (iii) is formed. Further, the contents of the compound (A), the inorganic phosphorus compound (BI), the organophosphorus compound (BO), and the mass ratios thereof are as described above, and the description thereof will be omitted in the production method.

[Step (i)]

In the step (i), a coating liquid (S) containing the aluminum-containing compound (A) is applied onto the substrate (X) to form a layer (Y) precursor layer on the substrate (X). Through the step (i), a structure containing the substrate (X) and the layer (Y) precursor layer can be obtained. The layer (Y) is a vapor-deposited layer (Ac) containing aluminum or an evaporated layer (Ad) of alumina, and these layers can be formed by the above-described general vapor deposition method. Therefore, the method of forming the precursor layer of the layer (Y1) containing the compound (Ab) will be described in detail below.

In a preferred embodiment, the coating liquid (S) (first coating liquid) can be obtained by mixing a metal oxide (Aa) and an inorganic phosphorus compound (BI) in a solvent. Specifically, for example, the coating liquid (S) is a method of mixing a dispersion of the metal oxide (Aa) with a solution containing an inorganic phosphorus compound (BI); A method of adding or mixing an inorganic phosphorus compound (BI) to the dispersion of (Aa) can be obtained. The temperature at the time of mixing is preferably 50 ° C or lower, more preferably 30 ° C or lower, and still more preferably 20 ° C or lower. The coating liquid (S) may contain other compounds (for example, the polymer compound (F)), and if necessary, may be selected from the group consisting of acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid. At least one oxygen compound (Q).

The dispersion of the metal oxide (Aa) can be, for example, mixed by using a known sol-gel method, for example, by mixing the compound (E), water, and, if necessary, an acid catalyst or an organic solvent to make the compound (E). Condensation or hydrolytic condensation. When the compound (E) is condensed or lyophilized to obtain a dispersion of the metal oxide (Aa), if necessary, the obtained dispersion may be subjected to a specific treatment (degumming in the presence of the oxygen compound (Q), etc.) )Wait. The solvent to be used is not particularly limited, and is preferably an alcohol such as methanol, ethanol or isopropanol; water; or a mixed solvent of these.

The solution containing the inorganic phosphorus compound (BI) can be produced by dissolving the inorganic phosphorus compound (BI) in a solvent. The solvent may be appropriately selected in combination with the type of the inorganic phosphorus compound (BI), and it is preferably a water-containing one. The solvent may also contain an organic solvent (for example, an alcohol such as methanol) as long as it does not interfere with the dissolution of the inorganic phosphorus compound (BI).

The solid content concentration of the coating liquid (S) is preferably from 1 to 20% by mass, and from 2 to 15% by mass, based on the storage stability of the coating liquid and the coating property to the substrate (X). Preferably, it is preferably 3 to 10% by mass. The solid content concentration, for example, the mass of the solid residue remaining after the solvent of the coating liquid (S) is distilled off, divided by the coating liquid (S) for treatment Calculated by the way of quality.

The coating liquid (S) was measured for viscosity using a Brookfield rotary viscometer (SB type viscometer: rotor No. 3, rotation speed of 60 rpm) at a temperature of 3,000 mPa·s at the time of coating. The following is preferable, and it is preferably 2,500 mPa·s or less, and more preferably 2,000 mPa·s or less. When the viscosity is 3,000 mPa ‧ or less, the flatness of the coating liquid (S) can be improved, and a multilayer structure having a more excellent appearance can be obtained. Further, the viscosity of the coating liquid (S) is preferably 50 mPa ‧ or more, more preferably 100 mPa ‧ s or more, and still more preferably 200 mPa ‧ s or more

The coating liquid (S) is not particularly limited, and the molar ratio of aluminum atoms to phosphorus atoms is preferably aluminum atoms: phosphorus atoms = 1.01: 1.00 to 1.50: 1.00, and 1.05: 1.00 to 1.45. : 1.00 is preferred. The molar ratio of the aluminum atom to the phosphorus atom can be calculated by performing a fluorescent X-ray analysis on the dry solid of the coating liquid (S).

The coating liquid (S) may be applied directly onto the surface of at least one side of the substrate (X) or may be applied to the substrate (X) via another layer (J). Further, before applying the coating liquid (S), the surface of the substrate (X) may be treated with a known fixing coating agent, or a known adhesive or the like may be applied to the surface of the substrate (X), and the substrate may be applied to the substrate. The surface of (X) may be formed as an adhesive layer (I).

The coating liquid (S) is not particularly limited, and a known method can be employed. Coating methods, for example, casting, dipping, roller coating, gravure coating, screen printing, reverse coating, spray coating, kiss coat, Extrusion coating method, melting A strip coating method, a chamber doctor, a coating method, a curtain coating method, a strip coating method, and the like.

Usually, in the step (i), the layer (Y1) precursor layer is formed by removing the solvent in the coating liquid (S). The method of removing the solvent is not particularly limited, and a known drying method can be used. The drying method is, for example, a hot air drying method, a hot roll contact method, an infrared heating method, a microwave heating method, or the like. The drying temperature is preferably at a temperature below which the substrate (X) starts to flow. The drying temperature after the application of the coating liquid (S) may be, for example, about 80 to 180 ° C or about 90 to 150 ° C. The drying time is not particularly limited. For example, it is preferably from 0.1 second to one hour, preferably from 1 second to 15 minutes, and more preferably from 5 to 300 seconds. Further, after the drying treatment, it is preferred to carry out heat treatment. The heat treatment temperature may be, for example, about 100 to 200 ° C or about 120 to 180 ° C, but it is preferably a temperature higher than the drying temperature. The heat treatment time is not particularly limited. For example, the heat treatment time is preferably from 1 second to 1 hour, preferably from 1 second to 15 minutes, and more preferably from 5 to 300 seconds. Thus, it is preferable to obtain a multilayer structure having good characteristics when heat treatment is performed before coating a coating liquid (T) containing an organic phosphorus compound (BO).

[Step (ii)]

In the step (ii), a coating liquid (T) (second coating liquid) containing an organic phosphorus compound (BO) is applied onto the precursor layer of the layer (Y) obtained in the step (i). Coating liquid (T), organic phosphorus compound (BO) and It can be prepared by mixing solvents. The solvent used for the coating liquid (T) may be appropriately selected in accordance with the type of the organic phosphorus compound (BO), and is not particularly limited, and is an alcohol such as methanol, ethanol or isopropanol; water; or Some mixed solvents are preferred.

The concentration of the solid component in the coating liquid (T) is preferably 0.01 to 60% by mass, preferably 0.1 to 50% by mass, and 0.2 to 40% by mass in terms of storage stability or coating property of the solution. % is better. The solid content concentration can be determined by the same method as that described for the coating liquid (S). Further, in the range of the effect of the invention, the coating liquid (T) may contain other components (for example, the polymer compound (F)) contained in the layer (Y).

After the coating liquid (T) is applied, the layer (Y) precursor layer is formed by removing the solvent. The method of applying the coating liquid (T) is not particularly limited as in the case of applying the coating liquid (S), and a known method can be employed. In the case of using an inorganic phosphorus compound (BI), the ratio of the mass of the inorganic phosphorus compound (BI) W _BI to the mass of the organic phosphorus compound (BO) W _BO in the coating amount of the coating liquid (T) W _BO /W _BI It is particularly preferable to satisfy the above specific relationship.

The method of removing the solvent of the coating liquid (T) is not particularly limited, and a known drying method can be used. The drying method is, for example, a hot air drying method, a hot roll contact method, an infrared heating method, a microwave heating method, or the like. The drying temperature is preferably at a temperature below which the substrate (X) starts to flow. The drying temperature after application of the coating liquid (T) may be, for example, about 90 to 240 ° C, and preferably 100 to 200 ° C.

[Step (iii)]

In the step (iii), the layer (Y1) of the precursor layer formed in the steps (i) and (ii) is heat-treated at a temperature of 140 ° C or higher to form a layer (Y1). The heat treatment temperature is preferably higher than the drying temperature after the coating liquid (T) is applied.

In the step (iii), the particles of the metal oxide (Aa) are bonded to each other via a phosphorus atom (a phosphorus atom produced by an inorganic phosphorus compound (BI)). From another point of view, the step (iii) is a reaction for the formation of the reaction product (D). In order to sufficiently carry out the reaction, the temperature of the heat treatment is 140 ° C or higher, preferably 170 ° C or higher, more preferably 180 ° C or higher, and even more preferably 190 ° C or higher. When the heat treatment temperature is too low, it takes a very long time to perform a sufficient degree of reaction, which is a cause of a decrease in productivity. The preferred upper limit of the heat treatment temperature varies depending on the type of the substrate (X) and the like. For example, when a thermoplastic resin film formed of a polyamide resin is used as the substrate (X), the temperature of the heat treatment is preferably 270 ° C or lower. Further, in the case where the thermoplastic resin film formed of the polyester resin is used as the substrate (X), the temperature of the heat treatment is preferably 240 ° C or lower. The heat treatment can be carried out under an air atmosphere, under a nitrogen atmosphere, or under an argon atmosphere. The heat treatment time is preferably from 0.1 second to one hour, preferably from 1 second to 15 minutes, and more preferably from 5 to 300 seconds.

One of preferred embodiments of the method for producing a multilayered structure of the present invention is that after applying the coating liquid (S), it is subjected to a drying treatment (No. 1 drying treatment), followed by heat treatment (first heat treatment) to form a precursor layer, and after applying the coating liquid (T), drying treatment (second drying treatment) is carried out, followed by heat treatment (second heat treatment). In this case, the temperature of the first heat treatment is higher than the temperature of the first drying treatment, the temperature of the second heat treatment is higher than the temperature of the second drying treatment, and the temperature of the second heat treatment is higher than the temperature of the first heat treatment. It is better if the temperature is higher.

In the multilayer structure of the present invention, the layer (Y) and the substrate (X) may be laminated in direct contact, and the layer (Y) may be laminated via other members (for example, the layer (I) and the other layer (J). )) can be laminated to the substrate (X).

