TW202340400A - Gas barrier laminate - Google Patents

Abstract

A gas barrier laminate, including a substrate layer; a gas barrier layer disposed on at least one surface of the substrate layer; and an inorganic matter layer disposed between the substrate layer and the gas barrier layer, is provided. The Zn composition ratio measured by X-ray photoelectron spectroscopy analysis of the gas barrier layer is 1 atomic% to 10 atomic%. When the mass peak strength of the 64ZnPO4H<SP>-</SP> and the mass peak strength of the C3H3O2<SP>-</SP>, measured by time of flight secondary ion mass spectroscopy analysis of the gas barrier layer, are set to I(64ZnPO4H<SP>-</SP>) and I(C3H3O2<SP>-</SP>), the value of I(64ZnPO4H<SP>-</SP>)/I(C3H3O2<SP>-</SP>) is 6*10<SP>-4</SP> or more and 5*10<SP>-2</SP> or less. The N composition ratio measured by X-ray photoelectron spectroscopy analysis of the gas barrier layer is more than 0 atomic% and 12 atomic% or less. When the mass peak strength of the CN<SP>-</SP>, measured by time of flight secondary ion mass spectroscopy analysis of the gas barrier layer, is set to I(CN<SP>-</SP>), the value of I(CN<SP>-</SP>)/I(C3H3O2<SP>-</SP>) is more than 0 and 2 or less.

Description

Gas barrier laminate

The present invention relates to a gas barrier laminate and related technologies.

Generally, as a gas barrier material against water vapor or oxygen, a laminate in which an inorganic layer having gas barrier properties is provided on a base material layer is used.

However, the inorganic layer is not resistant to friction, etc. In such a gas barrier laminate, cracks may occur in the inorganic layer due to friction or elongation during post-processing printing, lamination, or filling of contents, resulting in gas Barrier resistance reduced.

Therefore, as a gas barrier layer, for example, Patent Document 1 (International Publication No. 2016/017544) discloses a gas barrier coating material containing a polycarboxylic acid, a polyamine compound, a polyvalent metal compound, and a base, ( The molar number of the -COO- group contained in the polycarboxylic acid) / (the molar number of the amine group contained in the polyamine compound) = 100/20 to 100/90.

Patent Document 1 discloses that using such a gas barrier coating material can provide a gas barrier film with excellent gas barrier properties, especially oxygen barrier properties, under both conditions of low humidity and high humidity, and its gas barrier film can be provided. Laminated body.

In addition, Patent Document 2 (International Publication No. 03/091317) discloses a film using a polycarboxylic acid (A) and a polyvalent metal compound (B) as raw materials, and the peak ratio of the infrared absorption spectrum of the film is (A ₁₅₆₀ /A ₁₇₀₀ ) is above 0.25.

Patent Document 2 discloses that such a film has excellent gas barrier properties such as oxygen even in a high-humidity environment, and has the ability to not impair the appearance due to the influence of neutral water, high-temperature water vapor, and hot water. , shape and gas barrier water resistance, a film that is easily soluble in acids and/or alkali can be obtained.

In addition, Patent Document 3 (International Publication No. 2016/088534) discloses a gas barrier polymer formed by heating a mixture containing a polycarboxylic acid and a polyamine compound. ^{In the} infrared ^{absorption spectrum} of When the area is B, the area ratio of the amide bond represented by B/A is 0.370 or more.

Patent Document 3 discloses a gas barrier polymer. This polymer can achieve excellent gas barrier properties under high humidity and after boiling/cooking treatment, and can achieve stable appearance and size. Gas barrier films and gas barrier laminates with excellent balance between performance and productivity.

Furthermore, the following Patent Documents 4 to 6 can also be cited as prior art related to gas barrier materials. [Prior art documents] [Patent Document]

Patent Document 1: International Publication No. 2016/017544 Patent Document 2: International Publication No. 03/091317 Patent Document 3: International Publication No. 2016/088534 Patent Document 4: Japanese Patent Application Publication No. 2005-225940 Patent Document 5: Japanese Patent Application Publication No. 2013-10857 Patent Document 6: International Publication No. 2011/122036

[Problem to be solved by the invention]

The technical level required for various properties of gas barrier materials is gradually increasing.

According to the findings and preliminary studies of the present inventors, the conventional gas barrier materials described in Patent Documents 1 to 3, for example, have the following problems. The gas barrier material containing a system containing a polycarboxylic acid and a polyvalent metal compound as described in Patent Document 1 or Patent Document 2 has a problem that the barrier performance after retort treatment is deteriorated due to the two-layer laminated structure. In addition, the gas barrier material containing a system containing a polycarboxylic acid and a polyamine compound as described in Patent Document 3 has a problem that the barrier performance after retort treatment is deteriorated due to the three-layer laminate structure. As described above, the present inventors discovered that the conventional gas barrier materials as described in Patent Documents 1 to 3 had a problem of deterioration in barrier performance after retort treatment due to the laminate structure. That is, the present inventors found that there is room for improvement in conventional gas barrier materials from the viewpoint of barrier performance after retort treatment.

The present invention was made in view of the above-mentioned circumstances. One object of the present invention is to provide a barrier laminate that can be used as a barrier film having excellent barrier properties after retort treatment, such as a water vapor permeability in a two-layer laminate structure. (The purpose of this invention relates specifically to a first invention described below)

Among gas barrier materials, it is required to further improve the barrier properties of gases such as water vapor. For example, when manufacturing retort food, a retort process is performed, that is, the food is packaged with a gas barrier material and then heated. However, it is required that good barrier properties can also be obtained after the retort process. One object of the present invention is to provide a gas barrier material with improved barrier properties to gases such as water vapor. (The purpose of this invention is specifically related to a second invention described below)

According to the findings of the present inventors, conventional gas barrier materials such as those described in Patent Documents 1 to 3 have a problem that their barrier properties after retort treatment deteriorate due to their laminate structure. One object of the present invention is to provide a barrier laminate that can be used in a barrier film having good barrier properties after retort treatment regardless of the lamination structure. (The purpose of this invention is specifically related to a third invention described below)

According to the findings of the present inventors, there is still room for improvement in gas barrier materials from the viewpoint of improving productivity and barrier properties in a balanced manner. Until now, many technologies have focused on improving barrier properties, but no technology has been reported that improves barrier properties and productivity in a balanced manner. One object of the present invention is to provide a gas barrier material that has an excellent balance between productivity and barrier properties and can exhibit excellent barrier properties in various layer structures. (The purpose of this invention is specifically related to a fourth invention described below)

The technical level required for various properties of gas barrier materials is gradually increasing. According to the knowledge of the present inventors, gas barrier materials such as those described in Patent Document 4 and Patent Document 5 require heating at high temperatures for a long time in order to crosslink a polycarboxylic acid and a polyamine, and therefore are sometimes produced. Sexuality is reduced. In addition, in order to improve the productivity of such gas barrier materials, if the heat treatment time for cross-linking polycarboxylic acid and polyamine is shortened, amide formed by cross-linking polycarboxylic acid and polyamine may sometimes occur. The proportion of the keys is reduced and the blocking properties are reduced. Based on these, the present inventors found that there is room for improvement in conventional gas barrier materials from the viewpoint of improving productivity and barrier properties in a balanced manner. Until now, many technologies have focused on improving barrier properties, but no technology has been reported that improves barrier properties and productivity in a balanced manner. One object of the present invention is to provide a gas barrier material with an excellent balance between productivity and barrier properties. (The purpose of this invention relates specifically to a fifth invention described below) [Means to solve the problem]

The inventors of the present invention have repeatedly conducted research in order to achieve at least one of the above-mentioned subjects. As a result, it was found that, for example, a laminate in which Zn is within a specific composition ratio range as analyzed by X-ray Photoelectron Spectroscopy (XPS) has good barrier properties after retort treatment. A gas barrier layer in which the intensity ratio of a specific peak derived from Zn observed by Time of Flight Secondary Ion Mass Spectroscopy (TOF-SIMS) analysis falls within a certain range. The body includes a gas barrier layer in which the composition ratio of N is within a specific range by XPS analysis and the specific peak intensity ratio derived from N observed by TOF-SIMS analysis is within a specific range. Then, the following first invention was completed. In addition, the present inventors have completed the following second invention, third invention, fourth invention and fifth invention.

[First Invention] 1. A gas barrier laminated body, including: a base material layer; a gas barrier layer provided on at least one surface of the base material layer; and an inorganic layer provided between the base material layer and the base material layer. Between the gas barrier layers, the composition ratio of Zn measured by X-ray photoelectron spectrometry of the gas barrier layer is 1 atomic % to 10 atomic %, so that by analyzing the gas The mass peak intensity of ⁶⁴ ZnPO ₄ H ^- measured by time-of-flight secondary ion mass analysis of the barrier layer is set to I ( ⁶⁴ ZnPO ₄ H ^- ), and the mass peak intensity of C ₃ H ₃ O ₂ ^- is set to I. (C ₃ H ₃ O ₂ ^- ), the value of I ( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is 6×10 ^-4 or more and 5×10 ^-2 or less. By The composition ratio of N measured by X-ray photoelectron spectroscopy in the gas barrier layer exceeds 0 atomic % and is 12 atomic % or less, and the gas barrier layer is subjected to time-of-flight secondary ion mass analysis. When the measured mass peak intensity of CN ^- is set to I(CN ^- ), the value of I(CN ^- )/I(C ₃ H ₃ O ₂ ^- ) is greater than 0 and 2 or less. 2. The gas barrier laminate according to 1., wherein the mass peak intensity of PO ₂ ^- measured by the time-of-flight secondary ion mass spectrometry of the gas barrier layer is I (PO ₂ ^- ), when the mass peak intensity of PO ₃ ^- is set to I (PO ₃ ^- ), (I (PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) value is 0.02 or more and 5 or less. 3. The gas barrier laminate according to 1. or 2., wherein I(PO ₂ ^- )/I(PO) is the intensity ratio of the I(PO ₂ ^- ) to the I(PO ₃ ^- ). _3- ⁾ The value is 0.05 or more and 1 or less. 4. The gas barrier laminate according to any one of 1. to 3., wherein the gas barrier layer includes a hardened product of a mixture containing at least polycarboxylic acid, Zn, and one or more - P-OH group phosphorus compound or its salt. 5. The gas barrier laminate according to 4., wherein the concentration of P atoms of the phosphorus compound or its salt in the mixture is 5×10 ^-4 mol or more based on 1 mol of the polycarboxylic acid. And less than 0.3 mol. 6. The gas barrier laminate according to 4. or 5., wherein the mixture further contains a polyamine. 7. The gas barrier laminate according to 6., wherein the polyamine is polyethyleneimine. 8. The gas barrier laminate according to any one of 4. to 7., wherein the polycarboxylic acid contains polyacrylic acid, polymethacrylic acid, and a copolymer of acrylic acid and methacrylic acid. One or more polymers in a group. 9. The gas barrier laminate according to any one of 1. to 8., wherein the gas barrier layer has a thickness of 0.05 μm or more and 10 μm or less.

[Second invention] 1. A gas barrier laminated body, including: a base material layer; a gas barrier layer provided on at least one surface of the base material layer; and an inorganic layer provided between the base material layer and the base material layer. Between the gas barrier layers, the mass peak intensity of PO ₂ ^- when the gas barrier layer is subjected to time-of-flight secondary ion mass analysis is set to I (PO ₂ ^- ), and the mass peak intensity of PO ₃ ^- is When the peak intensity is set to I(PO ₃ ^- ) and the mass peak intensity of C ₃ H ₃ O ₂ ^- is set to I (C ₃ H ₃ O ₂ ^- ), (I (PO ₂ ^- ) + I (PO ₃ ^- ))/I(C ₃ H ₃ O ₂ ^- ) has a value of 0.02 to 5, and the gas barrier layer includes one or more types selected from the group consisting of Zn, Ca, Mg, Ba and Al. The composition ratio of the metal element in the gas barrier layer, which is determined by X-ray photoelectron spectroscopic analysis of the gas barrier layer, is 1 atomic % to 15 atomic %. 2. The gas barrier laminate as described in 1., wherein the mass peak intensity of CN ^- when the gas barrier layer is subjected to time-of-flight secondary ion mass analysis is set to I (CN ^- ), When the mass peak intensity of C ₃ H ₃ O ₂ ^- is set to I (C ₃ H ₃ O ₂ ^- ), the value of I (CN ^- )/I (C ₃ H ₃ O ₂ ^- ) is 2 or less. 3. The gas barrier laminate according to 1. or 2., wherein in the absorption spectrum obtained by subjecting the gas barrier layer to infrared spectrometry using a total reflection measurement method, the absorption band is 1493 cm When the total peak area in the range from ^-1 to 1780 cm ^-1 is A and the total peak area in the absorption band from 1493 cm ^-1 to 1598 cm ^-1 is D, the area ratio D/A is 0.5 or above. 4. The gas barrier laminated body according to any one of 1. to 3., wherein the inorganic layer is in contact with the base layer, or there is provided between the inorganic layer and the base layer. Basecoat. 5. The gas barrier laminate according to any one of 1. to 4., wherein the inorganic layer contains one or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum. . 6. The gas barrier laminate according to any one of 1. to 5., wherein the gas barrier layer has a thickness of 0.01 μm to 15 μm. 7. The gas barrier laminate according to any one of 1. to 6., wherein a sealant layer is further provided on the side of the gas barrier layer opposite to the inorganic layer. 8. The gas barrier laminate according to 7., wherein the sealant layer is in contact with the gas barrier layer, or the gas barrier layer and the sealant layer are connected through an adhesive layer. 9. The gas barrier laminate according to 7., wherein a polyamide-containing layer is provided between the gas barrier layer and the sealant layer. 10. The gas barrier laminate according to any one of 1. to 9. is used for food packaging. 11. The gas barrier laminate according to any one of 1. to 10., used for manufacturing retort food. 12. A packaging bag containing the gas barrier laminated body according to any one of 1. to 11. 13. A food packaged with the gas barrier laminated body according to any one of 1. to 12..

[Third invention] 1. A gas barrier laminate, including: a base material layer; a gas barrier layer provided on at least one surface of the base material layer; and an inorganic layer provided between the base material layer and the base material layer. Between the gas barrier layers, the composition ratio of Zn measured by X-ray photoelectron spectrometry of the gas barrier layer is 1 atomic % to 10 atomic %. The mass peak intensity of ⁶⁴ ZnPO ₄ H ^- measured by time-of-flight secondary ion mass analysis is set to I ( ⁶⁴ ZnPO ₄ H ^- ), and the mass peak intensity of C ₃ H ₃ O ₂ ^- is set to I (C ₃ H ₃ O ₂ ^- ), the value of I( ⁶⁴ ZnPO ₄ H ^- )/I(C ₃ H ₃ O ₂ ^- ) is 7×10 ^-4 or more and 5×10 ^-2 or less. 2. The gas barrier laminate according to 1., wherein the mass peak intensity of PO ₂ ^- measured by the time-of-flight secondary ion mass spectrometry of the gas barrier layer is I (PO ₂ ^- ), when the mass peak intensity of PO ₃ ^- is set to I (PO ₃ ^- ), (I (PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) value is 0.02 or more and 5 or less. 3. The gas barrier laminate according to 1. or 2., wherein I(PO ₂ ^- )/I(PO) is the intensity ratio of the I(PO ₂ ^- ) to the I(PO ₃ ^- ). _3- ⁾ The value is 0.05 or more and 1 or less. 4. The gas barrier laminate according to any one of 1. to 3., wherein the gas barrier layer includes a hardened product of a mixture containing at least polycarboxylic acid, Zn, and one or more - P-OH group phosphorus compound or its salt. 5. The gas barrier laminate according to 4., wherein the phosphorus compound or a salt thereof containing one or more -P-OH groups in the mixture is contained per 1 mol of the carboxyl group in the polycarboxylic acid. The concentration is 5×10 ^-4 mol or more and 0.3 mol or less. 6. The gas barrier laminate according to 4. or 5., wherein the polycarboxylic acid includes polyacrylic acid, polymethacrylic acid, and a copolymer of acrylic acid and methacrylic acid selected from the group consisting of One or more than two polymers. 7. The gas barrier laminate according to any one of 1. to 6., wherein the gas barrier layer has a thickness of 0.05 μm or more and 10 μm or less.

[Fourth invention] [1] A gas barrier laminated body including: a base material layer; a gas barrier layer provided on at least one surface of the base material layer; and an inorganic layer provided between the base material layer and Between the gas barrier layers, the gas barrier layer includes a hardened product of a mixture including a polycarboxylic acid, a polyamine compound, a polyvalent metal compound, and phosphorus containing one or more -P-OH groups. compound or its salt. [2] The gas barrier laminate according to [1], further comprising a primer layer provided between the base layer and the inorganic layer. [3] The gas barrier laminate according to [1] or [2], wherein the inorganic layer is provided on the base layer or between the base layer and the inorganic layer When there is an interposer layer, the evaporated film is disposed on the interposer layer and contains one or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum. [4] The gas barrier laminate according to any one of [1] to [3], wherein the infrared absorption spectrum of the gas barrier layer is between 1300 cm ^-1 and 1490 cm ^-1 Let α be the maximum peak height of the absorbance in the following range, and let γ be the maximum peak height of the absorbance in the range of 1690 cm ^-1 or more and 1780 cm ^-1 . The free carboxyl group represented by γ/α relative to NH The ratio of the _3- complex is 0.00 or more and 1.00 or less. [5] The gas barrier laminate according to any one of [1] to [4], wherein in the infrared absorption spectrum of the gas barrier layer, the absorption band is between 1493 cm ^-1 and 1780 cm Let the total peak area in the range of ^-1 and below be A. Let the total peak area in the range of the absorption band between 1598 cm ^-1 and 1690 cm ^-1 be B. Let the absorption band be between 1690 cm ^-1 and 1780 cm ^-1 When the total peak area in the following range is designated as C, and the total peak area in the range of the absorption band from 1493 cm ^-1 to 1598 cm ^-1 is designated as D, the area ratio of the amide bond represented by B/A is: 0.200 or more and 0.370 or less, the area ratio of the carboxylic acid represented by C/A is 0.150 or less, and the area ratio of the carboxylic acid salt represented by D/A is 0.580 or more and 0.800 or less. [6] The gas barrier laminate according to any one of [1] to [5], wherein the gas barrier layer has a thickness of 0.01 μm or more and 15 μm or less. [7] The gas barrier laminate according to any one of [1] to [6], wherein the polyvalent metal compound is selected from the group consisting of Zn, Ca, Mg, Ba, and Al A compound of one or two or more metals having a valence of more than two valences. [8] The gas barrier laminate according to any one of [1] to [7], wherein (the molar number of P atoms derived from the phosphorus compound or its salt in the mixture)/( The molar number of the -COO- group derived from the polycarboxylic acid in the mixture is 0.001 or more and 0.3 or less. [9] The gas barrier laminate according to any one of [1] to [8], wherein the phosphorus compound is selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid and salts thereof. One or more than two types of groups. [10] The gas barrier laminate according to any one of [1] to [9], wherein (moles of the polyvalent metal derived from the polyvalent metal compound in the mixture)/( The molar number of the -COO- group derived from the polycarboxylic acid in the mixture is 0.10 or more and 0.80 or less. [11] The gas barrier laminate according to any one of [1] to [10], wherein (moles of the polyvalent metal derived from the polyvalent metal compound in the mixture)/( The molar number of the amine group derived from the polyamine compound in the mixture is 0.25 or more and 0.65 or less. [12] The gas barrier laminate according to any one of [1] to [11], wherein the polycarboxylic acid contains a copolymer selected from the group consisting of polyacrylic acid, polymethacrylic acid, and acrylic acid and methacrylic acid. One or more than two polymers in a group. [13] The gas barrier laminate according to any one of [1] to [12], wherein the polyamine compound contains polyethyleneimine. [14] The gas barrier laminate according to any one of [1] to [13], wherein the base layer contains a material selected from the group consisting of polyamide, polyethylene terephthalate, and polyterephthalate. One or more resins in the group consisting of butylene formate.

[Fifth invention] [1] A gas barrier laminated body, including: a base material layer; a gas barrier layer provided on at least one surface of the base material layer; and an inorganic layer provided between the base material layer and Between the gas barrier layers, the gas barrier layer includes a hardened product of a mixture including a polycarboxylic acid, a polyamine compound, and a polyvalent metal compound. [2] The gas barrier laminate according to [1], further comprising a primer layer provided between the base layer and the inorganic layer. [3] The gas barrier laminate according to [1] or [2], wherein the inorganic layer is provided on the base layer or between the base layer and the inorganic layer When there is an interposer layer, the evaporated film is disposed on the interposer layer and contains one or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum. [4] The gas barrier laminate according to any one of [1] to [3], wherein the inorganic layer includes an aluminum oxide layer containing aluminum oxide. [5] The gas barrier laminate according to any one of [1] to [4], wherein the infrared absorption spectrum of the gas barrier layer is between 1300 cm ^-1 and 1490 cm ^-1 Let α be the maximum peak height of the absorbance in the following range, and let γ be the maximum peak height of the absorbance in the range of 1690 cm ^-1 or more and 1780 cm ^-1 . The free carboxyl group represented by γ/α relative to NH The ratio of the _3- complex is 0.00 or more and 1.00 or less. [6] The gas barrier laminate according to any one of [1] to [5], wherein in the infrared absorption spectrum of the gas barrier layer, the absorption band is between 1493 cm ^-1 and 1780 cm Let the total peak area in the range of ^-1 and below be A. Let the total peak area in the range of the absorption band between 1598 cm ^-1 and 1690 cm ^-1 be B. Let the absorption band be between 1690 cm ^-1 and 1780 cm ^-1 When the total peak area in the following range is designated as C, and the total peak area in the range of the absorption band from 1493 cm ^-1 to 1598 cm ^-1 is designated as D, the area ratio of the amide bond represented by B/A is: 0.200 or more and 0.370 or less, the area ratio of the carboxylic acid represented by C/A is 0.150 or less, and the area ratio of the carboxylic acid salt represented by D/A is 0.580 or more and 0.800 or less. [7] The gas barrier laminate according to any one of [1] to [6], wherein the gas barrier layer has a thickness of 0.01 μm or more and 15 μm or less. [8] The gas barrier laminate according to any one of [1] to [7], wherein the polyvalent metal compound is selected from the group consisting of Zn, Ca, Mg, Ba, and Al A compound of one or two or more metals having a valence of more than two valences. [9] The gas barrier laminate according to any one of [1] to [8], wherein (the number of moles of the polyvalent metal derived from the polyvalent metal compound in the mixture)/( The molar number of the -COO- group derived from the polycarboxylic acid in the mixture is 0.10 or more and 0.80 or less. [10] The gas barrier laminate according to any one of [1] to [9], wherein (moles of the polyvalent metal derived from the polyvalent metal compound in the mixture)/( The molar number of the amine group derived from the polyamine compound in the mixture is 0.25 or more and 0.75 or less. [11] The gas barrier laminate according to any one of [1] to [10], wherein the polycarboxylic acid contains a copolymer selected from the group consisting of polyacrylic acid, polymethacrylic acid, and acrylic acid and methacrylic acid. One or more than two polymers in a group. [12] The gas barrier laminate according to any one of [1] to [11], wherein the polyamine compound contains polyethyleneimine. [13] The gas barrier laminate according to any one of [1] to [12], wherein the base material layer is selected from the group consisting of polyamide, polyethylene terephthalate, and polyparaphenylene. A layer of one or more resins in the group consisting of butylene dicarboxylate. [Effects of the invention]

According to the present invention, for example, it is possible to provide a gas barrier laminate having excellent barrier properties after cooking. According to the present invention, for example, a gas barrier material with improved gas barrier properties can be provided. According to the present invention, for example, it is possible to provide a gas barrier laminate having excellent barrier properties after cooking regardless of the laminate structure. According to the present invention, for example, a gas barrier material can be provided that has an excellent balance between productivity and barrier properties and can exhibit excellent barrier properties in various layer structures. According to the present invention, for example, a gas barrier material excellent in balance between productivity and barrier properties can be provided.

Hereinafter, embodiments of the first to fifth inventions will be described using drawings. The embodiment of the first invention will be described as the first embodiment, the embodiment of the second invention will be described as the second embodiment, the embodiment of the third invention will be described as the third embodiment, and the embodiment of the fourth invention will be described This is the fourth embodiment, and the embodiment of the fifth invention is described as the fifth embodiment. All figures are schematics for illustrative purposes and may not correspond to actual size ratios. Regarding the symbols in the drawings, the same symbol may represent different elements in different embodiments. For example, in FIG. 2 , which is a diagram illustrating the first embodiment, reference numeral 10 indicates a “three-layer laminated structure barrier film”. On the other hand, in FIG. 2 , which is a diagram illustrating the fourth embodiment, Among 13, symbol 10 represents "gas barrier film". Unless otherwise specified, "～" between numerical values in the text means above to below.

In the expressions of groups (atomic groups) in this specification, expressions that do not describe substituted or unsubstituted include both expressions that do not have a substituent and expressions that have a substituent. For example, the so-called "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The expression "(meth)acrylic acid" in this specification represents a concept including both acrylic acid and methacrylic acid. The same applies to similar expressions such as "(meth)acrylate".

<First Embodiment> The gas barrier laminated body of the first embodiment is a gas barrier laminated body including: a base material layer; a gas barrier layer provided on at least one surface of the base material layer; and an inorganic layer , is provided between the base material layer and the gas barrier layer, and the composition ratio of Zn measured by X-ray photoelectron spectrometry of the gas barrier layer is 1 atomic % to 10 atomic %, at Let the peak intensity of ⁶⁴ ZnPO ₄ H ^- measured by time-of-flight secondary ion mass analysis of the gas barrier layer be I ( ⁶⁴ ZnPO ₄ H ^- ), and the peak intensity of C ₃ H ₃ O ₂ ^- When the peak intensity is I (C ₃ H ₃ O ₂ ^- ), the value of I ( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is 6 × 10 ^-4 or more and 5 × 10 ^-2 Hereinafter, the composition ratio of N measured by X-ray photoelectron spectrometry of the gas barrier layer exceeds 0 atomic % and is 12 atomic % or less, and the gas barrier layer will be analyzed by time-of-flight analysis. When the peak intensity of CN ^- measured by secondary ion mass analysis is set to I(CN ^- ), the value of I(CN ^- )/I(C ₃ H ₃ O ₂ ^- ) is greater than 0 and 2 or less.

When the composition ratio of Zn measured by X-ray photoelectron spectroscopy is 1 atomic % to 10 atomic %, it means that the gas barrier layer contains Zn at a certain concentration. In addition, the detection of C ₃ H ₃ O ₂ ^- from the gas barrier layer by mass analysis means that the gas barrier layer contains polyacrylic acid or its derivatives/similar compounds (polyacrylic acid, etc.). Furthermore, the value of I(C ₃ H ₃ O ₂ ^- ) is considered to be a value related to the amount (concentration) of carboxyl groups in the gas barrier layer. Since the gas barrier layer contains Zn at a certain concentration, and polycarboxylic acid having a carboxyl group is present in the gas barrier layer, it is considered that the polycarboxylic acid in the gas barrier layer forms a cross-linked body with Zn, forming a Zn cross-linked body. The combined gas barrier layer and the inorganic layer provided between the base material layer and the gas barrier layer together bear the gas barrier properties of the gas barrier laminate.

Furthermore, the detection of ⁶⁴ ZnPO ₄ H ^- from the gas barrier layer by mass analysis means that there is a bond between a phosphorus compound represented by phosphoric acid and Zn in the gas barrier layer, and it is considered that I ( ⁶⁴ ZnPO ₄ H ^- ) is a value related to the amount (concentration) of the bond between the phosphorus compound and Zn. Furthermore, it is inferred from this that Zn is not only bonded to the carboxyl group of the polycarboxylic acid, but also a part of the Zn is chemically bonded to each other via the polyvalent phosphate compound.

In addition, the value of I( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is considered to be a value related to the amount (concentration) of the bond between the phosphorus compound and Zn relative to the carboxyl group of the polycarboxylic acid. In addition, zinc phosphate is considered to be a water-insoluble compound, and the bond between the phosphorus compound and Zn is a bond that is difficult to cut due to hydration caused by retort treatment or the like. Therefore, it is considered that the presence of a bond between the phosphorus compound and Zn in the gas barrier layer suppresses the occurrence of damage to the adjacent inorganic layer due to excessive expansion and contraction of the gas barrier layer during retort processing, etc., resulting in a significant decrease in gas barrier properties. .

On the other hand, the detection of CN ⁻ from the gas barrier layer by mass analysis means that the gas barrier layer contains polyamine. It is considered that the composition ratio of N measured by X-ray photoelectron spectroscopy exceeds 0 atomic % and is 12 atomic % or less, and the value of I(CN ^- )/I(C ₃ H ₃ O ₂ ^- ) is greater than 0 and 2 or less. is a value related to the amount (concentration) of amine groups derived from a polyamine also present in the gas barrier layer containing a polycarboxylic acid. Since polyamine and polycarboxylic acid exist in a certain concentration in the gas barrier layer, the carboxyl group derived from the polycarboxylic acid can be bonded not only to Zn but also to the amine group. Furthermore, amide crosslinks can be formed through the dehydration condensation reaction of carboxyl groups and amine groups. It is considered that the polycarboxylic acid forms a cross-linked body by ionic cross-linking or amide cross-linking in a balanced manner through Zn or polyamine, and forms a gas barrier layer with a metal cross-linked body and is provided between the base material layer and the gas barrier layer. The inorganic layers between them jointly bear the gas barrier properties of the gas barrier laminate. That is, the composition ratio of Zn is 1 atomic % to 10 atomic %, or the value of I( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is 6 × 10 ^-4 or more and 5 × 10 ^-2 or less, furthermore, the composition ratio of N exceeds 0 atomic % and is 12 atomic % or less, and the value of I(CN ^- )/I(C ₃ H ₃ O ₂ ^- ) is greater than 0 and is 2 or less, the barrier performance after cooking Well maintained.

FIG. 1 shows a schematic cross-sectional view of an example of a two-layer laminated structure barrier film including the gas barrier laminate according to the first embodiment. The two-layer laminated structure barrier film 1 includes a gas barrier laminate 8 . This gas barrier laminate 8 includes: a base material layer 2; a gas barrier layer 5 on at least one surface of the base material layer 2; and an inorganic layer between the base material layer 2 and the gas barrier layer 5. 4. In addition, the undercoat layer (UC layer) 3 may be included below the inorganic layer 4 , that is, on the base layer 2 . Regarding the two-layer laminated structure barrier film 1 , for example, the gas barrier laminate 8 can be bonded to unstretched polypropylene (cast polypropylene (CPP)) 7 via the adhesive layer 6 .

In addition, FIG. 2 shows a schematic cross-sectional view of an example of a three-layer laminated structure barrier film including the gas barrier laminate of the first embodiment. In the three-layer laminated structure barrier film 10, for example, the nylon film 9 can be adhered to the first adhesive layer 61 of the barrier laminate 8 provided with the first adhesive layer 61, and the nylon film 9 can be connected through the second adhesive layer 62. 9 is followed by unstretched polypropylene 7.

The gas barrier layer 5 of the gas barrier laminate 8 of the first embodiment is a layer in which at least zinc (Zn) and nitrogen (N) are detected by X-ray photoelectron spectroscopy (XPS) analysis. In addition, the peak of ⁶⁴ ZnPO ₄ H ^- , the peak of C ₃ H ₃ O ₂ ^- , and the peak of CN ^- were detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis. In the gas barrier layer of the gas barrier laminate of the first embodiment, the peak of ⁶⁴ ZnPO ₄ H ^-, which has high water resistance, is detected, so that the gas barrier laminate has good barrier performance after cooking.

[XPS analysis] The composition of Zn contained in the gas barrier layer is 1 atomic % or more according to XPS analysis, preferably 1.5 atomic % or more, more preferably 2 atomic % or more. In addition, the composition of Zn contained in the gas barrier layer is 10 atomic % or less, preferably 8 atomic % or less, more preferably 7 atomic % or less. This corresponds to the peak intensity of Zn relative to the peak intensity of carbon, that is, Zn/C being 0.01 or more and 0.2 or less (atomic/atomic %). In this way, due to the presence of a certain amount of Zn in the gas barrier layer, the barrier performance after cooking becomes good.

In addition, the composition of the N contained in the gas barrier layer is greater than 0% by XPS analysis, preferably 2 atomic % or more, and more preferably 3 atomic %. In addition, the composition of N is 12 atomic % or less, preferably 10 atomic % or less, and more preferably 9 atomic % or less. This corresponds to the peak intensity of N relative to the peak intensity of carbon, that is, N/C being 0 or more and 0.2 or less (atomic/atomic %). In this way, when the composition ratio of N in the gas barrier layer exceeds 0 atomic % and is 12 atomic % or less, the barrier performance after cooking becomes good.

An example of specific conditions applicable to the XPS analysis of the first embodiment is shown below. Analytical device: AXIS-NOVA manufactured by KRATOS X-ray source: monochromated Al-Kα X-ray source output: 15 kV, 10 mA Analysis area: 300 μm×700 μm During analysis: Use a neutralizing gun for charged calibration For XPS analysis, a measurement sample of 1 cm×1 cm cut out from the gas barrier layer can be used. In addition, in order to analyze the inside of the gas barrier layer, it is preferable to perform sputter etching on the surface of the gas barrier layer before analysis. In order to reduce damage to the gas barrier layer, sputter etching ideally uses an Argon Gas Cluster Ion Beam (Ar-GCIB) source. Ar-gas cluster ion beam is known as a method of etching without destroying the chemical structure of the object to be inspected.

In XPS analysis, a wide scan is used to determine the detection elements, and a spectrum is obtained through a narrow scan for each element. Then, based on the obtained spectrum, the background is estimated by Shirley's method and the background is removed from the spectrum. For each element to be measured, a spectrum with the background removed is obtained, and based on the obtained peak area, the atomic composition ratio (atomic %) of the detected element is calculated using the relative sensitivity coefficient method. Furthermore, the detection sensitivity of the atomic composition ratio in general XPS analysis is about 0.1 atomic %. For example, when a trace amount of a phosphorus compound is added to the gas barrier layer, the content of P cannot be detected in XPS analysis.

[TOF-SIMS Analysis] Among the fragments detected in the TOF-SIMS analysis of the gas barrier layer, the peak intensity of ⁶⁴ ZnPO ₄ H ^- was set to I ( ⁶⁴ ZnPO ₄ H ^- ), and C ₃ H ₃ O When the peak intensity of the ₂ ^- fragment is I (C ₃ H ₃ O ₂ ^- ), the value of I ( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is 6 × 10 ^-4 or more, It is preferably 7×10 ^-4 or more, more preferably 1×10 ^-3 or more. In addition, it is 5×10 ^-2 or less, preferably 3×10 ^-2 or less, more preferably 2×10 ^-2 or less. In this way, the mass peak of ⁶⁴ ZnPO ₄ H ^- derived from the highly water-resistant bond is detected when the value of I ( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is within the above range. , it becomes a gas barrier laminate with good barrier properties after cooking. In addition, when the value of ( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is too large, fine particles of the zinc phosphate compound grow in the gas barrier layer, causing unevenness to the gas barrier layer. Furthermore, the barrier properties after retort tend to deteriorate.

In addition, when the mass peak intensity of CN ^- is I(CN ^- ) in the fragment detected by TOF-SIMS analysis of the gas barrier layer, I(CN ^- )/I(C ₃ H ₃ O ₂ ^- ) is greater than 0, preferably 0.2 or more, more preferably 0.4 or more. In addition, the value of I(CN ^- )/I(C ₃ H ₃ O ₂ ^- ) is 2 or less, preferably 1.8 or less, more preferably 1.5 or less. If it is such a gas barrier layer, it will become a gas barrier laminate with excellent barrier performance after retort.

An example of specific conditions applicable to TOF-SIMS analysis according to the first embodiment is shown below. In order to analyze the inside of the gas barrier layer, it is preferable to perform sputter etching on the surface layer of the gas barrier layer using the Ar-gas cluster ion beam (Ar-GCIB) attached to the TOF-SIMS analysis device before TOF-SIMS analysis. . The use of Ar-GCIB can reduce damage to the gas barrier layer. An example of specific conditions applicable to Ar-GCIB according to the first embodiment is shown. GCIB: 5 kV, 5 μA GCIB processing time: the time point when the spectral pattern of TOF-SIMS no longer changes

TOF-SIMS analysis can be performed, for example, as follows. Analysis device: PHI nano (nano)-TOFII manufactured by Nippon Vacuum (Ulvac-phi) Co., Ltd. Primary ion: Bi ₃ ²⁺ primary ion source output: 30 kV, 0.5 μA Analysis area: 300 μm × 300 μm (primary ion beam Scanning area) During analysis, charge neutralization can be carried out by low-energy electron beam and low-energy Ar ion irradiation attached to the device. In addition, in the TOF-SIMS analysis, like the XPS analysis, a 1 cm×1 cm measurement sample cut out from the gas barrier layer can be used.

At this time, let the mass peak intensity of PO ₂ ^- observed in the gas barrier layer by TOF-SIMS analysis be I (PO ₂ ^- ), and let the mass peak intensity of PO ₃ ^- be I (PO ₃ ^- ), the value of (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) is preferably 0.02 or more, more preferably 0.05 or more, and still more preferably 0.07 or more. In addition, the value of (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) is preferably 5 or less, more preferably 3 or less, and still more preferably 2.5 or less. The detection of a mass peak of PO ₂ ^- or PO ₃ ^- means that the gas barrier layer contains a phosphorus compound containing one or more P-OH groups, represented by phosphoric acid. Furthermore, the value of (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) is considered to be the amount of the phosphorus compound relative to the carboxyl group of the polycarboxylic acid in the gas barrier layer (concentration) related values.

At this time, the value of I(PO ₂ ^- )/I (PO ₃ ^- ), which is the intensity ratio of I (PO ₂ ^- ) and I (PO ₃ ^- ), is preferably 0.05 or more, more preferably 0.08 or more, Further preferably, it is 0.1. In addition, the value of I(PO ₂ ^- )/I(PO ₃ ^- ) is 1 or less, preferably 0.9 or less, more preferably 0.8 or less. The detection of mass peaks of PO ₂ ^- and PO ₃ ^- in TOF-SIMS analysis means that phosphorus compounds containing one or more P-OH groups, such as phosphoric acid (H ₃ PO ₄ ), are included, and the ratio is I( _PO2 ^- )/I( _PO3- ⁾ is a value reflecting the type of phosphorus-based compound. I( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ), which reflects the amount (concentration) of zinc phosphate bonds in the gas barrier layer, affects the type of phosphorus compound. That is, it is also related to the value of I(PO ₂ ^- )/I(PO ₃ ^- ). When the value of I(PO ₂ ^- )/I(PO ₃ ^- ) is 0.05 or more and 1 or less, let the value of I( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) be It is an appropriate range and the barrier performance after retort of the gas barrier laminate of the first embodiment can be maintained well.

The analysis method of data obtained by TOF-SIMS can be performed as follows. In order to perform detailed spectral analysis, in the first embodiment, for each positive and negative secondary ion, the analysis device obtains a raw data string pairing the mass number m _i and its corresponding count number c _i Total ion counts (C _T ). Here, i=0, 1, 2,···,N. In the original data string, m _i are arranged in ascending order. Furthermore, C _T is the total number of secondary ion counts detected by the detector.

The range of mass numbers around the mass spectrum peak of interest is set to i=n ₁ , n ₁ +1,..., n ₂ . The data c _i of the count number in this range obtained by analysis is approximated by _yi as shown in the following equation. Specifically, c _i is approximated by curve fitting using a background level b ⁰ and K triangular shape functions Y _j (mi ₎ . Here, b ⁰ is a constant.

[Number 1]

Y _j ( _mi ) is a function having a peak value Y ⁰ _j at the mass number x ⁰ _j as shown in Fig. 3, and is represented by the following equation.

[Number 2]

Here, b ⁰ , x ⁰ _j , Y ⁰ _j , B ^- _j , and B ⁺ _j become fitting parameters. In addition, j is j=1,···,K. For example, when the background of the spectrum is not a constant value but changes linearly with respect to m _i , b ⁰ is combined with the triangular shape function Y _j (mi ₎ to approximate the background. When the mass spectrum peak of interest is a single peak, except for the background, a triangle shape function is used for approximation. When it is close to other mass peaks, multiple triangle shape functions including other mass peaks are used for approximation. approximate. If the approximated mass spectrum peak of interest is the j=kth peak among K triangular shape functions, the peak intensity I is reduced to i=n ₁ ,···,n using the total ion count (C _T ) It is represented by the normalized numerical value of the sum of Y _k ( _mi ) up to ₂ , and is calculated according to the following formula.

[Number 3]

If there is a tail portion in a mass spectrum peak, it becomes difficult to define the range of masses that should be counted. In the first embodiment, in order to avoid this situation, a triangle shape function is used to approximate the mass spectrum peak. By this, the number of counts in the tail portion of the mass spectral peak is ignored. Curve fitting was performed in such a way that the central part of the mass spectral peak fit a triangular shape function. In addition, other components (for example, other types of mass peaks with the same mass number) that overlap with the target peak component may be observed. In this case, the target peak component is obtained by approximating other components that overlap with the target peak component using a triangle shape function. The mass number of the fragment of interest in the first embodiment was calculated and shown below. The atomic weight number of an isotope depends on http://physics.nist.gov/.

[Table 1] number of atoms isotope Atomic mass PO ₂ P O ₃ C ₃ H ₃ O ₂ EN ^64ZnPO4H _{_} ^1H 1.007825 3 1 ^12C 12 3 1 ^14N 14.00307 1 ^16O 15.99492 2 3 2 4 ^31P 30.97376 1 1 1 ^64Z 63.92914 1 mass number 62.9636 78.9585 71.0133 26.0031 159.89039

[Calculation of mass peak intensity of ⁶⁴ ZnPO ₄ H ^- ] Zn is known to have five isotopes, and in TOF-SIMS analysis, fragments associated with ⁶⁴ Zn, ⁶⁶ Zn, and ⁶⁸ Zn are mainly detected. In the first embodiment, attention is paid to ⁶⁴ Zn, which has the highest ratio. In the fragment showing the bond between ⁶⁴ Zn and the phosphorus compound containing P-OH, ⁶⁴ ZnPO ₄ H ^- , ⁶⁴ ZnP ₂ O ₆ H ^- , ⁶⁴ ZnP ₂ O ₇ H ^- , ⁶⁴ ZnP ₃ O ₉ ^- , etc. were detected. But focus on ⁶⁴ ZnPO ₄ H ^- which has a larger mass peak intensity. Focusing on the range of mass number = 159.5 to 160.3 in the negative secondary ion spectrum, a triangular shape function approximated by the mass peak near 159.890 corresponding to ⁶⁴ Zn ³¹ P ¹⁶ O ₄ ¹ H ^- and m _i Data, calculate the sum of the count numbers, and set the value normalized by C _T to the mass peak intensity of ⁶⁴ ZnPO ₄ H ^- .

An example of curve fitting is shown in FIG. 4 , and the calculation results of the sum of the parameters used at this time and the number of counts are shown in Table 2 . In the example shown in FIG. 4 , the total number of counts obtained based on the triangular shape function that approximates the mass peak of ⁶⁴ ZnPO ₄ H ^- as the target and the data of m _i is 1514. At this time, the total ion count (C _T ) of negative secondary ions = 8571746, so the mass peak intensity I ( ⁶⁴ ZnPO ₄ H ^- ) of ⁶⁴ ZnPO ₄ H ^- becomes I ( ⁶⁴ ZnPO ₄ H ^- ) = 1514/8571746 =1.77×10 ^-4 .

[Table 2] b ⁰ Y _j (m _i ) j 0 1 2(=target) b ⁰ 2 x ⁰ 159.934 159.934 159.885 B ⁺ 0.11 0.035 0.03 ^B- 0.11 0.035 0.03 Y ⁰ 20 50 62 sum 1791 1424 1514

Supplementary information is provided to Figure 4 showing an example of curve fitting. (i) In order to obtain an approximate curve _yi that reproduces the measurement data c _i near the target peak position, a curve of "the background b ⁰ " and "triangular shape function approximation of other components" and "the target triangle shape function" are required Y _j ( _mi )" curve. (ii) In the example of Figure 4, when the mass number (m/z) is 159.7 to 160.2, in order to obtain the "approximate curve yi _" that reproduces the measurement data c _i , the "background b ⁰ " and "target There are two curves of "triangular shape function Y _j ( _mi )" (j=2 in Table 2) and "triangular shape function approximation of other components" (j=0, 1 in Table 2).

[Calculation of mass peak intensity of C ₃ H ₃ O ₂ ^- ] Focusing on the range of mass number = 70.7 to 71.4 in the negative secondary ion spectrum, the equivalent of ¹² C ₃ ¹ H ₃ ¹⁶ obtained by fitting the autocurve Calculate the sum of the number of counts using the triangular shape function Y _k (mi) _{and m i approximated} by the mass peak near 71.013 of O ₂ ^- , and set the value normalized by C _T to C ₃ H ₃ O The mass peak intensity of ₂ ^- I (C ₃ H ₃ O ₂ ^- ).

[Calculation of mass peak intensity of PO ₂ ^- ] Focusing on the range of mass number = 62.5 to 63.3 in the negative secondary ion spectrum, it was calculated by approximating the mass peak near 62.964 corresponding to ³¹ P ¹⁶ O ₂ ^- From the data of the triangle shape function and m _i , calculate the sum of the number of counts, and set the value normalized by C _T as the mass peak intensity I (PO ₂ ^- ) of PO ₂ ^- .

[Calculation of mass peak intensity of PO ₃ ^- ] Focusing on the range of mass number = 78.5 to 79.3 in the negative secondary ion spectrum, it was calculated by approximating the mass peak near 78.959 corresponding to ³¹ P ¹⁶ O ₃ ^- From the data of the triangle shape function and m _i , calculate the sum of the count numbers, and set the value normalized by C _T as the mass peak intensity I (PO ₃ ^- ) of PO ₃ ^- .

