TWI687308B - Multi-layer structure, packaging materials and products using it, and protective sheets for electronic devices - Google Patents

Abstract

The present invention relates to a multilayer structure which is a multilayer structure comprising a substrate (X) and a layer (Y) laminated on the aforementioned substrate (X), the aforementioned layer (Y) being a compound containing aluminum (A) Phosphate (BP) with the polyvinyl alcohol resin, the phosphate esterification rate R _BP of the phosphate ester (BP) of the polyvinyl alcohol resin is 0.15 or more.

Description

Multi-layer structure, packaging materials and products using it, and protective sheets for electronic devices

The present invention relates to a multilayer structure, packaging materials and products using the same, and a protective sheet for electronic devices.

Multi-layer structures formed of a gas barrier layer using aluminum or aluminum oxide as a constituent component on a plastic film are widely known in the past. These multilayer structures are often used as packaging materials for protecting articles (for example, food) that are susceptible to oxygen and deteriorate. Most of these gas barrier layers are formed on the plastic film by using dry processes such as physical vapor growth (PVD) and chemical vapor growth (CVD). In addition, these multilayer structures are also used as constituent members of protective sheets for electronic devices that are required to have gas barrier properties and water vapor barrier properties for the purpose of protecting the characteristics of electronic devices.

For example, in addition to gas barrier properties, aluminum vapor-deposited films also have light-shielding properties, and are mainly used as packaging materials for dry food.

On the other hand, a transparent aluminum oxide vapor deposition film, It has the characteristics of recognizable content, and the use of metal detectors for foreign object inspection or the use of microwave ovens for heating. Therefore, this film has been widely used as a packaging material since retort pouch food packaging.

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. One method of forming the gas barrier layer is to apply a coating liquid containing aluminum oxide particles and a phosphorus compound on a plastic film. The method of drying and heat treatment is disclosed in Patent Document 1.

However, the conventional multi-layer structure with a gas barrier layer often has excellent gas barrier properties at the initial stage, but when physical pressure is applied due to deformation, impact, etc., defects such as cracks or sand holes occur in the gas barrier layer, and There may be cases where the gas barrier property is reduced.

Therefore, there has been disclosed a multi-layered structure that not only has excellent gas barrier properties but also maintains high gas barrier properties at high efficiency even when subjected to physical stress such as deformation and impact.

However, when the present inventors use the multilayer structure disclosed in Patent Document 1 and Patent Document 2 as packaging materials for sterilization bag foods, the interlayer adhesion after sterilization treatment may be reduced, resulting in failure to laminate, etc. The appearance is bad. In addition, when the inventors use the multilayer structure disclosed in Patent Document 1 and Patent Document 2 for electronic devices, delamination may occur after the temperature and humidity test.

Therefore, there is an urgent need to find a multi-layer structure having good gas barrier properties even after sterilization treatment. And, one used in high temperature. Under high humidity, it also has an adhesive force between high layers and an electronic device with a multilayer structure with high barrier properties.

[Prior Technical Literature] [Patent Literature]

[Patent Literature 1] WO2011/122036

[Patent Document 2] Japanese Patent Laid-Open No. 2013-208793

The object of the present invention is to provide a novel multi-layer structure with excellent gas barrier properties and water vapor barrier properties, as well as excellent sterilization resistance and packaging materials using the same.

In addition, the other object of the present invention is to provide a use having excellent gas barrier properties and water vapor barrier properties, and at high temperatures. A protective sheet for electronic devices with a novel multi-layer structure that also has adhesion between high layers under high humidity.

After intensive research, the inventors found that a multilayer structure containing a specific layer can achieve the above-mentioned object, and thus completed the present invention.

The present invention is to provide a multilayer structure which is a multilayer structure containing a substrate (X) and a layer (Y) laminated on the substrate (X), the layer (Y) being a compound containing aluminum (A) Phosphate (BP) with the polyvinyl alcohol resin, the phosphate esterification rate R _BP of the phosphate ester (BP) of the polyvinyl alcohol resin is 0.15 or more.

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

In the multilayer structure of the present invention, the phosphate esterification rate R _BP of the phosphate ester compound (BP) of the polyvinyl alcohol-based resin may be 0.24 or more.

In the multilayer structure of the present invention, the phosphated vinyl alcohol unit represented by the following general formula [III] in the phosphate ester (BP) may contain 15.0 to 99.8 mol %.

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

Moreover, the present invention is to provide a layer containing any of the foregoing Packaging materials for structures.

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

The aforementioned packaging material may be a vertical bag filled and sealed bag, a vacuum packaging bag, a pouch, a laminated tubular container, an infusion solution bag (bag), a paper container, a long bag, a cover material for a container, or may be a mold Inner label container.

In addition, the present invention is to provide an article using any of the aforementioned packaging materials as at least a part.

The aforementioned product may be one that contains contents, the contents are core materials, the inside of the product is decompressed, and has the function of a vacuum heat insulator.

Furthermore, the present invention provides a protective sheet for an electronic device containing any one of the aforementioned 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 lighting device.

Furthermore, the present invention is to provide an electronic device including any of the aforementioned protective sheets.

According to the content of the present invention, a novel multi-layer structure with excellent gas barrier properties and water vapor barrier properties, as well as excellent sterilization resistance and packaging materials using the same can be prepared. That is, according to the content of the present invention, it is possible to obtain an excellent gas barrier property and water vapor barrier property, which can maintain excellent gas barrier property and water vapor barrier property after sterilization, and will not Defective appearance such as delamination In this case, there is a novel multilayer structure with high interlayer adhesion (peel strength) and packaging materials using the same. In addition, according to the content of the present invention, one can obtain an excellent gas barrier property and water vapor barrier property at high temperature. A protective sheet for electronic devices with a novel multi-layer structure that also has adhesion between high layers under high humidity. That is, according to the content of the present invention, it is possible to obtain a product that not only has excellent gas barrier properties and water vapor barrier properties, but also maintains excellent gas barrier properties and water vapor barrier properties after a temperature and humidity test, as well as after a temperature and humidity test An electronic device containing a protective sheet with a novel multi-layer structure having a high interlayer adhesion (peel strength) without causing appearance defects such as peeling.

10‧‧‧ Vertical bag filled with sealed bag

11‧‧‧Multi-layer structure

11a‧‧‧End

11b‧‧‧Body

11c, 411,412,413,414,611

20‧‧‧flat pouch

360‧‧‧Container

361, 362, 363‧‧‧ multilayer labels

361a‧‧‧Through hole

370‧‧‧Container body

371‧‧‧Flange

372‧‧‧Body

373‧‧‧Bottom

371a‧‧‧Convex

40‧‧‧Electronic device

41‧‧‧Electronic device body

42‧‧‧Sealing material

43‧‧‧Protection sheet (multilayer structure)

401‧‧‧Infusion solution bag

420, 620‧‧‧ next door

431‧‧‧Infusion bag body

432‧‧‧port plug component

433‧‧‧Hanging hole

50‧‧‧Extrusion coating lamination device

51‧‧‧Extruder

52‧‧‧T

53‧‧‧cooling drum

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] A schematic diagram of a vertical bag-filled sealed bag according to an embodiment of the present invention.

[Fig. 2] A schematic diagram of a flat pouch according to one embodiment of the present invention.

[Fig. 3] A schematic diagram of an infusion solution bag according to one embodiment of the present invention.

[Fig. 4] A schematic diagram of an In Mold Labeling container according to an embodiment of the present invention.

[Fig. 5] A perspective view of a partial mode of an extrusion coating lamination device used in the manufacture of a multilayer structure according to one embodiment of the present invention.

[Fig. 6] A mold of a vacuum heat insulator according to an embodiment of the present invention Style diagram.

[Fig. 7] Another schematic diagram of a vacuum heat insulator according to an embodiment of the present invention.

[Fig. 8] A partial cross-sectional view of an electronic device according to one embodiment of the present invention.

The present invention will be explained with the following examples. In the following description, although there are cases where substances, conditions, methods, numerical ranges, etc. are exemplified, the present invention is not limited by these examples. In addition, the exemplified substances can be used alone or in combination of two or more without special notes.

When there is no special note, in this specification, it is described as "laminating a specific layer on a specific member (substrate, layer, etc.)", except for the case where the specific layer is laminated in contact with the member, It also includes the case where the specific layer is laminated on the member sandwiched by other layers. The descriptions of "a specific layer is formed on a specific member (substrate, layer, etc.)" and "a specific layer is arranged on a specific member (substrate, layer, etc.)" also have the same meaning. In addition, when there is no special note, the meaning of the description of "coating liquid (coating liquid, etc.) on a specific member (substrate, layer, etc.)", except for the case where the liquid is directly coated on the member, Including the case where the liquid is coated on other layers formed on the member.

In this manual, there will be a layer (Y) with a symbol (Y) like "layer (Y)" to distinguish it from other layers. Yu No Special Notes At this time, the symbol (Y) does not have technical significance. The same applies to the substrate (X), compound (A) and other symbols. However, like the hydrogen atom (H), except when the specific element is clearly marked.

[Multilayer structure]

The multilayer structure of the present invention includes a substrate (X) and an aluminum-containing layer (Y). The layer (Y) contains an aluminum-containing compound (A) (hereinafter, also simply referred to as "compound (A)") and a phosphate ester (BP) of a polyvinyl alcohol-based resin (hereinafter, also simply referred to as "phosphoric acid Ester (BP)"), the phosphate esterification rate R _BP of the phosphate ester (BP) of the polyvinyl alcohol-based resin is 0.15 or more. In the following description, unless otherwise noted, the phrase "multilayer structure" means a multilayer structure containing a substrate (X) and a layer (Y).

In the layer (Y), at least a part of the compound (A) and at least a part of the phosphate ester (BP) can react. Furthermore, when the layer (Y) contains an inorganic phosphorus compound (BI), at least a part of the compound (A) and at least a part of the inorganic phosphorus compound (BI) and/or phosphate ester (BP) may be React. In the case where the compound (A) in the layer (Y) reacts, the 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 included in the mass of the compound (A) in the layer (Y). In addition, in the case where the layer (Y) reacts with the inorganic phosphorus compound (BI) and/or phosphate ester (BP), part of the inorganic phosphorus compound (BI) and/or phosphate ester (BP) constituting the reaction product is regarded as It is inorganic phosphorus compound (BI) and/or phosphate ester (BP). In this case, the inorganic phosphorus compound used to form the reaction product (BI) and/or phosphate ester (BP) mass (inorganic phosphorus compound (BI) and/or phosphate ester (BP) mass before reaction), the inorganic phosphorus compound contained in the layer (Y) ( BI) and/or phosphate ester (BP) quality.

〔Substrate(X)〕

The material of the substrate (X) is not particularly limited, and substrates formed of various materials can be used. The material of the base material (X) is, for example, resins such as thermoplastic resins and thermosetting resins; fiber aggregates such as cloth and paper; wood; glass, etc. Among these, thermoplastic resins and fiber assemblies are more preferable, and thermoplastic resins are more preferable. The form of the base material (X) is not particularly limited, and it may be a layered film or sheet. The base material (X) preferably contains at least one selected from the group consisting of thermoplastic resin films and paper, preferably contains thermoplastic resin films, and more preferably thermoplastic resin films.

Thermoplastic resin used for the base material (X), for example, polyolefin resins such as polyethylene and polypropylene; polyethylene terephthalate (PET), polyethylene 2,6-naphthalene dicarboxylate, poly Polyester resins such as butylene phthalate or copolymers of these; polyamide resins such as nylon-6, nylon-66, nylon-12; and hydroxyl-containing resins such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers Polymer; Polystyrene; Poly(meth)acrylate; Polyacrylonitrile; Polyvinyl acetate; Polycarbonate; Polyacrylate; Regenerated cellulose; Polyimide; Polyetherimide; Polyphenol; Polyether ballast; polyether ether ketone; ionic polymer resin, etc. When the multilayer structure is used as a packaging material, the material of the base material (X) is made of polyethylene, polypropylene, polyethylene terephthalate At least one thermoplastic resin selected from the group consisting of ester, nylon-6, and nylon-66 is preferred.