[Extrusion coating lamination]

In the multilayer structure of the present invention, for example, the substrate (X) may be laminated directly or after the layer (I) to the layer (Y), and the other layer (J) may be directly or via the subsequent layer (I). The layer formed by extrusion coating lamination may be further formed by extrusion coating. The extrusion coating layer which can be used in the present invention is not particularly limited, and a known method can also be used. A typical extrusion coating method is to obtain a laminated film by feeding a molten thermoplastic resin into a T mold and cooling the thermoplastic resin taken out from the flat slit of the T mold.

In the extrusion coating layer method, the most common single layer method is exemplified and will be described below with reference to the drawings. An example of a device used in a separate layer is shown in FIG. Also, Figure 5 shows only the main part of the display device. The mode map is different from the actual device. The apparatus 50 of Fig. 5 includes an extruder 51, a T die 52, a cooling drum 53, and a rubber cylinder 54. The cooling drum 53 and the rubber roller 54 are disposed in a state in which the drum surfaces are in contact with each other.

The thermoplastic resin is melted by heating in an extruder and extruded from a flat slit of the T die 52 to form a resin film 502. On the other hand, the laminate 501 is sent out by the sheet feeding device (not shown), and is sandwiched between the cooling drum 53 and the rubber roller 54 at the same time as the resin film 502. Between the cooling drum 53 and the rubber cylinder 54, the laminate 501 and the resin film 502 are sandwiched as a result of lamination, and the laminate 501 and the resin film 502 are formed into a laminated film (multilayer structure). ) 503.

The extrusion coating layer other than the above separate layering method, for example, sandwich layering, tandem layering, and the like. Sandwich layering method for preparing a laminate by pressing a molten thermoplastic resin to a substrate on one side and supplying a second substrate by another unwinder (unwinder) . Tandem layering method is a method of producing a laminate having five layers of composition at a time in a single laminating machine.

When the above laminate is used, a multilayer structure which can maintain high barrier properties after extrusion coating lamination and which can reduce light transmittance can be obtained.

[Next layer (I)]

In the multilayer structure of the present invention, when the adhesive layer (I) is used, the adhesion between the substrate (X) and the layer (Y) is improved. Next, the layer (I) may be composed of an adhesive resin. The adhesive layer (I) composed of the resin can be formed by treating the surface of the substrate (X) with a known fixing agent or by applying a known adhesive to the surface of the substrate (X). The adhesive is preferably a two-liquid reaction type polyurethane-based adhesive which is obtained by mixing and reacting a polyisocyanate component and a polyhydric alcohol component. Further, in the case of fixing a coating agent or an adhesive, a small amount of an additive such as a known decane coupling agent may be added to improve the adhesion. The decane coupling agent is, for example, a decane coupling agent having a reactive group such as an isocyanate group, an epoxy group, an amine group, a urea group or a thiol group, but is not limited thereto. When the base material (X) and the layer (Y) are strongly adhered to each other via the adhesive layer (I), the gas barrier property or the deterioration of the appearance can be effectively suppressed when the multilayered structure of the present invention is processed by printing or lamination. Further, the drop strength of the packaging material using the multilayered structure of the present invention can be improved. Next, the thickness of the layer (I) is preferably 0.01 to 10.0 μm, more preferably 0.03 to 5.0 μm.

[Other layers (J)]

The multilayer structure of the present invention may contain other layers (J) from the viewpoint of improving various properties (for example, heat sealability, barrier properties, and mechanical properties). The multilayer structure of the present invention may, for example, be directly or after the substrate (X) is laminated to the layer (Y) via the subsequent layer (I), and then directly or via the other layer (J). Layer (I) followed by or formed Made. The other layer (J) is, for example, an ink layer; a thermoplastic resin layer such as a polyolefin layer or an ethylene-vinyl alcohol copolymer resin layer, but is not limited thereto.

The multilayer structure of the present invention may contain an ink layer used for printing a trade name or a pattern. The multilayer structure of the present invention can be obtained, for example, by directly or subliminating the substrate (X) to the layer (Y) and then directly forming the ink layer. The ink layer may be, for example, a film obtained by drying a liquid in which a polyurethane resin containing a pigment (for example, titanium oxide) is dispersed in a solvent, or may be a pigment-free polyurethane resin or The ink or the electronic circuit wiring of the other resin as a main component forms a film obtained by drying the photoresist. The method of applying the ink layer to the layer (Y) includes various coating methods such as a bar coating method, a spin coating method, and a squeeze coating method in addition to the gravure printing method. The thickness of the ink layer is preferably 0.5 to 10.0 μm, more preferably 1.0 to 4.0 μm.

In the multilayer structure of the present invention, in the case where the layer (Y) contains the polymer (Fa), it has a high affinity with the subsequent layer (I) or another layer (J) (for example, an ink layer). At least one functional group selected from the group consisting of an ether bond, a carbonyl group, a hydroxyl group, and a carboxyl group can improve the adhesion of the layer (Y) to other layers. Therefore, even if the interlayer adhesion is maintained after the sterilization treatment, it is possible to suppress the appearance defect such as peeling.

When the outermost layer of the multilayered structure of the present invention is a polyolefin layer, the multilayer structure can be provided with heat-sealing properties, and the mechanical properties of the multilayered structure can be improved. Polyolefins for improving heat sealability or mechanical properties Polypropylene or polyethylene is preferred. Further, for the purpose of improving the mechanical properties of the multilayer structure, at least one selected from the group consisting of a film formed of a polyester, a film formed of a polyamide, and a film formed of a polymer containing a hydroxyl group is selected. A film is better. From the viewpoint of improving mechanical properties, polyester is preferably polyethylene terephthalate, and polyamine is preferably nylon-6. Further, from the viewpoint of barrier properties of the entire layer, the hydroxyl group-containing polymer is preferably an ethylene-vinyl alcohol copolymer. Further, a layer formed by fixing a coating layer or an adhesive may be provided between the layers as necessary.

[Composition of multilayer structure]

Specific examples of the constitution of the multilayered structure of the present invention are shown below. The multilayer structure may have other members than the substrate (X) and the layer (Y) (for example, the layer (I) and the other layer (J)), but in the following specific examples, other members are omitted. Recorded. Further, in the following specific examples, lamination or combination of a plurality of layers may be performed.

(1) Layer (Y) / Polyester layer, (2) Layer (Y) / Polyester layer / Layer (Y), (3) Layer (Y) / Polyamide layer, (4) Layer (Y) / Polyamide layer/layer (Y), (5) layer (Y)/polyolefin layer, (6) layer (Y)/polyolefin layer/layer (Y), (7) layer (Y)/hydroxyl group Polymer layer, (8) layer (Y) / hydroxyl group-containing polymer layer / layer (Y), (9) layer (Y) / paper layer, (10) layer (Y) / paper layer / layer (Y), (11) layer (Y) / inorganic vapor deposition layer / polyester layer, (12) layer (Y) / inorganic evaporation layer / polyamine layer, ( 13) layer (Y) / inorganic vapor deposition layer / polyolefin layer, (14) layer (Y) / inorganic evaporation layer / hydroxyl group-containing polymer layer, (15) layer (Y) / polyester layer / polyamine layer / polyolefin layer, (16) layer (Y) / polyester layer / layer (Y) / polyamide layer / polyolefin layer, (17) polyester layer / layer (Y) / polyester layer / layer (Y )/Inorganic vapor deposition layer/hydroxyl-containing polymer layer/polyolefin layer, (18) polyester layer/layer (Y)/polyamidamide layer/polyolefin layer, (19) layer (Y)/polyamidide layer /polyester layer/polyolefin layer, (20) layer (Y) / polyamine layer / layer (Y) / polyester layer / polyolefin layer, (21) polyamide layer / layer (Y) / polyester Layer/polyolefin layer, (22) layer (Y) / polyolefin layer / polyamide layer / polyolefin layer, (23) layer (Y) / polyolefin layer / layer (Y) / polyamine layer / poly Olefin layer, (24) polyolefin layer/layer (Y)/polyamidole layer/polyolefin layer, (25) layer (Y)/polyolefin layer/polyolefin layer, (26) layer (Y)/polyolefin Layer/layer (Y)/polyolefin layer, (27) polyolefin layer/layer (Y)/polyolefin layer, (28) layer (Y)/polyester layer/polyolefin layer, (29) layer (Y) /polyester layer / layer (Y) / polyolefin layer, (30) polyester layer/layer (Y)/polyolefin layer, (31) layer (Y)/polyamidamide layer/polyolefin layer, (32) layer (Y)/polyamine layer/layer (Y) / polyolefin layer, (33) polyamine layer / layer (Y) / polyolefin layer, (34) layer (Y) / polyester layer / paper layer, (35) layer (Y) / polyamine layer / Paper layer, (36) layer (Y) / polyolefin layer / paper layer, (37) polyolefin layer / paper layer / polyolefin layer / layer (Y) / polyester layer / polyolefin layer, (38) polyolefin Layer/Paper Layer/Polyolefin Layer/Layer (Y)/Polylamamine Layer/Polyolefin Layer, (39) Polyolefin Layer/Paper Layer/Polyolefin Layer/Layer (Y)/Polyolefin Layer, (40) Paper Layer/polyolefin layer/layer (Y)/polyester layer/polyolefin layer, (41) polyolefin layer/paper layer/layer (Y)/polyolefin layer, (42) paper layer/layer (Y)/poly Ester layer/polyolefin layer, (43) paper layer/layer (Y)/polyolefin layer, (44) layer (Y)/paper layer/polyolefin layer, (45) layer (Y)/polyester layer/paper Layer/polyolefin layer, (46) polyolefin layer/paper layer/polyolefin layer/layer (Y)/polyolefin layer/hydroxyl-containing polymer layer, (47) polyolefin layer/paper layer/polyolefin layer/ Layer (Y) / polyolefin layer / polyamide layer, (48) polyolefin layer / paper layer / polyolefin layer / layer (Y) / polyolefin layer / polyester layer, (49) Inorganic deposited layer/layer (Y)/polyester layer, (50) inorganic deposited layer/layer (Y)/polyester layer/layer (Y)/inorganic deposited layer, (51) inorganic deposited layer/layer ( Y)/polyamine layer, (52) inorganic deposited layer/layer (Y)/polyamidamine layer/layer (Y)/inorganic deposited layer, (53) inorganic deposited layer/layer (Y)/polyolefin layer, (54) Inorganic deposited layer/layer (Y)/polyolefin layer/layer (Y)/inorganic deposited layer

In the above configuration, the protective sheet of the present invention preferably has any one of (1) to (8), (11) to (33), and (49) to (54).