[Calculation of mass peak intensity of CN ^- ] Focusing on the range of mass number = 25.5 to 26.3 in the negative secondary ion spectrum, a triangular shape is obtained by approximating the mass peak near 26.003 corresponding to ¹² C ¹⁴ N ^- Function and m _i data, calculate the sum of the count numbers, and set the value normalized by C _T as the mass peak intensity I of CN ^- (CN ^- ).

The gas barrier layer is preferably formed from a hardened product of a mixture containing polycarboxylic acid, Zn, and a phosphorus compound containing one or more -P-OH groups represented by phosphoric acid (H ₃ PO ₄ ) or Its salt. In the case of a gas barrier layer formed from a cured product of a mixture of these components, the carboxyl groups derived from the polycarboxylic acid form metal ion cross-links via Zn, and Zn also reacts with the phosphorus compound containing the P-OH group, Forms bonds that are water resistant. Although the detailed mechanism is not clear, it is thought that a tight gas barrier layer is formed by the uniform presence of an appropriate amount of these metal ion crosslinks via Zn or the bond between Zn and the phosphorus compound in the gas barrier layer, and by Suppresses excessive expansion and contraction of the gas barrier layer by retort treatment, etc.

The composition ratio of _Zn in the gas barrier layer of the first embodiment and the values of I ^{( 64} _ZnPO4H ^- )/I( _C3H3O2- ⁾ and (I( _{PO2 -} )+ in TOF-SIMS The value of I(PO ₃ ^- ))/I(C ₃ H ₃ O ₂ ^- ) and the value of I(PO ₂ ^- )/I(PO ₃ ^- ) can be appropriately adjusted by appropriately adjusting the manufacturing conditions of the gas barrier layer. control. In the first _embodiment , for example, the concentration of phosphoric acid relative to the polycarboxylic acid can be used as _a parameter for controlling the Zn composition ratio and the value of I( ⁶⁴ _ZnPO4H ^- )/I( _C3H3O2- ⁾ Listed as one of the factors.

Polycarboxylic acids, zinc or its compounds, phosphorus compounds, and other addable components applicable to the first embodiment will be described in detail below.

(polycarboxylic acid) Polycarboxylic acids have two or more carboxyl groups in the molecule. Specific examples include homopolymerization of α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, cinnamic acid, 3-hexenoic acid, and 3-hexenedioic acid. substances or copolymers of these. In addition, copolymers of the α,β-unsaturated carboxylic acid and esters such as ethyl ester, olefins such as ethylene, etc. may also be used.

Among these, homopolymers of acrylic acid and methacrylic acid or copolymers of these are preferred, and one or two selected from the group consisting of polyacrylic acid, polymethacrylic acid, and copolymers of acrylic acid and methacrylic acid are more preferred. The above polymer is more preferably at least one polymer selected from the group consisting of polyacrylic acid and polymethacrylic acid, and particularly preferably at least one polymer selected from the group consisting of acrylic acid homopolymers and methacrylic acid homopolymers.

Here, in the first embodiment, polyacrylic acid includes both homopolymers of acrylic acid and copolymers of acrylic acid and other monomers. In the case of a copolymer of acrylic acid and other monomers, the polyacrylic acid contains usually 90 mass% or more, preferably 95 mass% or more, and more preferably 99 mass% or more derived from acrylic acid in 100 mass% of the polymer. structural unit.

In addition, in the first embodiment, polymethacrylic acid includes both homopolymers of methacrylic acid and copolymers of methacrylic acid and other monomers. In the case of a copolymer of methacrylic acid and other monomers, polymethacrylic acid contains usually 90 mass% or more, preferably 95 mass% or more, and more preferably 99 mass% or more in 100 mass% of the polymer. Structural unit derived from methacrylic acid.

A polycarboxylic acid is a polymer obtained by polymerizing a carboxylic acid monomer. The molecular weight of the polycarboxylic acid is preferably 500 to 2,500,000 and more preferably 5,000 to 2,000,000 from the viewpoint of excellent balance between gas barrier properties and workability. , more preferably 10,000～1,500,000, further preferably 100,000～1,200,000.

Here, the molecular weight of the polycarboxylic acid is a weight average molecular weight in terms of polyethylene oxide, and can be measured using gel permeation chromatography (GPC).

By neutralizing the polycarboxylic acid with a volatile base, gelation can be suppressed when zinc or a polyamine described below is mixed with the polycarboxylic acid. Therefore, among polycarboxylic acids, from the viewpoint of preventing gelation, it is preferable to use a volatile base to form a partially neutralized product or a completely neutralized product of the carboxyl group. The neutralizer can be obtained by partially or completely neutralizing the carboxyl group of the polycarboxylic acid using a volatile base (ie, partially or completely making the carboxyl group of the polycarboxylic acid into a carboxylate salt). This prevents gelation when polyamine or zinc is added.

The partially neutralized product is prepared by adding a volatile base to an aqueous solution of the polycarboxylic acid polymer, and the desired degree of neutralization can be obtained by adjusting the ratio of the polycarboxylic acid to the volatile base. In the first embodiment, from the viewpoint of fully suppressing gelation caused by the neutralization reaction with the amine group of the polyamine, the degree of neutralization of the polycarboxylic acid by the volatile base is preferably 30 equivalent% to 100 equivalent%, more preferably 50 equivalent% to 100 equivalent%.

As the volatile base, any water-soluble base can be used.

Examples of the volatile base include tertiary amines such as ammonia, morpholine, alkylamine, 2-dimethylaminoethanol, N-methylmorpholine, ethylenediamine, and triethylamine, or aqueous solutions of these; or a mixture of these. From the viewpoint of obtaining good gas barrier properties, an ammonia aqueous solution is preferred.

The mixture constituting the gas barrier laminate of the first embodiment preferably further contains a carbonic acid ammonium salt. The carbonate-based ammonium salt is added in order to bring zinc, which will be described later, into the state of a zinc ammonium carbonate complex, improve the solubility of zinc, and prepare a uniform solution containing zinc.

Examples of carbonic acid-based ammonium salts include ammonium carbonate, ammonium bicarbonate, and the like. Ammonium carbonate is preferred in terms of being easily volatilized and not easily remaining in the obtained gas barrier layer.

(Zinc) Zinc (Zn) can form a water-resistant Zn phosphate bond with a phosphorus compound, and a mass peak represented by ⁶⁴ ZnPO ₄ H ^- can be detected by TOF-SIMS analysis. In addition, when the gas barrier layer contains a polycarboxylic acid, a salt is formed with the polycarboxylic acid. Zn may be any zinc or zinc compound that can be added to the mixture for forming the gas barrier layer. For example, metallic zinc, zinc oxide (ZnO), zinc compounds, etc. can be used. The amount of zinc added may be 0.1 mol or more and 0.5 mol or less per 1 mol of the carboxyl group of the polycarboxylic acid.

(Phosphorus Compound) As mentioned above, when performing mass analysis on the barrier layer, it is preferable to detect PO ₂ ^- and/or PO ₃ ^- . In order to provide such a barrier layer, the mixture before hardening preferably contains a phosphorus compound or a salt thereof. The phosphorus compound or the phosphorus compound in its salt contains more than one -P-OH group in the molecular structure. The phosphorus compound can also be formulated in the mixture as a salt. From the viewpoint of further improving the water vapor barrier property after retort treatment, the phosphorus compound preferably contains two or more -P-OH groups, and more preferably contains three or more -P-OH groups. In addition, from the viewpoint of productivity, the number of -P-OH groups in the phosphorus compound may be, for example, 10 or less. Specific examples of the phosphorus compound include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, and derivatives thereof. Specifically, polyphosphoric acid has a condensed structure of two or more phosphoric acids in its molecular structure. Examples thereof include diphosphoric acid (pyrophosphoric acid), triphosphoric acid, polyphosphoric acid in which four or more phosphoric acids are condensed, and the like. Specific examples of the derivatives include esters of the phosphorus compounds such as phosphorylated starch and phosphate cross-linked starch; halides such as chlorides; anhydrides such as tetraphosphoric acid decaoxide; and nitrotris(methylenephosphonic acid). ), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid) and other compounds having a structure in which the hydrogen atom bonded to the phosphorus atom is replaced by an alkyl group. From the viewpoint of further improving the balance between barrier properties and productivity, the phosphorus compound is one or two or more selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid and salts thereof. , more preferably at least one selected from the group consisting of phosphoric acid and phosphorous acid, phosphonic acid and salts thereof. Specific examples of salts among the salts of phosphorus compounds include salts of monovalent metals such as sodium and potassium; and ammonium salts. From the viewpoint of barrier properties, the salt of the phosphorus compound is preferably an ammonium salt. The concentration of P atoms of the phosphorus compound is typically 5 × 10 ^-4 mol or more, preferably 1 × 10 ^-3 mol or more, and more preferably 3 × relative to 1 mol of the carboxyl group of the polycarboxylic acid in the mixture. 10 ^-3 mol or more, and typically 0.3 mol or less, preferably 0.1 mol or less, more preferably 0.05 mol or less. For phosphorus compounds that contain one P atom in the chemical formula like phosphoric acid, the mole number of the P atom and the mole number of the phosphorus compound have the same meaning. It is thought that if the phosphorus compound derived from the phosphorus compound or its salt is of such a concentration, excessive expansion and contraction of the gas barrier layer during retort processing or the like can be suppressed by reliably forming a Zn bond with the water-resistant phosphorus compound. The gas barrier properties of the gas barrier laminate after the retort treatment are further improved. The presence of the phosphorus compound and the Zn bond is reflected in the mass peak of ⁶⁴ ZnPO ₄ H ^- obtained using the TOF-SIMS analysis.

(polyamine) The mixture constituting the gas barrier laminate of the first embodiment preferably further contains polyamine. By containing a polyamine, the barrier properties of the obtained gas barrier laminate can be improved, and the interlayer adhesion of the obtained gas barrier laminate can be improved, resulting in good delamination resistance.

Polyamines are polymers having two or more amine groups in the main chain, side chains or terminals. Specific examples include: aliphatic polyamines such as polyallylamine, polyvinylamine, polyethyleneimine, and poly(trimethyleneimine); side chains such as polylysine acid and polyarginine Polyamides with amine groups, etc. In addition, a polyamine in which part of the amine group has been modified may also be used. From the viewpoint of obtaining good gas barrier properties, polyethyleneimine is more preferred. The amount of polyamine added may be 0 mol or more and 0.9 mol or less per 1 mol of carboxyl groups contained in the polycarboxylic acid.

From the viewpoint of excellent balance between gas barrier properties and workability, the weight average molecular weight of the polyamine is preferably 50 to 2,000,000, more preferably 100 to 1,000,000, further preferably 1,500 to 500,000, still more preferably 1,500 to 100,000. More preferably, it is 1,500-50,000, still more preferably 3,500-20,000, still more preferably 5,000-15,000, and particularly preferably 7,000-12,000. Here, in the first embodiment, the molecular weight of the polyamine can be measured using the boiling point elevation method or the viscosity method.

(Method for manufacturing gas barrier layer) The gas barrier layer of the first embodiment can be produced as follows, for example. First, a completely or partially neutralized solution of the carboxyl groups constituting the polycarboxylic acid is prepared.

A volatile base is added to the polycarboxylic acid to completely or partially neutralize the carboxyl groups of the polycarboxylic acid. By neutralizing the carboxyl group of the polycarboxylic acid, gelation caused by the reaction between the carboxyl group constituting the polycarboxylic acid and the amine group constituting the zinc or polyamine is effectively prevented in the subsequent step when zinc or polyamine is added. , and obtain a uniform gas barrier coating intermediate.

Next, a zinc salt compound and a carbonic acid ammonium salt are added to the intermediate and dissolved, and the generated zinc ions are used to form a zinc salt with the -COO- group constituting the polycarboxylic acid. In this case, the -COO- group that forms a salt with zinc ions refers to both the carboxyl group that is not neutralized with the base and the -COO- group that is neutralized with the base. In the case of a -COO- group neutralized with a base, the zinc-derived zinc ions exchange and coordinate to form a zinc salt of the -COO- group. Furthermore, by adding phosphoric acid after forming a zinc salt, a gas barrier coating material (mixture) can be obtained. At this time, polyamine may be further added.

The gas barrier coating material (mixture) produced in the above manner is applied on an inorganic layer described below, and dried and hardened to form a gas barrier layer. The method of applying the gas barrier coating material to the base material layer is not particularly limited, and a common method can be used. For example, gravure coaters using Meyer bar coaters, air knife coaters, direct gravure coaters, indirect gravure, arc gravure coaters, reverse gravure and spray nozzle methods, etc. Top feed reverse coater, bottom feed reverse coater and nozzle feed reverse coater and other reverse roller coaters, five-roller coater, die lip coater, rod coater The coating method is performed by various well-known coating machines such as machine, reverse rod coater, die coater, etc.

The coating amount (wet thickness) of the gas barrier coating material (mixture) is preferably 0.05 μm or more, more preferably 1 μm or more. In addition, the coating amount is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 100 μm or less. In addition, the average thickness of the gas barrier layer after drying and hardening is preferably from 0.05 μm to 10 μm, more preferably from 0.08 μm to 5 μm, and even more preferably from 0.1 μm to 1 μm. When it is below the upper limit, curling of the obtained gas barrier laminate or gas barrier film can be suppressed. Moreover, when it is more than the said lower limit value, the barrier performance of the obtained gas barrier laminate or gas barrier film can be made more favorable.

Drying and heat treatment can be carried out after drying or at the same time.

The method of drying and heat treatment is not particularly limited as long as the object of the present invention can be achieved, as long as the gas barrier coating material can be hardened or the gas barrier coating material can be heat-cured. Examples include devices that utilize convection heat transfer such as ovens and dryers, devices that utilize conductive heat transfer such as heating rollers, devices that utilize radiation heat transfer using electromagnetic waves such as infrared, far-infrared, and near-infrared heaters, and devices that utilize internal heat transfer such as microwaves. Heating device. As an apparatus used for drying and heat treatment, from the viewpoint of manufacturing efficiency, an apparatus capable of performing both drying and heat treatment is preferred. Among them, specifically, it is preferable to use a hot air oven from the viewpoint that it can be used for various purposes such as drying, heating, and annealing. In addition, from the viewpoint of excellent heat conduction efficiency to the film, it is preferable to use heating. Roller. In addition, methods used for drying and heat treatment may be appropriately combined. A hot air oven and a heating roller may be used together. For example, if the gas barrier coating material is dried in a hot air oven and then heated using a heating roller, the time of the heating treatment step will be shortened, which is preferable from the viewpoint of manufacturing efficiency. In addition, it is preferable to perform drying and heating processing only by a hot air oven.

For example, the heat treatment temperature is preferably 80°C to 250°C and the heat treatment time is 1 second to 10 minutes. More preferably, the heat treatment temperature is 120°C to 240°C and the heat treatment time is 1 second to 1 minute. More preferably, the heat treatment temperature is 80°C to 250°C and the heat treatment time is 1 second to 10 minutes. Preferably, the heat treatment temperature is 170°C to 230°C and the heat treatment time is 1 second to 30 seconds. Furthermore, as mentioned above, by using a heating roller together, heat processing can be performed in a short time. It is important to adjust the heat treatment temperature and heat treatment time according to the wet thickness of the gas barrier coating material.

The gas barrier coating material (mixture) forms metal cross-links and water-resistant phosphate Zn bonds through the zinc salt of the -COO- group constituting the polycarboxylic acid (reflected in ⁶⁴ ZnPO ₄ obtained by the TOF-SIMS analysis) H ^- mass peak), drying and heat treatment can be performed to obtain a gas barrier layer with excellent gas barrier properties.

(Inorganic layer) Examples of the inorganic substances constituting the inorganic substance layer 4 include metals, metal oxides, metal nitrides, metal fluorides, and metal oxynitrides that can form a barrier thin film.

Examples of the inorganic substance constituting the inorganic substance layer 4 include elements selected from Group 2A of the Periodic Table such as beryllium, magnesium, calcium, strontium, and barium; transition elements of the Periodic Table such as titanium, zirconium, ruthenium, hafnium, and tantalum; Group 2B of the Periodic Table such as zinc; Elements; aluminum, gallium, indium, thallium and other periodic table group 3A elements; periodic table group 4A elements such as silicon, germanium and tin; periodic table group 6A elements such as selenium, tellurium and other elements, oxides, nitrides, fluorides, etc. or one or more of nitrogen oxides, etc. Furthermore, in the first embodiment, the group names of the periodic table are represented by the old CAS formula.

Furthermore, among the inorganic substances, one or two or more inorganic substances selected from the group consisting of silica, alumina, and aluminum are preferred in terms of excellent balance between barrier properties, cost, etc., and more preferred are aluminum oxide. Furthermore, the silicon oxide may also contain silicon monoxide and silicon suboxide in addition to silicon dioxide.

The inorganic substance layer is formed from the inorganic substance. The inorganic layer 4 may include a single inorganic layer or multiple inorganic layers. In addition, when the inorganic layer 4 includes a plurality of inorganic layers, it may include the same type of inorganic layer or may include different types of inorganic layers.

From the viewpoint of a balance between barrier properties, adhesion, operability, etc., the thickness of the inorganic layer 4 is usually from 1 nm to 1000 nm, preferably from 1 nm to 500 nm. In the first embodiment, the thickness of the inorganic layer can be determined from an observation image obtained by a transmission electron microscope or a scanning electron microscope.

The method for forming the inorganic layer is not particularly limited. For example, it can be vacuum evaporation, ion plating, sputtering, chemical vapor deposition, physical vapor deposition, chemical vapor deposition (CVD). Vapor Deposition method), plasma CVD method, sol-gel method, etc. to form the inorganic layer 4 on one or both sides of the base material layer 2. Among them, sputtering, ion plating, chemical vapor deposition (CVD), physical vapor deposition (PVD (Physical Vapor Deposition)), plasma CVD, or film formation under reduced pressure are ideal. Therefore, it is expected that chemically active molecular species containing silicon such as silicon nitride or silicon oxynitride react rapidly to improve the smoothness of the surface of the inorganic layer 4 and reduce the number of holes. In order to rapidly carry out these binding reactions, it is ideal that the inorganic atom or compound is a chemically active molecular species or atomic species.

(Substrate layer) The base material layer 2 can be used without particular limitation as long as it can be coated with a solution of the gas barrier coating material. Examples include: organic materials such as thermosetting resin, thermoplastic resin, or paper; inorganic materials such as glass, pottery, ceramics, silicon oxide, silicon oxynitride, silicon nitride, cement, aluminum, alumina, iron, copper, stainless steel, and other metals Material; a base material layer of a multilayer structure including a combination of organic materials or a combination of organic materials and inorganic materials, etc. Among these, for example, in the case of various film applications such as packaging materials and panels, it is preferable to use thermosetting resins, thermoplastic resins, plastic films, or organic materials such as paper.

As the thermosetting resin, a known thermosetting resin can be used. Examples include epoxy resin, unsaturated polyester resin, phenol resin, urea-melamine resin, polyurethane resin, silicone resin, polyimide, and the like.

As the thermoplastic resin, a known thermoplastic resin can be used. Examples include polyolefins (polyethylene, polypropylene, poly(4-methyl-1-pentene), poly(1-butene), etc.), polyesters (polyethylene terephthalate, poly(p-p) Butylene phthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, polyethylene glycol m-phenylenediamine, etc.), polyvinyl chloride, polyimide, Ethylene-vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, fluororesin, or a mixture thereof, etc.

Among these, from the viewpoint of improving transparency, it is preferable to be selected from the group consisting of polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, and poly(p-p). One or two or more resins in the group consisting of butylene phthalate are preferably selected from the group consisting of polyamide, polyamide and polyamide from the viewpoint of excellent pinhole resistance, crack resistance and heat resistance. One or more resins in the group consisting of ethylene terephthalate and polybutylene terephthalate. In addition, the base material layer 2 containing the thermoplastic resin may be a single layer or two or more layers depending on the use of the gas barrier laminate 8 . In addition, a film made of the thermosetting resin or thermoplastic resin may be stretched in at least one direction, preferably in a biaxial direction, to form a base material layer.

The base material layer 2 of the first embodiment is preferably made of polypropylene, polyethylene terephthalate, and polyethylene naphthalate from the viewpoint of excellent transparency, rigidity, and heat resistance. , a biaxially stretched film formed of one or more thermoplastic resins selected from the group consisting of polyamide, polyimide and polybutylene terephthalate, and more preferably a biaxially stretched film made of polyamide, polyimide and polybutylene terephthalate. A biaxially stretched film formed of one or more thermoplastic resins selected from ethylene formate and polybutylene terephthalate.

In addition, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, acrylic resin, urethane resin, etc. may also be coated on the surface of the base material layer 2 .

Furthermore, the base material layer 2 may be surface-treated in order to improve the adhesiveness. Specifically, surface activation treatments such as corona treatment, flame treatment, plasma treatment, and primer coat treatment can also be performed.

From the viewpoint of obtaining good film properties, the thickness of the base material layer 2 is preferably 1 μm to 1000 μm, more preferably 1 μm to 500 μm, and still more preferably 1 μm to 300 μm.

The shape of the base material layer 2 is not particularly limited, and examples include a sheet or film shape, a tray, a cup, a hollow body, and the like.

(base coat) In the gas barrier laminated body 8 , from the viewpoint of improving the adhesion between the base material layer 2 and the inorganic layer 4 , the primer layer 3 may be formed on the surface of the base material layer 2 . The undercoat layer is preferably a layer formed of an epoxy (meth)acrylate compound or a urethane (meth)acrylate compound.

The undercoat layer 3 is preferably a layer obtained by hardening at least one selected from the group consisting of epoxy (meth)acrylate compounds and urethane (meth)acrylate compounds.

Examples of the epoxy (meth)acrylate compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolak type epoxy compound, and a cresol novolac type epoxy compound. Compounds obtained by reacting epoxy compounds such as varnish-type epoxy compounds and aliphatic epoxy compounds with acrylic acid or methacrylic acid, and further examples include acid-modified rings obtained by reacting the epoxy compound with carboxylic acid or its anhydride. Oxy(meth)acrylate. These epoxy (meth)acrylate compounds are coated on the surface of the base material layer together with a photopolymerization initiator and a diluent including other photopolymerization initiators or heat-reactive monomers if necessary, and then irradiated Ultraviolet rays, etc. form a primer layer through a cross-linking reaction.

Examples of the urethane (meth)acrylate-based compound include acrylation of an oligomer containing a polyol compound and a polyisocyanate compound (hereinafter also referred to as a polyurethane-based oligomer). Those who become mature and so on.

The polyurethane oligomer can be obtained from a condensation product of a polyisocyanate compound and a polyol compound. Specific polyisocyanate compounds include methylene-bis(terphenylene diisocyanate), hexamethylene diisocyanate-hexanetriol adduct, hexamethylene diisocyanate, toluene diisocyanate, and toluene diisocyanate. Adduct of trimethylolpropane, 1,5-naphthalene diisocyanate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-toluene diisocyanate dimer, hydrogenated xylene diisocyanate, tris(4-phenyl isocyanate)thiophosphate, etc. Specific polyol compounds include polyether polyols such as polyoxytetramethylene glycol and polyadipate polyols. , polyester polyols such as polycarbonate polyol, copolymers of acrylates and hydroxyethyl methacrylate, etc. Examples of the monomer constituting the acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (meth)acrylate. Methoxyethyl acrylate, butoxyethyl (meth)acrylate, phenyl (meth)acrylate, etc.

These epoxy (meth)acrylate compounds and urethane (meth)acrylate compounds are used in combination as necessary. Examples of methods for polymerizing these compounds include various known methods, specifically methods by irradiating energy rays containing ionizing radiation, heating, or the like.

When hardening with ultraviolet rays is used to form the undercoat layer, acetophenones, benzophenones, Michler's benzoyl benzoate, and α-pentyl oxime are preferred. Esters, thioxanthones, etc. are used as photopolymerization initiators, and n-butylamine, triethylamine, tri-n-butylphosphine, etc. are used as photosensitizers, and are mixed and used. In addition, in the first embodiment, an epoxy (meth)acrylate compound and a urethane (meth)acrylate compound may be used together.

In addition, these epoxy (meth)acrylate compounds or urethane (meth)acrylate compounds are diluted with (meth)acrylic monomers. Examples of such a (meth)acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. , methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenyl (meth)acrylate, as the polyfunctional monomer, trimethylolpropane tri(meth)acrylic acid can be exemplified Esters, hexylene glycol (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc.

Among them, when a urethane (meth)acrylate compound is used as the undercoat layer, the oxygen gas barrier properties of the gas barrier laminate 8 obtained are further improved. The thickness of the undercoat layer of the first embodiment is usually in the range of 0.01 g/m ² to 100 g/m ² in terms of coating amount, preferably 0.05 g/m ² to 50 g/m ² .

(adhesive layer) In addition, the adhesive layer 6 may be provided on the gas barrier layer 5 . The adhesive layer 6 only needs to contain a known adhesive. Examples of adhesives include organic titanium-based resins, polyethyleneimine-based resins, urethane-based resins, epoxy-based resins, acrylic resins, polyester-based resins, oxazoline group-containing resins, modified Laminated adhesives composed of silicone resin, alkyl titanate, polyester-based polybutadiene, etc., or one-liquid or two-liquid polyols and polyisocyanates, water-based urethanes, ion polymerization Things etc. Alternatively, a water-based adhesive whose main raw material is acrylic resin, vinyl acetate resin, urethane resin, polyester resin, etc. can also be used.

In addition, other additives such as a hardener and a silane coupling agent may be added to the adhesive according to the use of the gas barrier laminate 8 . When the gas barrier laminate is used for hot water treatment such as steaming, a dry layer represented by a polyurethane adhesive is preferred from the viewpoint of heat resistance or water resistance. The pressure adhesive is more preferably a solvent-based two-liquid curing type polyurethane adhesive.

The gas barrier laminate 8 of the first embodiment has excellent gas barrier properties after cooking, and can be suitably used as packaging materials, especially food packaging materials for contents requiring high gas barrier properties. It can also be suitably used for medical purposes and industrial applications. Various packaging materials for use, daily groceries, etc.

In addition, the gas barrier laminate 8 of the first embodiment can be suitably used as, for example, a vacuum insulation film requiring high barrier performance; a sealing film for sealing electroluminescent elements, solar cells, and the like.

<Second Embodiment> FIG. 5 is a cross-sectional view schematically showing an example of the structure of a gas barrier laminate according to a second embodiment. The gas barrier laminate 100 includes a base material layer 101; a gas barrier layer 103 provided on at least one surface of the base material layer 101; and an inorganic layer 102 provided between the base material layer 101 and the gas barrier layer 103. Let the mass peak intensity of PO ₂ ^- when the gas barrier layer 103 be subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS) be I (PO ₂ ^- ), and the mass peak intensity of PO ₃ ^- be I (PO ₃ ^- ), when the mass peak intensity of C ₃ H ₃ O ₂ ^- is set to I (C ₃ H ₃ O ₂ ^- ), (I (PO ₂ ^- ) + I (PO ₃ ^- ))/I The value of (C ₃ H ₃ O ₂ ^- ) is 0.02 to 5, preferably 0.05 to 3. In addition, the gas barrier layer 103 includes one or more metal elements selected from the group consisting of Zn, Ca, Mg, Ba, and Al, and the gas barrier layer 103 is analyzed by X-ray photoelectron spectroscopy. The calculated composition ratio of the metal element in the gas barrier layer 103 is 1 atomic % to 15 atomic %, preferably 1.5 atomic % to 12 atomic %.

The value of (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) is 0.02 to 5, or the composition ratio of the metal element in the gas barrier layer 103 is 1 The meaning of atomic % to 15 atomic % is as follows.

The detection of PO ₂ ^- or PO ₃ ^- from the gas barrier layer 103 by mass analysis means that the gas barrier layer 103 contains a phosphorus compound represented by phosphoric acid. Furthermore, the value of I(PO ₂ ^- ) + I(PO ₃ ^- ) is considered to be a value related to the amount (concentration) of the phosphorus compound in the gas barrier layer 103 .

In addition, the detection of C ₃ H ₃ O ₂ ^- from the gas barrier layer 103 by mass analysis means that the gas barrier layer 103 contains polycarboxylic acid of polyacrylic acid or its derivatives/similar compounds (polyacrylic acid, etc.) . Furthermore, the value of I(C ₃ H ₃ O ₂ ⁻ ) is considered to be a value related to the amount (concentration) of carboxyl groups of the polycarboxylic acid contained in the gas barrier layer 103 .

According to the findings and research of the present inventors, phosphorus compounds, such as phosphoric acid as a representative example, can interact with polyvalent metals such as Zn, Ca, Mg, Ba, and Al to form phosphoric acid-polyvalent metal in the gas barrier layer 103 key. Although the details are not clear, it is believed that the bond between phosphoric acid and the polyvalent metal is difficult to break through hydration, and therefore it is resistant to retort processing. Good gas barrier properties can also be obtained.

When the value of (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) is 0.02 to 5, it means that the gas barrier layer 103 contains a polycarboxylic acid or the like. A relatively sufficient amount of phosphorus compound. In addition, when the composition ratio of the metal element in the gas barrier layer 103 is 1 atomic % to 15 atomic %, it means that the gas barrier layer 103 contains an appropriate amount of a polyvalent metal cross-linked with phosphoric acid or the like. That is, the value of (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) of the gas barrier layer 103 is 0.02 to 5 and the above-mentioned The case where the composition ratio of the metal element is 1 atomic % to 15 atomic % corresponds to the presence of a sufficient amount of phosphoric acid-polyvalent metal bonds in the gas barrier layer 103 (resistance to retort processing, etc.).

Incidentally, according to the findings of the present inventors, it is considered that when the gas barrier layer 103 contains at least one metal element among Zn, Ca, Mg, Ba, and Al, for example, A cross-linked structure like -COO···M···OOC- can be formed between the carboxyl groups of polyacrylic acid and the like and metal elements. It is considered that the barrier layer 103 includes such a cross-linked structure, thereby further improving the barrier properties. Just in case, the so-called "composition ratio of Zn, Ca, Mg, Ba, and Al in the gas barrier layer 103" means the total ratio of these metal elements when the gas barrier layer 103 contains a plurality of metal elements.

The analysis of the gas barrier layer 103 based on TOF-SIMS is supplemented in advance. In order to analyze the inside of the gas barrier layer 103, it is preferable to perform sputter etching on the surface layer of the gas barrier layer 103 using the Ar-gas cluster ion beam (Ar-GCIB) attached to the TOF-SIMS analysis device before analysis. Thereby, the inside of the gas barrier layer 103 is exposed. The use of Ar-GCIB mitigates damage to the gas barrier layer 103 caused by etching.

An example of specific conditions for Ar-GCIB etching is shown. GCIB output: 5 kV, 5 μA GCIB processing time: the time point when the spectral pattern of TOF-SIMS no longer changes

In addition, an example of specific conditions for TOF-SIMS analysis is shown. Analytical device: PHI Nano (NaNo) TOF II manufactured by Nippon Vacuum (Ulvac-phi) Co., Ltd. Primary ion: Bi ₃ ⁺⁺ primary ion source output: 30 kV, 0.5 μA Analysis area: 300 μm × 300 μm (as primary ion (beam scanning area) During analysis, charge neutralization is carried out by low-energy electron beam and low-energy Ar ion irradiation attached to the device.

The analysis method of data obtained by TOF-SIMS is described in advance. In order to conduct detailed mass spectrum analysis, for each positive and negative secondary ion, it is better to obtain the raw data string and total ion count pairing the mass number m _i and its corresponding count number c _i through an analysis device ( _CT ). Here, i=0, 1,···,N. In the original data string, m _i is arranged in ascending order. C _T is the total number of secondary ion counts detected by the detector. The range of mass numbers around the mass spectrum peak of interest is set to i=N ₁ , N ₁ +1,..., N ₂ . The data c _i of the count number in this range obtained by analysis is approximated using y _i as shown in the following equation. Specifically, c _i is approximated by curve fitting using a background level b ⁰ and K triangular shape functions Y _j (mi ₎ .

[Number 4]

In the above equation, b ⁰ is a constant. Y _j (m _i ) is a function (triangular shape function) having a peak value Y ⁰ _j at the mass number x ⁰ _j as shown in FIG. 7 , and is represented by the following equation.

[Number 5]

The half-value width of the triangle shape function Y _j ( _mi ) is (B ^- _j +B ⁺ _j )/2. b ⁰ , x ⁰ _j , Y ⁰ _j , B ^- _j , and B ⁺ _j become the fitting parameters. j is j=1,···,K. For example, when the background of the spectrum is not a constant value but changes linearly with respect to m _i , b ⁰ is combined with the triangular shape function Y _j (mi ₎ to approximate the background. When the mass spectrum peak of interest is a single peak, except for the background, a triangle shape function is used for approximation. When it is close to other mass peaks, multiple triangle shape functions including other mass peaks are used for approximation. approximate. If the approximated mass spectrum peak of interest is the j=kth peak among K triangular shape functions, the peak intensity I is reduced to i=n ₁ ,···,n using the total ion count (C _T ) It is represented by the normalized numerical value of the sum of Y _k ( _mi ) up to ₂ , and is calculated according to the following formula.

[Number 6]

If there is a tail portion in a mass spectrum peak, it becomes difficult to define the range of masses that should be counted. Therefore, in order to avoid this situation in the above, a triangle shape function is used to approximate the mass spectrum peak. By this, the number of counts in the tail portion of the mass spectral peak is ignored. Curve fitting was performed in such a way that the central part of the mass spectral peak fit a triangular shape function.

The mass number of the fragment of interest in the second embodiment was calculated and shown below. The atomic mass of an isotope depends on https://physics.nist.gov/.

[table 3] number of atoms isotope Atomic mass PO ₂ P O ₃ C ₃ H ₃ O ₂ EN ^1H 1.007825 3 ^12C 12 3 1 ^14N 14.003074 1 ^16O 15.994915 2 3 2 ^31P 30.973762 1 1 mass number 62.96359 78.95851 71.01331 26.00307

The calculation of the mass peak intensity of the fragment of interest in the second embodiment is supplemented in advance.

(Calculation of mass peak intensity of PO ₂ ^- ) Focusing on the range of mass number = 62.5 to 63.3 in the negative secondary ion spectrum, it was calculated by approximating the mass peak near 62.964 corresponding to ³¹ P ¹⁶ O ₂ ^- Based on the data of the triangle shape function and m _i , calculate the sum of the count numbers, and set the value normalized by C _T as the mass peak intensity I (PO ₂ ^- ) of PO ₂ ^- .

An example of curve fitting is shown in FIG. 8 , and the calculation results of the sum of the parameters used at this time and the number of counts are shown in the table below. The total number of counts obtained based on the triangular shape function that approximates the target mass peak shape of PO ₂ ^- and the data of m _i is 436. The total ion count (C _T ) of negative secondary ions at this time is 6838528, so the mass peak intensity I (PO ₂ ^- ) of PO ₂ ^- is as follows. I(PO ₂ ^- )=436/6838528=5.48×10 ^-5

[Table 4] b ⁰ Y _j (m _i ) J 0 1 (= target) b ⁰ 3 x ⁰ 63.025 62.964 B ⁺ 0.06 0.012 ^B- 0.06 0.012 Y ⁰ 12 28 Sum 1533 934 436

Figure 8 showing an example of curve fitting is supplemented in advance. (i) In order to obtain an approximate curve _yi that reproduces the measurement data c _i near the target peak position, a curve of "the background b ⁰ " and "triangular shape function approximation of other components" and "the target triangle shape function" are required Y _j ( _mi )" curve. (ii) In the example of Figure 8, when the mass number (m/z) is around 62.94 to 62.98, in order to obtain the "approximate curve _yi " that reproduces the measurement data c _i , "background b ⁰ " and "as the target The curve of the triangular shape function Y _j (m _i )" (j=1 in Table 2), and the curve of the "triangular shape function approximation of other components" (j=0 in Table 2). (iii) The reason why the large peak near m/z 63 to 63.05 is not approximated using a triangle shape function is that it clearly does not overlap with the target peak component.

(Calculation of mass peak intensity of PO ₃ ^- ) Focusing on the range of mass number = 78.5 to 79.3 in the negative secondary ion spectrum, it was calculated by approximating the mass peak near 78.959 corresponding to ³¹ P ¹⁶ O ₃ ^- From the data of the triangle shape function and m _i , calculate the sum of the count numbers, and set the value normalized by C _T as the mass peak intensity I (PO ₃ ^- ) of PO ₃ ^- .

(Calculation of the mass peak intensity of C ₃ H ₃ O ₂ ^- ) Focusing on the range of mass number = 70.7 to 71.4 in the negative secondary ion spectrum, the value obtained by fitting the autocurve is equivalent to ¹² C ₃ ¹ H ₃ ¹⁶ Calculate the sum of the number of counts using the triangular shape function Y _k (mi) _{and m i approximated} by the mass peak near 71.013 of O ₂ ^- , and set the value normalized by C _T to C ₃ H ₃ O The mass peak intensity of ₂ ^- I (C ₃ H ₃ O ₂ ^- ).

(Calculation of the mass peak intensity of CN ^- ) Focusing on the range of mass number = 70.7 to 71.4 in the negative secondary ion spectrum, the calculation was performed based on the mass peak near 26.003 corresponding to ¹² C ¹⁴ N ^- obtained by fitting the curve. The approximated triangular shape function Y _k (mi ₎ and the data of m _i are calculated as the sum of the number of counts, and the value normalized by C _T is set as the mass peak intensity I (CN ^- ) of CN ^- .

The analysis of the gas barrier layer 103 based on X-ray photoelectron spectroscopy is supplemented in advance. An example of specific conditions for analysis is shown. Analytical device: AXIS-NOVA manufactured by KRATOS X-ray source: monochromated Al-Kα X-ray source output: 15 kV, 10 mA Analysis area: 300 μm×700 μm A neutralizing electron gun for charged correction is used during analysis.

In order to analyze the inside of the gas barrier layer 103, it is ideal to perform sputter etching on the surface layer of the gas barrier layer before analysis. Among them, in order to reduce damage to the gas barrier layer caused by etching, etching based on an Ar-gas cluster ion beam source is ideal. Through wide scanning, the detection elements are determined, and spectra are obtained through narrow scanning for each element. Furthermore, the background determined by the Shirley method is removed from the obtained spectrum, and the atomic composition ratio (atomic %) of the detected element is calculated using the relative sensitivity coefficient method based on the obtained peak area. By the way, the detection sensitivity of the atomic composition ratio in general XPS analysis is about 0.1 atomic %. For example, when a trace amount of a phosphorus compound is added to the gas barrier layer, the content of P cannot be detected in XPS analysis.

From another viewpoint, the gas barrier layer 103 preferably contains a certain amount of carboxylate structures (and, as a result, the amount of free carboxyl groups is small). This situation can be said to mean that the gas barrier layer 103 contains a cross-linked structure of, for example, metal-carboxyl groups to some extent. By including a certain amount of carboxylate structures in the gas barrier layer 103, the gas barrier properties can be further improved. Specifically, in the absorption spectrum obtained by infrared spectrometry of the gas barrier layer 103 using a total reflection measurement method, the total peak area in the range of the absorption band from 1493 cm ^-1 to 1780 cm ^-1 When A is used and the total peak area in the range of the absorption band from 1493 cm ^-1 to 1598 cm ^-1 is D, the area ratio D/A is preferably 0.5 or more, more preferably 0.58 or more, still more preferably 0.6 above. The upper limit of D/A is, for example, 0.8 or less. According to conventional knowledge of infrared spectroscopy or the knowledge of the present inventors, the absorption of νC=O based on a free carboxylic acid is around 1700 cm ^-1 or the absorption based on ν (C=O) of a carboxylic acid salt is In the vicinity of 1540 cm ^-1 to 1560 cm ^-1 , D/A can be used as an index of the amount of the carboxylate structure contained in the gas barrier layer 103. Incidentally, as will be described later, when the gas barrier layer 103 contains a polyamine, the absorption of ν (C=O) based on the amide bond may be around 1630 cm ^-1 to 1685 cm ^-1 Visible.

Infrared spectrometry by total reflection measurement can be performed specifically as follows. First, a measurement sample of 1 cm×3 cm was cut out from the gas barrier layer 103 . Then, the infrared absorption spectrum of the surface of the gas barrier layer 103 is obtained by infrared total reflection measurement (ATR (Attenuated Total Reflection) method). In the obtained infrared absorption spectrum, a straight line (baseline: N) is used to connect the measurement point at 1493 cm ^-1 and the measurement point at 1780 cm ^-1 to obtain the difference spectrum between the obtained infrared absorption spectrum and N, and then as spectrum (S _BN ). When the thickness of the gas barrier layer 103 is approximately 0.5 μm or less, the measured infrared absorption spectrum includes the influence of the layer below the gas barrier layer. In this case, a base material including only a lower layer without a gas barrier layer was also prepared as a measurement sample, and the ATR-IR spectrum of the base material surface was obtained in the same way, and the difference spectrum from the baseline N was calculated and used as the spectrum ( _SSN ). In the wave number range of 1493 cm ^-1 to 1780 cm ^-1 , when a clear absorption peak is displayed, a difference spectrum analysis based on the following formula is performed to obtain a spectrum without the influence of the substrate (S _BN ') . <Spectrum (S _BN ')>=<Spectrum (S _BN )>-α*<Spectrum (S _SN )> Here, α is a coefficient for removing the influence of the base material, and is 0≦α<1.

In the obtained difference spectrum (S _BN '), the area of the spectrum in the wave number range of 1493 cm ^-1 to 1780 cm ^-1 is set as the total peak area A, and the area of the wave number range of 1493 cm ^-1 to 1598 cm ^-1 is The area of the spectrum in the numerical range is set as the total peak area D. Here, as a specific example, when the base material layer is a polyethylene terephthalate (PET) film, a method for determining the coefficient α for removing the influence of the base material including the base material layer, the inorganic layer, etc. Supplement. PET has a large absorption peak near 1700 cm ^-1 , thus affecting the calculation of the peak area in the wave number range from 1493 cm ^-1 to 1780 cm ^-1 . In order to remove this effect, a general difference spectrum analysis method is used. For example, as a sharp absorption peak of PET adjacent to the wave number range of 1493 cm ^-1 to 1780 cm ^-1 and not overlapping with the absorption peak of the gas barrier layer, an absorption peak near 1340 cm ^-1 is selected and as a reference peak. In the spectrum (S _BN ') obtained by the difference spectrum analysis, by adjusting the coefficient α to eliminate the reference peak near 1340 cm ^-1 , it is possible to obtain a spectrum in which the absorption peak of PET near 1700 cm ^-1 is removed. Effect spectrum (S _BN '). In addition, the coefficient α can also be obtained as the area ratio of the infrared absorption spectrum as follows. Regarding the infrared absorption spectrum measured from the surface of the gas barrier layer and the infrared absorption spectrum of the base material including only the lower layer without the gas barrier layer, a straight line (baseline: M) connects the measurement point at 1325 cm ^-1 and 1355 cm At the measurement point at ^-1 , in the wave number range of 1325 cm ^-1 to 1355 cm ^-1 , the difference spectrum between the obtained infrared absorption spectrum and the baseline M is obtained, which is regarded as spectrum (S _BM ) and spectrum (S _SM ) respectively. . Regarding the spectrum (S _BM ) and the spectrum (S _SM ), if the peak areas above 1325 cm ^-1 and below 1355 cm ^-1 are respectively the area (A _BM ) and the area (A _SM ), the coefficient α is given by the following formula Find out. α= _ABM / _ASM

For the measurement of infrared absorption spectrum (infrared total reflection measurement: ATR method), for example, the IRT-5200 device manufactured by JASCO Corporation can be used, equipped with a PKM-GE-S (Germanium) crystal, at an incident angle of 45 degrees, room temperature, The decomposition can be carried out under the conditions of 4 cm ^-1 and a cumulative number of 100 times.

FIG. 6 is a cross-sectional view schematically showing another structural example of the gas barrier laminate. The basic structure of the gas barrier laminated body 110 of FIG. 6 is the same as the gas barrier laminated body 100 of FIG. 5 , but the base material layer 101 and the inorganic material layer 102 are not in direct contact. The aspects of the base coat 104 differ between. Also in the gas barrier laminated body 110, the same effect as that of the gas barrier laminated body 100 can be obtained. In addition, in the gas barrier laminate 110, by providing the primer layer 104 between the base material layer 101 and the inorganic material layer 102, the adhesion between the base material layer 101 and the inorganic material layer 102 can be further improved.

The gas barrier laminate of the second embodiment can be produced by using an appropriate amount of appropriate raw materials and selecting an appropriate manufacturing method and manufacturing conditions. These details will be described later. In terms of forming the cross-linked structure, it is preferable to appropriately set the manufacturing conditions (heating to be described later) when forming the gas barrier layer 103 in addition to the type or amount of raw materials. temperature or time of treatment).

Hereinafter, the layers that can be included in the gas barrier laminate will be described in detail.

(gas barrier layer) The gas barrier layer 103 includes a hardened product of a mixture containing, for example, a polycarboxylic acid such as polyacrylic acid, a polyamine compound, and a polyvalent metal compound. More specifically, the gas barrier layer 103 is a film (gas barrier film 10 ) including the cured product. More specifically, the gas barrier layer 103 can be formed by applying a pre-hardened mixture (gas barrier coating material) on a layer such as the inorganic layer 102 and other layers immediately below the gas barrier layer 103 and then drying and heat-treating it. It is obtained by hardening the gas barrier coating material.

The components that can be contained in the mixture before hardening (gas barrier coating material) are explained below. By appropriately selecting the types or amounts of these components and providing the gas barrier layer 103, the gas barrier laminate of the second embodiment can be produced.

·carboxylic acid Polycarboxylic acids have two or more carboxyl groups in the molecule. Specific examples include homopolymerization of α,β-unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, fumaric acid, crotonic acid, cinnamic acid, 3-hexenoic acid, and 3-hexenedioic acid. substances or copolymers of these. In addition, copolymers of the α,β-unsaturated carboxylic acid and esters such as ethyl ester, olefins such as ethylene, etc. may also be used.