When the film formed from the thermoplastic resin is used as the substrate (X), the substrate (X) may be a stretched film or may not be a stretched film. From the viewpoint that the resulting multilayer structure has excellent processability (printing, lamination, etc.), the stretched film, particularly the biaxially stretched film is preferred. The biaxially stretched film may be a biaxially stretched film made by any of the simultaneous biaxial stretching method, the sequential biaxial stretching method, and the tubular stretching method.

The paper used for the substrate (X), for example, drawing paper, fine paper, molded paper, cellophane, parchment, synthetic paper, whiteboard paper, manila paper, milk carton base paper, cup base paper, ivory paper Wait. When paper is used as the substrate (X), a multilayer structure for paper containers can be produced.

When the base material (X) is a layer, its thickness is preferably 1 to 1,000 μm, preferably 5 to 500 μm, and preferably 9 to 200 μm from the viewpoint that the resulting multilayer structure has good mechanical strength and processability. For better.

[Layer (Y)]

The layer (Y) contains the compound (A) and the phosphate ester (BP). Compound (A) is a compound containing aluminum. In addition, it is preferable that the layer (Y) further contains an inorganic phosphorus compound (BI). Inorganic phosphorus compounds (BI) and phosphate esters (BP) have functional groups containing phosphorus atoms. Compound (A), inorganic phosphorus compound (BI), and The content of phosphate ester (BP) will be described below.

[Aluminum-containing compound (A)]

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

[Aluminum-containing metal oxide (Aa)]

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

The metal atoms constituting the metal oxide (Aa) containing aluminum (these are also collectively referred to as "metal atoms (M)") are at least 1 selected from the metal atoms belonging to groups 2 to 14 of the periodic table Kind of metal atoms, but at least contains aluminum. The metal atom (M) may be aluminum alone, or may contain aluminum and other metal atoms. Furthermore, for the metal oxide (Aa), two or more kinds of metal oxides (Aa) can be used in combination.

The proportion of metal atoms (M) is usually 50 mol% or more, and can also be 60-100 mol%, or 80-100 mol%. Examples of the metal oxide (Aa) include, for example, metal oxides prepared by methods such as liquid-phase synthesis, gas-phase synthesis, and solid pulverization.

The metal oxide (Aa) may be a hydrolyzed condensate of a compound (E) containing a metal atom (M) bonded to a hydrolyzable characteristic group. Examples of this characteristic base include, for example, R ^{1 of the} general formula [I] described later. The hydrolyzed condensate of compound (E) can be regarded as a metal oxide substantially. Therefore, in this specification, the hydrolyzed condensate of compound (E) may also be referred to as "metal oxide (Aa)". That is, in this 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 metal atom (M) bonded to hydrolyzable characteristic group]

From the viewpoint of easily controlling the reaction mechanism with the inorganic phosphorus compound (BI) and making the gas barrier properties of the resulting multilayer structure more excellent, the compound (E) contains the compound (Ea) represented by the following general formula [I] At least one of them is preferred.

Al(R ¹ ) _k (R ² ) _3-k 〔I〕

In the formula, R ¹ is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO ₃ , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, and a carbon number 2 to 2 which may have a substituent Acetyloxy group of 9, C3-C9 alkenyloxy group which may have a substituent, β-diketone group which may have a carbon number of 5-15, or C1-C9 which may have a substituent The diacyl group of the acyl 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 aryl group having 6 to 10 carbon atoms in the substituent. k is an integer from 1 to 3. There are cases where most of the R ^1, R ¹ may be the same as each other, also different. R ² is present the majority of circumstances, each of R ² may be the same or, different also.

The compound (E), in addition to the compound (Ea), may contain at least one compound (Eb) represented by the following general 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 kind of metal atom selected from the metal atoms belonging to groups 2 to 14 of the periodic table. R ³ is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO ₃ , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, and an alkoxy group having 2 to 9 carbon atoms which may have a substituent Oxygen group, optionally substituted C3-C9 alkenyloxy group, optionally substituted C5-C15 di-keto group, or optionally substituted C1-C9 acetyl group Of diacylmethyl. 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 aryl group having 6 to 10 carbon atoms in the substituent. 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.

The alkoxy groups of R ¹ and R ³ are, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert- Butoxy, benzyloxy, diphenylmethoxy, triphenylmethoxy, 4-methoxybenzyloxy, methoxymethoxy, 1-ethoxyethoxy, benzyloxymethoxy Oxy, 2-trimethylsilylethoxy, 2-trimethylsilylethoxymethoxy, phenoxy, 4-methoxyphenoxy, etc.

Acyloxy of R ¹ and R ³ , for example, acetyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyl Oxygen, sec-butylcarbonyloxy, tert-butylcarbonyloxy, n-octylcarbonyloxy, etc.

The alkenyloxy groups of R ¹ and R ^{3 are} , 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.

Β-diketone 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, benzoylacetone, etc.

Carbonyl groups of bis-methyl groups of R ¹ and R ³ , for example, carbon groups such as methyl group, ethyl group, propyl group (Propanoyl group), butyl group (butyl group), pentyl group (Pentanoyl group), hexyl group, etc. Number 1~6 aliphatic acyl groups; aromatic acyl groups such as benzoyl acyl group, tolyl acyl group (aromatic acyl group), etc.

R ² and R ⁴ alkyl groups, 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.

The aralkyl groups of R ² and R ^{4 are} , for example, benzyl, phenylethyl (phenethyl) and the like.

Alkenyl groups of R ² and R ⁴ , for example, vinyl, 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, etc.

The aryl groups of R ² and R ^{4 are} , for example, phenyl, 1-naphthyl, 2-naphthyl and the like.

Substituents in R ¹ , R ² , R ³ and R ⁴ , for example, C 1-6 alkyl; methoxy, ethoxy, n-propoxy, isopropoxy, _n -butoxy Group, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy , Cyclohexyloxy and other alkoxy groups having 1 to 6 carbon atoms; methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy Alkoxy groups with 1 to 6 carbon atoms such as carbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentyloxycarbonyl, etc. Carbonyl; aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl; halogen atoms such as fluorine, chlorine, bromine, and iodine; acetyl groups with 1 to 6 carbon atoms; aralkyl groups with 7 to 10 carbon atoms ; Aralkyloxy groups with carbon number 7-10; alkylamino groups with carbon number 1-6; dialkylamino groups with alkyl groups with carbon number 1-6, etc.

R ¹ and R ³ are halogen atoms, NO ₃ , alkoxy groups having 1 to 6 carbon atoms which may have substituents, alkoxy groups having 2 to 6 carbon atoms which may have substituents, and carbon numbers which may have substituents 5~10 β-diketone group, or a bismethyl group having 1 to 6 carbon groups that may have a substituent is preferred, and a 1 to 6 carbon alkoxy group that may have a substituent is preferred good.

R ² and R ^{4 are} preferably a C 1-6 alkyl group which may have a substituent. K of formula [I] is preferably 3.

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

In addition, although boron and silicon may be classified as semi-metals, in this specification, these are included in metals.

Compound (Ea), for example, aluminum chloride, aluminum nitrate, aluminum acetate, ginseng (2,4-pentanedione) aluminum, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, Aluminum triisopropoxide, aluminum tri-n-butoxy, aluminum tri-sec-butoxy, aluminum tri-tert-butoxy, etc. Among them, aluminum triisopropoxide and aluminum tri-sec- Aluminum butoxide is preferred. Compound (E) can be used in combination of two or more compounds (Ea).

Compound (Eb), for example, tetrakis(2,4-pentanedione) titanium, tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetrakis( Titanium compounds such as 2-ethylhexyloxy) titanium; zirconium compounds such as zirconium tetrakis(2,4-pentanedione), zirconium tetra-n-propoxy, zirconium tetra-n-butoxy, etc. One of these may be used alone, or two or more compounds (Eb) may be used in combination.

In the compound (E), the ratio of the compound (Ea) in the compound (E) is not particularly limited as long as the effect of the invention can be achieved. The proportion of compounds other than compound (Ea) (for example, compound (Eb)) in compound (E), for example, preferably 20 mol% or less, preferably 10 mol% or less, 5 mol Ear% or less is better, or 0 mole %.

When the compound (E) is hydrolyzed, at least a part of the hydrolyzable characteristic group possessed by the compound (E) can be converted into a hydroxyl group. In addition, when the hydrolyzate is condensed, it can form a compound in which a metal atom (M) is bonded via an oxygen atom (O). When this condensation reaction is repeated, a compound substantially regarded as a metal oxide can be formed. In addition, the surface of the metal oxide (Aa) formed by this method usually has hydroxyl groups.

In this specification, a compound whose ratio of [the number of moles of oxygen atoms (O) bonded only to metal atoms (M)]/[the number of moles of metal atoms (M)] is 0.8 or more is considered to be included 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, and 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 included. The above ratio in the metal oxide (Aa) is preferably 0.9 or more, preferably 1.0 or more, and more preferably 1.1 or more. The upper limit of this ratio is not particularly limited, but generally when the valence of the metal atom (M) is n, it is usually expressed as n/2.

In order to start the aforementioned hydrolysis condensation reaction, it is an important condition that the compound (E) has a hydrolyzable characteristic group. If these bases are not bonded, it will cause It is difficult to cause hydrolysis condensation reaction or the reaction is extremely slow, and it is extremely difficult to produce the target metal oxide (Aa).

The hydrolyzed condensate of the compound (E) can be prepared from a specific raw material using a known sol-gel method, for example. As the raw material, the compound (E), the partial hydrolysate of the compound (E), the complete hydrolysate of the compound (E), the compound formed by partial hydrolysis and condensation of the compound (E), and the compound (E) At least one selected from the group of compounds formed by condensation of a part of the complete hydrolysate.

Metal oxide (Aa) can be provided as a mixture with a substance containing inorganic phosphorus compound (BI) (inorganic phosphorus compound (BI), or a composition containing inorganic phosphorus compound (BI)) so as not to contain phosphorus substantially Atom is better.

[Compound (Ab)]

The reaction product (D) contained in the compound (Ab) is obtained by reacting the metal oxide (Aa) and the inorganic phosphorus compound (BI). Among them, the compound formed by the reaction of the metal oxide (Aa) and the inorganic phosphorus compound (BI) with other compounds is also included in the reaction product (D). In addition, the compound (Ab) may contain a part of the metal oxide (Aa) and/or the inorganic phosphorus compound (BI) not related to the reaction.

In the compound (Ab), the molar ratio of the metal atom constituting the metal oxide (Aa) and the phosphorus atom produced by the inorganic phosphorus compound (BI) is [metal atom constituting the metal oxide (Aa)]: [from inorganic Phosphorus atom produced by phosphorus compound (BI)】=1.0: 1.0~3.6: 1.0 is better, The range of 1.1:1.0~3.0:1.0 is better. Outside this range, the gas barrier performance will be reduced. The molar ratio in the compound (Ab) can be adjusted by the mixing ratio of the metal oxide (Aa) and the inorganic phosphorus compound (BI) in the coating solution 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 between the metal oxide (Aa) and 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) Phosphorus atom (P) forms a bond represented by MOP via oxygen atom (O). As a result, in the infrared absorption spectrum of the reaction product (D), a characteristic absorption band due to the bonding will be generated. The inventors found through research that the characteristic absorption band based on the MOP bond appears in the region of 1,080~1,130 cm ^-1 , and the resulting multilayer structure can show excellent gas barrier properties. In particular, when the characteristic absorption band occurs in the region of 800~1,400cm ^-1 where absorption occurs when various atoms bond with oxygen atoms, it is known that the multilayer structure can be obtained. Shows better gas barrier properties.

On the other hand, when a metal compound such as an alkoxy metal or a metal salt is preliminarily mixed with an inorganic phosphorus compound (BI) and then hydrolyzed and condensed, a metal atom generated from the metal compound and an inorganic phosphorus compound (BI) can be obtained Phosphorus atoms produced are reacted with almost uniform mixing. In this case, in the infrared absorption spectrum, the maximum absorption wavenumber in the region of 800 to 1,400 cm ^-1 is far from the range of 1,080 to 1,130 cm ^-1 .