The multilayer structure of the present invention has an oxygen permeability of 2.0 mL/(m ² ‧day‧atm) or less at a temperature of 20 ° C and 85% RH before and after the sterilization treatment, and is 0.5 mL/( m ² ‧day‧atm) is preferably the following, and preferably 0.3 mL/(m ² ‧day‧atm) or less. The conditions of the sterilization treatment, the measurement method of the oxygen permeability, and the measurement conditions are as described in the examples below.

In the multilayer structure of the present invention, the moisture permeability at 40 ° C and 90% RH is preferably 0.5 g / (m ² ‧day) or less, and 0.3 g / (m ² ) before and after the sterilization treatment. ‧day) The following are preferred. The conditions of the sterilization treatment, the measurement method of the moisture permeability, and the measurement conditions are as described in the examples below.

Moreover, in the multilayer structure of the present invention, after the sterilization treatment The peel strength of the layer (Y) and the subsequent layer (I) or the other layer (J) (for example, the ink layer) is preferably more than 100 g/15 mm, and more preferably more than 110 g/15 mm. The conditions of the sterilization treatment, the measurement method of the peel strength, and the measurement conditions are as described in the examples below.

The multilayer structure and the protective sheet of the present invention have an oxygen permeability of 2.0 mL/(m ² ‧day‧atm) or less at 20 ° C and 85% RH before the temperature and humidity test treatment and after the temperature and humidity test treatment Further, it is preferably 0.5 mL/(m ² ‧day ‧ atm) or less, and preferably 0.3 mL/(m ² ‧day ‧ atm) or less. The conditions of the temperature and humidity test treatment, the measurement method of the oxygen permeability, and the measurement conditions are as described in the examples below.

The multilayer structure and the protective sheet of the present invention preferably have a moisture permeability of 0.5 g/(m ² ‧day) or less at 40 ° C and 90% RH before the temperature and humidity test and after the temperature and humidity test. 0.3 g/(m ² ‧day) or less is preferred. The conditions of the temperature and humidity test, the measurement method of the moisture permeability, and the measurement conditions are as described in the examples below.

〔use〕

The multilayer structure of the present invention and the packaging material using the same have excellent gas barrier properties and water vapor barrier properties, and also have excellent bactericidal resistance and high transparency. Therefore, the multilayer structure of the present invention and the packaging material using the same can be applied to various uses.

〔Packaging material〕

The packaging material of the present invention comprises a substrate-containing substrate (X) and is laminated to the substrate. A multilayer structure of layer (Y) on the material (X). The packaging material can be composed only of a multilayer structure. That is, in the following description, the "packaging material" may also be referred to as a "multilayer structure". Also, typically, "packaging material" may be referred to as "packaging." The packaging material may also be composed of a multilayer structure and other components.

A packaging material according to a preferred embodiment of the present invention is an organic compound (for example, ethanol or liquefied petroleum gas) for inorganic gases (for example, hydrogen, helium, nitrogen, oxygen, carbon dioxide), natural gas, water vapor, and liquid at normal temperature and pressure. ) has barrier properties.

In the case where the packaging material of the present invention is a packaging bag, all of the packaging bags may be constructed using a multilayer structure, or a part of the packaging bag may be a multilayer structure. For example, 50% to 100% of the area of the packaging bag may be composed of a multilayer structure. The case where the packaging material is other than the packaging bag (for example, the container and the lid material) is also the same.

The packaging material of the present invention can be produced by various methods. For example, a sheet-like multilayer structure or a film material (hereinafter, simply referred to as "film material") containing the multilayer structure may be joined and formed into a specific container shape to obtain a container (packaging material). Also. The forming method is, for example, thermoforming, injection molding, extrusion flow molding, or the like. Further, a layer (Y) may be formed on the substrate (X) formed into a shape of a specific container to obtain a container (packaging material). The container obtained by using these methods is also referred to as "packaging container" in this specification.

The packaging material of the invention is suitable as a packaging material for food Material used. Moreover, the packaging material of the present invention is suitable as a packaging material for food, and is also suitable as a packaging material for packaging pesticides, pharmaceuticals, and the like; medical equipment, industrial parts such as mechanical parts, precision materials, and clothing materials.

Further, the packaging material containing the multilayered structure of the present invention can be obtained by secondary processing to obtain various molded articles. The molded articles may be vertical bag filling and sealing bags, vacuum packaging bags, pouches, laminated tubular containers, infusion bags, paper containers, long bags, container covers, in-mold labels (In Mold Labeling) container, vacuum insulation, or electronic device. These molded articles can also be heat-sealed.

[Vertical bag filling sealed bag]

The packaging material containing the multilayer structure of the present invention may be a vertical bag filled sealed bag. This is shown, for example, in Figure 1. The vertical bag-filled sealed bag 10 shown in Fig. 1 is formed by sealing the multilayer structure 11 of the present invention in a three-way manner with the two end portions 11a and the main body portion 11b. The vertical bag filling and sealing bag 10 can be manufactured using a vertical bag filling machine. The method of using the vertical bag-filling mechanism bag can be carried out by various methods, but in either method, the contents are supplied to the inside of the bag, and then the opening is sealed to obtain a vertical bag filling seal. bag. The vertical bag filling and sealing bag, for example, the upper end, the lower end, and the side portion, may be composed of one piece of heat-sealed film material. The vertical bag filling and sealing bag as the packaging container of the invention has excellent gas barrier property and water vapor barrier property, and can maintain the barrier property after the sterilization treatment, so the vertical bag can be filled with the sealed bag for a long period of time. The deterioration of the quality of the contents is suppressed.

[pouch]

The packaging material containing the multilayer structure of the present invention may be a pouch. This is shown, for example, in Figure 2. The flat pouch 20 of Fig. 2 is formed by joining two multilayer structures 11 by the peripheral portion 11c. In the present specification, the term "bag" is mainly intended to have a container made of a film material as a wall member, which is a food, a commodity, or a pharmaceutical. The bag, for example, according to its shape and use, can be distinguished as a spout pouch, a zipper bag, a flat bag, a stand up pouch, a horizontal bag filling and sealing bag, a retort pouch, etc. . The bag may be formed by laminating a multilayer structure with at least one other layer (J). The bag as a packaging container of the present invention has excellent gas barrier properties and water vapor barrier properties, and maintains its barrier property even after sterilization treatment. Therefore, when the bag is used, deterioration of the contents can be prevented even after transportation or after long-term storage. Moreover, in the example of the bag, since the transparency can be maintained, it is easy to confirm the contents and to confirm the deterioration of the contents due to deterioration.

[infusion bag (bag)]

The packaging material comprising the multilayer structure of the present invention may be an infusion solution bag. The infusion solution bag is a container in which the infusion preparation is a content thereof, and is provided with a film material which partitions the inside and the outside of the infusion preparation and serves as a partition wall. This is shown, for example, in Figure 3. Infusion bag as shown in Figure 3. (bag), in addition to the infusion bag main body 431 storing the contents, the peripheral portion 412 of the infusion solution bag main body 431 may be provided with a mouth plug member 432. The mouthpiece member 432 has a function as a passage for taking out the infusion liquid stored in the inside of the infusion solution bag body 431. Further, on the infusion solution bag, the infusion solution bag can be suspended. The hanging portion 433 can be provided in the peripheral portion 411 on the opposite side of the peripheral portion 412 of the mouth plug member 432. The infusion solution bag body 431 is formed by joining the two film materials 410a and 410b to the peripheral portions 411, 412, 413, and 414 thereof. The film materials 410a and 410b function as a partition between the inside of the infusion solution bag and the partition wall 420 outside the infusion solution bag in the central portion surrounded by the peripheral portions 411, 412, 413, and 414 of the infusion solution bag body 431. The infusion liquid bag as a packaging container of the present invention has excellent gas barrier properties, and can maintain its gas barrier property after heat treatment such as hot water treatment. Therefore, the infusion solution bag can prevent deterioration of the filled liquid medicine even before the heat sterilization treatment, in the heat sterilization treatment, after the heat sterilization treatment, after the transportation, and after the storage.

[In Mold Labeling container]

The packaging material comprising the multilayer structure of the present invention may be an in-mold label container. The in-mold label container is a multi-layer label (multilayer structure) comprising the container body and the present invention disposed on the surface of the container body. The container body is formed by injecting molten resin into the interior of the mold. The shape of the container body is not particularly limited and may be a cup shape, a bottle shape or the like.

An example of a method of manufacturing a container in the present invention is The first step of the multilayer label of the present invention is disposed in the cavity between the female mold portion and the male mold portion, and the molding of the container body and the multi-layer label of the present invention are simultaneously applied by injecting the molten resin into the mold cavity. In the second step of the container body. Except for using the multilayer label of the present invention, each step can be carried out using a known method.