Among these, homopolymers or copolymers of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, and cinnamic acid are preferred, and more preferred are selected from the group consisting of polyacrylic acid, polymethacrylic acid, and One or more polymers from the group consisting of copolymers of acrylic acid and methacrylic acid, more preferably at least one polymer selected from polyacrylic acid and polymethacrylic acid, further preferably selected from acrylic acid At least one polymer selected from the group consisting of a homopolymer and a homopolymer of methacrylic acid.

Here, in the second embodiment, polyacrylic acid includes both homopolymers of acrylic acid and copolymers of acrylic acid and other monomers. In the case of a copolymer of acrylic acid and other monomers, the polyacrylic acid contains usually 90 mass% or more, preferably 95 mass% or more, and more preferably 99 mass% or more derived from acrylic acid in 100 mass% of the polymer. structural unit. In addition, in the second embodiment, polymethacrylic acid includes both homopolymers of methacrylic acid and copolymers of methacrylic acid and other monomers. In the case of a copolymer of methacrylic acid and other monomers, polymethacrylic acid contains usually 90 mass% or more, preferably 95 mass% or more, and more preferably 99 mass% or more in 100 mass% of the polymer. Structural unit derived from methacrylic acid.

Polycarboxylic acids are polymers made from carboxylic acid monomers. From the viewpoint of excellent balance between gas barrier properties and workability, the molecular weight of the polycarboxylic acid is preferably 500 to 2,500,000, more preferably 5,000 to 2,000,000, more preferably 10,000 to 1,500,000, and still more preferably 100,000 to 1,200,000. Here, in the second embodiment, the molecular weight of the polycarboxylic acid is a weight average molecular weight in terms of polyethylene oxide, and can be measured using gel permeation chromatography (GPC).

At least a portion of the polycarboxylic acid can also be neutralized by a volatile base. By neutralizing the polycarboxylic acid with a volatile base, gelation can be suppressed when the polyvalent metal compound or polyamine compound is mixed with the polycarboxylic acid. Therefore, among polycarboxylic acids, from the viewpoint of preventing gelation, it is preferable to use a volatile base to form a partially neutralized product or a completely neutralized product of the carboxyl group. The neutralized product can be obtained by partially or completely neutralizing the carboxyl group of the polycarboxylic acid using a volatile base, that is, partially or completely converting the carboxyl group of the polycarboxylic acid into a carboxylic acid salt. This can prevent gelation when adding a polyamine compound or a polyvalent metal compound. The partially neutralized product is prepared by adding a volatile base to an aqueous solution of the polycarboxylic acid polymer, and the desired degree of neutralization can be obtained by adjusting the ratio of the polycarboxylic acid to the volatile base. In the second embodiment, from the viewpoint of fully suppressing gelation caused by the neutralization reaction with the amine group of the polyamine compound, the degree of neutralization of the polycarboxylic acid by the volatile base is preferably 70 equivalent % ~300 equivalent%, more preferably 90 equivalent% ~ 250 equivalent%, further preferably 100 equivalent% ~ 200 equivalent%.

As the volatile base, any water-soluble base can be used. Examples of the volatile base include tertiary amines such as ammonia, morpholine, alkylamine, 2-dimethylaminoethanol, N-methylmorpholine, ethylenediamine, and triethylamine, or aqueous solutions of these; or a mixture of these. From the viewpoint of obtaining good gas barrier properties, an ammonia aqueous solution is preferred.

·Polyamine compounds The mixture before hardening preferably contains a polyamine compound. Polyamine compounds can react with polycarboxylic acids to form cross-linked structures (amide bonds). Thereby, the gas barrier property can be further improved. The polyamine compound is a compound having two or more amine groups in the main chain, side chain or terminal, and is preferably a polymer. Specific examples include: aliphatic polyamines such as polyallylamine, polyvinylamine, polyethyleneimine, and poly(trimethyleneimine); such as polylysine and polyarginine, which have polyamines in their side chains. Amino-based polyamides, etc. In addition, a polyamine in which part of the amine group has been modified may also be used. From the viewpoint of obtaining good gas barrier properties, the polyamine compound preferably contains polyethyleneimine, more preferably polyethyleneimine.

From the viewpoint of excellent balance between gas barrier properties and workability, the number average molecular weight of the polyamine compound is preferably 50 to 2,000,000, more preferably 100 to 1,000,000, further preferably 1,500 to 500,000, still more preferably 1,500 to 100,000 , more preferably 1,500 to 50,000, still more preferably 3,500 to 20,000, still more preferably 5,000 to 15,000, still more preferably 7,000 to 12,000. The molecular weight of polyamine compounds can be measured using the boiling point elevation method or the viscosity method.

From the viewpoint of further improving the gas barrier performance after retort treatment, (the mole number of amine groups contained in the polyamine compound in the mixture) / (the number of -COO- groups contained in the polycarboxylic acid in the mixture The molar number) is preferably 0.20 or more, more preferably 0.25 or more, still more preferably 0.30 or more, still more preferably 0.35 or more, and still more preferably 0.40 or more. From the same viewpoint, (the mole number of amine groups contained in the polyamine compound in the mixture)/(the mole number of -COO- groups contained in the polycarboxylic acid in the mixture) is preferably 0.90 or less, more preferably 0.85 or less, still more preferably 0.80 or less, still more preferably 0.75 or less, still more preferably 0.70 or less. The details of this reason are not yet clear, but it is thought that the amide crosslinking by the amine group constituting the polyamine compound and the metal crosslinking by the polyvalent metal constituting the salt of the polycarboxylic acid and the polyvalent metal are balanced. By forming a dense structure, the gas barrier layer 103 and the gas barrier laminate having the gas barrier layer 103 having excellent gas barrier properties after the retort treatment can be obtained.

In relation to the polyamine compound, the peak intensity of CN ^- when the gas barrier layer 103 is subjected to time-of-flight secondary ion mass analysis is assumed to be I (CN ^- ), and the peak intensity of C ₃ H ₃ O ₂ ^- is When I (C ₃ H ₃ O ₂ ^- ) is used, the value of I (CN ^- )/I (C ₃ H ₃ O ₂ ^- ) is 2 or less, preferably 1.8 or less, more preferably 1.5 or less. The lower limit of the value of I(CN ^- )/I(C ₃ H ₃ O ₂ ^- ) is, for example, 0, preferably 0.2, further preferably 0.4. Details regarding time-of-flight secondary ion mass analysis are as described above. The CN ^- detected by mass analysis is considered to be derived from polyamines. Therefore, it is considered that the value of I(CN ^- )/I(C ₃ H ₃ O ₂ ^- ) is an appropriate numerical value and is related to the above-mentioned "amide crosslinking by the amine group constituting the polyamine compound, and the "Metal cross-linking by polyvalent metals such as salts of carboxylic acids and polyvalent metals forms a dense structure in a balanced manner."

·Metal As mentioned above, the gas barrier layer 103 preferably contains one or more metal elements selected from the group consisting of Zn, Ca, Mg, Ba, and Al. Therefore, the mixture before hardening is preferably a compound containing these metals. Among these, in view of application to packaging of retort foods, Mg-containing compounds and Zn-containing compounds are preferred, and Zn-containing compounds are more preferred. Examples of metal compounds include oxides, hydroxides, halides, carbonates, phosphates, phosphites, hypophosphites, sulfates, and sulfites of the metal. From the viewpoint of water resistance, impurities, etc., metal oxides or metal hydroxides are preferred.

Metal compounds that can be preferably used are those selected from oxides such as magnesium oxide, calcium oxide, barium oxide, zinc oxide, and magnesium hydroxide; and hydroxides such as calcium hydroxide, barium hydroxide, and zinc hydroxide. One or more compounds in the group are more preferably at least one of zinc oxide and zinc hydroxide, and further preferably zinc oxide.

In the second embodiment, from the viewpoint of further improving the gas barrier performance after retort treatment, (the molar number of the metal compound in the mixture)/(the -COO- group contained in the polycarboxylic acid in the mixture) The molar number) is preferably 0.1 or more, more preferably 0.13 or more, still more preferably 0.15 or more, still more preferably 0.18 or more. From the same viewpoint, (the mole number of the polyvalent metal compound in the mixture)/(the mole number of the -COO- group contained in the polycarboxylic acid in the mixture) is preferably 0.80 or less, more preferably 0.70 or less, more preferably 0.60 or less, still more preferably 0.55 or less, still more preferably 0.50 or less.

In the second embodiment, from the viewpoint of further improving the gas barrier performance after the retort treatment, (moles of the metal compound in the mixture)/(moles of the amine groups derived from the polyamine compound in the mixture) number) is preferably 0.25 or more, more preferably 0.35 or more, and still more preferably 0.40 or more. From the same viewpoint, (the molar number of the metal compound in the mixture)/(the molar number of the amine group derived from the polyamine compound in the mixture) is preferably 0.75 or less, more preferably 0.60 or less, and still more preferably is below 0.55.

·Phosphorus compound or its salt As mentioned above, when the barrier layer 103 is mass-analyzed, PO ₂ ^- and/or PO ₃ ^- are detected. In order to provide such a barrier layer 103, the mixture before hardening preferably contains a phosphorus compound or a salt thereof. The phosphorus compound or the phosphorus compound in its salt contains more than one -P-OH group in the molecular structure. The phosphorus compound can also be formulated in the mixture as a salt. From the viewpoint of further improving the water vapor barrier property after retort treatment, the phosphorus compound preferably contains two or more -P-OH groups, and more preferably contains three or more -P-OH groups. In addition, from the viewpoint of productivity, the number of -P-OH groups in the phosphorus compound may be, for example, 10 or less.

Specific examples of the phosphorus compound include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, and derivatives thereof. Specifically, polyphosphoric acid has a condensed structure of two or more phosphoric acids in its molecular structure. Examples thereof include diphosphoric acid (pyrophosphoric acid), triphosphoric acid, polyphosphoric acid in which four or more phosphoric acids are condensed, and the like. Specific examples of the derivatives include esters of the phosphorus compounds such as phosphorylated starch and phosphate cross-linked starch; halides such as chlorides; anhydrides such as tetraphosphorus decaoxide; and nitrotris(methylenephosphonic acid). ), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid) and other compounds having a structure in which the hydrogen atom bonded to the phosphorus atom is replaced by an alkyl group.

From the viewpoint of further improving the balance between barrier properties and productivity, the phosphorus compound is one or two or more selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid and salts thereof. , more preferably at least one selected from the group consisting of phosphoric acid and phosphorous acid, phosphonic acid and salts thereof.

Specific examples of salts among the salts of phosphorus compounds include salts of monovalent metals such as sodium and potassium; and ammonium salts. From the viewpoint of barrier properties, the salt of the phosphorus compound is preferably an ammonium salt.

In the second embodiment, from the viewpoint of barrier improvement, (the mole number of P atoms of the phosphorus compound derived from the phosphorus compound or its salt in the mixture)/(- derived from the polycarboxylic acid in the mixture) The molar number of the COO group) is preferably 0.0005 or more, more preferably 0.001 or more, still more preferably 0.003 or more, still more preferably 0.005 or more. In phosphorus compounds that contain a P atom in the chemical formula like phosphoric acid, the molar number of the P atom and the molar number of the phosphorus compound have the same meaning. In addition, from the viewpoint of barrier properties and productivity (stability of the coating liquid, uniformity/appearance of the coating film), (the number of moles of the phosphorus compound derived from the phosphorus compound or its salt in the mixture) / (the mixture The molar number of the -COO- group derived from the polycarboxylic acid) is preferably 0.3 or less, more preferably 0.1 or less, still more preferably 0.08 or less, still more preferably 0.05 or less.

·Other ingredients The mixture before hardening may contain components other than the above-mentioned components. For example, the mixture preferably further contains carbonic acid ammonium salt. The carbonate-based ammonium salt is added in order to convert the polyvalent metal compound into the state of a polyvalent metal ammonium carbonate complex, improve the solubility of the polyvalent metal compound, and prepare a uniform solution containing the polyvalent metal compound. By including the ammonium carbonate salt in the mixture before hardening, the dissolved amount of the polyvalent metal compound can be increased. As a result, the mixture prepared with the polyvalent metal compound can be made more homogeneous. Examples of carbonic acid-based ammonium salts include ammonium carbonate and ammonium bicarbonate. Ammonium carbonate is preferred in that it is easily volatilized and is less likely to remain in the obtained gas barrier layer. From the viewpoint of further improving the solubility of the polyvalent metal compound, (the molar number of the carbonic acid ammonium salt in the mixture)/(the molar number of the metal compound in the mixture) is preferably 0.05 or more, more preferably 0.10 or more, more preferably 0.25 or more, still more preferably 0.50 or more, particularly preferably 0.75 or more. In addition, from the viewpoint of further improving the coating properties of the gas barrier coating material, (the molar number of the carbonic acid ammonium salt in the gas barrier coating material)/(the mole number of the metal compound in the gas barrier coating material) Mohr number) is preferably 10.0 or less, more preferably 5.0 or less, still more preferably 2.0 or less, still more preferably 1.5 or less.

In addition, from the viewpoint of suppressing shrinkage during application as a gas barrier coating material, the mixture before curing preferably further contains a surfactant. When the total solid content of the mixture is 100% by mass, the added amount of the surfactant is preferably 0.01% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass.

Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like. From the viewpoint of obtaining good coating properties, nonionic surfactants are preferred. Surfactants are preferably polyoxyethylene alkyl ethers.

Examples of nonionic surfactants include polyoxyalkylene alkyl aryl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, sorbitan fatty acid esters, Silicone surfactants, acetylenol surfactants, fluorine-containing surfactants, etc.

Examples of the polyoxyalkylene alkylaryl ethers include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene dodecylphenyl ether. wait. Examples of the polyoxyalkylene alkyl ethers include polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether. Examples of the polyoxyalkylene fatty acid esters include polyoxyethylene oleate, polyoxyethylene laurate, polyoxyethylene distearate, and the like. Examples of sorbitan fatty acid esters include sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, poly Oxyethylene monooleate, polyoxyethyl stearate, etc. Examples of silicone surfactants include dimethylpolysiloxane and the like. Examples of the acetylenic alcohol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 3,6-dimethyl-4-octyne-3. 6-diol, 3,5-dimethyl-1-hexyn-3-ol, etc. Examples of fluorine-containing surfactants include fluoroalkyl esters and the like.

The mixture before hardening may also contain additives other than the above-mentioned components. For example, various additives such as lubricants, slip agents, anti-adhesive agents, antistatic agents, anti-fogging agents, pigments, dyes, and inorganic or organic fillers may be included.

In addition, from the viewpoint of improving the coating properties when applying as a gas barrier coating material, the solid content concentration of the mixture before curing is preferably 0.5 mass % to 15 mass %, and more preferably 1 Mass%～10 mass%.

·Method for manufacturing gas barrier layer Specifically, the gas barrier layer 103 can be produced by applying a pre-cured mixture (gas barrier coating material) and curing the mixture. The mixture can be obtained as follows. First, the carboxyl group of the polycarboxylic acid is completely or partially neutralized by appropriately adding a volatile base to the polycarboxylic acid. Furthermore, a polyvalent metal salt compound and a suitable ammonium carbonate salt are mixed to form a mixture of all or part of the carboxyl groups of the polycarboxylic acid neutralized with the volatile base and the carboxyl groups of the polycarboxylic acid not neutralized with the volatile base. Metal salts. Then, a polyamine compound is further added, and finally a phosphorus compound or a salt thereof is added, thereby obtaining a mixture before hardening. Thereby, a salt is formed between the phosphorus compound and the polyvalent metal compound or the amine group of the polyamine. By mixing a polycarboxylic acid, a polyvalent metal salt compound, a phosphorus compound or a salt thereof, a suitable carbonic acid ammonium salt, and a polyamine compound in this order, the formation of aggregates can be suppressed and a more uniform mixture can be obtained. Thereby, the dehydration condensation reaction of the -COO- group contained in the polycarboxylic acid and the amine group contained in the polyamine compound can be promoted more effectively.

More details are as follows. Hereinafter, the case where a volatile base and a carbonic acid ammonium salt are mixed into a mixture will be demonstrated as an example. First, a completely or partially neutralized solution of the carboxyl groups constituting the polycarboxylic acid is prepared. A volatile base is added to the polycarboxylic acid to completely or partially neutralize the carboxyl groups of the polycarboxylic acid. By neutralizing the carboxyl group of the polycarboxylic acid, it is possible to effectively prevent the reaction between the carboxyl group constituting the polycarboxylic acid and the amine group constituting the polyvalent metal compound or polyamine compound when a polyvalent metal compound or polyamine compound is added. of gelation, resulting in a more homogeneous mixture. Next, a polyvalent metal salt compound and a carbonic acid ammonium salt are added and dissolved, and the generated polyvalent metal ions are used to form a polyvalent metal salt with the -COO- group constituting the polycarboxylic acid. In this case, the -COO- group that forms a salt with the polyvalent metal ion refers to both the carboxyl group that is not neutralized with the base and the -COO- group that is neutralized with the base. In the case of a -COO- group neutralized with a base, the multivalent metal ions derived from the multivalent metal compound are exchanged and coordinated to form a multivalent metal salt of the -COO- group. Then, after the polyvalent metal salt is formed, a polyamine compound and a phosphorus compound or a salt thereof are further added to obtain a mixture. At this time, the multivalent metal salt coordinated to the -COO- group is also coordinated to the -PO ^- group in the phosphorus compound, forming a -COO- multivalent metal-OP- structure. In addition, an ionic bond is formed between the -NH ₂ group in the polyamine and the -PO ^- group in the phosphorus compound.

The mixture produced in the above manner is applied as a gas barrier coating material on the inorganic layer 102 or the interlayer formed on the inorganic layer 102 and the gas barrier layer 103, and is dried and hardened to form a gas. Barrier layer 103. At this time, the polyvalent metal constituting the polyvalent metal salt of the -COO- group of the polycarboxylic acid forms a metal cross-link, and the amine group constituting the polyamine forms an amide cross-link, forming a -PO ^- group in the phosphorus compound and The gas barrier layer 103 having excellent gas barrier properties can be obtained by ionic cross-linking of amine groups in polyvalent metals or polyamines. A more detailed manufacturing method of the gas barrier layer 103 will be described later.

From the viewpoint of improving barrier properties, the thickness of the dried and hardened gas barrier layer 103 is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more. In addition, from the viewpoint of thinning the entire gas barrier laminate, the thickness of the gas barrier layer 103 after drying and curing is preferably 15 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less.

(Substrate layer) The base material layer 101 may be a single layer or two or more layers. The shape of the base material layer 101 is not limited, and examples include a sheet or film shape, a tray, a cup, a hollow body, and the like.

The material of the base layer 101 can be used without any limitation as long as it can stably form the inorganic layer 102 on the base layer 101 and apply a solution of the gas barrier coating material on top of the inorganic layer 102 . Examples of materials for the base layer 101 include resins such as thermosetting resins and thermoplastic resins, and organic materials such as paper; glass, pottery, ceramics, silicon oxide, silicon oxynitride, silicon nitride, cement, aluminum, and alumina. , iron, copper, stainless steel and other metals and other inorganic materials; a multi-layer structure base material layer including a combination of organic materials or a combination of organic materials and inorganic materials, etc. Among these, for example, in the case of various film applications such as packaging materials and panels, it is preferable to use at least one organic material such as a plastic film or paper selected from the group consisting of a thermosetting resin and a thermoplastic resin.

As the thermosetting resin, a known thermosetting resin can be used. Examples include epoxy resin, unsaturated polyester resin, phenol resin, urea-melamine resin, polyurethane resin, silicone resin, polyimide, and the like.

As the thermoplastic resin, a known thermoplastic resin can be used. Examples include polyolefins (polyethylene, polypropylene, poly(4-methyl-1-pentene), poly(1-butene), etc.), polyesters (polyethylene terephthalate, poly(p-p) Butylene phthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, polyethylene glycol m-phenylenediamine, etc.), polyvinyl chloride, polyimide, Ethylene-vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, fluororesin, or a mixture thereof, etc.

Among these, from the viewpoint of improving transparency, it is preferable to be selected from the group consisting of polypropylene, polyethylene terephthalate (PET), polyethylene naphthalate, polyamide, and polyimide. One or more resins in the group consisting of polybutylene terephthalate and polybutylene terephthalate. In addition, from the viewpoint of excellent pinhole resistance, crack resistance, heat resistance, etc., it is preferably selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. One or more resins in a group. From the same point of view, the base material layer 101 preferably contains one or more types selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. The resin layer is preferably a layer of one or more than two of these resins.

In addition, when the base material layer 101 uses a hygroscopic material such as polyamide, in the gas barrier laminate, the base material layer 101 absorbs moisture and swells, and the gas barrier performance under high humidity or after retort treatment The gas barrier performance and the gas barrier performance when filling acidic contents are easily reduced. However, in the second embodiment, even when a hygroscopic material is used as the base material layer 101, it is better to Suppresses the gas barrier performance of the gas barrier laminate under high humidity or the decrease in gas barrier performance after retort treatment.

In addition, the base material layer 101 may be formed by stretching a film made of a thermosetting resin or a thermoplastic resin in at least one direction, preferably in a biaxial direction. From the viewpoint of excellent transparency, rigidity, and heat resistance, the base material layer 101 is preferably made of polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, or polyamide. A biaxially stretched film formed of one or more thermoplastic resins from the group consisting of imine and polybutylene terephthalate, preferably a biaxially stretched film selected from the group consisting of polyamide, polyethylene terephthalate A biaxially stretched film formed of one or more thermoplastic resins from the group consisting of diester and polybutylene terephthalate.

In addition, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, acrylic resin, urethane resin, etc. may also be coated on the surface of the base material layer 101 . Furthermore, the base material layer 101 may be surface-treated in order to improve the adhesion with the gas barrier layer 103 . Specifically, surface activation treatment such as corona treatment, flame treatment, plasma treatment, and primer coating treatment may be performed on the surface facing the gas barrier layer 103 of the base layer 101 .

From the viewpoint of obtaining good film characteristics, the thickness of the base material layer 101 is preferably 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and further preferably 1000 μm or less, more preferably 1000 μm or less, more preferably 500 μm or less, more preferably 300 μm or less.

(base coat) As illustrated in FIG. 6 , a primer layer 104 may be provided between the base layer 101 and the inorganic layer 102 . By providing the undercoat layer 104, the adhesion between these layers can be further improved, and the barrier properties after retort treatment can be further improved.

From the viewpoint of improving the adhesion between the base layer 101 and the inorganic layer 102, examples of the material of the undercoat layer 104 include polyurethane resin, polyester resin, oxazoline resin, (methane resin), etc. One or more of the group consisting of acrylic resins.

Examples of the polyurethane resin include various polyurethane resins, polyurethane polyurea resins, and prepolymers thereof. Specific examples of such urethane resins include toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, and isophorone diisocyanate. Diisocyanate components such as isocyanate and dicyclohexyl diisocyanate are combined with ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, bisphenol, and polyester Reactants of diol components such as diols, polyether diols, polycarbonate diols, and polyethylene glycols; urethane prepolymers with isocyanate groups at the end and amine compounds, amine sulfonates, Reactants of polyhydroxycarboxylic acid, hydrogen sulfite, etc.

In addition, from the viewpoint of further improving the barrier properties after the retort treatment and the adhesion between the base layer 101 and the inorganic layer 102 , it is also preferable that the undercoat layer 104 contains a polyurethane resin. Polyurethane resin with an aromatic ring structure in the main chain. A polyurethane resin having an aromatic ring structure in the main chain can be obtained as a water-dispersed polyurethane resin by reacting a polyol with an organic polyisocyanate and a chain extender, for example. Thereby, an aromatic ring structure can be introduced into the main chain of the polyurethane resin. As the polyurethane resin having an aromatic ring structure in the main chain, more specifically, those described in Japanese Patent Application Laid-Open No. 2018-171827 can be used.

For polyurethane resins such as water-dispersed polyurethane resin, a cross-linking agent may be used together for the purpose of improving heat resistance, water resistance, hydrolysis resistance, etc. The cross-linking agent may be an external cross-linking agent that is a component different from the polyurethane resin, or it may be an internal cross-linking agent that introduces reaction points that become a cross-linked structure into the molecular structure of the polyurethane resin in advance. combination agent.

As the cross-linking agent, compounds having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silyl alcohol group, etc. are preferably used, and more preferably, a compound having a carbodiimide group is used. compound of. In addition, when using a compound having a carbodiimide group as a cross-linking agent, the amount of the compound having a carbodiimide group is added relative to 1.0 mol of the carboxyl group in the polyurethane resin. The carbodiimide group is preferably in an amount of 0.1 mol to 3.0 mol, more preferably 0.2 mol to 2.0 mol, and particularly preferably 0.3 mol to 1.0 mol.

Examples of the polyester resin used in the undercoat layer 104 include various polyester resins and modified products thereof. Specific examples of such polyester resins include terephthalic acid, phthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, 2-sulfoisophthalic acid, and 5-sulfoisophthalic acid. Polyisophthalic acid, adipic acid, sebacic acid, succinic acid, dodecanedioic acid and other polycarboxylic acid components are combined with ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, The reactants of diol components such as neopentyl glycol, cyclohexanedimethanol, and bisphenol also include modified products based on acrylic resin, epoxy resin, etc.

When the base coat 104 uses an oxazoline resin, the base coat 104 preferably includes an oxazoline-based resin composition, and the oxazoline-based resin composition includes an oxazoline group-containing aqueous polymer, Water-based (meth)acrylic resin and water-based polyester resin. The oxazoline-based resin composition includes, for example, an oxazoline group-containing aqueous polymer with an oxazoline group content of 6.0 mmol/g to 9.0 mmol/g, and an aqueous polymer with a carboxyl group content of 0.5 mmol/g to 3.5 mmol/g. Meth)acrylic resin and water-based polyester resin with carboxyl content between 0.5 mmol/g and 2.0 mmol/g. In addition, regarding the oxazoline-based resin composition, the total amount of the oxazoline group-containing aqueous polymer, the aqueous (meth)acrylic resin, and the aqueous polyester resin is 100% by mass. For example, the oxazoline-based resin composition contains 10% by mass to 55% by mass. Mass % of the oxazoline group-containing water-based polymer, 10 mass % to 80 mass % of the water-based (meth)acrylic resin, and 10 mass % to 80 mass % of the water-based polyester resin. In addition, in the oxazoline-based resin composition, for example, the ratio of the molar number of the oxazoline group to the molar number of the carboxyl group [from the molar number of the oxazoline group (x mmol) and the molar number of the carboxyl group The ratio (x/y) × 100 [mol%] of (y mmol) is 150 mol% ~ 420 mol%. As the oxazoline resin used in the undercoat layer 104, more specifically, those described in International Publication No. 2016/186074 can be used.

From the viewpoint of obtaining good adhesion, the thickness of the primer layer 104 is preferably 0.001 μm or more, more preferably 0.005 μm or more, still more preferably 0.01 μm or more, still more preferably 0.05 μm or more, and still more preferably 0.05 μm or more. 0.1 μm or more, more preferably 0.2 μm or more. In addition, from the viewpoint of economy, the thickness of the undercoat layer 104 is preferably 1.0 μm or less, more preferably 0.6 μm or less, still more preferably 0.5 μm or less, still more preferably 0.1 μm, and even more preferably 0.05 μm. the following.

(Inorganic layer) Examples of the inorganic substances constituting the inorganic substance layer 102 include metals, metal oxides, metal nitrides, metal fluorides, and metal oxynitrides that can form a barrier thin film. Examples of the inorganic substance constituting the inorganic substance layer 102 include elements selected from Group 2A of the Periodic Table such as beryllium, magnesium, calcium, strontium, and barium; transition elements of the Periodic Table such as titanium, zirconium, ruthenium, hafnium, and tantalum; Group 2B of the Periodic Table such as zinc; Elements; aluminum, gallium, indium, thallium and other periodic table group 3A elements; periodic table group 4A elements such as silicon, germanium and tin; periodic table group 6A elements such as selenium, tellurium and other elements, oxides, nitrides, fluorides, etc. Or one or more of nitrogen oxides, etc. (the group name of the periodic table is represented by the old CAS formula).

Furthermore, among the inorganic substances, in terms of excellent balance between barrier properties, cost, etc., one or two or more inorganic substances selected from the group consisting of silica, alumina, and aluminum are preferred, and more preferred are aluminum oxide. Furthermore, the silicon oxide may also contain silicon monoxide and silicon suboxide in addition to silicon dioxide.

The inorganic substance layer 102 is formed of the above-mentioned inorganic substance. In terms of excellent balance between barrier properties, cost, etc., the inorganic layer 102 preferably includes an aluminum oxide layer containing aluminum oxide. The inorganic layer 102 may include a single inorganic layer or multiple inorganic layers. In addition, when the inorganic layer 102 includes a plurality of inorganic layers, it may include the same type of inorganic layer or may include different types of inorganic layers.

From the viewpoint of a balance between improved barrier properties and improved operability, the thickness of the inorganic layer 102 is usually 1 nm or more, preferably 4 nm or more, and is usually 1000 nm or less, preferably 500 nm or less. Here, the thickness of the inorganic layer 102 can be determined from an observation image obtained by a transmission electron microscope or a scanning electron microscope, for example.

The method of forming the inorganic layer 102 is not limited, and may be, for example, vacuum evaporation, ion plating, sputtering, chemical vapor deposition, physical vapor deposition, or chemical vapor deposition (CVD). , plasma CVD method, sol-gel method, etc. to form the inorganic layer 102 on one or both sides of the base material layer 101 . Among them, sputtering, ion plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma CVD, or film formation under reduced pressure are ideal. Therefore, it is expected that chemically active molecular species containing silicon, such as silicon nitride or silicon oxynitride, react rapidly to improve the smoothness of the surface of the inorganic layer 102 and reduce the number of holes. In order to rapidly carry out these binding reactions, it is ideal that the inorganic atom or compound is a chemically active molecular species or atomic species. In addition, from the viewpoint of improving the balance between the barrier properties and productivity of the gas barrier laminate, the inorganic layer 102 is preferably a vapor-deposited film.

From the viewpoint of improving the balance between the barrier properties and productivity of the gas barrier laminate, the inorganic layer 102 is provided on the base material layer 101 or when an intermediary layer is provided between the base material layer 101 and the inorganic layer 102 The evaporated film on the interposer layer includes one or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum.

(Sealant layer) From a practical viewpoint such as manufacturing of retort food, it is preferable to provide a sealant layer on the opposite surface side of the gas barrier layer 103 from the inorganic layer 102 . The sealant layer is in contact with the gas barrier layer 103, or the gas barrier layer 103 and the sealant layer are connected through an adhesive layer. The adhesive layer will be described later.

Examples of the sealant layer include homopolymers or copolymers containing α-olefins such as ethylene, propylene, butene-1, hexene-1, 4-methyl-1-pentene, octene-1, etc. , high-density polyethylene, medium-density polyethylene, linear low-density polyethylene, low-density polyethylene and other polyethylenes, homopolypropylene (homo polypropylene), propylene and α with a carbon number of 2 or more than 4 and less than 10 - A layer formed of a resin composition of one or more polyolefins such as olefin random copolymers, low crystallinity or amorphous ethylene-propylene random copolymers; composed of ethylene-vinyl acetate copolymers A layer formed of a resin composition of EVA; a layer formed of a resin composition containing EVA and polyolefin, etc.

Among these, from the viewpoint of heat-sealability, it is preferable to include a compound selected from the group consisting of low-density polyethylene, linear low-density polyethylene, homopolypropylene, and propylene and α-C2 or 4-10 carbon atoms. One or more thermoplastic resins of random copolymers of olefins.

In addition, as the form of the thermoplastic resin, unstretched or stretched low-density polyethylene, linear low-density polyethylene (stretched linear low-density polyethylene (LLDPE)), propylene Random copolymers with α-olefins having a carbon number of 2 or 4 or more and 10 or less, etc. From the viewpoint of application in the manufacture of retort foods, the sealant layer preferably contains an unstretched polypropylene-based polymer. Examples of the polypropylene-based polymer include homopolymers of propylene, random copolymers of propylene and α-olefin having a carbon number of 2 or 4 or more and 10 or less, and the like.

The sealant layer may contain components other than thermoplastic resin. For example, additives such as anti-fog agents or anti-blocking agents, and adhesive resins such as urethane resins, urea resins, melamine resins, epoxy resins, and alkyd resins may also be included.

In addition, the sealant layer can also be provided as an adhesive by using an adhesive resin such as an acrylic resin, a urethane resin, a urea resin, a melamine resin, an epoxy resin, or an alkyd resin. The adhesive is dried and hardened to set.

The thickness of the sealant layer is preferably 10 μm to 100 μm, more preferably 15 μm to 80 μm, further preferably 20 μm to 60 μm. By setting this thickness, sufficient heat sealability can be obtained, and the handleability of the film can be improved.

(adhesive layer) The gas barrier laminated body may further be provided with an adhesive layer. Specifically, the gas barrier layer 103 and the sealant layer may also be connected through an adhesive layer. The adhesive layer only needs to contain a known adhesive. Examples of adhesives include organic titanium resin, polyethyleneimine resin, urethane resin, epoxy resin, acrylic resin, polyester resin, oxazoline group-containing resin, modified silicone resin, and titanium resin. Laminated adhesives composed of alkyl acid esters, polyester polybutadiene, etc., or one-liquid or two-liquid polyols and polyisocyanates, water-based urethanes, ionic polymers, etc. Alternatively, a water-based adhesive whose main raw material is acrylic resin, vinyl acetate resin, urethane resin, polyester resin, etc. can also be used. In addition, other additives such as a hardener and a silane coupling agent may be added to the adhesive according to the use of the gas barrier laminate. When the gas barrier laminate is used for hot water treatment such as steaming, dry lamination represented by a polyurethane adhesive is preferred from the viewpoint of heat resistance or water resistance. Use an adhesive, preferably a solvent-based two-liquid hardening type polyurethane adhesive.

(Polyamide-containing layer) A polyamide-containing layer (for example, a nylon layer) may or may not be provided between the gas barrier layer 103 and the sealant layer. By providing a polyamide-containing layer, the strength of the film itself can be improved. For example, the bag is not easily broken when the packaging body falls. The polyamide-containing layer may include, for example, one or more of nylon-6, nylon-66, poly(adipamide-m-xylylenediamine), and the like. When a polyamide-containing layer is provided, its thickness is preferably 8 μm to 100 μm, more preferably 10 μm to 50 μm, and particularly preferably 13 μm to 30 μm.

(Method for manufacturing gas barrier laminate) In the second embodiment, the manufacturing method of the gas barrier laminate 100 may include: preparing the base material layer 101; forming the inorganic layer 102 on the base layer 101; and forming the inorganic layer 102 on the base material. A step of forming a gas barrier layer 103 on top of layer 101 . The step of forming the undercoat layer 104 on the inorganic layer 102 may also be included after the step of forming the inorganic layer 102 and before the step of forming the gas barrier layer 103 .

Regarding the step of forming the inorganic layer 102 on the base material layer 101, the formation method of the inorganic layer 102 is as described above.

The step of forming the gas barrier layer 103 includes, for example, applying the uncured mixture as a gas barrier coating material to the inorganic layer 102 and then drying it to obtain a coating layer; and applying the coating layer to the gas barrier layer 103 . A step of heating to cause a dehydration condensation reaction between the carboxyl groups contained in the polycarboxylic acid and the amine groups contained in the polyamine compound, thereby forming the gas barrier layer 103 having a amide bond.

The method of applying the gas barrier coating material to the inorganic layer 102 is not limited, and a known method can be used. For example, gravure coaters using Meyer rod coaters, air knife coaters, direct gravure coaters, indirect gravure, arc gravure coaters, reverse gravure and spray nozzle methods, top feed reverse gravure coaters, etc. Reverse roll coaters such as reverse roll coaters, bottom feed reverse coaters and nozzle feed reverse coaters, five-roller coaters, die lip coaters, rod coaters, reverse The coating method is performed using a known coater such as a bar coater or a die coater.

From the viewpoint of improving the barrier performance of the gas barrier laminate obtained, the coating amount (wet thickness) is preferably 0.05 μm, more preferably 1 μm or more. In addition, from the viewpoint of suppressing curling of the obtained gas barrier laminate and more effectively promoting the dehydration condensation reaction of the -COO- group contained in the polycarboxylic acid and the amine group contained in the polyamine compound , the wet thickness is preferably 300 μm or less, more preferably 200 μm or less, further preferably 100 μm or less.

Regarding drying and heat treatment, heat treatment can be performed after drying, or drying and heat treatment can be performed at the same time. The method of drying and heat treatment is not limited as long as the effects of the present invention can be obtained, as long as the gas barrier coating material can be hardened or the gas barrier coating material can be heat-cured. Examples include devices that utilize convection heat transfer such as ovens and dryers, devices that utilize conductive heat transfer such as heating rollers, devices that utilize radiation heat transfer using electromagnetic waves such as infrared, far-infrared, and near-infrared heaters, and devices that utilize internal heat transfer such as microwaves. Heating device. As an apparatus used for drying and heat treatment, from the viewpoint of manufacturing efficiency, an apparatus capable of performing both drying and heat treatment is preferred. Among them, specifically, it is preferable to use a hot air oven from the viewpoint of being usable in various applications such as drying, heating, and annealing. In addition, from the viewpoint of excellent heat conduction efficiency to the film, it is preferable to use heating. Roller. In addition, methods used for drying and heat treatment may be appropriately combined. Specifically, a hot air oven and a heating roller may be used together. For example, if the gas barrier coating material is dried in a hot air oven and then heated using a heating roller, the time of the heating treatment step will be shortened, and from the viewpoint of manufacturing efficiency Better. In addition, it is preferable to perform drying and heating processing only by a hot air oven.

Regarding the heat treatment conditions, for example, the heat treatment temperature is 80°C to 250°C and the heat treatment time is 1 second to 10 minutes. Preferably, the heat treatment temperature is 120°C to 240°C and the heat treatment time is 1 second to 1 minute. More preferably, the heat treatment temperature is 170°C to 230°C and the heat treatment time is 1 second to 30 seconds. Still more preferably, the heat treatment temperature is 200°C to 220°C and the heat treatment time is 1 second to 10 seconds. Furthermore, as mentioned above, by using a heating roller together, heat processing can be performed in a short time. Furthermore, it is important from the viewpoint of effectively promoting the formation of a cross-linked structure (for example, the formation of a amide bond between a -COO- group contained in a polycarboxylic acid and an amine group contained in a polyamine compound). The heat treatment temperature and heat treatment time are adjusted according to the wet thickness of the gas barrier coating material. An appropriate cross-linked structure is formed by selecting an appropriate heat treatment temperature and heat treatment time.

By drying and heat-treating the gas barrier coating material, the carboxyl groups of the polycarboxylic acid react with the polyamine or polyvalent metal compound to form covalent bonds and/or ionic cross-linking, thereby forming a coating with good properties even after retort treatment. gas barrier layer 103.

(Specific example of layer structure) Specific examples of the laminated structure including the gas barrier laminated body in the second embodiment are shown below. (Laminated structure example 1) Base material layer 101 (PET base material)/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyolefin layer (Laminated structure example 2) Base material layer 101 (PET base material)/undercoat layer 104/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyolefin layer (Laminated structure example 3) Base material layer 101 (PET base material)/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyamide layer/adhesive layer/polyolefin layer (Laminated structure example 4) Base material layer 101 (PET base material)/undercoat layer 104/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyamide layer/adhesive layer/ polyolefin layer Here, since the laminated structure includes a polyolefin layer containing polyolefins such as polyethylene, polypropylene, poly(4-methyl-1-pentene), and poly(1-butene), the gas barrier laminated body Medium can improve pinhole resistance, crack resistance, heat resistance, etc., and further suppress the decrease in gas barrier performance under high humidity or gas barrier performance after retort processing.

(use) The gas barrier laminate of the second embodiment has excellent gas barrier properties and can be suitably used for medical applications, industrial applications, and daily miscellaneous goods, as represented by packaging materials and food packaging materials for contents requiring high gas barrier properties. and other various packaging materials. The gas barrier laminated body of the second embodiment is preferably used particularly for food packaging purposes, and more preferably is used for the production of retort food.

In addition, the gas barrier laminate of the second embodiment can also be suitably used as a vacuum heat-insulating film requiring high barrier performance; a sealing film for sealing electroluminescent elements, solar cells, etc.;

(Packaging bags containing gas barrier laminated materials, food packaged with gas barrier laminated materials) A packaging bag can be formed from the gas barrier laminate. This packaging bag can be preferably used in the manufacture of retort food, for example. That is, food (retort food) packaged with the gas barrier laminated body can be produced. In the gas barrier laminate constituting the packaging bag, generally, the side with the base material layer becomes the outer surface side, and the side with the gas barrier layer becomes the inner surface side. When there is a sealant layer, the side with the sealant layer becomes the inner surface side.

The method of manufacturing the retort food can adopt the usual method in this field. By using pressurized hot water/steam above 100°C to sterilize food heat-sealed in packaging bags (for example, at 130°C for about 30 minutes), food that can be stored at room temperature for a long time can be produced.

<Third Embodiment> The gas barrier laminate of the third embodiment is a gas barrier laminate including: a base material layer; a gas barrier layer provided on at least one surface of the base material layer; and an inorganic layer , is provided between the base material layer and the gas barrier layer, and the composition ratio of Zn measured by X-ray photoelectron spectrometry of the gas barrier layer is 1 atomic % to 10 atomic %, at Let the mass peak intensity of ⁶⁴ ZnPO ₄ H ^- measured by time-of-flight secondary ion mass analysis of the gas barrier layer be I ( ⁶⁴ ZnPO ₄ H ^- ), and C ₃ H ₃ O ₂ ^- When the mass peak intensity of is set to I (C ₃ H ₃ O ₂ ^- ), the value of I ( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is 7 × 10 ^-4 or more and 5 × 10 ^-2 or less.

When the composition ratio of Zn measured by X-ray photoelectron spectroscopy is 1 atomic % to 10 atomic %, it means that the gas barrier layer contains Zn at a certain concentration. In addition, the detection of C ₃ H ₃ O ₂ ^- from the gas barrier layer by mass analysis means that the gas barrier layer contains polyacrylic acid or its derivatives/similar compounds (polyacrylic acid, etc.). Furthermore, the value of I(C ₃ H ₃ O ₂ ^- ) is considered to be a value related to the amount (concentration) of carboxyl groups of the polycarboxylic acid contained in the gas barrier layer. Since the gas barrier layer contains Zn at a certain concentration, and polycarboxylic acid having a carboxyl group exists in the gas barrier layer, it is considered that the polycarboxylic acid in the gas barrier layer forms a cross-linked body with Zn, forming a Zn cross-linked body. The combined gas barrier layer and the inorganic layer provided between the base material layer and the gas barrier layer together bear the gas barrier properties of the gas barrier laminate.

Furthermore, the detection of ⁶⁴ ZnPO ₄ H ^- from the gas barrier layer by mass analysis means that there is a bond between a phosphorus compound represented by phosphoric acid and Zn in the gas barrier layer, and it is considered that I ( ⁶⁴ ZnPO ₄ H ^- ) is a value related to the amount (concentration) of the bond between the phosphorus compound and Zn. Furthermore, it is presumed from this that Zn is not only bonded to the carboxyl group of the polycarboxylic acid, but also a part of Zn is chemically bonded to each other via the polyvalent phosphorus compound. In addition, the value of I( ⁶⁴ ZnPO ₄ H ^- )/I(C ₃ H ₃ O ₂ ^- ) is considered to be a value related to the amount (concentration) of the bond between phosphoric acid and Zn relative to the carboxyl group of the polycarboxylic acid. Zinc phosphate is widely known as a compound insoluble in water, and the bond between the phosphorus compound and Zn is a bond that is difficult to be cut by water, which is one of the causes of the decrease in barrier properties after retort treatment. Therefore, it is considered that the presence of a bond between the phosphorus compound and Zn in the gas barrier layer suppresses the excessive swelling and shrinkage of the gas barrier layer during retort processing, etc., which causes damage to the adjacent inorganic layer and thus greatly reduces the gas barrier properties. . That is, when the composition ratio of Zn is 1 atomic % to 10 atomic %, or the value of I( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is 7×10 ^-4 or more and 5×10 Below ^-2 , the barrier performance after cooking can be well maintained.

FIG. 9 shows a schematic cross-sectional view of an example of a two-layer laminated structure barrier film including the gas barrier laminate according to the third embodiment. The two-layer laminated structure barrier film 1 includes a gas barrier laminate 8 . This gas barrier laminate 8 includes: a base material layer 2; a gas barrier layer 5 on at least one surface of the base material layer 2; and an inorganic layer between the base material layer 2 and the gas barrier layer 5. 4. In addition, the undercoat layer (UC layer) 3 may be included below the inorganic layer 4 , that is, on the base layer 2 . Regarding the two-layer laminated structure barrier film 1 , for example, the gas barrier laminate 8 can be bonded to the unstretched polypropylene (CPP) 7 via the adhesive layer 6 .

In addition, FIG. 10 shows a schematic cross-sectional view of an example of a three-layer laminated structure barrier film including the gas barrier laminate of the third embodiment. In the three-layer laminated structure barrier film 10, for example, the nylon film 9 can be adhered to the first adhesive layer 61 of the barrier laminate 8 provided with the first adhesive layer 61, and the nylon film 9 can be connected through the second adhesive layer 62. 9 is followed by unstretched polypropylene 7.

The gas barrier layer 5 of the gas barrier laminate 8 of the third embodiment is a layer in which at least zinc (Zn) is detected by X-ray photoelectron spectroscopy (XPS) analysis. In addition, the peak of ⁶⁴ ZnPO ₄ H ^- and the peak of C ₃ H ₃ O ₂ ^- were detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis. In the gas barrier layer of the gas barrier laminated body of the third embodiment, by detecting the peak of ⁶⁴ ZnPO ₄ H ^- which has high water resistance, the gas barrier performance after cooking is good regardless of the laminate structure. Barrier laminate.