Infrared layer (Y) of the absorption spectrum, the half width of 800 to a maximum value of absorption band in the region of 1,400cm ^-1 (the FWHM), the viewpoint of the gas barrier property of the resultant multilayer structure, the following is to 200cm ^-1 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 pattern of layer (Y) can be measured according to 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, attenuation total reflection method, layer (Y) from a multilayer structure, and nujol mull method can also be used , Lozenge, etc. may be measured by methods such as measurement, but it is not limited to these methods.

In the compound (Ab), the particles of the metal oxide (Aa) may have a structure in which phosphorus atoms generated by the inorganic phosphorus compound (BI) are bonded. The particles of the metal oxide (Aa) used as the raw material of the compound (Ab) can change the shape or size during the formation of the compound (Ab).

[Inorganic Phosphorus Compound (BI)]

The inorganic phosphorus compound (BI) contains a site that can react with the metal oxide (Aa), and typically contains many such sites. The inorganic phosphorus compound (BI) is preferably a compound containing 2 to 20 such sites (atomic groups or functional groups). Examples of such sites include condensation reaction with functional groups (for example, hydroxyl groups) present on the surface of the metal oxide (Aa) Should be. Such sites include, for example, halogen atoms directly bonded to phosphorus atoms and oxygen atoms directly bonded to phosphorus atoms. The functional group (for example, hydroxyl group) present on the surface of the metal oxide (Aa) is usually bonded to the metal atom (M) constituting the metal oxide (Aa).

Inorganic phosphorus compounds (BI), such as phosphoric acid, phosphorous acid, phosphorous acid, phosphonic acid, phosphonic acid, phosphonic acid, phosphonic acid, etc. Acids, and these salts (for example, sodium phosphate), derivatives of these (for example, halides (for example, phosphoramidyl chloride), dehydrates (for example, phosphorus pentoxide)), and the like.

These inorganic phosphorus compounds (BI) may be used alone or in combination of two or more. Among these inorganic phosphorus compounds (BI), it is preferable to use phosphoric acid alone or to combine phosphoric acid with other inorganic phosphorus compounds (BI). When phosphoric acid is used, the stability of the coating liquid (S) described later and the gas barrier properties of the resulting multilayer structure can be improved. In the case of using phosphoric acid together with an inorganic phosphorus compound (BI) other than that, it is preferable that 50 mol% or more of the inorganic phosphorus compound (BI) is phosphoric acid.

〔Phosphorus-containing polymer (BO)〕

The multilayer structure of the present invention is preferably one that does not contain a phosphorus atom-containing polymer (BO) other than the phosphate ester (BP) of the polyvinyl alcohol-based resin. Phosphorus atom-containing functional groups of the phosphorus atom-containing polymer (BO), for example, phosphoric acid group, phosphorous acid (phosphonous acid) group, phosphonic acid (Phosphonic acid) group, phosphorous acid (Phosphonous acid) group, phosphine Phosphonic acid group, Phosphonous acid group, and those derived from them Functional groups (for example, salts, (partial) ester compounds, halides (for example, chlorides), dehydrates), and the like. The phosphorus atom-containing polymer (BO) is, for example, a polymer compound containing more than 10 phosphorus atoms.

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

The multilayer structure may further contain an inorganic vapor-deposited layer. The inorganic vapor-deposited layer can be formed by vapor-depositing an inorganic substance. Inorganic substances, for example, metals (for example, aluminum), metal oxides (for example, silicon oxide, aluminum oxide), metal nitrides (for example, silicon nitride), metal nitride oxides (for example, acid silicon nitride), or Metal carbide nitride (for example, silicon carbonitride) and the like. Among them, the inorganic vapor-deposited layer formed of aluminum oxide, silicon oxide, magnesium oxide, or silicon nitride is preferable from the viewpoint of having 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 a vapor-deposited layer (Ac) of aluminum and/or a vapor-deposited layer (Ad) of aluminum oxide.

The method of forming the inorganic vapor deposition layer is not particularly limited, such as vacuum vapor deposition method (for example, resistance heating vapor deposition, electron beam vapor deposition, molecular wire epitaxy method, etc.), sputtering method, ion plating method and other physical gases Phase growth method, thermal chemical vapor growth method (for example, catalyst chemical vapor growth method), photochemical vapor growth method, plasma chemical vapor growth method (for example, capacity bonding plasma, inductively coupled plasma) , Surface wave plasma, electron cyclotron resonance, dual-magnetron sputtering (dual-magnetron), atomic layer deposition method, etc.), organic metal vapor growth method and other chemical vapor growth methods.

The thickness of the inorganic vapor-deposited layer depends on the composition of the inorganic vapor-deposited layer The type of serving varies, generally 0.002 to 0.5 μm is preferred, 0.005 to 0.2 μm is preferred, and 0.01 to 0.1 μm is more preferred. Within this range, it is sufficient to select a thickness having good barrier properties or mechanical properties of the multilayer structure. When the thickness of the inorganic vapor-deposited layer is less than 0.002 μm, there is a tendency to reduce the reproducibility of the barrier property to the inorganic vapor-deposited layer of oxygen or water vapor. In addition, the inorganic vapor-deposited layer may fail to produce sufficient barrier properties. . In addition, when the thickness of the inorganic vapor-deposited layer exceeds 0.5 μm, the barrier property of the inorganic vapor-deposited layer tends to decrease when the multilayer structure is stretched or bent.

[Phosphate Ester of Polyvinyl Alcohol Resin (BP)]

The phosphate ester compound (BP) of the polyvinyl alcohol resin is prepared by esterifying the polyvinyl alcohol resin and phosphoric acid. Polyvinyl alcohol-based resins, for example, polyvinyl alcohol, partial saponification of polyvinyl acetate, ethylene-vinyl alcohol copolymer, partial saponification of ethylene-vinyl acetate copolymer, etc. Among them, polyvinyl alcohol Ethylene-vinyl alcohol copolymer is preferred, with polyvinyl alcohol being preferred. The aforementioned phosphate ester (BP) is particularly preferably one containing 15.0 to 99.8 mol% of phosphorylated vinyl alcohol unit represented by the following general formula [III]. From the viewpoint of productivity, the content of phosphorylated vinyl alcohol units is preferably 99.0 mol% or less, and more preferably 95.0 mol% or less. In addition, from the viewpoint of obtaining a multilayer structure having excellent interlayer adhesion, the content of phosphated vinyl alcohol unit is preferably 30.0 mol% or more, more preferably 45.0 mol% or more, and 60.0 mol. More than% is particularly good.

[Chem 2]

The saponification degree of the polyvinyl alcohol-based resin used in the present invention is preferably from 75.0 to 99.85 mol%, and from the viewpoint of producing a multilayer structure having excellent interlayer adhesion, 80.0 to 99.5 mol% is preferred , 85.0~99.3 mol% is better, and 90.0~99.1 mol% is especially good. The degree of saponification is a value obtained in accordance with JIS K 6726 (1994).

The average polymerization degree of viscosity of the polyvinyl alcohol-based resin used in the present invention is preferably from 100 to 4,000, from the viewpoint of producing a multilayer structure with excellent interlayer adhesion, preferably from 200 to 3,500, preferably from 300 to 3,000 is better, 500~2,800 is especially good. The average polymerization degree of viscosity is a value obtained in accordance with JIS K 6726 (1994).

The viscosity of the polyvinyl alcohol resin used in the present invention is 1.0 to 200 mPa. s is better, you can produce a multi-layer structure with excellent interlayer adhesion, from 3.0 to 150mPa. s is better, with 11~90mPa. s is better, with 20~85mPa. s is very good. Viscosity is the value measured with a B-type rotary viscometer using a 4 mass% aqueous solution at 20°C in accordance with JIS K 6726 (1994).

The polyvinyl alcohol resin used in the present invention has a saponification degree of 85.0 to 99.3 mol%, an average viscosity degree of polymerization of 200 to 3,500, and a viscosity of 11 to 90 mPa. s is better, the saponification degree is 85.0~99.3 mole %, the average viscosity polymerization degree is 500~2,800, and the viscosity of 20~85mPa‧s is better.

Phosphate ester (BP) may be used as long as it can form a phosphate group in the manufacturing process of the multilayer structure.

To produce a multilayer structure having a high level of focus indirectly, phosphate compound (BP) of R _BP phosphate ratio is 0.15 or more. From the viewpoint of producing a multilayer structure having excellent interlayer adhesion, 0.24 or more is preferable, 0.37 or more is more preferable, and 0.54 or more is more preferable. The phosphate esterification rate R _BP can be calculated from the addition amount of the polyvinyl alcohol resin and phosphoric acid in the esterification reaction of the polyvinyl alcohol resin and phosphoric acid according to the following formula.

Esterification rate R _BP = {inorganic phosphorus compound (BI) addition amount (g)/inorganic phosphorus compound (BI) molecular weight}/[{(saponification degree/100)×polyvinyl alcohol resin addition amount (g)}/ 44.05〕

The ratio (weight ratio) of the addition amount of polyvinyl alcohol resin and phosphoric acid is preferably polyvinyl alcohol resin: phosphoric acid=20:80~85:15, preferably 25:85~70:30, preferably 30: 70~65:35 is better.

The layer (Y) contained in the multilayer structure of the present invention may be composed only of the aluminum-containing compound (A), the inorganic phosphorus compound (BI), and the phosphate ester (BP); it may be composed of only Aluminum-containing metal oxides (Aa), inorganic phosphorus compounds (BI), and phosphate esters (BP) may also be used; it may be composed only of aluminum-containing metal oxides (Aa) and inorganic phosphorus compounds (BI ) The reaction product (D) of the compound (Ab), the inorganic phosphorus compound (BI), and the phosphate ester (BP) may also be constituted; it may be composed only of the aluminum-containing metal oxide (Aa), containing aluminum The reaction product of metal oxide (Aa) and inorganic phosphorus compound (BI) (D) The compound (Ab), the inorganic phosphorus compound (BI), and the phosphate ester (BP) may be constituted. In addition, in any of the foregoing embodiments, the layer (Y) may further contain other components. Other ingredients, for example, carbonate, hydrochloride, nitrate, bicarbonate, sulfate, bisulfate, borate and other inorganic acid metal salts; oxalate, acetate, tartrate, stearate, etc. Organic acid metal salts; metal complexes such as cyclopentadienyl metal complexes (for example, titanocene), cyano metal complexes (for example, Prussian blue); layered clay compounds; crosslinking agents; high Molecular compound (F): plasticizer; antioxidant; ultraviolet absorber; flame retardant, etc. The content of the aforementioned other components in the layer (Y) in the multilayer structure is preferably 50% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and 5% by mass or less Very good, it can also be 0% by mass (excluding other ingredients).

〔High molecular compound (F)〕

As described above, the layer (Y) may contain the polymer compound (F). The polymer compound (F) may have, for example, 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 acid anhydride group, and a salt of a carboxyl group.

Polymer (Fa), for example, polyethylene glycol; polyketone; polyvinyl alcohol, denatured polyvinyl alcohol containing 1 to 50 mol% of α-olefin units with a carbon number of 4 or less, polyvinyl acetal (for example, poly (Vinyl butyral) and other polyvinyl alcohol polymers; cellulose, starch, cyclodextrin and other polysaccharides; poly(meth)acrylic acid hydroxyethyl, poly(meth)acrylic acid, ethylene-acrylic acid copolymer, etc. Base) acrylic polymer; hydrolysate of ethylene-maleic anhydride copolymer, benzene Maleic acid-based polymers such as hydrolysates of ethylene-maleic anhydride copolymers and isobutylene-maleic anhydride copolymers, etc. Among these, a polyvinyl alcohol-based polymer is more preferable, and specifically, a polyvinyl alcohol and a modified polyvinyl alcohol containing 1 to 15 mole% of α-olefin units having a carbon number of 4 or less are preferable.