A cross-sectional view exemplified in one of the containers of the present invention is shown in FIG. The container 360 is a container body 370 including a cup shape and a plurality of layers of labels 361 to 363 attached to the surface of the container body 370. The multilayer labels 361 to 363 are the multilayer labels of the present invention. The container body 370 includes a flange portion 371 and a body portion 372 and a bottom portion 373. The flange portion 371 has a convex portion 371a that protrudes up and down at its front end. The multilayer label 361 is disposed to cover the outer surface of the bottom portion 373. The center of the multilayer label 361 is formed with a through hole 361a for injecting a resin when the in-mold label is formed. The multilayer label 362 is disposed so as to cover the outer surface of the main body portion 372 and the lower surface of the flange portion 371. The multilayer label 363 is disposed so as to cover a portion of the inner surface of the main body portion 372 and the upper surface of the flange portion 371. The multilayer labels 361 to 363 are fused to the container body 370 via an in-mold label forming method and integrated with the container body 360. As shown in FIG. 4, the end face of the multilayer label 363 is fused to the container body 360 and is not exposed to the outside.

[vacuum insulation]

The article of the present invention using the aforementioned packaging material as at least a portion may be a vacuum insulation. The vacuum insulation is provided with a covering material, and The heat insulator of the core material disposed inside the covering material, and the inside of the core material is in a state of being decompressed. The vacuum heat insulator can achieve a heat insulating property equivalent to that of the heat insulating body formed of the polyurethane foam in a lighter and thinner heat insulator. The vacuum heat insulator of the present invention can be used as a heat insulating material for household appliances such as refrigerators, water heaters, and electric cookers; residential heat insulating materials, vehicle ceiling materials, and automatic use for walls, ceilings, eaves, and floors; Heat-insulating panels such as vending machines; heat-moving machines such as heat storage machines and heating pump applications. The multilayer structure of the present invention used as a coating material may further contain an ethylene-vinyl alcohol copolymer resin layer and an inorganic vapor deposition layer, and may have, for example, a polyester layer/layer (Y)/polyester layer/layer (Y)/ The composition of the inorganic deposited layer/ethylene-vinyl alcohol copolymer layer/polyolefin layer.

An example of the vacuum heat insulator of the present invention is shown in FIG. The vacuum heat insulator 601 of Fig. 6 is a core material 651 containing particles, and two multilayer structures 631 and 632 of the present invention as coating materials. Two multilayer structures 631 and 632 are provided in the peripheral portion. In 611, they are inter-joiners. The internal space formed by the two multilayer structures 631, 632 is a filled core 651 whose internal space is in a reduced pressure state. The multilayer structures 631 and 632 have a function as a partition wall that blocks the inside and the outside of the storage core member 651, and adhere to the core member 651 via a pressure difference between the inside and the outside of the vacuum heat insulator 601. The inside of the core material 652 is in a state of being decompressed.

Another example of the vacuum heat insulator of the present invention is shown in FIG. The vacuum heat insulator 602 has the same structure as the vacuum heat insulator 601 except that the core material 651 is replaced with an integrally formed core material 652. to make. The core material 652 as a molded body is typically exemplified as a resin foam.

The material and shape of the core material are not particularly limited as long as they are suitable for heat insulation. Core material, for example, pearlite powder, cerium oxide powder, precipitated cerium oxide powder, diatomaceous earth, calcium citrate, glass wool, asbestos, artificial (synthetic) cotton, resin foam (for example , styrene foam, polyurethane foam, and the like. As the core material, a hollow container, a honeycomb structure, or the like which is formed by a specific shape can be used.

[electronic device]

The packaging material comprising the multilayer structure of the present invention can also be used in an electronic device. One of the electronic devices of the present invention is exemplified, and a partial cross-sectional view thereof is shown in FIG. The electronic device 40 of FIG. 8 is provided with an electronic device body 41, a sealing material 42 for sealing the electronic device body 41, and a protective sheet (multilayer structure) 43 for protecting the surface of the electronic device body 41. The sealing material 42 covers the entire surface of the electronic device body 41. The protective sheet 43 is disposed on the surface on one side of the electronic device body 41 via a sealing material 42. The protective sheet 43 may be disposed on the surface opposite to the surface on which the protective sheet 43 is disposed. In this case, the protective sheet disposed on the surface of the opposite side may be the same as or different from the protective sheet 43. The protective sheet 43 may be disposed on the surface of the electronic device body 41 via another member such as the sealing material 42 or may be disposed directly on the surface of the electronic device body 41.

The electronic device body 41 is not particularly limited. For example, photoelectric conversion devices such as solar cells; information display devices such as organic EL displays, liquid crystal displays, and electronic paper; and illumination devices such as organic EL light-emitting devices. The sealing material 42 can be appropriately attached to any member in accordance with the type and use of the electronic device body 41. The sealing material 42 is, for example, an ethylene-vinyl acetate copolymer, polyvinyl butyral or the like.

A preferred example of the electronic device body 41 is, for example, a solar cell. Solar cells, for example, lanthanide solar cells, compound semiconductor solar cells, organic thin film solar cells, and the like. Tantalum solar cells, for example, single crystal germanium solar cells, polycrystalline germanium solar cells, amorphous germanium solar cells, and the like. A compound semiconductor solar cell, for example, a III-V compound semiconductor solar cell, a II-VI compound semiconductor solar cell, an I-III-VI compound semiconductor solar cell, or the like. Further, the solar cell may be an integrated solar cell in which a plurality of unit cells are connected in series, or a non-accumulated solar cell.

The multilayer structure of the present invention and the packaging material containing the same are suitably used as a display member for a substrate film for an LCD, a substrate film for an organic EL, a substrate film for an electronic paper, a sealing film for an electronic device, and a film for a PDP; Solar cell modules such as solar cell modules, backsheets for solar cells, and protective films for solar cells. When the multilayer structure is used as a member of a display, it can be used, for example, as a low-reflection film. In either case, when the multilayer structure needs to be translucent, the layer (Y) may use a layer (Y) having light transmissivity.

The electronic device body 41 can also be manufactured by a so-called roll-to-roll method depending on the type thereof. Volume to roll In the (Roll-to-Roll) method, the flexible substrate (for example, a stainless steel substrate or a resin substrate) that is curled onto the roller can be fed out, and the electronic device body 41 can be formed by forming components on the substrate. The electronic device body 41 is taken up by a take-up reel. At this time, the protective sheet 43 may be prepared in the form of a flexible long sheet, and more specifically, in the form of a curled body having a long sheet. For example, the protective sheet 43 fed by the delivery roller is laminated on the electronic device body 41 before being taken up by the take-up reel, and is taken up together with the electronic device body 41. In another example, the electronic device body 41 of the take-up reel is taken up in advance and the roller is fed out, and the protective sheet 43 may be laminated. In a preferred embodiment of the invention, the electronic device itself is flexible.

The protective sheet 43 is a multilayered structure containing the present invention. The protective sheet 43 can be composed only of a multilayer structure. Alternatively, the protective sheet 43 may contain a multilayer structure and other members laminated to the multilayer structure (for example, other layers (J)). The protective sheet 43 is a layered laminate suitable as a surface for protecting an electronic device, and the thickness and material thereof are not particularly limited when the multilayered structure is contained.

The protective sheet may, for example, comprise a surface protective layer disposed on one side surface or both side surfaces of the multilayer structure. The surface protective layer is preferably a layer formed of a resin which is not easily damaged. Further, in the case of a surface protective layer of a device used outdoors, as in the case of a solar battery, it is preferably formed of a resin having high weather resistance (for example, light resistance). Further, when the protection must pass through the surface of the light, it is preferable to use a surface protective layer having high light transmittance. a material for a surface protective layer (surface protective film), for example, poly(methyl) propyl Ethacrylate, polycarbonate, polyethylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) ), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), Tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and the like. An example of the protective sheet is a layer comprising a poly(meth)acrylate disposed on one surface.

From the viewpoint of improving the durability of the surface protective layer, various additives (for example, ultraviolet absorbers) may be added to the surface protective layer. A preferred example of the surface protective layer having high weather resistance is, for example, an acrylic resin layer to which an ultraviolet absorber is added. Ultraviolet absorbers, for example, benzotriazole, benzophenone, salicylate, cyanoacrylate, nickel, three It is a UV absorber or the like, but is not limited to these contents. Further, other stabilizers, light stabilizers, antioxidants, and the like may be used in combination.

[Examples]

In the following, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples, and various changes can be made by those having ordinary knowledge in the field within the technical idea of the present invention. . The analysis and evaluation performed in the following examples and comparative examples were carried out in the following manner.

(1) Determination of infrared absorption spectrum

Using a Fourier transform infrared spectrophotometer, based on attenuated total reflection It was measured. The measurement conditions are as follows.

Device: Spectrum One manufactured by PerkinElmer Co., Ltd.

Measurement mode: attenuated total reflection method

Measurement area: 800~1,400cm ^-1

(2) Determination of the thickness of each layer

The multilayer structure was cut using a focused ion beam (FIB) to prepare a section for cross-sectional observation. The prepared chips were fixed on a sample stage using a carbon tape, and platinum ion sputtering was performed for 30 seconds at an acceleration voltage of 30 kV. The cross section of the multilayer structure was observed using an electric field emission transmission electron microscope, and the thickness of each layer was calculated. The measurement conditions are as follows.

Device: JEM-2100F manufactured by JEOL Ltd.

Acceleration voltage: 200kV

Magnification: 250,000 times

(3) Analysis of the composition of the depth direction of the multilayer structure

Composition analysis was performed from the lateral direction of the layer (Y) using a time-of-flight secondary ion mass spectrometer. The primary ion source is a cesium cluster ion source (Bi ₃ ²⁺ ), a current value of 0.2 picoampere, an acceleration voltage of 25 kV, and a measurement mode of high quality decomposition energy mode (bunching mode). The sputter ion source was a fullerene ion source (C ₆₀ ²⁺ ), a current value of 1 nanoampere (Nanoampere), and an acceleration voltage of 10 kV. The secondary ions having a cycle time of 100 microseconds and a mass-to-charge ratio of about 800 were obtained. At the time of analysis, the measurement range was divided by 128 × 128 pixels, and the irradiation mode of the ion beam was to scan the measurement range using the random gloss mode. The depth direction analysis was performed by setting a non-interleaved mode (Non Interraced Mode), and measurement was performed by sputtering once every two ion beam scanning measurement ranges (2 frames) (2 frame/scan). In the measurement, in order to prevent static electricity in the measurement area, a flood gun (electron gun) was used for measurement while continuously irradiating the electron beam. At this time, the range scanned by the primary ion source is set to the center of the sputtering range, and the sputtering range should be noted as 10 times or more of the scanning range. The measurement conditions are as follows.