[XPS analysis] The composition of Zn contained in the gas barrier layer is 1 atomic % or more according to XPS analysis, preferably 2 atomic % or more, more preferably 3 atomic % or more. In addition, the composition of Zn contained in the gas barrier layer is 10 atomic % or less, preferably 9.5 atomic % or less, more preferably 9 atomic % or less. This corresponds to the peak intensity of Zn relative to the peak intensity of carbon, that is, Zn/C being 0.01 or more and 0.2 or less (atomic/atomic %). In this way, due to the presence of a certain amount of Zn in the gas barrier layer, the barrier performance after cooking becomes good.

An example of specific conditions applicable to the XPS analysis of the third embodiment is shown below. Analytical device: AXIS-NOVA manufactured by KRATOS X-ray source: monochromated Al-Kα X-ray source output: 15 kV, 10 mA Analysis area: 300 μm×700 μm During analysis: Use a neutralizing gun for charged calibration For XPS analysis, a measurement sample of 1 cm×1 cm cut out from the gas barrier layer can be used. In addition, in order to analyze the inside of the gas barrier layer, it is preferable to perform sputter etching on the surface of the gas barrier layer before analysis. To mitigate damage to the gas barrier layer, sputter etching ideally uses an Ar-gas cluster ion beam (Ar-GCIB) source. Ar-gas cluster ion beam etching is known as a method capable of etching without destroying the chemical structure of a subject.

In XPS analysis, a wide scan is used to determine the detection elements, and a spectrum is obtained through a narrow scan for each element. Then, based on the obtained spectrum, the background is estimated by Shirley's method and the background is removed from the spectrum. For each element to be measured, a spectrum with the background removed is obtained, and based on the obtained peak area, the atomic composition ratio (atomic %) of the detected element is calculated using the relative sensitivity coefficient method. Furthermore, the detection sensitivity of the atomic composition ratio in general XPS analysis is about 0.1 atomic %. For example, when a trace amount of a phosphorus compound is added to the gas barrier layer, the content of P cannot be detected in XPS analysis.

[TOF-SIMS Analysis] Among the fragments detected in the TOF-SIMS analysis of the gas barrier layer, the peak intensity of ⁶⁴ ZnPO ₄ H ^- was set to I ( ⁶⁴ ZnPO ₄ H ^- ), and C ₃ H ₃ O When the peak intensity of the ₂ ^- fragment is I (C ₃ H ₃ O ₂ ^- ), the value of I ( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is 7 × 10 ^-4 or more, It is preferably 1×10 ^-3 or more, more preferably 2×10 ^-3 or more. In addition, it is 5×10 ^-2 or less, preferably 3×10 ^-2 or less, more preferably 2×10 ^-2 or less. In this way, the mass peak of ⁶⁴ ZnPO ₄ H ^- , which is a fragment derived from a highly water-resistant bond, is detected, and the value of I ( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is within the above range. In the case of the gas barrier laminate, the gas barrier laminate has good barrier properties after cooking regardless of the laminate structure. In addition, when the value of ( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) is too large, fine particles of zinc phosphate bonds grow in the gas barrier layer, causing unevenness to the gas barrier layer. Furthermore, the gas barrier performance tends to deteriorate.

An example of specific conditions applicable to TOF-SIMS analysis according to the third embodiment is shown below. In order to analyze the inside of the gas barrier layer, it is preferable to perform sputter etching on the surface layer of the gas barrier layer using the Ar-gas cluster ion beam (Ar-GCIB) attached to the TOF-SIMS analysis device before TOF-SIMS analysis. . The use of Ar-GCIB can reduce damage to the gas barrier layer. An example of specific conditions applicable to Ar-GCIB of the third embodiment is shown. GCIB: 5 kV, 5 μA GCIB processing time: the time point when the spectral pattern of TOF-SIMS no longer changes

TOF-SIMS analysis can be performed, for example, as follows. Analysis device: PHI nano (nano)-TOFII manufactured by Nippon Vacuum (Ulvac-phi) Co., Ltd. Primary ion: Bi ₃ ²⁺ primary ion source output: 30 kV, 0.5 μA Analysis area: 300 μm × 300 μm (primary ion beam Scanning area) During analysis, charge neutralization can be carried out by low-energy electron beam and low-energy Ar ion irradiation attached to the device. In addition, in the TOF-SIMS analysis, like the XPS analysis, a 1 cm×1 cm measurement sample cut out from the gas barrier layer can be used.

At this time, let the mass peak intensity of PO ₂ ^- observed in the gas barrier layer by TOF-SIMS analysis be I (PO ₂ ^- ), and let the mass peak intensity of PO ₃ ^- be I (PO ₃ ^- ), the value of (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) is preferably 0.02 or more, more preferably 0.07 or more, and still more preferably 0.1 or more. In addition, the value of (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) is preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. The detection of a mass peak of PO ₂ ^- or PO ₃ ^- means that the gas barrier layer contains a phosphorus compound containing one or more P-OH groups, represented by phosphoric acid. Furthermore, the value of (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) is considered to be the amount of the phosphorus compound relative to the carboxyl group of the polycarboxylic acid in the gas barrier layer (concentration) related values.

At this time, the value of I(PO ₂ ^- )/I (PO ₃ ^- ), which is the intensity ratio of I (PO ₂ ^- ) and I (PO ₃ ^- ), is preferably 0.05 or more, more preferably 0.08 or more, Further preferably, it is 0.1. In addition, the value of I(PO ₂ ^- )/I(PO ₃ ^- ) is 1 or less, preferably 0.9 or less, more preferably 0.8 or less. The detection of mass peaks of PO ₂ ^- and PO ₃ ^- in TOF-SIMS analysis means that phosphorus compounds such as phosphoric acid (H ₃ PO ₄ ) are included, and the ratio is I (PO ₂ ^- )/I (PO ₃ ^- ). It is a value reflecting the type of phosphorus compound containing a P-OH group. I( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ), which reflects the amount (concentration) of zinc phosphate bonds, affects the type of phosphorus compound. That is, it is also related to the value of I(PO ₂ ^- )/I(PO ₃ ^- ). When the value of I(PO ₂ ^- )/I(PO ₃ ^- ) is 0.05 or more and 1 or less, let the value of I( ⁶⁴ ZnPO ₄ H ^- )/I (C ₃ H ₃ O ₂ ^- ) be If it is an appropriate range, the barrier performance after retort of the gas barrier laminate of the third embodiment can be maintained well.

The analysis method of data obtained by TOF-SIMS analysis can be performed as follows. In order to perform detailed spectral analysis, in the third embodiment, for each positive and negative secondary ion, an analysis device is used to obtain a raw data string pairing the mass number m _i and its corresponding count number c _i Total ion count (C _T ). Here, i=0, 1, 2,···,N. In the original data string, m _i are arranged in ascending order. Furthermore, C _T is the total number of secondary ion counts detected by the detector.

The range of mass numbers around the mass spectrum peak of interest is set to i=n ₁ , n ₁ +1,..., n ₂ . The data c _i of the count number in this range obtained by analysis is approximated by _yi as shown in the following equation. Specifically, c _i is approximated by curve fitting using a background level b ⁰ and K triangular shape functions Y _j (mi ₎ . Here, b ⁰ is a constant.

[Number 7]

Y _j (m _i ) is a function having a peak value Y ⁰ _j at the mass number x ⁰ _j as shown in Fig. 11, and is represented by the following equation.

[Number 8]

Here, b ⁰ , x ⁰ _j , Y ⁰ _j , B ^- _j , and B ⁺ _j become fitting parameters. In addition, j is j=1,···,K. For example, when the background of the spectrum is not a constant value but changes linearly with respect to m _i , b ⁰ is combined with the triangular shape function Y _j (mi ₎ to approximate the background. When the mass spectrum peak of interest is a single peak, except for the background, a triangle shape function is used for approximation. When it is close to other mass peaks, multiple triangle shape functions including other mass peaks are used for approximation. approximate. If the approximated mass spectrum peak of interest is the j=kth peak among K triangular shape functions, the peak intensity I is reduced to i=n ₁ ,···,n using the total ion count (C _T ) It is represented by the normalized numerical value of the sum of Y _k ( _mi ) up to ₂ , and is calculated according to the following formula.

[Number 9]

If there is a tail portion in a mass spectrum peak, it becomes difficult to define the range of masses that should be counted. In the third embodiment, in order to avoid this situation, the mass spectrum peak is approximated using a triangle shape function. By this, the number of counts in the tail portion of the mass spectral peak is ignored. Curve fitting was performed in such a way that the central part of the mass spectral peak fit a triangular shape function. In addition, other components (for example, other types of mass peaks with the same mass number) that overlap with the target peak component may be observed. In this case, the target peak component is obtained by approximating other components that overlap with the target peak component using a triangle shape function. The mass number of the fragment of interest in the third embodiment was calculated and shown below. The atomic weight number of an isotope depends on http://physics.nist.gov/.

[table 5] number of atoms isotope Atomic mass PO ₂ P O ₃ C ₃ H ₃ O ₂ EN ^64ZnPO4H _{_} ¹ H 1.007825 3 1 ^12C 12 3 1 ^14N 14.00307 1 ^16O 15.99492 2 3 2 4 ^31P 30.97376 1 1 1 ^64Z 63.92914 1 mass number 62.9636 78.9585 71.0133 26.0031 159.89039

[Calculation of the mass peak intensity of ⁶⁴ ZnPO ₄ H ^- ] It is known that Zn has 5 isotopes. In TOF-SIMS analysis, the fragments associated with ⁶⁴ Zn, ⁶⁶ Zn and ⁶⁸ Zn are mainly detected. In the third embodiment, attention is paid to ⁶⁴ Zn, which has the highest ratio. In the fragment showing the bond between ⁶⁴ Zn and the phosphorus compound containing P-OH, ⁶⁴ ZnPO ₄ H ^- , ⁶⁴ ZnP ₂ O ₆ H ^- , ⁶⁴ ZnP ₂ O ₇ H ^- , ⁶⁴ ZnP ₃ O ₉ H ^- , etc. were detected. , but focusing on ⁶⁴ ZnPO ₄ H ^- which has a larger mass peak intensity. Focusing on the range of mass number = 159.5 to 160.3 in the negative secondary ion spectrum, a triangular shape function approximated by the mass peak near 158.890 corresponding to ⁶⁴ Zn ³¹ P ¹⁶ O ₄ ¹ H ^- and m _i Data, calculate the sum of the count numbers, and set the value normalized by C _T to the mass peak intensity I of ⁶⁴ ZnPO ₄ H ^- ( ⁶⁴ ZnPO ₄ H ^- ).

An example of curve fitting is shown in FIG. 12 , and the calculation results of the sum of the parameters used at this time and the number of counts are shown in Table 6 . In the example shown in FIG. 12 , the total number of counts obtained based on the triangular shape function that approximates the target mass peak of ⁶⁴ ZnPO ₄ H ^- and the data of m _i is 1514. At this time, the total ion count (C _T ) of negative secondary ions = 8571746, so the peak intensity I ( ⁶⁴ ZnPO ₄ H ^{- )} of ⁶⁴ ZnPO ₄ H ^- becomes I ( ⁶⁴ ZnPO ₄ H ^- ) = 1514/8571746= 1.77×10 ^-4 .

[Table 6] b ⁰ Y _j (m _i ) j 0 1 2(=target) b ⁰ 2 x ⁰ 159.934 159.934 159.885 B ⁺ 0.11 0.035 0.03 ^B- 0.11 0.035 0.03 Y ⁰ 20 50 62 sum 1791 1424 1514

Supplementary information is provided to Figure 12 showing an example of curve fitting. (i) In order to obtain an approximate curve _yi that reproduces the measurement data c _i near the target peak position, a curve of "the background b ⁰ " and "triangular shape function approximation of other components" and "the target triangle shape function" are required Y _j ( _mi )" curve. (ii) In the example of Figure 12, when the mass number (m/z) is 159.7 to 160.2, in order to obtain the "approximate curve yi _" that reproduces the measurement data c _i , the "background b ⁰ " and "target There are two curves of "triangular shape function Y _j ( _mi )" (j=2 in Table 2) and "triangular shape function approximation of other components" (j=0, 1 in Table 6).

[Calculation of mass peak intensity of C ₃ H ₃ O ₂ ^- ] Focusing on the range of mass number = 70.7 to 71.4 in the negative secondary ion spectrum, the equivalent of ¹² C ₃ ¹ H ₃ ¹⁶ obtained by fitting the autocurve Calculate the sum of the number of counts using the triangular shape function Y _k (mi) _{and m i approximated} by the mass peak near 71.013 of O ₂ ^- , and set the value normalized by C _T to C ₃ H ₃ O The mass peak intensity of ₂ ^- I (C ₃ H ₃ O ₂ ^- ).

[Calculation of mass peak intensity of PO ₂ ^- ] Focusing on the range of mass number = 62.5 to 63.3 in the negative secondary ion spectrum, it was calculated by approximating the mass peak near 62.964 corresponding to ³¹ P ¹⁶ O ₂ ^- Based on the data of the triangle shape function and m _i , calculate the sum of the count numbers, and set the value normalized by C _T as the mass peak intensity I (PO ₂ ^- ) of PO ₂ ^- .

[Calculation of mass peak intensity of PO ₃ ^- ] Focusing on the range of mass number = 78.5 to 79.3 in the negative secondary ion spectrum, it was calculated by approximating the mass peak near 78.959 corresponding to ³¹ P ¹⁶ O ₃ ^- From the data of the triangle shape function and m _i , calculate the sum of the count numbers, and set the value normalized by C _T as the mass peak intensity I (PO ₃ ^- ) of PO ₃ ^- .

The gas barrier layer is preferably formed from a hardened product of a mixture containing polycarboxylic acid, Zn, and a phosphorus compound containing one or more P-OH groups represented by phosphoric acid (H ₃ PO ₄ ) or other compounds thereof. salt. In the case of a gas barrier layer formed from a cured product of a mixture of these components, the carboxyl groups derived from the polycarboxylic acid form metal ion cross-links via Zn, and Zn also reacts with the phosphorus compound containing the P-OH group, Forms bonds that are water resistant. Although the detailed mechanism is unclear, it is thought that a tight gas barrier layer is formed by the uniform presence of an appropriate amount of these metal ion crosslinks via Zn or the bond between Zn and the phosphorus compound in the gas barrier layer, and by Steaming treatment, etc. suppresses excessive swelling and shrinkage of the gas barrier layer.

The Zn composition ratio of the gas barrier layer of the third embodiment and the value of I( ⁶⁴ ZnPO ₄ H ^- )/I(C ₃ H ₃ O ₂ ^- ) and (I(PO ₂ ^- ) + in TOF-SIMS The value of I(PO ₃ ^- ))/I(C ₃ H ₃ O ₂ ^- ) and the value of I(PO ₂ ^- )/I(PO ₃ ^- ) can be adjusted by appropriately adjusting the manufacturing conditions of the gas barrier layer. control. In _the third embodiment, for example, the concentration of phosphoric acid relative to the polycarboxylic acid can be used as _a parameter for controlling the Zn composition ratio and the value of I( ⁶⁴ _ZnPO4H ^- )/I( _C3H3O2- ⁾ Listed as one of the factors.

Polycarboxylic acids, zinc or its compounds, phosphorus compounds, and other addable components applicable to the third embodiment will be described in detail below.

(polycarboxylic acid) Polycarboxylic acids have two or more carboxyl groups in the molecule. Specific examples include homopolymerization of α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, cinnamic acid, 3-hexenoic acid, and 3-hexenedioic acid. substances or copolymers of these. In addition, copolymers of the α,β-unsaturated carboxylic acid and esters such as ethyl ester, olefins such as ethylene, etc. may also be used.

Among these, homopolymers of acrylic acid and methacrylic acid or copolymers of these are preferred, and one or two or more types selected from the group consisting of polyacrylic acid, polymethacrylic acid, and copolymers of acrylic acid and methacrylic acid are more preferred. The polymer is more preferably at least one polymer selected from the group consisting of polyacrylic acid and polymethacrylic acid, and particularly preferably at least one polymer selected from the group consisting of acrylic acid homopolymer and methacrylic acid homopolymer.

Here, in the third embodiment, polyacrylic acid includes both homopolymers of acrylic acid and copolymers of acrylic acid and other monomers. In the case of a copolymer of acrylic acid and other monomers, the polyacrylic acid contains usually 90 mass% or more, preferably 95 mass% or more, and more preferably 99 mass% or more derived from acrylic acid in 100 mass% of the polymer. structural unit.

In addition, in the third embodiment, polymethacrylic acid includes both homopolymers of methacrylic acid and copolymers of methacrylic acid and other monomers. In the case of a copolymer of methacrylic acid and other monomers, polymethacrylic acid contains usually 90 mass% or more, preferably 95 mass% or more, and more preferably 99 mass% or more in 100 mass% of the polymer. Structural unit derived from methacrylic acid.

A polycarboxylic acid is a polymer obtained by polymerizing a carboxylic acid monomer. The molecular weight of the polycarboxylic acid is preferably 500 to 2,500,000 and more preferably 5,000 to 2,000,000 from the viewpoint of excellent balance between gas barrier properties and workability. , more preferably 10,000～1,500,000, further preferably 100,000～1,200,000.

Here, the molecular weight of the polycarboxylic acid is a weight average molecular weight in terms of polyethylene oxide, and can be measured using gel permeation chromatography (GPC).

By neutralizing the polycarboxylic acid with a volatile base, gelation can be suppressed when zinc and the polycarboxylic acid described below are mixed. Therefore, among polycarboxylic acids, from the viewpoint of preventing gelation, it is preferable to use a volatile base to form a partially neutralized product or a completely neutralized product of the carboxyl group. The neutralizer can be obtained by partially or completely neutralizing the carboxyl group of the polycarboxylic acid using a volatile base (ie, partially or completely making the carboxyl group of the polycarboxylic acid into a carboxylate salt). This prevents gelation when zinc is added.

The partially neutralized product is prepared by adding a volatile base to an aqueous solution of the polycarboxylic acid polymer, and the desired degree of neutralization can be obtained by adjusting the ratio of the polycarboxylic acid to the volatile base. In the third embodiment, the degree of neutralization of the polycarboxylic acid by the volatile base is preferably 30 equivalent% to 100 equivalent%, more preferably 50 equivalent% to 100 equivalent%.

As the volatile base, any water-soluble base can be used.

Examples of the volatile base include tertiary amines such as ammonia, morpholine, alkylamine, 2-dimethylaminoethanol, N-methylmorpholine, ethylenediamine, and triethylamine, or aqueous solutions of these; or a mixture of these. From the viewpoint of obtaining good gas barrier properties, an ammonia aqueous solution is preferred.

The mixture constituting the gas barrier laminate of the third embodiment preferably further contains a carbonic acid ammonium salt. The carbonate-based ammonium salt is added in order to bring zinc, which will be described later, into the state of a zinc ammonium carbonate complex, improve the solubility of zinc, and prepare a uniform solution containing zinc.

Examples of carbonic acid-based ammonium salts include ammonium carbonate, ammonium bicarbonate, and the like. Ammonium carbonate is preferred in terms of being easily volatilized and not easily remaining in the obtained gas barrier layer.

(Zinc) Zinc (Zn) can form a water-resistant Zn phosphate bond with a phosphorus compound, and a mass peak represented by ⁶⁴ ZnPO ₄ H ^- can be detected by TOF-SIMS analysis. In addition, when the gas barrier layer contains a polycarboxylic acid, a salt is formed with the polycarboxylic acid. Zn may be any zinc or zinc compound that can be added to the mixture for forming the gas barrier layer. For example, metallic zinc, zinc oxide (ZnO), zinc compounds, etc. can be used. The amount of zinc added may be 0.1 mol or more and 0.5 mol or less per 1 mol of the carboxyl group of the polycarboxylic acid.

(Phosphorus Compound) As mentioned above, when performing mass analysis on the gas barrier layer, it is preferable to detect PO ₂ ^- and/or PO ₃ ^- . In order to provide such a gas barrier layer, the mixture before hardening preferably contains a phosphorus compound or a salt thereof. The phosphorus compound or the phosphorus compound in its salt contains more than one -P-OH group in the molecular structure. The phosphorus compound can also be formulated in the mixture as a salt. From the viewpoint of further improving the water vapor barrier property after retort treatment, the phosphorus compound preferably contains two or more -P-OH groups, and more preferably contains three or more -P-OH groups. In addition, from the viewpoint of productivity, the number of -P-OH groups in the phosphorus compound may be, for example, 10 or less. Specific examples of the phosphorus compound include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, and derivatives thereof. Specifically, polyphosphoric acid has a condensed structure of two or more phosphoric acids in its molecular structure. Examples thereof include diphosphoric acid (pyrophosphoric acid), triphosphoric acid, polyphosphoric acid in which four or more phosphoric acids are condensed, and the like. Specific examples of the derivatives include esters of the phosphorus compounds such as phosphorylated starch and phosphate cross-linked starch; halides such as chlorides; anhydrides such as tetraphosphoric acid decaoxide; and nitrotris(methylenephosphonic acid). ), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid) and other compounds having a structure in which the hydrogen atom bonded to the phosphorus atom is replaced by an alkyl group. From the viewpoint of further improving the balance between barrier properties and productivity, the phosphorus compound is one or two or more selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid and salts thereof. , more preferably at least one selected from the group consisting of phosphoric acid and phosphorous acid, phosphonic acid and salts thereof. Specific examples of salts among the salts of phosphorus compounds include salts of monovalent metals such as sodium and potassium; and ammonium salts. From the viewpoint of barrier properties, the salt of the phosphorus compound is preferably an ammonium salt. The concentration of P atoms in the phosphorus compound is typically 5 × 10 ^-4 mol or more, preferably 1 × 10 ^-3 mol or more, and more preferably 5 ×10 ^-3 mol or more, and typically 0.3 mol or less, preferably 0.15 mol or less, more preferably 0.1 mol or less. For phosphorus compounds that contain one P atom in the chemical formula like phosphoric acid, the mole number of the P atom and the mole number of the phosphorus compound have the same meaning. It is thought that the phosphorus compound derived from the phosphorus compound or its salt at such a concentration can suppress excessive swelling and shrinkage of the gas barrier layer during retort processing or the like by reliably forming a Zn bond with the water-resistant phosphorus compound. The gas barrier properties of the gas barrier laminate after the retort treatment are further improved. The presence of the phosphorus compound and the Zn bond is reflected in the mass peak of ⁶⁴ ZnPO ₄ H ^- obtained using the TOF-SIMS analysis.

(Other components) The mixture constituting the gas barrier layer of the third embodiment may or may not contain polyamine as other components, for example. When polyamine is contained, the barrier properties of the obtained gas barrier laminate can be improved, and the interlayer adhesion of the obtained gas barrier laminate can be improved, resulting in good delamination resistance. Furthermore, the fragments detected in the TOF-SIMS analysis are detected independently, so I( ⁶⁴ ZnPO ₄ H ^- )/I(C ₃ H ₃ O ₂ ^- ) obtained by analyzing the TOF-SIMS analysis results , (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) and I (PO ₂ ^- )/I (PO ₃ ^- ) values are not affected by the presence or absence of polyamine.

Polyamines are polymers having two or more amine groups in the main chain, side chains or terminals. Specific examples include: aliphatic polyamines such as polyallylamine, polyvinylamine, polyethyleneimine, and poly(trimethyleneimine); side chains such as polylysine acid and polyarginine Polyamides with amine groups, etc. In addition, a polyamine in which part of the amine group has been modified may also be used. The amount of polyamine added can be an amount such that the active hydrogen in the polyamine becomes 0 mol or more and 0.9 mol or less per 1 mol of carboxyl groups contained in the polycarboxylic acid.

From the viewpoint of excellent balance between gas barrier properties and workability, the weight average molecular weight of the polyamine is preferably 50 to 2,000,000, more preferably 100 to 1,000,000, further preferably 1,500 to 500,000, still more preferably 1,500 to 100,000. More preferably, it is 1,500-50,000, still more preferably 3,500-20,000, still more preferably 5,000-15,000, and particularly preferably 7,000-12,000. Here, in the third embodiment, the molecular weight of the polyamine can be measured using the boiling point elevation method or the viscosity method.

(Method for manufacturing gas barrier layer) The gas barrier layer of the third embodiment can be produced as follows, for example. First, a completely or partially neutralized solution of the carboxyl groups constituting the polycarboxylic acid is prepared.

A volatile base is added to the polycarboxylic acid to completely or partially neutralize the carboxyl groups of the polycarboxylic acid. By neutralizing the carboxyl groups of the polycarboxylic acid, gelation caused by the reaction with the carboxyl groups constituting the polycarboxylic acid when adding zinc is effectively prevented in the subsequent step, thereby obtaining a uniform gas barrier coating intermediate body.

Next, a zinc salt compound and a carbonic acid ammonium salt are added to the intermediate and dissolved, and the generated zinc ions are used to form a zinc salt with the -COO- group constituting the polycarboxylic acid. In this case, the -COO- group that forms a salt with zinc ions refers to both the carboxyl group that is not neutralized with the base and the -COO- group that is neutralized with the base. In the case of a -COO- group neutralized with a base, the zinc-derived zinc ions exchange and coordinate to form a zinc salt of the -COO- group. Furthermore, by adding phosphoric acid after forming a zinc salt, a gas barrier coating material (mixture) can be obtained.

The gas barrier coating material (mixture) produced in the above manner is applied on an inorganic layer described below, and dried and hardened to form a gas barrier layer. The method of applying the gas barrier coating material to the base material layer is not particularly limited, and a common method can be used. For example, gravure coaters using Meyer rod coaters, air knife coaters, direct gravure coaters, indirect gravure, arc gravure coaters, reverse gravure and spray nozzle methods, top feed reverse gravure coaters, etc. Reverse roll coaters such as reverse roll coaters, bottom feed reverse coaters and nozzle feed reverse coaters, five-roller coaters, die lip coaters, rod coaters, reverse The coating method is performed using various well-known coaters such as bar coaters and die coaters.

The coating amount (wet thickness) of the gas barrier coating material (mixture) is preferably 0.05 μm or more, more preferably 1 μm or more. In addition, the coating amount is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 100 μm or less. In addition, the average thickness of the gas barrier layer after drying and hardening is preferably from 0.05 μm to 10 μm, more preferably from 0.08 μm to 5 μm, and even more preferably from 0.1 μm to 1 μm. When it is below the upper limit, curling of the obtained gas barrier laminate or gas barrier film can be suppressed. Moreover, when it is more than the said lower limit value, the barrier performance of the obtained gas barrier laminate or gas barrier film can be made more favorable.

Drying and heat treatment can be carried out after drying or at the same time.

The method of drying and heat treatment is not particularly limited as long as the object of the present invention can be achieved, as long as the gas barrier coating material can be hardened or the gas barrier coating material can be heat-cured. Examples include devices that utilize convection heat transfer such as ovens and dryers, devices that utilize conductive heat transfer such as heating rollers, devices that utilize radiation heat transfer using electromagnetic waves such as infrared, far-infrared, and near-infrared heaters, and devices that utilize internal heat transfer such as microwaves. Heating device. As an apparatus used for drying and heat treatment, from the viewpoint of manufacturing efficiency, an apparatus capable of performing both drying and heat treatment is preferred. Among them, specifically, it is preferable to use a hot air oven from the viewpoint that it can be used for various purposes such as drying, heating, and annealing. In addition, from the viewpoint of excellent heat conduction efficiency to the film, it is preferable to use heating. Roller. In addition, methods used for drying and heat treatment may be appropriately combined. A hot air oven and a heating roller may be used together. For example, if the gas barrier coating material is dried in a hot air oven and then heated using a heating roller, the time of the heating treatment step will be shortened, which is preferable from the viewpoint of manufacturing efficiency. In addition, it is preferable to perform drying and heating processing only by a hot air oven.

For example, the heat treatment temperature is preferably 80°C to 250°C and the heat treatment time is 1 second to 10 minutes. More preferably, the heat treatment temperature is 120°C to 240°C and the heat treatment time is 1 second to 1 minute. More preferably, the heat treatment temperature is 80°C to 250°C and the heat treatment time is 1 second to 10 minutes. Preferably, the heat treatment temperature is 170°C to 230°C and the heat treatment time is 1 second to 30 seconds. Furthermore, as mentioned above, by using a heating roller together, heat processing can be performed in a short time. It is important to adjust the heat treatment temperature and heat treatment time according to the wet thickness of the gas barrier coating material.

The gas barrier coating material (mixture) forms metal cross-links and water-resistant phosphate Zn bonds through the zinc salt of the -COO- group constituting the polycarboxylic acid (reflected in ⁶⁴ ZnPO ₄ H obtained by the TOF-SIMS analysis) ^- mass peak), drying, and heat treatment can be performed to obtain a gas barrier layer with excellent gas barrier properties.

(Inorganic layer) Examples of the inorganic substances constituting the inorganic substance layer 4 include metals, metal oxides, metal nitrides, metal fluorides, and metal oxynitrides that can form a barrier thin film.

Examples of the inorganic substance constituting the inorganic substance layer 4 include elements selected from Group 2A of the Periodic Table such as beryllium, magnesium, calcium, strontium, and barium; transition elements of the Periodic Table such as titanium, zirconium, ruthenium, hafnium, and tantalum; Group 2B of the Periodic Table such as zinc; Elements; aluminum, gallium, indium, thallium and other periodic table group 3A elements; periodic table group 4A elements such as silicon, germanium and tin; periodic table group 6A elements such as selenium, tellurium and other elements, oxides, nitrides, fluorides, etc. or one or more of nitrogen oxides, etc. Furthermore, in the third embodiment, the group names of the periodic table are represented by the old CAS formula.

Furthermore, among the inorganic substances, one or two or more inorganic substances selected from the group consisting of silica, alumina, and aluminum are preferred in terms of excellent balance between barrier properties, cost, etc., and more preferred are aluminum oxide. Furthermore, the silicon oxide may also contain silicon monoxide and silicon suboxide in addition to silicon dioxide.

The inorganic substance layer is formed from the inorganic substance. The inorganic layer 4 may include a single inorganic layer or multiple inorganic layers. In addition, when the inorganic layer 4 includes a plurality of inorganic layers, it may include the same type of inorganic layer or may include different types of inorganic layers.

From the viewpoint of a balance between barrier properties, adhesion, operability, etc., the thickness of the inorganic layer 4 is usually from 1 nm to 1000 nm, preferably from 1 nm to 500 nm. In the third embodiment, the thickness of the inorganic layer can be determined from an observation image obtained by a transmission electron microscope or a scanning electron microscope.

The method of forming the inorganic layer is not particularly limited. For example, it can be vacuum evaporation, ion plating, sputtering, chemical vapor deposition, physical vapor deposition, or chemical vapor deposition (CVD). , plasma CVD method, sol-gel method, etc. to form the inorganic layer 4 on one or both sides of the base material layer 2 . Among them, sputtering, ion plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma CVD, or film formation under reduced pressure are ideal. Therefore, it is expected that chemically active molecular species containing silicon such as silicon nitride or silicon oxynitride react rapidly to improve the smoothness of the surface of the inorganic layer 4 and reduce the number of holes. In order to rapidly carry out these binding reactions, it is ideal that the inorganic atom or compound is a chemically active molecular species or atomic species.

(Substrate layer) The base material layer 2 can be used without particular limitation as long as it can be coated with a solution of the gas barrier coating material. Examples include: organic materials such as thermosetting resin, thermoplastic resin, or paper; inorganic materials such as glass, pottery, ceramics, silicon oxide, silicon oxynitride, silicon nitride, cement, aluminum, alumina, iron, copper, stainless steel, and other metals Material; a base material layer of a multilayer structure including a combination of organic materials or a combination of organic materials and inorganic materials, etc. Among these, for example, in the case of various film applications such as packaging materials and panels, it is preferable to use thermosetting resins, thermoplastic resins, plastic films, or organic materials such as paper.

As the thermosetting resin, a known thermosetting resin can be used. Examples include epoxy resin, unsaturated polyester resin, phenol resin, urea-melamine resin, polyurethane resin, silicone resin, polyimide, and the like.

As the thermoplastic resin, a known thermoplastic resin can be used. Examples include polyolefins (polyethylene, polypropylene, poly(4-methyl-1-pentene), poly(1-butene), etc.), polyesters (polyethylene terephthalate, poly(p-p) Butylene phthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, polyethylene glycol m-phenylenediamine, etc.), polyvinyl chloride, polyimide, Ethylene-vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, fluororesin, or a mixture thereof, etc.

Among these, from the viewpoint of improving transparency, it is preferable to be selected from the group consisting of polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, and poly(p-p). One or two or more resins in the group consisting of butylene phthalate are preferably selected from the group consisting of polyamide, polyamide and polyamide from the viewpoint of excellent pinhole resistance, crack resistance and heat resistance. One or more resins in the group consisting of ethylene terephthalate and polybutylene terephthalate. In addition, the base material layer 2 containing the thermoplastic resin may be a single layer or two or more layers depending on the use of the gas barrier laminate 8 . In addition, a film made of the thermosetting resin or thermoplastic resin may be stretched in at least one direction, preferably in a biaxial direction, to form a base material layer.

The base material layer 2 of the third embodiment is preferably made of polypropylene, polyethylene terephthalate, and polyethylene naphthalate from the viewpoint of excellent transparency, rigidity, and heat resistance. , a biaxially stretched film formed of one or more thermoplastic resins selected from the group consisting of polyamide, polyimide and polybutylene terephthalate, and more preferably a biaxially stretched film made of polyamide, polyimide and polybutylene terephthalate. A biaxially stretched film formed of one or more thermoplastic resins selected from ethylene formate and polybutylene terephthalate.

In addition, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, acrylic resin, urethane resin, etc. may also be coated on the surface of the base material layer 2 .

Furthermore, the base material layer 2 may be surface-treated in order to improve the adhesiveness. Specifically, surface activation treatments such as corona treatment, flame treatment, plasma treatment, and primer coating treatment can also be performed.

From the viewpoint of obtaining good film properties, the thickness of the base material layer 2 is preferably 1 μm to 1000 μm, more preferably 1 μm to 500 μm, and still more preferably 1 μm to 300 μm.

The shape of the base material layer 2 is not particularly limited, and examples include a sheet or film shape, a tray, a cup, a hollow body, and the like.

(base coat) In the gas barrier laminated body 8 , from the viewpoint of improving the adhesion between the base material layer 2 and the inorganic layer 4 , the primer layer 3 may be formed on the surface of the base material layer 2 . The undercoat layer is preferably a layer formed of an epoxy (meth)acrylate compound or a urethane (meth)acrylate compound.

The undercoat layer 3 is preferably a layer obtained by hardening at least one selected from the group consisting of epoxy (meth)acrylate compounds and urethane (meth)acrylate compounds.

Examples of the epoxy (meth)acrylate compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolak type epoxy compound, and a cresol novolac type epoxy compound. Compounds obtained by reacting epoxy compounds such as varnish-type epoxy compounds and aliphatic epoxy compounds with acrylic acid or methacrylic acid, and further examples include acid-modified rings obtained by reacting the epoxy compound with carboxylic acid or its anhydride. Oxy(meth)acrylate. These epoxy (meth)acrylate compounds are coated on the surface of the base material layer together with a photopolymerization initiator and a diluent including other photopolymerization initiators or heat-reactive monomers if necessary, and then irradiated Ultraviolet rays, etc. form a primer layer through a cross-linking reaction.

Examples of the urethane (meth)acrylate-based compound include acrylation of an oligomer containing a polyol compound and a polyisocyanate compound (hereinafter also referred to as a polyurethane-based oligomer). Those who become mature and so on.

The polyurethane oligomer can be obtained from a condensation product of a polyisocyanate compound and a polyol compound. Specific polyisocyanate compounds include methylene-bis(terphenylene diisocyanate), hexamethylene diisocyanate-hexanetriol adduct, hexamethylene diisocyanate, toluene diisocyanate, and toluene diisocyanate. Adduct of trimethylolpropane, 1,5-naphthalene diisocyanate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-toluene diisocyanate dimer, hydrogenated xylene diisocyanate, tris(4-phenyl isocyanate)thiophosphate, etc. Specific polyol compounds include polyether polyols such as polyoxytetramethylene glycol and polyadipate polyols. , polyester polyols such as polycarbonate polyol, copolymers of acrylates and hydroxyethyl methacrylate, etc. Examples of the monomer constituting the acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (meth)acrylate. Methoxyethyl acrylate, butoxyethyl (meth)acrylate, phenyl (meth)acrylate, etc.

These epoxy (meth)acrylate compounds and urethane (meth)acrylate compounds are used in combination as necessary. Examples of methods for polymerizing these compounds include various known methods, specifically methods by irradiating energy rays containing ionizing radiation, heating, or the like.

When hardening with ultraviolet rays is used to form the undercoat layer, acetophenones, benzophenones, Michaelis benzoyl benzoate, α-amyl oxime ester or thioxanthone are preferred. are used as photopolymerization initiators, and n-butylamine, triethylamine, tri-n-butylphosphine, etc. are used as photosensitizers, and are mixed and used. In the third embodiment, an epoxy (meth)acrylate compound and a urethane (meth)acrylate compound can also be used together.

In addition, these epoxy (meth)acrylate compounds or urethane (meth)acrylate compounds are diluted with (meth)acrylic monomers. Examples of such a (meth)acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. , methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenyl (meth)acrylate, as the polyfunctional monomer, trimethylolpropane tri(meth)acrylic acid can be exemplified Esters, hexylene glycol (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc.

Among them, when a urethane (meth)acrylate compound is used as the undercoat layer, the oxygen gas barrier properties of the gas barrier laminate 8 obtained are further improved. The thickness of the undercoat layer of the third embodiment is usually in the range of 0.01 g/m ² to 100 g/m ² in terms of coating amount, preferably 0.05 g/m ² to 50 g/m ² .

(adhesive layer) In addition, the adhesive layer 6 may be provided on the gas barrier layer 5 . The adhesive layer 6 only needs to contain a known adhesive. Examples of adhesives include organic titanium-based resins, polyethyleneimine-based resins, urethane-based resins, epoxy-based resins, acrylic resins, polyester-based resins, oxazoline group-containing resins, modified Laminated adhesives composed of silicone resin, alkyl titanate, polyester-based polybutadiene, etc., or one-liquid or two-liquid polyols and polyisocyanates, water-based urethanes, ion polymerization Things etc. Alternatively, a water-based adhesive whose main raw material is acrylic resin, vinyl acetate resin, urethane resin, polyester resin, etc. can also be used.

In addition, other additives such as a hardener and a silane coupling agent may be added to the adhesive according to the use of the gas barrier laminate 8 . When the gas barrier laminate is used for hot water treatment such as steaming, a dry layer represented by a polyurethane adhesive is preferred from the viewpoint of heat resistance or water resistance. The pressure adhesive is more preferably a solvent-based two-liquid curing type polyurethane adhesive.

The gas barrier laminate 8 according to the third embodiment has excellent gas barrier performance after retort regardless of the laminate structure. Therefore, it can be suitably applied to packaging materials, especially food packaging materials for contents requiring high gas barrier properties. In addition, it is also suitable for various packaging materials such as medical use, industrial use, and daily groceries.

In addition, the gas barrier laminate 8 of the third embodiment can be suitably used as, for example, a vacuum heat-insulating film requiring high barrier performance; a sealing film for sealing electroluminescent elements, solar cells, and the like.

<Fourth Embodiment> FIG. 13 is a cross-sectional view schematically showing an example of the structure of the gas barrier laminate according to the fourth embodiment. The gas barrier laminate 100 shown in FIG. 13 includes: a base material layer 101; a gas barrier layer 103 provided on at least one surface of the base material layer 101; and an inorganic layer 102 provided between the base material layer 101 and the gas barrier layer. between layers 103. Furthermore, the gas barrier layer 103 includes a hardened product of a mixture containing a polycarboxylic acid, a polyamine compound, a polyvalent metal compound, a phosphorus compound containing one or more -P-OH groups, or a salt thereof. The specific structure of each layer will be described later.

In the gas barrier laminate 100, the base material layer 101, the inorganic layer 102, and the gas barrier layer 103 are laminated in this order, and the gas barrier layer 103 contains a cured product of the mixture. Therefore, the balance between barrier properties and productivity is excellent. It can exert better barrier properties in various layer structures. More specifically, the gas barrier laminate 100 has excellent barrier properties such as oxygen barrier properties and water vapor barrier properties after retort treatment. In addition, in the gas barrier layered body 100, the gas barrier layer 103 contains a cured product of the mixture. Therefore, for example, even if the curing time, specifically the heat treatment time, when obtaining the gas barrier layer 103 is short, the barrier can be obtained. The gas barrier laminate 100 has excellent gas barrier properties. In addition, the gas barrier layer 103 includes a hardened product of a mixture including a polycarboxylic acid, a polyamine compound, a polyvalent metal compound, and a phosphorus compound or a salt thereof containing one or more -P-OH groups. Therefore, it also becomes For example, the gas barrier laminate 100 having excellent barrier properties and water resistance can be obtained.

FIG. 14 is a cross-sectional view schematically showing another structural example of the gas barrier laminate. The basic structure of the gas barrier laminate 110 shown in FIG. 14 is the same as the gas barrier laminate 100 described with reference to FIG. 13 , but further includes a primer layer 104 provided between the base material layer 101 and the inorganic layer 102 . Different aspects. Also in the gas barrier laminated body 110, the same effect as that of the gas barrier laminated body 100 can be obtained. In addition, in the gas barrier laminate 110, by providing the primer layer 104 between the base material layer 101 and the inorganic material layer 102, the adhesion between the base material layer 101 and the inorganic material layer 102 can be further improved. Hereinafter, the structure of the layers included in the gas barrier laminate will be described in more detail. First, the gas barrier layer 103 will be described.

(gas barrier layer) The gas barrier layer 103 includes a hardened product of a mixture including a polycarboxylic acid, a polyamine compound, and a polyvalent metal compound. More specifically, the gas barrier layer 103 is a film (gas barrier film 10 ) including the cured product. More specifically, the gas barrier layer 103 can be formed by applying a pre-cured mixture, that is, a gas barrier coating material on a layer such as the inorganic layer 102 and other layers arranged directly below the gas barrier layer 103, and then drying and heat-treating it. It is obtained by hardening the gas barrier coating material.

In the infrared absorption spectrum of the gas barrier layer 103, let the maximum peak height of the absorbance in the range of 1300 cm ^-1 or more and 1490 cm ^-1 be α, and let α be the maximum peak height of the absorbance in the range of 1690 cm ^-1 or more and 1780 cm ^-1 When the maximum peak height of the absorbance in the range is γ, from the viewpoint of the liquid stability of the gas barrier coating material before coating, the ratio of free carboxyl groups to NH ₃ complex represented by γ/α is preferable It is 0.00 or more, more preferably, it is 0.01 or more, and still more preferably, it is 0.02 or more. In addition, from the viewpoint of improving the barrier properties of the gas barrier layer 103 obtained after coating, the γ/α is preferably 1.00 or less, more preferably 0.80 or less, even more preferably 0.60 or less, and still more preferably 0.60 or less. 0.40 or less, more preferably 0.20 or less, still more preferably 0.10 or less.

In addition, in the infrared absorption spectrum of the gas barrier layer 103, let the total peak area in the range of the absorption band 1493 cm ^-1 or more and 1780 cm ^-1 be A, and let the absorption band 1598 cm ^-1 or more and 1690 cm Let the total peak area in the range of ^-1 and below be B, let the total peak area in the range of the absorption band 1690 cm ^-1 and above and 1780 cm ^-1 be C, and let the absorption band 1493 cm ^-1 and above and 1598 cm ^-1 When the total peak area in the following range is assumed to be D, preferred examples of the area ratio are shown below. In the infrared absorption spectrum of the gas barrier layer 103, from the viewpoint of further improving the gas barrier performance after the retort treatment, the area ratio of the amide bond represented by B/A is preferably 0.200 or more, more preferably 0.220 or more, preferably 0.250 or more. In addition, from the viewpoint of further improving the balance between barrier properties and productivity, the area ratio of the amide bond represented by B/A is preferably 0.370 or less, more preferably 0.350 or less, and even more preferably 0.300 or less. .

In the infrared absorption spectrum of the gas barrier layer 103, from the viewpoint of further improving the gas barrier performance after retort treatment, the area ratio of carboxylic acid represented by C/A is preferably 0.150 or less, more preferably 0.100. or less, more preferably 0.080 or less, still more preferably 0.060 or less. In addition, the lower limit of the area ratio of the carboxylic acid represented by C/A is not limited, but may be, for example, 0.000 or more. Alternatively, it may be, for example, 0.0001 or more.

In the infrared absorption spectrum of the gas barrier layer 103, from the viewpoint of further improving the balance between barrier properties and productivity, the area ratio of the carboxylate represented by D/A is preferably 0.580 or more, more preferably 0.600 and above. In addition, from the viewpoint of further improving the gas barrier performance after retort treatment, the D/A is preferably 0.800 or less, more preferably 0.780 or less, further preferably 0.760 or less, still more preferably 0.740 or less.

Furthermore, from the viewpoint of further improving the balance between productivity and barrier properties of the gas barrier laminate, it is also preferred that the area ratio of the amide bond represented by B/A is 0.200 or more and 0.370 or less, and C The area ratio of the carboxylic acid represented by /A is 0.150 or less, and the area ratio of the carboxylic acid salt represented by D/A is 0.580 or more and 0.800 or less.

In the infrared absorption spectrum of the gas barrier layer 103, from the viewpoint of improving the barrier properties, the area ratio of the carboxylate represented by D/A with respect to the area ratio of the amide bond represented by B/A The area ratio is preferably 1.2 or more, more preferably 1.5 or more, and more preferably 2.0 or more. In addition, from the viewpoint of improving barrier properties after cooking, the area ratio of the carboxylate represented by D/A to the area ratio of the amide bond represented by B/A is preferably 4.0 or less. , more preferably 3.5 or less, and still more preferably 3.0 or less.

Here, in the gas barrier layer 103, the absorption of νC=O based on the unreacted carboxylic acid in the infrared absorption spectrum is visible near 1700 cm ^-1 , and the absorption based on νC=O based on the amide bond which is the cross-linked structure Absorption is visible around 1630 cm ^-1 ~ 1685 cm ^-1 , νC=O absorption based on carboxylate is visible around 1540 cm ^-1 ~ 1560 cm ^-1 , absorption based on δN-H of ammonia forming a complex Visible around 1300 cm ^-1 ~ 1490 cm ^-1 .