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

The molecular weight of the polymer (Fa) is not particularly limited. From the viewpoint of obtaining a multilayer structure having better gas barrier properties and mechanical strength, the number average molecular weight of the polymer (Fa) is preferably 5,000 or more. , More preferably 8,000 or more, 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 multilayer structure, the content of the polymer (Fa) in the layer (Y) is preferably 85% by mass or less when the mass of the layer (Y) is used as a reference (100% by mass). It is preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The polymer (Fa) may react with the components in the layer (Y), or it may not react.

The thickness of the layer (Y) (when the multilayer structure has more than two 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 thinning the layer (Y), the printing, During processing such as lamination, the dimensional change of the multilayer structure can be suppressed to a lower level. Furthermore, since the flexibility of the multilayer structure can be increased, its mechanical properties can approach the mechanical properties of the substrate itself. When the multilayer structure of the present invention has two or more layers (Y), from the viewpoint of gas barrier properties, the thickness of each layer (Y) is preferably 0.05 μm or more. The thickness of the layer (Y) can be controlled using the concentration of the coating liquid (T) described later used for forming the layer (Y) or its coating method.

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

[Manufacturing method of multilayer structure]

Since the descriptions of the multilayer structure of the present invention can be applied to the manufacturing method of the present invention, the repeated description will be omitted below. In addition, the description of the manufacturing method of the present invention is also applicable to the multilayer structure of the present invention.

The manufacturing method of the multilayer structure of the present invention includes, for example, a precursor layer forming step (i), a coating solution (T) containing a phosphate ester (BP) coating step (ii), and a gas barrier layer (Y) The manufacturing method of the forming step (iii), etc. In addition, the content of the compound (A), the inorganic phosphorus compound (BI), the phosphate ester (BP), and these mass ratios are as described above, and repeated explanations will be omitted in the manufacturing method.

[Step (i)]

Step (i) is to apply the coating liquid (S) containing the aluminum-containing compound (A) on the substrate (X), and form a layer (Y) precursor layer on the substrate (X). through From step (i), a structure containing the precursor layer of the substrate (X) and the layer (Y) can be prepared. The layer (Y) is in the case of a vapor-deposited layer (Ac) containing aluminum or a vapor-deposited layer (Ad) of aluminum oxide. These layers can be formed according to the general vapor deposition method described above. Therefore, the method of forming the precursor layer of the layer (Y1) containing the compound (Ab) will be described in detail below.

A preferred embodiment is that the coating liquid (S) (first coating liquid) can be prepared by mixing and reacting the metal oxide (Aa) and the inorganic phosphorus compound (BI) in a solvent. Specifically, for example, the coating liquid (S) is a method of mixing a dispersion liquid of a metal oxide (Aa) with a solution containing an inorganic phosphorus compound (B1); a dispersion liquid of a metal oxide (Aa) It can be prepared by adding or mixing inorganic phosphorus compound (BI). The temperature during the mixing is preferably 50°C or lower, more preferably 30°C or lower, and even more preferably 20°C or lower. The coating liquid (S) may contain other compounds (for example, polymer compound (F)), and if necessary, may contain acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid. At least one oxygen compound (Q).

The dispersion liquid of the metal oxide (Aa) can be, for example, a method using a known sol-gel method, for example, by mixing the compound (E), water, and an acid catalyst or organic solvent added if necessary to make the compound (E ) Condensation or hydrolysis condensation to prepare. When the compound (E) is condensed or hydrolytically condensed to obtain a dispersion of the metal oxide (Aa), if necessary, the resulting dispersion can be subjected to specific treatment (degumming in the presence of the aforementioned oxygen compound (Q), etc. )Wait. The solvent used is not particularly limited, and alcohols such as methanol, ethanol, and isopropanol; water; or mixed solvents of these are preferred.

The solution containing the inorganic phosphorus compound (BI) can be prepared by dissolving the inorganic phosphorus compound (BI) in a solvent. The solvent may be appropriately selected according to the type of inorganic phosphorus compound (BI), and it is better to contain water. As long as it does not hinder the dissolution of the inorganic phosphorus compound (BI), the solvent may include an organic solvent (for example, alcohols such as methanol).

The solid concentration of the coating liquid (S) is preferably 1-20% by mass, and 2-15% by mass from the viewpoint of the storage stability of the coating liquid and the coating property to the substrate (X) Preferably, 3 to 10% by mass is more preferable. The aforementioned solid content concentration can be calculated, for example, by dividing the mass of the solid content remaining after distilling off the solvent of the coating liquid (S) by dividing the mass of the coating liquid (S) for treatment.

The coating liquid (S), the viscosity measured using a Brookfield rotary viscosity meter (SB type viscometer: rotor No. 3, rotation speed 60rpm), at the temperature of the coating, at 3,000mPa. Below s is better, at 2,500mPa. Below s is better, with 2,000mPa. Below s is better. The viscosity is 3,000mPa. At s or less, the flatness of the coating liquid (S) can be improved, and a multilayer structure having a better appearance can be produced. In addition, the viscosity of the coating liquid (S) is 50 mPa. s is better than 100mPa. s above is better, with 200mPa. Above s is better.

There is no particular limitation in the coating solution (S). Among them, 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 better. The molar ratio of aluminum atoms to phosphorus atoms can be calculated by fluorescent X-ray analysis of the dry solids of the coating liquid (S).

The coating liquid (S) may be directly coated on at least one side of the substrate (X), or may be coated on the substrate (X) through another layer (J). In addition, before applying the coating liquid (S), the surface of the substrate (X) may be treated with a known fixed coating agent, or a known adhesive agent or the like may be applied to the surface of the substrate (X). The adhesion layer (I) may be formed on the surface of (X).

The coating method of the coating liquid (S) is not particularly limited, and a known method can be used. Coating methods, for example, casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, single-side kiss coat method , Extrusion coating method, molten strip coating method, sealed doctor blade (chamber doctor) combined use coating method, curtain coating method, strip coating method, etc.

Normally, in step (i), the precursor layer of the layer (Y1) is formed by removing the solvent in the coating liquid (S). The method for removing the solvent is not particularly limited, and a known drying method can be used. Drying methods, for example, hot air drying method, hot roller contact method, infrared heating method, microwave heating method and the like. The drying temperature is preferably below the temperature at which the base material (X) starts to flow. The drying temperature after applying 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 0.1 second to 1 hour, preferably 1 second to 15 minutes, and more preferably 5 to 300 seconds. Furthermore, it is preferable to perform heat treatment after drying treatment. The heat treatment temperature may be, for example, about 100 to 200°C or 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 1 second to 1 hour, and 1 second to 15 minutes is better, and 5 to 300 seconds is better.

[Step (ii)]

Step (ii) is to apply a coating solution (T) (second coating solution) containing a phosphate ester (BP) on the precursor layer before the layer (Y) obtained in step (i). The coating liquid (T) can be prepared by mixing a phosphate ester (BP) and a solvent. The solvent used in the coating liquid (T) can be appropriately selected according to the type of phosphate ester (BP), and is not particularly limited, and alcohols such as methanol, ethanol, isopropanol, etc.; water; Or these mixed solvents are preferable.

The concentration of the solid content in the coating solution (T) is preferably 0.01 to 60% by mass, preferably 0.1 to 50% by mass, and 0.2 to 40% from the viewpoint of the storage stability or coating properties of the solution % Is better. The solid content concentration can be obtained by the same method as described in the coating liquid (S). In addition, as far as the effect of the invention can be achieved, the coating liquid (T) may contain other components (for example, the polymer compound (F)) contained in the layer (Y).

After applying the coating liquid (T), a solvent removal treatment is performed to form a layer (Y) precursor layer. As with the application of the coating liquid (S), the method of applying the coating liquid (T) is not particularly limited, and a known method can be used.

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

[Step (iii)]

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

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

The preferred implementation of the manufacturing method of the multilayer structure of the present invention One aspect is that, after applying the coating liquid (S), a drying process (first drying process) is performed, 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 performed, followed by heat treatment (second heat treatment). At this time, 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 The higher the temperature, the better.

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 interposed by other members (for example, the adhesion layer (I), other layers (J )) and those laminated on the substrate (X) are also acceptable.

[Extrusion coating lamination]

The multilayer structure of the present invention can, for example, laminate the substrate (X) directly or via the adhesive layer (I) on the layer (Y), and then another layer (J) to directly or via the adhesive layer (I) ) In the way that the extrusion coating layer is legally formed, it may further have a layer formed by extrusion coating lamination. The law of the extrusion coating layer that can be used in the present invention is not particularly limited, and known methods can also be used. The typical extrusion coating method is to send the melted thermoplastic resin into the T-die and cool the thermoplastic resin taken out from the flat slot of the T-die to prepare a laminated film.

In the extrusion coating layer method, the most common example of a separate layer method will be explained as follows with reference to the drawings. An example of a device used by a separate layer is shown in Figure 5. 5 is a schematic diagram showing only the main part of the device, so it is different from the actual device. The device 50 of FIG. 5, It contains an extruder 51, a T-die 52, a cooling drum 53, and a rubber drum 54. The cooling drum 53 and the rubber drum 54 are arranged with the drum surfaces in contact with each other.

The thermoplastic resin is melted by heating in the extruder and extruded from the flat slot of the T-die 52 to form a resin film 502. On the other hand, the laminate 501 is sent out by a sheet feeding device (not shown in the figure), and is sandwiched between the cooling roller 53 and the rubber roller 54 together with the resin film 502. Between the cooling roller 53 and the rubber roller 54, the laminate 501 and the resin film 502 are sandwiched in a laminated state, and the laminate 501 and the resin film 502 are formed into an integrated laminate film (multilayer structure )503.

Extrusion coating layer methods other than the aforementioned separate layer method, for example, sandwich layer method, tandem layer method, etc. Sandwich lamination is a method for preparing a laminate by extruding molten thermoplastic resin to a substrate on one side and supplying a second substrate from another unwinder (unwinder) for lamination . The tandem lamination method is a method for making a laminate having 5 layers of composition content by connecting two laminators in series at a time.

When the above-mentioned laminate is used, a multilayer structure that can maintain high barrier properties after extrusion coating lamination and can reduce light transmission can be prepared.

[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) may be improved. Next layer (I) Resin can also be used. The adhesive layer (I) composed of an adhesive resin can be formed by treating the surface of the substrate (X) with a known fixed coating agent or applying a known adhesive to the surface of the substrate (X). The adhesive is preferably a two-liquid reactive polyurethane adhesive which is a mixture and reaction of a polyisocyanate component and a polyol component. In addition, in the fixing coating agent or the adhesive, by adding a small amount of additives such as a well-known silane coupling agent, the adhesiveness may be further improved. The silane coupling agent is, for example, a silane coupling agent having reactive groups such as an isocyanate group, an epoxy group, an amine group, a urea group, and a hydrogen sulfide group, etc., but it is not limited to these contents. When the base material (X) and the layer (Y) are strongly bonded through the adhesive layer (I), when the multilayer structure of the present invention is printed or laminated, the deterioration of the gas barrier property or appearance can be effectively suppressed In addition, the drop strength of the packaging material using the multilayer structure of the present invention can be improved. The thickness of the next layer (I) is preferably from 0.01 to 10.0 μm, preferably from 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 characteristics (for example, heat sealability, barrier properties, and mechanical properties). For the multilayer structures of the present invention, for example, the substrate (X) can be laminated directly or via the adhesive layer (I) on the layer (Y), and then directly or via the adhesive layer with other layers (J) (I) It is made by way of continuation or formation. Other layers (J), for example, an ink layer; a polyolefin layer, a thermoplastic resin layer such as an ethylene-vinyl alcohol copolymer resin layer, etc., are not limited to this content.

The multilayer structure of the present invention may contain a printed trade name Or the ink layer used for patterns, etc. The multilayer structures of the present invention can be prepared, for example, by laminating the substrate (X) directly or via the adhesive layer (I) on the layer (Y), and then directly forming the ink layer. The ink layer is, for example, a coating obtained by drying a liquid in which a polyurethane resin containing pigment (for example, titanium dioxide) is dispersed in a solvent, or a polyurethane resin containing no pigment or A film obtained by drying other resins as a main agent for ink or for forming photoresist for electronic circuit wiring. The method of applying the ink layer to the layer (Y) includes, in addition to the gravure printing method, various coating methods such as a bar coating method, a spin coating method, and an extrusion coating method. The thickness of the ink layer is preferably 0.5-10.0 μm, preferably 1.0-4.0 μm.