Device: TOF-SIMS5 (FIVE) made by ION-TOF

Sputtering range: 750μm × 750μm

2nd ion acquisition range: 200μm×200μm in the center of the sputtering range

(4) Determination of oxygen permeability

In the oxygen permeation amount measuring device, a sample was placed so that the layer of the substrate faced the carrier gas side, and the oxygen permeability was measured by an equal pressure method. The measurement conditions are as follows.

Device: MOCON OX-TRAN2/20 manufactured by Hyundai Control Co., Ltd.

Temperature: 20 ° C

Oxygen supply side humidity: 85% RH

Humidity on the carrier gas side: 85% RH

Oxygen pressure: 1.0atm

Carrier gas pressure: 1.0atm

(5) Determination of moisture permeability

In the water vapor transmission amount measuring device, a sample was placed so that the layer of the substrate faced the carrier gas side, and the moisture permeability (water vapor permeability) was measured by an isostatic method. The measurement conditions are as follows.

Installation: MOCON PERMATRAN W3/33, a modern control company

Temperature: 40 ° C

Humidity on the water supply side: 90% RH

Humidity on the carrier gas side: 0% RH

(6) Adjunct assessment

The adhesion was evaluated using a T-peel strength measurement (adhesion force at a width of 15 mm each). The measurement was carried out 5 times and the average value was taken. The measurement conditions are as follows.

Device: Shimadzu Corporation's autoclave AGS-H

Peeling speed: 250mm/min

Temperature: 23 ° C

Humidity: 50% RH

<Production Example of Coating Liquid (S-1)>

230 parts by mass of distilled water was heated to 70 ° C with stirring. 88 parts by mass of aluminum triisopropoxide was dropped into the distilled water over 1 hour, and the liquid temperature was gradually raised to 95 ° C, and the produced isopropanol was distilled off to carry out hydrolysis condensation. To the obtained liquid, 4.0 parts by mass of a 60% by mass aqueous solution of nitric acid was added, and the mixture was stirred at 95 ° C for 3 hours to condense the particles of the hydrolyzed condensate. Polymer degumming. Subsequently, the liquid was concentrated to a solid content concentration of 10% by mass in terms of alumina to prepare a solution. To 22.50 parts by mass of the solution obtained in this manner, 54.29 parts by mass of distilled water and 18.80 parts by mass of methanol were added, and the mixture was stirred until homogeneous to obtain a dispersion. Subsequently, the liquid temperature was maintained at 15 ° C, and 4.41 parts by mass of an 85 mass % phosphoric acid aqueous solution was added dropwise to the continuously stirring dispersion, and stirring was continued at 15 ° C until the viscosity reached 1,500 mPa ‧ s. Coating liquid (S-1). In the coating liquid (S-1), the molar ratio of the aluminum atom to the phosphorus atom is: aluminum atom: phosphorus atom = 1.15: 1.00.

<Production Example of Coating Liquid (S-2)>

230 parts by mass of distilled water was heated to 70 ° C with stirring. 88 parts by mass of aluminum triisopropoxide was dropped into the distilled water over 1 hour, and the liquid temperature was gradually raised to 95 ° C, and the produced isopropanol was distilled off to carry out hydrolysis condensation. To the obtained liquid, 4.0 parts by mass of a 60% by mass aqueous solution of nitric acid was added, and the mixture was stirred at 95 ° C for 3 hours to deagglomerate the particle agglomerates of the hydrolyzed condensate. Subsequently, the liquid was concentrated to a solid content concentration of 10% by mass in terms of alumina to prepare a solution. To 22.39 parts by mass of the solution obtained in this manner, 53.62 parts by mass of distilled water and 18.80 parts by mass of methanol were added, and the mixture was stirred until homogeneous to obtain a dispersion. Subsequently, the liquid temperature was maintained at 15 ° C, and the dispersion was continuously stirred, and 4.39 parts by mass of an 85% by mass aqueous phosphoric acid solution and 0.19 parts by mass of a 10% by mass aqueous solution of the polymer (BO-2) were added dropwise. Stirring was continued at 15 ° C until the viscosity reached 1,500 mPa ‧ s, and the desired coating liquid (S-2) was obtained. In the coating liquid (S-2), the molar ratio of the aluminum atom to the phosphorus atom is: aluminum atom: phosphorus atom = 1.15: 1.00, inorganic phosphorus compound (BI) mass W _BI and organic phosphorus compound (BO) The ratio of mass W _BO is W _BO /W _BI =0.50/99.50.

<Synthesis Example of Organophosphorus Compound (BO-1)>

10 g of vinylphosphonic acid and 0.025 g of 2,2'-azobis(2-methylamidinopropane) 2 hydrochloride were dissolved in 5 g of water under a nitrogen atmosphere, and stirred at 80 ° C for 3 hours. After cooling, 15 g of water was added to the polymerization solution for dilution, and filtration was carried out using "Spectra/Por" (registered trademark) manufactured by Spectrum Laboratories, Inc. of a cellulose film. After distilling off the water in the filtrate, vacuum drying was carried out at 50 ° C for 24 hours to obtain a polymer (BO-1). The polymer (BO-1) is poly(vinylphosphonic acid). As a result of GPC analysis, the number average molecular weight of the polymer was 10,000 in terms of polyethylene glycol.

<Synthesis Example of Organophosphorus Compound (BO-2)>

In a 12 g of methyl ethyl ketone (hereinafter, also referred to as "MEK") which is refluxed at 80 ° C under a nitrogen atmosphere, a phosphonium oxypolyoxypropylene glycol monomethacrylate (hereinafter, also referred to as " PPM") A mixed solution of 8.5 g, MEK 5g, and azobisisobutyronitrile 100 mg was added dropwise at a constant rate for 10 minutes. After the completion of the dropwise addition, the temperature was maintained at 80 ° C and stirring was continued for about 12 hours to obtain a yellow sticky liquid solution.

The polymer solution was poured into about 10 times the amount of 1,2-dichloroethane, and the supernatant was removed by decantation to recover the precipitate, and the polymer was isolated. Dissolving the recovered polymer in tetrahydrogen as a good solvent for the polymer In furan (hereinafter, also referred to as "THF"), the operation is repeated three times to reprecipitate in about 10 times the amount of 1,2-dichloroethane to carry out purification to obtain a polymer (BO-2). ). As a result of GPC analysis of the polymer (BO-2), the number average molecular weight of the polymer was 10,000 in terms of polyethylene glycol.

<Production Example of Coating Liquid (T-1)>

67% by mass of the organophosphorus compound (BO-1) obtained in the above-mentioned synthesis example, and polyvinyl alcohol (KURARAY-POVAL (registered trademark) PVA124, manufactured by KURARAY Co., Ltd.); saponification degree: 98.5 mol%, viscosity average degree of polymerization A mixture of 2,400, 4% by mass aqueous solution at 20 ° C and a viscosity of 60 mPa ‧ s) of 33% by mass. This mixture was dissolved in a mixed solvent of water and methanol (mass ratio: water: methanol = 7:3) to obtain a coating liquid (T-1) having a solid content concentration of 1% by mass.

<Production Example of Coating Liquid (T-2)>

The organophosphorus compound (BO-2) obtained in the above synthesis example is dissolved in a mixed solvent of water and methanol (mass ratio: water: methanol = 7:3) to obtain a coating liquid having a solid content concentration of 1% by mass (T -2).

<Production Example of Coating Liquid (T-3)>

Prepared polyethylene glycol ("PEG-20000" manufactured by Sanyo Chemical Industries Co., Ltd.; number 20,000") containing 67% by mass of the organic phosphorus compound (BO-1) obtained in the above Synthesis Example and having an average molecular weight of 20,000. A mixture of mass %. This mixture was dissolved in a mixed solvent of water and methanol (mass ratio: water: methanol = 7:3) to obtain a coating liquid (T-3) having a solid content concentration of 1% by mass.

The details of the films used in the examples and comparative examples are as follows.

1) PET12: extended polyethylene terephthalate film; manufactured by Toray Co., Ltd., "LUMIRROR P60" (trade name), thickness 12μm

2) PET50: a polyethylene terephthalate film which is improved in adhesion to an ethylene-vinyl acetate copolymer; "SHINEBEAN Q1A15" (trade name) manufactured by Toyobo Co., Ltd., thickness 50 μm

3) ONY: extended nylon film; UNITIKA Co., Ltd., "EMBLEM ONBC" (trade name), thickness 15μm

4) CPP60: non-stretched polypropylene film; manufactured by Mitsui Chemicals TOHCELLO Co., Ltd., "RXC-21" (trade name), thickness 60μm

5) CPP70: non-stretched polypropylene film; manufactured by Mitsui Chemicals TOHCELLO Co., Ltd., "RXC-21" (trade name), thickness 70μm

6) CPP100: non-stretched polypropylene film; manufactured by Mitsui Chemicals TOHCELLO Co., Ltd., "RXC-21" (trade name), thickness 100μm

[Example 1] <Example 1-1>

First, PET12 (hereinafter, also simply referred to as "X-1") as the substrate (X) is prepared. On this substrate, a coating liquid (S-1) was applied by a bar coater so as to have a thickness of 0.3 μm after drying. The film after coating was dried at 110 ° C for 5 minutes, and then subjected to heat treatment at 160 ° C for 1 minute to form a layer (Y-1-1) precursor layer on the substrate. In this manner, a structure having a substrate (X-1) / layer (Y-1-1) precursor structure was obtained. Next, on the above-mentioned structure, the mass of the inorganic phosphorus compound (BI) W _BI and the mass of the organic phosphorus compound (BO) W _{BO were} applied by a bar coater at a coating amount of 3 mg/m ² . The coating liquid (T-1) having a ratio W _BO /W _BI = 0.33/99.67 was dried at 110 ° C for 3 minutes. Subsequently, heat treatment was performed at 220 ° C for 1 minute to form a layer (Y-1-1). In this manner, a multilayered structure (1-1-1) having a structure of the substrate (X-1) / layer (Y-1-1) can be obtained.