The maximum peak height α of the absorbance in the range of 1300 cm ^-1 to 1490 cm ^-1 in the infrared absorption spectrum is considered to be an index of the amount of ammonia that forms a complex, and 1690 cm ^-1 to 1780 cm ^-1 The maximum peak height γ in the following range represents an index of the amount of free, that is, unreacted, carboxylic acid present.

In the fourth embodiment, the maximum peak heights α and γ can be specifically measured according to the following procedure. That is, a measurement sample of 1 cm×3 cm was cut out from the gas barrier layer 103 . Then, the infrared absorption spectrum of the surface of the gas barrier layer 103 is obtained by infrared total reflection measurement (ATR method). In the obtained infrared absorption spectrum, a straight line connecting the absorbance of 900 cm ^-1 and the absorbance of 1900 cm ^-1 was used as a baseline, and the maximum peak height in each absorbance range was calculated.

In addition, the total peak area A in the range of the absorption band from 1493 cm ^-1 to 1780 cm ^-1 in the infrared absorption spectrum is considered to be an index of the total amount of carboxylic acid, amide bond and carboxylate, and the absorption band is 1598 cm The total peak area B in the range from ^-1 to 1690 cm ^-1 is an indicator of the amount of amide bonds present. Furthermore, it is considered that the total peak area C in the range of the absorption band from 1690 cm ^-1 to 1780 cm ^-1 represents an index of the amount of unreacted carboxylic acid, and the absorption band from 1493 cm ^-1 to 1598 cm ^-1 is considered to be an indicator of the amount of unreacted carboxylic acid present. The total peak area D of the range represents an indicator of the amount of carboxylate present.

In the fourth embodiment, the total peak area A to total peak area D can be specifically measured according to the following procedure. First, a measurement sample of 1 cm×3 cm was cut out from the gas barrier layer 103 . Then, the infrared absorption spectrum of the surface of the gas barrier layer 103 is obtained by infrared total reflection measurement (ATR method). Based on the obtained infrared absorption spectrum, the total peak areas A to D are calculated according to the following procedures (1) to (4). (1) Connect the absorbance at 1780 cm ^-1 and 1493 cm ^-1 with a straight line (N), and take the area surrounded by the absorption spectrum in the range of the absorption band 1493 cm ^-1 and above and below 1780 cm ^-1 and N as the total peak area. A. (2) Draw a straight line (O) vertically from the absorbance (Q) of 1690 cm ^-1 , let the intersection point of N and O be P, draw a straight line (S) vertically from the absorbance (R) of 1598 cm ^-1 , Let the intersection point of N and S be T, and compare the absorption spectrum in the range of the absorption band from 1598 cm ^-1 to 1690 cm ^-1 with straight line S, point T, straight line N, point P, straight line O, absorbance Q, absorbance The area surrounded by R is taken as the total peak area B. (3) The area surrounded by the absorption spectrum and absorbance Q, straight line O, point P, and straight line N in the range of the absorption band from 1690 cm ^-1 to 1780 cm ^-1 is the total peak area C. (4) The area surrounded by the absorption spectrum and the absorbance R, the straight line S, the point T, and the straight line N in the range of the absorption band from 1493 cm ^-1 to 1598 cm ^-1 is the total peak area D. Next, the area ratio B/A, the area ratio C/A, and the area ratio D/A are determined based on the areas determined by the above method.

Furthermore, in the fourth embodiment, the infrared absorption spectrum (infrared total reflection measurement: ATR method) can be measured using, for example, an IRT-5200 device manufactured by JASCO Corporation and equipped with a PKM-GE-S (Germanium) crystal. , carried out under the conditions of incident angle 45 degrees, room temperature, decomposition energy 4 cm ^-1 and cumulative number of 100 times.

The maximum peak heights α and γ of the gas barrier layer 103, the area ratio of the amide bond represented by B/A, the area ratio of the carboxylic acid represented by C/A, and the carboxylic acid represented by D/A The area ratio of the salt can be controlled by appropriately adjusting the manufacturing conditions of the gas barrier layer 103 . Specifically, the blending ratio of the polycarboxylic acid, the polyamine compound, the polyvalent metal compound and the phosphorus compound, the preparation method of the mixture before hardening, the method of heat treatment of the mixture, temperature, time, etc. can be used as factors for controlling the gas barrier properties. The maximum peak heights α and γ of the layer 103, the area ratio of the amide bond represented by B/A, the area ratio of the carboxylic acid represented by C/A, and the area ratio of the carboxylate salt represented by D/A ratio factors.

Next, the components contained in the mixture before hardening (gas barrier coating material) will be described. (polycarboxylic acid) Polycarboxylic acids have two or more carboxyl groups in the molecule. Specific examples include homopolymerization of α,β-unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, fumaric acid, crotonic acid, cinnamic acid, 3-hexenoic acid, and 3-hexenedioic acid. substances or copolymers of these. In addition, copolymers of the α,β-unsaturated carboxylic acid and esters such as ethyl ester, olefins such as ethylene, etc. may also be used.

Among these, homopolymers or copolymers of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, and cinnamic acid are preferred, and more preferred are selected from the group consisting of polyacrylic acid, polymethacrylic acid, and One or two or more polymers in the group consisting of copolymers of acrylic acid and methacrylic acid, more preferably at least one polymer selected from polyacrylic acid and polymethacrylic acid, and even more preferably selected from At least one polymer selected from a homopolymer of acrylic acid and a homopolymer of methacrylic acid.

Here, in the fourth embodiment, polyacrylic acid includes both homopolymers of acrylic acid and copolymers of acrylic acid and other monomers. In the case of a copolymer of acrylic acid and other monomers, the polyacrylic acid contains usually 90 mass% or more, preferably 95 mass% or more, and more preferably 99 mass% or more derived from acrylic acid in 100 mass% of the polymer. structural unit. In addition, in the fourth embodiment, polymethacrylic acid includes both homopolymers of methacrylic acid and copolymers of methacrylic acid and other monomers. In the case of a copolymer of methacrylic acid and other monomers, polymethacrylic acid contains usually 90 mass% or more, preferably 95 mass% or more, and more preferably 99 mass% or more in 100 mass% of the polymer. Structural unit derived from methacrylic acid.

Polycarboxylic acids are polymers made from carboxylic acid monomers. From the viewpoint of excellent balance between gas barrier properties and workability, the molecular weight of the polycarboxylic acid is preferably 500 to 2,500,000, more preferably 5,000 to 2,000,000, more preferably 10,000 to 1,500,000, and still more preferably 100,000 to 1,200,000. Here, in the fourth embodiment, the molecular weight of the polycarboxylic acid is a weight average molecular weight in terms of polyethylene oxide, and can be measured using gel permeation chromatography (GPC).

At least a portion of the polycarboxylic acid can also be neutralized by a volatile base. By neutralizing the polycarboxylic acid with a volatile base, gelation can be suppressed when the polyvalent metal compound or polyamine compound is mixed with the polycarboxylic acid. Therefore, among polycarboxylic acids, from the viewpoint of preventing gelation, it is preferable to use a volatile base to form a partially neutralized product or a completely neutralized product of the carboxyl group. The neutralized product can be obtained by partially or completely neutralizing the carboxyl group of the polycarboxylic acid using a volatile base, that is, partially or completely converting the carboxyl group of the polycarboxylic acid into a carboxylic acid salt. This can prevent gelation when adding a polyamine compound or a polyvalent metal compound. The partially neutralized product can be prepared by adding a volatile base to the aqueous solution of the polycarboxylic acid polymer, and the desired degree of neutralization can be obtained by adjusting the ratio of the polycarboxylic acid to the volatile base. In the fourth embodiment, from the viewpoint of fully suppressing gelation caused by the neutralization reaction with the amine group of the polyamine compound, the degree of neutralization of the polycarboxylic acid by the volatile base is preferably 70 equivalent% ~300 equivalent%, more preferably 90 equivalent% ~ 250 equivalent%, further preferably 100 equivalent% ~ 200 equivalent%.

As the volatile base, any water-soluble base can be used. Examples of the volatile base include tertiary amines such as ammonia, morpholine, alkylamine, 2-dimethylaminoethanol, N-methylmorpholine, ethylenediamine, and triethylamine, or aqueous solutions of these; or a mixture of these. From the viewpoint of obtaining good gas barrier properties, an ammonia aqueous solution is preferred.

(polyamine compound) The mixture before hardening contains polyamine compounds. By including a polyamine compound, the barrier properties of the obtained gas barrier material can be improved. The polyamine compound is a compound having two or more amine groups in the main chain, side chain or terminal, and is preferably a polymer. Specific examples include: aliphatic polyamines such as polyallylamine, polyvinylamine, polyethyleneimine, and poly(trimethyleneimine); side chains such as polylysine acid and polyarginine Polyamides with amine groups, etc. In addition, a polyamine in which part of the amine group has been modified may also be used. From the viewpoint of obtaining good gas barrier properties, the polyamine compound preferably contains polyethyleneimine, more preferably polyethyleneimine.

From the viewpoint of excellent balance between gas barrier properties and workability, the number average molecular weight of the polyamine compound is preferably 50 to 2,000,000, more preferably 100 to 1,000,000, further preferably 1,500 to 500,000, still more preferably 1,500 to 100,000 , more preferably 1,500 to 50,000, still more preferably 3,500 to 20,000, still more preferably 5,000 to 15,000, still more preferably 7,000 to 12,000. Here, in the fourth embodiment, the molecular weight of the polyamine compound can be measured using the boiling point elevation method or the viscosity method.

From the viewpoint of further improving the gas barrier performance after retort treatment, (the mole number of amine groups contained in the polyamine compound in the mixture) / (the number of -COO- groups contained in the polycarboxylic acid in the mixture The molar number) is preferably 0.20 or more, more preferably 0.25 or more, still more preferably 0.30 or more, still more preferably 0.35 or more, and still more preferably 0.40 or more. From the same viewpoint, (the mole number of amine groups contained in the polyamine compound in the mixture)/(the mole number of -COO- groups contained in the polycarboxylic acid in the mixture) is preferably 0.90 or less, more preferably 0.85 or less, still more preferably 0.80 or less, still more preferably 0.75 or less, still more preferably 0.70 or less. The details of this reason are not yet clear, but it is thought that the amide crosslinking by the amine group constituting the polyamine compound and the metal crosslinking by the polyvalent metal constituting the salt of the polycarboxylic acid and the polyvalent metal are balanced. By forming a dense structure, the gas barrier layer 103 and the gas barrier laminate having the gas barrier layer 103 having excellent gas barrier properties after the retort treatment can be obtained.

(polyvalent metal compound) Specifically, polyvalent metal compounds are metals and metal compounds belonging to Groups 2 to 13 of the periodic table. More specifically, they include magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). ), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al) and other divalent or higher metals, oxides, hydroxides, and halides of these metals substances, carbonates, phosphates, phosphites, hypophosphites, sulfates or sulfites, etc. From the viewpoint of water resistance, impurities, etc., metal oxides or metal hydroxides are preferred.

From the viewpoint of further improving the gas barrier performance after retort treatment, the metal having a divalent or higher valence in the multivalent metal compound is preferably one or two selected from the group consisting of Zn, Ca, Mg, Ba and Al. More than one metal, preferably Zn. From the same viewpoint, the polyvalent metal compound is preferably a compound of one or more bivalent or higher metals selected from the group consisting of Zn, Ca, Mg, Ba and Al, and more preferably Zn compound of. From the same viewpoint, the polyvalent metal compound is preferably selected from oxides such as magnesium oxide, calcium oxide, barium oxide, zinc oxide, and magnesium hydroxide, and hydroxides such as calcium hydroxide, barium hydroxide, and zinc hydroxide. One or two or more compounds in the group are more preferably at least one of zinc oxide and zinc hydroxide, and even more preferably zinc oxide.

In the fourth embodiment, from the viewpoint of further improving the gas barrier performance after retort treatment, (mol number of the polyvalent metal compound in the mixture)/(-COO contained in the polycarboxylic acid in the mixture) The molar number of - base) is preferably 0.10 or more, more preferably 0.13 or more, still more preferably 0.15 or more, and still more preferably 0.18 or more. From the same viewpoint, (the mole number of the polyvalent metal compound in the mixture)/(the mole number of the -COO- group contained in the polycarboxylic acid in the mixture) is preferably 0.80 or less, more preferably 0.70 or less, more preferably 0.60 or less, still more preferably 0.55 or less, still more preferably 0.50 or less.

In the fourth embodiment, from the viewpoint of further improving the gas barrier performance after retort treatment, (the molar number of the polyvalent metal compound in the mixture)/(the number of moles derived from the amine group of the polyamine compound in the mixture Mohr number) is preferably 0.25 or more, more preferably 0.35 or more, and still more preferably 0.40 or more. From the same viewpoint, (the molar number of the polyvalent metal compound in the mixture)/(the molar number of the amine group derived from the polyamine compound in the mixture) is preferably 0.65 or less, more preferably 0.60 or less, More preferably, it is 0.55 or less.

(phosphorus compound or its salt) The phosphorus compound or the phosphorus compound in its salt contains more than one -P-OH group in the molecular structure. The phosphorus compound can also be formulated in the mixture as a salt. From the viewpoint of further improving the water vapor barrier property after retort treatment, the phosphorus compound preferably contains two or more -P-OH groups, and more preferably contains three or more -P-OH groups. In addition, from the viewpoint of improving the liquid stability of the gas barrier coating material, the number of -P-OH groups in the phosphorus compound may be, for example, two or less.

Specific examples of the phosphorus compound include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, and derivatives thereof. Specifically, polyphosphoric acid has a condensed structure of two or more phosphoric acids in its molecular structure. Examples thereof include diphosphoric acid (pyrophosphoric acid), triphosphoric acid, polyphosphoric acid in which four or more phosphoric acids are condensed, and the like. Specific examples of derivatives include esters of the phosphorus compounds such as phosphorylated starch and phosphate cross-linked starch; Halides such as chloride; Anhydrides such as tetraphosphorus decaoxide; and Nitrotris(methylenephosphonic acid), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid), etc. have a structure in which the hydrogen atom bonded to the phosphorus atom is replaced by an alkyl group. compound of.

From the viewpoint of further improving the balance between barrier properties and productivity, the phosphorus compound is one or two or more selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid and salts thereof. , more preferably at least one selected from the group consisting of phosphoric acid and phosphorous acid.

Specific examples of salts among the salts of phosphorus compounds include salts of monovalent metals such as sodium and potassium; and ammonium salts. From the viewpoint of improving barrier properties, the salt of the phosphorus compound is preferably an ammonium salt.

In the fourth embodiment, from the viewpoint of improving barrier properties, (the molar number of P atoms derived from the phosphorus compound or its salt in the mixture)/(the -COO- group derived from the polycarboxylic acid in the mixture) The molar number) is, for example, 0.0001 or more, preferably 0.001 or more, more preferably 0.003 or more, still more preferably 0.005 or more. In phosphorus compounds that contain a P atom in the chemical formula like phosphoric acid, the molar number of the P atom and the molar number of the phosphorus compound have the same meaning. In addition, from the viewpoint of improving the liquid stability of the barrier coating material (mixture), (the mole number of P atoms derived from the phosphorus compound or its salt in the mixture) / (the number of moles of P atoms derived from the polycarboxylic acid in the mixture) The molar number of the COO group) is preferably 0.3 or less, more preferably 0.1 or less, still more preferably 0.08 or less, still more preferably 0.005 or less.

The mixture before hardening may contain components other than the above-mentioned components. For example, the mixture preferably further contains carbonic acid ammonium salt. The carbonate-based ammonium salt is added in order to convert the polyvalent metal compound into the state of a polyvalent metal ammonium carbonate complex, improve the solubility of the polyvalent metal compound, and prepare a uniform solution containing the polyvalent metal compound. By including the ammonium carbonate salt in the mixture before hardening, the dissolved amount of the polyvalent metal compound can be increased. As a result, the mixture prepared with the polyvalent metal compound can be made more homogeneous. Examples of carbonic acid-based ammonium salts include ammonium carbonate and ammonium bicarbonate. Ammonium carbonate is preferred in that it is easily volatilized and is less likely to remain in the obtained gas barrier layer. From the viewpoint of further improving the solubility of the polyvalent metal compound, (the molar number of the carbonic acid ammonium salt in the mixture)/(the molar number of the polyvalent metal compound in the mixture) is preferably 0.05 or more, more preferably Preferably it is 0.10 or more, more preferably 0.25 or more, still more preferably 0.50 or more, still more preferably 0.75 or more. In addition, from the viewpoint of further improving the coating properties of the gas barrier coating material, (moles of the carbonate ammonium salt in the gas barrier coating material)/(polyvalent metal in the gas barrier coating material) The molar number of the compound) is preferably 10.0 or less, more preferably 5.0 or less, still more preferably 2.0 or less, still more preferably 1.5 or less.

In addition, from the viewpoint of suppressing shrinkage during application as a gas barrier coating material, the mixture before curing preferably further contains a surfactant. When the total solid content of the mixture is 100% by mass, the added amount of the surfactant is preferably 0.01% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass.

Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like. From the viewpoint of obtaining good coating properties, nonionic surfactants are preferred. As the surfactant, polyoxyalkylene alkyl ethers are more preferred, and polyoxyethylene alkyl ethers are more preferred.

Examples of nonionic surfactants include polyoxyalkylene alkyl aryl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, sorbitan fatty acid esters, Silicone surfactants, acetylenol surfactants, fluorine-containing surfactants, etc.

Examples of the polyoxyalkylene alkylaryl ethers include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene dodecylphenyl ether. wait. Examples of the polyoxyalkylene alkyl ethers include polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether. Examples of the polyoxyalkylene fatty acid esters include polyoxyethylene oleate, polyoxyethylene laurate, polyoxyethylene distearate, and the like. Examples of sorbitan fatty acid esters include sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, poly Oxyethylene monooleate, polyoxyethyl stearate, etc. Examples of silicone surfactants include dimethylpolysiloxane and the like. Examples of the acetylenic alcohol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 3,6-dimethyl-4-octyne-3. 6-diol, 3,5-dimethyl-1-hexyn-3-ol, etc. Examples of fluorine-containing surfactants include fluoroalkyl esters and the like.

The mixture before hardening may also contain additives other than the above-mentioned components. For example, various additives such as lubricants, slip agents, anti-adhesive agents, antistatic agents, anti-fogging agents, pigments, dyes, and inorganic or organic fillers can be added.

In addition, from the viewpoint of improving the coating properties when applying as a gas barrier coating material, the solid content concentration of the mixture before curing is preferably 0.5 mass % to 15 mass %, and more preferably 1 Mass%～10 mass%.

(Method for manufacturing gas barrier layer) Specifically, the gas barrier layer 103 can be produced by applying a pre-cured mixture (gas barrier coating material) and curing the mixture. The mixture can be obtained as follows. First, the carboxyl group of the polycarboxylic acid is completely or partially neutralized by appropriately adding a volatile base to the polycarboxylic acid. Furthermore, a polyvalent metal salt compound and a suitable ammonium carbonate salt are mixed to form a mixture of all or part of the carboxyl groups of the polycarboxylic acid neutralized with the volatile base and the carboxyl groups of the polycarboxylic acid not neutralized with the volatile base. Metal salts. Then, a polyamine compound is further added, and finally a phosphorus compound or a salt thereof is added, thereby obtaining a mixture before hardening. Thereby, a salt is formed between the phosphorus compound and the polyvalent metal compound or the amine group of the polyamine. By mixing a polycarboxylic acid, a polyvalent metal salt compound, a phosphorus compound or a salt thereof, a suitable carbonic acid ammonium salt, and a polyamine compound in this order, the formation of aggregates can be suppressed and a more uniform mixture can be obtained. Thereby, the dehydration condensation reaction of the -COO- group contained in the polycarboxylic acid and the amine group contained in the polyamine compound can be promoted more effectively.

More details are as follows. Hereinafter, the case where a volatile base and a carbonic acid ammonium salt are mixed into a mixture will be demonstrated as an example. First, a completely or partially neutralized solution of the carboxyl groups constituting the polycarboxylic acid is prepared. A volatile base is added to the polycarboxylic acid to completely or partially neutralize the carboxyl groups of the polycarboxylic acid. By neutralizing the carboxyl group of the polycarboxylic acid, it is possible to effectively prevent the carboxyl group constituting the polycarboxylic acid from reacting with the amine group constituting the polyvalent metal compound or polyamine compound when a polyvalent metal compound or polyamine compound is added. of gelation, resulting in a more homogeneous mixture. Next, a polyvalent metal salt compound and a carbonic acid ammonium salt are added and dissolved, and the generated polyvalent metal ions are used to form a polyvalent metal salt with the -COO- group constituting the polycarboxylic acid. In this case, the -COO- group that forms a salt with the polyvalent metal ion refers to both the carboxyl group that is not neutralized with the base and the -COO- group that is neutralized with the base. In the case of a -COO- group neutralized with a base, the multivalent metal ions derived from the multivalent metal compound are exchanged and coordinated to form a multivalent metal salt of the -COO- group. Then, after the polyvalent metal salt is formed, a polyamine compound and a phosphorus compound or a salt thereof are further added to obtain a mixture. At this time, the multivalent metal salt coordinated to the -COO- group is also coordinated to the -PO ^- group in the phosphorus compound, forming a -COO- multivalent metal-OP- structure. In addition, an ionic bond is formed between the -NH ₂ group in the polyamine and the -PO ^- group in the phosphorus compound.

The mixture produced in the above manner is applied as a gas barrier coating material on the inorganic layer 102 or the interlayer formed on the inorganic layer 102 and the gas barrier layer 103, and is dried and hardened to form a gas. Barrier layer 103. At this time, the polyvalent metal constituting the polyvalent metal salt of the -COO- group of the polycarboxylic acid forms a metal cross-link, and the amine group constituting the polyamine forms an amide cross-link, forming a -PO ^- group in the phosphorus compound and The gas barrier layer 103 having excellent gas barrier properties can be obtained by ionic cross-linking of amine groups in polyvalent metals or polyamines. A more detailed manufacturing method of the gas barrier layer 103 will be described later.

From the viewpoint of improving barrier properties, the thickness of the dried and hardened gas barrier layer 103 is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more. In addition, from the viewpoint of thinning the entire gas barrier laminate, the thickness of the gas barrier layer 103 after drying and curing is preferably 15 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less.

(Substrate layer) The base material layer 101 may be a single layer or two or more layers. The shape of the base material layer 101 is not limited, and examples include a sheet or film shape, a tray, a cup, a hollow body, and the like.

The material of the base layer 101 can be used without any limitation as long as it can stably form the inorganic layer 102 on the base layer 101 and apply a solution of the gas barrier coating material on top of the inorganic layer 102 . Examples of materials for the base layer 101 include resins such as thermosetting resins and thermoplastic resins, and organic materials such as paper; glass, pottery, ceramics, silicon oxide, silicon oxynitride, silicon nitride, cement, aluminum, and alumina. , iron, copper, stainless steel and other metals and other inorganic materials; a multi-layer structure base material layer including a combination of organic materials or a combination of organic materials and inorganic materials, etc. Among these, for example, in the case of various film applications such as packaging materials and panels, it is preferable to use at least one organic material such as a plastic film or paper selected from the group consisting of a thermosetting resin and a thermoplastic resin.

As the thermosetting resin, a known thermosetting resin can be used. Examples include epoxy resin, unsaturated polyester resin, phenol resin, urea-melamine resin, polyurethane resin, silicone resin, polyimide, and the like.

As the thermoplastic resin, a known thermoplastic resin can be used. Examples include polyolefins (polyethylene, polypropylene, poly(4-methyl-1-pentene), poly(1-butene), etc.), polyesters (polyethylene terephthalate, poly(p-p) Butylene phthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, polyethylene glycol m-phenylenediamine, etc.), polyvinyl chloride, polyimide, Ethylene-vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, fluororesin, or a mixture thereof, etc.

Among these, from the viewpoint of improving transparency, it is preferable to be selected from the group consisting of polypropylene, polyethylene terephthalate (PET), polyethylene naphthalate, polyamide, and polyimide. One or more resins in the group consisting of polybutylene terephthalate. In addition, from the viewpoint of excellent pinhole resistance, crack resistance, heat resistance, etc., it is preferably selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. One or more resins in a group. From the same point of view, the base material layer 101 preferably contains one or more types selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. The resin layer is preferably a layer of one or more than two of these resins.

In addition, when the base material layer 101 uses a hygroscopic material such as polyamide, in the gas barrier laminate, the base material layer 101 absorbs moisture and swells, and the gas barrier performance under high humidity or after retort treatment The gas barrier performance and the gas barrier performance when filling acidic contents are easily reduced. However, in the fourth embodiment, even when a hygroscopic material is used as the base material layer 101, it is better to Suppresses the gas barrier performance of the gas barrier laminate under high humidity or the decrease in gas barrier performance after retort treatment.

In addition, the base material layer 101 may be formed by stretching a film made of a thermosetting resin or a thermoplastic resin in at least one direction, preferably in a biaxial direction. From the viewpoint of excellent transparency, rigidity, and heat resistance, the base material layer 101 is preferably made of polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, or polyamide. A biaxially stretched film formed of one or more thermoplastic resins from the group consisting of imine and polybutylene terephthalate, preferably a biaxially stretched film selected from the group consisting of polyamide, polyethylene terephthalate A biaxially stretched film formed of one or more thermoplastic resins from the group consisting of diester and polybutylene terephthalate.

In addition, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, acrylic resin, urethane resin, etc. may also be coated on the surface of the base material layer 101 . Furthermore, the base material layer 101 may be surface-treated in order to improve the adhesion with the gas barrier layer 103 . Specifically, surface activation treatment such as corona treatment, flame treatment, plasma treatment, and primer coating treatment may be performed on the surface facing the gas barrier layer 103 of the base layer 101 .

From the viewpoint of obtaining good film characteristics, the thickness of the base material layer 101 is preferably 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and further preferably 1000 μm or less, more preferably 1000 μm or less, more preferably 500 μm or less, more preferably 300 μm or less.

(Inorganic layer) Examples of the inorganic substances constituting the inorganic substance layer 102 include metals, metal oxides, metal nitrides, metal fluorides, and metal oxynitrides that can form a barrier thin film. Examples of the inorganic substance constituting the inorganic substance layer 102 include elements selected from Group 2A of the Periodic Table such as beryllium, magnesium, calcium, strontium, and barium; transition elements of the Periodic Table such as titanium, zirconium, ruthenium, hafnium, and tantalum; Group 2B of the Periodic Table such as zinc; Elements; aluminum, gallium, indium, thallium and other periodic table group 3A elements; periodic table group 4A elements such as silicon, germanium and tin; periodic table group 6A elements such as selenium, tellurium and other elements, oxides, nitrides, fluorides, etc. or one or more of nitrogen oxides, etc. Furthermore, in the fourth embodiment, the group name of the periodic table of the inorganic layer 102 is represented by the old CAS formula.

Furthermore, among the inorganic substances, in terms of excellent balance between barrier properties, cost, etc., one or two or more inorganic substances selected from the group consisting of silica, alumina, and aluminum are preferred, and more preferred are aluminum oxide. Furthermore, the silicon oxide may also contain silicon monoxide and silicon suboxide in addition to silicon dioxide.

The inorganic substance layer 102 is formed of the above-mentioned inorganic substance. In terms of excellent balance between barrier properties, cost, etc., the inorganic layer 102 preferably includes an aluminum oxide layer containing aluminum oxide. The inorganic layer 102 may include a single inorganic layer or multiple inorganic layers. In addition, when the inorganic layer 102 includes a plurality of inorganic layers, it may include the same type of inorganic layer or may include different types of inorganic layers.

From the viewpoint of a balance between improved barrier properties and improved operability, the thickness of the inorganic layer 102 is usually 1 nm or more, preferably 4 nm or more, and is usually 1000 nm or less, preferably 500 nm or less. Here, the thickness of the inorganic layer 102 can be determined from an observation image obtained by a transmission electron microscope or a scanning electron microscope, for example.

The method of forming the inorganic layer 102 is not limited, and may be, for example, vacuum evaporation, ion plating, sputtering, chemical vapor deposition, physical vapor deposition, or chemical vapor deposition (CVD). , plasma CVD method, sol-gel method, etc. to form the inorganic layer 102 on one or both sides of the base material layer 101 . Among them, sputtering, ion plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma CVD, or film formation under reduced pressure are ideal. Therefore, it is expected that chemically active molecular species containing silicon, such as silicon nitride or silicon oxynitride, react rapidly to improve the smoothness of the surface of the inorganic layer 102 and reduce the number of holes. In order to rapidly carry out these binding reactions, it is ideal that the inorganic atom or compound is a chemically active molecular species or atomic species. In addition, from the viewpoint of improving the balance between the barrier properties and productivity of the gas barrier laminate, the inorganic layer 102 is preferably a vapor-deposited film.

From the viewpoint of improving the balance between the barrier properties and productivity of the gas barrier laminate, the inorganic layer 102 is provided on the base material layer 101 or when an intermediary layer is provided between the base material layer 101 and the inorganic layer 102 The evaporated film on the interposer layer includes one or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum.

(base coat) A primer layer 104 can also be provided between the base material layer 101 and the inorganic layer 102 (Fig. 14). By providing the primer layer 104, the adhesion between these layers can be further improved. In addition, the barrier properties after cooking can be further improved. sex.

From the viewpoint of improving the adhesion between the base layer 101 and the inorganic layer 102, examples of the material of the undercoat layer 104 include polyurethane resin, polyester resin, oxazoline resin, (methane resin), etc. One or more of the group consisting of acrylic resins.

Examples of the polyurethane resin include various polyurethane resins, polyurethane polyurea resins, and prepolymers thereof. Specific examples of such urethane resins include toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, and isophorone diisocyanate. Diisocyanate components such as isocyanate and dicyclohexyl diisocyanate are combined with ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, bisphenol, and polyester Reactants of diol components such as diols, polyether diols, polycarbonate diols, and polyethylene glycols; urethane prepolymers with isocyanate groups at the end and amine compounds, amine sulfonates, Reactants of polyhydroxycarboxylic acid, hydrogen sulfite, etc.

In addition, from the viewpoint of further improving the barrier properties after the retort treatment and the adhesion between the base layer 101 and the inorganic layer 102 , it is also preferable that the undercoat layer 104 contains a polyurethane resin. Polyurethane resin with an aromatic ring structure in the main chain. A polyurethane resin having an aromatic ring structure in the main chain can be obtained as a water-dispersed polyurethane resin by reacting a polyol with an organic polyisocyanate and a chain extender, for example. Thereby, an aromatic ring structure can be introduced into the main chain of the polyurethane resin. As the polyurethane resin having an aromatic ring structure in the main chain, more specifically, those described in Japanese Patent Application Laid-Open No. 2018-171827 can be used.

In addition, from the viewpoint of improving heat resistance, water resistance, hydrolysis resistance, etc., a crosslinking agent may be used in combination with the water-dispersed polyurethane resin. The crosslinking agent may be an external crosslinking agent added as a third component to the water-dispersed polyurethane resin, or may be introduced in advance into the molecular structure of the water-dispersed polyurethane resin. Internal cross-linking agent at the reaction site of the cross-linking structure.

As the cross-linking agent, compounds having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silyl alcohol group, etc. are preferably used, and more preferably, a compound having a carbodiimide group is used. compound of. In addition, when using a compound having a carbodiimide group as a cross-linking agent, the amount of the compound having a carbodiimide group is added relative to 1.0 mol of the carboxyl group in the polyurethane resin. The carbodiimide group is preferably in an amount of 0.1 mol to 3.0 mol, more preferably 0.2 mol to 2.0 mol, and still more preferably 0.3 mol to 1.0 mol.

Examples of the polyester resin used in the undercoat layer 104 include various polyester resins and modified products thereof. Specific examples of such polyester resins include terephthalic acid, phthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, 2-sulfoisophthalic acid, and 5-sulfoisophthalic acid. Polyisophthalic acid, adipic acid, sebacic acid, succinic acid, dodecanedioic acid and other polycarboxylic acid components are combined with ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, The reactants of diol components such as neopentyl glycol, cyclohexanedimethanol, and bisphenol also include modified products based on acrylic resin, epoxy resin, etc.

When the base coat 104 uses an oxazoline resin, the base coat 104 preferably includes an oxazoline-based resin composition, and the oxazoline-based resin composition includes an oxazoline group-containing aqueous polymer, Water-based (meth)acrylic resin and water-based polyester resin. The oxazoline-based resin composition includes, for example, an oxazoline group-containing aqueous polymer with an oxazoline group content of 6.0 mmol/g to 9.0 mmol/g, and an aqueous polymer with a carboxyl group content of 0.5 mmol/g to 3.5 mmol/g. Meth)acrylic resin and water-based polyester resin with carboxyl content between 0.5 mmol/g and 2.0 mmol/g. In addition, regarding the oxazoline-based resin composition, the total amount of the oxazoline group-containing aqueous polymer, the aqueous (meth)acrylic resin, and the aqueous polyester resin is 100% by mass. For example, the oxazoline-based resin composition contains 10% by mass to 55% by mass. Mass % of the oxazoline group-containing water-based polymer, 10 mass % to 80 mass % of the water-based (meth)acrylic resin, and 10 mass % to 80 mass % of the water-based polyester resin. In addition, in the oxazoline-based resin composition, for example, the ratio of the molar number of the oxazoline group to the molar number of the carboxyl group [from the molar number of the oxazoline group (x mmol) and the molar number of the carboxyl group The ratio (x/y) × 100 [mol%] of (y mmol) is 150 mol% ~ 420 mol%. As the oxazoline resin used in the undercoat layer 104, more specifically, those described in International Publication No. 2016/186074 can be used.

From the viewpoint of obtaining good adhesion, the thickness of the primer layer 104 is preferably 0.001 μm or more, more preferably 0.005 μm or more, still more preferably 0.01 μm or more, still more preferably 0.05 μm or more, and still more preferably 0.05 μm or more. 0.1 μm or more, more preferably 0.2 μm or more. In addition, from the viewpoint of economy, the thickness of the undercoat layer 104 is preferably 1.0 μm or less, more preferably 0.6 μm or less, further preferably 0.5 μm or less, and may be, for example, 0.1 μm or less, or may be, for example, Below 0.05 μm.

(adhesive layer) The gas barrier laminated body may further be provided with an adhesive layer. Furthermore, the primer layer 104 is removed from the adhesive layer. The adhesive layer is, for example, provided between the gas barrier layer 103 and the upper layer of the gas barrier layer 103 . In addition, when the upper layer is formed of a plurality of layers, an adhesive layer may be provided between the plurality of layers. Here, the upper layer of the gas barrier layer 103 refers to a layer laminated on the surface of the gas barrier layer 103 opposite to the surface facing the inorganic layer 102 . The adhesive layer only needs to contain a known adhesive. Examples of adhesives include organic titanium resin, polyethyleneimine resin, urethane resin, epoxy resin, acrylic resin, polyester resin, oxazoline group-containing resin, modified silicone resin, and titanium resin. Laminated adhesives composed of alkyl acid esters, polyester polybutadiene, etc., or one-liquid or two-liquid polyols and polyisocyanates, water-based urethanes, ionic polymers, etc. Alternatively, a water-based adhesive whose main raw material is acrylic resin, vinyl acetate resin, urethane resin, polyester resin, etc. can also be used. In addition, other additives such as a hardener and a silane coupling agent may be added to the adhesive according to the use of the gas barrier laminate 100 . When the gas barrier laminate is used for hot water treatment such as steaming, dry lamination represented by a polyurethane adhesive is preferred from the viewpoint of heat resistance or water resistance. Use an adhesive, preferably a solvent-based two-liquid hardening type polyurethane adhesive.

(Method for manufacturing gas barrier laminate) In the fourth embodiment, the manufacturing method of the gas barrier laminate 100 includes, for example: the steps of preparing the base material layer 101; the step of forming the inorganic layer 102 on the base layer 101; and the step of forming the inorganic layer 102 on the base material. A step of forming a gas barrier layer 103 on top of layer 101 . In addition, the step of forming the undercoat layer 104 on the inorganic layer 102 may be further included after the step of forming the inorganic layer 102 and before the step of forming the gas barrier layer 103 .

The step of forming the inorganic layer 102 on the base material layer 101 may use, for example, the method for forming the inorganic layer 102 described above.

The step of forming the gas barrier layer 103 includes, for example, applying the uncured mixture as a gas barrier coating material to the inorganic layer 102 and then drying it to obtain a coating layer; and applying the coating layer to the gas barrier layer 103 . A step of heating to cause a dehydration condensation reaction between the carboxyl groups contained in the polycarboxylic acid and the amine groups contained in the polyamine compound, thereby forming the gas barrier layer 103 having a amide bond.

The method of applying the gas barrier coating material to the inorganic layer 102 is not limited, and a common method can be used. For example, gravure coaters using Meyer rod coaters, air knife coaters, direct gravure coaters, indirect gravure, arc gravure coaters, reverse gravure and spray nozzle methods, top feed reverse gravure coaters, etc. Reverse roll coaters such as reverse roll coaters, bottom feed reverse coaters and nozzle feed reverse coaters, five-roller coaters, die lip coaters, rod coaters, reverse The coating method is performed using a known coater such as a bar coater or a die coater.

From the viewpoint of improving the barrier performance of the gas barrier laminate obtained, the coating amount (wet thickness) is preferably 0.05 μm, more preferably 1 μm or more. In addition, from the viewpoint of suppressing curling of the obtained gas barrier laminate and more effectively promoting the dehydration condensation reaction of the -COO- group contained in the polycarboxylic acid and the amine group contained in the polyamine compound , the wet thickness is preferably 300 μm or less, more preferably 200 μm or less, further preferably 100 μm or less.

Drying and heat treatment can be carried out after drying or at the same time. The method of drying and heat treatment is not limited as long as the effects of the present invention can be obtained, as long as the gas barrier coating material can be hardened or the gas barrier coating material can be heat-cured. Examples include devices that utilize convection heat transfer such as ovens and dryers, devices that utilize conductive heat transfer such as heating rollers, devices that utilize radiation heat transfer using electromagnetic waves such as infrared, far-infrared, and near-infrared heaters, and devices that utilize internal heat transfer such as microwaves. Heating device. As an apparatus used for drying and heat treatment, from the viewpoint of manufacturing efficiency, an apparatus capable of performing both drying and heat treatment is preferred. Among them, specifically, it is preferable to use a hot air oven from the viewpoint of being usable in various applications such as drying, heating, and annealing. In addition, from the viewpoint of excellent heat conduction efficiency to the film, it is preferable to use heating. Roller. In addition, methods used for drying and heat treatment may be appropriately combined. Specifically, a hot air oven and a heating roller may be used together. For example, if the gas barrier coating material is dried in a hot air oven and then heated using a heating roller, the time of the heating treatment step will be shortened, and from the viewpoint of manufacturing efficiency Better. In addition, it is preferable to perform drying and heating processing only by a hot air oven.

Regarding the heat treatment conditions, for example, the heat treatment temperature is 80°C to 250°C and the heat treatment time is 1 second to 10 minutes. Preferably, the heat treatment temperature is 120°C to 240°C and the heat treatment time is 1 second to 1 minute. More preferably, the heat treatment temperature is 170°C to 230°C and the heat treatment time is 1 second to 30 seconds. Still more preferably, the heat treatment temperature is 200°C to 220°C and the heat treatment time is 1 second to 10 seconds. Furthermore, as mentioned above, by using a heating roller together, heat processing can be performed in a short time. Furthermore, from the viewpoint of effectively promoting the dehydration condensation reaction between the -COO- group contained in the polycarboxylic acid and the amine group contained in the polyamine compound, it is important that the heat treatment temperature and heat treatment time are adjusted according to the gas The wet thickness of the barrier coating is adjusted. An appropriate cross-linked structure is formed by selecting an appropriate heat treatment temperature and heat treatment time.

By drying and heat-treating the gas barrier coating material, the carboxyl group of the polycarboxylic acid reacts with the polyamine or polyvalent metal compound to form covalent bonds and ionic cross-linking, thereby forming a gas that has good properties even after retort treatment. Barrier gas barrier layer 103 .

In the fourth embodiment, the gas barrier laminate has excellent gas barrier properties and can be suitably used in medical applications, industrial applications, and daily life as represented by packaging materials and food packaging materials for contents requiring high gas barrier properties. Various packaging materials for groceries and other purposes.

In addition, the gas barrier laminate of the fourth embodiment can be suitably used as, for example, a vacuum insulation film requiring high barrier performance; a sealing film for sealing electroluminescent elements, solar cells, and the like.

Specific examples of the laminated structure including the gas barrier laminated body in the fourth embodiment are shown below. (Laminated structure example 1) Base material layer 101 (PET base material)/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyolefin layer (Laminated structure example 2) Base material layer 101 (PET base material)/undercoat layer 104/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyolefin layer (Laminated structure example 3) Base material layer 101 (PET base material)/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyamide layer/adhesive layer/polyolefin layer (Laminated structure example 4) Base material layer 101 (PET base material)/undercoat layer 104/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyamide layer/adhesive layer/ polyolefin layer Here, since the laminated structure includes a polyolefin layer containing polyolefins such as polyethylene, polypropylene, poly(4-methyl-1-pentene), and poly(1-butene), the gas barrier laminated body Medium can improve pinhole resistance, crack resistance, heat resistance, etc., and further suppress the decrease in gas barrier performance under high humidity or gas barrier performance after retort processing.

<Fifth Embodiment> FIG. 15 is a cross-sectional view schematically showing an example of the structure of the gas barrier laminate according to the fifth embodiment. The gas barrier laminate 100 shown in FIG. 15 includes: a base material layer 101; a gas barrier layer 103 provided on at least one surface of the base material layer 101; and an inorganic layer 102 provided between the base material layer 101 and the gas barrier layer. between layers 103. Furthermore, the gas barrier layer 103 includes a hardened product of a mixture including a polycarboxylic acid, a polyamine compound, and a polyvalent metal compound. The specific structure of each layer will be described later.

In the gas barrier laminated body 100, the base material layer 101, the inorganic layer 102, and the gas barrier layer 103 are laminated in this order, and the gas barrier layer 103 contains a cured product of the mixture. Therefore, the balance between barrier properties and productivity is excellent. More specifically, the gas barrier laminate 100 has excellent barrier properties such as oxygen barrier properties and water vapor barrier properties after retort treatment. In addition, in the gas barrier layered body 100, the gas barrier layer 103 contains a cured product of the mixture. Therefore, for example, even if the curing time, specifically the heat treatment time, when obtaining the gas barrier layer 103 is short, the barrier can be obtained. The gas barrier laminate 100 has excellent gas barrier properties.

FIG. 16 is a cross-sectional view schematically showing another structural example of the gas barrier laminate. The basic structure of the gas barrier laminate 110 shown in FIG. 16 is the same as the gas barrier laminate 100 described with reference to FIG. 15 , but further includes a primer layer 104 provided between the base material layer 101 and the inorganic layer 102 Different aspects. Also in the gas barrier laminated body 110, the same effect as that of the gas barrier laminated body 100 can be obtained. In addition, in the gas barrier laminate 110, by providing the primer layer 104 between the base material layer 101 and the inorganic material layer 102, the adhesion between the base material layer 101 and the inorganic material layer 102 can be further improved. Hereinafter, the structure of the layers included in the gas barrier laminate will be described in more detail. First, the gas barrier layer 103 will be described.

(gas barrier layer) The gas barrier layer 103 includes a hardened product of a mixture including a polycarboxylic acid, a polyamine compound, and a polyvalent metal compound. More specifically, the gas barrier layer 103 is a film (gas barrier film 10 ) including the cured product. More specifically, the gas barrier layer 103 can be formed by applying a pre-cured mixture, that is, a gas barrier coating material on a layer such as the inorganic layer 102 and other layers arranged directly below the gas barrier layer 103, and then drying and heat-treating it. It is obtained by hardening the gas barrier coating material.

In the infrared absorption spectrum of the gas barrier layer 103, let the maximum peak height of the absorbance in the range of 1300 cm ^-1 or more and 1490 cm ^-1 be α, and let α be the maximum peak height of the absorbance in the range of 1690 cm ^-1 or more and 1780 cm ^-1 When the maximum peak height of the absorbance in the range is γ, from the viewpoint of the liquid stability of the gas barrier coating material before coating, the ratio of free carboxyl groups to NH ₃ complex represented by γ/α is preferable It is 0.00 or more, more preferably, it is 0.01 or more, and still more preferably, it is 0.02 or more. In addition, from the viewpoint of improving the barrier properties of the gas barrier layer 103 obtained after coating, the γ/α is preferably 1.00 or less, more preferably 0.80 or less, even more preferably 0.60 or less, and still more preferably 0.60 or less. 0.40 or less, more preferably 0.20 or less, still more preferably 0.10 or less.

In addition, in the infrared absorption spectrum of the gas barrier layer 103, let the total peak area in the range of the absorption band 1493 cm ^-1 or more and 1780 cm ^-1 be A, and let the absorption band 1598 cm ^-1 or more and 1690 cm Let the total peak area in the range of ^-1 and below be B, let the total peak area in the range of the absorption band between 1690 cm ^-1 and 1780 cm ^-1 be C, and let the absorption band be 1493 cm ^-1 and above and 1598 cm ^-1 When the total peak area in the following range is assumed to be D, preferred examples of the area ratio are shown below. In the infrared absorption spectrum of the gas barrier layer 103, from the viewpoint of further improving the gas barrier performance after retort treatment, the area ratio of the amide bond represented by B/A is preferably 0.200 or more, more preferably 0.250 or more, more preferably 0.270 or more, still more preferably 0.290 or more, still more preferably 0.310 or more. In addition, from the viewpoint of further improving the balance between barrier properties and productivity, the area ratio of the amide bond represented by B/A is preferably 0.370 or less, more preferably 0.360 or less, and even more preferably 0.350 or less. .