In the multilayer structure of the present invention, the phosphate ester (BP) has a phosphate group having a high affinity with the compound (A), and has a high affinity with the adhesive layer (I) or other layers (J) The hydroxyl group and the like can improve the adhesion between the layer (Y) and other layers. Therefore, even after the sterilization treatment, the interlayer adhesive force can be maintained, and the appearance defects such as peeling can be suppressed.

When the outermost layer of the multilayer structure of the present invention is a polyolefin layer, the multilayer structure can be given heat sealability, and the mechanical properties of the multilayer structure can be improved. From the viewpoint of improving heat sealability or mechanical properties, polypropylene or polyethylene is preferred. In addition, for the purpose of improving the mechanical properties of the multilayer structure, at least 1 selected from the group consisting of a film formed of polyester, a film formed of polyamide, and a film formed of a polymer containing hydroxyl groups A thin film is better. From the viewpoint of improving the mechanical properties, polyethylene terephthalate is preferred, and nylon-6 is preferred for polyamide. In addition, from the viewpoint that the entire layer has barrier properties, the hydroxyl group-containing polymer is copolymerized with ethylene-vinyl alcohol Good is better. In addition, between the layers, if necessary, a layer formed by a fixed coating layer or an adhesive may be provided.

[Structure of multilayer structure]

Specific examples of the structure of the multilayer structure of the present invention are shown below. Multi-layer structure may have other members (for example, adhesive layer (I), other layer (J)) other than the base material (X) and layer (Y), but in the following specific examples, the other members are omitted Record. In addition, in the following specific examples, a plurality of layers may be laminated or combined.

(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)/hydroxy-containing Polymer layer, (8) layer (Y)/hydroxyl-containing polymer layer/layer (Y), (9) layer (Y)/paper layer, (10) layer (Y)/paper layer/layer (Y) , (11) layer (Y)/inorganic vapor deposited layer/polyester layer, (12) layer (Y)/inorganic vapor deposited layer/polyamide layer, (13) layer (Y)/inorganic vapor deposited layer/polyolefin layer, (14) layer (Y)/inorganic vapor deposition layer/hydroxyl-containing polymer layer, (15) layer (Y)/polyester layer/polyamide 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-deposited layer /Hydroxyl-containing polymer layer/polyolefin layer, (18) polyester layer/layer (Y)/polyamide layer/polyolefin layer, (19) layer (Y)/polyamide layer/polyester layer/ Polyolefin layer, (20) layer (Y)/polyamide 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)/polyamide layer/polyolefin layer, (24 ) Polyolefin layer/layer (Y)/polyamide 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)/polyamide layer/polyolefin layer, (32) layer (Y)/ Polyamide layer/layer (Y)/polyolefin layer, (33) Polyamide layer/layer (Y)/polyolefin layer, (34) layer (Y)/polyester layer/paper layer, (35) layer (Y)/polyamide 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)/polyamide 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)/polyester 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 Vapor deposition layer/layer (Y)/polyester layer, (50) inorganic vapor deposition layer/layer (Y)/polyester layer/layer (Y)/inorganic vapor deposition layer, (51) inorganic vapor deposition layer/layer (Y)/poly Amine layer, (52) inorganic vapor deposition layer/layer (Y)/polyamide layer/layer (Y)/inorganic vapor deposition layer, (53) inorganic vapor deposition layer/layer (Y)/polyolefin layer, (54) inorganic Vapor deposited layer/layer (Y)/polyolefin layer/layer (Y)/inorganic vapor deposited layer

The protective sheet of the present invention is preferably one of (1) to (8), (11) to (33), and (49) to (54) in the above configuration.

Before the sterilization and after the sterilization, the multilayer structure of the present invention has an oxygen permeability of 2.0 mL/(m ² .day.atm) or less at 0.5 mL/(m ² .day.atm) or less, preferably 0.3mL/(m ² .day.atm) or less. The conditions of the sterilization treatment, the measurement method and the measurement conditions of the oxygen permeability are as described in the examples described later.

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

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

The multilayer structure and protective sheet of the present invention have an oxygen permeability of 2.0 mL/(m ² .day.atm) or less under the conditions of 20° C. and 85% RH before and after the temperature and humidity test. 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, the measurement method and the measurement conditions of the oxygen permeability are as described in the examples described later.

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

In addition, the multilayer structure and protective sheet of the present invention have a peel strength of the layer (Y) and the adhesive layer (I) or other layers (J) (for example, ink layer) after a temperature and humidity test exceeding 170 g/15 mm Whichever is better, more preferably 200g/15mm or more, more preferably 260g/15mm or more. The conditions of the temperature and humidity test, the measurement method and the measurement conditions of the peel strength are as described in the examples described later.

[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 even after sterilization treatment, they also have excellent gas barrier properties and water vapor barrier properties without peeling and other appearances Defective phenomenon, with adhesion between high layers (peel strength). Therefore, the multilayer structure of the present invention and the packaging material using the same can be applied to various uses.

〔Packaging Materials〕

The packaging material of the present invention is a multilayer structure including a base material (X) and a layer (Y) laminated on the base material (X). The packaging material may be composed of only a multilayer structure. That is, in the following description, "packaging material" may also be referred to as "multilayer structure". Also, typically, "packaging materials" can be called "packaging." Packaging materials can also be constructed from multilayer structures and other components to make.

The packaging material of the preferred embodiment of the present invention is suitable for inorganic gases (for example, hydrogen, helium, nitrogen, oxygen, carbon dioxide), natural gas, water vapor, and organic compounds that are liquid at normal temperature and pressure (for example, ethanol, petroleum gas) ) Has barrier properties.

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

The packaging material of the present invention can be prepared using various methods. For example, a sheet-like multilayer structure or a film material containing the multilayer structure (hereinafter, also simply referred to as "film material") can be joined and shaped according to a specific container shape to produce a container (packaging material) Also. Molding methods, for example, thermoforming, injection molding, extrusion flow molding, etc. Furthermore, a container (packaging material) may be produced by forming a layer (Y) on a base material (X) shaped into a specific container shape. The containers made by these methods are also called "packaging containers" in this specification.

The packaging material of the present invention is suitable for use as a packaging material for food. In addition, the packaging material of the present invention is not only suitable as a packaging material for food, but also suitable for packaging pesticides, medicines and other pharmaceuticals; medical equipment; mechanical parts, precision materials and other industrial materials; clothing materials and other packaging materials used.

Moreover, the packaging material containing the multilayer structure of the present invention, Various molded products can be produced using secondary processing. These molded products can be vertical bag filled sealed bags, vacuum packaging bags, pouches, laminated tubular containers, infusion solution bags (bags), paper containers, long bags, lid materials for containers, in-mold labels (In Mold Labeling) containers, vacuum insulation, or electronic devices. These molded products can also be heat-sealed.

〔Vertical bags filled with sealed bags〕

The packaging material containing the multi-layer structure of the present invention can be a vertical bag filled and sealed bag. This is shown in Figure 1, for example. The vertical bag-filled and sealed bag 10 shown in FIG. 1 is formed by sealing the multilayer structure 11 of the present invention with two ends 11a and a body 11b in a three-way manner. The vertical bag-filling sealed bag 10 can be manufactured using a vertical bag-filling machine. The method of using the vertical bag-filling mechanism bag can be performed by various methods, but in any method, the content is supplied to the inside of the upper opening of the bag, and then the opening is sealed to prepare the vertical bag filling and sealing bag. The vertical bag filling and sealing bag, for example, the upper end, the lower end, and the sides, can be composed of a heat-sealed film material. The vertical bag filled and sealed bag as a packaging container of the present invention has excellent gas barrier properties and water vapor barrier properties, and the barrier performance can also be maintained after sterilization treatment. Therefore, the vertical bag filled and sealed bag can suppress the content for a long period of time The quality of things deteriorates.

〔Pouch

The packaging material containing the multilayer structure of the present invention may be a pouch. This is shown in Figure 2 for example. Figure 2 flat pouch (flat pouch) 20, is composed of 2 pieces The multi-layer structure 11 is formed by joining its peripheral portions 11c to each other. In this specification, the term "bag" mainly means a container having a film material as a wall member with food, daily necessities, or pharmaceuticals as contents. Pouches, for example, can be divided into spout pouches, chain pouches, flat pouches, stand up pouches, horizontal pouches, sealed pouches according to their shape and usage, Sterilization bags (retort pouch), etc. The bag can be formed by laminating a multilayer structure with at least one other layer (J). The bag of the present invention as a packaging container has excellent gas barrier properties and water vapor barrier properties, and can maintain its barrier properties even after sterilization treatment. Therefore, when the bag is used, the contents can be prevented from deterioration even after being transported or after long-term storage. In addition, in the example of the bag, since good transparency can be maintained, it is easy to confirm the contents and confirm the deterioration of the contents due to the deterioration.

〔Infusion bag (bag)〕

The packaging material containing the multilayer structure of the present invention may be an infusion solution bag. The infusion solution bag is a container with a liquid preparation as its content, and it is provided with a film material that separates the inside and the outside of the infusion solution preparation as a partition wall. This is shown in Figure 3, for example. As shown in FIG. 3, in addition to the infusion bag body 431 storing the contents, the infusion bag (bag) may also be provided with a flap member 432 at the peripheral portion 412 of the infusion bag body 431. The orifice member 432 has a function as a path for taking out infusion liquid stored in the infusion bag body 431. In addition, on the infusion solution bag, for the purpose of hanging the infusion solution bag, the phase of the peripheral portion 412 on which the mouth stopper member 432 is installed The peripheral portion 411 on the opposite side may be provided with a hanging hole 433. The infusion bag body 431 is formed by two film materials 410a, 410b being joined to each other on the peripheral portions 411, 412, 413, 414. The film materials 410a and 410b function as a partition wall 420 between the inside of the infusion solution bag and the outside of 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 solution bag as a packaging container of the present invention has excellent gas barrier properties, and can still maintain its gas barrier properties after sterilization treatment such as hot water treatment. Therefore, the infusion solution bag can prevent the filled liquid medicine from being deteriorated even before the heat sterilization treatment, during the heat sterilization treatment, after the heat sterilization treatment, after transportation, and after storage.

[In Mold Labeling Container]

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

An example of the method of manufacturing a container in the present invention is that the first step of arranging the multilayer label of the present invention in the cavity between the female model part and the male model part, and the method of pouring molten resin into the cavity, simultaneously The second step of forming the container body and applying the multilayer label of the present invention to the container body. Except for the use of the multilayer label of the present invention, each step can be implemented using a well-known method.

An exemplary cross-sectional view of one container of the present invention is shown in FIG. 4. The container 360 includes a cup-shaped container body 370 and multi-layer labels 361-363 attached to the surface of the container body 370. Multilayer labels 361-363 are multilayer labels of the present invention. The container body 370 includes a flange portion 371, a body portion 372, and a bottom portion 373. The flange portion 371 has a convex portion 371a protruding up and down at the front end. The multilayer label 361 is arranged so as to cover the outer surface of the bottom 373. In the center of the multilayer label 361, a through hole 361a for resin injection is formed when the in-mold label is formed. The multilayer label 362 is arranged so as to cover the outer surface of the body portion 372 and the lower surface of the flange portion 371. The multilayer label 363 is arranged so as to cover a part of the inner surface of the body portion 372 and the upper surface of the flange portion 371. The multi-layer labels 361 to 363 are fused to the container body 370 through an in-mold label forming method, and are integrated with the container body 360. As shown in FIG. 4, the end surface of the multilayer label 363 is fused to the container body 360 and is not exposed to the outside.