The infrared absorption spectrum of the multilayer structure (1-1-1) was measured, and it was found that the maximum absorption wave number in the region of 800 to 1,400 cm ^-1 was 1,108 cm ^-1 , and the maximum absorption band of the maximum absorption band ( FWHM) is 37cm ^-1 .

As a result of analyzing the composition of the depth direction of the multilayered structure (1-1-1), the intensity of the negative secondary ion having the highest intensity among the secondary ions generated by the aluminum-containing compound (A-1) is I _A- the negative secondary ion intensity and _a maximum intensity arising from an organic phosphorus compound _{(BO-1) I BO-} 1 _BO-1 ratio of I / I _a-1 is less than 0.05 up to the necessary sputtering ions irradiated The amount was 4.17 × 10 ¹² ions/cm ² .

An ink layer was formed on the obtained multilayered structure (1-1-1), and it was left to stand at 40 ° C for one day for etching. Subsequently, an adhesive layer was formed, and ONY was laminated on the adhesive layer to prepare a laminate. Next, after forming an adhesive layer on the ONY of the laminate, CPP70 was laminated on the adhesive layer and allowed to stand at 40 ° C for 5 days for etching. In this way, it can be formed Multilayer structure (1-1-2) of the structure of the substrate (X-1) / layer (Y-1-1) / ink layer / adhesive layer / ONY / adhesive layer / CPP. The two subsequent layers were formed by applying a two-component type adhesive after drying to a thickness of 3 μm using a bar coater. "A-525S" (trademark) of "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "TAKANATE" (registered trademark) by Mitsui Chemicals Co., Ltd. "A-50" (Trademark) and the formed two-liquid reaction type polyurethane-based adhesive. Further, the ink layer was formed by applying a thickness of 2 μm after drying using a bar coater and drying it. The ink is an ink formed by "R641AT White" (trademark) of "FINESTAR" (registered trademark) manufactured by Toyo Ink Co., Ltd. and "LP Super Hardener" (trademark) manufactured by Toyo Ink Co., Ltd. The oxygen permeability and the moisture permeability of the multilayered structure (1-1-2) were measured. The results are shown in Table 2.

The multilayer structure (1-1-2) was heat-sealed to make a pouch, and 100 g of water was filled into the bag. Subsequently, the obtained bag was subjected to sterilization treatment (hot water storage type) under the following conditions.

Sterilization treatment device: Flavor Ace RSC-60 manufactured by Risaka Manufacturing Co., Ltd.

Temperature: 130 ° C

Time: 30 minutes

Pressure: 0.21MPaG

Immediately after the hot water treatment, the sample for measurement was cut out from the bag, and the oxygen permeability, the moisture permeability, and the T-peel strength of the sample were measured by the above method. its The results are shown in Table 2. Further, in the multilayered structure (1-1-2), no appearance defect such as peeling was observed.

<Example 1-2>

The same procedure as in the production of the multilayered structure (1-1-1) of Example 1-1 was carried out except that the coating amount of the coating liquid (T-1) was changed to 9 mg/m ² . Multilayer structure (1-2-1). In addition, the multilayer structure (1-1-1) is changed to the multilayer structure (1-2-1), and the other is the same as the multilayer structure (1-1-2) of the first embodiment. The method of making a multi-layer structure (1-2-2). Subsequently, the obtained multilayer structure was evaluated. The results are shown in Table 2. As in the case of Example 1-1, in the multilayered structure (1-2-2), no appearance defect such as peeling was observed.

<Examples 1-3 and 1-4>

The multilayer structure (1-1-1) of Example 1-1 was used except that the coating liquid (T-1) was used instead of the coating liquids (T-2) and (T-3). In the same manner, a multi-layer structure (1-3-1) and (1-4-1) were produced. Further, the multilayer structure (1-1-1) is changed to the multilayer structure (1-3-1) and (1-4-1), and the multilayer structure of the first embodiment (1-1) 1-2) The same method was used to produce a multi-layer structure (1-3-2) and (1-4-2). Subsequently, the obtained multilayer structure was evaluated. The results are shown in Table 2. In the multilayer structures (1-3-2) and (1-4-2), no appearance defects such as peeling were observed as in the case of Example 1-1. phenomenon.

<Comparative Example 1-1>

The same procedure as in the production of the multilayered structure (1-1-1) of Example 1-1 was carried out except that the coating amount of the coating liquid (T-1) was changed to 50 mg/m ² . The multilayer structure (C1-1-1) of Comparative Example 1-1 was obtained. Further, the multilayer structure (1-1-1) was changed to a multilayer structure (C1-1-1), and the other was based on the multilayer structure (1-1-2) of Example 1-1. For the same method, a multi-layer structure (C1-1-2) was produced. Subsequently, the obtained multilayer structure was evaluated. The results are shown in Table 2.

<Comparative Example 1-2>

The multilayer structure of Comparative Example 1-2 was obtained in the same manner as in the production of the multilayered structure (1-1-1) of Example 1-1, except that the coating liquid (T-1) was not applied. Body (C1-2-1). Further, the multilayer structure (1-1-2) was changed to a multilayer structure (C1-2-1), and the other was produced in accordance with the multilayer structure (1-1-2) of Example 1-1. For the same method, a multi-layer structure (C1-2-2) was produced. Subsequently, the obtained multilayer structure was evaluated. The results are shown in Table 2.

<Comparative Example 1-3>

The multilayer structure of Example 1-1 except for the coating liquid (S-1) was changed to the coating liquid (S-2), and the coating liquid (T-1) was not applied. -1) was produced in the same manner, and the multilayer structure of Comparative Example 1-3 was obtained. Body (C1-3-1). Further, the multilayer structure (1-1-2) was changed to the multilayer structure (C1-3-1), and the other was produced in accordance with the multilayer structure (1-1-2) of Example 1-1. For the same method, a multi-layer structure (C1-3-2) was produced. Subsequently, the obtained multilayer structure was evaluated. The results are shown in Table 2.

The manufacturing conditions of the multilayered structures of the examples and the comparative examples are shown in Table 1.

[Example 2] Vertical bag filling sealed bag <Example 2-1>

The multilayer structure (1-1-2) produced in Example 1-1 was made wide The 400 mm type is cut, and the non-stretched polypropylene film layer is heat-sealed in contact with each other, and is supplied to a vertical bag filling and packaging machine (manufactured by ORIHIRO Co., Ltd.). Through the vertical bag filling and packaging machine, a vertical bag filling and sealing bag (2-1-3) (width: 160 mm, length: 470 mm) which was attached in a palm-fitting manner as shown in Fig. 1 was obtained. The oxygen permeability and the moisture permeability before the sterilization treatment of the vertical bag filling and sealing bag (2-1-3) were measured. The results are shown in Table 3. A pouch was prepared by heat-sealing the vertical bag filling sealed bag (2-1-3), and 300 mL of water was filled into the bag. Subsequently, the obtained bag was subjected to sterilization treatment (hot water storage type) under the same conditions as in Example 1-1.

Immediately after the hot water treatment, the sample for measurement was cut out from the bag, and the oxygen permeability, the moisture permeability, and the T-peel strength of the sample were measured by the above method. The results are shown in Table 3. At this time, no appearance defect such as peeling was observed.

<Examples 2-2 to 2-4 and Comparative Examples 2-1 to 2-3>

The multilayer structures (1-2-2) to (1-4-2) and (C1-1-2) obtained by using Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3. ) (C1-3-2) is the same as the vertical bag filling and sealing bag (2-1-3) of the embodiment 2-1 except for the multilayer structure (1-1-2). Form a vertical bag filled sealed bag (2-2-3)~(2-4-3) and (C2-1-3)~(C2-3-3). Each of the obtained vertical pouches was filled with a sealed pouch, and various items were measured in the same manner as in Example 2-1. The results are shown in Table 3.

[Example 3] Flat pouch <Example 3-1>

The multilayer structure (1-1-2) obtained in Example 1-1 was cut in a width of 200 mm × 130 mm, and two multilayer structures were overlapped on the inner side of the CPP layer, on the sides of the rectangle. The outer edge is heat sealed with a width of 5 mm. Next, a sheet of Teflon (registered trademark) having a width of 30 mm was inserted from the end of the opening, and heat-sealed in this state. After heat sealing, the sheet of Teflon was removed to obtain a flat bag (3-1-3). The oxygen permeability and the moisture permeability before the sterilization treatment of the flat bag (3-1-3) were measured. The results are shown in Table 4.

Subsequently, 100 mL of water was filled in a flat bag (3-1-3), and sterilizing treatment (hot water storage type) was carried out under the same conditions as in Example 1-1. Immediately after the hot water treatment, the sample for measurement was cut out from the flat bag, and the oxygen permeability, the moisture permeability, and the T-peel strength of the sample were measured by the above method. The results are shown in Table 4. At this time, no appearance defect such as peeling was observed.

<Examples 3-2 to 3-4 and Comparative Examples 3-1 to 3-3>

The multilayer structure obtained by using the multilayer structure (1-2-2) to (1-4-2) obtained in Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3 (C1-1-2)~(C1-3-2) is the same as the flat bag (3-1-3) of Production Example 3-1 except for the multilayer structure (1-1-2). In the method, flat bags (3-2-3)~(3-4-3) and (C3-1-3)~(C3-3-3) were obtained. Each of the obtained flat bags was subjected to measurement of various items in the same manner as in Example 3-1. The results are shown in Table 4.