In the infrared absorption spectrum of the gas barrier layer 103, from the viewpoint of further improving the gas barrier performance after retort treatment, the area ratio of carboxylic acid represented by C/A is preferably 0.150 or less, more preferably 0.100. or less, more preferably 0.080 or less, still more preferably 0.060 or less. In addition, the lower limit of the area ratio of the carboxylic acid represented by C/A is not limited, but may be, for example, 0.000 or more. Alternatively, it may be, for example, 0.0001 or more.

In the infrared absorption spectrum of the gas barrier layer 103, from the viewpoint of further improving the balance between barrier properties and productivity, the area ratio of the carboxylate represented by D/A is preferably 0.580 or more, more preferably 0.600 and above. In addition, from the viewpoint of further improving the gas barrier performance after retort treatment, the D/A is preferably 0.800 or less, more preferably 0.720 or less, still more preferably 0.700 or less, still more preferably 0.680 or less.

Furthermore, from the viewpoint of further improving the balance between productivity and barrier properties of the gas barrier laminate, it is also preferred that the area ratio of the amide bond represented by B/A is 0.200 or more and 0.370 or less, and C The area ratio of the carboxylic acid represented by /A is 0.150 or less, and the area ratio of the carboxylic acid salt represented by D/A is 0.580 or more and 0.800 or less.

In the infrared absorption spectrum of the gas barrier layer 103, from the viewpoint of improving the barrier properties, the area ratio of the carboxylate represented by D/A with respect to the area ratio of the amide bond represented by B/A The area ratio is preferably 1.2 or more, more preferably 1.6 or more, more preferably 1.8 or more. In addition, from the viewpoint of improving barrier properties after cooking, the area ratio of the carboxylate represented by D/A to the area ratio of the amide bond represented by B/A is preferably 4.0 or less. , more preferably 3.5 or less, still more preferably 3.0 or less, still more preferably 2.5 or less.

Here, in the gas barrier layer 103, the absorption of νC=O based on the unreacted carboxylic acid in the infrared absorption spectrum is visible near 1700 cm ^-1 , and the absorption based on νC=O based on the amide bond which is the cross-linked structure Absorption is visible around 1630 cm ^-1 ~ 1685 cm ^-1 , νC=O absorption based on carboxylate is visible around 1540 cm ^-1 ~ 1560 cm ^-1 , absorption based on δN-H of ammonia forming a complex Visible around 1300 cm ^-1 ~ 1490 cm ^-1 .

The maximum peak height α of the absorbance in the range of 1300 cm ^-1 to 1490 cm ^-1 in the infrared absorption spectrum is considered to be an index of the amount of ammonia that forms a complex, and is considered to be 1690 cm ^-1 to 1780 cm ^-1 The maximum peak height γ in the following range represents an index of the amount of free, that is, unreacted, carboxylic acid present.

In the fifth embodiment, the maximum peak heights α and γ can be specifically measured according to the following procedure. That is, a measurement sample of 1 cm×3 cm was cut out from the gas barrier layer 103 . Then, the infrared absorption spectrum of the surface of the gas barrier layer 103 is obtained by infrared total reflection measurement (ATR method). In the obtained infrared absorption spectrum, a straight line connecting the absorbance of 900 cm ^-1 and the absorbance of 1900 cm ^-1 was used as a baseline, and the maximum peak height of each absorbance range was calculated.

In addition, the total peak area A in the range of the absorption band from 1493 cm ^-1 to 1780 cm ^-1 in the infrared absorption spectrum is considered to be an index of the total amount of carboxylic acid, amide bond and carboxylate, and the absorption band is 1598 cm The total peak area B in the range from ^-1 to 1690 cm ^-1 is an indicator of the amount of amide bonds present. Furthermore, it is considered that the total peak area C in the range of the absorption band from 1690 cm ^-1 to 1780 cm ^-1 represents an indicator of the amount of unreacted carboxylic acid, and the absorption band from 1493 cm ^-1 to 1598 cm ^-1 is considered to be an indicator of the amount of unreacted carboxylic acid present. The total peak area D of the range represents an indicator of the amount of carboxylate present.

In the fifth embodiment, the total peak area A to total peak area D can be specifically measured according to the following procedure. First, a measurement sample of 1 cm×3 cm was cut out from the gas barrier layer 103 . Then, the infrared absorption spectrum of the surface of the gas barrier layer 103 is obtained by infrared total reflection measurement (ATR method). Based on the obtained infrared absorption spectrum, the total peak areas A to D are calculated according to the following procedures (1) to (4). (1) Connect the absorbance at 1780 cm ^-1 and 1493 cm ^-1 with a straight line (N), and take the area surrounded by the absorption spectrum in the range of the absorption band 1493 cm ^-1 and above and below 1780 cm ^-1 and N as the total peak area. A. (2) Draw a straight line (O) vertically from the absorbance (Q) of 1690 cm ^-1 , let the intersection point of N and O be P, draw a straight line (S) vertically from the absorbance (R) of 1598 cm ^-1 , Let the intersection point of N and S be T, and compare the absorption spectrum in the range of the absorption band from 1598 cm ^-1 to 1690 cm ^-1 with straight line S, point T, straight line N, point P, straight line O, absorbance Q, absorbance The area surrounded by R is taken as the total peak area B. (3) The area surrounded by the absorption spectrum and absorbance Q, straight line O, point P, and straight line N in the range of the absorption band from 1690 cm ^-1 to 1780 cm ^-1 is the total peak area C. (4) The area surrounded by the absorption spectrum and the absorbance R, the straight line S, the point T, and the straight line N in the range of the absorption band from 1493 cm ^-1 to 1598 cm ^-1 is the total peak area D. Next, the area ratio B/A, the area ratio C/A, and the area ratio D/A are determined based on the areas determined by the above method.

Furthermore, in the fifth embodiment, the infrared absorption spectrum (infrared total reflection measurement: ATR method) can be measured using, for example, an IRT-5200 device manufactured by JASCO Corporation, equipped with a PKM-GE-S (Germanium) crystal. , carried out under the conditions of incident angle 45 degrees, room temperature, decomposition energy 4 cm ^-1 and cumulative number of 100 times.

The maximum peak heights α and γ of the gas barrier layer 103, the area ratio of the amide bond represented by B/A, the area ratio of the carboxylic acid represented by C/A, and the carboxylic acid represented by D/A The area ratio of the salt can be controlled by appropriately adjusting the manufacturing conditions of the gas barrier layer 103 . Specifically, the mixing ratio of the polycarboxylic acid, the polyamine compound, and the polyvalent metal compound, the preparation method of the mixture before hardening, the method of heating the mixture, temperature, time, etc. can be used as the parameters for controlling the gas barrier layer 103 Factors for the maximum peak heights α and γ, the area ratio of the amide bond represented by B/A, the area ratio of the carboxylic acid represented by C/A, and the area ratio of the carboxylate salt represented by D/A And enumerate.

Next, the components contained in the mixture before hardening (gas barrier coating material) will be described. (polycarboxylic acid) Polycarboxylic acids have two or more carboxyl groups in the molecule. Specific examples include homopolymerization of α,β-unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, fumaric acid, crotonic acid, cinnamic acid, 3-hexenoic acid, and 3-hexenedioic acid. substances or copolymers of these. In addition, copolymers of the α,β-unsaturated carboxylic acid and esters such as ethyl ester, olefins such as ethylene, etc. may also be used.

Among these, homopolymers or copolymers of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, and cinnamic acid are preferred, and more preferred are selected from the group consisting of polyacrylic acid, polymethacrylic acid, and One or more polymers from the group consisting of copolymers of acrylic acid and methacrylic acid, more preferably at least one polymer selected from polyacrylic acid and polymethacrylic acid, more preferably selected from acrylic acid At least one polymer selected from the group consisting of a homopolymer of and a homopolymer of methacrylic acid.

Here, in the fifth embodiment, polyacrylic acid includes both homopolymers of acrylic acid and copolymers of acrylic acid and other monomers. In the case of a copolymer of acrylic acid and other monomers, the polyacrylic acid contains usually 90 mass% or more, preferably 95 mass% or more, and more preferably 99 mass% or more derived from acrylic acid in 100 mass% of the polymer. structural unit. In addition, in the fifth embodiment, polymethacrylic acid includes both homopolymers of methacrylic acid and copolymers of methacrylic acid and other monomers. In the case of a copolymer of methacrylic acid and other monomers, polymethacrylic acid contains usually 90 mass% or more, preferably 95 mass% or more, and more preferably 99 mass% or more in 100 mass% of the polymer. Structural unit derived from methacrylic acid.

Polycarboxylic acids are polymers made from carboxylic acid monomers. From the viewpoint of excellent balance between gas barrier properties and workability, the molecular weight of the polycarboxylic acid is preferably 500 to 2,500,000, more preferably 5,000 to 2,000,000, more preferably 10,000 to 1,500,000, and still more preferably 100,000 to 1,200,000. Here, in the fifth embodiment, the molecular weight of the polycarboxylic acid is a weight average molecular weight in terms of polyethylene oxide, and can be measured using gel permeation chromatography (GPC).

At least a portion of the polycarboxylic acid can also be neutralized by a volatile base. By neutralizing the polycarboxylic acid with a volatile base, gelation can be suppressed when the polyvalent metal compound or polyamine compound is mixed with the polycarboxylic acid. Therefore, among polycarboxylic acids, from the viewpoint of preventing gelation, it is preferable to use a volatile base to form a partially neutralized product or a completely neutralized product of the carboxyl group. The neutralized product can be obtained by partially or completely neutralizing the carboxyl group of the polycarboxylic acid using a volatile base, that is, partially or completely converting the carboxyl group of the polycarboxylic acid into a carboxylic acid salt. This can prevent gelation when adding a polyamine compound or a polyvalent metal compound. The partially neutralized product can be prepared by adding a volatile base to the aqueous solution of the polycarboxylic acid polymer, and the desired degree of neutralization can be obtained by adjusting the ratio of the polycarboxylic acid to the volatile base. In the fifth embodiment, from the viewpoint of fully suppressing gelation caused by the neutralization reaction with the amine group of the polyamine compound, the degree of neutralization of the polycarboxylic acid by the volatile base is preferably 70 equivalent% ~300 equivalent%, more preferably 90 equivalent% ~ 250 equivalent%, further preferably 100 equivalent% ~ 200 equivalent%.

As the volatile base, any water-soluble base can be used. Examples of the volatile base include tertiary amines such as ammonia, morpholine, alkylamine, 2-dimethylaminoethanol, N-methylmorpholine, ethylenediamine, and triethylamine, or aqueous solutions of these; or a mixture of these. From the viewpoint of obtaining good gas barrier properties, an ammonia aqueous solution is preferred.

(polyamine compound) The mixture before hardening contains polyamine compounds. By including a polyamine compound, the barrier properties of the obtained gas barrier material can be improved. The polyamine compound is a compound having two or more amine groups in the main chain, side chain or terminal, and is preferably a polymer. Specific examples include: aliphatic polyamines such as polyallylamine, polyvinylamine, polyethyleneimine, and poly(trimethyleneimine); such as polylysine and polyarginine, which have polyamines in their side chains. Amino-based polyamides, etc. In addition, a polyamine in which part of the amine group has been modified may also be used. From the viewpoint of obtaining good gas barrier properties, the polyamine compound preferably contains polyethyleneimine, more preferably polyethyleneimine.

From the viewpoint of excellent balance between gas barrier properties and workability, the number average molecular weight of the polyamine compound is preferably 50 to 2,000,000, more preferably 100 to 1,000,000, further preferably 1,500 to 500,000, still more preferably 1,500 to 100,000 , more preferably 1,500 to 50,000, still more preferably 3,500 to 20,000, still more preferably 5,000 to 15,000, still more preferably 7,000 to 12,000. Here, in the fifth embodiment, the molecular weight of the polyamine compound can be measured using the boiling point elevation method or the viscosity method.

From the viewpoint of further improving the gas barrier performance after retort treatment, (the mole number of amine groups contained in the polyamine compound in the mixture) / (the number of -COO- groups contained in the polycarboxylic acid in the mixture The molar number) is preferably 0.20 or more, more preferably 0.25 or more, still more preferably 0.30 or more, still more preferably 0.35 or more, and still more preferably 0.40 or more. From the same viewpoint, (the mole number of amine groups contained in the polyamine compound in the mixture)/(the mole number of -COO- groups contained in the polycarboxylic acid in the mixture) is preferably 0.90 or less, more preferably 0.85 or less, still more preferably 0.80 or less, still more preferably 0.75 or less, still more preferably 0.70 or less. The details of this reason are not yet clear, but it is thought that the amide crosslinking by the amine group constituting the polyamine compound and the metal crosslinking by the polyvalent metal constituting the salt of the polycarboxylic acid and the polyvalent metal are balanced. By forming a dense structure, the gas barrier layer 103 and the gas barrier laminate having the gas barrier layer 103 having excellent gas barrier properties after the retort treatment can be obtained.

(polyvalent metal compound) Specifically, polyvalent metal compounds are metals and metal compounds belonging to Groups 2 to 13 of the periodic table. More specifically, they include magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). ), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al) and other divalent or higher metals, oxides, hydroxides, and halides of these metals substances, carbonates, phosphates, phosphites, hypophosphites, sulfates or sulfites, etc. From the viewpoint of water resistance, impurities, etc., metal oxides or metal hydroxides are preferred.

From the viewpoint of further improving the gas barrier performance after retort treatment, the metal having a divalent or higher valence in the multivalent metal compound is preferably one or two selected from the group consisting of Zn, Ca, Mg, Ba and Al. More than one metal, preferably Zn. From the same viewpoint, the polyvalent metal compound is preferably a compound of one or more bivalent or higher metals selected from the group consisting of Zn, Ca, Mg, Ba and Al, and more preferably Zn compound of. From the same viewpoint, the polyvalent metal compound is preferably selected from oxides such as magnesium oxide, calcium oxide, barium oxide, zinc oxide, and magnesium hydroxide, and hydroxides such as calcium hydroxide, barium hydroxide, and zinc hydroxide. One or two or more compounds in the group are more preferably at least one of zinc oxide and zinc hydroxide, and even more preferably zinc oxide.

In the fifth embodiment, from the viewpoint of further improving the gas barrier performance after retort treatment, (mol number of the polyvalent metal compound in the mixture)/(-COO contained in the polycarboxylic acid in the mixture) The molar number of - base) is preferably 0.10 or more, more preferably 0.13 or more, still more preferably 0.15 or more, still more preferably 0.18 or more, still more preferably 0.20 or more, still more preferably 0.25 or more, still more preferably 0.28 or above. From the same viewpoint, (the mole number of the polyvalent metal compound in the mixture)/(the mole number of the -COO- group contained in the polycarboxylic acid in the mixture) is preferably 0.80 or less, more preferably 0.70 or less, more preferably 0.60 or less, still more preferably 0.55 or less, still more preferably 0.50 or less.

In the fifth embodiment, from the viewpoint of further improving the gas barrier performance after the retort treatment, (the molar number of the polyvalent metal compound in the mixture)/(the number of moles derived from the amine group of the polyamine compound in the mixture Mohr number) is preferably 0.25 or more, more preferably 0.35 or more, and still more preferably 0.40 or more. From the same viewpoint, (the molar number of the polyvalent metal compound in the mixture)/(the molar number of the amine group derived from the polyamine compound in the mixture) is preferably 0.75 or less, more preferably 0.65 or less, More preferably, it is 0.60 or less, and still more preferably, it is 0.55 or less.

The mixture before hardening may contain components other than the above-mentioned components. For example, the mixture preferably further contains carbonic acid ammonium salt. The carbonate-based ammonium salt is added in order to convert the polyvalent metal compound into the state of a polyvalent metal ammonium carbonate complex, improve the solubility of the polyvalent metal compound, and prepare a uniform solution containing the polyvalent metal compound. By including the ammonium carbonate salt in the mixture before hardening, the dissolved amount of the polyvalent metal compound can be increased. As a result, the mixture prepared with the polyvalent metal compound can be made more homogeneous. Examples of carbonic acid-based ammonium salts include ammonium carbonate and ammonium bicarbonate. Ammonium carbonate is preferred in that it is easily volatilized and is less likely to remain in the obtained gas barrier layer. From the viewpoint of further improving the solubility of the polyvalent metal compound, (the molar number of the carbonic acid ammonium salt in the mixture)/(the molar number of the polyvalent metal compound in the mixture) is preferably 0.05 or more, more preferably Preferably it is 0.10 or more, more preferably 0.25 or more, still more preferably 0.50 or more, still more preferably 0.75 or more. In addition, from the viewpoint of further improving the coating properties of the gas barrier coating material, (moles of the carbonate ammonium salt in the gas barrier coating material)/(polyvalent metal in the gas barrier coating material) The molar number of the compound) is preferably 10.0 or less, more preferably 5.0 or less, still more preferably 2.0 or less, still more preferably 1.5 or less.

In addition, from the viewpoint of suppressing shrinkage during application as a gas barrier coating material, the mixture before curing preferably further contains a surfactant. When the total solid content of the mixture is 100% by mass, the added amount of the surfactant is preferably 0.01% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass.

Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like. From the viewpoint of obtaining good coating properties, nonionic surfactants are preferred. As the surfactant, polyoxyalkylene alkyl ethers are more preferred, and polyoxyethylene alkyl ethers are more preferred.

Examples of nonionic surfactants include polyoxyalkylene alkyl aryl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, sorbitan fatty acid esters, Silicone surfactants, acetylenol surfactants, fluorine-containing surfactants, etc.

Examples of the polyoxyalkylene alkylaryl ethers include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene dodecylphenyl ether. wait. Examples of the polyoxyalkylene alkyl ethers include polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether. Examples of the polyoxyalkylene fatty acid esters include polyoxyethylene oleate, polyoxyethylene laurate, polyoxyethylene distearate, and the like. Examples of sorbitan fatty acid esters include sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, poly Oxyethylene monooleate, polyoxyethyl stearate, etc. Examples of silicone surfactants include dimethylpolysiloxane and the like. Examples of the acetylenic alcohol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 3,6-dimethyl-4-octyne-3. 6-diol, 3,5-dimethyl-1-hexyn-3-ol, etc. Examples of fluorine-containing surfactants include fluoroalkyl esters and the like.

The mixture before hardening may also contain additives other than the above-mentioned components. For example, various additives such as lubricants, slip agents, anti-adhesive agents, antistatic agents, anti-fogging agents, pigments, dyes, and inorganic or organic fillers can be added.

In addition, from the viewpoint of improving the coating properties when applying as a gas barrier coating material, the solid content concentration of the mixture before curing is preferably 0.5 mass % to 15 mass %, and more preferably 1 Mass%～10 mass%.

(Method for manufacturing gas barrier layer) Specifically, the gas barrier layer 103 can be produced by applying a pre-cured mixture (gas barrier coating material) and curing the mixture. The mixture can be obtained as follows. First, the carboxyl group of the polycarboxylic acid is completely or partially neutralized by appropriately adding a volatile base to the polycarboxylic acid. Furthermore, a polyvalent metal salt compound and a suitable ammonium carbonate salt are mixed to form a mixture of all or part of the carboxyl groups of the polycarboxylic acid neutralized with the volatile base and the carboxyl groups of the polycarboxylic acid not neutralized with the volatile base. Metal salts. Then, a polyamine compound is further added, thereby obtaining a mixture before hardening. By mixing the polycarboxylic acid, the polyvalent metal salt compound, the appropriate carbonic acid ammonium salt, and the polyamine compound in this order, the formation of aggregates can be suppressed and a more uniform mixture can be obtained. Thereby, the dehydration condensation reaction of the -COO- group contained in the polycarboxylic acid and the amine group contained in the polyamine compound can be promoted more effectively.

More details are as follows. Hereinafter, the case where a volatile base and a carbonic acid ammonium salt are mixed into a mixture will be demonstrated as an example. First, a completely or partially neutralized solution of the carboxyl groups constituting the polycarboxylic acid is prepared. A volatile base is added to the polycarboxylic acid to completely or partially neutralize the carboxyl groups of the polycarboxylic acid. By neutralizing the carboxyl group of the polycarboxylic acid, it is possible to effectively prevent the carboxyl group constituting the polycarboxylic acid from reacting with the amine group constituting the polyvalent metal compound or polyamine compound when a polyvalent metal compound or polyamine compound is added. of gelation, resulting in a more homogeneous mixture. Next, a polyvalent metal salt compound and a carbonic acid ammonium salt are added and dissolved, and the generated polyvalent metal ions are used to form a polyvalent metal salt with the -COO- group constituting the polycarboxylic acid. In this case, the -COO- group that forms a salt with the polyvalent metal ion refers to both the carboxyl group that is not neutralized with the base and the -COO- group that is neutralized with the base. In the case of a -COO- group neutralized with a base, the multivalent metal ions derived from the multivalent metal compound are exchanged and coordinated to form a multivalent metal salt of the -COO- group. Then, after the polyvalent metal salt is formed, a polyamine compound is further added, whereby a mixture can be obtained.

The mixture produced in the above manner is applied as a gas barrier coating material on the inorganic layer 102 or the interlayer formed on the inorganic layer 102 and the gas barrier layer 103, and is dried and hardened to form a gas. Barrier layer 103. In this case, the polyvalent metal constituting the polyvalent metal salt of the -COO- group of the polycarboxylic acid forms metal crosslinks, and the amine group constituting the polyamine forms amide crosslinks, thereby obtaining a gas with excellent gas barrier properties. Barrier layer 103. A more detailed manufacturing method of the gas barrier layer 103 will be described later.

From the viewpoint of improving barrier properties, the thickness of the dried and hardened gas barrier layer 103 is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more. In addition, from the viewpoint of thinning the entire gas barrier laminate, the thickness of the gas barrier layer 103 after drying and curing is preferably 15 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less.

(Substrate layer) The base material layer 101 may be a single layer or two or more layers. The shape of the base material layer 101 is not limited, and examples include a sheet or film shape, a tray, a cup, a hollow body, and the like.

The material of the base layer 101 can be used without any limitation as long as it can stably form the inorganic layer 102 on the base layer 101 and apply a solution of the gas barrier coating material on top of the inorganic layer 102 . Examples of materials for the base layer 101 include resins such as thermosetting resins and thermoplastic resins, and organic materials such as paper; glass, pottery, ceramics, silicon oxide, silicon oxynitride, silicon nitride, cement, aluminum, and alumina. , iron, copper, stainless steel and other metals and other inorganic materials; a multi-layer structure base material layer including a combination of organic materials or a combination of organic materials and inorganic materials, etc. Among these, for example, in the case of various film applications such as packaging materials and panels, it is preferable to use at least one organic material such as a plastic film or paper selected from the group consisting of a thermosetting resin and a thermoplastic resin.

As the thermosetting resin, a known thermosetting resin can be used. Examples include epoxy resin, unsaturated polyester resin, phenol resin, urea-melamine resin, polyurethane resin, silicone resin, polyimide, and the like.

As the thermoplastic resin, a known thermoplastic resin can be used. Examples include polyolefins (polyethylene, polypropylene, poly(4-methyl-1-pentene), poly(1-butene), etc.), polyesters (polyethylene terephthalate, poly(p-p) Butylene phthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, polyethylene glycol m-phenylenediamine, etc.), polyvinyl chloride, polyimide, Ethylene-vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, fluororesin, or a mixture thereof, etc.

Among these, from the viewpoint of improving transparency, it is preferable to be selected from the group consisting of polypropylene, polyethylene terephthalate (PET), polyethylene naphthalate, polyamide, and polyimide. One or more resins in the group consisting of polybutylene terephthalate. In addition, from the viewpoint of excellent pinhole resistance, crack resistance, heat resistance, etc., it is preferably selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. One or more resins in a group. From the same point of view, the base material layer 101 preferably contains one or more types selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. The resin layer is preferably a layer of one or more than two of these resins.

In addition, when the base material layer 101 uses a hygroscopic material such as polyamide, in the gas barrier laminate, the base material layer 101 absorbs moisture and swells, and the gas barrier performance under high humidity or after retort treatment The gas barrier performance and the gas barrier performance when filling acidic contents are easily reduced. However, in the fifth embodiment, even when a hygroscopic material is used as the base material layer 101, it is better to Suppresses the gas barrier performance of the gas barrier laminate under high humidity or the decrease in gas barrier performance after retort treatment.

In addition, the base material layer 101 may be formed by stretching a film made of a thermosetting resin or a thermoplastic resin in at least one direction, preferably in a biaxial direction. From the viewpoint of excellent transparency, rigidity, and heat resistance, the base material layer 101 is preferably made of polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, or polyamide. A biaxially stretched film formed of one or more thermoplastic resins from the group consisting of imine and polybutylene terephthalate, preferably a biaxially stretched film selected from the group consisting of polyamide, polyethylene terephthalate A biaxially stretched film formed of one or more thermoplastic resins from the group consisting of diester and polybutylene terephthalate.

In addition, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, acrylic resin, urethane resin, etc. may also be coated on the surface of the base material layer 101 . Furthermore, the base material layer 101 may be surface-treated in order to improve the adhesion with the gas barrier layer 103 . Specifically, surface activation treatment such as corona treatment, flame treatment, plasma treatment, and primer coating treatment may be performed on the surface facing the gas barrier layer 103 of the base layer 101 .

From the viewpoint of obtaining good film characteristics, the thickness of the base material layer 101 is preferably 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and further preferably 1000 μm or less, more preferably 1000 μm or less, more preferably 500 μm or less, more preferably 300 μm or less.

(Inorganic layer) Examples of the inorganic substances constituting the inorganic substance layer 102 include metals, metal oxides, metal nitrides, metal fluorides, and metal oxynitrides that can form a barrier thin film. Examples of the inorganic substance constituting the inorganic substance layer 102 include elements selected from Group 2A of the Periodic Table such as beryllium, magnesium, calcium, strontium, and barium; transition elements of the Periodic Table such as titanium, zirconium, ruthenium, hafnium, and tantalum; Group 2B of the Periodic Table such as zinc; Elements; aluminum, gallium, indium, thallium and other periodic table group 3A elements; periodic table group 4A elements such as silicon, germanium and tin; periodic table group 6A elements such as selenium, tellurium and other elements, oxides, nitrides, fluorides, etc. or one or more of nitrogen oxides, etc. Furthermore, in the fifth embodiment, the group name of the periodic table of the inorganic layer 102 is represented by the old CAS formula.

Furthermore, among the inorganic substances, in terms of excellent balance between barrier properties, cost, etc., one or two or more inorganic substances selected from the group consisting of silica, alumina, and aluminum are preferred, and more preferred are aluminum oxide. Furthermore, the silicon oxide may also contain silicon monoxide and silicon suboxide in addition to silicon dioxide.

The inorganic substance layer 102 is formed of the above-mentioned inorganic substance. From the viewpoint of excellent balance between barrier properties, cost, etc., the inorganic layer 102 preferably includes an aluminum oxide layer containing aluminum oxide. The inorganic layer 102 may include a single inorganic layer or multiple inorganic layers. In addition, when the inorganic layer 102 includes a plurality of inorganic layers, it may include the same type of inorganic layer or may include different types of inorganic layers.

From the viewpoint of a balance between improved barrier properties and improved operability, the thickness of the inorganic layer 102 is usually 1 nm or more, preferably 4 nm or more, and is usually 1000 nm or less, preferably 500 nm or less. Here, the thickness of the inorganic layer 102 can be determined from an observation image obtained by a transmission electron microscope or a scanning electron microscope, for example.

The method of forming the inorganic layer 102 is not limited, and may be, for example, vacuum evaporation, ion plating, sputtering, chemical vapor deposition, physical vapor deposition, or chemical vapor deposition (CVD). , plasma CVD method, sol-gel method, etc. to form the inorganic layer 102 on one or both sides of the base material layer 101 . Among them, sputtering, ion plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma CVD, or film formation under reduced pressure are ideal. Therefore, it is expected that chemically active molecular species containing silicon, such as silicon nitride or silicon oxynitride, react rapidly to improve the smoothness of the surface of the inorganic layer 102 and reduce the number of holes. In order to rapidly carry out these binding reactions, it is ideal that the inorganic atom or compound is a chemically active molecular species or atomic species. In addition, from the viewpoint of improving the balance between the barrier properties and productivity of the gas barrier laminate, the inorganic layer 102 is preferably a vapor-deposited film.

From the viewpoint of improving the balance between the barrier properties and productivity of the gas barrier laminate, the inorganic layer 102 is provided on the base material layer 101 or when an intermediary layer is provided between the base material layer 101 and the inorganic layer 102 The evaporated film on the interposer layer includes one or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum.

(base coat) A primer layer 104 can also be provided between the base material layer 101 and the inorganic layer 102 (Fig. 16). By providing the primer layer 104, the adhesion between these layers can be further improved. In addition, the barrier properties after cooking can be further improved. sex.

From the viewpoint of improving the adhesion between the base layer 101 and the inorganic layer 102, examples of the material of the undercoat layer 104 include polyurethane resin, polyester resin, oxazoline resin, (methane resin), etc. One or more of the group consisting of acrylic resins.

Examples of the polyurethane resin include various polyurethane resins, polyurethane polyurea resins, and prepolymers thereof. Specific examples of such urethane resins include toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, and isophorone diisocyanate. Diisocyanate components such as isocyanate and dicyclohexyl diisocyanate are combined with ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, bisphenol, and polyester Reactants of diol components such as diols, polyether diols, polycarbonate diols, and polyethylene glycols; urethane prepolymers with isocyanate groups at the end and amine compounds, amine sulfonates, Reactants of polyhydroxycarboxylic acid, hydrogen sulfite, etc.

In addition, from the viewpoint of further improving the barrier properties after the retort treatment and the adhesion between the base layer 101 and the inorganic layer 102 , it is also preferable that the undercoat layer 104 contains a polyurethane resin. Polyurethane resin with an aromatic ring structure in the main chain. A polyurethane resin having an aromatic ring structure in the main chain can be obtained as a water-dispersed polyurethane resin by reacting a polyol with an organic polyisocyanate and a chain extender, for example. Thereby, an aromatic ring structure can be introduced into the main chain of the polyurethane resin. As the polyurethane resin having an aromatic ring structure in the main chain, more specifically, those described in Japanese Patent Application Laid-Open No. 2018-171827 can be used.

In addition, from the viewpoint of improving heat resistance, water resistance, hydrolysis resistance, etc., a crosslinking agent may be used in combination with the water-dispersed polyurethane resin. The crosslinking agent may be an external crosslinking agent added as a third component to the water-dispersed polyurethane resin, or may be introduced in advance into the molecular structure of the water-dispersed polyurethane resin. Internal cross-linking agent at the reaction site of the cross-linking structure.

As the cross-linking agent, compounds having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silyl alcohol group, etc. are preferably used, and more preferably, a compound having a carbodiimide group is used. compound of. In addition, when using a compound having a carbodiimide group as a cross-linking agent, the amount of the compound having a carbodiimide group is added relative to 1.0 mol of the carboxyl group in the polyurethane resin. The carbodiimide group is preferably in an amount of 0.1 mol to 3.0 mol, more preferably 0.2 mol to 2.0 mol, and still more preferably 0.3 mol to 1.0 mol.

Examples of the polyester resin used in the undercoat layer 104 include various polyester resins and modified products thereof. Specific examples of such polyester resins include terephthalic acid, phthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, 2-sulfoisophthalic acid, and 5-sulfoisophthalic acid. Polyisophthalic acid, adipic acid, sebacic acid, succinic acid, dodecanedioic acid and other polycarboxylic acid components are combined with ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, The reactants of diol components such as neopentyl glycol, cyclohexanedimethanol, and bisphenol also include modified products based on acrylic resin, epoxy resin, etc.

When the base coat 104 uses an oxazoline resin, the base coat 104 preferably includes an oxazoline-based resin composition, and the oxazoline-based resin composition includes an oxazoline group-containing aqueous polymer, Water-based (meth)acrylic resin and water-based polyester resin. The oxazoline-based resin composition includes, for example, an oxazoline group-containing aqueous polymer with an oxazoline group content of 6.0 mmol/g to 9.0 mmol/g, and an aqueous polymer with a carboxyl group content of 0.5 mmol/g to 3.5 mmol/g. Meth)acrylic resin and water-based polyester resin with carboxyl content between 0.5 mmol/g and 2.0 mmol/g. In addition, regarding the oxazoline-based resin composition, the total amount of the oxazoline group-containing aqueous polymer, the aqueous (meth)acrylic resin, and the aqueous polyester resin is 100% by mass. For example, the oxazoline-based resin composition contains 10% by mass to 55% by mass. Mass % of the oxazoline group-containing water-based polymer, 10 mass % to 80 mass % of the water-based (meth)acrylic resin, and 10 mass % to 80 mass % of the water-based polyester resin. In addition, in the oxazoline-based resin composition, for example, the ratio of the molar number of the oxazoline group to the molar number of the carboxyl group [from the molar number of the oxazoline group (x mmol) and the molar number of the carboxyl group The ratio (x/y) × 100 [mol%] of (y mmol) is 150 mol% ~ 420 mol%. As the oxazoline resin used in the undercoat layer 104, more specifically, those described in International Publication No. 2016/186074 can be used.

From the viewpoint of obtaining good adhesion, the thickness of the primer layer 104 is preferably 0.001 μm or more, more preferably 0.005 μm or more, still more preferably 0.01 μm or more, still more preferably 0.05 μm or more, and still more preferably 0.05 μm or more. 0.1 μm or more, more preferably 0.2 μm or more. In addition, from the viewpoint of economy, the thickness of the undercoat layer 104 is preferably 1.0 μm or less, more preferably 0.6 μm or less, further preferably 0.5 μm or less, and may be, for example, 0.1 μm or less, or may be, for example, Below 0.05 μm.

(adhesive layer) The gas barrier laminated body may further be provided with an adhesive layer. Furthermore, the primer layer 104 is removed from the adhesive layer. The adhesive layer is, for example, provided between the gas barrier layer 103 and the upper layer of the gas barrier layer 103 . In addition, when the upper layer is formed of a plurality of layers, an adhesive layer may be provided between the plurality of layers. Here, the upper layer of the gas barrier layer 103 refers to a layer laminated on the surface of the gas barrier layer 103 opposite to the surface facing the inorganic layer 102 . The adhesive layer only needs to contain a known adhesive. Examples of adhesives include organic titanium resin, polyethyleneimine resin, urethane resin, epoxy resin, acrylic resin, polyester resin, oxazoline group-containing resin, modified silicone resin, and titanium resin. Laminated adhesives composed of alkyl acid esters, polyester polybutadiene, etc., or one-liquid or two-liquid polyols and polyisocyanates, water-based urethanes, ionic polymers, etc. Alternatively, a water-based adhesive whose main raw material is acrylic resin, vinyl acetate resin, urethane resin, polyester resin, etc. can also be used. In addition, other additives such as a hardener and a silane coupling agent may be added to the adhesive according to the use of the gas barrier laminate 100 . When the gas barrier laminate is used for hot water treatment such as steaming, dry lamination represented by a polyurethane adhesive is preferred from the viewpoint of heat resistance or water resistance. Use an adhesive, preferably a solvent-based two-liquid hardening type polyurethane adhesive.

(Method for manufacturing gas barrier laminate) In the fifth embodiment, the manufacturing method of the gas barrier laminate 100 includes, for example: the steps of preparing the base material layer 101; the step of forming the inorganic layer 102 on the base layer 101; and the step of forming the inorganic layer 102 on the base material. A step of forming a gas barrier layer 103 on top of layer 101 . In addition, the step of forming the undercoat layer 104 on the inorganic layer 102 may be further included after the step of forming the inorganic layer 102 and before the step of forming the gas barrier layer 103 .

The step of forming the inorganic layer 102 on the base material layer 101 may use, for example, the method for forming the inorganic layer 102 described above.

The step of forming the gas barrier layer 103 includes, for example, applying the uncured mixture as a gas barrier coating material to the inorganic layer 102 and then drying it to obtain a coating layer; and applying the coating layer to the gas barrier layer 103 . A step of heating to cause a dehydration condensation reaction between the carboxyl groups contained in the polycarboxylic acid and the amine groups contained in the polyamine compound, thereby forming the gas barrier layer 103 having a amide bond.

The method of applying the gas barrier coating material to the inorganic layer 102 is not limited, and a common method can be used. For example, gravure coaters using Meyer rod coaters, air knife coaters, direct gravure coaters, indirect gravure, arc gravure coaters, reverse gravure and spray nozzle methods, top feed reverse gravure coaters, etc. Reverse roll coaters such as reverse roll coaters, bottom feed reverse coaters and nozzle feed reverse coaters, five-roller coaters, die lip coaters, rod coaters, reverse The coating method is performed using a known coater such as a bar coater or a die coater.

From the viewpoint of improving the barrier performance of the gas barrier laminate obtained, the coating amount (wet thickness) is preferably 0.05 μm, more preferably 1 μm or more. In addition, from the viewpoint of suppressing curling of the obtained gas barrier laminate and more effectively promoting the dehydration condensation reaction of the -COO- group contained in the polycarboxylic acid and the amine group contained in the polyamine compound , the wet thickness is preferably 300 μm or less, more preferably 200 μm or less, further preferably 100 μm or less.

Drying and heat treatment can be carried out after drying or at the same time. The method of drying and heat treatment is not limited as long as the effects of the present invention can be obtained, as long as the gas barrier coating material can be hardened or the gas barrier coating material can be heat-cured. Examples include devices that utilize convection heat transfer such as ovens and dryers, devices that utilize conductive heat transfer such as heating rollers, devices that utilize radiation heat transfer using electromagnetic waves such as infrared, far-infrared, and near-infrared heaters, and devices that utilize internal heat transfer such as microwaves. Heating device. As an apparatus used for drying and heat treatment, from the viewpoint of manufacturing efficiency, an apparatus capable of performing both drying and heat treatment is preferred. Among them, specifically, it is preferable to use a hot air oven from the viewpoint of being usable in various applications such as drying, heating, and annealing. In addition, from the viewpoint of excellent heat conduction efficiency to the film, it is preferable to use heating. Roller. In addition, methods used for drying and heat treatment may be appropriately combined. Specifically, a hot air oven and a heating roller may be used together. For example, if the gas barrier coating material is dried in a hot air oven and then heated using a heating roller, the time of the heating treatment step will be shortened, and from the viewpoint of manufacturing efficiency Better. In addition, it is preferable to perform drying and heating processing only by a hot air oven.

Regarding the heat treatment conditions, for example, the heat treatment temperature is 80°C to 250°C and the heat treatment time is 1 second to 1 minute. Preferably, the heat treatment temperature is 120°C to 240°C and the heat treatment time is 1 second to 31 minutes. More preferably, the heat treatment temperature is 170°C to 230°C and the heat treatment time is 1 second to 30 seconds. Still more preferably, the heat treatment temperature is 200°C to 220°C and the heat treatment time is 1 second to 10 seconds. Furthermore, as mentioned above, by using a heating roller together, heat processing can be performed in a short time. Furthermore, from the viewpoint of effectively promoting the dehydration condensation reaction between the -COO- group contained in the polycarboxylic acid and the amine group contained in the polyamine compound, it is important that the heat treatment temperature and heat treatment time are adjusted according to the gas The wet thickness of the barrier coating is adjusted.

By drying and heat-treating the gas barrier coating material, the carboxyl group of the polycarboxylic acid reacts with the polyamine or polyvalent metal compound to form covalent bonds and ionic cross-linking, thereby forming a gas that has good properties even after retort treatment. Barrier gas barrier layer 103 .

In the fifth embodiment, the gas barrier laminate has excellent gas barrier properties and can be suitably used in medical applications, industrial applications, and daily life as represented by packaging materials and food packaging materials for contents requiring high gas barrier properties. Various packaging materials for groceries and other purposes.

In addition, the gas barrier laminate of the fifth embodiment can be suitably used as, for example, a vacuum heat-insulating film requiring high barrier performance; a sealing film for sealing electroluminescent elements, solar cells, and the like.

Specific examples of the laminated structure including the gas barrier laminated body in the fifth embodiment are shown below. (Laminated structure example 1) Base material layer 101 (PET base material)/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyolefin layer (Laminated structure example 2) Base material layer 101 (PET base material)/undercoat layer 104/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyolefin layer (Laminated structure example 3) Base material layer 101 (PET base material)/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyamide layer/adhesive layer/polyolefin layer (Laminated structure example 4) Base material layer 101 (PET base material)/undercoat layer 104/inorganic layer 102 (aluminum oxide vapor deposition layer)/gas barrier layer 103/adhesive layer/polyamide layer/adhesive layer/ polyolefin layer Here, since the laminated structure includes a polyolefin layer containing polyolefins such as polyethylene, polypropylene, poly(4-methyl-1-pentene), and poly(1-butene), the gas barrier laminated body Medium can improve pinhole resistance, crack resistance, heat resistance, etc., and further suppress the decrease in gas barrier performance under high humidity or gas barrier performance after retort processing.

The first to fifth embodiments have been described above with reference to the drawings. However, these are examples of the first to fifth inventions, and various structures other than those described above may be adopted. [Example]

*The table numbers have been completely revised. There are also tables before the embodiment. Hereinafter, the first to fifth embodiments will be described in detail with reference to Examples and Comparative Examples. In addition, the first to fifth embodiments are not limited at all by the description of these Examples.

<Example of the first embodiment> (Example 1) (1) Preparation of gas barrier coating material Purified water was used to prepare a polyacrylic acid (PPA) aqueous solution (manufactured by Toagosei Co., Ltd., product name: AC-10H, Weight average molecular weight: 800,000) was diluted to prepare an aqueous solution with a concentration of 10% of PPA, and 10% ammonia was added so that 1 mol% of ammonia relative to the carboxyl group became 1.5 mol, thereby obtaining an aqueous solution of ammonium polyacrylate with a concentration of PPA of 7.38%. . Next, zinc oxide (ZnO: manufactured by Kanto Chemical Co., Ltd.) and ammonium carbonate (manufactured by Kanto Chemical Co., Ltd.) were added to the obtained ammonium polyacrylate aqueous solution and mixed and stirred. Here, the addition amount of zinc oxide is an amount such that (zinc oxide)/(carboxyl group of PPA) becomes 0.3 in molar ratio. In addition, the ammonium carbonate is an amount such that the molar ratio becomes 0.3 relative to the carboxyl group of PPA. Prepare mixture (A) as above. Next, purified water was added to polyethylene imine (PEI (polyethylene imine): manufactured by Nippon Shokubai, product name: SP-200, number average molecular weight: 10,000) to obtain polyethylene that was an aqueous solution with a concentration of 10% of PEI. imine aqueous solution. Next, the polyethyleneimine aqueous solution was mixed into the mixed liquid (A) at a molar ratio of (nitrogen of PEI)/(carboxyl group of PAA) of 0.55 to prepare a mixed liquid (B). Furthermore, purified water was added to the mixed liquid (B) so that the solid content concentration of PPA+ZnO+PEI became 2%, and the mixture was stirred until it became a homogeneous solution. Furthermore, an ammonium hydrogenphosphate aqueous solution with a solid content concentration of 2% was added and stirred so that 1 mol of ammonium hydrogenphosphate ((NH ₄ ) ₂ HPO ₄ : manufactured by Kanto Chemical Co., Ltd.) became 1×10 ^-3 mol with respect to 1 mol of carboxyl groups of PPA. Then, an active agent aqueous solution with a solid content concentration of 1% was mixed and adjusted so that the active agent (manufactured by Kao Corporation, trade name: Emulgen 120) became 0.3 mass % with respect to the solid content of PPA+ZnO+PEI. Gas barrier coating material.

(2) Production of gas barrier laminate A transparent vapor-deposited film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., model: TL-PET-H) with aluminum oxide as an inorganic layer was vapor-deposited on a 12 μm PET film prepared as a base material layer. The film was adhered to a glass plate, and the gas barrier coating material was applied using an applicator so that the film thickness after drying became 0.2 μm. Then, the glass plate was dried using a hot air dryer at 120° C. for 5 minutes. After fixing both ends of the dried membrane to make the membrane hollow, heat treatment was performed with a hot air dryer at 150° C. for 1 minute. Through the above, a gas barrier layer is formed on the transparent vapor deposition film, and a gas barrier laminate is produced. Table 7 shows the production conditions of the gas barrier layer.

(3) Analysis of gas barrier layer In addition, XPS analysis and TOF-SIMS analysis were performed on the gas barrier layer of the gas barrier laminate obtained in the above (2).

XPS analysis conditions Analytical device: AXIS-NOVA manufactured by KRATOS X-ray source: monochromated Al-Kα X-ray source output: 15 kV, 10 mA Analysis area: 300 μm×700 μm During analysis: Use a neutralizing gun for charged calibration Sample size: 1 cm×1 cm The results of XPS analysis are shown in Table 8.

TOF-SIMS analysis conditions Measurement pre-processing: Surface etching using Ar-GCIB GCIB: 5 kV, 5 μA GCIB processing time: The time point when the TOF-SIMS spectral pattern no longer changes Analysis equipment: Nippon Vacuum (Ulvac-phi) Co., Ltd. Manufactured PHI nano (nano)-TOFII Primary ion: Bi ₃ ²⁺ Primary ion source output: 30 kV, 0.5 μA Analysis area: 300 μm × 300 μm (scanning area of primary ion beam) During analysis, use the included device Low-energy electron beam and low-energy Ar ion irradiation for charged neutralization. The results of analyzing the data obtained by TOF-SIMS analysis based on the method are shown in Table 9. The so-called relative mass peak intensity normalized by the intensity of C ₃ H ₃ O ₂ ^- refers to the mass peak intensity of each fragment divided by the intensity of C ₃ H ₃ O ₂ ^- (I (C ₃ H ₃ O ₂ ^- )). Worth it.

(4) Production of a gas barrier laminate with a two-layer laminated structure An adhesive was applied to the corona discharge-treated surface of unstretched polypropylene (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) with a thickness of 70 μm, and was obtained in the above (2) The gas barrier surface of the gas barrier laminate is bonded to produce a gas barrier laminate with a two-layer laminated structure. The adhesive used was prepared with 9 parts by mass of Takelac A525S, a product manufactured by Mitsui Chemicals, 1 part by mass of an isocyanate hardener (Takenate A50, a product of Mitsui Chemicals), and acetic acid. It contains 7.5 parts by mass of ethyl ester.