〔Vacuum heat insulator〕

The product of the present invention using the aforementioned packaging material as at least a part may be a vacuum heat insulator. The vacuum insulation body is a heat insulation body provided with a coating material and a core material arranged inside surrounded by the coating material, and the inside of the core material is arranged in a reduced pressure state. The vacuum insulation body can achieve a heat insulation property equal to that of the heat insulation body formed of the polyurethane foam with a lighter and thinner heat insulation body. The vacuum insulation body of the present invention can be used as a heat insulation material for household appliances such as refrigerators, water heaters and electric pots; walls, Insulation materials for residential use, vehicle roof materials, heat insulation boards for vending machines, etc. used in ceilings, eaves interiors, floors, etc.; heat moving equipment such as heat storage equipment, heating pump application equipment, etc. The multilayer structure of the present invention used as a coating material may also contain an ethylene-vinyl alcohol copolymer resin layer and an inorganic vapor deposition layer, for example, may have a polyester layer/layer (Y)/polyester layer/layer (Y)/ Composition of inorganic vapor deposition layer/ethylene-vinyl alcohol copolymer layer/polyolefin layer.

An example of the vacuum heat insulator of the present invention is shown in FIG. 6. The vacuum heat insulator 601 of FIG. 6 is composed of a core material 651 in the form of particles, and two sheets of the multi-layer structure 631,632 of the present invention as the coating material covering it. Two sheets of the multi-layer structure 631,632 are at the periphery In 611, they are engaged with each other. The internal space formed by the two-piece multilayer structure 631, 632 is filled with the core material 651, and the internal space is in a decompressed state. The multilayer structures 631 and 632 have a function as a partition that blocks the inside and the outside of the core material 651, and is closely adhered to the core material 651 through the pressure difference between the inside and the outside of the vacuum heat insulator 601. The inside of the core material 652 is in a decompressed state.

Another example of the vacuum heat insulator of the present invention is shown in FIG. 7. 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. The molded body is the core material 652 of the molded body, and a typical example is 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, silica powder, precipitated silica powder, diatomaceous earth, silicic acid Calcium, glass wool, asbestos, artificial (synthetic) cotton, resin foam (for example, styrene foam, polyurethane foam), etc. For the core material, a hollow container, a honeycomb structure, etc. formed by a specific shape can be used.

〔Electronic device〕

The packaging material including the multilayer structure of the present invention can also be used in electronic devices. An example of an electronic device of the present invention, a partial cross-sectional view is shown in FIG. 8. The electronic device 40 of FIG. 8 includes an electronic device body 41, a sealing material 42 that seals the electronic device body 41, and a protective sheet (multilayer structure) 43 that protects 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 the sealing material 42. The surface opposite to the surface on which the protective sheet 43 is arranged may also be arranged with the protective sheet 43. In this case, the protective sheet arranged on the surface on the opposite side may be the same as or different from the protective sheet 43. The protective sheet 43 may be disposed on the electronic device body 41 via other members such as the sealing material 42 or may be directly disposed 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, electronic papers; lighting devices such as organic EL light-emitting elements. The sealing material 42 can be appropriately added to any component according to the type and application of the electronic device body 41. The sealing material 42 is, for example, 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, silicon-based solar cells, compound semiconductor solar cells, organic thin-film solar cells, etc. Silicon-based solar cells, for example, monocrystalline silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, etc. Compound semiconductor solar cells, for example, group III-V compound semiconductor solar cells, group II-VI compound semiconductor solar cells, group I-III-VI compound semiconductor solar cells, and the like. In addition, the solar cell may be an integrated solar cell obtained by connecting a plurality of unit cells in series, or a non-integrated solar cell.

The multilayer structure of the present invention and the packaging material containing it are suitable for use as display members such as LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films, etc.; IC label films , Solar cell module, solar cell back sheet, solar cell protective film and other solar cell components. When the multilayer structure is used as a member of a display, it can be used as a low-reflection film, for example. In any case, when the multilayer structure requires light transmission, the layer (Y) may use a layer (Y) having light transmission.

The electronic device body 41 can also be produced by a so-called roll-to-roll method according to its type. In the roll-to-roll method, a flexible substrate (for example, a stainless steel substrate, a resin substrate, etc.) that is curled on the delivery roller can be delivered, and the electronic device body 41 can be manufactured by forming an element on the substrate Then, the electronic device body 41 is wound up on the winding drum. At this time, the protective sheet 43 may also be prepared in the form of a flexible long sheet, more specifically, to prepare for The shape of the curled body of the long thin sheet. For example, the protective sheet 43 sent out by the feed roller is laminated on the electronic device body 41 before being taken up by the take-up roller, and is taken up together with the electronic device body 41. Another example is a method in which the electronic device body 41 wound around the winding drum is sent out in advance, and then laminated with the protective sheet 43. In a preferred example of the present invention, the electronic device itself is flexible.

The protective sheet 43 is a multilayer structure containing the present invention. The protective sheet 43 may be composed of only a multilayer structure. Or, the protective sheet 43 may contain a multilayer structure, and may be other members laminated on the multilayer structure (for example, other layers (J)). The protective sheet 43 is a layered laminate suitable for protecting the surface of an electronic device, and when the aforementioned multilayer structure is included, its thickness and material are not particularly limited.

The protective sheet, for example, may include a surface protective layer disposed on one side surface or both side surfaces of the multilayer structure. The surface protection layer is preferably a layer formed of a resin that is not easily damaged. In addition, like a solar cell, when it is a surface protective layer of a device used outdoors, it is preferably formed of a resin with high weather resistance (for example, light resistance). In addition, when protecting the surface that must pass through the light, a surface protection layer with high transparency is preferred. The material of the surface protective layer (surface protective film), for example, poly(meth)acrylate, polycarbonate, polyethylene terephthalate, polyethylene 2,6-naphthalene dicarboxylate, 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) etc. An example of the protective sheet includes a poly(meth)acrylate layer disposed on one surface.

系之紫外線吸收劑等，但並不僅限定於該些內容。又，亦可併用其他之安定劑、光安定劑、抗氧化劑等。 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 a surface protective layer with high weather resistance is an acrylic resin layer added with an ultraviolet absorber. UV absorbers, for example, benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, trivalent

The ultraviolet absorber, etc., but not limited to these contents. In addition, other stabilizers, light stabilizers, antioxidants, etc. may be used in combination.

[Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these embodiments. Within the technical idea of the present invention, persons with ordinary knowledge in the field can make various changes. . The analysis and evaluation performed in the following examples and comparative examples are performed in the following manner.

(1) Determination of infrared absorption spectrum

Using Fourier transform infrared spectrophotometer, it was measured according to the attenuation total reflection method. The measurement conditions are shown below.

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

Measurement mode: Attenuated total reflection method

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

(2) Thickness measurement of each layer

A focused ion beam (FIB) was used to cut the multilayer structure to prepare a slice for cross-sectional observation. The prepared slices were fixed on the sample table using carbon tape, and platinum ion sputtering was performed at an acceleration voltage of 30 kV for 30 seconds. Observe the cross-section of the multilayer structure using an electric field emission transmission electron microscope and calculate the thickness of each layer. The measurement conditions are shown below.

Device: JEM-2100F manufactured by Japan Electronics Corporation

Acceleration voltage: 200kV

Magnification: 250,000 times

(3) Measurement of oxygen permeability

A sample is installed on the oxygen permeability measuring device with the layer of the base material facing the carrier gas side, and the oxygen permeability is measured by the isobaric method. The measurement conditions are shown below.

Device: MOCON OX-TRAN2/20 made by Hyundai Control Company

Temperature: 20℃

Humidity on the oxygen supply side: 85% RH

Humidity of carrier gas side: 85% RH

Oxygen pressure: 1.0atm

Carrier gas pressure: 1.0atm

(4) Determination of moisture permeability

On the water vapor transmission rate measuring device, install the sample with the layer of the base material facing the carrier gas side, and use the isobaric method to measure the moisture permeability (water vapor Transmittance). The measurement conditions are shown below.

Device: MOCON PERMATRAN W3/33 made by Hyundai Control Corporation

Temperature: 40℃

Humidity on the water vapor supply side: 90% RH

Humidity of carrier gas side: 0% RH

(5) Adequacy assessment

The adhesion was evaluated using a T-shaped peel strength measurement (adhesion force at each 15 mm width). Five measurements were made and the average value was taken. The measurement conditions are shown below.

Device: Autoclave AGS-H manufactured by Shimadzu Corporation

Peeling speed: 250mm/min

Temperature: 23℃

Humidity: 50% RH

<Manufacturing example of coating liquid (S-1)>

230 mass parts of distilled water was heated to 70 degreeC with stirring. 88 parts by mass of aluminum triisopropoxide was dropped into this distilled water over 1 hour, the liquid temperature was gradually raised to 95°C, and the produced isopropanol was distilled off for hydrolysis and condensation. To the obtained liquid, 4.0 parts by mass of a 60% by mass nitric acid aqueous solution was added, and the mixture was stirred at 95° C. for 3 hours to degel the particle condensate of the hydrolyzed condensate. Subsequently, the liquid was concentrated to a solid concentration of 10% by mass in terms of alumina, and a solution was prepared. For the solution obtained in this way 22.50 parts by mass, 54.29 parts by mass of distilled water and 18.80 parts by mass of methanol were added, and the mixture was stirred to make a dispersion. Subsequently, the liquid temperature was maintained at 15 ℃ state, in the continuous stirring dispersion, 84.1 mass parts of phosphoric acid aqueous solution of 4.41 parts by mass was added dropwise, and stirring was continued at 15 ℃ until the viscosity reached 1,500 mPa. s, the desired coating solution (S-1). In this coating solution (S-1), the molar ratio of aluminum atoms to phosphorus atoms is aluminum atoms: phosphorus atoms = 1.15: 1.00.

<Synthesis example of poly(2-phosphonooxyethyl methacrylate) (PPEM)>

Under a nitrogen atmosphere, 8.5 g of 2-phosphonooxyethyl methacrylate and 0.1 g of azobisisobutyronitrile were dissolved in 17 g of methyl ethyl ketone and stirred at 80° C. for 12 hours. After cooling, the resulting polymerization solution was added to 170 g of 1,2-dichloroethane, and the target polymer was recovered as a precipitate through decantation treatment. Subsequently, the polymer was dissolved in tetrahydrofuran, 1,2-dichloroethane was used as a lean solvent, and reprecipitation purification was performed. After reprecipitation purification three times, vacuum drying was performed at 50°C for 24 hours to obtain the desired PPEM. According to GPC analysis results, the number average molecular weight of the polymer is 2,950 in terms of polystyrene.

<Synthesis example of poly(ethylenephosphonic acid) (PVPA)>

Under a nitrogen atmosphere, 10 g of ethylenephosphonic acid and 0.025 g of 2,2'-azobis(2-carboxamidopropane) 2 hydrochloride were dissolved in 5 g of water, and stirred at 80°C for 3 hours. After cooling, 15 g of water was added to the polymerization solution for dilution, and the cellulose membrane was used by Spectrum Laboratories <Spectra/ Por (registered trademark)> filter. After distilling off the water in the filtrate, vacuum drying was carried out at 50°C for 24 hours to obtain the desired PVPA. According to GPC analysis results, the number average molecular weight of the polymer is 10,800 in terms of polyethylene glycol.

<Synthesis Example of Phosphate (BP-1)>

Using a phosphoric acid esterification rate R _BP =0.67, 0.71 parts by mass of 85% by mass phosphoric acid aqueous solution and 5% by mass of polyvinyl alcohol ("KURARAY-POVAL (registered trademark) PVA124" manufactured by KURARAY Co., Ltd.; saponification degree 98.5 mol) %, viscosity average polymerization degree 2,400, 4 mass% aqueous solution viscosity at 20°C 60mPa.s) 8.0 parts by mass of aqueous solution were mixed, and stirred at 25°C for 1 hour. Subsequently, water was distilled off from the obtained mixed liquid using a rotary evaporator, and the depressurization treatment was carried out at 40°C for 12 hours to obtain a dry solid. This dry solid substance was subjected to a heat treatment at 120°C for 3 minutes using a hot air dryer to obtain a phosphoric acid ester (BP-1) white solid of the target substance. By measuring the infrared absorption spectrum of the phosphate ester (BP-1), it was confirmed that there was a specific absorption of the P=O stretching vibration of the phosphate ester at 1,250 to 1,300 cm ^-1 .