[Example 4] Infusion bag (bag) <Example 4-1>

From the multilayered structure (1-1-2) obtained in Example 1-1, two multilayer structures of 120 mm × 100 mm were cut out. Subsequently, the two multilayer structures which were cut out were superposed so that the CPP layer was inside, and the spout (mouth plug member) made of polypropylene was heat-sealed while heat-sealing the periphery. In this way, an infusion solution bag (4-1-3) having the same configuration as that of Fig. 3 was obtained. And measuring the oxygen before the sterilization treatment of the infusion solution bag (4-1-3) Transmittance and moisture permeability. The results are shown in Table 5.

Subsequently, 100 mL of water was filled in the infusion solution bag (4-1-3), and sterilization treatment (hot water storage type) was carried out under the same conditions as in Example 1-1. Immediately after the hot water treatment, the sample for measurement was cut out from the infusion solution bag, and the oxygen permeability, the moisture permeability, and the T-peel strength of the sample were measured by the above method. The results are shown in Table 5. At this time, no appearance defect such as peeling was observed.

<Examples 4-2 to 4-4 and Comparative Examples 4-1 to 4-3>

The multilayer structure obtained by using the multilayer structure (1-2-2) to (1-4-2) obtained in Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3 (C1-1-2)~(C1-3-2), in addition to the multilayer structure (1-1-2), the infusion bag (4-1-3) according to the production example 4-1 was In the same way, infusion bags (4-2-3)~(4-4-3) and (C4-1-3)~(C4-3-3) were prepared. Each of the obtained infusion solution bags was measured for various items in the same manner as in Example 4-1. The results are shown in Table 5.

[Example 5] Cover material for containers <Example 5-1>

From the multilayered structure (1-1-2) obtained in Example 1-1, a circular multilayer structure having a diameter of 100 mm was cut out as a lid member for a container. In addition, the container body is prepared by a container (Friday, Ltd., "Hiretoflex" (registered trademark), "HR78-84" (trade name)). The container has a cup shape having an upper diameter of 78 mm and a height of 30 mm. The upper surface of the container is open, and the width of the flange portion formed at the periphery thereof is 6.5 mm. The vessel was constructed of a 3-layer laminate of an olefin layer/steel layer/olefin layer. Next, water was filled in the above-mentioned container body to almost the full cup, and the lid member was heat-sealed to the flange portion, and the lid container (5-1-3) was obtained. At this time, the non-stretched polypropylene layer of the lid member was placed in contact with the flange portion, and the lid member was heat-sealed. A square measurement sample having a length of 4.5 cm was cut out from the lid of the container (5-1-3), and placed on a 10 cm square aluminum foil (thickness 30 μm) and cut into a 2.0 cm diameter circle. The sample and the aluminum foil were sealed with a two-liquid curing epoxy-based adhesive. Using this sample, the oxygen permeability and the moisture permeability before the sterilization treatment were measured. The results are shown in Table 6.

Subsequently, the container (5-1-3) to be covered was subjected to sterilization treatment (hot water storage type) under the same conditions as in Example 1-1. Immediately after the hot water treatment, the sample for measurement was cut out from the lid material, and the oxygen permeability and the moisture permeability of the sample were measured in the same manner as before the sterilization treatment. The T-peel strength was measured by the above method. The results are shown in Table 6. At this time, no appearance defect such as peeling was observed.

<Examples 5-2 to 5-4 and Comparative Examples 5-1 to 5-3>

The multilayer structure obtained by using the multilayer structure (1-2-2) to (1-4-2) obtained in Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3 (C1-1-2)~(C1-3-2), in addition to the multilayer structure (1-1-2), the other container (5-1-3) according to the production example 5-1 The method is the same method, and the covered containers (5-2-3)~(5-4-3) and (C5-1-3)~(C5-3-3) are obtained. Each of the obtained containers was subjected to measurement of various items in the same manner as in Example 5-1. The results are shown in Table 6.

[Example 6] In Mold Labeling container <Example 6-1>

Two sheets of CPP100 were applied to the two-pack type adhesive by using a bar coater so as to have a thickness of 3 μm after drying, and dried. The two-component type adhesive is "A-525S" and Mitsui Chemicals, which are "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals, Inc. A two-liquid reaction type polyurethane-based adhesive formed by "A-50" of "TAKANATE" (registered trademark) manufactured by the company. Next, two sheets of CPP100 were laminated with the multilayered structure (1-1-1) of Example 1-1, and allowed to stand at 40 ° C for 5 days for etching. In this manner, a multilayered label (6-1-2) having a configuration of CPP/back layer/substrate (X-1)/layer (Y-1-1)/adhesion layer/CPP can be obtained. The oxygen permeability and moisture permeability of the obtained multilayered label (6-1-2) were measured by the above method. The results are shown in Table 7.

The multi-layer label (6-1-2) is cut into the inner wall surface shape of the female mold portion of the container forming mold, and is attached to the inner wall surface of the female mold portion. Next, the male model part is squeezed into the female model part. Next, the molten polypropylene ("EAVA" (registered trademark) "EA7A" manufactured by Japan POLYPRO Co., Ltd.) was injected into a cavity between the male mold portion and the female mold portion at 220 °C. In this manner, the target container (6-1-3) is formed by performing injection molding. The container body had a thickness of 700 μm and a surface area of 83 cm ² . The entire outer side of the container is covered by a multi-layer label (6-1-2), and the connection hole overlaps the multi-layer label (6-1-2), and the outer side of the container is not covered by the multi-layer label (6-1-2). At this time, the interlayer label was not found to be peeled off, and the appearance of the container (6-1-3) was good.

<Examples 6-2 to 6-4 and Comparative Examples 6-1 to 6-3>

The multilayer structure obtained by using the multilayer structure (1-2-1) to (1-4-1) obtained in Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3 (C1-1-1)~(C1-3-1) In place of the multilayer structure (1-1-1), In the same manner as the multilayer label (6-1-2) of Example 6-1, a multi-layer label (6-2-2)~(6-4-2) and (C6-1-2) were produced. )~(C6-3-2). Next, in place of the multilayer label (6-2-2)~(6-4-2) and (C6-1-2)~(C6-3-2), the multilayer label of Example 6-1 (6-1) Other than -2), the containers (6-2-3)~(6-4-3) and (C6-1-3)~ are prepared in the same manner as in the production of the container (6-1-3). C6-3-3). The appearance of the obtained in-mold label container (6-2-3) to (6-4-3) was good. On the other hand, no interlaminar peeling was observed in the obtained in-mold label containers (C6-1-3) to (C6-3-3). Subsequently, each of the obtained multilayer labels was subjected to measurement in the same manner as in Example 6-1. The results are shown in Table 7.

[Example 7] extrusion coating lamination <Example 7-1>

In Example 1-1, after forming an adhesive layer on the layer (Y) on the multilayered structure (1-1-1), a polyethylene resin (density; 0.917 g/cm ³ , melt flow rate; 8 g / 10 minutes) extrusion coating was applied to the adhesive layer at 295 ° C in a thickness of 20 μm. In this manner, a laminate (7-1-2) having a structure of a substrate (X-1) / layer (Y-1-1) / an adhesion layer (I-1) / polyethylene was obtained. The above-mentioned adhesive layer (I-1) was formed by applying a two-pack type adhesive to a thickness of 0.3 μm after drying using a bar coater, and drying. "A-3210" of "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "A-3070" of "TAKANATE" (registered trademark) manufactured by Mitsui Chemicals, Inc. The formed two-liquid reaction type polyurethane-based adhesive.

The oxygen permeability and the moisture permeability of the laminate (7-1-2) were measured by the above method. The results are shown in Table 8.

<Examples 7-2 to 7-4 and Comparative Examples 7-1 to 7-3>

The multilayer structure obtained by using the multilayer structure (1-2-1) to (1-4-1) obtained in Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3 (C1-1-1)~(C1-3-1), except for the multilayer structure (1-1-1), the laminate was prepared in the same manner as in Example 7-1 (7-2-2). )~(7-4-2) and (C7-1-2)~(C7-3-2). The laminates (C7-1-2) to (C7-3-2) were found to have a part of the interlayer peeling at the time of winding. Each of the obtained laminates was measured for each item in the same manner as in Example 7-1. The results are shown in Table 8.

[Example 8] Effect of filler <Example 8-1>

In the flat bag (3-1-3) obtained in Example 3-1, 500 mL of a 1.5% ethanol aqueous solution was filled, and a sterilization treatment apparatus (Flavor Ace RCS-60, manufactured by HISAKA, Ltd.) was used at 120 ° C, 0.15. The sterilizing treatment was carried out in hot water for 30 minutes at MPaG. The sample for measurement was cut out from the flat bag after the sterilization treatment, and the oxygen permeability of the sample was measured. The sample had an oxygen permeability of 0.2 mL/(m ² ‧day‧atm).

<Examples 8-2 to 8-9>

The sterilizing treatment was carried out in the same manner as in Example 8-1 except that another filling 500 mL was used instead of 500 mL of a 1.5% aqueous ethanol solution and filled in a flat bag (3-1-3). Subsequently, the sample for measurement was cut out from the flat bag after the sterilization treatment, and the oxygen permeability of the sample was measured. For other fillers, for example, 1.0% aqueous ethanol solution (Example 8-2), edible vinegar (Example 8-3), pH 2 bismuth rubber aqueous solution (Example 8-4), edible oil (Example 8) can be used. -5), tomato sauce (Example 8-6), soy sauce (Examples 8-7), and ginger sauce (Examples 8-8). In either case, the oxygen permeability of the sample after the sterilization treatment was 0.2 mL/(m ² ‧day‧atm). Further, in the container (5-1-3) prepared in Example 5-1, the orange juice was filled with almost full cup, and the others were sterilized in the same manner as in Example 8-1 (Example 8 - 9). The sample for measurement was cut out from the lid material of the container after the sterilization treatment, and the oxygen permeability of the sample was measured, and the oxygen permeability was found to be 0.2 mL/(m ² ‧day‧atm).