(5) Evaluation of water vapor permeability of a two-layer laminate structure The gas barrier laminate obtained in (4) was folded so that the unstretched polypropylene became the inner surface, and both sides were heat-sealed to make a bag. After the bag is formed, add 70 cc of water as the content, heat-seal the other side to make a bag, and use a high-temperature and high-pressure cooking sterilization device to cook it at 130°C for 30 minutes. After the steaming process, the water in the contents is drained, the sealing part is removed, and the membrane after the steaming process (water-filled) is obtained. The gas barrier laminated film was folded so that the unstretched polypropylene became the inner surface of the retort-treated film obtained by the above method, and both sides were heat-sealed to form a bag, and then chlorinated Calcium is used as the content, and the other side is heat-sealed to make a bag with a surface area of 0.01 m ² . The bag is left for 300 hours under conditions of 40°C and 90% RH. The water vapor permeability is measured by the change in weight before and after leaving the bag [ g/(m ² ·day)]. Table 10 shows the gas barrier property evaluation results after the retort treatment.

(Example 2) A gas barrier layer was produced in the same manner as in Example 1, except that the concentration of ammonium hydrogen phosphate was 0.01 mol per mol of carboxyl groups of polyacrylic acid. The production conditions are also shown in Table 3. In addition, the obtained gas barrier layer was subjected to XPS analysis and TOF-SIMS analysis. The results of XPS analysis and TOF-SIMS analysis are shown in Tables 8 and 9. Table 10 shows the gas barrier property evaluation results after the retort treatment.

(Example 3) A gas barrier laminate was produced in the same manner as in Example 1 except that the concentration of ammonium hydrogen phosphate was 0.1 mol per mol of carboxyl groups of polyacrylic acid. The production conditions are also shown in Table 3. In addition, the obtained gas barrier layer was subjected to XPS analysis and TOF-SIMS analysis. The results of XPS analysis and TOF-SIMS analysis are shown in Tables 8 and 9. Table 10 shows the gas barrier property evaluation results after the retort treatment.

(Example 4) A gas barrier laminate was produced in the same manner as in Example 1, except that the concentration of ammonium hydrogen phosphate was 0.2 mol per mol of carboxyl groups of polyacrylic acid. The production conditions are also shown in Table 3. In addition, the obtained gas barrier layer was subjected to XPS analysis and TOF-SIMS analysis. The results of XPS analysis and TOF-SIMS analysis are shown in Tables 8 and 9. Table 10 shows the gas barrier property evaluation results after the retort treatment.

(Example 5) In place of the aqueous solution of ammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) with a solid content concentration of 2% in Example 1, ammonium water was used to neutralize phosphonic acid (also known as phosphorous acid) (manufactured by Kanto Chemical Co., Ltd. , H ₃ PO ₃ ), an aqueous solution of ammonium phosphonate salt ((NH ₄ ) ₂ HPO ₃ ) with a solid concentration of 2%, and the concentration of the ammonium phosphonate salt is 0.01 mol relative to 1 mol of carboxyl groups of polyacrylic acid, and A gas barrier laminate was produced in the same manner as in Example 1. The production conditions are also shown in Table 3. In addition, XPS analysis and TOF-SIMS analysis were performed on the gas barrier layer of the obtained gas barrier laminate. The results of XPS analysis and TOF-SIMS analysis are shown in Tables 8 and 9. Table 10 shows the gas barrier property evaluation results after the retort treatment.

(Comparative example 1) A gas barrier laminate was produced in the same manner as in Example 1 except that the concentration of ammonium hydrogen phosphate was 0.0001 mol per mol of carboxyl groups of polyacrylic acid. The production conditions are also shown in Table 3. In addition, XPS analysis and TOF-SIMS analysis were performed on the gas barrier layer of the obtained gas barrier laminate. The results of XPS analysis and TOF-SIMS analysis are shown in Tables 8 and 9. Table 10 shows the gas barrier property evaluation results after the retort treatment.

[Table 7] Base material layer + inorganic layer gas barrier layer dry heat treatment thickness PEI/PPA ZnO/PPA Phosphorus compounds/PPA Temperature (℃) Time (minutes) Temperature (℃) Time (minutes) μm Kind Adding amount Example 1 TL-PET 0.55 0.3 Phosphoric acid 0.001 120 5 150 1 0.2 Example 2 TL-PET 0.55 0.3 Phosphoric acid 0.01 120 5 150 1 0.2 Example 3 TL-PET 0.55 0.3 Phosphoric acid 0.1 120 5 150 1 0.2 Example 4 TL-PET 0.55 0.3 Phosphoric acid 0.2 120 5 150 1 0.2 Example 5 TL-PET 0.55 0.3 Phosphonic acid 0.01 120 5 150 1 0.2 Comparative example 1 TL-PET 0.55 0.3 Phosphoric acid 1×10 ^-4 120 5 150 1 0.2

[Table 8] XPS measurement results (atomic %) C O N Zn P Example 1 64.1 24.4 7.7 3.8 0 Example 2 63.7 24.8 7.7 3.7 0.1 Example 3 60.5 27.7 7.3 3.5 1.0 Example 4 57.4 30.5 6.9 3.4 1.8 Example 5 63.8 24.7 7.7 3.7 0.1 Comparative example 1 64.2 24.3 7.6 3.9 0

[Table 9] Total ion count Mass peak intensity Relative mass peak intensity normalized by intensity of C ₃ H ₃ O ₂ ^- Positive secondary ions Negative secondary ions CN ^- C ₃ H ₃ O ₂ ^- PO ₂ ^{- PO} _3- ⁶⁴ ZnPO _4H ^- CN ^- C ₃ H ₃ O ₂ ^- PO ₂ ^{- PO} _3- PO ₂ ^- +PO ₃ ^{- PO} _2- / ^PO _3- ⁶⁴ ZnPO _4H ^- Example 1 6491689 7747805 0.044 0.034 0.00046 0.0022 3.8× ^10-5 1.3 1.0 0.013 0.065 0.078 0.21 1.1× ^10-3 Example 2 6898339 8571746 0.042 0.033 0.0044 0.019 1.8×10 ^-4 1.3 1.0 0.13 0.56 0.69 0.23 5.3× ^10-3 Example 3 7741692 8556996 0.038 0.038 0.0063 0.030 4.9× ^10-4 0.99 1.0 0.17 0.80 0.96 0.21 1.3× ^10-2 Example 4 8510871 9036240 0.031 0.039 0.0078 0.037 8.9× ^10-4 0.81 1.0 0.20 0.95 1.1 0.21 2.3× ^10-2 Example 5 6661788 8178350 0.042 0.032 0.0097 0.020 6.9×10 ^-5 1.3 1.0 0.30 0.63 0.93 0.47 2.1× ^10-3 Comparative example 1 6838528 7950414 0.047 0.038 0.00054 0.0037 2.1× ^10-5 1.2 1.0 0.014 0.097 0.11 0.15 5.4× ^10-4

[Table 10] Two-layer laminate construction Water vapor transmission rate after cooking [g/(m ² ·day)] Example 1 2.1 Example 2 0.60 Example 3 0.70 Example 4 1.3 Example 5 1.6 Comparative example 1 5.1

In the TOF-SIMS analysis, in the comparative example where the mass peak intensity of ⁶⁴ ZnPO ₄ H ^- , which is a fragment indicating the presence of a phosphate-zinc bond that is a highly water-resistant bond, was small, the two-layer laminate structure was boiled. Low water vapor barrier. On the other hand, according to the gas barrier laminate of the first embodiment, a gas barrier laminate showing high gas barrier properties after the retort treatment can be produced.

<Additional example of the first embodiment: two-layer laminate structure> In the above-mentioned Examples 1 to 5 and Comparative Examples, the water vapor permeability of the two-layer laminate structure was evaluated. In addition to these, the oxygen permeability of a two-layer laminated structure and the gas barrier laminate of a three-layer laminated structure were also produced and evaluated (oxygen permeability and water vapor permeability) in the following manner.

(Example 1') (1) Production of gas barrier coating materials In the same manner as in Example 1, first, a gas barrier coating material was produced.

(2) Production of gas barrier laminate As the gas barrier coating material, the above-mentioned ones were used, and a two-layer laminate structure retort-processed film was obtained in the same manner as in Example 1.

(3) The water vapor permeability of the two-layer laminated structure was evaluated using OX-TRAN2/1 manufactured by MOCON, in accordance with Japanese Industrial Standards (JIS) K 7126, at 20°C, 90% The oxygen permeability [mL/(m ² ·day·MPa)] of the obtained two-layer laminated structure steamed membrane was measured under RH conditions.

(4) Production of gas barrier laminate with three-layer laminated structure First, an adhesive was applied to the corona discharge-treated surface of unstretched polypropylene (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) with a thickness of 60 μm, and a thickness of 15 μm was attached. A laminated body of a μm nylon film (manufactured by Unitika, trade name: Emblem ONBC). An adhesive is applied to the nylon film surface of the laminate and bonded to the gas barrier surface of the gas barrier laminate obtained in (2) of Example 1' to produce a gas barrier laminate with a three-layer laminate structure. body. The adhesive used is the same as (4) of Example 1. The obtained gas barrier laminate was folded so that the unstretched polypropylene became the inner surface, and both sides were heat-sealed to form a bag shape. 70 cc of water was added as the content, and the other side was heat-sealed. Make a bag and steam it for 30 minutes using a high-temperature and high-pressure cooking sterilization device at 130°C. After the steaming process, the water in the contents is drained, the sealing part is removed, and the membrane after the steaming process (water-filled) is obtained.

(5) Evaluation of gas barrier properties of three-layer laminate structures The water vapor permeability of the gas barrier laminate of the three-layer laminated structure obtained in Example 1' was evaluated by the same method as the water vapor permeability of Example 1. In addition, the oxygen permeability was evaluated by the same method as (1) of Example 1'. Table 11 shows the gas barrier property evaluation results after the retort treatment.

(Example 2') A gas barrier laminated body was produced in the same manner as in Example 1', except that the manufacturer in Example 2 was used as the gas barrier coating material. Furthermore, the gas barrier properties after the retort treatment (oxygen permeability of the two-layer laminated structure, oxygen permeability and water vapor permeability of the three-layer laminated structure) were evaluated in the same manner as in Example 1'. Table 11 shows the gas barrier property evaluation results after the retort treatment.

(Example 3') A gas barrier laminate was produced in the same manner as in Example 1', except that the manufacturer in Example 3 was used as the gas barrier coating material. Furthermore, the gas barrier properties (oxygen permeability of the two-layer laminated structure) after the retort treatment were evaluated in the same manner as in Example 1'. Table 11 shows the gas barrier property evaluation results after the retort treatment.

(Example 4') A gas barrier laminated body was produced in the same manner as in Example 1', except that the manufacturer in Example 5 was used as the gas barrier coating material. Furthermore, the gas barrier properties after the retort treatment (oxygen permeability of the two-layer laminated structure, oxygen permeability and water vapor permeability of the three-layer laminated structure) were evaluated in the same manner as in Example 1'. Table 11 shows the gas barrier property evaluation results after the retort treatment.

(Comparative example') A gas barrier laminate was produced in the same manner as in Example 1', except that the manufacturer in the comparative example was used as the gas barrier coating material. Furthermore, the gas barrier properties after the retort treatment (oxygen permeability of the two-layer laminated structure, oxygen permeability and water vapor permeability of the three-layer laminated structure) were evaluated in the same manner as in Example 1'. Table 11 shows the gas barrier property evaluation results after the retort treatment.

[Table 11] Two-layer laminate construction Three-layer laminate construction Oxygen permeability after cooking Oxygen permeability after cooking Water vapor permeability after cooking [ml/(m ² ·day·MPa)] [ml/(m ² ·day·MPa)] [g/(m ² ·day)] Example 1' 0.80 0.80 1.1 Example 2' 0.80 0.70 1.3 Example 3' 2.5 - - Example 4' 0.90 1.0 1.5 Comparative example 1 3.6 0.90 1.9

As shown in Table 11, high gas barrier properties were also confirmed in Examples 1' to 4'.

<Example of the second embodiment> (Example 1) (1) Preparation of gas barrier coating material Purified water was used to prepare a polyacrylic acid (PAA) aqueous solution (manufactured by Toagosei Co., Ltd., product name: AC-10H, weight average molecular weight : 800,000) to prepare a 10% aqueous solution of PAA. Add 10% ammonia water to this aqueous solution. The amount of ammonia was set to 1.5 mol of ammonia per 1 mol of carboxyl groups of PAA. In this way, a polyacrylic ammonium aqueous solution with a PAA concentration of 7.38% was obtained. Next, zinc oxide (ZnO: manufactured by Kanto Chemical Co., Ltd.) and ammonium carbonate (manufactured by Kanto Chemical Co., Ltd.) were added to the obtained ammonium polyacrylate aqueous solution and mixed and stirred. Here, the addition amount of zinc oxide is an amount such that (zinc oxide)/(carboxyl group of PAA) becomes 0.3 in molar ratio. In addition, the ammonium carbonate is an amount such that the molar ratio becomes 0.3 relative to the carboxyl group of PAA. Prepare mixture (A) as above. Next, purified water was added to polyethyleneimine (PEI: manufactured by Nippon Shokubai Co., Ltd., product name: SP-200, number average molecular weight: 10,000) to obtain a polyethyleneimine aqueous solution with a PEI concentration of 10%. Next, the mixed liquid (A) and the polyethyleneimine aqueous solution were mixed at a molar ratio of (nitrogen of PEI)/(carboxyl group of PAA) of 0.55 to prepare a mixed liquid (B). Furthermore, purified water was added to the mixed liquid (B) so that the solid content concentration of PAA+ZnO+PEI became 2%, and the mixture was stirred until a uniform solution was obtained. Furthermore, an ammonium hydrogenphosphate aqueous solution with a solid content concentration of 2% was added so that the amount of ammonium hydrogenphosphate ((NH ₄ ) ₂ HPO ₄ manufactured by Kanto Chemical Co., Ltd.) became 1×10 ^-3 mol based on 1 mol of carboxyl groups of PAA. Stir. Then, an active agent aqueous solution with a solid content concentration of 1% was mixed so that the amount of the active agent (manufactured by Kao Corporation, brand name: Emulgen 120) became 0.3% by mass relative to the solid content of PAA+ZnO+PEI. . In this way, a gas barrier coating material is prepared.

(2) Production of gas barrier laminate A transparent vapor-deposited film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., model: TL-PET-H) with aluminum oxide as an inorganic layer vapor-deposited on the 12 μm PET film of the base layer was adhered to the glass. plate. The gas barrier coating material was applied to the vapor deposition surface of the transparent vapor deposition film using an applicator so that the film thickness after drying would be 0.2 μm. After coating, the glass plate was dried using a hot air dryer at 120°C for 5 minutes. After fixing both ends of the dried film so that the film is in a hollow state, heat treatment is performed using a hot air dryer at 150° C. for 1 minute to form a gas barrier layer on the transparent evaporated film. In this way, a gas barrier laminate is produced. Table 12 shows the production conditions of the gas barrier layer.

(3) Analysis of gas barrier layer The gas barrier layer of the gas barrier laminate obtained in the above (2) was subjected to ATR-IR analysis, XPS analysis, and TOF-SIMS analysis.

(3-1)ATR-IR analysis As described above, a spectrum without the influence of the base material (PET) was obtained. Then, based on the spectrum, the peak area ratio D/A is calculated. The results are shown in Table 13.

(3-2) XPS analysis The gas barrier laminate was analyzed using a sample cut into 1 cm×1 cm. Specific analysis conditions are as described above. The results are shown in Table 13.

(3-3) TOF-SIMS analysis First, as a pretreatment, Ar-GCIB etching was performed to expose the inside of the gas barrier layer. The specific conditions for Ar-GCIB etching are as described above. Then, TOF-SIMS analysis was performed. The specific conditions are as described above. The results of analyzing the data obtained by TOF-SIMS analysis based on the method are shown in Table 14. In Table 14, the relative mass peak intensity normalized by the intensity of C ₃ H ₃ O ₂ ^- refers to the mass peak intensity of each fragment divided by the intensity of C ₃ H ₃ O ₂ ^- : I (C ₃ H ₃ O _2- ⁾ .

(4) Production of a gas barrier laminate with a two-layer laminated structure An adhesive was applied to the corona discharge-treated surface of unstretched polypropylene (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) with a thickness of 70 μm, and was obtained in the above (2) The gas barrier surface of the gas barrier laminate is bonded to produce a gas barrier laminate with a two-layer laminated structure. As an adhesive, a mix of 9 parts by mass of Takelac A525S, a product manufactured by Mitsui Chemicals, and 1 part of an isocyanate-based hardener (Takenate A50, a product of Mitsui Chemicals) were used. Parts by mass and ethyl acetate: 7.5 parts by mass.

(5) Evaluation of gas barrier properties after retort treatment The gas barrier laminate obtained in (4) was folded so that the unstretched polypropylene became the inner surface, and both sides were heat-sealed to form a bag. Then, add 70 cc of water as the content, and make a bag by heat-sealing the other side. Use a high-temperature and high-pressure cooking sterilization device to steam the bag at 130°C for 30 minutes. After the steaming process, the water in the contents is drained, the sealing part is removed, and the membrane after the steaming process (water-filled) is obtained. The retort-processed film obtained by the above method was stacked so that the unstretched polypropylene became the inner surface, the gas barrier laminated film was folded, and both sides were heat-sealed to form a bag. Then, calcium chloride is added as the content, and the other side is heat-sealed to create a bag so that the surface area becomes 0.01 m ² . The bag was placed for 300 hours at 40°C and 90%RH. The water vapor permeability [g/(m ² ·day)] was measured based on the weight change before and after standing. Table 15 shows the gas barrier property evaluation results after the retort treatment.

(Example 2) A gas barrier coating material was produced in the same manner as in Example 1, except that the concentration of ammonium hydrogen phosphate was 0.01 mol per mol of carboxyl groups of polyacrylic acid, and a gas barrier laminate was also produced. The production conditions are shown in Table 12. Similar to Example 1, the results of analyzing the gas barrier layer of the obtained gas barrier laminate are shown in Tables 13 and 14. In addition, the gas barrier property evaluation results after the retort treatment are shown in Table 15.

(Example 3) A gas barrier coating material was produced in the same manner as in Example 1, except that the concentration of ammonium hydrogen phosphate was 0.1 mol per mol of carboxyl groups of polyacrylic acid, and a gas barrier laminate was also produced. The production conditions are shown in Table 12. Similar to Example 1, the results of analyzing the gas barrier layer of the obtained gas barrier laminate are shown in Tables 13 and 14. In addition, the gas barrier property evaluation results after the retort treatment are shown in Table 15.

(Example 4) A gas barrier coating material was produced in the same manner as in Example 1, except that the concentration of ammonium hydrogen phosphate was 0.2 mol per mol of carboxyl groups of polyacrylic acid, and a gas barrier laminate was also produced. The production conditions are shown in Table 12. Similar to Example 1, the results of analyzing the gas barrier layer of the obtained gas barrier laminate are shown in Tables 13 and 14. In addition, the gas barrier property evaluation results after the retort treatment are shown in Table 15.

(Example 5) Instead of the aqueous solution of ammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) with a solid content concentration of 2% in Example 1, phosphonic acid (also known as phosphorous acid) neutralized with ammonia water (manufactured by Kanto Chemical Co., Ltd. , H ₃ PO ₃ ), an aqueous solution of an ammonium phosphonate salt ((NH ₄ ) ₂ HPO ₃ ) with a solid content concentration of 2%, such that the concentration of the ammonium phosphonate salt is 0.01 mol relative to 1 mol of the carboxyl group of the polyacrylic acid, A gas barrier coating material was produced in the same manner as in Example 1, and a gas barrier laminated body was also produced. The production conditions are shown in Table 12. Similar to Example 1, the results of analyzing the gas barrier layer of the obtained gas barrier laminate are shown in Tables 13 and 14. In addition, the gas barrier property evaluation results after the retort treatment are shown in Table 15.

(Example 6) Instead of the aqueous solution of ammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) with a solid content concentration of 2% in Example 1, phosphinic acid (alias, hypophosphorous acid) neutralized with ammonia water was used (Kanto Chemical Co., Ltd. An aqueous solution of ammonium phosphinic acid salt ((NH ₄ )H ₂ PO ₂ ) with a solid content concentration of 2% (H ₃ PO ₂ ) was produced, and the concentration of ammonium phosphinic acid salt was adjusted to 1 mol of carboxyl groups of polyacrylic acid. Except for 0.01 mol, a gas barrier coating material was produced in the same manner as in Example 1, and a gas barrier laminated body was also produced. The production conditions are shown in Table 12. Similar to Example 1, the results of analyzing the gas barrier layer of the obtained gas barrier laminate are shown in Tables 13 and 14. Table 6 shows the gas barrier property evaluation results after the retort treatment.

(Comparative example 1) A gas barrier coating material was produced in the same manner as in Example 1, except that the concentration of ammonium hydrogen phosphate was 0.0001 mol based on 1 mol of carboxyl groups of polyacrylic acid, and a gas barrier laminate was also produced. The production conditions are shown in Table 3. Similar to Example 1, the results of analyzing the gas barrier layer of the obtained gas barrier laminate are shown in Tables 4 and 5. In addition, the gas barrier property evaluation results after the retort treatment are shown in Table 15.

(Example 7) (1) Preparation of gas barrier coating material First, 10% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the ammonia content of the 10% ammonia water was relative to polyacrylic acid (manufactured by Toagosei Co., Ltd., product name: AC-10H, weight average molecular weight: 800,000) carboxyl group to 150 equivalent%, and purified water was added to obtain an ammonium polyacrylate aqueous solution with a concentration of 7.29 mass%. Next, zinc oxide (manufactured by Kanto Chemical Co., Ltd.) and ammonium carbonate were added to the obtained ammonium polyacrylate aqueous solution and mixed and stirred to prepare a mixed liquid (A). Here, the amount of zinc oxide added is (the mole number of zinc oxide in the gas barrier coating material)/(the mole number of -COO- groups contained in the polyacrylic acid in the gas barrier coating material). Amount of 0.225. In addition, ammonium carbonate is an amount such that (the mole number of the carbonic acid ammonium salt in the gas barrier coating material)/(the mole number of the zinc oxide in the gas barrier coating material) is 1.0. Next, purified water was added to polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., product name: SP-200, number average molecular weight: 10,000) to obtain a polyethyleneimine aqueous solution that was a 10% solution. Separately, purified water was added to diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ manufactured by Kanto Chemical Co., Ltd.) to prepare a 10% aqueous solution. Next, the mixed liquid (A), the polyethyleneimine aqueous solution, and the diammonium hydrogen phosphate solution are mixed with (the number of moles of amine groups contained in the polyethyleneimine in the gas barrier coating material) / (the mole number of -COO- groups contained in the polyacrylic acid in the gas barrier coating material) becomes 0.55 and (the mole number of (NH ₄ ) ₂ HPO ₄ ) / (the -COO contained in the polyacrylic acid -based molar number) were mixed at a ratio of 0.01 to prepare a mixed liquid (B). Furthermore, purified water was added so that the solid content concentration of the mixed liquid (B) became 1.5%, and it was stirred until it became a homogeneous solution. Then, the active agent (manufactured by Kao Corporation, trade name: Emulgen 120) was added and mixed so that the solid content of the mixed liquid (B) became 0.3 mass %. In this way, a gas barrier coating material is prepared.

(2) Production of gas barrier laminate An undercoat (UC) layer was formed on the corona-treated surface of a 12-μm-thick biaxially stretched polyethylene terephthalate film (PET12 manufactured by Unitika) using the following method. A biaxially stretched polyethylene terephthalate film (PET12 manufactured by Unitika) with a thickness of 12 μm was used as the base material, and the resin of the following composition was coated on this single side using a Meyer rod. composition and dried. Thereby, a dry undercoat (UC) layer with a thickness of 0.20 μm is formed. (composition) Main agent: polyurethane resin aqueous dispersion (manufactured by Mitsui Chemicals, product name: Takelac WS-4033, aromatic polyester type polyurethane resin) Cross-linking agent: Compound having a carbodiimide group (manufactured by Nisshinbo Chemical Co., Ltd., product name: Carbodilite SV-02) Preparation ratio: The cross-linking agent is prepared in the main agent so that the carbodiimide group in the cross-linking agent becomes 0.4 mol relative to 1.0 mol of the carboxyl group of the polyurethane resin in the main agent.

Next, an aluminum oxide evaporation layer was formed on the undercoat layer using the following method. Aluminum is heated and evaporated on the UC layer through high-frequency induction heating, and oxygen is introduced while evaporating to form an aluminum oxide film with a thickness of 7 nm. Thereby, an alumina vapor-deposited PET film is obtained. The water vapor permeability of the alumina evaporated PET film is 1.5 g/(m ² ·24 h). Then, apply the gas barrier coating material produced in the above (1) on the vapor deposition layer using a Meyer rod so that the coating amount after drying becomes 0.2 μm, and use a hot air dryer at a temperature of: 130°C. Time: 6.5 seconds for heat treatment. The production conditions are shown in Table 12.

(3) Analysis of gas barrier layer The gas barrier layer of the gas barrier laminate obtained in the above (2) was subjected to the same analysis as in (3) of Example 1. The analysis results are shown in Table 13 and Table 14.

(4) Production of a gas barrier laminate with a two-layer laminated structure Regarding the gas barrier layer of the gas barrier laminate obtained in the above (2), a gas barrier laminate having a two-layer laminated structure was produced in the same manner as in (4) of Example 1.

(5) Evaluation of gas barrier properties after cooking treatment In the same manner as (6) of Example 1, the gas barrier layered body obtained in the above (4) was evaluated for gas barrier properties after the retort treatment. The results are shown in Table 15.

(Example 8) A gas barrier coating material was produced in the same manner as in Example 7, except that the concentration of diammonium hydrogen phosphate was 0.03 mol per mol of carboxyl groups of polyacrylic acid, and a gas barrier laminate was also produced. The production conditions are shown in Table 12. Similar to Example 7, the results of analyzing the gas barrier layer of the obtained gas barrier laminate are shown in Tables 13 and 14. In addition, the gas barrier property evaluation results after the retort treatment are shown in Table 15.

[Table 12] Base material layer + inorganic layer gas barrier layer dry heat treatment thickness PEI/PPA ZnO/PPA Phosphorus compound/PAA Temperature (℃) Time (minutes) Temperature (℃) time (seconds) μm Kind Adding amount Example 1 TL-PET-H 0.55 0.3 Phosphoric acid 0.001 120 5 150 60 0.2 Example 2 TL-PET-H 0.55 0.3 Phosphoric acid 0.01 120 5 150 60 0.2 Example 3 TL-PET-H 0.55 0.3 Phosphoric acid 0.1 120 5 150 60 0.2 Example 4 TL-PET-H 0.55 0.3 Phosphoric acid 0.2 120 5 150 60 0.2 Example 5 TL-PET-H 0.55 0.3 Phosphonic acid (phosphorous acid) 0.01 120 5 150 60 0.2 Example 6 TL-PET-H 0.55 0.3 Phosphinic acid (hypophosphorous acid) 0.01 120 5 150 60 0.2 Comparative example 1 TL-PET-H 0.55 0.3 Phosphoric acid 1×10 ^-4 120 5 150 60 0.2 Example 7 UC-PET+alumina 0.55 0.225 Phosphoric acid 0.01 - - 130 6.5 0.2 Example 8 UC-PET+alumina 0.55 0.225 Phosphoric acid 0.03 - - 130 6.5 0.2

[Table 13] XPS measurement results (atomic %) ATR-IR analysis results C O N Zn P Peak area ratio D/A Example 1 64.1 24.4 7.7 3.8 0.0 0.67 Example 2 63.7 24.8 7.7 3.7 0.1 0.67 Example 3 60.5 27.7 7.3 3.5 1.0 0.63 Example 4 57.4 30.5 6.9 3.4 1.8 0.61 Example 5 63.8 24.7 7.7 3.7 0.1 0.69 Example 6 63.9 24.6 7.6 3.8 0.1 0.69 Comparative example 1 64.2 24.3 7.6 3.9 0.0 0.67 Example 7 64.9 24.1 8.1 2.8 0.1 0.75 Example 8 64.8 24.0 8.0 2.9 0.3 0.76

[Table 14] Total ion count Mass peak intensity Relative mass peak intensity normalized by intensity of C ₃ H ₃ O ₂ ^- Positive secondary ions Negative secondary ions CN ^- C ₃ H ₃ O ₂ ^- PO ₂ ^{- PO} _3- CN ^- C ₃ H ₃ O ₂ ^- PO ₂ ^{- PO} _3- PO ₂ ^- +PO ₃ ^- Example 1 6491689 7747805 0.0439 0.0341 0.0005 0.0022 1.29 1.00 0.01 0.06 0.08 Example 2 6898339 8571746 0.0420 0.0335 0.0044 0.0186 1.25 1.00 0.13 0.56 0.69 Example 3 7741692 8556996 0.0376 0.0380 0.0063 0.0302 0.99 1.00 0.17 0.80 0.96 Example 4 8510871 9036240 0.0311 0.0386 0.0078 0.0366 0.81 1.00 0.20 0.95 1.15 Example 5 6661788 8178350 0.0415 0.0323 0.0097 0.0204 1.28 1.00 0.30 0.63 0.93 Example 6 7099614 9634023 0.0413 0.0346 0.0148 0.0121 1.19 1.00 0.43 0.35 0.78 Comparative example 1 6838528 7950414 0.0467 0.0379 0.0001 0.0004 1.23 1.00 0.00 0.01 0.01 Example 7 5786522 8046471 0.0389 0.0351 0.0041 0.0187 1.11 1.00 0.12 0.53 0.65 Example 8 5129453 7745046 0.0367 0.0318 0.0090 0.0392 1.16 1.00 0.28 1.24 1.52

[Table 15] Gas barrier laminate two-layer laminated structure Water vapor permeability after cooking [g/(m ² ·day)] Example 1 2.1 Example 2 0.6 Example 3 0.7 Example 4 1.3 Example 5 1.6 Example 6 3.9 Comparative example 1 5.1 Example 7 1.6 Example 8 1.8

Based on the information shown in each table, including the value of (I(PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) (normalized by the intensity of C ₃ H ₃ O ₂ ^- The strength of PO ₂ ^- +PO ₃ ^- ) is large to some extent and the composition ratio of the metal element (Zn) is 1 atomic % to 15 atomic % (Example 1 to Implementation) Example 8) also showed smaller water vapor permeability after cooking treatment.

<Additional example of the second embodiment: Preparation and evaluation of a gas barrier laminate with a three-layer laminate structure> In Examples 1 to 8 described above, a gas barrier laminate having a two-layer laminated structure was produced and evaluated. In addition to these, a gas barrier laminate having a three-layer laminated structure was also produced and evaluated in the following manner.

(Example 2') (1) Preparation of gas barrier coating materials In the same manner as in Example 2, first, a gas barrier coating material was produced.

(2) Production of gas barrier laminate A gas barrier laminated body was produced in the same manner as in (2) of Example 1, except that the above-mentioned ones were used as the gas barrier coating material.

(3) Production of gas barrier laminate with three-layer laminated structure First, an adhesive was applied to the corona discharge-treated surface of unstretched polypropylene (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) with a thickness of 60 μm, and a thickness of 15 μm was adhered. A laminated body of nylon membrane (manufactured by Unitika, trade name: Emblem ONBC). An adhesive is applied to the nylon film surface of the laminated body and bonded to the gas barrier surface of the gas barrier laminated body obtained in (2) to prepare a gas barrier laminated body with a three-layer laminated structure. The adhesive used is the same as (4) of Example 1.

(4) Evaluation of gas barrier properties after retort treatment The gas barrier laminate obtained in (3) was folded so that the unstretched polypropylene became the inner surface, and both sides were heat-sealed to form a bag. Then, add 70 cc of water as the content, and make a bag by heat-sealing the other side. Use a high-temperature and high-pressure cooking sterilization device to steam the bag at 130°C for 30 minutes. After the steaming process, the water in the contents is drained, the sealing part is removed, and the membrane after the steaming process (water-filled) is obtained. Using OX-TRAN2/21 manufactured by MOCON, the oxygen permeability [mL/( m ² ·day·MPa)]. In addition, the gas barrier laminated film was folded so that the unstretched polypropylene became the inner surface of the retort-processed film obtained by the above method, and both sides were heat-sealed to form a bag shape. Then, calcium chloride is added as the content, and the other side is heat-sealed to create a bag so that the surface area becomes 0.01 m ² . The bag was placed for 300 hours at 40°C and 90%RH. The water vapor permeability [g/(m ² ·day)] was measured based on the weight change before and after standing. Table 16 shows the gas barrier property evaluation results after the retort treatment.

(Example 5') A gas barrier laminated body was produced in the same manner as in Example 2', except that the manufacturer in Example 5 was used as the gas barrier coating material. Furthermore, the gas barrier properties after the retort treatment were evaluated in the same manner as in Example 2'. The evaluation results are shown in Table 16.

(Example 6') A gas barrier laminate was produced in the same manner as in Example 2', except that the manufacturer in Example 6 was used as the gas barrier coating material. Furthermore, the gas barrier properties after the retort treatment were evaluated in the same manner as in Example 2'. The evaluation results are shown in Table 16.

[Table 16] Gas barrier laminate Three-layer laminated structure Oxygen permeability after cooking Water vapor permeability after cooking [ml/(m ² ·day·MPa)] [g/(m ² ·day)] Example 2' 0.7 1.3 Example 5' 1.0 1.5 Example 6' 0.8 1.5

As shown in Table 16, even when the layer structure is different from Examples 1 to 8, the gas barrier properties after retort are good.

<Example of the third embodiment> (Example 1) (1) Preparation of gas barrier coating material Using purified water, polyacrylic acid (PPA) aqueous solution (manufactured by Toagosei Co., Ltd., product name: AC-10H, weight average molecular weight : 800,000) to prepare a 10% aqueous solution of PPA. Aqueous ammonia with a concentration of 10% was added to this aqueous solution so that it became 1.5 mol of ammonia relative to 1 mol of carboxyl groups in PPA, thereby obtaining an aqueous ammonium polyacrylate solution with a concentration of PPA of 7.38%. Next, zinc oxide (ZnO) (manufactured by Kanto Chemical Co., Ltd.) and ammonium carbonate (manufactured by Kanto Chemical Co., Ltd.) were added to the obtained ammonium polyacrylate aqueous solution and mixed and stirred to obtain a mixed liquid. Here, the addition amount of zinc oxide is an amount such that (zinc oxide)/(carboxyl group of polyacrylic acid) becomes 0.3 in molar ratio. In addition, ammonium carbonate is an amount such that the molar ratio becomes 0.3 relative to the carboxyl group of polyacrylic acid. Furthermore, purified water was added to the mixed liquid so that the solid content concentration of PPA+ZnO became 2%, and the mixture was stirred until a uniform solution was obtained. Furthermore, an ammonium hydrogenphosphate aqueous solution with a solid content concentration of 2% was added and stirred so that ammonium hydrogenphosphate ((NH ₄ ) ₂ HPO ₄ ) (manufactured by Kanto Chemical Co., Ltd.) became 0.01 mol based on 1 mol of carboxyl groups of PPA. Furthermore, an active agent aqueous solution with a solid content concentration of 1% was mixed so that the active agent (manufactured by Kao Corporation, product name: Emulgen 120) became 0.3 mass % with respect to the solid content of PPA+ZnO, and was prepared. Gas barrier coating material.

(2) Production of gas barrier laminate A transparent vapor-deposited film (Mitsui Chemicals Tohcello Co., Ltd., model: TL-PET-H) with aluminum oxide as an inorganic layer was vapor-deposited on a 12 μm PET film prepared as a base material layer. This film was attached to a glass plate with the inorganic vapor deposition layer as the upper surface, and a gas barrier coating material was applied using an applicator so that the film thickness after drying became 0.2 μm. Then, the glass plate was dried using a hot air dryer at 120° C. for 5 minutes. After fixing both ends of the dried membrane to make the membrane hollow, heat treatment was performed with a hot air dryer at 150° C. for 1 minute. Thereby, a gas barrier laminate in which the gas barrier layer is formed on the transparent vapor deposition film is produced. The production conditions are summarized in Table 17.

(3) Analysis of gas barrier layer In addition, XPS analysis and TOF-SIMS analysis were performed on the gas barrier layer of the gas barrier laminate obtained in the above (2).

XPS analysis conditions Analytical device: AXIS-NOVA manufactured by KRATOS X-ray source: monochromated Al-Kα X-ray source output: 15 kV, 10 mA Analysis area: 300 μm×700 μm During analysis: Use a neutralizing gun for charged calibration Sample size: 1 cm×1 cm The results of XPS analysis are shown in Table 18.

TOF-SIMS analysis conditions Measurement pre-processing: Surface etching using Ar-GCIB GCIB: 5 kV, 5 μA GCIB processing time: The time point when the TOF-SIMS spectral pattern no longer changes Analysis equipment: Nippon Vacuum (Ulvac-phi) Co., Ltd. Manufactured PHI nano (nano)-TOFII Primary ion: Bi ₃ ²⁺ Primary ion source output: 30 kV, 0.5 μA Analysis area: 300 μm × 300 μm (scanning area of primary ion beam) During analysis, use the included device Low-energy electron beam and low-energy Ar ion irradiation for charged neutralization. The results of analyzing the data obtained by TOF-SIMS analysis based on the method are shown in Table 19. In Table 19, the relative mass peak intensity normalized by the intensity of C ₃ H ₃ O ₂ ^- refers to the mass peak intensity of the fragment divided by the intensity of C ₃ H ₃ O ₂ ^- I (C ₃ H ₃ O ₂ ^- ).

(4) Production of a gas barrier laminate with a two-layer laminated structure An adhesive was applied to the corona discharge-treated surface of unstretched polypropylene (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) with a thickness of 70 μm, and was obtained in the above (2) The gas barrier surface of the gas barrier laminate is bonded together to produce a gas barrier laminate with a two-layer laminated structure. The adhesive used was prepared by mixing 9 parts by mass of Takelac A5252S, a product manufactured by Mitsui Chemicals, 1 part by mass of an isocyanate hardener (Takenate A50, a product of Mitsui Chemicals), and acetic acid. It contains 7.5 parts by mass of ethyl ester.

(5) Production of gas barrier laminate with three-layer laminated structure First, an adhesive was applied to the corona discharge-treated surface of unstretched polypropylene (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) with a thickness of 60 μm, and a thickness of 15 μm was attached. A laminated body of a μm nylon film (manufactured by Unitika, trade name: Emblem ONBC). An adhesive is applied to the nylon film surface of the laminated body and bonded to the gas barrier surface of the gas barrier laminated body obtained in (2) to prepare a gas barrier laminated body with a three-layer laminated structure. The adhesive used is the same as described in (4).

(6) Evaluation of gas barrier properties after cooking treatment The gas barrier laminate obtained in (4) and (5) was folded so that the unstretched polypropylene became the inner surface, and both sides were heat-sealed to form a bag shape. Then, add 70 cc of water as the content, and make a bag by heat-sealing the other side. Use a high-temperature and high-pressure cooking and sterilization device to process the bag at 130°C for 30 minutes. After the steaming process, the water in the contents is drained, the sealing part is removed, and the membrane after the steaming process (water-filled) is obtained.

Using OX-TRAN2/21 manufactured by MOCON, the oxygen permeability [mL/( m ² ·day·MPa)]. In addition, the gas barrier laminated film was folded so that the unstretched polypropylene became the inner surface of the retort-processed film obtained by the above method, and both sides were heat-sealed to form a bag shape. Then, calcium chloride is added as the content, and the other side is heat-sealed to create a bag so that the surface area becomes 0.01 m ² . Then, it was left for 300 hours under the conditions of 40°C and 90%RH. The water vapor permeability [g/(m ² ·day)] was measured based on the weight change before and after standing. Table 20 shows the gas barrier property evaluation results after the retort treatment.

(Example 2) A gas barrier laminated body was produced in the same manner as in Example 1, except that the ammonium hydrogenphosphate ((NH ₄ ) ₂ HPO ₄ ) was set to 0.03 mol relative to 1 mol of the carboxyl group of the polyacrylic acid. The production conditions are shown in Table 17. In addition, XPS analysis and TOF-SIMS analysis were performed on the gas barrier layer of the obtained gas barrier laminate. The results of XPS analysis and TOF-SIMS analysis are shown in Table 18 and Table 19. Table 20 shows the gas barrier property evaluation results after the retort treatment.

(Example 3) A gas barrier laminated body was produced in the same manner as in Example 1, except that the ammonium hydrogenphosphate ((NH ₄ ) ₂ HPO ₄ ) was set to 0.05 mol relative to 1 mol of the carboxyl group of the polyacrylic acid. The production conditions are shown in Table 17. In addition, XPS analysis and TOF-SIMS analysis were performed on the gas barrier layer of the obtained gas barrier laminate. The results of XPS analysis and TOF-SIMS analysis are shown in Table 18 and Table 19. Table 20 shows the gas barrier property evaluation results after the retort treatment.

(Comparative example) A gas barrier laminate was produced in the same manner as in Example 1 except that ammonium phosphate was not added. The production conditions are shown in 17. In addition, XPS analysis and TOF-SIMS analysis were performed on the gas barrier layer of the obtained gas barrier laminate. The results of XPS analysis and TOF-SIMS analysis are shown in Table 18 and Table 19. Table 20 shows the gas barrier property evaluation results after the retort treatment. Among them, after the retort treatment, some delamination will occur in the gas barrier laminate.

[Table 17] Base material layer - inorganic layer gas barrier layer dry heat treatment thickness ZnO/PPA Phosphorus compounds/PPA Temperature (℃) Time (minutes) Temperature (℃) Time (minutes) μm Kind Adding amount Example 1 TL-PET-H 0.3 Phosphoric acid 0.01 120 5 150 1 0.2 Example 2 TL-PET-H 0.3 Phosphoric acid 0.03 120 5 150 1 0.2 Example 3 TL-PET-H 0.3 Phosphoric acid 0.05 120 5 150 1 0.2 Comparative example TL-PET-H 0.3 - - 120 5 150 1 0.2

[Table 18] XPS measurement results (atomic %) C O Zn P Example 1 62.0 32.9 5.0 0.1 Example 2 61.2 33.5 4.9 0.4 Example 3 60.2 34.3 4.8 0.7 Comparative example 62.4 32.5 5.1 0

[Table 19] Total ion count Mass peak intensity Relative mass peak intensity normalized with intensity of C ₃ H ₃ O ₂ Positive secondary ions Negative secondary ions C ₃ H ₃ O ₂ ^- PO ₂ ^- PO ₃ ^{- 64} ZnPO _4H ^- C ₃ H ₃ O ₂ ^- PO ₂ ^{- PO} _3- PO ₂ ^- +PO ₃ ^{- PO} _2- / ^PO _3- ⁶⁴ ZnPO _4H ^- Example 1 6049843 7508849 3.3× ^10-2 4.5× ^10-3 1.8× ^10-2 1.8×10 ^-4 1.0 1.4× ^10-1 5.5× ^10-1 6.9× ^10-1 2.5× ^10-1 5.5× ^10-3 Example 2 6201607 7428275 3.5× ^10-2 1.2× ^10-2 5.2× ^10-2 4.2× ^10-4 1.0 3.5× ^10-1 1.5 1.8 2.3× ^10-1 1.2× ^10-2 Example 3 6049843 7585995 3.4× ^10-2 1.5× ^10-2 6.2× ^10-2 7.9× ^10-4 1.0 4.4× ^10-1 1.8 2.2 2.4× ^10-1 2.4× ^10-2 Comparative example 5922165 6845306 3.8× ^10-2 0 0 0 1.0 0 0 0 - 0

[Table 20] Gas barrier laminate two-layer laminated structure Three-layer laminated structure Oxygen permeability after cooking Water vapor permeability after cooking Oxygen permeability after cooking Water vapor permeability after cooking [mL/(m ² ·day·MPa)] [g/(m ² ·day)] [mL/(m ² ·day·MPa)] [g/(m ² ·day)] Example 1 2.2 1.4 1.8 3.3 Example 2 1.6 0.7 1.9 2.4 Example 3 1.7 1.7 3.4 2.9 Comparative example 133.9 5.1 72.1 5.7

As described above, the gas barrier properties of the gas barrier laminate of the comparative example in which the phosphorus compound was not contained and the mass peak of ^{the 64} ZnPO ₄ H ^- fragment was not detected after the retort treatment was lower than that of Examples 1 to 3. In addition, some delamination will occur.

<Example of the fourth embodiment> (Example 1) (1) Preparation of gas barrier coating material 10% ammonia solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the ammonia content of the 10% ammonia solution would be higher than that of polyacrylic acid (Toa Manufactured by Synthetic Co., Ltd., product name: AC-10H, weight average molecular weight: 800,000) carboxyl group to 150 equivalent%, and then added purified water to obtain a polyacrylic ammonium aqueous solution with a concentration of 7.29 mass%. Next, zinc oxide (manufactured by Kanto Chemical Co., Ltd.) and ammonium carbonate were added to the obtained ammonium polyacrylate aqueous solution and mixed and stirred to prepare a mixed liquid (A). Here, the amount of zinc oxide added is (the mole number of zinc oxide in the gas barrier coating material)/(the mole number of -COO- groups contained in the polyacrylic acid in the gas barrier coating material). The amount of the value shown in the column of ZnO/PAA in Table 1. In addition, ammonium carbonate is an amount such that (the molar number of the carbonic acid ammonium salt in the gas barrier coating material)/(the molar number of zinc oxide in the gas barrier coating material) becomes 1.0. Next, purified water was added to polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., product name: SP-200, number average molecular weight: 10,000) to obtain a polyethyleneimine aqueous solution that was a 10% solution. Separately, purified water was added to diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ manufactured by Kanto Chemical Co., Ltd.) to prepare a 10% aqueous solution. Next, the mixed liquid (A), the polyethyleneimine aqueous solution, and the diammonium hydrogen phosphate solution are mixed with (the number of moles of amine groups contained in the polyethyleneimine in the gas barrier coating material) / (the mole number of -COO- groups contained in the polyacrylic acid in the gas barrier coating material) becomes the value shown in the column of PEI/PAA in Table 1 and the mole number of ((NH ₄ ) ₂ HPO ₄ The number of ears)/(the number of moles of the -COO- group contained in the polyacrylic acid) are mixed at a ratio such that the value shown in the addition amount of the oxygen compound/PAA column in Table 1 is obtained, and a mixed liquid (B) is prepared. . Furthermore, purified water was added so that the solid content concentration of the mixed liquid (B) became 1.5%, and the mixture was stirred until it became a uniform solution, so that the active agent (manufactured by Kao Corporation, trade name: Emulgen 120) was mixed with each other. Mix the liquid mixture (B) so that the solid content becomes 0.3% by mass, and prepare a gas barrier coating material.