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

The phosphate ester (BP-1) was dissolved in a mixed solvent of 69.30 parts by mass of water and 29.70 parts by mass of methanol to obtain a coating solution (T-1) with a solid content concentration of 1.0% by mass.

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

0.71 parts by mass of 85% by mass phosphoric acid aqueous solution and 5% by mass of polyvinyl alcohol ("KURARAY-POVAL (registered trademark) PVA124" manufactured by KURARAY Co., Ltd.; saponification degree 98.5 mol%, average viscosity polymerization degree 2,400, at 20 ℃ 4% by mass aqueous solution viscosity 60mPa.s) 8.0 parts by mass of aqueous solution, dissolved in a mixed solvent of 61.59 parts by mass of water and 29.70 parts by mass of methanol to obtain a coating solution (T-2) with a solid concentration of 1.0% by mass.

The details of the films used in Examples and Comparative Examples are shown below.

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

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

3) ONY: stretch nylon film; "EMBLEM ONBC" (trade name) manufactured by UNITIKA Corporation, 15 μm thick

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

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

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

[Example 1] <Example 1-1>

First, PET12 (hereinafter, also simply referred to as "X-1") as a base material (X) is prepared. On this substrate, a bar coater was used to apply the coating liquid (S-1) so that the thickness after drying was 0.3 μm. After the coated film was dried at 110°C for 5 minutes, the film was heat-treated at 160°C for 1 minute, and a precursor (Y-1-1) was formed on the substrate. In addition, the coating liquid (S-1) was applied so that the coating amount of phosphate ester (BP) reached 30 mg/m ² using a bar coater, and dried at 110° C. for 3 minutes. Subsequently, heat treatment at 220°C for 1 minute was performed to form a layer (Y-1-1). In this way, a multilayer structure (1-1-1) having a structure of base material (X-1)/layer (Y-1-1) was produced.

By measuring the infrared absorption spectrum of the multilayer structure (1-1-1), it is found that the maximum absorption wavenumber in the region of 800~1,400 cm ^-1 is 1,108 cm ^-1 , and the half-height width of the maximum absorption band is ( FWHM) is 37 cm ^-1 .

An ink layer was formed on the obtained multilayered structure (1-1-1), and it was allowed to stand at 40°C for 1 day for etching. Subsequently, an adhesive layer is formed, and ONY is 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 it was etched by standing at 40°C for 5 days. In this way, a multilayer structure (1-1-2) having a structure of the substrate (X-1)/layer (Y-1-1)/ink layer/adhesive layer/ONY/adhesive layer/CPP can be formed . Using a bar coater, coat the two adhesive layers with a thickness of 3 μm after drying to apply a 2-liquid type joint. The agent is formed after drying. The two-component adhesive is "A-525S" (trademark) using "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "A-50" (registered trademark) using "TAKANATE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. "(Trademark) and the formed two-liquid reactive polyurethane adhesive. In addition, the aforementioned ink layer is formed by coating with a bar coater so that the thickness after drying is 2 μm, and drying. The ink used "F641" (registered trademark) "F641STAR white" (trademark) manufactured by Toyo Ink Co., Ltd. and "LP Super Hardener" (trademark) manufactured by Toyo Ink Co., Ltd. and the resulting ink. The oxygen permeability and moisture permeability of the multilayer structure (1-1-2) were measured. The results are shown in Table 1.

The multilayer structure (1-1-2) was heat-sealed to make a pouch, and 100 g of water was filled in the pouch. Subsequently, the resulting bag was sterilized according to the following conditions (hot water storage type).

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

Temperature: 130℃

Time: 30 minutes

Pressure: 0.21MPaG

Immediately after the hot water treatment, the measurement sample was cut from the bag, and the oxygen permeability, moisture permeability, and T-peel strength of the sample were measured according to the above method. In addition, in the multilayer structure (1-1-2), no appearance defects such as peeling were observed.

<Examples 1-2~1-6>

Except that the phosphate esterification rate R _BP and coating amount of the phosphate ester (BP) were changed according to the content of Table 1, the multilayer structure (1-1-2) of Example 1-1 was used to produce the same method Multi-layer structure (1-2-2) ~ (1-6-2), and evaluate. As in Example 1-1, in the multilayer structures (1-2-2) to (1-6-2), no appearance defects such as peeling were observed.

<Comparative Examples 1-1~1-3>

Except that the phosphate ester compound (BP) was changed to poly(methacrylic acid 2-phosphonooxyethyl) (PPEM) and poly(vinylphosphonic acid) (PVPA), all others were in accordance with Table 1 and according to Example 1. The multi-layer structure (1-1-2) of -1 is a multi-layer structure (C1-1-2) to (C1-3-2) made by the same method and evaluated.

The manufacturing conditions of the multilayer structure of Examples and Comparative Examples are shown in Table 1.

[Example 2] Longitudinal bag filling and sealing bag <Example 2-1>

The multilayer structure (1-1-2) produced in Example 1-1 was cut with a width of 400 mm, and the CPP layers were in contact with each other for heat sealing, and supplied to a vertical bag-filling packaging machine (ORIHIRO Co., Ltd. system). A vertical bag-filling sealed bag (2-1-3) (width 160 mm, length 470 mm) was produced by a vertical-type bag-filling and packaging machine as shown in FIG. 1. And measure the oxygen permeability and moisture permeability of the vertical bag filled sealed bag (2-1-3) before sterilization treatment. The results are shown in Table 2. A pouch was prepared by heat-sealing a vertical bag-filled sealed bag (2-1-3), and 300 mL of water was filled into the bag. Subsequently, the resulting bag was subjected to sterilization treatment under the same conditions as in Example 1-1 (hot water storage type).

Immediately after the hot water treatment, the measurement sample was cut from the bag, and the oxygen permeability, moisture permeability, and T-peel strength of the sample were measured according to the above method. The results are shown in Table 2. In addition, the samples after hot water treatment did not show any appearance defects such as peeling.

<Examples 2-2~2-6 and Comparative Examples 2-1~2-3>

Except for using the multilayer structures (1-2-2)~(1-6-2) and (C1-1-2)~(Examples 1-2~1-6 and Comparative Examples 1-1~1-3 C1-3-2) Except for replacing the multilayer structure (1-1-2), the others are prepared in the same manner as in Example 2-1, where the vertical bag filled and sealed bag (2-1-3) is produced Bag-filling sealed bags (2-2-3)~(2-6-3) and (C2-1-3)~(C2-3-3). Subsequently, the resulting longitudinal bags The sealed bag was filled, and various items were measured in the same manner as in Example 2-1. The results are shown in Table 2.

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

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

Subsequently, 100 mL of water was filled in a flat bag (3-1-3) and subjected to sterilization treatment under the same conditions as in Example 1-1 (hot water storage type). Immediately after hot water treatment, a sample for measurement was cut from a flat bag, and the oxygen permeability, moisture permeability, and T-peel strength of the sample were measured according to the above method. The results are shown in Table 3. At this time, the samples after hot water treatment did not show any appearance defects such as peeling.

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

Except for the use of the multilayer structures (1-2-2) to (1-6-2) and (C1-1-2 produced in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 )~(C1-3-2) except for the multi-layer structure (1-1-2), the others are made in the same way as the flat bag (3-1-3) of Example 3-1 Bags (3-2-3)~(3-6-3) and (C3-1-3)~(C3-3-3). The obtained flat bags were measured in the same manner as in Example 3-1. The results are shown in Table 3.

[Example 4] Infusion solution bag <Example 4-1>

For the multilayer structure (1-1-2) produced in Example 1-1, two pieces of 120 mm×100 mm multilayer structure were cut out. Subsequently, the two cut multilayer structures were stacked with the CPP layer as the inner side, and while heat sealing the periphery, a spout (mouth plug member) made of polypropylene was provided through heat sealing. In this way, an infusion solution bag (4-1-3) having the same structure as FIG. 3 is prepared. And measure the oxygen permeability and moisture permeability of the infusion solution bag (4-1-3) before sterilization treatment. The results are shown in Table 4.

Subsequently, 100 mL of water was filled in the infusion solution bag (4-1-3), and sterilization treatment (hot water storage type) was performed under the same conditions as in Example 2-1. Immediately after hot water treatment, the measurement sample was cut from the infusion solution bag, and the oxygen permeability, moisture permeability, and T-peel strength of the sample were measured according to the above method. The results are shown in Table 4. At this time, no appearance defects such as peeling were observed in the samples.

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

Except for the use of the multilayer structures (1-2-2) to (1-6-2) and (C1-1-2 produced in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 )~(C1-3-2) except for the multi-layer structure (1-1-2), the others are prepared in the same way as the infusion solution bag (4-1-3) of Example 4-1. Infusion solution bags (bag) (4-2-3)~(4-6-3) and (C4-1-3)~(C4-3-3). The obtained infusion solution bags were subjected to the measurement of various items in the same manner as in Example 4-1. The results are shown in Table 4. Show.

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

For the multilayer structure (1-1-2) produced in Example 1-1, a circular multilayer structure with a diameter of 100 mm was cut out and used as a cover material for containers. In addition, the container body is intended to prepare a container with a flange (made by Toyo Can Co., Ltd., "Hiretoflex" (registered trademark), "HR78-84" (trade name)). The container has a cup shape with 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 formed on the periphery is 6.5 mm. The container is composed of a three-layer laminate of olefin layer/steel layer/olefin layer. Secondly, fill the above-mentioned container body with water to almost full cup, after As a result of heat sealing the lid material to the flange portion, a container (5-1-3) with a lid can be obtained. At this time, the CPP layer of the cover material is arranged so as to contact the flange portion, and the cover material is heat-sealed. A sample for measurement of a square with a side length of 4.5 cm is cut from the cover material of the container with a lid (5-1-3), and placed on a 10 cm square aluminum foil (thickness 30 μm) on a cut circle with a diameter of 2.0 cm. The sample and the aluminum foil were sealed with a two-liquid curing type epoxy adhesive. Using this sample, the oxygen permeability and moisture permeability before sterilization treatment were measured. The results are shown in Table 5.

Subsequently, the covered container (5-1-3) was subjected to sterilization treatment under the same conditions as in Example 1-1 (hot water storage type). After the hot water treatment, the measurement sample was immediately cut from the cover material, and the oxygen permeability and the moisture permeability of the sample were measured in the same way as before the sterilization treatment. The T-peel strength was measured according to the above method. The results are shown in Table 5. At this time, no appearance defects such as peeling were observed in the samples.

<Examples 5-2 to 5-6 and Comparative Examples 5-1 to 5-3>

Except for the use of the multilayer structures (1-2-2) to (1-6-2) and (C1-1-2 produced in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 )~(C1-3-2) except for the multi-layer structure (1-1-2), the other methods are the same as the method of making the container (5-1-3) with the lid in Example 5-1, The containers with cover (5-2-3)~(5-6-3) and (C5-1-3)~(C5-3-3) were prepared. The obtained containers with respective lids were measured in the same manner as in Example 5-1. The results are shown in Table 5.

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

Two pieces of CPP100 were applied using a bar coater, and the two-component adhesive was applied and dried to a thickness of 3 μm after drying. Two-component adhesive is formed by using "A-525S" of "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "A-50" of "TAKANATE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. The two-liquid reactive polyurethane adhesive. Next, two pieces of CPP100 were laminated with the multilayer structure (1-1-1) of Example 1-1, and were left to stand at 40°C for 5 days for etching. In this way, a multilayer label (6-1-2) having a structure of CPP/adhesive layer/substrate (X-1)/layer (Y-1-1)/adhesive layer/CPP can be produced. The oxygen permeability and moisture permeability of the obtained multilayer label (6-1-2) were measured according to the above method. The results are shown in Table 6.