It is known from Examples 8-1 to 8-9 that the packaging material of the present invention exhibits good barrier properties even after being sterilized in a state in which various foods are filled.

[Example 9] Vacuum heat insulator <Example 9-1>

The two-component type adhesive used in Example 6-1 was applied onto CPP60 so as to have a thickness of 3 μm after drying, and dried to form an adhesive layer. This CPP was bonded to the PET layer of the multilayered structure (1-1-2) obtained in Example 1-1 to obtain a laminate (9-1-1). Subsequently, the two-liquid reaction type polyurethane-based adhesive was applied to ONY so as to have a thickness of 3 μm after drying, and dried to form an adhesive layer. Subsequently, this ONY was bonded to the laminate (9-1-1) to obtain a multilayered structure (9-1-2) having a CPP/layer/multilayer structure/layer/ONY structure.

The multilayer structure (9-1-2) was cut, and two laminates having a size of 70 cm × 30 cm were obtained. The two laminates are mutually CPP layer The inner surface was attached in a manner, and the three sides were heat-sealed with a width of 10 mm to obtain a three-square bag (open pocket). Next, the heat-insulating core material was filled in the opening of the three-square bag, and the three-square bag was sealed at 20 ° C and an internal pressure of 10 Pa using a vacuum packaging machine. In this way, a vacuum heat insulator (9-1-3) was obtained. The core material for heat insulation is a fine powder of cerium oxide. After the vacuum heat insulator (9-1-3) was allowed to stand under the conditions of 40 ° C and 15% RH for 360 days, the internal pressure of the vacuum heat insulator was measured using a PEGANI vacuum gauge to be 37.0 Pa.

The sample for measurement was cut out from the vacuum heat insulator (9-1-3), and the oxygen permeability and the water vapor permeability of the sample were measured.

Using a constant temperature and humidity machine, the vacuum heat insulator (9-1-3) was stored under an atmosphere of atmospheric pressure at 85 ° C and 85% RH for 1,000 hours (temperature and humidity test), and then vacuum insulation was used. (9-1-3) The sample for measurement was cut out, and the oxygen permeability, the moisture permeability, and the T-peel strength of the sample were measured by the above method. The results are shown in Table 9. Further, no appearance defects such as peeling were observed.

<Examples 9-2 to 9-4 and Comparative Examples 9-1 to 9-3>

The multilayer structure obtained by using the multilayer structure (1-2-2) to (1-4-2) obtained in Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3 (C1-1-2)~(C1-3-2) In place of the multilayer structure (1-1-2), the vacuum insulation (9-1-3) of Example 9-1 was produced. In the same manner, vacuum heat insulators (9-2-3)~(9-4-3) and (C9-1-3)~(C9-3-3) were obtained. Each of the obtained vacuum heat insulators, and Example 9-1 In the same manner, the measurement of each item is performed. The results are shown in Table 9.

[Example 10] Protective sheet <Example 10-1>

An adhesive layer was formed on the multilayered structure (1-1-1) obtained in Example 1-1, and an acrylic resin film (thickness: 50 μm) was laminated on the adhesive layer to obtain a laminate. Subsequently, after forming an adhesive layer on the multilayer structure (1-1-1) of the laminate, the laminate was laminated with PET50. In this manner, a protective sheet (10-1-2) having a PET/back layer/substrate (X-1)/layer (Y-1-1)/adhesion layer/acrylic resin film can be obtained. The two subsequent layers were formed by applying a two-liquid type adhesive to a thickness of 3 μm after drying, and drying. The two-component type of adhesive is formed by "A-1102" of "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "A-3070" of "TAKANATE" (registered trademark) manufactured by Mitsui Chemicals, Inc. A two-liquid reaction type polyurethane-based adhesive. The oxygen permeability and the moisture permeability of the obtained protective sheet (10-1-2) were measured. The results are shown in Table 10.

Subsequently, the durability test of the obtained protective sheet (10-1-2) was carried out by using a constant temperature and humidity tester under the atmosphere of atmospheric pressure, 85 ° C, and 85% RH for 1,000 hours of storage of the protective sheet (temperature). Wet test). The results of the oxygen permeability and the moisture permeability of the protective sheet after the test are shown in Table 10. Further, the results of the evaluation of the adhesion of the protective sheet are shown in Table 10. No appearance defects such as peeling were observed.

<Examples 10-2 to 10-4 and Comparative Examples 10-1 to 10-3>

The multilayer structure obtained by using the multilayer structure (1-2-1) to (1-4-1) obtained in Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3 (C1-1-1)~(C1-3-1) A protective sheet (10-2-2) was obtained in the same manner as in Example 10-1 except for the multilayer structure (1-1-1). )~(10-4-2) and (C10-1-2)~(C10-3-2). Each of the obtained protective sheets was measured in the same manner as in Example 10-1. The results are shown in Table 10. The protective sheet (10-2-2) to (10-4-2) did not show any appearance defects such as peeling after the temperature and humidity test. On the other hand, the protective sheets (C10-1-2) to (C10-3-2) were found to be peeled off between the layers in a temperature and humidity test, and the appearance was poor.

<Example 10-5>

A solar cell module was produced using the protective sheet (10-1-2) obtained in Example 10-1. Specifically, first, an amorphous germanium solar cell unit cell provided on a 10 cm square tempered glass was sandwiched between an ethylene-vinyl acetate copolymer film having a thickness of 450 μm. Next, on the film, the protective sheet (10-1-2) is bonded to the outer side of the protective sheet (10-1-2) to form a solar cell. Module. The bonding method was carried out by vacuum suction at 150 ° C for 3 minutes, followed by pressing for 9 minutes. The solar cell module produced in this manner can be well actuated and exhibits good power output characteristics over a long period of time.

[Industrial use]

The present invention can be utilized in a multilayer structure, a packaging material using the same, and a method of manufacturing a multilayer structure. According to the present invention, it is possible to obtain a multilayer structure which has excellent interlayer adhesion and which does not cause appearance defects such as peeling even after sterilization treatment. Also, using the multilayer junction of the present invention In the case of a structure, an excellent packaging material can be obtained. Further, the present invention can be utilized in a protective sheet having a multilayer structure and an electronic device using the same. According to the present invention, an electronic device using a protective sheet of a multilayered structure having excellent gas barrier properties and water vapor barrier properties and having high-level adhesion between high-temperature and high-humidity can be obtained. Therefore, according to the content of the present invention, an electronic device capable of maintaining high characteristics can be obtained in a plurality of use stages other than the production of the step and the flow stage, and which is extended to a long period.

Claims (14)

A multilayer structure comprising a substrate (X) and a layered structure (Y) laminated on the substrate (X), wherein the layer (Y) is a compound containing aluminum ( A) with the organophosphorus compound (BO), the flight time of a fullerene ion (C ₆₀ ²⁺ ) source having a source of cesium cluster ions (Bi ₃ ²⁺ ) as a primary ion source as a sputter ion source The secondary ion mass spectrometer, when the composition analysis is performed in the depth direction of the layer (Y), the intensity I _A of the negative secondary ion having the highest intensity among the secondary ions generated from the aluminum-containing compound (A) The ratio of the intensity I _BO of the negative secondary ions having the highest intensity among the secondary ions generated by the organophosphorus compound (BO), I _BO /I _A , is the necessary amount of sputtering ions to be as low as 0.05. 3.10 × 10 ¹² ions/cm ² or more and 7.30 × 10 ¹³ ions/cm ² or less. The multilayer structure of claim 1, wherein the aluminum-containing compound (A) is a compound (Ab) containing a reaction product (D) of an aluminum-containing metal oxide (Aa) and an inorganic phosphorus compound (BI). The multilayer structure according to claim 1 or 2, wherein the layer (Y) is an inorganic phosphorus compound (BI), and the mass of the inorganic phosphorus compound (BI) in the layer (Y) is _WBI and an organic phosphorus compound (BO). The ratio of the mass W _BO to W _BO /W _BI is such that it satisfies the relationship of 0.01/99.99 ≦ W _BO /W _BI <1.00/99.00. The multilayer structure according to any one of claims 1 to 3, wherein the aforementioned organophosphorus compound (BO) has a phosphate group, a phosphorous acid group, a phosphine group A polymer of at least one functional group selected from the group consisting of an acid, a phosphinic acid group, a phosphinic acid group, and a phosphinic acid group. The multilayer structure according to any one of claims 1 to 4, wherein the layer (Y) contains a polymer compound (F) having an ether bond, a carbonyl group, a hydroxyl group, and The polymer (Fa) having at least one functional group selected from the group consisting of carboxyl groups, and the mass ratio of the organic phosphorus compound (BO) to the polymer (F) is in the range of 60:40 to 99:1. The multilayer structure according to any one of claims 1 to 5, wherein the substrate (X) is a layer containing at least one selected from the group consisting of a thermoplastic resin film and paper. A packaging material characterized by comprising the multilayer structure of any one of claims 1 to 6. The packaging material of claim 7 which still has a layer formed by extrusion coating lamination. The packaging material of claim 7 or 8, which is a vertical bag filling sealed bag, a vacuum packaging bag, a pouch, a laminated tubular container, an infusion liquid bag, a paper container, a long bag, a lid for a container, or In-mold label container. An article wherein at least a portion is a packaging material using any one of claims 7 to 9. The article of claim 10, wherein the product contains a content, the content is a core material, and the inside of the product is decompressed and has a function of a vacuum heat insulator. A protective sheet for an electronic device, characterized by containing a request The multilayer structure of any one of items 1 to 6. The protective sheet of the electronic device of claim 12, which is a protective sheet for protecting the surface of the photoelectric conversion device, the information display device, or the illumination device. An electronic device characterized by having a protective sheet of claim 12 or 13.