(2) Preparation of gas barrier laminate A biaxially stretched polyethylene terephthalate film (PET12 manufactured by Unitika) with a thickness of 12 μm was used as the base material, and on this single side ( Corona treated surface) The resin composition of the following composition is applied using a Meyer rod and dried to form a primer (UC) layer with a thickness of 0.20 μm after drying. (Composition) Main ingredient: polyurethane resin aqueous dispersion (manufactured by Mitsui Chemicals, product name: Takelac WS-4033, aromatic polyester polyurethane resin) Cross-linking agent : Compound with carbodiimide group (manufactured by Nisshinbo Chemical Co., Ltd., product name: Carbodilite SV-02) Mixing ratio: relative to the polyurethane resin in the main agent The cross-linking agent is prepared in the main agent so that the carbodiimide group in the cross-linking agent becomes 0.4 mol for 1.0 mol of the carboxyl group. Next, an aluminum oxide evaporation layer was formed on the undercoat layer using the following method. Aluminum is heated and evaporated on the UC layer through high-frequency induction heating, and oxygen is introduced while evaporating to form an aluminum oxide film with a thickness of 7 nm. Thereby, an alumina vapor-deposited PET film is obtained. The water vapor permeability of the alumina evaporated PET film is 1.5 g/(m ² ·24 h). Then, use the gas barrier coating material obtained in the Meyer bar coating procedure (1) on the vapor deposition layer so that the coating amount after drying becomes 0.2 μm, and use a hot air dryer in the heat treatment column in Table 1 Heat treatment is performed under the conditions shown in to obtain a gas barrier laminate. Table 21 shows a list of production conditions.

(3) Analysis of Gas Barrier Layer In addition, the gas barrier layer of the gas barrier laminate obtained in the above procedure (2) was subjected to infrared absorption spectrum analysis based on the ATR method shown below. The infrared absorption spectrum was measured (infrared total reflection measurement: ATR method) using an IRT-5200 device manufactured by Nippon Spectroscopic Corporation, equipped with a PKM-GE-S (Germanium) crystal, at an incident angle of 45 degrees, room temperature, and a decomposition energy of 4 cm ^-1 and the cumulative number is 100 times. The obtained absorption spectrum is analyzed using the above method, the maximum peaks α and γ are obtained, and the total peak area A to total peak area D are calculated. Then, the area ratio B/A, the area ratio C/A, and the area ratio D/A are determined from the total peak area A to the total peak area D. The results of infrared absorption spectrum analysis based on the ATR method are shown in Table 22.

(4) Production of two-layer laminated structure Apply an adhesive to the corona discharge-treated surface of unstretched polypropylene (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) with a thickness of 70 μm, and follow the procedure (2) above. The gas barrier surfaces (the surfaces on the gas barrier layer side, the same below) of the obtained gas barrier laminates are bonded together to produce a laminated structure having a two-layer laminated structure. The adhesive used was prepared with Mitsui Chemicals Co., Ltd.'s brand name: Takelac A525S: 9 parts by mass, and an isocyanate-based hardener (Mitsui Chemicals Co., Ltd.'s brand name: Takenate A50): 1 mass part. and ethyl acetate: 7.5 parts by mass.

(5) Production of three-layer laminated structure First, an adhesive was applied to the corona discharge-treated surface of unstretched polypropylene (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) with a thickness of 60 μm, and a thickness of 15 μm was adhered. A laminated body of nylon membrane (manufactured by Unitika, trade name: Emblem ONBC). An adhesive is applied to the nylon film surface of the laminated body and adhered to the gas barrier surface of the gas barrier laminated body obtained in step (2) to prepare a laminated structure of a three-layer laminated structure. The adhesive used is the same as in sequence (4).

(6) Evaluation of gas barrier properties after retort treatment. The laminated structure obtained in procedures (4) and (5) was folded so that the unstretched polypropylene became the inner surface, and both sides were heat-sealed. After the bag is formed, add 70 mL of water as the content, heat-seal the other side to make a bag, and use a high-temperature and high-pressure cooking sterilization device to cook it at 130°C for 30 minutes. After the steaming process, the water in the contents is drained, the sealing part is removed, and the membrane after the steaming process (water-filled) is obtained. Oxygen permeability [ml/( m ² ·day·MPa)]. In addition, the retort-treated film obtained by the above method was folded so that the unstretched polypropylene became the inner surface, and the laminated structure was folded, and both sides were heat-sealed to form a bag, and then chlorine was added. Calcium oxide is used as the content, and the other side is heat-sealed to make a bag with a surface area of 0.01 m ² . The bag is left for 300 hours at 40°C and 90% RH. The water vapor permeability is measured by measuring the weight change before and after being left. Rate [g/(m ² ·day)]. Table 23 shows the gas barrier property evaluation results after the retort treatment.

(Example 2 to Example 8) Regarding each Example, a gas barrier laminated body and each laminated structure were obtained according to Example 1, except that the preparation of raw materials and the production conditions were respectively changed to the numerical values shown in Table 21. The results of analyzing the gas barrier layer of the gas barrier laminate obtained according to Example 1 are shown in Table 22. In addition, the gas barrier property evaluation results after the retort treatment are shown in Table 23.

(Comparative example 1) A gas barrier laminated body and a three-layer laminated structure were obtained according to Example 1 except that zinc oxide and ammonium carbonate were not used, and a diammonium hydrogen phosphate solution was not used. The results of analyzing the gas barrier layer of the gas barrier laminate obtained according to Example 1 are shown in Table 22. In addition, the gas barrier property evaluation results after the retort treatment are shown in Table 23.

(Example 9) (1) Preparation of gas barrier coating material A polyacrylic acid (PAA) aqueous solution (manufactured by Toagosei Co., Ltd., product name: AC-10H, weight average molecular weight: 800,000) was diluted with purified water to prepare PAA. To an aqueous solution with a concentration of 10%, add 10% ammonia so that it becomes 1.5 mol of ammonia relative to the carboxyl group, and obtain a polyacrylic ammonium aqueous solution with a PAA concentration of 7.38%. Next, zinc oxide (ZnO: manufactured by Kanto Chemical Co., Ltd.) and ammonium carbonate (manufactured by Kanto Chemical Co., Ltd.) were added to the obtained ammonium polyacrylate aqueous solution and mixed and stirred. Here, the addition amount of zinc oxide is an amount such that (zinc oxide)/(carboxyl group of PAA) becomes 0.3 in molar ratio. In addition, the ammonium carbonate is an amount such that the molar ratio becomes 0.3 relative to the carboxyl group of PAA. Prepare mixture (A) as above. Next, purified water was added to polyethyleneimine (PEI: manufactured by Nippon Shokubai Co., Ltd., product name: SP-200, number average molecular weight: 10,000) to obtain a polyethyleneimine aqueous solution having a concentration of 10% of PEI. . Next, the mixed liquid (A) and the polyethyleneimine aqueous solution were mixed at a molar ratio of (nitrogen of PEI)/(carboxyl group of PAA) of 0.55 to prepare a mixed liquid (B). Furthermore, purified water was added to the mixed liquid (B) so that the solid content concentration of PAA+ZnO+PEI became 2%, and the mixture was stirred until it became a homogeneous solution. Furthermore, a diammonium hydrogen phosphate aqueous solution with a solid content concentration of 2% was added so that diammonium hydrogen phosphate (manufactured by Kanto Chemical Co., Ltd., (NH ₄ ) ₂ HPO ₄ ) became 1 × 10 ^-3 mol with respect to 1 mol of carboxyl groups of PAA. After stirring, an active agent aqueous solution with a solid content concentration of 1% was mixed so that the active agent (manufactured by Kao Corporation, trade name: Emulgen 120) became 0.3 mass % with respect to the solid content of PAA+ZnO+PEI. , to prepare gas barrier coating materials.

(2) Production of gas barrier laminate A transparent evaporated film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., model: TL-PET-H) with aluminum oxide as an inorganic layer evaporated on the 12 μm PET film of the base material layer was adhered to the glass plate. The gas barrier coating material obtained in step (1) was applied with an applicator so that the dried film thickness became 0.2 μm, and the glass plate was dried with a hot air dryer at 120° C. for 5 minutes. After fixing both ends of the dried film so that the film becomes hollow, heat treatment is performed with a hot air dryer at 150°C for 1 minute to form a gas barrier layer on the transparent vapor deposition film to produce gas. Barrier laminate. Table 21 shows the production conditions of the gas barrier layer.

(3) Analysis of gas barrier layer The gas barrier layer of the gas barrier laminate obtained in the above procedure (2) was analyzed in the same manner as in the procedure (3) of Example 1. The results of the analysis are shown in Table 22.

(4) Production of a gas barrier laminate with a two-layer laminated structure Using the gas barrier layer of the gas barrier laminate obtained in the above procedure (2), a two-layer laminated structure was produced in the same manner as in the procedure (4) of Example 1.

(5) Production of gas barrier laminate with three-layer laminated structure Using the gas barrier layer of the gas barrier laminate obtained in the above procedure (2), a three-layer laminated structure was produced in the same manner as in the procedure (5) of Example 1.

(6) Evaluation of gas barrier properties after cooking treatment In the same manner as the procedure (6) of Example 1, the gas barrier properties after the retort treatment were evaluated on the laminated structures obtained in the procedures (4) and (5). The results are shown in Table 23.

(Example 10) A gas barrier laminated body and each laminated structure were produced according to Example 9 except that the concentration of diammonium hydrogen phosphate was 0.01 mol based on 1 mol of carboxyl groups of polyacrylic acid. The production conditions are also shown in Table 21. The results of analyzing the gas barrier layer of the gas barrier laminate obtained according to Example 9 are shown in Table 22. In addition, the gas barrier property evaluation results after the retort treatment are shown in Table 23.

(Example 11) A gas barrier laminated body and each laminated structure were produced according to Example 9 except that the concentration of diammonium hydrogen phosphate was 0.03 mol based on 1 mol of carboxyl groups of polyacrylic acid. The production conditions are also shown in Table 21. The results of analyzing the gas barrier layer of the gas barrier laminate obtained according to Example 9 are also shown in Table 22. In addition, the gas barrier property evaluation results after the retort treatment are shown in Table 23.

[Table 21] Gas barrier laminate Base material layer + inorganic layer gas barrier layer dry heat treatment thickness PEI/PPA ZnO/PPA ZnO/PEI Oxygen compound/PAA Temperature (℃) Time (minutes) Temperature (℃) time (seconds) μm Kind Adding amount Example 1 UC-PET+alumina 0.55 0.2 0.36 Phosphoric acid 0.03 - - 210 6.5 0.2 Example 2 UC-PET+alumina 055 0.2 0.36 Phosphoric acid 0.03 - - 130 6.5 0.2 Example 3 UC-PET+alumina 0.55 0.225 0.41 Phosphoric acid 0.03 - - 130 6.5 0.2 Example 4 UC-PET+alumina 0.55 0.175 0.32 Phosphoric acid 0.03 - - 130 6.5 0.2 Example 5 UC-PET+alumina 0.55 0.25 0.45 Phosphoric acid 0.01 - - 130 6.5 0.2 Example 6 UC-PET+alumina 0.55 0.225 0.41 Phosphoric acid 0.01 - - 130 6.5 0.2 Example 7 UC-PET+alumina 0.55 0.225 0.41 Phosphoric acid 0.03 - - 140 6.5 0.2 Example 8 UC-PET+alumina 0.55 0.225 0.41 Phosphoric acid 0.03 - - 150 6.5 0.2 Comparative example 1 UC-PET+alumina 0.55 0 0.00 - 0 - - 210 6.5 0.2 Example 9 TL-PET-H 0.55 0.3 0.55 Phosphoric acid 0.001 120 5 150 60 0.2 Example 10 TL-PET-H 0.55 0.3 0.55 Phosphoric acid 0.01 120 5 150 60 0.2 Example 11 TL-PET-H 0.55 0.3 0.55 Phosphoric acid 0.03 120 5 150 60 0.2

[Table 22] Gas barrier laminate Infrared absorption spectrum analysis results based on ATR method IR peak area ratio IR peak height C/A Β/Α D/Α α γ γ/α Example 1 0.07 0.32 0.62 0.045 0.014 0.32 Example 2 0.00 0.26 0.74 0.070 0.001 0.01 Example 3 0.00 0.24 0.76 0.060 0.000 0.00 Example 4 0.00 0.24 0.76 0.045 0.000 0.00 Example 5 0.01 0.24 0.75 0.086 0.005 0.06 Example 6 0.01 0.24 0.75 0.072 0.007 0.10 Example 7 0.00 0.24 0.76 0.068 0.003 0.04 Example 8 0.01 0.27 0.72 0.065 0.002 0.03 Comparative example 1 0.35 0.31 0.34 0.023 0.024 1.07 Example 9 0.00 0.33 0.67 0.128 0.030 0.23 Example 10 0.00 0.33 0.67 0.136 0.032 0.23 Example 11 0.06 0.32 0.62 0.175 0.056 0.32

[Table 23] Gas barrier laminate two-layer laminated structure Three-layer laminated structure Oxygen permeability after cooking Water vapor permeability after cooking Oxygen permeability after cooking Water vapor permeability after cooking [ml/(m ² ·day·MPa)] [g/(m ² ·day)] [ml/(m ² ·day·MPa)] [g/(m ² ·day)] Example 1 0.3 0.8 0.9 0.8 Example 2 1.8 2 0.8 1.7 Example 3 1 1·8 1.1 1.5 Example 4 2.7 2 1.6 1.5 Example 5 1.6 1.5 0.7 1.4 Example 6 1.7 1.6 0.8 1.2 Example 7 1.8 1.9 1.2 1.4 Example 8 1.7 1.8 0.9 1.4 Comparative example 1 - - 42 5.7 Example 9 0.8 2.1 0.8 1.1 Example 10 0.8 0.6 0.7 1.3 Example 11 0.8 1.7 0.9 1.8

According to Tables 21 to 23, in each of the Examples, even when either a two-layer laminated body or a three-layer laminated body is produced, the barrier after the retort treatment can be obtained with good productivity. A laminate with excellent properties.

<Example of fifth embodiment> (Example 1) (1) Production of gas barrier coating materials 10% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the ammonia content of the 10% ammonia water became 150 equivalent % relative to the carboxyl group of polyacrylic acid (manufactured by Toagosei Co., Ltd., product name: AC-10H, weight average molecular weight: 800,000) , and then added purified water to obtain an ammonium polyacrylate aqueous solution with a concentration of 7.29 mass%. Next, zinc oxide (manufactured by Kanto Chemical Co., Ltd.) and ammonium carbonate were added to the obtained ammonium polyacrylate aqueous solution and mixed and stirred to prepare a mixed liquid (A). Here, the amount of zinc oxide added is (the mole number of zinc oxide in the gas barrier coating material)/(the mole number of -COO- groups contained in the polyacrylic acid in the gas barrier coating material). Amounts of values shown in Table 1. In addition, ammonium carbonate is an amount such that (the molar number of the carbonic acid ammonium salt in the gas barrier coating material)/(the molar number of zinc oxide in the gas barrier coating material) becomes 1.0. Next, purified water was added to polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., product name: SP-200, number average molecular weight: 10,000) to obtain a polyethyleneimine aqueous solution that was a 10% solution. Next, the mixed solution (A) and the polyethyleneimine aqueous solution are mixed at the ratio of (the number of moles of amine groups contained in the polyethyleneimine in the gas barrier coating material)/(the number of moles in the polyethyleneimine in the gas barrier coating material). The molar number of -COO- groups contained in the polyacrylic acid) were mixed at a ratio such that the values shown in Table 1 become the values shown in Table 1, to prepare a mixed liquid (B). Furthermore, purified water was added so that the solid content concentration of the mixed liquid (B) became 1.5%, and the mixture was stirred until it became a uniform solution, so that the active agent (manufactured by Kao Corporation, trade name: Emulgen 120) was mixed with each other. Mix the liquid mixture (B) so that the solid content becomes 0.3% by mass, and prepare a gas barrier coating material.

(2) Preparation of gas barrier laminated film A biaxially stretched polyethylene terephthalate film (manufactured by Unitika, PET12) with a thickness of 12 μm was used as the base material. The treated surface is heated and evaporated by high-frequency induction heating, and oxygen is introduced while evaporation is performed, thereby forming an aluminum oxide film with a thickness of 7 nm. Thereby, an alumina vapor-deposited PET film is obtained. The water vapor permeability of the alumina evaporated PET film is 1.5 g/(m ² ·24 h). Next, a gas barrier coating material was applied on the vapor deposition layer using a Meyer rod so that the coating amount after drying would be 0.3 μm, and heat treatment was performed with a hot air drying device: 130°C, time: about 6.5 seconds, to obtain a gas barrier. Sexual laminated membrane. The following evaluation was performed on the obtained gas barrier laminated film. The results are shown in Table 24.

(Example 2) In addition to (the mole number of zinc oxide in the gas barrier coating material) / (the mole number of -COO- groups contained in the polyacrylic acid in the gas barrier coating material) and (the mole number of the -COO- group in the gas barrier coating material) The molar number of the amine group contained in the polyethyleneimine) / (the molar number of the -COO- group contained in the polyacrylic acid in the gas barrier coating material) are respectively changed to the values shown in Table 1, and The drying temperature in the hot air dryer was set to other than the temperature shown in Table 1, and the gas barrier laminated film was obtained according to Example 1. The following evaluation was performed on the obtained gas barrier laminated film. The results are shown in Table 24.

(Comparative example 1) A gas barrier laminated film was obtained according to Example 1 except that zinc oxide and ammonium carbonate were not used. The following evaluation was performed on the obtained gas barrier laminated film. The results are shown in Table 24.

(Example 3) (1) Preparation of a gas barrier coating material In addition to (moles of zinc oxide in the gas barrier coating material)/(-COO- contained in the polyacrylic acid in the gas barrier coating material) Molar number of amine groups) and (Molar number of amine groups contained in the polyethyleneimine in the gas barrier coating material) / (Molar number of -COO- groups contained in the polyacrylic acid in the gas barrier coating material molar number) were changed to values other than those shown in Table 1, and the procedure was carried out according to Example 1. (2) Preparation of gas barrier laminated film A biaxially stretched polyethylene terephthalate film (manufactured by Unitika, PET12) with a thickness of 12 μm was used as the base material on this single side. The resin composition of the following composition is coated with a Meyer rod and dried to form an undercoat (UC) layer with a thickness of 0.20 μm after drying. (Composition) Main ingredient: polyurethane resin aqueous dispersion (manufactured by Mitsui Chemicals, product name: Takelac WS-4033, aromatic polyester polyurethane resin) Cross-linking agent : Compound with carbodiimide group (manufactured by Nisshinbo Chemical Co., Ltd., product name: Carbodilite SV-02) Mixing ratio: relative to the polyurethane resin in the main agent The cross-linking agent is prepared in the main agent so that the carbodiimide group in the cross-linking agent becomes 0.4 mol for 1.0 mol of the carboxyl group. Then, aluminum is heated and evaporated on the UC layer by high-frequency induction heating, and oxygen is introduced while evaporation is performed, thereby forming an aluminum oxide film with a thickness of 7 nm. Thereby, an alumina vapor-deposited PET film is obtained. The water vapor permeability of the alumina evaporated PET film is 1.5 g/(m ² ·24 h). Then, a gas barrier coating material was applied on the vapor deposition layer using a Meyer rod so that the coating amount after drying would become 0.3 μm, and heat treatment was performed with a hot air drying device: 210°C, time: about 6.5 seconds, to obtain a gas barrier. Sexual laminated membrane. The following evaluation was performed on the obtained gas barrier laminated film. The results are shown in Table 24.

(Example 4 to Example 11) In addition to (the mole number of zinc oxide in the gas barrier coating material) / (the mole number of -COO- groups contained in the polyacrylic acid in the gas barrier coating material) and (the mole number of the -COO- group in the gas barrier coating material) The molar number of the amine group contained in the polyethyleneimine) / (the molar number of the -COO- group contained in the polyacrylic acid in the gas barrier coating material) are respectively changed to the values shown in Table 1, and The drying temperature in the hot air drying device was set to a temperature other than the temperature shown in Table 1, and a gas barrier laminated film was obtained according to Example 3. The following evaluations were performed on each of the obtained gas barrier laminated films, and the results are shown in Table 24.

(Comparative example 2) A gas barrier laminated film was obtained according to Example 3 except that zinc oxide and ammonium carbonate were not used. The following evaluation was performed on the obtained gas barrier laminated film. The results are shown in Table 24.

(evaluation method) (1) Apply an ester-based adhesive (polyurethane-based adhesive) to both sides of a nylon film with a thickness of 15 μm (Unitika company, trade name: Emblem ONBC) Adhesive (manufactured by Mitsui Chemicals, brand name: Takelac A525S): 9 parts by mass, isocyanate hardener (manufactured by Mitsui Chemicals, brand name: Takenate A50): 1 part by mass and Ethyl acetate: 7.5 parts by mass). Then, the barrier surface (the surface coated with the gas barrier coating material) of the gas barrier laminated film obtained in the Example and the Comparative Example and the uncoated film with a thickness of 60 μm were bonded to both sides of the nylon film to which the adhesive was provided. A polypropylene film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) was stretched to obtain a film before retort treatment.

(2) Steaming treatment (water filling) The film before retort treatment obtained in the above (1) was folded so that the unstretched polypropylene film became the inner surface, and both sides were heat-sealed to form a bag shape, and then 70 mL of water was added as the content. Heat-seal the other side to make a bag, and cook it using a high-temperature and high-pressure cooking sterilization device at 130°C for 30 minutes. After the retort treatment, the water in the contents is removed to obtain a post-retort treatment (water-filled) membrane.

(3) Oxygen permeability [mL/(m ² ·day·MPa)] Using OX-TRAN2/21 manufactured by MOCON, in accordance with JIS K 7126, under the conditions of temperature 20°C and humidity 90%RH The oxygen permeability of the membrane before the retort treatment and the membrane after the retort treatment (water filling) obtained by the above method were measured. Those whose oxygen permeability before cooking or after cooking are 6.0 mL/(m ² ·day·MPa) or less are considered qualified.

(4) Water vapor permeability [g/(m ² ·day)] For the film before retort treatment and the film after retort treatment (water filling) obtained by the above method, the unstretched polypropylene film is The gas barrier laminated film is folded so as to overlap the inner surface, and the three sides are heat-sealed to form a bag. Calcium chloride is added as the content, and the other side is heat-sealed to produce a bag with a surface area of 0.01 ^m2 . The bags were placed at 40°C and 90% RH for 300 hours, and the water vapor permeability was measured based on the difference in weight. Those whose water vapor permeability before cooking or after cooking is 5.5 g/(m ² ·day) or less are considered qualified.

(5) Maximum Peak Peak and Area Ratio of IR The gas barrier layer of the gas barrier laminated film obtained in each example was subjected to infrared absorption spectrum analysis based on the ATR method. That is, the infrared absorption spectrum was measured (infrared total reflection measurement: ATR method) using an IRT-5200 device manufactured by JASCO Corporation, with a PKM-GE-S (Germanium) crystal attached, at an incident angle of 45 degrees, at room temperature. , the resolution is 4 cm ^-1 , and the measurement is carried out under the conditions of 100 cumulative times. The obtained absorption spectrum is analyzed by the above method, the maximum peaks α and γ are obtained, and the total peak area A to total peak area D are calculated. Then, the area ratio B/A, the area ratio C/A, and the area ratio D/A are determined from the total peak area A to the total peak area D.

[Table 24] Base material layer/undercoat layer/inorganic layer gas barrier layer blocking evaluation Processing temperature Coating formula Coating film IR area ratio [-] Coated film IR peak height [-] Before cooking After steaming at 130°C for 30 minutes (Number of moles of amine groups contained in polyethyleneimine/Number of moles of -COO- groups contained in polyacrylic acid) (Molar number of zinc oxide/mol number of -COO- groups contained in polyacrylic acid) (moles of zinc oxide/moles of amine groups derived from polyamine compounds) (C/A) (carboxylic acid) (B/A) (amide) (D/A) (carboxylate) carboxylate/amide α (NH ₃ complex) γ (free carboxyl group) γ/α Oxygen permeability [mL/m ² /d/MPa] Water vapor permeability g/m ² /d Oxygen permeability [mL/m ² /d/MPa] Water vapor permeability g/m ² /d Example 1 PTE/-/alumina evaporation 130℃ 0.55 0.300 0.55 0.00 0.29 0.71 2.43 0.07 0.00 0.05 6.0 1.0 0.7 1.9 Comparative example 1 PTE/-/alumina evaporation 130℃ 0.55 0.000 0.00 0.00 0.29 0.71 2.43 0.07 0.00 0.05 15 1.5 30 4.0 Example 3 PET/UC/alumina evaporation 210℃ 0.55 0.300 0.55 0.00 0.32 0.68 2.13 0.06 0.00 0.02 0.5 0.4 0.6 2.4 Example 4 PET/UC/alumina evaporation 210℃ 0.55 0.200 0.36 0.09 0.32 0.59 1.81 0.04 0.01 0.31 0.6 0.4 1.2 1.8 Example 5 PET/UC/alumina evaporation 210℃ 0.55 0.400 0.73 0.00 0.32 0.68 2.08 0.05 0.00 0.00 0.6 0.4 1.6 5.0 Example 6 PET/UC/alumina evaporation 210℃ 0.45 0.300 0.67 0.01 0.32 0.67 2.10 0.06 0.00 0.04 0.6 0.4 1.0 3.4 Example 7 PET/UC/alumina evaporation 210℃ 0.65 0.300 0.46 0.00 0.33 0.66 1.99 0.05 0.00 0.03 0.7 0.4 1.7 2.7 Comparative example 2 PET/UC/alumina evaporation 210℃ 0.55 0.000 0.00 0.35 0.31 0.34 1.09 0.02 0.02 1.07 - - 42 5.7 Example 2 PET/-/alumina evaporation 130℃ 0.55 0.200 0.36 0.01 0.28 0.71 2.52 0.05 0.00 0.03 4.5 0.9 1.2 1.9 Example 8 PET/UC/alumina evaporation 150℃ 0.55 0.200 0.36 0.00 0.29 0.71 2.45 0.06 0.00 0.08 2.0 0.6 0.9 2.2 Example 9 PET/UC/alumina evaporation 210℃ 0.55 0.200 0.36 0.04 0.33 0.63 1.92 0.06 0.01 0.20 1.0 0.4 0.6 1.3 Example 10 PET/UC/alumina evaporation 210℃ 0.55 0.225 0.41 0.01 0.33 0.66 1.97 0.05 0.01 0.19 0.9 0.4 0.7 1.5 Example 11 PET/UC/alumina evaporation 210℃ 0.55 0.175 0.32 0.09 0.31 0.60 1.91 0.05 0.02 0.39 0.8 0.4 0.9 2.2

[Explanation of symbols used in FIGS. 1 to 4 for describing the first embodiment] 1: Two-layer laminated structure barrier film 2: Base material layer 3: Base coat (UC layer) 4: Inorganic layer 5: Gas barrier layer (OC layer) 6:Add layer 7: Unstretched polypropylene film (CCP) 8: Barrier laminate 9:Nylon membrane 10: Three-layer laminated structure barrier film 61: First bonding layer 62:Second bonding layer [Explanation of symbols used in FIGS. 5 to 8 for describing the second embodiment] 10: Gas barrier film 100: Gas barrier laminate 101:Substrate layer 102:Inorganic layer 103: Gas barrier layer 104: Primer coating 110: Gas barrier laminate [Explanation of symbols used in FIGS. 9 to 12 for describing the third embodiment] 1: Two-layer laminated structure barrier film 2: Base material layer 3: Base coat (UC layer) 4: Inorganic layer 5: Gas barrier layer (OC layer) 6:Add layer 7: Unstretched polypropylene film (CCP) 8: Barrier laminate 9:Nylon membrane 10: Three-layer laminated structure barrier film 61: First bonding layer 62:Second bonding layer [Explanation of symbols used in FIGS. 13 and 14 for describing the fourth embodiment] 10: Gas barrier film 100: Gas barrier laminate 101:Substrate layer 102:Inorganic layer 103: Gas barrier layer 104: Primer coating 110: Gas barrier laminate [Explanation of symbols used in FIGS. 15 and 16 for describing the fifth embodiment] 10: Gas barrier film 100: Gas barrier laminate 101:Substrate layer 102:Inorganic layer 103: Gas barrier layer 104: Primer coating 110: Gas barrier laminate

FIG. 1 is a cross-sectional view schematically showing an example of the structure of a two-layer laminated structure gas barrier laminate in the first embodiment. FIG. 2 is a cross-sectional view schematically showing an example of the structure of a three-layer laminated structure gas barrier laminate in the first embodiment. FIG. 3 is a diagram (graph) for explaining the triangular shape function Y _j (m) used in data analysis for mass analysis in the first embodiment. FIG. 4 is a diagram (graph) showing an example of curve fitting of mass analysis data in the first embodiment. FIG. 5 is a cross-sectional view schematically showing an example of the structure of the gas barrier laminate in the second embodiment. 6 is a cross-sectional view schematically showing an example of the structure of the gas barrier laminate in the second embodiment. FIG. 7 is a diagram (graph) for explaining the triangular shape function Y _j (m) used in data analysis for mass analysis in the second embodiment. FIG. 8 is a diagram (graph) showing an example of curve fitting of mass analysis data in the second embodiment. 9 is a cross-sectional view schematically showing an example of the structure of a two-layer laminated structure gas barrier laminate in the third embodiment. 10 is a cross-sectional view schematically showing an example of the structure of a three-layer laminated structure gas barrier laminate in the third embodiment. FIG. 11 is a diagram (graph) for explaining the triangular shape function Y _j (m) used in data analysis for mass analysis in the third embodiment. FIG. 12 is a diagram (graph) showing an example of curve fitting of mass analysis data in the third embodiment. 13 is a cross-sectional view schematically showing an example of the structure of the gas barrier laminate in the fourth embodiment. 14 is a cross-sectional view schematically showing an example of the structure of the gas barrier laminate in the fourth embodiment. FIG. 15 is a cross-sectional view schematically showing an example of the structure of the gas barrier laminate in the fifth embodiment. FIG. 16 is a cross-sectional view schematically showing an example of the structure of the gas barrier laminate in the fifth embodiment.

1: Two-layer laminated structure barrier film

2: Base material layer

3: Base coat (UC layer)

4: Inorganic layer

5: Gas barrier layer (OC layer)

6:Add layer

7: Unstretched polypropylene film (CPP film)

8: Barrier laminate

Claims (56)

A gas barrier laminate including: a base material layer; a gas barrier layer provided on at least one surface of the base material layer; and an inorganic layer provided between the base material layer and the gas barrier layer , the composition ratio of Zn measured by X-ray photoelectron spectrometry of the gas barrier layer is 1 atomic % to 10 atomic %, and the gas barrier layer will be analyzed by subjecting the gas barrier layer to time-of-flight secondary ions. When the mass peak intensity of ⁶⁴ ZnPO ₄ H ^- measured by mass analysis is set to I ( ⁶⁴ ZnPO ₄ H ^- ), and the mass peak intensity of C ₃ H ₃ O ₂ ^- is set to I ( C ₃ H ₃ O ₂ ^- ) , the value of I( ⁶⁴ ZnPO ₄ H ^- )/I(C ₃ H ₃ O ₂ ^- ) is 6×10 ^-4 or more and 5×10 ^-2 or less, by subjecting the gas barrier layer to X-ray photoelectron testing The composition ratio of N measured by spectroscopic analysis exceeds 0 atomic % and is 12 atomic % or less, assuming that the mass peak intensity of CN ^- measured by time-of-flight secondary ion mass analysis of the gas barrier layer is When it is I(CN ^- ), the value of I(CN ^- )/I(C ₃ H ₃ O ₂ ^- ) is greater than 0 and 2 or less. The gas barrier laminate according to claim 1, wherein the mass peak intensity of PO ₂ ^- measured by the time-of-flight secondary ion mass spectrometry of the gas barrier layer is set to I (PO ₂ ^- ), when the mass peak intensity of PO ₃ ^- is set to I (PO ₃ ^- ), (I (PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) The value is above 0.02 and below 5. The gas barrier laminate according to claim 1 or claim 2, wherein I(PO ₂ ^- )/I(PO) is the intensity ratio of the I(PO ₂ ^- ) to the I(PO ₃ ^- ). _3- ⁾ The value is 0.05 or more and 1 or less. The gas barrier laminate according to any one of claims 1 to 3, wherein the gas barrier layer includes a hardened product of a mixture containing at least polycarboxylic acid, Zn, and at least one - P-OH group phosphorus compound or its salt. The gas barrier laminate according to claim 4, wherein the concentration of P atoms of the phosphorus compound or its salt in the mixture is 5×10 ^-4 mol or more based on 1 mol of the polycarboxylic acid, and 0.3 mol or less. The gas barrier laminate according to claim 4 or 5, wherein the mixture further contains a polyamine. The gas barrier laminate according to claim 6, wherein the polyamine is polyethyleneimine. The gas barrier laminate according to any one of claims 4 to 7, wherein the polycarboxylic acid includes polyacrylic acid, polymethacrylic acid, and a copolymer of acrylic acid and methacrylic acid. One or more polymers in the group. The gas barrier laminate according to any one of claims 1 to 8, wherein the gas barrier layer has a thickness of 0.05 μm or more and 10 μm or less. A gas barrier laminate including: a base material layer; a gas barrier layer provided on at least one surface of the base material layer; and an inorganic layer provided between the base material layer and the gas barrier layer , when the gas barrier layer is subjected to time-of-flight secondary ion mass analysis, the mass peak intensity of PO ₂ ^- is set to I (PO ₂ ^- ), and the mass peak intensity of PO ₃ ^- is set to I (PO ₃ ^- ), when the mass peak intensity of C ₃ H ₃ O ₂ ^- is set to I (C ₃ H ₃ O ₂ ^- ), (I (PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) is 0.02 to 5, and the gas barrier layer includes one or more metal elements selected from the group consisting of Zn, Ca, Mg, Ba and Al. The composition ratio of the metal element in the gas barrier layer, as determined by X-ray photoelectron spectrometry analysis of the gas barrier layer, is 1 atomic % to 15 atomic %. The gas barrier laminate according to claim 10, wherein the mass peak intensity of CN ^- when the gas barrier layer is subjected to time-of-flight secondary ion mass analysis is set to I (CN ^- ), and C When the mass peak intensity of ₃ H ₃ O ₂ ^- is I (C ₃ H ₃ O ₂ ^- ), the value of I (CN ^- )/I (C ₃ H ₃ O ₂ ^- ) is 2 or less. The gas barrier laminate according to Claim 10 or 11, wherein in the absorption spectrum obtained by subjecting the gas barrier layer to infrared spectrometry using a total reflection measurement method, the absorption band is 1493 cm When the total peak area in the range from ^-1 to 1780 cm ^-1 is A and the total peak area in the absorption band from 1493 cm ^-1 to 1598 cm ^-1 is D, the area ratio D/A is 0.5 or above. The gas barrier laminated body according to any one of claims 10 to 12, wherein The inorganic layer is in contact with the base layer, or a primer layer is provided between the inorganic layer and the base layer. The gas barrier laminated body according to any one of claims 10 to 13, wherein The inorganic layer includes one or two or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum. The gas barrier laminated body according to any one of claims 10 to 14, wherein The thickness of the gas barrier layer is 0.01 μm˜15 μm. The gas barrier laminated body according to any one of claims 10 to 15, wherein Furthermore, a sealant layer is provided on the side of the gas barrier layer opposite to the inorganic layer. The gas barrier laminate according to Claim 16, wherein The sealant layer is in contact with the gas barrier layer, or the gas barrier layer and the sealant layer are connected through an adhesive layer. The gas barrier laminate according to claim 16, wherein A polyamide-containing layer is provided between the gas barrier layer and the sealant layer. The gas barrier laminate according to any one of claims 1 to 9, For food packaging purposes. The gas barrier laminated body according to any one of claims 10 to 19, Used to make steamed food. A packaging bag including the gas barrier laminate according to any one of claims 10 to 20. A food packaged with the gas barrier laminated body according to any one of claims 10 to 20. A gas barrier laminate including: a base material layer; a gas barrier layer provided on at least one surface of the base material layer; and an inorganic layer provided between the base material layer and the gas barrier layer , the composition ratio of Zn measured by X-ray photoelectron spectrometry of the gas barrier layer is 1 atomic % to 10 atomic %, and the gas barrier layer will be analyzed by subjecting the gas barrier layer to time-of-flight secondary ions. When the mass peak intensity of ⁶⁴ ZnPO ₄ H ^- measured by mass analysis is set to I ( ⁶⁴ ZnPO ₄ H ^- ), and the mass peak intensity of C ₃ H ₃ O ₂ ^- is set to I ( C ₃ H ₃ O ₂ ^- ) , the _value of I( ^{64ZnPO4H -} )/I( _C3H3O2- ⁾ _is 7× ^10-4 or _more and 5× ^10-2 or less. The gas barrier laminate according to claim 23, wherein the mass peak intensity of PO ₂ ^- measured by the time-of-flight secondary ion mass spectrometry of the gas barrier layer is set to I (PO ₂ ^- ), when the mass peak intensity of PO ₃ ^- is set to I (PO ₃ ^- ), (I (PO ₂ ^- ) + I (PO ₃ ^- ))/I (C ₃ H ₃ O ₂ ^- ) The value is above 0.02 and below 5. The gas barrier laminate according to claim 23 or 24, wherein I(PO ₂ ^- )/I(PO) is the intensity ratio of the I(PO ₂ ^- ) to the I(PO ₃ ^- ). _3- ⁾ The value is 0.05 or more and 1 or less. The gas barrier laminate according to any one of claims 23 to 25, wherein the gas barrier layer includes a hardened product of a mixture containing at least polycarboxylic acid, Zn, and at least one - P-OH group phosphorus compound or its salt. The gas barrier laminate according to Claim 26, wherein the phosphorus compound or salt thereof containing one or more -P-OH groups in the mixture is 1 mol relative to 1 mol of the carboxyl group in the polycarboxylic acid. The concentration is 5×10 ^-4 mol or more and 0.3 mol or less. The gas barrier laminate according to claim 26 or 27, wherein the polycarboxylic acid includes polyacrylic acid selected from the group consisting of polyacrylic acid, polymethacrylic acid, and copolymers of acrylic acid and methacrylic acid. One or more than two polymers. The gas barrier laminate according to any one of claims 23 to 28, wherein the gas barrier layer has a thickness of 0.05 μm or more and 10 μm or less. A gas barrier laminate including: base material layer; a gas barrier layer disposed on at least one surface of the base material layer; and an inorganic layer disposed between the base material layer and the gas barrier layer, The gas barrier layer includes a hardened product of a mixture including a polycarboxylic acid, a polyamine compound, a polyvalent metal compound, and a phosphorus compound containing one or more -P-OH groups or a salt thereof. The gas barrier laminate according to claim 30, further comprising a primer layer provided between the base material layer and the inorganic layer. The gas barrier laminate according to Claim 30 or 31, wherein the inorganic layer is provided on the base material layer, or has an intermediary layer between the base material layer and the inorganic layer. The evaporated film is disposed on the interposer layer and includes one or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum. The gas barrier laminate according to any one of claims 30 to 32, wherein the infrared absorption spectrum of the gas barrier layer is in a range from 1300 cm ^-1 to 1490 cm ^-1 Let α be the maximum peak height of the absorbance, and let γ be the maximum peak height of the absorbance in the range of 1690 cm ^-1 or more and 1780 cm ^-1 or less. The free carboxyl group represented by γ/α is complexed with NH ₃ The ratio of objects is above 0.00 and below 1.00. The gas barrier laminate according to any one of claims 30 to 33, wherein in the infrared absorption spectrum of the gas barrier layer, the absorption band is from 1493 cm ^-1 to 1780 cm ^-1 Let the total peak area in the range of the absorption band be A, let the total peak area in the range of the absorption band 1598 cm ^-1 or more and 1690 cm ^-1 be B, let the absorption band be 1690 cm ^-1 or more and 1780 cm ^-1 When the total peak area of the absorption band in the range of 1493 cm ^-1 or more and 1598 cm ^-1 or less is designated as D, the area ratio of the amide bond represented by B/A is 0.200 or more and 0.370 or less, the area ratio of the carboxylic acid represented by C/A is 0.150 or less, and the area ratio of the carboxylic acid salt represented by D/A is 0.580 or more and 0.800 or less. The gas barrier laminate according to any one of claims 30 to 34, wherein the gas barrier layer has a thickness of 0.01 μm or more and 15 μm or less. The gas barrier laminate according to any one of claims 30 to 35, wherein the multivalent metal compound is one or two selected from the group consisting of Zn, Ca, Mg, Ba and Al. Compounds of more than two valent metals. The gas barrier laminate according to any one of claims 30 to 36, wherein (the molar number of P atoms derived from the phosphorus compound or its salt in the mixture)/(the mixture (the molar number of the -COO- group derived from the polycarboxylic acid) is 0.001 or more and 0.3 or less. The gas barrier laminate according to any one of claims 30 to 37, wherein the phosphorus compound is selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid and salts thereof. One or more than two types of groups. The gas barrier laminated body according to any one of claims 30 to 38, wherein (moles of the polyvalent metal derived from the polyvalent metal compound in the mixture)/(the mixture The molar number of the -COO- group derived from the polycarboxylic acid) is 0.10 or more and 0.80 or less. The gas barrier laminate according to any one of Claims 30 to 39, wherein (the mole number of the polyvalent metal derived from the polyvalent metal compound in the mixture)/(the mixture (the molar number of the amine group derived from the polyamine compound) is 0.25 or more and 0.65 or less. The gas barrier laminate according to any one of claims 30 to 40, wherein the polycarboxylic acid includes polyacrylic acid, polymethacrylic acid, and a copolymer of acrylic acid and methacrylic acid. One or more polymers in the group. The gas barrier laminate according to any one of claims 30 to 41, wherein the polyamine compound contains polyethyleneimine. The gas barrier laminate according to any one of claims 30 to 42, wherein the base material layer contains a material selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. One or more resins in the group consisting of esters. A gas barrier laminate including: base material layer; a gas barrier layer disposed on at least one surface of the base material layer; and an inorganic layer disposed between the base material layer and the gas barrier layer, The gas barrier layer includes a hardened product of a mixture including a polycarboxylic acid, a polyamine compound, and a polyvalent metal compound. The gas barrier laminate according to claim 44, further comprising a primer layer provided between the base material layer and the inorganic layer. The gas barrier laminate according to Claim 44 or 45, wherein the inorganic layer is provided on the base material layer, or has an intermediary layer between the base material layer and the inorganic layer. The evaporated film is disposed on the interposer layer and includes one or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum. The gas barrier laminate according to any one of claims 44 to 46, wherein the inorganic layer includes an aluminum oxide layer containing aluminum oxide. The gas barrier laminate according to any one of claims 44 to 47, wherein the infrared absorption spectrum of the gas barrier layer is in a range from 1300 cm ^-1 to 1490 cm ^-1 Let α be the maximum peak height of the absorbance, and let γ be the maximum peak height of the absorbance in the range of 1690 cm ^-1 or more and 1780 cm ^-1 or less. The free carboxyl group represented by γ/α is complexed with NH ₃ The ratio of objects is above 0.00 and below 1.00. The gas barrier laminate according to any one of claims 44 to 48, wherein in the infrared absorption spectrum of the gas barrier layer, the absorption band is from 1493 cm ^-1 to 1780 cm ^-1 Let the total peak area in the range of the absorption band be A, let the total peak area in the range of the absorption band 1598 cm ^-1 or more and 1690 cm ^-1 be B, let the absorption band be 1690 cm ^-1 or more and 1780 cm ^-1 When the total peak area of the absorption band in the range of 1493 cm ^-1 or more and 1598 cm ^-1 or less is designated as D, the area ratio of the amide bond represented by B/A is 0.200 or more and 0.370 or less, the area ratio of the carboxylic acid represented by C/A is 0.150 or less, and the area ratio of the carboxylic acid salt represented by D/A is 0.580 or more and 0.800 or less. The gas barrier laminate according to any one of claims 44 to 49, wherein the gas barrier layer has a thickness of 0.01 μm or more and 15 μm or less. The gas barrier laminate according to any one of claims 44 to 50, wherein the polyvalent metal compound is one or two selected from the group consisting of Zn, Ca, Mg, Ba and Al. Compounds of more than two valent metals. The gas barrier laminate according to any one of Claims 44 to 51, wherein (the number of moles of the polyvalent metal derived from the polyvalent metal compound in the mixture)/(the mixture The molar number of the -COO- group derived from the polycarboxylic acid) is 0.10 or more and 0.80 or less. The gas barrier laminate according to any one of claims 44 to 52, wherein (moles of the polyvalent metal derived from the polyvalent metal compound in the mixture)/(the mixture (the molar number of the amine group derived from the polyamine compound) is 0.25 or more and 0.75 or less. The gas barrier laminate according to any one of claims 44 to 53, wherein the polycarboxylic acid includes polyacrylic acid, polymethacrylic acid, and a copolymer of acrylic acid and methacrylic acid. One or more polymers in a group. The gas barrier laminate according to any one of claims 44 to 54, wherein the polyamine compound contains polyethyleneimine. The gas barrier laminate according to any one of claims 44 to 55, wherein the base material layer is selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. A layer of one or more resins in a group of diesters.