The multilayer label (6-1-2) is cut in accordance with the shape of the inner wall surface of the female model part of the container forming casting mold, and mounted on the inner wall surface of the female model part. Next, squeeze the male model part into the female model part. Next, molten polypropylene ("EA7A" of "NOVATEC" (registered trademark) manufactured by Japan Polypro Co., Ltd.) was injected into the cavity between the male model part and the female model part at 220°C. In this way, by performing injection molding, the intended container (6-1-3) is formed. The thickness of the container body is 700 μm, and the surface area is 83 cm ² . The entire outer side of the container is covered with a multi-layer label (6-1-2), and the connecting hole is overlaid with a multi-layer label (6-1-2). At this time, the multi-layer label was not peeled between layers, and the appearance of the container (6-1-3) was good.

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

Except for the use of the multilayer structures (1-2-1) to (1-6-1) and (C1-1-1 produced in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 )~(C1-3-1) except for the multilayer structure (1-1-1), the others are prepared in the same way as the multilayer label (6-1-2) of Example 6-1. Multi-layer labels (6-2-2)~(6-6-2) and (C6-1-2)~(6-3-2). Secondly, in addition to using (6-2-2)~(6-6-2) and (C6-1-2)~(6-3-2) instead of the multilayer label (6-1-2 of Example 6-1) ), all others are produced in the same way as the container (6-1-3). The containers (6-2-3)~(6-6-3) and (C6-1-3)~( C6-3-3). The appearance of the in-mold label containers (6-2-3) to (6-6-3) is good. On the other hand, in the obtained in-mold label containers (C6-1-3) to (C6-3-3), no delamination phenomenon was observed. The obtained multi-layer labels were tested for various items in the same way as in Example 6-1 set. The results are shown in Table 6.

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

In Example 1-1, after forming an adhesive layer on the layer (Y) on the multilayer structure (1-1-1), a polyethylene resin (density; 0.917 g/cm ³ , melt flow rate; 8 g (/10 minutes) At a thickness of 20 μm, the coating layer was extrusion-coated at 295° C. on the adhesive layer. In this way, a laminate (7-1-2) having a structure of base material (X-1)/layer (Y-1-1)/adhesive layer (I-1)/polyethylene was prepared. The adhesive layer (I-1) is formed by coating a two-component adhesive with a bar coater so that the thickness after drying is 0.3 μm. The two-component adhesive is used for "A-3210" of "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "A-3070" for "TAKANATE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. The formed two-liquid reactive polyurethane adhesive.

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

<Examples 7-2 to 7-6 and Comparative Examples 7-1 to 7-3>

In addition to using the multilayer structures (1-2-1) to (1-6-1) and (C1-1-1) to (1-2-1 to 1-6 and Comparative Examples 1-1 to 1-3) C1-3-1) Instead of the multi-layer structure (1-1-1), the others were all prepared in the same manner as in Example 7-1 to obtain laminates (7-2-2) to (7-6-2) And (C7-1-2)~(C7-3-2). The laminates (C7-1-2) ~ (C7-3-2) were found to have a partial delamination during winding. The obtained laminates were measured for each item in the same manner as in Example 7-1. The results are shown in Table 7.

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

The flat bag (3-1-3) prepared in Example 3-1 was filled with 500 mL of a 1.5% ethanol aqueous solution, and a sterilization treatment device (Flavor Ace RCS-60 manufactured by Nisaka Manufacturing Co., Ltd.) was used at 120°C, 0.15 Under MPaG, sterilize in hot water for 30 minutes. The sample for measurement was cut out from the flat bag after sterilization treatment, and the oxygen permeability of the sample was measured. The oxygen permeability of this sample was 0.2 mL/(m ² .day.atm).

<Example 8-2~8-9>

Except that 500 mL of other fillers were used instead of 500 mL of 1.5% ethanol aqueous solution and filled in a flat bag (3-1-3), the others were sterilized in the same manner as in Example 8-1. Subsequently, a 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, a 1.0% ethanol aqueous solution (Example 8-2), edible vinegar (Example 8-3), a pH 2 aqueous solution of citric acid (Example 8-4), and edible oil (Example 8) -5), tomato paste (Example 8-6), soy sauce (Example 8-7), and ginger paste (Example 8-8). In any case, the oxygen permeability of the sample after sterilization treatment is 0.2mL/(m ² .day.atm). In addition, in the container with a lid (5-1-3) prepared in Example 5-1, in order to fill the almost full cup of marmalade, the others are sterilized in the same manner as in Example 8-1 (Example 8- 9). A sample for measurement was cut out from the lid material of the container with a lid after sterilization treatment, and the oxygen permeability of the sample was measured to find that the oxygen permeability was 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 shows good barrier performance even after sterilization treatment in a state filled with various foods.

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

The two-component adhesive used in Example 6-1 was applied to CPP60 so that the thickness after drying was 3 μm, and the adhesive layer was formed after drying. This CPP was bonded to the PET layer of the multilayer structure (1-1-2) produced in Example 1-1 to obtain a laminate (9-1-1). Subsequently, the aforementioned two-liquid reactive polyurethane adhesive was applied to ONY in such a way that the thickness after drying was 3 μm, and the adhesive layer was formed after drying. Subsequently, this ONY was laminated with the laminate (9-1-1) to obtain a multilayer structure (9-1-2) having a structure of CPP/adhesive layer/multilayer structure/adhesive layer/ONY.

The multilayer structure (9-1-2) was cut to obtain two laminates with a size of 70 cm × 30 cm. The two-piece laminate was bonded with the CPP layers as inner surfaces, and the three sides were heat-sealed at 10 mm to produce a three-sided bag (open bag). Next, the opening of the three-square bag is filled with a heat-insulating core material, and the three-square bag is sealed using a vacuum packaging machine at 20°C and an internal pressure of 10 Pa. In this way, a vacuum heat insulator (9-1-3) was prepared. The core material of heat insulation is silicon dioxide fine powder. After placing the vacuum heat insulator (9-1-3) at 40°C and 15% RH for 360 days, use Piran The Ni vacuum gauge measured the internal pressure of the vacuum insulation body and found 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 water vapor permeability of the sample were measured.

Using a constant temperature and humidity machine, under the atmospheric pressure, 85 ℃, 85% RH atmosphere, the vacuum insulation body (9-1-3) was stored for 1,000 hours test (temperature and humidity test), the vacuum insulation body (9-1-3) Cut out the sample for measurement, and measure the oxygen permeability, moisture permeability, and T-peel strength of the sample according to the above method. The results are shown in Table 8. In addition, the sample did not show any appearance defects such as peeling.

<Examples 9-2 to 9-6 and Comparative Examples 9-1 to 9-3>

Except for using the multilayer structures (1-2-2)~(1-6-2) and (C1-1-2)~(Examples 1-2~1-6 and Comparative Examples 1-1~1-3 C1-3-2) Substitute for the multi-layer structure (1-1-2), the other method is the same as the manufacturing method of the vacuum heat insulator (9-1-3) of Example 9-1, and the vacuum is obtained Heat insulation (9-2-3)~(9-6-3) and (C9-1-3)~(C9-3-3). The vacuum insulation bodies obtained were measured in the same manner as in Example 9-1. The results are shown in Table 8.

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

An adhesive layer was formed on the multilayer structure (1-1-1) produced 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 way, a protective sheet (10-1-2) composed of PET/adhesive layer/substrate (X-1)/layer (Y-1-1)/adhesive layer/acrylic resin film can be produced. The above two adhesive layers are formed by applying two-component adhesives so as to have a thickness of 3 μm after drying, and drying them. The two-component adhesive is formed by using "A-1102" of "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "A-3070" of "TAKANATE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. Part 2 Liquid Reactive Polyurethane Ester adhesive. The oxygen permeability and moisture permeability of the obtained protective sheet (10-1-2) were measured. The results are shown in Table 9.

Subsequently, the durability test of the obtained protective sheet (10-1-2) was to use a constant temperature and humidity testing machine under atmospheric pressure, 85°C, 85% RH atmosphere for 1,000 hours to store the protective sheet test (temperature Wet test). The protective sheet after the test, the results of measuring oxygen permeability and moisture permeability are shown in Table 9. In addition, the evaluation results of the adhesion of the protective sheet are shown in Table 9. No appearance defects such as peeling were found.

<Examples 10-2 to 10-6 and Comparative Examples 10-1 to 10-3>

In addition to using the multilayer structures (1-2-1) to (1-6-1) and (C1-1-1) to (1-2-1 to 1-6 and Comparative Examples 1-1 to 1-3) C1-3-1) The protective sheets (10-2-2) to (10-6-2) were prepared in the same way as in Example 10-1 except for replacing the multilayer structure (1-1-1) And (C10-1-2) ~ (C10-3-2), and evaluate the protective sheets obtained. The results are shown in Table 9. In the same way as in Example 10-1, the protective sheets (10-2-2) to (10-6-2) did not show any appearance defects such as peeling after the temperature and humidity test. On the other hand, as a result of the temperature and humidity tests of the protective sheets (C10-1-2) to (C10-3-2), it was found that partial peeling occurred between the layers and the appearance was poor.

<Example 10-7>

The protective sheet (10-1-2) obtained in Example 10-1 was used to produce a solar cell module. Specifically, first, an amorphous silicon solar cell unit provided on a 10 cm square strengthened glass is sandwiched in an ethylene-vinyl acetate copolymer film with a thickness of 450 μm. Secondly, on this film, the protective sheet (10-1-2) is laminated with the polyethylene terephthalate layer of the protective sheet (10-1-2) as the outer side, to produce a solar cell module . The lamination method was carried out by performing vacuum suction at 150° C. for 3 minutes and then pressing for 9 minutes. The solar cell module produced in this way shows good operability, and even after a long period of time, it shows good power output characteristics.

[Industrial utility]

The invention can be used in multi-layer structures and packages using the same Packing materials, and methods of manufacturing multilayer structures. According to the content of the present invention, it is possible to obtain a multilayer structure having excellent interlayer adhesion and no appearance defect such as peeling even after sterilization treatment. In addition, when the multilayer structure of the present invention is used, excellent packaging materials can be obtained.

Claims (13)

A multilayer structure comprising a substrate (X) and a layer (Y) laminated on the substrate (X), characterized in that the layer (Y) contains an aluminum-containing compound ( A) Phosphate (BP) with polyvinyl alcohol-based resin, the phosphate esterification rate R _BP of the phosphate ester (BP) of the polyvinyl alcohol-based resin is 0.15 or more, and the layer (Y) is obtained by The coating solution (S) containing the compound (A) containing aluminum is coated on the substrate (X) to obtain the precursor layer, and the coating solution (T) containing the phosphate compound (BP) is applied and carried out Heat treatment of the resulting layer. The multilayer structure according to claim 1, wherein the aluminum-containing compound (A) is a compound (Ab) containing the reaction product (D) of the aluminum-containing metal oxide (Aa) and the inorganic phosphorus compound (BI). The multilayer structure according to claim 1 or 2, wherein the phosphate esterification rate R _BP of the phosphate ester compound (BP) of the polyvinyl alcohol-based resin is 0.24 or more. The multilayer structure according to claim 1 or 2, wherein the phosphate ester (BP) is a phosphated vinyl alcohol unit represented by the following general formula [III] containing 15.0 to 99.8 mol %;

The multilayer structure according to claim 1 or 2, wherein the aforementioned substrate (X) is a layer containing at least one selected from the group consisting of thermoplastic resin film and paper. A packaging material characterized by comprising the multilayer structure according to any one of claims 1 to 5. The packaging material as claimed in claim 6 still has a layer formed by extrusion coating lamination. Packaging materials as in claim 6 or 7, which are vertical bag filled sealed bags, vacuum packaging bags, bags, laminated tubular containers, infusion bags, paper containers, long bags, lid materials for containers, or in-mold labels container. An article, characterized in that at least a part of it uses the packaging material according to any one of claims 6 to 8. The product according to claim 9, wherein the product contains a content, the content is a core material, the inside of the product is decompressed, and has the function of a vacuum heat insulator. A protective sheet for an electronic device, characterized in that it contains a multilayer structure as described in any one of claims 1 to 5. The protective sheet of the electronic device according to claim 11 is a protective sheet for protecting the surface of the photoelectric conversion device, information display device, or lighting device. An electronic device characterized by having a protection sheet as in claim 11 or 12.

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